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A Comprehensive Review of Lubricant Chemistry Technology Selection and Design
A Comprehensive Review of Lubricant Chemistry Technology Selection and Design
Lubricant Chemistry,
Technology,
Selection,
and Design
Syed Q. A. Rizvi
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Pos 10 10
A Comprehensive Review of
Lubricant Chemistry,
Technology, Selection, and
Design
Syed Q. A. Rizvi, Ph.D.
ASTM International
100 Barr Harbor Drive
PO Box C700
West Conshohocken, PA 19428–2959
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Library of Congress Cataloging-in-Publication Data
Rizvi, Syed Q. A., 1945–
A comprehensive review of lubricant chemistry, technology, selection, and design / Syed Q. A. Rizvi.
“ASTM stock number: MNL59.”
ISBN 978-0-8031-7000-1
1. Lubricating oils. I. Title.
TJ1077.R48 2008
621.8⬘9—dc22 2008003579
Copyright © 2009 ASTM International, West Conshohocken, PA. All rights reserved. This material may not be reproduced
or copied, in whole or in part, in any printed, mechanical, electronic, film, or other distribution and storage media, with-
out the written consent of the publisher.
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NOTE: The Society is not responsible, as a body, for the statements and opinions expressed in this publication. ASTM
International does not endorse any products represented in this publication.
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Contents
Preface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ix
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Film-forming Agents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 149
Emulsifiers and Demulsifiers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 181
Polymeric Additives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 187
Other Additives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 206
Multifunctional Nature of Additives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 207
Environmental Impact of Additives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 207
The Introduction of a New Additive . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 208
The Approval Process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 210
Permissions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 601
Appendix . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 603
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 635
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ix
Preface
This book provides an overview of the technology of lubricants and its use in devising new ones. During my research, I found
lubricant literature, both academic and commercial, to be rich with respect to information, with the Worldwide Web being an
excellent source. The monographs pertaining to lubricant technology and tribology that I found most useful are listed below.
1. Motor Oils and Engine Lubrication by Alphonse Schilling, published by Scientific Publications, Great Britain, 1968.
2. Lubricants and Related Properties—Synthesis, Properties, Applications, International Standards, authored by Profes-
sor Dieter Klamann, published by Verlag Chemie, Hamburg, 1984.
3. Chemistry and Technology of Lubricants, Edited by R. M. Mortier and S. T. Orszulik, published by VCH Publishers, Inc.
共Blackie兲, New York, 1992.
4. Automotive Lubricants Reference Handbook by Arthur Caines and Roger Haycock, published by SAE International,
1996.
5. Lubricant Additives: Chemistry and Applications, Leslie R. Rudnick, Ed., Marcel Dekker, Inc., New York, 2003.
6. Fuels and Lubricants Handbook: Technology, Properties, and Testing, George E. Totten, Ed., ASTM International,
Philadelphia, 2003.
7. CRC Handbook of Lubrication, Vol. I, Theory and Practice of Tribology: Applications and Maintenance, Richard E.
Booser, Ed., CRC Press, Boca Raton, 1983; CRC Handbook of Lubrication, Theory and Practice in Tribology, Vol. II,
Theory and Design, Richard E. Booser Ed., CRC Press, Boca Raton, 1988; CRC Handbook of Lubrication, Theory and
Practice in Tribology, Vol. III, Monitoring, Materials, Synthetic Lubricants, and Applications, Richard E. Booser, Ed.,
CRC Press, Boca Raton, 1993.
8 Handbook of Lubrication and Tribology, Vol. I, Applications and Maintenance, 2nd ed., George E. Totten, Ed., CRC
Press, Boca Raton, 2006.
9 Fundamentals of Tribology, N. P. Suh and N. Saka, Eds., MIT Press, Cambridge, Massachusetts, 1980.
10. Friction, Wear, Lubrication: A Text Book of Tribology, Kenneth C. Ludema, Ed., CRC Press, Boca Raton, 1996.
11. Introduction to Tribology, Bharat Bhushan, John Wiley & Sons, Inc., 2002.
The present manuscript differs from these in that it is written both from a chemist’s perspective and a lubrication engineer’s
perspective and therefore places equal emphasis on the chemistry and the formulation of lubricants. In addition, it includes
additive technology that is used in petroleum exploration, refining, and fuels.
The finalizing of this manuscript would not have been possible without the help of many of my colleagues, at Lubrizol and
elsewhere, my wife Marie, and my children Sophia and Ali. My colleagues provided me the technical advice and my family
provided the needed moral support. In addition, I am indebted to Marie and Sophia for typing portions of the manuscript and
reviewing the document for content, legibility, and grammar. I also wish to express my gratitude to the ASTM publications staff
including Monica Siperko, most of who worked behind the scenes to make this publication possible. Above all, I am indebted to
Kathy Dernoga of ASTM International who faciliated the completion of this book by providing continuous support.
Syed Q. Rizvi
January 2009
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MNL59-EB/Mar. 2009
1
Lubrication Fundamentals
THIS CHAPTER DEALS WITH THE FUNDAMENTALS and dissipates the heat away from the critical moving
of lubrication. It covers the lubricant functions, nature and parts of the equipment, thereby decreasing the possi-
composition of the lubricants market, concepts of friction, bility of the machine component deformation and
lubrication, viscosity, and wear, lubricant types, and lubri- wear. The heat is either frictional heat that results
cant selection, performance specifications, and composi- from the metal surfaces rubbing against one another,
tion. A brief description of the lubricant classes and addi- such as in gears, or is conducted and radiated heat,
tives is also provided. The concepts addressed in this which is due to the close proximity of the parts to a
chapter are invaluable in understanding the modern lubri- combustion source, such as the combustion chamber
cant technology and the material covered in the subse- in an automobile engine.
quent chapters. 3. Cleaning and Suspending—Lubricant facilitates
Almost all modern machines require the use of a lubri- smooth operation of the equipment by removing and
cant. Power generation in such equipment is achieved by suspending potentially harmful products, such as car-
the use of engines that mostly comprise metal parts that bon, sludge, and varnish, and the other materials, such
move against one another. In many cases, there is metal-to- as dirt and wear debris. This lubricant function is im-
metal contact that leads to the generation of friction and portant in operations that involve high operating tem-
heat, which results in wear. The extent of wear in equip- peratures, as in the case of an internal combustion en-
ment depends upon the degree of the metal-to-metal con- gine or a transmission. This is because in these
tact, either due to the equipment design or the nature of applications the lubricant gets oxidized to form de-
the operation. For example, the equipment that is designed posit precursors that can separate on hot surfaces and
to experience minimal metal-to-metal contact, as is the get converted into deposits.
case in most parts of an internal combustion engine, there 4. Protection—Lubricant prevents metal damage due to
is little friction and wear. However, the parts that are de- oxidation products, corrosion, and wear. It achieves
signed to have intimate metal-to-metal contact, such as this by forming a physical film on metal surfaces that
gears and bearings, wear due to friction is extensive. With is impervious to oxygen, water, and acids, or by form-
respect to the effect of equipment operation on wear, high- ing physical and chemical films by additives, such as
speed, low-load operation leads to lower wear than slow- rust and corrosion inhibitors, extreme-pressure 共EP兲
speed, high-load operation. This is because in the former additives, and anti-wear agents, that are present in the
case there is minimal metal-to-metal contact. A lubricant lubricant.
can be a solid, liquid, or gas, and lubrication is its primary 5. Transfer Power—Lubricant is used as a power transfer
function. The usual objective of the lubrication is to lubri- medium in some applications, for example, in hydrau-
lic systems. The lubricant performs this function in ad-
cate surfaces to minimize direct metal-to-metal contact
dition to its normal function of lubrication. Examples
and, hence, reduce friction and wear. The term lubricant is
of equipment that use hydraulics technology include
also loosely applied to many other fluids that do not spe-
transmissions, circulating systems, lifts used in auto-
cifically perform this function. Examples include power
motive service stations, log splitters, fork lifts, dump
and heat transmission fluids, hydraulic fluids, dielectric
trucks, and underground continuous mining equip-
fluids, process oils, and the others. Incidentally, in this
ment such as drills, loaders, and miners.
book the term “lubricant” pertains to a finished lubricant,
that is, it comprises base fluid and additives. Lubricant Market
A lubricant performs many diverse functions, which
help protect and prolong the life of the equipment 关1兴. The world lubricant market for the year 2006 is estimated at
These include the following: around 38.5 million metric tons 共85 billion pounds兲, with the
1. Lubrication 共reduce friction and wear兲—Lubricant United States consuming about 9.5 million metric tons 共21
helps reduce friction and wear by introducing a lubri- billion pounds兲, or almost 25 % of the total world use 关2兴.
cating film between mechanical moving parts, such as Asia Pacific and the Near/Middle East have the next highest
gears and bearings. Essentially, the presence of a lubri- share and are the regions with the fastest growth in lubricant
cating film minimizes the metal-to-metal contact and consumption. They are followed by Central and Eastern Eu-
reduces the force necessary to move one surface rope, Western Europe, and the others. The 2005 world de-
against the other, thereby reducing wear and saving mand breakdown by geographic areas is presented in Table
energy. 1.1 and in Fig. 1.1 关2兴. The demand for lubricants is projected
2. Cooling 共heat transfer兲—Lubricant acts as a heat sink to increase at an average rate of ⬃2 % over the next decade,
1
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2 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
• On-board oil monitoring. cient, signified by the symbol . The coefficient of friction 共兲
• New performance classifications or specifications. is a unit-less ratio that equals FM / FN, where FM represents
• Government regulations pertaining to the stringent the frictional force experienced by the two contacting bodies
emissions standards and lowering of the certain chemi- in motion and FN represents the normal force pressing the
cal elements, such as phosphorus, chlorine, and some same two bodies together. The value of the coefficient of fric-
metals, in lubricants due to their real or perceived ad- tion typically ranges from 0 to 1; the higher the value, the
verse effects on the environment. higher the frictional force or the resistance of the contacting
• Extended service intervals. bodies towards motion. Under boundary lubrication condi-
• Filled-for-life, sealed-for-life drive lines. tions, usually approaches 1.
• Fuel cell technology. Minimizing friction is one of the fundamental functions
• Development and or growth of electric cars and hybrid of a lubricant. If friction is not controlled it can lead to wear
cars. and surface damage, and ultimately to catastrophic failure
of the equipment. Because of a generally direct correlation
Friction and Lubrication between friction and wear 关5,6兴, proper lubrication of the
Tribology and tribo-technology are two terms that are equipment is important if its integrity is to be preserved over
often used in relation to lubrication and wear. Tribology is its designated lifetime. However, it is important to note that
the science and technology of friction, wear, and lubrication, the correlation between friction and wear is a function of the
derived from the Greek word tribo, meaning “to rub.” The system and is not always direct 关7兴.
term was first introduced in a British study in 1966 共The Jost In lubricant-related applications, we are concerned
Report兲, which pointed out the magnitude of the annual with all three types of friction, that is, solid friction, fluid
monetary loss in the U.K. ascribed to the consequences of friction, and the internal friction. The major function of a lu-
friction, wear, and corrosion. Since then the term has gained bricant is to minimize solid friction which it achieves by
worldwide use in lubrication and mechanical engineering. forming a fluid film between the two contacting 共metal兲 sur-
More precisely, tribology is the science and technology of the faces. Usually, a fluid’s internal friction is not of any major
interacting surfaces in relative motion, irrespective of consequence except at very low temperatures. At these tem-
whether or not they involve mechanics 关3兴. Tribology is an peratures the lubricant gains viscosity which can interfere
interdisciplinary approach that involves a scientific basis to with the smooth operation of the equipment. Internal fric-
understand surfaces in contact and the lubrication needs of tion is important while dealing with a lubricant’s intrinsic
a given tribological system. The term friction has its origin properties, such as viscosity and pour point.
from the Latin word “fricare” that means “to rub.” Applied All metal surfaces, irrespective of their finish, contain
tribology, or tribo-technology, primarily deals with the main- ridges, valleys, asperities, and depressions. When two metal
tenance of machines and the minimization of wear and en- surfaces come in contact, solid friction, sometimes called
ergy losses due to friction. static or adhesive friction, ensues and the surfaces undergo
adhesion and cold welding. The strength of such an associa-
Friction tion depends upon the hardness of the materials, the cleanli-
Friction is the force that hinders or resists the relative mo- ness of the surfaces, and the electronic structure of the met-
tion of the two contacting bodies and, depending on the ap- als as related to their tendency to form metal-metal
plication, high friction may either be desirable or undesir- solutions, or alloys 关8,9兴. As soon as the surfaces start to
able. For example, in tire traction on pavement and braking, move, kinetic friction comes into play. Kinetic friction re-
high friction is desirable. However, in applications such as sults from plowing of the asperities of the one surface across
the operation of engines or of equipment with bearings and the other surface, plastic deformation or elastic hysteresis,
gears, high friction is undesirable. This is because friction and wear debris getting lodged between the moving surfaces
causes wear and generates heat which can lead to premature 关9兴.
failure of the functioning machine parts. Frictional heat not Friction is also related to the type of motion of the two
only causes wear through welding but it is also considered a contacting bodies. Sliding motion, for instance, leads to
waste since it does not result in useful work. Friction origi- higher friction than rolling motion, and hence results in
nates from complex molecular and mechanical interactions more wear. Rolling friction and sliding friction are two gen-
between the contacting surfaces. Two bodies in direct con- eral cases of friction. For example, when force is applied to
tact with each other experience dry or solid friction. When slide a steel block sitting on a steel table, both will experience
they are separated by a solid, liquid, or gaseous medium, sliding friction. If a weight, or load, is placed on top of the
they experience fluid friction. Between these two extremes is metal block, the force necessary to cause sliding will in-
the situation where some parts of the two bodies are in direct creases significantly. When a metal cylinder is made to roll
contact while the others are separated by a fluid film. This is on the surface of metal table, the cylinder will experience
called mixed friction. Friction between two solids is depen- rolling friction, or the rolling resistance. Experience shows
dent upon the size of the contact zone, surface roughness that in general less force is required to roll an object than to
共asperities兲, and load or pressure, on surfaces, but is inde- slide or drag it. For lubricated surfaces, friction is governed
pendent of the materials. The friction may even involve a by different laws than those for dry surfaces 关10兴. Table 1.2
single body, in which case it is related to the dissipation of shows the relationship between wear and different types of
the internal energy within the body and is called internal friction 关4兴.
friction 关4兴. The data in the table show the following:
Friction is commonly represented by the friction coeffi- • A positive relationship exists between the coefficient of
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4 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
ber of national and international organizations and the end- A formulated lubricant comprises a base fluid and a per-
users. Specifications are established by considering many formance package, and in the case of multi-grade oils, an ad-
equipment-related parameters. These include system de- ditional viscosity modifier. The amount of each of these com-
sign, operating conditions, lubrication needs of the equip- ponents varies based upon the application and the desired
ment, duration of use, safety, health, and environmental service. Figure 1.7 provides the approximate ranges of each
considerations, and cost. Typically, lubricants designed for in the lubricant and Table 1.4 关20兴 provides the typical ranges
one application are not suitable for use in another applica- of additives and the viscosity modifier used in automotive lu-
tion, without deterioration in performance. Original equip- bricants. The performance package contains a number of
ment manufacturers 共OEMs兲 play a predominant role in rec- additives, the quality and quantity of which depend upon the
ommending viscosity grades and lubricant quality, which quality of the base fluid and the lubricant’s intended use. The
are based upon their system needs. A user must follow performance package can make up to 20 %, and sometimes
manufacturer recommendations to ensure warranty protec- even higher, of the total lubricant composition, depending
tion. Lubricant properties that are commonly considered for upon the desired performance level and the severity of the
assessing the suitability of a lubricant for a particular appli- end-use requirements. In general, the base fluids of inferior
cation include the following. Incidentally, lubrication- quality need better additives and in larger amounts than the
related terms, acronyms, and organizations are included in base fluids of good quality. Likewise, the applications, such
the appendix. as combustion engines and automotive gears, which place a
1. Viscosity higher demand on the lubricant, require superior additives
2. Fluidity Range than the less-demanding applications, such as some indus-
3. Viscosity-temperature Relationship 共Viscosity Index兲 trial and metalworking operations. Since the base fluid is the
4. Low-temperature Fluidity
5. Oxidation Stability 共Inhibited兲
6. Hydrolytic Stability
7. Thermal Stability
8. Mineral Oil Compatibility
9. Additive Solvency
10. Volatility
11. Rust Control 共Inhibited兲
12. Boundary Lubrication
13. Fire Resistance
14. Elastomer Compatibility, Especially with Buna Rubber
15. Relative Cost
In addition, there are other properties that are important in
some end-use applications. These include color, density, API
gravity, volatility, bulk modulus, viscosity-pressure relation-
ship, shear stability, acidity and alkalinity, detergency, dis-
persancy, and foaming and air release tendency. Lubricant
properties of high importance for various applications are
listed in Table 1.3. Fig. 1.7—Lubricant composition.
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8 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
largest component in the lubricant, its properties primarily overhead valve engine’s lubrication system 关21b兴. While such
determine the properties of the lubricant. These are consid- a system primarily employs full-pressure and force-feed lu-
ered in detail in the sections that follow. brication, other methods, such as splash and air-oil mist lu-
As far as the automotive applications are concerned, we brication, are also used for certain parts 关22兴. Large engines
are primarily interested in liquid lubrication, that is, to sepa- and most automotive engines use a full-pressure system.
rate the contacting surfaces by introducing a liquid film. Fig- Small engines use a splash or modified splash system 关23兴.
ure 1.8 depicts the general arrangement of a cam-in-block In the full-pressure system, the oil is pumped from the
oil sump to the main bearing and connecting rods and up the
connecting rods to the piston pin. In overhead valve engines,
a portion of the pumped oil travels through push rods 共in
some cases兲, over rocker arms, past valve stems, and down
the valve guides. In many engines, the cylinder walls and the
piston pins depend upon splash lubrication by the oil that is
thrown off of the main bearing. Air-oil mist lubrication is
used to lubricate the rocker boxes.
The choice of a lubrication method for equipment other
than the combustion engines depends upon its nature and
use. As mentioned previously, for transmissions, axles, and
enclosed gears, forced feed and splash lubrication are the
methods of choice. For open gears, drop feed or air-oil mist
lubrication may be appropriate.
Viscosity and Wear
Viscosity
The role of viscosity in forming effective lubricating films
makes it one of the most important properties of the lubri-
cant 关24兴. Viscosity is defined as a fluid’s resistance to flow
and, as mentioned earlier, is primarily a consequence of the
internal friction of the fluid 关4兴. A simple model to help ex- units of m2 / s 共square metres per second兲. One m2 / s is equal
plain the concept of viscosity is presented in Fig. 1.9 关23兴. to 106 centistokes 共cSt兲 and 1 cSt equals 1 mm2 / s. For an ex-
The model shows the fluid in the form of parallel layers act inter-conversion of the two viscosities, the density of the
of certain molecular thickness between a stationary plane liquid at the temperature of measurement must be known.
and a movable plane. When a tangential force F is applied, This is because the drop in the viscosity of an oil with an in-
the top plane moves at a constant velocity V. The force that crease in temperature is related to a decrease in its density
tends to cause the plane of an area to slide on adjacent planes 关4兴, which is not the same across all temperature ranges. The
is called shear. Because the fluid usually wets or adheres to measured viscosity-temperature data for a paraffinic oil and
surfaces, the layer of the fluid next to the moving plane will a naphthenic oil, oils of different densities, are presented in
move at velocity V, the same velocity as that of the moving Table 1.5 关4兴. While in both cases there is a decrease in viscos-
plane. This movement is transmitted through successive lay- ity with increasing temperature, the decrease at each tem-
ers of the fluid in a dissipating manner until the fluid velocity perature for the lower density paraffinic oil is larger in mag-
approaches zero near the stationary plane. The slowdown in nitude than that for the higher density naphthenic oil. In the
movement occurs due to friction between the fluid layers, absence of the knowledge of the oil density at a particular
each of which drags the layer above it and the layer below it. temperature, a temperature coefficient of density
The overall effect is the fluid’s resistance to free flow, termed 0.00065 K−1 is often used for mineral-based lubricants 共see
viscosity. Viscosity without the influence of gravity is called DIN 51 757 or ASTM D1250 conversion tables兲. Dynamic vis-
absolute or dynamic viscosity and that under the influence of cosity is required for comprehending the lubrication pro-
gravity is called kinematic viscosity. cesses in bearings, gears, etc. However, determining this vis-
Absolute or dynamic viscosity 共兲 equals / s, where cosity is not straight forward. On the other hand, the
represents the shear stress and s represents the shear rate. kinematic viscosity is easy to measure and with greater pre-
Shear stress 共兲, the force applied per unit area, is denoted by cision. It is therefore the preferred viscosity for production
F / A, where F represents the force in the shearing direction control and the characterization of the lubricants 关4兴.
and A represents the area. Shear rate 共s兲, the velocity gradi-
The popularly used viscosity units, Poise and Stoke, are
ent, is denoted by V / Y, where V is the velocity of the moving
named after the scientists Dr. J. L. M. Poiseuille and Sir
plane and Y is the fluid film thickness.
George Stokes in honor of their work on viscosity and vis-
cous fluids 关24兴. Previously, Saybolt Seconds Universal 共SSU
F/A
= = or SUS兲 and Saybolt Furol Seconds 共SFS兲 were also used to
s V/Y express the kinematic viscosity. However, these units are
The viscosity of certain fluids is independent of the now obsolete. The methodology to convert these units into
shear rate. Such fluids are called Newtonian, named after Sir Stokes is described in the ASTM Standard D2161.
Isaac Newton, who first made this observation 关24兴. Con- A number of factors can affect viscosity. These include
versely, fluids whose viscosities vary with the shear rate are temperature, pressure, time, and the structures of the or-
called non-Newtonian. The addition of chemicals with poly- ganic compounds present in the fluid and their response to
meric structures, for example, viscosity improvers and dis- the shear forces 关4兴. Viscosity decreases with increasing tem-
persants, to Newtonian fluids makes them non-Newtonian. perature, increases with increasing pressure, and generally
Hence, mineral base oils are Newtonian, but the finished lu- decreases with increased shear. Viscosity also depends upon
bricants are non-Newtonian. chemical structures that make up the lubricant and their
Absolute viscosity is commonly expressed in poise 共P兲 molecular size and shape. Within the same structural type, it
units. The SI 共Système International d’Unites兲 unit of abso- increases with the molecular size 关25,26兴. Aliphatic struc-
lute viscosity is Pascal-second 共Pa·s兲, which is equal to 103 tures 共paraffinics兲 are less sensitive to temperature than cy-
centipoise 共cP兲. Certain methods, such as capillary or efflu- cloaliphatic and aromatic structures 共naphthenics and
ent viscometers, measure viscosity under the accelerating bright stocks兲. In the case of the mineral oil base stocks,
influence of gravity. This type of viscosity, termed kinematic which contain molecules that are derived from all three
viscosity 共兲, equals absolute viscosity 共兲 divided by fluid types of structures, the viscosity-temperature 共VT兲 relation-
density 共兲, or / . Kinematic viscosity is expressed in SI ship depends upon the ratio of the number of carbon atoms
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10 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
TABLE 1.6—Basic L and H values for kinematic viscosity in 40– 100° C system, ASTM D2270 †28‡.
Kinematic Kinematic Kinematic Kinematic Kinematic Kinematic
Viscosity Viscosity Viscosity Viscosity Viscosity Viscosity
at at at at at at
100° C 100° C 100° C 100° C 100° C 100° C
mm2 / s mm2 / s mm2 / s mm2 / s mm2 / s mm2 / s
„cSt… „cSt… „cSt… „cSt… „cSt… „cSt…
L H L H L H L H L H L H
2.00 7.994 6.394 7.00 78.00 48.57 12.0 201.9 108.0 17.0 369.4 180.2 24.0 683.9 301.8 42.5 1935 714.9
2.10 8.640 6.894 7.10 80.25 49.61 12.1 204.8 109.4 17.1 373.3 181.7 24.2 694.5 305.6 43.0 1978 728.2
2.20 9.309 7.410 7.20 82.39 50.69 12.2 207.8 110.7 17.2 377.1 183.3 24.4 704.2 309.4 43.5 2021 741.3
2.30 10.00 7.944 7.30 84.53 51.78 12.3 210.7 112.0 17.3 381.0 184.9 24.6 714.9 313.0 44.0 2064 754.4
2.40 10.71 8.496 7.40 86.66 52.88 12.4 213.6 113.3 17.4 384.9 186.5 24.8 725.7 317.0 44.5 2108 767.6
2.50 11.45 9.063 7.50 88.85 53.98 12.5 216.6 114.7 17.5 388.9 188.1 25.0 736.5 320.9 45.0 2151 780.9
2.60 12.21 9.647 7.60 91.04 55.09 12.6 219.6 116.0 17.6 392.7 189.7 25.2 742.2 324.9 45.5 2197 794.5
2.70 13.00 10.25 7.70 93.20 56.20 12.7 222.6 117.4 17.7 396.7 191.3 25.4 758.2 328.8 46.0 2243 808.2
2.80 13.80 10.87 7.80 95.43 57.31 12.8 225.7 118.7 17.8 400.7 192.9 25.6 769.3 332.7 46.5 2268 821.9
2.90 14.63 11.50 7.90 97.72 58.45 12.9 228.8 120.1 17.9 404.6 194.6 25.8 779.7 336.7 47.0 2333 835.5
3.00 15.49 12.15 8.00 100.0 59.60 13.0 231.9 121.5 18.0 408.6 196.2 26.0 790.4 340.5 47.5 2380 849.2
3.10 16.36 12.82 8.10 102.3 60.74 13.1 235.0 122.9 18.1 412.6 197.8 26.2 801.6 344.4 48.0 2426 863.0
3.20 17.26 13.51 8.20 104.6 61.89 13.2 238.1 124.2 18.2 416.7 199.4 26.4 812.8 348.4 48.5 2473 876.9
3.30 18.18 14.21 8.30 106.9 63.05 13.3 241.2 125.6 18.3 420.7 201.0 26.6 824.1 352.3 49.0 2521 890.9
3.40 19.12 14.93 8.40 109.2 64.18 13.4 244.3 127.0 18.4 424.9 202.6 26.8 835.5 356.4 49.5 2570 905.3
3.50 20.09 15.66 8.50 111.5 65.32 13.5 247.4 128.4 18.5 429.0 204.3 27.0 847.0 360.5 50.0 2618 919.6
3.60 21.08 16.42 8.60 113.9 66.48 13.6 250.6 129.8 18.6 433.2 205.9 27.2 857.5 364.6 50.5 2667 933.6
3.70 22.09 17.19 8.70 116.2 67.64 13.7 253.8 131.2 18.7 437.3 207.6 27.4 869.0 368.3 51.0 2717 948.2
3.80 23.13 17.97 8.80 118.5 68.79 13.8 257.0 132.6 18.8 441.5 209.3 27.6 880.6 372.3 51.5 2767 962.9
3.90 24.19 18.77 8.90 120.9 69.94 13.9 260.1 134.0 18.9 445.7 211.0 27.8 892.3 376.4 52.0 2817 977.5
4.00 25.32 19.56 9.00 123.3 71.10 14.0 263.3 135.4 19.0 449.9 212.7 28.0 904.1 380.6 52.5 2867 992.1
4.10 26.50 20.37 9.10 125.7 72.27 14.1 266.6 136.8 19.1 454.2 214.4 28.2 915.8 384.6 53.0 2918 1007
4.20 27.75 21.21 9.20 128.0 73.42 14.2 269.8 138.2 19.2 458.4 216.1 28.4 927.6 388.8 53.5 2969 1021
4.30 29.07 22.05 9.30 130.4 74.57 14.3 273.0 139.6 19.3 462.7 217.7 28.6 938.6 393.0 54.0 3020 1036
4.40 30.48 22.92 9.40 132.8 75.73 14.4 276.3 141.0 19.4 467.0 219.4 28.8 951.2 396.6 54.5 3073 1051
4.50 31. 96 23.81 9.50 135.3 76.91 14.5 279.6 142.4 19.5 471.3 221.1 29.0 963.4 40 1.1 55.0 3126 1066
4.60 33.52 24.71 9.60 137.7 78.08 14.6 283.0 143.9 19.6 475.7 222.8 29.2 975.4 405.3 55.5 3180 1082
4.70 35.13 25.63 9.70 140.1 79.27 14.7 286.4 145.3 19.7 479.7 224.5 29.4 987.1 409.5 56.0 3233 1097
4.80 36.79 26.57 9.80 142.7 80.46 14.8 289.7 146.8 19.8 483.9 226.2 29.6 998.9 413.5 56.5 3286 1112
4.90 38.50 27.53 9.90 145.2 81.67 14.9 293.0 148.2 19.9 488.6 227.7 29.8 1011 417.6 57.0 3340 1127
5.00 40.23 28.49 10.0 147.7 82.87 15.0 296.5 149.7 20.0 493.2 229.5 30.0 1023 421. 7 57.5 3396 1143
5.10 41.99 29.46 10.1 150.3 84.08 15.1 300.0 151.2 20.2 501.5 233.0 30.5 1055 432.4 58.0 3452 1159
5.20 43.76 30.43 10.2 152.9 85.30 15.2 303.4 152.6 20.4 510.8 236.4 31.0 1086 443.2 58.5 3507 1175
5.30 45.53 31.40 10.3 155.4 86.51 15.3 306.9 154.1 20.6 519.9 240.1 31.5 1119 454.0 59.0 3563 1190
5.40 47.31 32.37 10.4 158.0 87.72 15.4 310.3 155.6 20.8 528.8 243.5 32.0 1151 464.9 59.5 3619 1206
5.50 49.09 33.34 10.5 160.6 88.95 15.5 313.9 157.0 21.0 538.4 247.1 32.5 1184 475.9 60.0 3676 1222
5.60 50.87 34.32 10.6 163.2 90.19 15.6 317.5 158.6 21.2 547.5 250.7 33.0 1217 487.0 60.5 3734 1238
5.70 52.64 35.29 10.7 165.8 91.40 15.7 321.1 160.1 21.4 556.7 254.2 33.5 1251 498.1 61.0 3792 1254
5.80 54.42 36.26 10.8 168.5 92.65 15.8 324.6 161.6 21.6 566.4 257.8 34.0 1286 509.6 61.5 3850 1270
5.90 56.20 37.23 10.9 171.2 93.92 15.9 328.3 163.1 21.8 575.6 261.5 34.5 1321 521.1 62.0 3908 1286
6.00 57.97 38.19 11.0 173.9 95.19 16.0 331. 9 164.6 22.0 585.2 264.9 35.0 1356 532.5 62.5 3966 1303
6.10 59.74 39.17 11.1 176.6 96.45 16.1 335.5 166.1 22.2 595.0 268.6 35.5 1391 544.0 63.0 4026 1319
6.20 61.52 40.15 11.2 179.4 97.71 16.2 339.2 167.7 22.4 604.3 272.3 36.0 1427 555.6 63.5 4087 1336
6.30 63.32 41.13 11.3 182.1 98.97 16.3 342.9 169.2 22.6 614.2 275.8 36.5 1464 567.1 64.0 4147 1352
6.40 65.18 42.14 11.4 184.9 100.2 16.4 346.6 170.7 22.8 624.1 279.6 37.0 1501 579.3 64.5 4207 1369
6.50 67.12 43.18 11.5 187.6 101.5 16.5 350.3 172.3 23.0 633.6 283.3 37.5 1538 591.3 65.0 4268 1386
6.60 69.16 44.24 11.6 190.4 102.8 16.6 354.1 173.8 23.2 643.4 286.8 38.0 1575 603.1 65.5 4329 1402
6.70 71.29 45.33 11.7 193.3 104.1 16.7 358.0 175.4 23.4 653.8 290.5 38.5 1613 615.0 66.0 4392 1419
6.80 73.48 46.44 11.8 196.2 105.4 16.8 361.7 177.0 23.6 663.3 294.4 39.0 1651 627.1 66.5 4455 1436
6.90 75.72 47.51 11.9 199.0 106.7 16.9 365.6 178.6 23.8 673.7 297.9 39.5 1691 639.2 67.0 4517 1454
40.0 1730 651.8 67.5 4580 1471
40.5 1770 664.2 68.0 4645 1488
41.0 1810 676.6 68.5 4709 1506
41.5 1851 689.1 69.0 4773 1523
42.0 1892 701.9 69.5 4839 1541
70.0 4906 1558
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12 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
of the ASTM Standards D2270 or D39B 关27兴. These stan- particular temperature can be easily obtained from the VT
dards contain VI data for many hypothetical reference oils. line. It is important to note that the values near or below the
All one has to do is to measure the 40° C and 100° C kine- cloud point of the oil or at very high temperatures may devi-
matic viscosities of the new oil, choose the oil from the table ate from the straight-line relationship. This is because at
with the matching 100° C viscosity, and read the VI based on these temperatures phase transitions, such as precipitation
its 40° C viscosity. Table 1.6 provides L and H values for oils or thermal degradation, are possible. Such transitions can
with different 100° C viscosities 关28兴. lead to unexpected changes in viscosity, thereby leading to
The next VT measure that is proposed f‘or differentiat- erroneous results. This is aptly demonstrated by the data de-
ing oils with a low VT relationship is viscosity-temperature picted in Fig. 1.12 关4兴. As one can see, the measured viscosi-
constant 共VTC兲 关29,30兴. While the procedure works well for ties below 0 ° C, represented by the solid line, are much
the high VI oils, it does not numerically differentiate oils
with moderate or poor VT characteristics 关4兴. For additional
information, refer to Chapter 3 on Synthetic Base Fluids. Pe-
troleum oils exhibit a change in viscosity with temperature
which is near logarithmic within a limited temperature
range. ASTM International has produced a chart which is
somewhat better than an ordinary logarithmic chart, with a
near linear viscosity-temperature function. By using this
chart, the slope of the viscosity-temperature lines of the vari-
ous lubricants can be compared. Since viscosity has an in-
verse relationship to temperature, the smaller values for the
slope are better. This implies that the drop in viscosity is
lower with increasing temperature. Standard viscosity-
temperature charts for liquid petroleum products in six
ranges are provided in ASTM Standard D341. A unique ad-
vantage of these charts is that it is convenient to predict kine-
matic viscosity of a petroleum oil, or a liquid hydrocarbon, at
any temperature within a limited range, if the kinematic vis-
cosities of the oil at two temperatures are known. These
charts also have the advantages of needing only two data
points, magnifying small differences that exist between oils,
and providing the ability to read viscosities at other tempera-
tures from the VT line by interpolation. The data in Fig. 1.10,
Part A, are replotted in Part B, using a logarithmic scale to
achieve linearity and because of this the viscosity value at a Fig. 1.13—Viscosity-pressure relationship.
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CHAPTER 1 䊏 LUBRICATION FUNDAMENTALS 13
Fig. 1.16—Relationship between Saybolt Seconds Universal 共SSU兲 and kinematic viscosity 共cSt兲 scales 关28兴.
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CHAPTER 1 䊏 LUBRICATION FUNDAMENTALS 15
Abrasive Wear
This is the most common type of wear that occurs in me-
chanical equipment. It primarily results from the hard par-
ticles, such as foreign matter, and hard protuberances or as-
perities that are either forced against or move between the
surfaces when they mesh. All metal surfaces, irrespective of
the quality of the surface finish, are rough on a microscopic
scale. They consist of protuberances, or asperities, and de-
pressions. Figure 1.24 depicts the mechanism for this kind of
wear. Abrasive wear can be controlled by the use of filters,
strainers, magnetic drain plugs to remove iron particles, and
periodic draining and refilling of the equipment with clean
oil.
Corrosive Wear
This type of wear results from the attack of the lubricant or
the corrosive contaminants, such as salts, water, and acids,
on the metal surfaces. These materials cause chemical or
electrochemical reaction with the metal. See the section on
corrosion inhibitors in Chapter 4, the Additives section. The
surfaces that experience metal-to-metal contact show a
great deal more damage than those that do not. This is pri-
marily due to the generation of the frictional heat and the
fresh metal. The mechanism for this type of wear is shown in
Fig. 1.25. Corrosive wear, which causes pitting or polishing
of the metal surfaces, can be minimized by using acid-
neutralizing and film-forming agents. Acid-neutralizing
agents, such as basic detergents, remove acids. Film-
forming agents adsorb on or chemically react with the sur-
Fig. 1.23—Scanning Brookfield Viscometer 关318兴. Reprinted with
faces to form protective films, thereby keeping acids, salts,
permission from the Lubrizol Corporation.
and water away from the metal.
measurement methods in terms of shear rates and their ap- Fatigue Wear
plication. Fatigue wear results from repeated stressing of the metal
surfaces. Such stressing arises from continuous tempera-
Wear ture changes due to frictional heat, periodic impacts, re-
When the lubricant fails to provide an adequate protection peated contacts with abrasive asperities, or the rubbing
by forming an effective film, wear initiates, which if not pro- cycles. This kind of wear usually starts as a surface or subsur-
tected against can lead to equipment seizure. Wear can sim- face crack which progressively grows until a piece of metal is
ply be defined as the damage to a surface due to a progressive removed from the surface. This damage is called pitting;
loss of material. The lost material becomes a part of the lu- when pits grow larger the damage is called spalling. Fatigue
bricant directly or indirectly, that is, via transfer to the other failure commonly occurs in pinion gears and bearings that
surface. Such material is referred to as wear metals, if it is experience a large amount of stress during service. Figure
present in the liquid phase and is in a nonoxidized form. As 1.26 illustrates the mechanism of the fatigue wear. This type
mentioned earlier, the wear is a consequence of friction. of wear is not easy to control. However, fatigue life of the
Four major types of wear that occur in machinery are abra- equipment can be improved by using a good lubricant, by se-
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CHAPTER 1 䊏 LUBRICATION FUNDAMENTALS 19
Fig. 1.25—Mechanism of corrosive wear 关318兴. Reprinted with per- Fig. 1.27—Mechanism of adhesive wear 关318兴. Reprinted with per-
mission from the Lubrizol Corporation. mission from the Lubrizol Corporation.
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20 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
that meets the OEM’s performance criteria, irrespective of soap content that help suspend the polar products in oil.
the identity of the lubricant manufacturer. Additional fac- These materials are alkali metal or alkaline earth metal salts
tors that need to be considered while selecting a lubricant of organic acids, with or without the reserve base. Common
are described in Ref. 关32兴. In the absence of the manufactur- acids include alkylbenzenesulfonic acids, alkylphenols, and
er’s specifications, one must consider lubricants that are be- fatty carboxylic acids.
ing used in the intended application and determine their ad-
equacy prior to selecting one. A list of such lubricants can be Dispersants
obtained from the various lubricant producers. These additives perform the same function as the soap com-
We stated earlier in the chapter that in this book we will ponent of the detergents. That is, they suspend polar con-
classify lubricants into engine lubricants and nonengine lu- taminants of low oil solubility in the bulk lubricant. They do
bricants, primarily because of the differences in their operat- so by associating with these species via their polar ester or
ing environments. Table 1.8 contains a list of lubricants be- imide functionalities and keeping them dissolved in oil by
longing to the two classes. Almost all lubricants must meet associating with it via their nonpolar hydrocarbon chains.
the SAE, ISO, and ASTM established viscosity requirements Dispersants are more effective in performing this function
and the performance requirements established by various than detergents because of their higher molecular weight,
organizations, which for each lubricant type are listed be- that is, the higher hydrocarbon content. The suspended
low: harmful products are removed when the oil is changed.
1. Engine Oils Common dispersants are polyamine and polyhydric alcohol-
a. Passenger Car—ILSAC, API, ACEA, JASO derived polyisobutylene derivatives.
b. Heavy-duty Diesel—API, OEMs, U.S. Military
2. Transmission Fluids
Oxidation Inhibitors
a. Automatic—OEMs 共GM, Ford, Chrysler兲 These additives control the oxygen-initiated degradation of
b. Power—OEMs the lubricant. They belong to three general classes: hydrop-
3. Automotive Gear Oils—API, U.S. Military eroxide decomposers, free radical scavengers, and metal de-
4. Tractor Fluids—OEMs activators. Hydroperoxide decomposers promote the decom-
5. Industrial Lubricants position of the hydroperoxides either to innocuous materials
a. Anti-wear Hydraulic Fluids—OEMs, Government or to free radicals. Common additives of this class include
Agencies, Standards Organizations organo-sulfur and organo-phosphorus compounds. Free
b. Industrial Gear Oils—United States Steel 共USS兲, radical scavengers remove the free radicals that are primarily
AGMA, Cincinnati Machine responsible for the oxidation chain reaction. Common addi-
c. R&O Turbine Oils—OEMs, U.S. Military, Technical tives of this class are zinc dialkyl dithiophosphates 共ZDTPs兲,
Societies hindered phenols, and alkylated arylamines. Metal deactiva-
6. Metalworking Fluids—Some Standardization Tests tors complex with metallic cations, which are oxidation cata-
7. Greases—NLGI lysts, and make them inactive. Poly-functional 共poly-
Lubricant Composition dentate兲 compounds, such as ethylenediaminetetraacetic
acid 共EDTA兲 and salicylaldoxime, are useful in controlling
Almost all commercial lubricants are formulated oils, oxidation by this mechanism.
that is, they comprise base stock共s兲 and performance addi-
tives. When present in the proper concentration, these com- Rust and Corrosion Inhibitors
ponents impart the formulated lubricant properties neces- These additives protect metal surfaces against the attack of
sary to perform effectively in the intended application. In oxygen, water, acids, bases, and salts. They achieve this by
addition to performing the principle functions of lubrica- physically adsorbing on the metal surfaces via their polar
tion, cooling, containment/suspension, corrosion protec- functional group and by maintaining a resilient protective
tion, and power transfer, the lubricant must also fulfill addi- film on the surfaces by associating with the lubricant. Rust
tional functions that are unique to the application. inhibitors are additives that protect ferrous metals and cor-
Lubrication is the base oil’s or the base fluid’s exclusive do- rosion inhibitors are additives that protect nonferrous met-
main but for achieving the other functions the additives play als. Both types perform by coating the surfaces of the metal
a predominant role. Additives belong to two general classes: parts and forming a barrier between them and the environ-
those that affect or impart to the physical properties of the ment.
base oil and those that improve the chemical properties of
the base oil. While in-depth discussions on additives are pre- Friction Modifiers
sented in Chapter 4, the functions of some of these are briefly These are additives that usually reduce friction. The mecha-
described below. nism of their performance is similar to that of the rust and
corrosion inhibitors in that they form durable low-
Detergents resistance lubricant films via adsorption on surfaces and via
These additives perform two major functions. They neutral- association with the oil. Common materials that are used for
ize the acidic by-products of combustion and lubricant oxi- this purpose include long-chain fatty acids, their derivatives,
dation and keep the deposit precursors and contaminants, and the molybdenum compounds. In addition to reducing
which have marginal oil solubility, in oil. This minimizes de- friction, the friction modifiers also reduce wear, especially at
posit formation on engine or transmission parts. It is their low temperatures where the anti-wear agents are inactive,
base reserve, or the TBN, that help neutralize acids and the and they improve fuel efficiency.
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22 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
Anti-wear Agents and Extreme-pressure Additives low level that will make it lose its ability to maintain a lubri-
These additives form extremely durable protective films by cating film on surfaces. Viscosity modifiers are polymers
thermo-chemically reacting with the metal surfaces. This that help a lubricant maintain its lubricating ability at high
film can withstand extreme temperatures and mechanical temperatures. They do so by increasing their molecular size,
pressures and minimizes direct contact between surfaces, hence increasing association with the oil so that it does not
thereby protecting them from scoring and seizing. Typically, flow away from the surfaces. These additives increase both
anti-wear 共AW兲 agents have a lower activation temperature the low-temperature viscosity and the high-temperature vis-
than the extreme-pressure 共EP兲 agents. The latter are also re- cosity of the oil, but to a varying degree. They are often used
ferred to as anti-seize and anti-scuffing additives. Organo- to make multi-grade oils. Common polymers that are used in
sulfur and organo-phosphorus compounds, such as organic this capacity include polymethacrylates, olefin copolymers
polysulfides, phosphates, dithiophosphates, and dithiocar- 共OCPs兲, styrene-diene copolymers, and styrene-ester copoly-
bamates are the most commonly used AW and EP agents. mers.
For further details of the film-forming mechanism, please re-
fer to the section on film-forming agents in Chapter 4.
Pour Point Depressants
Foam Inhibitors Petroleum base oil-derived fluids contain waxes, which at
Formation of foam in most lubrication applications is unde- low temperatures start to crystallize to form network struc-
sirable since it impedes lubrication, promotes lubricant oxi- tures. These structures absorb oil and impede its flow. Pour
dation, obstructs narrow passages, and reduces a lubricant’s point depressants 共PPDs兲 prevent crystalline network forma-
cooling ability. Foam inhibitors are additives that reduce the tion and permit oil flow at low temperatures. Common PPDs
foam-forming tendency of the lubricant. Common additives include wax-alkylated naphthalenes and phenols, poly-
used to accomplish foaming control include polysiloxanes methacrylates, and styrene-ester copolymers
and styrene ester polymers. These materials have borderline In addition to the types of additives described here,
oil solubility and perform by lowering the surface tension of there are additional types. They will be discussed in the Addi-
the foam bubbles.
tives chapter, Chapter 4. Also, please note that not all lubri-
Viscosity Modifiers cants contain all types of additives and in the same amounts.
The viscosity of liquids decreases with an increase in tem- Typically, automotive lubricants contain more classes of ad-
perature. An oil’s viscosity at high temperatures can drop to a ditives and in greater amounts than industrial lubricants.
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MNL59-EB/Mar. 2009
2
Mineral Base Oils
IN THIS CHAPTER WE DESCRIBE PETROLEUM ity, based on wax content, or by geographical region.
composition and the oil field and refinery chemicals that Petroleum, or crude oil, as it is recovered from the
are used to facilitate petroleum drilling to extract crude ground is primarily composed of organics and residuum,
petroleum from beneath the earth’s surface and refine it to which are mixed with metals and the metal salts as contami-
yield value-added products, such as fuels, lubricant base nants. The organic portion of petroleum consists of satu-
stocks, and petrochemicals. The chapter also describes rated hydrocarbons, unsaturates, aromatics, asphaltenes,
many of the refinery processes in some detail to explain the high molecular weight resins, and hetero-organic com-
manner in which the hydrocarbon cuts from petroleum pounds containing sulfur, nitrogen, and oxygen atoms in
with suitable properties for use as lubricant base stocks are their structures. Hydrocarbons are the major constituent of
obtained. Commonly referred to as mineral oils, they are the crude petroleum. These compounds contain carbon and
the cheapest and the most abundant base stocks available hydrogen atoms only and are classified into alkanes, alkenes,
and therefore are often used to formulate lubricants. Dis- alicyclics, and aromatics. Alkanes, also known as paraffins,
cussion also includes the desirable properties of the min- are compounds with saturated linear or branched struc-
eral oils that are critical to formulating a quality lubricant. tures. The latter are also called iso-paraffins. They do not
Untreated or nonformulated lubricants 共mineral base contain cyclic structures, or rings; hence they are sometimes
oils and synthetic base stocks兲 do not possess the necessary referred to as acyclics. Alkenes, also known as olefins, are un-
properties to perform effectively in today’s demanding lu- saturated molecules 共contain double bonds兲 that do not oc-
bricating environments. To function properly in such envi- cur to a great degree in crude petroleum but result from
ronments, base fluids need the help of chemicals, called cracking or dehydrogenation reaction during certain refin-
additives. Additives improve the lubricating ability of the ing processes. Naphthenes, also called alicyclics, are satu-
base oils either by enhancing the desirable properties al- rated compounds that contain five- or six-membered cyclic
ready present or by adding new properties. Most of today’s rings. Aromatics also contain cyclic rings, but these rings are
lubricants are formulated lubricants, and additives are aromatic; that is, they contain conjugated double bonds 共al-
their integral part 关33兴. ternating single and double bonds兲. When present in the
The world consumption of lubricant additives has in- crude oil, they are primarily based on the six-membered ben-
creased from 2.6 million metric tons 共5.7 billion lb兲 in 1997 zene ring. Average aromatics content of the most crude oils
to about 3 million metric tons 共⬃6.6 billion lb兲 in 2006. The is around 50 %, but it can range from 25 % in the light paraf-
consumption is expected either to plateau or grow slowly finic crudes to 75 % in the heavy crudes. In the crude petro-
in North America and Western Europe, which consume the leum most compounds have composite structures; that is,
largest share of the total. The developing economies of they contain linear or branched hydrocarbon chains and
Asia, such as India and China, and of Latin America, such
rings in the same structure. Paraffins to naphthenes ratio
as Brazil, Chile, and Argentina, are expected to see a faster
varies widely among the crude oils from different sources
growth.
and is used to classify them as paraffinic or naphthenic.
A formulated lubricant comprises a base fluid and a
Other components in the crude oils are undesired and must
performance package, and in the case of multi-grade oils,
be removed during the manufacture of fuels and base oils.
an additional viscosity modifier. The amount of the base
In addition to the simple hydrocarbon molecules de-
fluid in a lubricant can be anywhere from 70 % to greater
scribed so far, crude petroleum contains compounds that
than 99 %, based on the desired performance level and the
have elements other than carbon and hydrogen, either in the
severity of the end-use requirements. Base fluid is derived
side chain or in a ring. When nitrogen, oxygen, sulfur, or
from three sources: petroleum, synthetic, and biological,
other elements, commonly found in petroleum, are present
i.e., plant or animal in origin.
in cyclic structures, the compounds are called heterocyclics.
Petroleum Composition Oxygen-containing compounds are usually noncyclic, such
as carboxylic acids, and therefore are not classified as het-
Petroleum, or the crude oil, is the main source of a number erocyclics. Sulfur- and nitrogen-containing compounds, on
of products that are essential to modernization. These in- the other hand, are usually cyclic. Asphaltenes are very high
clude fuels for household, industrial, and transportation molecular weight compounds with heterocyclic and aro-
use, lubricants, and chemicals that are used as raw materials matic structures.
to manufacture a variety of synthetic products. Crude oils Figure 2.1 depicts the structures of these classes of com-
are classified as light, medium, and heavy, based on density, pounds. The size of the molecules that make up petroleum
sweet or sour, based on sulfur level, low quality or high qual- ranges from very simple gaseous molecules, such as meth-
23
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24 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
4. Contain formation pressures to reduce the risk of a ing formation damage. Such fluids include water-based
blowout. muds, oil-based muds, saltwater fluids, and brines. One such
Drilling fluids, sometimes called drilling muds because fluid is an emulsion 共oil-in-water兲 composed of water, oil,
of their consistency and appearance, are usually composed and a blend of zinc and calcium bromides. Fracture acidizing
of a liquid phase 共aqueous or organic兲, soluble inorganic and fluids are used prior to mechanical fracturing of the forma-
organic additives, and suspended solids. For hard rock drill- tion. They etch heterogeneous carbonates, thereby increas-
ing, the gas-based muds derived from dry gas or natural gas ing porosity and wall productivity. These are used as acid-in-
are often used. Based on the liquid phase, the drilling fluids oil emulsions to avoid direct contact between the acid and
are classified into three types: water-based fluids, oil-based the carbonates in the rock.
fluids, and synthetic oil-based fluids.
Drilling Fluid Properties
Water-based Drilling Fluids For drilling fluids to be effective they must possess a number
These drilling fluids are the most common. They employ of properties. These include suitable density, viscosity, flow
fresh water, seawater, or the common saltwater mixture. properties, wall-building properties, filtration properties,
Saltwater-based drilling fluids are used when drilling and stability, both during manufacture and use 关36–38兴. Den-
through salt beds or domes. Over 85 % of the wells drilled in sity relates to a fluid’s ability to withstand the hydrostatic
the United States use these fluids because they are more en- pressures. Powdered high density solids or salts are used to
vironmentally acceptable than the other types. In most build up the fluid density. High-density fluids can withstand
cases, both the drilling fluid and the cuttings can be dis- the formation pressures better than the low-density fluids, as
charged overboard from off-shore rigs. Water-based fluids well as prevent the collapse of weak formations into the bore
can be of dispersed or nondispersed types. The dispersed hole. Most drilling fluids have a fluid density above that of
systems use dispersants, such as lignosulfonates, to help sus- water, that is, from 1000 kg/ m3 共8.33 lb/ gal兲 to over
pend clay particles and fines in the mud. This is the mud type 2500 kg/ m3 共20.8 lb/ gal兲.
of choice in the United States, both for on-shore and off- Fluid viscosity and annular flow viscosity are the flow
shore drilling, primarily because of its relatively low cost. characteristics of interest in the drilling fluids. The fluid vis-
Nondispersed systems, such as polymer muds, do not use cosity relates to a fluid’s ability to be pumped down the drill
dispersants because they do not depend on clays to impart and to suspend the resulting debris. The annular flow viscos-
viscosity. They use water-compatible polymers instead 关36兴. ity reflects its ability to carry the suspended material up the
Potassium chloride-based saltwater polymer mud, a mud of annulus to the surface for separation and disposal. This can
the nondispersed type belonging to the class of shale- be achieved for both low-viscosity and high-viscosity fluids,
inhibitive muds, is invaluable for drilling highly reactive by simply adjusting the circulation flow rate. While develop-
shales in the North Sea. ing a fluid of proper flow characteristics it is important to
Oil-based Drilling Fluids consider the drill speed because it can influence the effective
Oil-based drilling fluids are used for drilling high angle or ex- viscosity due to shear. Non-Newtonian fluids are the best in
tended reach wells, drilling through reactive shales, and meeting the desired flow characteristics. They have lower
when high temperatures are involved. These fluids are water- viscosity under the influence of shear and higher viscosity in
in-oil emulsions with brine as the dispersed phase. Oil-based the absence of shear.
fluids usually contain mineral oil or diesel oil as the continu- Wall-building properties of the drilling fluids are also
ous phase. Therefore, the used fluid and the drilled debris important. Since drilling fluids are introduced under pres-
cannot be discharged overboard and must be brought back sure, they can enter the pores and crevices of the formation.
to the shore for disposal 关37兴. However, if the pores are too small to allow the suspended
Synthetic Oil-based Drilling Fluids particles to enter, the solids stay at the surface as a cake and
These fluids are developed as environmentally friendly alter- the liquid passes into the formation. This is called leak-off or
natives to the oil-based drilling fluids and are water-in-oil the filtration loss. High liquid loss is undesired because it can
emulsions, with brine as the dispersed phase. However, they lead to drilling difficulties. These arise from an increase in
are formulated using synthetic fluids, such as esters, ethers, fluid viscosity and an increase in the thickness of the wall
polyalphaolefins, and olefin isomers. Their characteristics cake, both of which hinder the fluid circulation. A similar
are similar to those of the oil-based drilling fluids. For ex- situation results when the formation hydrates and swells be-
ample, they can be used for drilling high angle and extended cause it contains clay or shale and the fluid contains water.
reach wells, and highly reactive shales. They have inherent The amount of filtration loss depends on the porosity of the
lubricity and therefore require fewer lubricity additives than formation and the permeability of the cake. The more po-
the water-based drilling fluids. However, for certain applica- rous and fractured the formation, the higher the loss, and the
tions, such as extended reach wells, the lubricity additives more permeable the cake, the higher the loss. On the other
may still be required. Because of the low toxicity and good hand, an impermeable cake can hinder and even stop circu-
biodegradability of these fluids, in many cases the drilled de- lation by preventing the fluid’s approach to the formation. To
bris can be discharged directly overboard while the drilling control the loss of circulation, additives are used that help
fluid can be saved for re-use 关37兴. form a low permeability cake on the surface of the forma-
A number of synthetic oil-based fluids unrelated to drill- tion. This type of cake maintains reasonable circulation and
ing applications are also used in oil recovery. These include low fluid loss. The additives, either colloidal solids or or-
completion fluids and fracture-acidizing fluids. Completion ganic polymers, can hinder the drilling process. This is coun-
fluids are used to finish work on wells after the drilling is tered by the use of other additives that control excessive fluid
complete. They control formation pressure while minimiz- loss and cake buildup.
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26 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
Water is an essential ingredient in all but the gaseous Filtration Control Agents
drilling fluids. It is present as a mist or in an emulsified form Proper flow does not always require an increase in viscosity.
in oil-based fluids, and as a continuous phase in water-based Sometimes, a decrease in viscosity is desired. Because the
fluids. The quality of water can therefore affect the stability drilling muds have a high solids content and thixotropic 共gel-
of the dispersed phase in these fluids. The water’s low salt ling兲 behavior over time, they can be treated as Bingham flu-
content and low pH can destabilize the colloidal dispersion ids. Hence, their flow can be described in terms of their yield
and destroy the fluid’s structural integrity. For good mud sta- point and plastic flow. Yield point and thixotropy reflect the
bility, a salt content of 20 % or greater and a pH of greater tendency of the clay sheets to interlock 共structure兲 and plas-
than 8 are most suitable 关37,38兴. Hence, it is important to tic flow relates to the force necessary to move them past one
monitor the quality of water and its effect on the drilling another. All three flow properties, that is, plastic flow, yield
mud stability. point, and thixotropy, are believed to involve charge interac-
tions. These properties can be improved by lowering the
Drilling Fluid Composition mud viscosity. This can be achieved by decreasing the solids
Drilling fluids contain many organic and inorganic compo- content or by the use of viscosity-reducing agents, or thin-
nents, each of which performs a very specialized function ners. These chemicals function by minimizing the clay’s ten-
关36,37,38兴. dency to form structure 共presumably by neutralizing
Density Enhancers charges兲, thereby facilitating flow. In the water-based muds,
Mud density is controlled by the use of the weighting mate- polyphosphates, tannins, lignites, lignosulfates, and low mo-
rial, barite 共BaSO4兲 being the most common. Other materi- lecular weight polyacrylates are used for this purpose.
als that are used to build the mud density include hematite Alkalinity Aids
共Fe2O3兲, magnetite 共Fe3O4兲, ilmenite 共TiO2 · FeO兲, siderite Most muds have a pH in the range of 6–13. For the water-
共FeCO3兲, dolomite 共CaCO3 · MgCO3兲, calcite 共CaCO3兲, and based muds, alkalinity agents are used to maintain the pH on
sodium chloride 共NaCl兲. While the drilled solids can also be the basic side in order to control corrosion. The bases used
used for this purpose, their small size may lead to the forma- include sodium hydroxide, potassium hydroxide, calcium
tion of the impervious cakes, thus hindering the fluid circu- oxide 共lime兲, and magnesium oxide. Sometimes there is a
lation. For solids-free fluids that are used for work-over and need to lower the pH, which is achieved by the use of the or-
completion operations, water soluble salts, such as alkali ganic acids, such as acetic acid, citric acid, and oxalic acid,
and alkaline earth metal halides and formates are often or mild inorganic acidic materials, such as sodium bicar-
used. bonate and sodium acid pyrophosphate.
lowers the flow of water from the drilling fluid to the forma- fatty acid esters, synthetic hydrocarbons, and vegetable oil
tion by osmosis, thereby leading to its stabilization. Potas- derivatives. Sometimes solid lubricants, such as graphite
sium, ammonium, and magnesium salts also convert so- and plastic or glass beads, are also used to minimize pipe
dium clays into less sensitive potassium, ammonium, and sticking, a situation that arises when the drill pipe stops
magnesium clays. However, the ammonium mud is not al- against the formation wall due to a physical obstruction. An-
ways preferred because of its highly alkaline nature. other type of sticking, called differential sticking, results
A number of organic polymers are used to perform the when the mud and the formation pressure differential holds
same function. They can be added to a fresh water mud or a the pipe against the formation wall. In such instances, water-
mud that contains one or more of the salts mentioned above.
or oil-based spotting fluids are introduced into the interface
These polymers form a barrier against water on the forma-
to break the pressure lock. Water-based spotting fluids have
tion surface. Nonionic polymers do this simply through
a composition similar to that of the lubricants.
physical association. Cationic and anionic polymers, on the
other hand, are believed to associate with the clay through Corrosion Inhibitors
electrostatic charge interactions, with opposite charges on Corrosion is a major problem in drilling and is caused by
the clay surface. The formation-stabilizing activity of these oxygen or acidic gases. Oxygen corrosion is more prevalent
polymers is hard to determine because they also behave as at pH of ⬍11, hence maintaining a higher pH rectifies this
filtration control agents. Commonly used polymers include problem. Acidic gases, such as carbon dioxide and hydrogen
modified starches, cellulosics, gums such as guar and xan- sulfide cause chemical corrosion and again a high pH takes
than, quaternary ammonium salts, high molecular weight care of it. Zinc and iron compounds, such as oxides, hydrox-
polyacrylamides, cationic polyacrylamides, and poly共vinyl ides, and carbonates, are used to scavenge sulfide, and
alcohol兲. sulfites are used to scavenge oxygen.
Surfactants Drilling Rate Enhancers
Surfactants perform a number of important functions in
Drilling debris from some formations tends to stick to the
drilling fluids. They can help emulsify oil and organic addi-
drill bit which can seriously impair drilling. The use of oil- or
tives in water, water in oil, and act as foaming and defoaming
agents. However, their most prevalent use is as emulsifiers. A synthetic oil-based muds can minimize this. For water-
wide variety of natural and synthetic materials have poten- based muds, with a higher tendency to experience this prob-
tial use. However, lignites, lignosulfonates, alkylarylsul- lem, water-soluble glycols and some terpenes are somewhat
fonates and sulfates, and polyalkylated acids and esters are helpful.
among those most commonly used.
Environmental Aspects
Lost Circulation Additives
As stated earlier, circulation can be lost if the fluid encoun- North American Off-shore Drilling
ters highly permeable and or fractured formation because of The Environmental Protection Agency 共EPA兲 has established
the leak-off. If drilling is to continue, circulation must be re- a list of water-based drilling fluid formulations that are used
generated. This can be achieved by the use of a wide variety in the field. The “eight generic muds,” as they are called, are
of materials. Lost circulation additives, based on their tex- standardized fluids that are used to test additives. The 96-h
ture, can be classified as flaky, fibrous, and granular. Flaky LC50 Test, or the “shrimp test,” is used to determine toxicity.
materials include cellophane, paper, mica, and rice and cot- The minimum LC50 value allowable for discharge is
ton seed hulls; fibrous materials include cellulose, saw dust, 30, 000 ppm SPP 共Suspended Particulate Phase兲, which cor-
sugar cane residue 共bagasse兲 after the juice is removed; and relates to the toxicity of Generic Mud #1, the most toxic of
the granular materials include ground rubber, nylon, plas- the eight generic muds. Generic Mud #7 is the preferred
tics, asphalt, and ground nut shells. Basically, any imagin- drilling fluid for this determination. Most major mud com-
able material can be used. The prerequisite is its particle size panies prefer LC50 values greater than 30,000 ppm. Because
which must be large enough to plug up the pores and crev- the regulations for off-shore drilling are more stringent than
ices to avoid the fluid loss.
those for on-shore drilling, the additives restricted for off-
Flocculating Agents shore use, in some instances, can be used for on-shore drill-
Solids that result from drilling are removed from the mud ing fluids. In the United States, the LC50 test is not generally
either mechanically, through dilution, or by flocculation. required for testing additives in the oil-based drilling fluids.
The suspended solids slow down the drilling operation. For
separation, all drilled solids must be removed so that the North Sea Drilling
drilling fluid is clean. Polymers, such as high molecular In this region, drilling is regulated by the MAFF 共Ministry of
weight polyacrylamides 共with various degrees of hydrolysis兲 Agriculture Fisheries and Food兲 of the U.K., the State Super-
and vinyl acetate-maleic anhydride copolymers, are used to vision of Mines of the Netherlands, and the SFT 共State Pollu-
remove solids by flocculation. tion Control Authority兲 of Norway. The toxicity tests to
Lubricants and Spotting Fluids evaluate additives include a 48-h LC50 Acartia Test and a
Drill string may experience resistance during raising and 72-h EC50 Algae Test. These tests are used for both the water-
lowering if the well is straight, during angular entry if the based and the oil-based drilling fluids. For use in Europe, the
hole changes directions, and during rotation when against additives are tested independent of the drilling fluid. Other
the formation. In order to overcome this problem, muds are important tests include a ten-day LC50 Corophium Test,
treated with lubricants. Modern lubricants are basically OECD 306 Biodegradation Test, and OECD 117 Octanol/
blends of anionic or nonionic surfactants, glycols, glycerols, Water Partitioning Test.
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28 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
ing large drums of hot oil at 450° C and 5 – 10 psi and collect- xylene from para-xylene through distillation since both have
ing the cracked vapors that form in the head space. Fluid close boiling points. They are separated either via crystalli-
coking, on the other hand, involves spraying the hot re- zation or by the use of the molecular sieves.
siduum into a fluidized bed of hot coke particles that are held
at 22– 36 psi and 51° C, or higher. The vaporized and cracked Alkylation
feed forms a liquid film on the particle surface, which is ulti- Alkylation reaction involves the reaction of a low molecular
mately collected. weight olefin 共containing 3, 4, or 5 carbon atoms兲 with an al-
kane, alkene, or an aromatic compound. The reaction of
Vis-breaking isobutylene with isobutane yields 2,2,4-trimethylpentane
The purpose of vis-breaking is to decrease the viscosity of the 共isooctane兲—a high octane product. The reaction is carried
heavy fuel oil to permit its handling at lower temperatures. out in the presence of sulfuric acid or hydrofluoric acid cata-
This, like coking, is also a thermal cracking process using lyst and at a temperature of 4 – 15° C and slightly higher than
only heat to crack the residuum to lower boiling products. atmospheric pressure. Similarly, benzene is alkylated with
The process involves heating of heavy oil in a furnace at ethylene to form ethylbenzene, which is ultimately con-
⬃480° C for a sufficient time to obtain gas, naphtha, and the verted into styrene, and with propylene to ultimately pro-
distillate gas oil. duce alkylphenol. Both these materials are important petro-
chemicals that are used in a variety of chemical
Solvent Deasphalting transformations.
This process is used to remove asphaltenes from the re- Alkylation of an alkane with an olefin requires tertiary
siduum, so that its useful components can be processed in a alkanes; primary and secondary alkanes do not undergo
cracking unit. The removal of the asphaltenes is warranted alkylation. This is because tertiary alkanes have a carbon
since these are highly aromatic entities containing nitrogen that has single hydrogen attached to it. This hydrogen is
and sulfur that are difficult to crack. The process involves more reactive than the hydrogens on a secondary or a pri-
dissolving the vacuum residue in a hydrocarbon, such as mary carbon. Alkylation of benzene and phenol are straight
propane, butane, or pentane. The insoluble asphaltenes are forward reactions. Again, 98–99 % sulfuric acid 共H2SO4兲, or
removed and after removing the solvent from the soluble concentrated hydrofluoric acid 共HF兲 are used as catalysts.
phase, the residue is sent to the cracking unit. Sulfuric acid catalyzed alkylations are carried out at low
temperatures 共5 – 10° C兲 to minimize olefin polymerization.
Steam Cracking
Steam cracking is used to convert ethane, butane, and naph- Hydrofluoric acid 共HF兲 alkylation can be carried out at
tha into olefins that are used as raw materials for the manu- 25– 50° C, which eliminates the need for refrigeration, mak-
facture of the petrochemicals. The process involves thermal ing it a lower cost process than H2SO4 catalyzed alkylations.
cracking at ⬃800– 850° C at slightly above the atmospheric The use of the solid catalysts is presently being explored.
pressure.
Isomerization
This process is used mainly to convert normal paraffins into
Catalytic Reforming
This process is used to convert the straight-run naphtha 共oc- isoparaffins. The technology is employed to increase the oc-
tane number 30-50兲 into motor gasoline 共octane number 94- tane quality of the light straight run gasoline/naphtha by
103兲. The feed is usually a C6-C10 cut. The process involves converting n-pentane and n-hexane into mixed C5 – C6 iso-
passing the naphtha fraction of boiling range 80– 230° C paraffins. The process is also employed to convert n-butane
over a catalyst held at 430– 530° C and 145– 870 psi. Reform- into isobutane, either to provide feed for the alkylation pro-
ing reactions improve octane by converting linear molecules cess or for use to make methyl tert-butyl ether 共MTBE兲 oc-
into cyclic molecules 共naphthenes兲, dehydrogenating naph- tane improver, when isobutylene is not available. The pro-
thenes into aromatics, and by converting high-boiling large cess involves reacting paraffins feed and hydrogen at a
hydrocarbons into low-boiling lighter compounds. Origi- temperature of 180– 260° C in the presence of an isomeriza-
nally, an alumina base promoted with 0.25–0.75 % platinum tion catalyst.
was used as the reforming catalyst. However, today’s produc-
Gasoline Blending and Treating
ers are using proprietary technology and the catalyst may be These processes are used to obtain different grades of gaso-
platinum alone, or bi- or tri-metallic systems based on addi- line by blending separate components. Blending involves
tional metals, such as rhenium and tin. Some producers may adding alcohol as an anti-icing aid and treatment involves
even be using zeolites. removing sulfur and gum by the use of caustic, clay, and
This process is a major source of industrial raw materi- other chemicals. Hydrotreating and hydrofinishing are also
als, such as benzene, toluene, and ortho- and para-xylenes. used to take care of these problems.
These materials are obtained by extracting reformate with a
solvent, such as sulfolane; or di, tri, and tetra共ethylene gly- Lubricant Base Stock Manufacture
col兲s. The aromatics become part of the extract, from which The base stock manufacture involves vacuum distillation/
the solvent is distilled off to yield the aromatic products. The fractionation of the bottoms fraction 共the vacuum gas oil兲, or
component consisting of paraffins and naphthenes, which is the residuum, that is left after the removal of the low boiling
not soluble in these solvents, is the raffinate. This is mar- fractions used to manufacture fuels. There are many critical
keted as a solvent for various end uses or is used as a feed to requirements for a finished lubricant, as we will discuss
ethylene plants running on naphtha. The aromatics fraction later. Base oil quality is primarily determined by its viscosity
is separated into its components by passing it through a se- index, low-temperature properties 共pour point兲, and volatil-
ries of distillation columns. It is not easy to separate meta- ity 共flash point兲. In terms of the chemical composition, the
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CHAPTER 2 䊏 MINERAL BASE OILS 31
erations to overcome fouling. The processes that use anti- ever, this process involves two steps. During the first step the
foulants include distillation, hydroprocessing, catalytic oxides are reduced to the free metals and during the second
cracking, delayed coking, vis-breaking, and catalytic reform- step the metals are converted into their sulfides. The prob-
ing. Many classes of compounds have potential as anti- lems the refiners encounter are that the first step generates
foulants: dispersants, detergents, and oxidation and corro- excessive exotherms and that it takes time to convert the
sion inhibitors are among those used most often. Oxidation metal oxides into sulfides during which the feed stream goes
inhibitors are useful when fouling results from thermo- untreated. Refineries overcome both these problems
oxidative degradation of organics, such as asphaltenes. through presulfiding. During use, the metal sulfide catalysts
However, once the deposits form, conventional detergents get reduced to free metals and must be regenerated to their
and dispersants can help in removing them. For inorganic active sulfide form. The chemicals used for this purpose are
deposits, dispersants are deemed to be more effective. Since organic polysulfides of high sulfur content.
fouling is likely to involve both the inorganic salts and the Trace amounts of metal ions, such as those of nickel
organic-derived thermo-oxidative decomposition products, 共Ni兲, vanadium 共V兲, iron 共Fe兲, and sodium 共Na兲, are known to
a combination strategy using oxidation inhibitors, deter- lower the catalyst activity. This problem can be suppressed
gents, and dispersants has a higher degree of success. by the use of the metal passivators that perform through
A number of tests are used to determine the effective- various mechanisms, including chelation. Typical nickel
ness of the anti-foulants. These include the Static Thermal/ passivators for fluid catalytic cracking catalysts are anti-
Gum Polymerization Test, Static Rod/Filament Deposition mony 共Sb兲, bismuth 共Bi兲, and cerium 共Ce兲 compounds; typi-
Test, and Hot Liquid Process Simulator 共HLPS兲 Test. The cal vanadium passivators are tin 共Sn兲 compounds; and typi-
HLPS Test is used most widely in the industry and consists of cal sodium passivators are aluminum 共Al兲 compounds.
a resistance heated tube-in-shell exchanger with dynamic
once-through or a recycle flow. The apparatus is pressurized Lubricant Base Stocks
with nitrogen to reduce volatility. The lines, pump, and the
vessel are heated to ensure flow of the test sample. A sample The term “lubricant” is used to describe materials, usu-
of untreated refinery feedstock is passed through the simula- ally liquid, that are employed to perform a number of diverse
tor to determine its fouling tendency. The fouling tendency functions in machinery to prolong its useful life. These func-
of an anti-foulant treated feedstock is then determined in a tions were commented upon in Chapter 1 while discussing
similar manner. Comparison of the two results helps in de- the Fundamentals of Lubrication. A modern lubricant com-
termining the additive’s ability to prevent fouling. prises a base fluid and chemical additives.
A vast majority of lubricants are based on mineral oils,
Corrosion and Foam Inhibitors which is because of their low cost, ready availability, and
Acidic components and salts, present in petroleum, can lead overall adequate performance. Since the base fluid makes up
to chemical and electrochemical corrosion. Corrosion can the bulk of the lubricant, its properties greatly impact the
also contribute towards fouling because it produces metal properties of the lubricant. The properties of a mineral base
oxides and salts. Corrosion inhibitors are used to control this stock depend on its source, viscosity, and the degree of refin-
type of metal damage. These inhibitors are of two types: ing. As stated before, mineral base stocks or oils are classi-
film-forming agents and acid-neutralizing agents; see Chap- fied on the basis of the predominant hydrocarbon type
ter 4 on Additives. Some protect against corrosion by both present in their composition, that is, as paraffinic, naph-
mechanisms. Acid-neutralizing agents guard against chemi- thenic, and aromatic, or bright stocks. Unfortunately, the
cal attack and film-forming agents guard against both hydrocarbon-based classification is not clear cut but is vague
chemical and electrochemical attack. Amines, commonly because these base stocks are manufactured based on vis-
used to control pH, are examples of the acid-neutralizing cosity and not on structural composition. Hence, neither
agents and organic soaps, such as neutral metal sulfonates, base stock is purely paraffinic, naphthenic, or aromatic, but
are examples of the film-forming agents. Basic detergents is a blend of all three types of hydrocarbons.
protect against both fouling 共deposition兲 and corrosion. This While each type of hydrocarbons has its own advantages
is because of their ability to form protective surface films due and disadvantages, to formulate lubricants for most applica-
to their soap content and their acid-neutralizing ability be- tions, the paraffinic base stocks are often preferred. How-
cause of the base reserve. Foaming in coking units is a preva- ever, they do suffer from poor low-temperature performance
lent problem. It is controlled by the use of silicone-type foam because of the wax formation, which incidentally is cor-
inhibitors. rected by the use of additives, called pour point depressants.
Naphthenic base stocks are the next best in desirable overall
Miscellaneous Additives properties. While these base stocks have mediocre viscosity
A variety of additives that perform diverse functions are also indices and oxidative stability, they have good viscosity-
used. These include scaling and biological growth inhibitors pressure relationship and good low-temperature properties.
for cooling towers, poly-electrolytes and demulsifiers for ef- Aromatics are the least suited to formulate most modern lu-
fluent treatment, and combustion improvers for furnaces bricants, but they do have good solvency, thermal stability,
关43兴. Another class of additives, called the catalyst presulfid- and viscosity-pressure properties. Their oxidation stability
ing agents, is used to produce new hydrogen treatment cata- and VI characteristics are the poorest among the three
lysts or to regenerate them. Sulfide is the active form of the groups. As a general rule, the base oils of different origin may
catalyst. During hydrotreating and hydrocracking, sulfur be similar in many respects, but they subtly differ in some
and its compounds can generate hydrogen sulfide that can properties, such as oxidation stability, which are determined
convert the metal oxide catalysts into metal sulfides. How- by their overall structural composition. Desirable base oil
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CHAPTER 2 䊏 MINERAL BASE OILS 33
TABLE 2.4—Physical properties of hydrofinished HVI stocks †44‡. Reprinted with permission from
the Lubrizol Corporation.
Kinematic Viscosity „cSt…
Specific Gravity at Viscosity Pour Point
60° F Sulfur „% wt… Index at 40° C at 100° C „°C… COC Flash „°C…
Source 1
100 Neutral 0.860 0.065 101 20.39 4.11 −13 192
200 Neutral 0.872 0.096 99 40.74 6.23 −20 226
350 Neutral 0.877 0.126 97 65.59 8.39 −18 252
650 Neutral 0.882 0.155 96 117.90 12.43 −18 272
150 Bright Stock 0.895 0.263 95 438.00 29.46 −18 302
Source 2
150 Neutral 0.861 0.036 98 24.38 4.55 −23 210
250 Neutral 0.872 0.055 96 48.96 6.94 −21 238
600 Neutral 0.878 0.099 95 108.00 11.64 −23 262
150 Bright Stock 0.892 0.147 95 473.00 30.90 −15 294
Source 3 共Hydrotreated兲
100 Neutral 0.868 0.018 100 25.18 4.66 −20 200
200 Neutral 0.869 0.012 101 39.78 6.19 −21 216
500 Neutral 0.869 0.015 105 89.37 10.78 −21 254
Source 4
100 Neutral 0.862 0.278 107 21.26 4.28 −16 186
200 Neutral 0.877 0.571 103 30.53 5.26 −13 194
500 Neutral 0.888 0.729 98 95.48 10.89 −10 244
600 Neutral 0.891 0.760 96 111.80 11.99 −13 258
150 Bright Stock 0.903 0.843 96 477.80 30.99 −13 290
properties include good oxidation resistance, high viscosity try uses API Gravity, which is related to specific gravity as
index, good low-temperature performance, and low volatil- provided in the equation below.
ity. The refining process has the flexibility to produce base
stocks where these properties are optimized. However, the 141.5
challenge is to achieve this cost effectively. Good quality API Gravity = − 131.5
Specific Gravity at 60 ° F
crudes, such as those from the Middle East, help accomplish
this manufacturing goal. Base stock production results in a Thus, a heavy oil with a specific gravity of 1.0, the same as of
number of products based upon viscosity. Properties of some water, would have an API Gravity of 共141.5/ 1.0兲 − 131.5
of these products are provided in Table 2.4 关44兴. = 10.0° API. API Gravity is an arbitrary scale which was de-
These base stocks are blended to make base oils of the vised jointly by the American Petroleum Institute and the
desired viscometrics. The resulting base oils do not always United States National Bureau of Standards, for expressing
possess the optimal properties for use in a specific applica- the gravity, or the density, of the liquid oil products. The API
tion. Hence, they need performance-enhancing additives. Gravity scale was designed so that most values fell between
Some additives enhance physical properties of the base oils 10 and 70°API. Sixty degrees Fahrenheit is used as the nor-
while others impart or improve their chemical properties mal value for the measurements and further tables give ad-
and behavior. justments for temperature, see the ASTM D1298 Standard
关27兴. Crude oils are classified as light, medium, or heavy, ac-
cording to the API Gravity. Light crude oils have an API Grav-
Comparison between Naphthenic and Paraffinic ity of higher than 31.1°API, medium oils have API Gravity
Base Oils between 22.3 and 31.1°API, and heavy oils have an API Grav-
The base oils/stocks are classified the same as the crude oils ity of less than 22.3°API. Oils that do not flow at normal tem-
into paraffinic, naphthenic, or aromatic, depending upon peratures or without dilution, normally called bitumen,
the predominant proportion of the hydrocarbon molecules have an API Gravity of less than 10°API. API Gravity values
they contain. Mixed-base crude oils have the varying 共ASTM D287, D1298兲 are sensitive to the relative amounts of
amounts of each type of hydrocarbons. The refinery crude paraffins, cycloparaffins, and aromatics in crude oil; a
base stocks usually consist of mixtures of two or more differ- higher paraffinic content increases the API Gravity values.
ent crude oils; hence they will affect the composition of the Universal Oil Products’ characterization factor 共UOP K
obtained base stocks. Three methods that are commonly factor兲 is based upon gravity and boiling point or the viscos-
used to classify the crude oils are API Gravity, Universal Oil ity data. The UOP K factor is indicative of the origin and the
Products’ characterization factor 共UOP “K” factor兲, and the nature of the petroleum stock. Values of 12.5 and higher in-
United States Bureau of Mining classification. dicate a material predominantly paraffinic in nature. Highly
API 共American Petroleum Institute兲 gravity is based aromatic materials have characterization factors of 10.0 or
upon specific gravity, or relative weight, at 60° F 共15.6° C兲. less. The value between 10 and 12.5 indicates a crude oil of
Specific gravity 共SG兲 is the density of a substance divided by high naphthenic content. Typical API Gravity values of the
the density of water at a specific temperature. The oil indus- mineral base oil fractions are provided in Table 2.5 关45兴.
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34 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
Fig. 2.5—Solvent refining process versus hydro-treatment and hydro-isomerization processes 关514兴.
to formulate lubricants. The refining processes achieve two distillation unit. Vacuum is provided at the top of the unit.
goals. They help isolate components with desirable proper- The pressure at the top of the column is 60– 80 mm of Hg
ties and they help minimize gross variations in the base and at the bottom is 100– 140 mm of Hg. The temperature at
stocks that exist in crude oils from different sources. These the top is about 140° C and at the bottom is about 360° C. The
processes are described below 关41兴. vaporizing steam-feedstock mixture separates into different
Distillation is the primary process for separating frac- boiling range fractions, usually three, which are collected
tions based on boiling point. Atmospheric distillation of the using various devices. The residue, which typically has a
crude yields components that boil below 350° C, such as boiling point above 550° C, is drawn from the base of the
gases, naphtha, kerosene, and gas oil. Atmospheric residue tower.
is the source of the lubricant base stocks. Since hydrocar- The major goals of distillation are to isolate products
bons that form such base stocks generally have boiling based on viscosity and to improve flash point. Viscosity of a
points above 350° C at atmospheric pressure, vacuum distil- base stock depends upon the boiling range of the compo-
lation is necessary to isolate them. Typically, steam is in- nents present. Since this component parameter is hard to
jected into the atmospheric residue feedstock, and the mix- control, distillation is used to obtain a variety of distillation
ture preheated in a furnace before entering it into the cuts, including base stocks, which are later blended to obtain
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36 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
products with the desired viscometrics 共Table 2.4兲. Flash sary for bleaching and, hence, smaller amounts of oil losses.
point of a fraction is largely due to the presence of the small Deasphalting is the removal of asphaltic and resinous
amounts of the low-boiling components, which are removed components, present in the vacuum distillation residue, by
during the distillation process. the use of a solvent. This process is analogous to that used to
Base stock refining involves the removal of certain mate- prepare the residuum for the cracking unit. The process in-
rials from the vacuum distillate, which if not removed, will volves mixing the distillation residue, a viscous black liquid,
cause darkening of the base oils and hence the lubricants, with a hydrocarbon liquid, such as propane, butane, pen-
their viscosity increase, and the formation of the oil- tane, or hexane. The hydrocarbon insoluble phase, which
insoluble matter, called sludge. These materials include ole- settles to the bottom, contains asphaltic and resinous com-
fins, acids such as naphthenic acid, certain sulfur com- ponents. The hydrocarbon phase, which is removed from the
pounds, some polyaromatics, nitrogen compounds, and top, contains the deasphalted oil dissolved in the solvent.
asphaltenes and resins. The paraffin wax present in the The oil is recovered by removing the solvent, which is re-
vacuum distillate must also be removed to obtain base oils cycled. Propane deasphalting is a low yield process, but
with better low-temperature properties. Refining consists of product quality is good. These oils are used as lubricant
acid refining, solvent refining, and hydrotreating. bright stocks, which are useful in certain applications. Bu-
The goal of the acid refining is to remove olefins and un- tane, pentane, and hexane deasphalted oils contain contami-
desirable aromatic compounds. The process involves treat- nants that make them less suitable for use as base stocks.
ment of the base stock distillates with sulfuric acid or oleum Besides solvent, other processing variables that affect
共fuming sulfuric acid兲. During acid treatment, olefins and deasphalted oil quality include extraction temperature, ex-
undesirable aromatics are converted into sulfates and sul- traction pressure, and the solvent to oil ratio. At constant
fonates, which because of high polarity separate out from pressure and the solvent to oil ratio, the lower extraction
the raffinate as a dark liquid. Since this process generates a temperature increases the oil yield but decreases the quality,
significant amount of acid waste, it is being replaced by less and vice versa. This is because high extraction temperatures
waste-generating processes. Acid washing not only improves reduce the solubility of the heavier feedstock components,
color and aging stability, it also improves other desirable which get removed with asphaltenes. However, the extrac-
properties, such as viscosity, viscosity index, and oxidative tion temperature is limited by the critical temperature of the
stability. All these properties relate to the removal of aromat- solvent. This is the temperature at which none of the feed-
ics, which have higher density, low oxidative stability, and a stock components dissolve, therefore separation is not pos-
very low VI. The major disadvantages of acid refining in- sible. The solubility of the oil in propane increases with in-
clude a large amount of waste generation, loss of viscosity, creasing pressure. This is because higher pressures ensure
and an increase in the pour point of the raffinates. The latter solvent-oil mixture to stay liquid, thereby improving contact
occurs due to the removal of materials, such as alkylaromat- and improving extraction efficiency. A higher solvent to oil
ics, which have the ability to act as pour point depressants. ratio improves the deasphalted oil quality by facilitating the
Because of the waste issue, acid refining is only used if separation of the various components.
the objective is to manufacture white oil and produce sul- The viscosity index of the solvent-neutral oils from the
fonic acids. Sulfonic acids are used in a variety of industries paraffinic crudes is usually between 90 and 100, and the re-
as raw materials and for a variety of uses. The major uses in- sidual aromatics content is between 5 and 25 % 关42兴. Solvent
clude lubricant additive manufacture, as catalysts 共cure deasphalting does not remove these molecules because they
agents兲 in paints, coatings, and inks, etching agents to pro- have low aromatic character due to the presence of the long
duce electronic circuit boards, and polymerization catalysts. alkyl chains. For this reason and because of their relatively
The oil after the treatment with sulfuric acid contains acidic low amount, they have little or no negative effect on the VI
resins and traces of sulfuric acid, which are removed by behavior and the aging characteristics of the base oil. In ad-
treating with calcium hydroxide and an adsorbent, usually a dition to improving the aging stability, solvent deasphalting
bleaching clay. After these treatments, the resulting raffinate lowers the density and the viscosity of the raffinates. Viscos-
is neutral and is light in color. The temperature in this step is ity index improves because of the removal of a significant
kept low so that the reactions are slow and easier to control. amount of aromatics, which have a very low VI. Asphaltene
This is especially true for the low viscosity oils. For high vis- removal has little effect on the flash point. The pour point of
cosity oils, higher reaction temperatures are needed to per- the raffinates is higher than that of the feed distillates be-
mit better mixing. In general, aromatics react with oleum cause many alkylated polyaromatics that are removed have
共SO3兲 at a faster rate than olefins. The treatment time is usu- pour point depressing properties. Sulfur content is greatly
ally on the order of 20 to 40 minutes. A significant amount reduced, by as much as 50 %, and the carbon residue, color,
of material is lost during the acid treatment. The quantity and color stability are also improved.
losses essentially depend upon the quality of the crude oil Despite the removal of the aromatics and some olefins,
and the processing conditions. Acid refining can be carried raffinates still contain traces of olefins and unstable com-
out as a batch process or as a continuous process, although pounds. In this respect, solvent deasphalting is less efficient
most modern refineries prefer continuous process because than acid refining, for removing the undesirables. These con-
of the higher throughput and better economy. The continu- taminants must be removed to make the raffinates suitable
ous sulfuric acid refining process has the additional advan- for use as base stocks. The inability to completely remove
tages of reduced acid consumption due to better mixing, and olefins is due to their solubility in the hydrocarbon solvents
more efficient removal of the acid tar from the base oil. The that are used in deasphalting. In terms of solubility, they lie
latter factor translates into the lower amount of clay neces- between the saturated hydrocarbons and the aromatics;
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CHAPTER 2 䊏 MINERAL BASE OILS 37
hence, they persist in raffinates. Previously, the sulfuric acid molybdenum catalysts supported on alumina. Hydrofinish-
treatment was used to remove them, but today they are re- ing improves color, oxidative and thermal stability, demulsi-
moved by hydrogen finishing. fication properties, and electrical insulating properties. The
Solvent refining, or solvent extraction, improves the oxi- removal of the organo-nitrogen compounds improves the oil
dative stability and the viscosity-temperature 共VT兲 charac- color and stability.
teristics of the base oils through preferential removal of the Refining by the use of adsorbents is an alternative to hy-
undesirable polar materials and aromatics. A variety of ma- drotreating. Adsorbents, such as bleaching clay, have been
terials are used for this purpose. They include sulfur dioxide, used for many years to remove the trace amounts of impuri-
furfural, phenol, and N-methyl-2-pyrrolidone which is also ties from liquids, such as edible oils. The same adsorbents
called N-methyl-2 pyrrolidinone. Among these, furfural and have been used to remove color compounds such as asphalt-
N-methylpyrrolidone are by far the most commonly used enes and resins from the petroleum oils. But the refiners pre-
solvents 关47,48兴. Since this step lowers the base stock yield fer hydrotreating because of the lower amount of the mate-
and can remove some beneficial lubricant components, over- rial loss and the difficulty in disposing of spent absorbents.
extraction is avoided. However, in some specialty products, clay refining is still
Sulfur dioxide is one of the first materials used on a large used.
scale. Its use has dwindled over the years because of its low Dewaxing—Petroleum distillates have high pour points
selectivity and the formation of the corrosive sulfurous acid because of the tendency to precipitate wax on cooling. As
in the presence of water. Furfural has better selectivity than such this makes them unsuitable for use in formulating lu-
that of sulfur dioxide and its selectivity decreases less with bricants. The wax content in these oils is reduced in three
increasing temperature than that of the other extractants. ways: solvent dewaxing, urea dewaxing, and isodewaxing.
Furfural is especially useful for refining paraffinic oils that The first method involves dissolving the oil in a solvent, such
have higher pour points, hence require higher extraction as methyl ethyl ketone, and cooling the solution to precipi-
temperatures. Furfural is a good solvent for materials tate wax. The second method involves the use of urea, which
present in the distillates that are highly prone to oxidation forms an inclusion complex with wax that is removed from
and form sludge and coke. It is also effective in removing col- the oil through filtration 关4兴. Isodewaxing, or catalytic dew-
ored constituents, resins, and sulfur from the raffinates. It axing, is essentially hydrocracking which isomerizes linear
has the further advantages of being noncorrosive and of chain hydrocarbons 共wax兲 into branched hydrocarbons. The
forming an azeotropic mixture with water that has a boiling latter compounds have better low-temperature properties
point of 97° C. With respect to properties, phenol is very than their unbranched analogues.
similar to furfural. It forms an azeotrope with water that has In solvent dewaxing, a variety of solvents can be used.
a boiling point of 99.5° C. N-Methyl-2-pyrrolidone 共NMP兲 is These include ketones, such as dimethyl ketone, methyl
a highly effective, nontoxic solvent which has gained popu- ethyl ketone 共MEK兲, and methyl isobutyl ketone; chlorinated
larity during the past few years. Its selectivity can be further hydrocarbons, such as dichloromethane and dichloroet-
improved by the addition of water, the same as in the case of hane; propane, toluene; and blends of these compounds. The
phenol. An NMP-water system can be used to extract the lu- dewaxed oil yield depends upon the wax content of the feed
bricating oil distillates of low quality and the bright stocks to and the required pour point: the higher the wax content and
make high quality base stocks. A heterogeneous solvent sys- the lower the pour point desired, the lower the yield, and vice
tem comprising propane, phenol, and cresols has been versa.
found effective in removing the undesirable aromatics, Ketone dewaxing process is the classical method. In this
naphthenes, asphaltenes, resins, and unsaturated and highly method, the oil is mixed with the ketone and the solution
colored constituents. The propane portion removes asphalt- cooled to ⬍10° C. The precipitated wax is filtered off and the
enes and resins and phenol and cresols remove the other solvent removed from the filtrate to obtain the dewaxed oil.
components. This solvent system essentially carries out the The solvent is then recycled 关4兴. The use of dichloroethane–
functions of deasphalting and solvent extraction 关4兴. Despite dichloromethane 共methylene chloride兲 mixtures, sometimes
the effectiveness and the use of various extractants, nontox- called DiMe solvent, is used to produce low pour point lubri-
icity, good selectivity, and adaptability to process both paraf- cating oils. This solvent system removes both hard and soft
finic and naphthenic oils make NMP an attractive candidate waxes from the oil. A newer process, called the DILCHILL
for use. 共Dilution Chilling兲 process, involves adding a large quantity
Hydrogen finishing or hydrofinishing is mild hydrotreat- of the chilled solvent to the raffinate, causing the wax to pre-
ing, which is applied after solvent refining to remove rem- cipitate. This dewaxing technology is superior to the other
nants of the undesirable compounds that remain. The pro- solvent dewaxing technologies because of the following rea-
cess basically involves the removal of the trace amounts of sons.
olefins and undesirable oxygen, nitrogen, and sulfur- 1. Crystal size is larger, which facilitates filtration.
containing impurities, through selective catalytic hydroge- 2. Pour points of the dewaxed oil are lower 共by as much as
nation, or hydrotreating. Depending upon the process con- −35° C兲.
ditions, aromatics, if present in the oil, are partially or fully 3. Yields are higher.
hydrogenated. During hydrotreating, there is little material 4. Operating and maintenance costs are lower.
loss. The process involves heating the raffinate at tempera- Urea dewaxing is based upon the fact that urea forms an
tures of 150– 420° C and pressures of 14– 170 bars with hy- inclusion complex 共adduct兲 with straight chain hydrocar-
drogen in the presence of a catalyst. Typically, the reaction is bons, such as waxes. An inclusion complex forms between
carried out at 250– 350° C and 20– 60 bars, using nickel and the host 共urea兲, which forms a cavity in which the guest
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38 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
共n-paraffins or wax兲 resides. In this process, the waxy distil- TABLE 2.6—Oil classification according to
late, diluent 共methylene chloride兲, and saturated aqueous ASTM D2226.
urea solution are mixed in a reaction vessel. The urea–wax
Oil Type Asphaltenes Polar Compounds Saturates
adduct that forms as a solid is separated from the liquid via
Aromatic
filtration. The solvent is removed from the filtrate through 101 0.75 % max 25 % max 20 % max
distillation to yield the dewaxed base oil. The solid urea–wax 102 0.5 % max 12 % max 20.1–35.1 % max
adduct is subjected to water at high temperature, which re- Naphthenic
sults in two layers: the top layer is the wax and the bottom 103 0.3 % max 6 % max 35.1–65 % max
layer is the aqueous urea solution. To this urea solution at Paraffinic
70 ° C, more urea is added to make a saturated solution for 104 0.1 % max 1 % max 65 % min
re-use.
Hydrogen cracking or hydrocracking solvent refining is
very effective in removing the undesirable polar materials because they are solvent refined and they have a pH close to
and aromatics from the raffinate. However, a substantial 7, which is the pH of neutral liquids and solutions. A high VI
amount of the material loss occurs, which is worse in distil- oil is extremely desirable since it will experience a relatively
lates derived from the poor quality crude oils that contain smaller drop in viscosity with increasing temperature than a
high concentrations of polyaromatic compounds. Refiners lower VI oil, thereby making it a better choice in formulating
minimize or eliminate this material loss by the use of hydro- high temperature lubricants. The viscosity index of oil can
cracking. The process involves treatment of the distillate be determined by measuring its kinematic viscosity at 40° C
with hydrogen at high pressures 共l500– 4000+ psi兲 in the and 100° C 关27,28兴 and using the ASTM tables 关49兴, see Table
presence of a catalyst. This converts the aromatic molecules 1.6. High viscosity base oils, also known as high viscosity in-
into naphthenes and cracks larger molecules to compounds dex 共HVI兲 oils, owe their good viscosity-temperature charac-
of molecular weight that are suitable for use as base oils 关47兴. teristics to the presence of higher amounts of paraffinic
The conversion of the low VI aromatics into the medium VI structures. Their low temperature properties are a result of
naphthenes improves the VI of the oil. In addition, the ole- solvent refining 共low-temperature dewaxing兲, and their good
fins are converted into saturates, the normal paraffins are oxidative stability is a consequence of the catalytic hydroge-
isomerized to branched alkanes which improves the pour nation. Paraffinic base oils make excellent general purpose
point, and the sulfur and nitrogen containing compounds lubricants and are used extensively to formulate engine oils,
are removed. transmission fluids, journal oils, gear oils, hydraulic oils, pa-
Hydrocracking under certain conditions provides frac- per machine oils, metalworking fluids, and greases 关46兴.
tions that are useful as very high VI base stocks and at a very Naphthenic base oils, manufactured in smaller quanti-
reasonable cost. Conventional base oils with 100° C viscosity ties than paraffinic base oils, have naturally low pour points
of about 12 mm2 / s 共12 cSt兲 have a VI of between 95 and 100, because they are wax-free and have excellent solvency. How-
but the hydrocracked oils have a VI of 120 or higher. For ex- ever, their VT characteristics are inferior to those of the par-
ample, hydrocracking of slack waxes from the dewaxing affinics; that is, they have low to medium VI. These base
plants, followed by distillation and dewaxing yields oils of a stocks are preferred only in those applications that will ben-
viscosity index of up to 150. These oils are referred to as very efit from their lower wax content and lower pour points, and
high viscosity index 共VHVI兲 oils. where the low VI is acceptable. Since such oils are devoid of
When the objective of hydrocracking is primarily to wax, no dewaxing is needed during their manufacture.
minimize wax in the distillate by isomerizing linear hydro- Nonetheless, solvent extraction and hydrotreatment are car-
carbons into branched hydrocarbons, the process is called ried out to reduce the aromatics content, especially the poly-
iso-dewaxing. The details of this process will be discussed cyclic aromatics which are potential carcinogens. Some
later. base oil producers are using hydrocracking technology,
Each refinery produces base stocks of different viscosi- which hydrogenates aromatics to naphthenics, to achieve
ties and chemical properties for use in different applica- this goal. The same as paraffinics, naphthenic base oils are
tions. More highly refined oils have little or no organic sulfur also used to make good general purpose lubricants, espe-
and, hence, are more prone to oxidation. The oxidation resis- cially for low-temperature applications. They are used to for-
tance of oils, which are more susceptible to oxidation due to mulate turbine oils, hydraulic oils, metalworking lubricants,
the presence of unsaturation, can be greatly improved rubber process oils, cylinder lubricants, and greases.
through hydrogenation. Most automotive and industrial lu- Bright stocks are manufactured from the residue left af-
bricants and greases use solvent-extracted base oils. Solvent- ter the isolation of the paraffinic and the naphthenic base
extracted and hydrotreated base oils are mainly used for pre- stocks, as discussed in the previous sections. The residue is
mium products such as turbine fluids, hydraulic fluids, and subjected to propane deasphalting, solvent extraction, and
circulating oils 关35兴. solvent or catalytic dewaxing to obtain these oils. These
As stated earlier, mineral oil base stocks typically consist stocks have a high aromatic content and are the least pre-
of hydrocarbon molecules that contain 20–70 or more car- ferred because of their poor oxidation resistance, tendency
bon atoms and are characterized as paraffinic, naphthenic, to form black sludge at high engine operating temperatures,
or aromatic. Paraffinic base oils are also called solvent neu- low VI character, and suspect carcinogenic nature. They are
tral 共SN兲 oils. They possess good viscosity-temperature 共VT兲 usually used as high viscosity blending stocks to formulate
characteristics 共VI兲, adequate low-temperature properties, engine oils, gear oils, hydraulic oils, and greases.
and good oxidative stability. They are called solvent neutral Generally, the paraffinic oils have light color and good
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CHAPTER 2 䊏 MINERAL BASE OILS 39
thermo-oxidative stability, but have a high cost. Aromatic manufactured via hydrocracking. Chevron has the flexibility
oils, or bright stocks, are darker in color, have poor thermo- to produce consistent products from any crude, irrespective
oxidative stability, possess good solvency towards polar of its source. While it produces base stocks that meet the
compounds, and have lower cost. Naphthenic oils fall in be- present market specifications, the Chevron catalyst is versa-
tween the two. Table 2.6 provides the composition of three tile enough to make base stocks of diverse properties,
classes of oils, as described in ASTM Standard D2226 关27兴. through more extensive cracking or cracking in the presence
Table 2.7 presents the relationship between various lubri- of waxes; thereby making the base stocks of even a higher VI
cant properties and chemical structures 关50兴. accessible. RLOP stocks are primarily cycloparaffinic and
In addition to these categories, the base oil manufactur- are more oxidatively stable than the solvent refined base
ers produce a variety of other oils, such as cylinder oils, elec- stocks and are consistent in quality. The consistency aspect
trical oils, process oils, agricultural spray oils, refrigeration is greatly preferred by the OEMs, such as GM and Ford,
oils, transformer oils, turbine oils, and white oils. These oils, which produce passenger cars. The oxidative stability of
used in specialty applications, usually require more severe these stocks is attributed to the absence of unsaturation and
and extensive processing methods in their manufacture. nitrogen. However, the same attributes become drawbacks
Recently developed catalyst technology by Chevron Oil as far as their deposit-suspending ability, or the solvency, is
Company has made it possible for Chevron to manufacture concerned. Many other refiners, such as Petro Canada,
base stocks with higher VI and oxidative stability than con- Pennzoil-Conoco, and Texaco are licensing Chevron catalyst
ventional petroleum-derived base stocks. These stocks, technology and are either already producing or plan to pro-
popularly known as RLOP stocks, named after the place of duce similar base stocks for the North American Market. The
first manufacture—Richmond Lubricating Oil Plant, are process to make these base stocks, along with that used to
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40 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
manufacture conventional base stocks, is provided in Fig. ferent components. Table 2.8 lists these processes and their
2.5. Figure 2.6 shows consolidated refining scheme to pro- effect on the yield of the base stocks 关52兴.
duce mineral oil base stocks. As shown in the figure, the One of the primary requirements for the organic com-
manufacture of Group I base oils involves steps 7–12, the pounds that comprise base oils is that they must be fluid at
manufacture of Group II base oils involves steps 13 and 14, least at ambient temperature and may be below and have a
and the manufacture of Group III base oils involves steps reasonably low volatility and high oxidative stability during
7–10 and 15–17. service. In a number of applications, fluidity at lower tem-
Processes used in refining can be divided into two peratures 共down to a temperature of −40° C兲 is also required.
groups: those that involve separation and those that involve Fluidity is related to the molecular weight and the type of hy-
conversion. The first group includes chemical treatment to drocarbons present in the base oil. Alkanes 共paraffins兲, alicy-
remove impurities and the undesirables by the use of the clics 共naphthenes兲, and aromatics of the same molecular
chemicals, for example acid refining, and physical separa- weight have different physical and chemical characteristics.
tion, such as distillation or cooling. The second group in- Alkanes have lower density and viscosity than alicyclics
cludes processes, such as hydrorefining and hydrocracking, 共naphthenics兲, which in turn have lower density and viscos-
which convert various components of the raffinate into dif- ity than aromatics. Viscosity-temperature characteristics
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CHAPTER 2 䊏 MINERAL BASE OILS 41
Base Oil Properties their oxidative stability and the antiwear performance.
The presence of the nitrogen compounds in base oils
Oxidation Properties promotes oxidation and decreases useful life of the derived
Good oxidation properties in a base oil and a lubricant are a lubricants. This is because most nitrogen compounds
pre-requisite to their use in most applications, especially so present in the base oil, such as pyridines, are basic in charac-
for applications such as engine oils that are exposed to high ter. They react with acids, which have oxidation-inhibiting
operating temperatures. Oxidation is initiated by the reac- ability, to form salts.
tion of oxygen with the hydrocarbon materials to initially
form hydroperoxides and peroxides, which thermally de- Other Properties
compose or rearrange to form precursors to harmful prod-
In addition to the properties discussed so far, the base oil
ucts. See Chapter 4 on additives and Ref. 关55兴 for the detailed
composition affects a number of other physical properties.
oxidation mechanism. The effects of excessive lubricant oxi-
dation are noticeable by oil thickening and the formation of These include rheology, volatility, solvency, and elastomer
the insolubles, such as sludge, varnish, lacquer, and hard car- compatibility.
bonaceous deposits on hot surfaces. Some oxidation prod- Rheology, or the flow properties, of a lubricant depends
ucts are acidic and therefore cause corrosion of the metal upon the base oil composition used in its formulation. Flow
surfaces. Hydrocarbon oil oxidation is initiated by the attack properties include viscosity index 共VI兲, low-temperature flu-
of oxygen on the weak carbon hydrogen bonds. These com- idity, and the pour point. Viscosity index is a measure of the
monly occur in the vicinity of a double bond 共allylic hydro- viscosity-temperature 共VT兲 relationship. All liquids lose vis-
gens兲 or are next to an aromatic ring 共benzylic hydrogens兲. cosity with an increase in temperature. It is the rate of loss in
Because of this, the presence of unsaturation or the aromatic viscosity which is of concern in lubricants; a lower decrease
rings in the base oils is not desired. While the presence of the rate is preferred in most applications. With respect to this
unsaturated compounds in hydrocarbon base oils is uncom- property, paraffinics are the best, which are followed by
mon, they do form during base oil processing, as a result of naphthenics and then aromatics, if the molecular weight of
the cracking reactions. Just the same, they are removed dur- the components is the same. Hence, to formulate lubricants
ing the hydrofinishing or the clay treatment step 关47兴. On the
for use in high temperature applications, base oils with a
other hand, aromatics occur abundantly in the mineral base
high paraffinic content are chosen. With respect to the low-
oils. Even the API Group II and Group III oils, which are
temperature fluidity, oils that contain a large amount of lin-
hydro-processed, contain a significant amount of aromatic
content, see data in Tables 2.9 and 2.11. In saturated hydro- ear paraffins 共paraffinics兲 have the tendency to form wax at
carbons, carbon hydrogen bond strength of the tertiary hy- low temperatures. This is not desired since waxes formed
drogen is weaker than that of the secondary hydrogens, have a network structure which act like a sponge and adsorb
which in turn is weaker than that of the primary hydrogens. most of the oil and hinder its flow. Fortunately, they respond
Hence, the hydrocarbons with tertiary and secondary hydro- well to additives, called the pour point depressants. This
gens are also highly susceptible to the oxygen attack. This makes it possible to formulate lubricants from paraffinic
suggests that paraffinics with less branched structures or the base oils that have good low- and high-temperature proper-
cyclic rings will have better oxidation properties than naph- ties. Naphthenic and aromatic base oils have good low-
thenics that have more cyclic rings, hence more secondary temperature properties, because they do not form waxes at
and tertiary hydrogens. For further details, please refer to low temperatures. However, their VI is too low for use in
the Oxidation Inhibitors section of Chapter 4. Lubricant oxi- some applications. Figure 2.8 depicts the viscosity-
dation is controlled by the use of the oxidation inhibitors. temperature behavior of oils of various VIs. The top portion
Common oxidation inhibitors are alkylphenols, arylamines, of the figure shows their behavior across the full tempera-
organic sulfides and polysulfides, and metal and amine salts
ture range of −40° C to 150° C and the bottom half of the fig-
of dialkyl dithiocarbamic and dialkyl dithiophosphoric ac-
ure shows behavior of these oils in the 40° C to 100° C range,
ids. As a general rule, oils rich in aromatics require a higher
which is used to define the viscosity index of an oil. As ex-
amount of oxidation inhibitors than those that contain
higher amounts of naphthenic and paraffinic hydrocarbons. pected, high VI oils have a shallower slope than the low VI
oils, in the 40° C to 100° C range. Slopes across the whole
range are presented in Table 2.12. Data show that while the
Effects of Sulfur and Nitrogen Compounds
magnitude of the slopes outside this range is different, the
For many years, the presence of sulfur in oil was equated
oils maintain their viscosity-temperature behavior in the
with quality, primarily because such oils had good oxidation
same order as indicated in the VI temperature range.
stability. The sulfur in oil exists in the form of organo-sulfur
Viscosity-pressure 共VP兲 relationship is another important
compounds and in domestic base oils its amount can range
from ⬍0.05 to 0.4 % by weight for light base stocks and up to property of the base oil that needs to be addressed. Many lu-
0.8 to 1.0 % for heavy base stocks. Sulfur levels in the base bricant applications involve compression of the lubricant,
oils used in other countries is even higher. Modern base such as hydraulics, roller element bearings, metalworking,
stocks are required to have low sulfur levels 共see Table 2.10兲, and continuously variable transmissions 共CVTs兲. Unlike the
which is achieved by the use of the better refining tech- VT relationship where an increase in temperature causes a
niques. These were discussed in the base oil manufacture decrease in viscosity, in the VP relationship an increase in
section. However, the sulfur-containing additives are often pressure leads to an increase in viscosity. This behavior is
used in these oils to formulate lubricants in order to improve represented by the following equation 关56–58兴.
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CHAPTER 2 䊏 MINERAL BASE OILS 43
Oil 0°C 40° C Slope „m… 40° C 100° C Slope „m… 100° C 150° C Slope „m…
75 VI Oil 192.0 21.0 −4.2750 21.0 4.0 −0.4250 4.0 1.87 −0.0426
100 VI Oil 155.0 19.5 −3.3875 19.5 4.0 −0.2583 4.0 1.91 −0.0418
125 VI Oil 117.0 17.7 −2.4825 17.7 4.0 −0.2283 4.0 1.97 −0.0406
150 VI Oil 92.0 16.3 −1.8925 16.3 4.0 −0.2050 4.0 2.03 −0.0394
In addition, in some applications, such as engine oils, gear minimized or the worker exposure to such oils is eliminated.
oils, and transmission fluids, the lubricant is required to dis- The ASTM D3239 method can be used to determine the poly-
solve or suspend the polar contaminants resulting from oxi- cyclic aromatic content of the light and medium viscosity
dation or the additive degradation. The measure of an oil sol- base oils, that is, those that are 70 to 150 Neutral or have a
vency is its aniline point. Aniline point is determined by 100° C viscosity of 3–5 cSt. However, the method does not
mixing aniline, a polar compound, with the base oil 共ASTM work well for medium to heavy grade oils, that is, those that
D611兲. Aniline point is essentially the temperature at which are 320–850 Neutral. The method underestimates their poly-
the two phase aniline-base oil mixture becomes a single cyclic content 关42兴. Biodegradability is another desired prop-
phase. Typically, base oils of high paraffinic content have erty that is gaining importance. It is the ability of a lubricant
aniline points of ⬎230° F 共110° C兲, solvent-refined base oils to degrade naturally in the environment. Biodegradability
have aniline points of 200– 215° F 共93– 102° C兲, and naph- depends upon the structure of the hydrocarbon materials
thenic base oils have an aniline point of ⬍150° F 共65° C兲, see that are present in the base oil. A number of standards are
the data presented in Table 2.13 关45兴. In cases where aniline used to determine the biodegradability of the lubricants;
point is too high, that is, the base oil has a low solvency; the ASTM D5864, D6066, and the CEC-L-33-T-82 being among
additives may not dissolve, creating a problem to formulate them.
a lubricant. In such cases, the problem can be overcome by In the year 2003, the API has published a summary of
the addition of a small amount of the polar materials, such as the toxicological and ecotoxicological data on the lubricat-
polyol ester or an alkylbenzene. These are sometimes called ing oil base stocks. Biodegradability data summary from
base oil extenders. various studies is provided in Section 3E of the report. While
Volatility relates to base oil or its components to evapo- the data are confusing because of the various methods used,
rate under the influence of high temperatures. High volatil- most studies indicate paraffinic base stocks to be more bio-
ity in modern lubricants is not acceptable because of its degradable than naphthenic base stocks and bright stocks
negative effect on the environment and the possibility of ig- 关54兴. Of all the test methods used, the CEC method provides
nition. When a lubricant is used in applications that are open the highest biodegradability values. It is important to note
to the environment, such as some metalworking fluids, it can that the base oils are expected to have higher biodegradabil-
pose a health hazard to workers. Flash Point is used as a ity than the finished lubricants. This is because all of the ad-
measure of an oil’s volatility. In general, the paraffinic oils ditives used to formulate lubricants may not be biodegrad-
have the lowest volatility, the aromatic oils have the highest
volatility, and the naphthenic oils fall in between the two ex-
tremes. Table 2.14 compares the flash points of the different
types of oils of the same viscosity 关45兴.
Elastomer compatibility of the base oil is important be-
cause during service a lubricant comes in contact with elas-
tomer seals, gaskets, O-rings, and similar components.
While some base oils are innocuous to elastomers, others are
not. Base oil components can interact with the seals in many
ways, some of which can lead to structural damage. For ex-
ample, they can migrate into the elastomer matrix causing it
to swell, or remove the plasticizer. Naphthenic and aromatic
oils with high solvency 共low aniline points兲 lead to elastomer
swelling via migration. This causes a loss of proper fit and
may impair proper functioning of the part. On the other
hand, paraffinic oils and PAOs that have high aniline points
remove the plasticizer, thereby causing elastomer parts to
crack and a loss of lubricant. Additives, called the seal swell
agents can help overcome this problem.
Biocompatibility of the lubricant with the environment
is becoming increasingly important because of the health
concerns. Base oils can contain components, such as polycy-
clic aromatic hydrocarbons, that are known to have toxicity,
carcinogenicity, and mutagenic activity. Hence, it is impor-
tant that either the amount of these components in the oil is Fig. 2.9—Viscosity-pressure relationship 关4兴.
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CHAPTER 2 䊏 MINERAL BASE OILS 45
able or they may even lower the biodegradability rating generated recent interest in obtaining mineral base stocks is
because of being toxic to some of the microorganisms used gas to liquid technology 关68兴.
in testing. It is therefore not too surprising that the hydraulic Gas to liquids 共GTL兲 technology involves converting
fluids based on mineral oils degraded to a level of only 40 %, natural gas into synthetic oil, which can be processed into
while the average biodegradability of the paraffinic base fuels and other hydrocarbon-based products. The process
stocks is 66 %. The above report provides a biodegradability essentially involves combining smaller natural gas mol-
range of 51–75 % for the paraffinic base stocks. ecules, such ac methane, into larger molecules that are suit-
Table 2.15 summarizes the effect of the base oil compo- able as diesel fuel, naphtha, and other liquid petroleum
sition on various base oil properties. A number of research products. The molecules that contain over 20 carbon atoms
articles correlating base oil composition with real engine are suitable as base stocks for lubricants. Because of the way
performance have been published 关59–64兴. Similar studies these hydrocarbons are manufactured, they are devoid of
pertaining to industrial lubricants have also been reported the undesirable compounds, such as aromatics. These base
关60,63,66,67兴. Testing standards and test methods used to as- stocks, dubbed as isoparaffins, are good substitutes for the
sess various properties of the base stocks are provide else- blends of the API Group III and IV base stocks because of
where 关42兴. similar properties. Such mixtures are in great demand for
use in automotive engine oils because of the increased em-
Gas to Liquid Technology phasis on reduced emissions and energy efficiency, and
While discussing mineral base oils, we concentrated on pe- shortages are expected.
troleum refining and alteration of the base oil composition The process to manufacture GTL base stocks involves
by the use of hydrorefining, hydrocracking, and hydroi- first converting the natural gas, primarily methane, into syn-
somerization technologies. Another technology that has
TABLE 2.13—Aniline points of mineral oil frac- TABLE 2.15—Effect of composition on various
tions †45‡. base oil properties.
Aniline Point Range Base Oil Property Paraffins Naphthenes Aromatics
Viscosity Index 共VI兲 Excellent Poor-Good Poor
Oil Type °F °C Volatility Low Medium High
Paraffinic 200–250 93–121 Low-temperature Poor Good Good
Relative Naphthenic 190–225 88–107 Fluiditya
Naphthenic 130–195 54–91 Low-temperature Excellent Good Good
Aromatic 80–130 27–54 Fluidityb
Pour Point Poor Good Excellent
Viscosity-Pressure Poor Good Excellent
Relationship
TABLE 2.14—Typical values for flash points Oxidation/Thermal Excellent Poor-Good Poor
†45‡. Stability
Flash Point Solvency Towards Poor Good Excellent
Additives
Oil Type Viscosity cSt °F °C Toxicity None Low High
Aromatic 3000 430 221 Biodegradability High Medium Low
Naphthenic 3000 450 232 a
Paraffinic 3000 575 302 Without pour point depressant.
b
With pour point depressant.
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46 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
thesis gas, a mixture of hydrogen and carbon monoxide, via ing commercializing the GTL based products in the near fu-
partial oxidation in the presence of a proprietary catalyst. ture. Isoparaffins possess structural resemblance to PAOs
The synthesis gas is then converted into the synthetic crude and have extremely high viscosity indices. In addition, these
oil, which can be processed to yield hydrocarbon fractions branched paraffinics exhibit excellent low- and high-
suitable as lubricant base stocks. The synthesis is based temperature viscometrics, high oxidation resistance, low
upon Fischer-Tropsch technology. For further details, see the pour points, and low volatility, which are at par with or supe-
section on Hydrocarbon Polymers in Chapter 3. Sasol and rior to the commercially available API Group III base stocks,
Mossgas of South Africa and Shell are the present producers see data in Table 2.16. The performance in several ILSAC
of the GTL base stocks and a number of major oil companies, GF-3 tests conducted on lubricants derived from these base
such as BP/Amoco, Conoco, and ExxonMobil are consider- stocks indicates these to perform well 关68兴.
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MNL59-EB/Mar. 2009
3
Synthetic and Biological „Natural… Base
Stocks
THIS CHAPTER COVERS NON-PETROLEUM and chemical stability. Synthetic fluids belong to two broad
lubricant base stocks. These are either man-made 共syn- groups: synthetic hydrocarbons and other fluids. Synthetic
thetic兲 or biological in origin. These base stocks possess hydrocarbons comprise polyalphaolefins, polybutenes
certain advantages over mineral base stocks, which make 共polyisobutylenes兲, and dialkylbenzenes and alkylnaphtha-
their use more suitable in lubricants that are employed in lenes. Other fluids include dicarboxylate esters 共di-esters兲,
applications that experience temperature extremes or oper- polyol esters, poly共alkylene glycol兲s, phosphate esters, pol-
ating conditions, or both. Interest in the base stocks of bio- ysiloxanes 共silicones兲, poly共phenyl ether兲s, and perfluoro-
logical origin is primarily due to their superior environ- alkyl and chlorofluoroalkyl ethers. Depending upon the ad-
mental compatibility and availability from renewable vantages and the disadvantages some synthetic fluids are
sources. In this chapter, we discuss their chemistry, synthe- suitable for use in some applications but not in others.
sis or isolation, and the advantages. Unlike petroleum-derived base oils 共mineral oils兲 that
As stated previously, the base stocks used for formulat- occur in nature, synthetic base fluids are man-made prod-
ing lubricants are derived from three sources: petroleum, ucts. These are manufactured from the petroleum-derived
raw materials derived from petroleum, and plants and ani- low-molecular weight raw materials by chemical reactions
mal 共natural兲. Here we will discuss materials that are either such as alkylation, polymerization, and esterification. These
synthesized from petroleum-derived raw materials or are materials have a well-defined structure or structures with
isolated from seeds and fruits. Animal fats, except for fish predictable properties. This is in contrast to mineral oils
oils, because of their nonfluid nature at room temperature which are complex mixtures because of which they have
are unsuitable for use as liquid base stocks. At one time fish less-defined properties. Previously, the term synthetic was
oils were abundantly used either as base fluids or starting limited to base stocks that were made outside the refining
materials to manufacture additives, such as sulfurized unit. However, the distinction is becoming less clear since
sperm oil, for use as EP agents. However, fish oils are no some base stocks, such as Chevron’s RLOP type, discussed in
longer readily available because of the conservation inter- Chapter 2, which are produced in the refinery, are being mar-
est against the slaughter of the oil-bearing large fish. keted as synthetic base stocks. We consider the first defini-
tion of synthetic as proper. Based on this definition, the fol-
Synthetic Base Stocks lowing classes of synthetic base fluids are commercially
available 关69–74兴:
Synthetics have a number of advantages or disadvantages
1. Synthetic Hydrocarbon Polymers
over the mineral oils which pertain to the following proper-
a. Polyalphaolefins
ties:
b. Polybutenes
1. Thermal stability
c. Alkylated Aromatics
2. Oxidation stability
2. Carboxylate Esters
3. Viscosity-temperature behavior
a. Aliphatic Esters
4. Hydrolytic stability
b. Polyol Esters
5. Tribological properties 共lubricity and load-carrying
3. Phosphate Esters
properties兲
4. Poly共alkylene glycol兲s
6. Corrosion resistance
5. Silicon Compounds
7. Volatility
a. Silicones
8. Biodegradability
b. Silicate Esters
9. Toxicity
6. Poly 共phenyl ether兲s
10. Compatibility with other materials
7. Halogenated Hydrocarbons
11. Miscibility with mineral oils
12. Solvency 共additive solubility兲
Synthetic Hydrocarbon „SHC… Polymers
13. General availability and only in certain viscosity grades
14. Ionizing radiation stability Polyalphaolefins
15. Cost Most olefins can be polymerized to yield hydrocarbon mol-
It is important to note that no one base stock has all of ecules of the size that can be used as lubricant base stocks.
the listed attributes. Two properties that are common to Common olefins which are used to make these polymers in-
most synthetic fluids are good thermo-oxidative stability clude ethylene, propylene, isobutylene, ␣-olefins 共alphaole-
47
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48 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
The boron trifluoride-alcohol 共BF3-ROH兲 catalyst sys- Fig. 3.9—Compositional comparison of polyalphaolefins and min-
tem is another Friedel-Crafts type catalyst system that can be eral oil 关87兴.
used to synthesize PAOs. Under proper conditions, this sys-
tem yields an oligomer mixture that is rich in the trimer.
Other co-catalysts that also lead to trimer-rich PAOs are wa- ment of the intermediates via a methide 共CH3−兲 or a hydride
ter and carboxylic acids 关84兴. As mentioned earlier, 1-decene 共H−兲 shift, as is shown in Fig. 3.8. Since the polyalphaolefins
is one of the most common olefins used. After the oligomer- are classified based on their 100° C viscosity; in general the
ization is complete, water is added to the crude reaction mix- higher the viscosity, the longer the average pendant group
ture to quench the catalyst and the obtained product mixture chain length.
hydrogenated and fractionated to yield the desired polyal- In order to synthesize 2 – 10 cSt PAO, BF3-ROH 关85兴 and
phaolefin fraction. The number of monomer units in the BF3 – H2O 关86兴 are often used, but for synthesizing higher
polyolefin depends upon the starting olefin, the type of cata- viscosity PAOs, it is necessary to use Ziegler-Natta catalyst
lyst, the reaction temperature, and the reaction time and systems 关86兴. Even in the latter case, the resulting polyolefin
pressure. For example, if one uses BF3 / n-butanol at 30° C, oligomer contains a double bond, which must be removed by
the product primarily contains tridecene 共C30兲, with only mi- hydrogenation. Besides ␣-decene, other olefins may also be
nor amounts of the other oligomers. Tridecene does not used, either as such or as mixtures with dodecene-1. The use
comprise a single structure but is a mixture of as much as 30 of the olefin mixtures provides polyalphaolefins with
isomers, resulting from various carbon size pendent groups. uniquely different properties. This is because the polymer
The formation of the isomers occurs due to the rearrange- structure has different carbon size branches and different
isomers.
One of the reasons for the popularity of PAOs is their
similarity to the hydrocarbon base oils, but without the pres-
ence of naphthenics and aromatics that negatively impacts
properties, such as VI, volatility, and oxidation stability. As
stated earlier, commercial PAOs are classified according to
their approximate kinematic viscosity at 100° C. For ex-
ample, the PAO of viscosity 1.80 is classified as PAO 2 and the
PAO of viscosity 9.87 is classified as PAO 10. Common PAOs
are of 2, 4, 6, 8, 40, and 100 cSt viscosities. PAOs have supe-
rior low and high temperature properties relative to those of
the similar viscosity mineral base oils. These properties in-
clude low pour point, high viscosity index, and high flash
and fire points. Because of these, the PAOs are excellent base
stocks for use in applications that experience broad tem-
perature ranges. Good low-temperature properties are due
to the presence of the long branches because of which at low
temperatures these materials do not form crystalline net-
works. Good volatility is because of their uniform or close to
uniform composition. In mineral oils, it is the presence of
the low molecular weight low boiling components that
causes volatility problems. PAOs are essentially free of such
components, hence they have better volatility. Figure 3.9
compares the compositional difference between PAO and a
mineral oil of similar viscosity, as determined by the gas
chromatography 共GC兲 关87兴. As one can see, the PAO has a nar-
Fig. 3.8—Polypropylene oligomerization and rearrangement reac- rower composition than the mineral oil. PAOs are also ther-
tions. mally more stable than the mineral base oils, as indicated by
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CHAPTER 3 䊏 SYNTHETIC AND BIOLOGICAL BASE STOCKS 51
the Panel Coker Test. This is primarily because of the PAOs mine these properties are described in the ASTM Annual
being free of the aromatics that are the reason for poor per- Book of Standards 关27兴.
formance of mineral oil in the test. Prior to the use of ethylene-derived ␣-olefins, cracked
Table 3.1 summarizes the physical properties of the olefins were used to make the polyolefin oligomers. The poly-
polyalphaolefins 关87兴. As one can see, PAOs 2 to10 have excel- merization process involved the use of AlCl3 at 20 to 100° C
lent low-temperature properties; they flow at −40° C and and the obtained polyolefins had good low- and high-
have a pour point of less than −54° C. Therefore, they are es- temperature properties 关4兴.
pecially suitable in formulating lubricants for use in cold cli- The major application area for the PAOs is automotive
mates, such as that of North America and Northern Europe, engine oils that require low pour point, low volatility, and
without the need of a pour point depressant. Their viscosity good thermo-oxidative stability. In automotive lubricants,
indices are well over 122, making them suitable to formulate PAOs have better oxidation and deposit control and fuel
lubricants for the warm climates as well. The VI increases economy than those that are mineral oil derived 关70兴. Hence,
with the increasing molecular weight of the starting olefin. PAOs are the most frequently used synthetic fluids. This is
The main advantage of the good viscosity index is that the detailed in the section that compares petroleum and syn-
base oil does not need a viscosity improver to maintain its thetic base stocks. Other automotive applications include
two-stroke cycle engine oils, automatic transmission fluids,
viscosity at high temperatures. Flash points of the PAOs are
multi-grade gear oils, and greases. PAOs are also used in in-
almost equivalent to those of the mineral oils of similar vis-
dustrial applications, such as hydraulic fluids, compressor
cosity.
oils, heat transfer fluids, food grade oils, and greases. Engine
Higher viscosity grades, PAO 40 and PAO 100, are also
oils based on the PAOs are claimed to have extended drain
listed in Table 3.1. These are similar to the low viscosity
intervals, improved fuel economy, enhanced wear protec-
grade PAOs in having good viscometrics and therefore have
tion, and broad temperature performance. These and other
possible use in broad temperature applications. New PAOs
beneficial properties of PAOs are described in Ref 关87兴.
with medium viscosity grades 5, 7, and 9; and very high vis- While PAOs have a number of very desirable properties,
cosity grades, of up to 3000 cSt, have also been developed for they do not reflect a high degree of biodegradability relative
use in specialty applications 关88兴. The volatility of these base to that of the synthetic and natural esters. The biodegrad-
oils is somewhat superior to that of the mineral oils, which ability of the PAOs decreases as their molecular weight and
will be discussed later. The lower volatility of the PAOs can be the viscosity increases 关87兴, see Fig. 3.10. In general, biode-
ascribed to their structural homogeneity, that is, they con- gradability performance of the decene-based PAOs with vis-
tain well defined hydrocarbon structures. There are no light cosities greater than 2 cSt is poor, even in the CEC-L33-A93
ends to evaporate, which is the case in the mineral oil base
stocks. The volatility of the PAO 2 is too high to use it in lubri-
cants for high temperature applications. Low volatility in a
base oil is desired to eliminate the need to replenish the lost
oil, an increase in viscosity during use, and the negative im-
pact of the evaporated oil on the environment. In addition, it
lowers the flash and the fire points. While the PAOs 4-10 are
suitable for use in lubricants for broad temperature applica-
tions, the PAO 40 and 100 are only useful in formulating
products for use in high temperature applications. This is
because their pour points are somewhat higher. Some of
these properties among PAOs are compared in Table 3.1
关79,87兴. With respect to the resistance to oxidation, PAOs are
at least equivalent to mineral oils that have low or no aro-
matics. However, they are superior to mineral oils with sig-
nificant aromatics content. Their response to oxidation in-
hibitors is similar to that of the mineral oils. PAOs are
essentially nontoxic and have a reasonable biodegradability.
These properties make them well suited for use in insulating
oils, cable impregnating oils etc. ASTM methods to deter- Fig. 3.10—PAO biodegradability after 21 days 关87兴.
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CHAPTER 3 䊏 SYNTHETIC AND BIOLOGICAL BASE STOCKS 53
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58 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
ture. In the case of the synthetic esters derived from the high rics, low-temperature properties, and volatility. Table 3.4
boiling polyhydric alcohols, the carboxylic acid is used in ex- compares various physical properties of the different types
cess, which is removed at the end of the esterification reac- of esters 关4,106兴. Complex esters, on account of being oligo-
tion. Alternatively, such esters can be produced via the trans- meric, have higher molecular weights than those of the
esterification reaction between a polyhydric alcohol and a simple esters. Hence, they have higher base viscosities, but
low molecular weight alcohol carboxylate. Synthesis of es- their VI, pour point, and flash points are not much different
ters via esterification reaction is depicted in Fig. 3.24. from those of the simple esters 关4兴. Chemical properties of
Acid number 共ASTM D974兲 and hydroxyl number interest in the synthetic esters include thermal stability, hy-
共ASTM E326兲 are two of the parameters used to make certain drolytic stability, and oxidative stability.
that the unreacted starting materials have been completely
Viscometrics
removed from the product. Common catalysts used in the es- The viscosity of the synthetic esters is easily controlled by se-
terification reaction include p-toluenesulfonic acid and or- lecting the proper starting materials. Synthetic esters with
ganic complexes of titanium and tin. Heterogeneous cata- 40° C viscosities of 5 cSt for simple diesters and up to
lysts, such as ion exchange resins 共Amberlysts®兲 may also be
⬎1000 cSt for complex esters are therefore commercially
used. Homogeneous catalysts need to be removed prior to
available 关79兴. Viscosity index, or the VI, a measure of a loss
purification by adding water and a base. If it is not done, the
of viscosity with increasing temperature, is a function of the
product will revert back to the starting materials in the pres-
degree and the type of branching in the molecule. In general,
ence of water. Distillation is the common process used to pu-
the more linear the structure, the greater is the VI. Again, es-
rify esters.
ters of a good VI can be obtained by the proper selection of
Properties of Synthetic Esters the starting materials, that is, those that have linear struc-
Ester properties that need to be considered are the same as tures 关79兴. However, such materials form esters that have the
those discussed in the PAO section. These include viscomet- tendency to wax out at low temperatures. Hence, there is an
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CHAPTER 3 䊏 SYNTHETIC AND BIOLOGICAL BASE STOCKS 59
optimal chain length in both the acid and the alcohol portion intermolecular interaction translates into esters having
of the ester to yield esters with good VI and low pour point. lower volatility, and hence higher flash points.
The size of the optimal chain length is around eight carbon Stability
atoms. Since branching in the hydrocarbon chain lowers the Unlike hydrocarbon materials where oxidation stability is of
pour point without significantly affecting the VI, the syn- primary concern, in the case of the synthetic esters, hydro-
thetic esters for use in the low-temperature applications are lytic stability and thermal stability also need to be consid-
made by using a mixture of linear and branched starting ma- ered. As stated earlier, all hydrocarbon materials are suscep-
terials. tible to oxidation and their rate of oxidation depends upon
The presence of the ester functional group has no effect the type of the hydrocarbon structures present and the ambi-
on the viscosity due to the hydrocarbon chain of the syn- ent temperature. Since the esters contain hydrocarbon
thetic ester molecule. Hence the synthetic ester viscosity is chains in both the carboxylic acid and the alcohol portions of
comparable to that of the hydrocarbons of similar molecular their structure, the oxidation stability in esters is also of con-
weight and branching. One way to explain the similarity of cern. Esters differ in their rates of oxidation, depending
most physical properties between synthetic esters and hy- upon the structure and the branching of the hydrocarbon
drocarbon oils is by considering the ester functional group chains. This is shown in Fig. 3.25. Data for the figure were
an equivalent of a methylene group. Properties that differ be- taken from Ref 关115兴. Like other hydrocarbon materials, the
tween the two as a consequence of the ester functional group oxidation rate of esters is higher at higher temperatures. Fig-
include VI, boiling points, and pour points. All three param- ure 3.26 aptly demonstrates this 关115兴. Primary oxidation
eters are lower in esters than in hydrocarbons of the same products are hydroperoxides and free radicals, the forma-
molecular size. tion of which must be controlled; otherwise an increase in oil
Since synthetic esters contain hydrocarbon chain in the viscosity and the formation of sludge and deposits on hot
alcohol- and the acid-derived portion, their properties vary surfaces will occur. See the section on oxidation in Chapter
depending upon the structures of these moieties. Detailed 4, the Additives chapter. Hence, ester-derived lubricants
viscometrics, VI, pour point, flash point, and vapor pressure
data on synthetic esters made from the same acid but differ-
ent alcohols, and those made from the same alcohol and dif-
ferent acids are reported elsewhere 关4兴. These are visually
summarized in Fig. 3.14. The graphs on the left side of the
figure depict the effect of the acid-derived hydrocarbon por-
tion and the graphs on the right side depict the effect of the
alcohol-derived hydrocarbon portion. As the figure shows,
an increase in the chain length of the acid increases viscosity,
viscosity index, and pour point of a synthetic ester. Con-
versely, an increase in the chain length of the alcohol only in-
creases viscosity but decreases viscosity index and pour
point.
Volatility
The carbon oxygen bond in ester functional group is polar
due to the electronegativity difference between carbon and
oxygen atoms. This causes ester molecules to interact
strongly with one another than the hydrocarbon molecules
of similar carbon number and branching. Such forces are Fig. 3.26—Effect of temperature on oxidation stability of ester-
called London Forces, or van der Waals Forces. The greater type hydraulic fluids 共ASTM D2272兲 关115兴.
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60 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
clude PAOs and some API Group III oils, which have little or 共hydroxymethyl兲-1,3-propanediol兴 ester of heptanoic acid,
no aromatic components that impart solvency. Because of TMP/ C9 is a trimethylolpropane ester of nonanoic acid, and
the compatibility of esters with both polar and nonpolar the dimer ester is di-2-ethylhexyl ester of the dimer 共C36兲
base stocks, they are sometimes used for material compat- acid. The figure shows a direct correlation between polarity
ibility, such as poly共alkylene glycol兲s and mineral oils, which and wear, and between concentration and wear. The higher
are ordinarily immiscible. the polarity, the lower the nonpolarity index, the higher is the
Higher polarity of these base stocks has its own reper- wear; and the higher the concentration, the higher the wear.
cussions. It makes esters more surface active, because of TMP/ C7, with a nonpolarity index of 42 shows higher wear
which they compete with the surface-active additives, such than TMP/ C9 with a nonpolarity index of 61. The dimer ester
as EP/antiwear agents and rust and corrosion inhibitors, for baseline with a nonpolarity index of over 200 shows mini-
the surface 关107兴. These additives are designed to separate mum wear, even when present alone 共at 100 %兲. These results
on and react with the metal surfaces to form protective indicate that increasing the molecular weight decreases the
chemical films. Ester lubricants overwhelm the surface,
surface activity, or improves the lubricity.
thereby preventing the absorption of these additives. This in-
We commented earlier on the oxidation stability of the
terferes with the EP mechanism and the result is increased
synthetic esters. We stated that they are prone to oxidation,
wear. This problem can be solved by increasing the amount
the same as any other hydrocarbon material. Oxidation sta-
of such additives in the formulation, but of course at an in-
bility of esters is slightly better than that of the mineral oils
creased cost. The additive treat rate in an ester-derived lubri-
and is comparable to that of the synthetic hydrocarbons,
cant may need to be higher than in a mineral oil formulation
in order to ensure an effective surface concentration of the such as PAOs. In order to use them in high-temperature ap-
additive. plications with oxygen exposure, they need to be supple-
Whether an ester lubricant will associate strongly or mented with oxidation inhbitors. Their response to these ad-
weakly with the surface depends upon its overall affinity for ditives is excellent 关79兴.
the metal, which is a function of its polarity. Polarity can be Esters are commonly used as synthetic base oils to for-
increased or decreased by varying the size of the hydrocar- mulate engine oils, two-stroke cycle oils, compressor oils,
bon chains of the alcohol and the acid. The less polar 共or hydraulic fluids, greases, and aviation oils. Synthetic engine
more nonpolar兲 the base fluid, the lower is the interference oils often contain ester-PAO blends for improved perfor-
in the EP mechanism; hence, the lower the wear. G. van der mance. Table 3.5 predicts the oxidation life of various fluids
Waal used the nonpolarity index to differentiate between dif- and their blends, with and without additives, by the use of
ferent ester lubricants 关107兴. He defines the index as: high pressure differential scanning calorimetry 共PDSC兲 关79兴.
Oxidation onset temperature 共OOT兲 is the temperature at
Nonpolarity index which the oxidation begins. In the instrument this is indi-
cated by a deflection in the baseline resulting in a signal. The
Total number of C atoms ⫻ Molecular weight
= method used to measure OOT is called the nonisothermal
Number of carboxylic acid groups ⫻ 100
process, that is, the temperature of the measuring cell that
The nonpolarity index is high for nonpolar materials contains the test oil is raised by an increment of 10° C while
and low for polar materials. Average and maximum wear maintaining the oxygen pressure. Higher OOT suggests bet-
data for esters of different polarity at various concentrations ter oxidative stability of the oil. OOT suffers from the disad-
in engine oils are presented in Fig. 3.28 关107兴. vantages of the large measurement error and poor discrimi-
TMP/ C7 is a trimethylolpropane 关2-ethyl-2- nation, which makes drawing meaningful conclusions from
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CHAPTER 3 䊏 SYNTHETIC AND BIOLOGICAL BASE STOCKS 63
weight poly共ethylene glycol兲s can have viscosity index 共VI兲 ing a mixture of olefin oxides. In some applications, such as
values of 400 or more. fire-resistant hydraulic fluids, metalworking fluids, and tex-
A number of physical properties of the commercial tile lubricants, their water miscibility is beneficial since the
PAGs are listed in Table 3.7 关79兴. These include viscosities at fluid can be washed off the part or the equipment by the use
40° C and 100° C 共ASTM D445兲, viscosity index 共ASTM of water. The water miscibility of the PAGs is also an advan-
D2270兲, molecular weight, density 共ASTM D70兲, cloud point tage in the food, pharmaceutical, tobacco, and cosmetics in-
共ASTM D2024兲, pour point 共ASTM D97兲, and flash point dustries.
共ASTM D92兲. Items 1–4 employ only propylene oxide and Poly共alkylene glycol兲s possess a number of unique prop-
Items 5–9 employ mixtures of ethylene oxide and propylene erties, which facilitate their use in industrial gear oils,
oxide. Molecular weight of the polymer is calculated by mul- greases, brake fluids, compressor lubricants, metalworking
tiplying the number of OH groups in the initiator with fluids, aqueous quenching fluids, and fire-resistant hydrau-
56,100 and dividing it with the initiator’s OH value. The lic fluids. These include good thermal and shear stability,
cloud point of the PAGs by the ASTM D2024 method is deter- good VT properties, high flash points, low toxicity, and low
mined as an aqueous solution. Examination of the data in flammability of their aqueous solutions.
the table suggests the following: PAGs possess good thermal and hydrolytic stability, but
1. The viscosity of the PAGs spans a wide range and it cor- poor oxidative stability. Their rate of decomposition is a
relates well with the molecular weight of the resulting function of the temperature and the presence of oxygen. In
polymer. The molecular weight in turn depends upon the absence of oxygen, PAGs are thermally stable up to
the number of OH groups in the initiator and the alky- 250° C. However, in the presence of oxygen, their stability
lene oxide/s used. drops to around 180° C. Decomposition products are acids
2. Increasing the number of OH groups in the initiator which result from the oxidation of the aldehyde depolymer-
from one to two causes a drop in the VI. Compare Items ization products and their condensates. Since bases catalyze
2 and 3. The reasons for selecting these items to draw this decomposition reaction, it is important to completely
this conclusion are that they use the same ethylene remove the basic catalysts used in the manufacture of PAGs.
oxide/propylene oxide ratio 共solely uses propylene ox- Oxidative stability of the PAGs can be improved by the use of
ide兲 and have similar 40° C and 100° C viscosities. the arylamine-type oxidation inhibitors, such as phenyl
3. Increasing the ethylene oxide/propylene oxide ratio ␣-naphthylamine, or PANA. In the absence of oxygen, ther-
leads to an increase in the VI. Compare Item 2 with Item mal decomposition results in the formation of alcohols,
5. ethers, hydrocarbons, carbonyl compounds, and lower mo-
4. The water solubility of the polymers increases with an lecular weight polymeric fragments. The decomposition
increase in ethylene oxide content of the alkylene oxides mechanism involves the formation of the oxygen-initiated
mixture. Compare the cloud point data for Items 1-4 free radicals, which lead to the fragmentation of the poly-
with Items 5–9. mer. The use of oxidation inhibitors does improve oxidation
5. Most PAGs have excellent pour points and flash points. properties of the PAGs. Interestingly, PAGs do not form car-
6. An increase in molecular weight leads to an increase in bon residue on combustion. The carbon-forming tendency
the VI, pour point, and flash point. of a fluid is determined by the use of two tests: Conradson
Poly共alkylene glycol兲s exhibit inverse solubility in water; carbon and Ramsbottom carbon 共ASTM D189 and D524兲.
that is, they become less soluble as the solution temperature Typical values for PAGs are less than 0.01 %. Residue-free de-
increases. This phenomenon is believed to occur due to a de- composition is an advantage in some applications, such as
crease in hydrogen bonding with water at elevated tempera- high-temperature chain oils and compressor fluids.
tures. This is reflected by the high cloud point of these mate- PAGs have low toxicity and are highly biodegradable, es-
rials. The cloud point is the temperature at which the pecially those that have a high ethylene oxide content. This is
reversal of water solubility occurs. The higher the ethylene partly due to their hydrophilic nature. Biodegradability is
oxide content, the higher the cloud point. Below the cloud high in PAGs that are largely based upon ethylene oxide, for
point, the normal solubility is observed. The PAGs, on ac- example around 80 % for PAGs of 80 % ethylene oxide con-
count of being polar, are compatible with other polar materi- tent. This is because such polymers have a linear structure,
als, for example, hydrofluorocarbon 共HFC兲 refrigerants, which usually provides favorable results in the OECD 301
such as R134a or 1,1,1,2-tetrafluoroethane. This makes biodegradability test.
PAGs an ideal replacement for mineral oil lubricants that are The higher polarity of these polymers makes them
not miscible with HFCs and hence cannot be used 关117兴. In highly surface-active. As a consequence, they form durable
addition, the PAGs are compatible with most system compo- lubricating films, which minimize metal-to-metal contact,
nents and have excellent thermal stability. hence wear. These lubricating films are persistent even at
All PAGs are hygroscopic, which is primarily due to the high temperatures and heavy loads. High polarity has a
presence of the hydroxyl end groups, so is their water solu- number of disadvantages as well. These include PAGs’ ag-
bility. Both of these properties decrease with an increase in gressiveness towards coatings and some elastomers, and in-
the molecular weight and the number of ether linkages. compatibility with lubricant additives of low polarity, such
PAGs derived from ethylene oxide are readily water soluble, as olefin copolymers 共OCPs兲 and hydrogenated styrene-
regardless. PAGs derived from propylene oxide are largely butadiene polymers. Such polymers are often used as viscos-
water insoluble but are readily soluble in organic sub- ity improvers. In addition, just like the synthetic esters, PAGs
stances, if their molecular weight is above 900 g / mol. These compete with surface-active additives, such as EP/antiwear
properties are difficult to predict if the PAGs are made by us- agents and rust and corrosion inhibitors, for the surface,
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66 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
thereby interfering in their performance. Increasing the pro- dency, low toxicity, resistance to bacteria, noncorrosivity to
pylene oxide content can improve the situation but only to a most metals, and safety of use. As mentioned earlier, PAGs, if
limited degree. The rust situation gets further complicated they are water soluble, lose their water solubility at high tem-
because PAGs tend to retain water because of their hydro- peratures and come out of solution to coat the surfaces. That
philic nature. is how they provide lubricity that facilitates the metalwork-
ing process. Their heat transfer properties are superior to
Applications those of the hydrocarbon fluids. This, along with their high
PAGs possess a number of desirable properties due to which flash points, fire points, and clean thermal decomposition,
they are used as base fluids in a variety of applications. These makes them ideal for use as heat transfer fluids. PAGs with a
properties include lubricity, water miscibility, high viscosity
variety of end groups, such as hydroxyl, alkoxy, and alky-
index, high solvency, clean decomposition, thermal and hy-
lamino, are commercially available for use in metalworking
drolytic stability, low pour point, high boiling point and flash
applications.
point, thermal conductivity, and elastomer compatibility.
PAGs are excellent as base fluids to suspend solids, such
Lubricity implies low coefficient of friction, which means
as graphite and molybdenum disulfide 共MoS2兲, commonly
improved antiwear properties. Water miscibility is related to
used in lubricating greases for high-temperature applica-
the ethylene oxide content and organic compatibility is re-
tions, such as refractory kiln car bearings, which encounter
lated to the propylene oxide or higher olefin oxide content.
temperatures of 2000°F 共1093° C兲, and oven chain drives and
The compatibility with the hydrocarbon materials can be
gears. In these applications, the sludge-free decomposition
further improved by capping or blocking the hydroxyl end
group with a long chain alcohol or a carboxylic acid, via of the PAGs is an added advantage. On decomposition,
ether formation or esterification. High solvency of the PAGs polyglycol decomposition products flash off or burn clean,
makes them dissolve many types of surface deposits, thereby leaving the solid lubricant without any tar deposits.
keeping metal surfaces clean. Ash-free decomposition al- The use of the PAGs in compressor lubricants is due to
lows their use in applications involving high temperatures. their excellent lubricity, high temperature stability, and
Their clean decomposition is contrary to other synthetic flu- clean thermal decomposition. Gas compression leads to en-
ids, except polybutenes, which leave a residue on decompo- trainment of the gas into the lubricant, which causes the vis-
sition. High thermal and hydrolytic stability allows their use cosity of the lubricant to drop. As a consequence, the lubri-
in lubricants with long service life, especially after supple- cant loses its ability to form an effective lubricating film
menting them with oxidation inhibitors to improve their oxi- between the metal surfaces. PAG base fluids are ideally
dation stability as well. High boiling points and flash points suited for this application because of their high polarity
make PAGs safe to use. Good high temperature properties, since gases, being of low polarity, are not soluble in them.
excellent thermal stability, and low pour points make PAGs Hence, no drop in the lubricating ability of oil is observed.
suitable in applications that involve a broad temperature Polypropylene glycol works extremely well in propane gas
range. They also have good thermal conductivity, which in refrigeration compressors. Poly共ethylene glycol兲 lubricant of
combination with water solubility makes poly共ethylene ISO viscosity grade 150 is highly resistant to thinning due to
glycol兲-based lubricants ideal for use in polyethylene extrud- condensable hydrocarbons with four or more carbons. In
ers. Their compatibility with most elastomer materials is applications, such as well gas that involves both the con-
good to excellent, except with the Buna S elastomer, where it densable hydrocarbons and the water vapor, a poly共ethylene
is fair. High viscosity PAGs are somewhat less aggressive to- glycol兲/poly共propylene glycol兲 co-polymer lubricant is suit-
ward elastomers than the low viscosity poly共alkylene gly- able. While the poly共alkylene glycol兲 lubricants can be de-
col兲s; hence they can be used without any problems as hy- signed to resist dilution, the hydrocarbons will condense at
draulic brake fluids for brake systems based upon natural high operating pressures. If such a lubricant enters the com-
and synthetic rubbers, for example Buna S and N, butyl, neo- pressor, a bearing failure will occur.
prene, and silicone rubbers. As stated earlier, PAGs are good base fluids for refrigera-
PAGs are used as base fluids to formulate compressor lu- tion applications, which is because of their compatibility
bricants, gear oils, engine oils, lubricating greases, brake flu- with new chlorine-free hydrofluorocarbon refrigerants. The
ids, metalworking fluids, fire resistant hydraulic fluids, in- impetus to replace chlorofluoro-hydrocarbons 共CFCs兲 with
dustrial lubricants, and refrigeration lubricants. Very high hydrofluorocarbons 共HFCs兲 is to protect against chlorine-
viscosity water-soluble PAGs are used in glycol-water based initiated damage to the ozone layer. Compatibility of the re-
fire resistant hydraulic fluids as shear-stable thickening frigerant with the lubricant is important because in mobile
agents and as pour point depressants. Industrial lubricants air conditioning units, for example, those used in automo-
benefit from good lubricity, low pour points, clean thermal biles, the lubricant travels through the system together with
degradation, high VIs and shear stability of the PAGs. These the refrigerant. PAGs, because of their superior lubricity,
characteristics allow PAG-based industrial lubricants to be help lubricate the critical parts of the refrigeration system.
used year-round and over a broad temperature range. PAGs are also used to formulate lubricants for heavy-
PAGs are ideal for use in water-based metalworking flu- duty worm gears, plain and rolling contact bearings, and
ids, such as metal removal fluids, metal forming fluids, and other industrial gearing. Worm gears are used in conveyers,
quenching fluids. Water is the best coolant and its presence escalators, material handling equipment, press drives, pack-
extends tool life. Ethylene oxide-based PAGs have a number aging machinery, ski lifts, and agitators and mixers. Other
of advantages, which include water miscibility in all propor- gear and bearing applications are in the cement, metalwork-
tions, hydrolytic stability, little affect by water quality, good ing, plastics, food, rubber, paper, and textile industries. In
lubricity, wetting and penetrating ability, low foaming ten- these applications, PAG’s low coefficient of friction, high VI,
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CHAPTER 3 䊏 SYNTHETIC AND BIOLOGICAL BASE STOCKS 67
and superior load-carrying capacity under boundary lubri- plications. Of course, the cost of producing them is largely
cation conditions are beneficial. Worm gears experience a irrelevant since no other material/s are good substitutes.
high degree of sliding motion which results in extensive This section covers these specialized fluids.
metal-to-metal contact. The result is the high surface tem-
peratures due to friction. PAGs provide lubricity and cooling Silicon Compounds 关74兴
because of their high heat capacity. Heat capacity is defined Silicones and silicate esters are two types of silicon com-
as the amount of heat needed to raise the temperature of a pounds that are used as synthetic lubricants. Of these, sili-
material by one degree. Liquids that exhibit hydrogen bond- cones are the most popular and are used in high-
ing, such as water and alcohols, have higher heat capacities temperature lubricants. The term silicone is used for
than those that do not have hydrogen bonding, such as hy- polysiloxanes. Polysiloxanes are linear polymers that con-
drocarbons. That is, they require greater amounts of heat to tain Si-O-Si linkages with pendent hydrocarbon groups: the
increase their temperatures than do substances with low methyl group being the most common alkyl pendent group
heat capacities. The reason for this is that part of the energy and phenyl being the most common aryl pendent group.
supplied to such liquids is consumed to break the hydrogen Other alkyl or aryl groups can also be used if the improve-
bonds that are present in their structure. Despite their supe- ment of certain properties is the objective. Polysiloxanes are
rior load-carrying capacity relative to the mineral oils 关4兴, products of hydrolysis of the dialkyldichlorosilane. This in-
PAGs need to be supplemented with rust-inhibiting and termediate is made by the Rochow synthesis, which involves
extreme-pressure additives. However, such additives for use direct reaction of an alkyl halide, such as methyl chloride,
in PAGs need to have better water tolerance and different with silicon metal. One obtains a mixture of alkylchlorosi-
solubility characteristics than those used to formulate hy- lanes that contains 70–90 % dimethyldichlorosilane,
drocarbon lubricants. This is again due to their competing 共CH3兲2SiCl2. This silane is isolated from the others by distil-
with the additives for the surface, the same as in the case of lation and reacted with water to yield the dimethylsiloxane
synthetic esters. polymer—关Me2SiO兴n. Since dichlorosilanes are bifunc-
Polyglycols have been tested extensively for use in auto- tional, polymerization continues until it is terminated by the
mobile engines but have not gained much use, primarily be- use of a mono-functional blocking agent, such as trialkyl-
cause of their corrosion tendency that cannot be controlled chlorosilane or hexamethyldisiloxane. The reaction scheme
in the presence of the acidic fuel combustion products. How- to make these materials is provided in Fig. 3.33.
ever, the diesters made by the fatty carboxylic acid blocking Molecular weight and many of the other properties,
of the poly共ethylene glycol兲s and poly共propylene glycol兲s, such as viscosity, are determined by the number of the
made from the glycol initiators, are used in gasoline. These monomer units in the polymer and the nature of the pendent
can be mixed with the mineral oil and used in two-stroke group. Silicone fluids have a viscosity range of between 1 cSt
cycle applications. Such blends have the advantages of pro- and 500,000 cSt. Their desirable properties include high
viding proper lubrication without causing extensive exhaust compressibility, low pour points, low surface tension, low
port deposits 关4兴. volatility, good fire resistance, excellent thermal and chemi-
cal resistance, good dielectric properties, and a good VT rela-
Other Synthetic Base Stocks tionship.
There are many specialized applications which require a Silicone fluids have relatively high boiling points, hence
unique set of properties in a lubricant that are not present in have low volatility 共low vapor pressure兲 and high flash
the base stocks described so far. By taking advantage of the points; depending upon the molecular weight and the viscos-
flexibility of the synthetic methods, a number of materials ity. Silicones with viscosities above 50 mm2 / s 共50 cSt兲 at
have been developed that meet the requirements of such ap- 25° C do not reach their boiling points, even under vacuum.
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68 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
Volatility is a function of the molecular size of the polymer for the impregnation of the porous bronze bearings, and as
chain, hence substituting a phenyl group in place of a methyl VI improvers for silicate esters. Silicones of high aromatic
group has little or no effect on volatility. Pour points and set- content are used to make lubricants for turbines, ball bear-
ting points 共solidification temperatures兲 increase with vis- ings, watches, electric shavers, and various other devices.
cosity, but they can be lowered by partially replacing the me- Since they have excellent thermal stability and high flash
thyl groups with higher carbon number groups, such as ethyl points, they are used in a variety of high-temperature appli-
or phenyl. Density also increases with viscosity, but within a cations. These properties, combined with the low pour
given class. Silicones, especially dimethylsiloxanes, have ex- points and the imperviousness to water, makes silicones
cellent VT behavior relative to that of the mineral oil. How- ideal for use in hydraulic, brake, and heat transfer fluids, and
ever, an increase in the phenyl content of the polymer leads refrigerator oils.
to slight to mediocre deterioration of the VT properties 关4兴. Silicones are also used in textile applications as fiber,
Silicone fluids have good shear stability. However, higher thread, and yarn lubricants, which is primarily due to their
molecular weight polysiloxanes lose their apparent viscosity low surface tension. Silicones are not compatible with min-
with increased shear more rapidly than their lower molecu- eral oils and other synthetic base fluids, which makes them
lar weight counterparts. This loss is temporary and the poly- unsuitable for use as lubricant base stocks. Their use as foam
mer viscosity reverts once the shear forces are removed. inhibitors is primarily due to their low surface tension and
Silicones are good lubricants for bearings and gears incompatibility with other fluids. However, their use in met-
with rolling friction. However, when the mechanism in- alworking fluids to suppress foam is not preferred because
volves high sliding friction, their lubricating properties de- they leave a film on metal parts, which precludes adhesion of
pend on the metal pairs. In the case of steel-on-steel, the per- paint. These fluids are nonbiodegradable, because they lin-
formance of silicones is not very good, presumably because ger in the environment for an extremely long period. Their
of their low surface tension and the weakness of the lubricat- excellent thermal stability is beneficial to their use as heat
ing film, due to low affinity for the metal surface. Such a film transfer oils and their good dielectric properties justify their
is easy to remove because of high shear in sliding contacts. use as dielectric fluids in transformers. Their load-carrying
When the metals involved are dissimilar, such as steel and capacity is extremely poor; hence they are not normally used
the nonferrous metals, the lubricating properties of these as base fluids, except in specialty greases. Such greases are
polymers parallel those of the aliphatic hydrocarbons. The made by using both organic and inorganic thickeners.
use of the conventional EP/AW agents causes only limited Silicone-based lithium soap greases can be used at tempera-
change in performance. Silicones are excellent lubricants tures up to 200° C. Specialty silicone greases based on car-
for bearings that are made from polymeric materials, such bon black, phthalocyanins, polytetrafluoroethylene, Indan-
as polyamides and polystyrene 关4兴. threne Blue, and arylureas can be used in applications that
Silicones are thermally stable up to approximately experience temperatures up to 370° C. While the rheological
315° C, beyond which they decompose. The reason is the properties of these greases are similar to those of the mineral
presence of water, catalysts 共bases and acids兲, and other oil-based greases, these have better chemical stability, com-
ionic materials that catalyze the decomposition of polysilox- patibility with plastics and rubber materials, and ability to
anes to dimethylcyclosiloxanes, carbon monoxide, carbon function over a broad range of temperatures. These charac-
dioxide, silicon dioxide, and formaldehyde. The stability of teristics make them suitable for use in filled-for-life lubrica-
silicones can be increased to 425– 450° C by incorporating tion. Silicone greases are also well suited for lubricating roll-
phenyl groups in the polysiloxane structure. Despite the fact ing element bearings operating at elevated temperatures.
that silicones dissolve oxygen, they are oxidatively stable up The low vapor pressure of these greases makes them suitable
to 200° C, which is much higher than the additive-free hy- for use in equipment involving high vacuum, such as diffu-
drocarbons, esters, and poly共alkylene glycol兲s. Above this sion pumps and aerospace applications. Silicone-based
temperature, their oxidation results in siloxyl and silyl free greases are also used in aviation and automotive industries
radicals, which cross link to form structures with gel-like to lubricate linkages, bearings and bushings, and instrument
properties. Since the carbon side chains are the first point of components 关79,118兴. Silicones are also used to formulate
attack, phenyl substitution improves the oxidation stability. hydraulic fluids and brake fluids.
Oxidation can be controlled by the use of the aromatic Unlike silicones that contain silicon-carbon bonds, sili-
amines and a variety of other types of oxidation inhibitors. cate esters contain none 关4兴. They contain only silicon-
Silicones are also susceptible to hydrolysis at high tem- oxygen bonds. They are organic esters of orthosilicic acid,
peratures. The result is silica 共SiO2兲 and silicic acid gel for- H4SiO4. Materials that are commonly used as base fluids in-
mation. Ionizing radiation stability of these polymers is clude hexa-alkoxy and hexa-aryloxy di- and tri-siloxanes.
similar to their oxidation stability, that is, dimethyl deriva- Alkyl and aryl groups may or may not contain substituent
tives are more likely to decompose to form gel-like products groups, such as chloro, fluoro, nitro, alkoxy, and thioalkoxy.
than those that contain the phenyl groups. These esters are prepared by the hydrolysis of the di- and or
Silicones are used as lubricants both in industrial and tri-alkoxysilicon chloride, prepared from the reaction of sili-
military applications. Dialkylsilicones are used to lubricate con tetrachloride with an alcohol. Representative structures
equipment that uses dissimilar metal pairs, such as bronze/ of the silicate esters are provided in Fig. 3.34. The properties
brass on aluminum and copper and zinc. Examples of such of these compounds radically differ from those of the sili-
equipment are precision mechanisms, speedometers, syn- cones. Although low volatility and excellent viscosity-
chronous motors, and those containing plastic and rubber temperature characteristics make them suitable for use as
parts. Silicones are also used as switch and transformer oils, lubricant base stocks, their applications are limited due to
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CHAPTER 3 䊏 SYNTHETIC AND BIOLOGICAL BASE STOCKS 69
Demnum®, PFPE-D for short, is produced by polymerizing are devoid of hydrogens, they are transparent over most of
hexafluorooxetane, followed by fluorination to replace the the infrared region. They have an absorbance below
remaining C-H bonds with C-F bonds 关124兴. Krytox® is a Du- 1400 cm−1.
pont trade name, Fomblin® is an Ausimont trade name, and PFPEs have poor radiation resistance. They can degrade
Demnum® is a Diakin trade name. All four products are poly- from low-energy and high-energy electrons, and ion beams.
disperse polymers, that is, they contain a distribution of dif- Demnum® is the most stable of the three examined. The
ferent size molecules, or the different molecular weight com- other two are Fomblin® Z-25 and Krytox® 16256 关120兴. Oxi-
ponents. They are subjected to fractional distillation to dation resistance of these fluids is only a concern because in
obtain components with the desired physical properties. De- the low earth orbit neutral atomic oxygen exists. Experimen-
spite the structural differences between the different types, tal data indicate these fluids to be almost completely imper-
they have similar gross properties. A structure of each type is vious to oxygen, which is not too surprising since they are
shown in Fig. 3.36 and their properties are summarized in free of the carbon hydrogen bonds 关128兴. In addition to being
Table 3.8 关120兴. resistant to oxidation, PFPEs are resistant to most corrosive
For aerospace applications, a lubricant must have chemicals, such as acids and alkalis. Because of these at-
vacuum stability, low creeping tendency, high VI 共broad tem- tributes, they are suitable for use in many fill-for-life applica-
perature operating range兲, resistance to radiation and oxida- tions.
tion, optical transparency, and good boundary and EHD Film-forming ability of a lubricant is another consider-
film-forming ability 关120兴. Creep is the tendency of a liquid ation. Elasto-hydrodynamic 共EHD兲 properties are important
lubricant to migrate from one environment into another. It is in continuously rotating medium- to high-speed bearings.
inversely proportional to the surface tension. PFPEs have ex- Lubricant properties that determine the quality of the EHD
tremely low surface tensions 共17 to 25 dynes/ cm at 20° C兲; film are its absolute viscosity 共兲 and its viscosity-pressure
hence their creeping tendency is expected to be high. Al- coefficient 共␣兲. Viscosity of a fluid in turn depends upon its
though these fluids are contained by using low surface en- molecular weight and structure. For low molecular weight
ergy fluorocarbon barrier films 关125兴, PFPEs can dissolve fluids, such as PFPEs, viscosity-pressure coefficient 共␣兲
such films on prolonged contact 关126兴. solely determines the EHD film-forming ability of the fluid.
PFPE products are available with 40° C viscosities rang- The ␣ values for various fluids including three PFPEs are
ing from about 5 to about 500 cSt and have high viscosity in- presented in Table 3.9 关74,129兴. Typical bearings tempera-
dices. Among the four types of PFPEs, the K and Y types have tures for most space applications are 0 to 40° C. Hence, from
lower VI than the D and Z types. Space applications typically the EHD lubrication viewpoint, Krytox® 143AB with the
involve temperatures of between −20° C to 60° C, hence high highest ␣ value is the preferred fluid. In the boundary lubri-
VI in fluids is not a requirement, but the pour point is. These cation regime, where the surface-to-surface contact is high,
materials have extremely low pour points. Their VI is related protection against adhesive wear is usually provided by the
to the carbon to oxygen ratio in the polymer repeating unit. thermally labile EP/AW agents, which react with metal sur-
The presence of the pendent group, as in the case of Krytox® faces to form chemical protective films. Since PFPEs are
and Fomblin® Y, lowers the VI. Demnum® is the next best, pure, additive-free fluids, they must perform the boundary
and Fomblin® Z is the best. High temperature volatility is
generally low 关127兴. This is a very desirable feature since in
space mechanisms the lubricant loss over the long term TABLE 3.9—Pressure-viscosity coefficient „␣a,
共7 – 30 years兲 is a concern 关120兴. In this regard, Fomblin® Z is Pa−1 ⫻ 108… for various base fluids †129‡.
the best, which is followed by Krytox® 143AC, Apiezon® C
共mineral oil兲, synthetic ester, and polyolefins. Vapor pressure
data in Table 3.8 shows the comparative volatilities of the
four PFPEs. Fomblin® Z has the lowest volatility and hence
is the best, which is followed by Demnum® S-200, Krytox®
143AC, and Krytox® 143AB.
The concern for optical properties of a lubricant is re-
lated to the sensitive optical components, such as mirrors
that are used in the measurement devices. Incidental con-
tamination of the component surfaces by a lubricant of inap-
propriate quality can hinder precise data collection. Hence,
optically transparent lubricants are preferred. Since PFPEs
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CHAPTER 3 䊏 SYNTHETIC AND BIOLOGICAL BASE STOCKS 71
lar solvents, such as alcohols, esters, ethers, aromatic hydro- at 0.2 or less, and controlling air entrainment. Vacuum is
carbons, poly共alkylene glycol兲s, and triaryl phosphates, they sometimes used to remove the water and the entrained air.
are incompatible with aliphatic hydrocarbons, mineral oils, Poor thermal stability of these materials is advantageous in
poly共phenyl ether兲s, silicones, and silicate esters. They are their use as additives in applications such as gear oils, trans-
also incompatible with some seal materials since they re- mission fluids, and hydraulic fluids that require EP/AW per-
move the plasticizer. Because of their high thermal stability, formance. In such applications, these materials thermally
high dielectric constants, and low solvency, they are suitable decompose to phosphoric acid, which can react with the
for use in high-temperature electrical applications. Greases metal surfaces to form a protective metal phosphate film. In-
made from these fluids and soap and nonsoap thickeners hibited phosphate esters possess excellent oxidation stabil-
共copper phthalocyanins兲 are sometimes used in electrical ity and good antiwear properties under critical loading con-
machinery. The high density of these esters allows their use ditions.
in submarines 关4兴. Phosphate esters are primarily used in fire-resistant syn-
thetic fluids and aircraft hydraulic fluids. These are tertiary
Phosphate Esters 关74兴 esters of ortho phosphoric acid, O = P共OH兲3, and may be tri-
These esters can be expressed by the general formula
aryl, trialkyl, and alkyl/aryl. At present, triaryl phosphates
共RO兲3PO where R can be aliphatic or aromatic. Phosphate
are the most significant commercial fire-resistant products
esters are usually prepared by the reaction of an alcohol or a
关74兴. All three organic groups in the phosphate ester may be
phenol with phosphoryl chloride 共phosphorus oxychloride兲
the same, as in tricresyl or trixylenyl phosphate, or may be
in the presence of a metal catalyst. For making aryl phos-
different, as in iso-propylphenyl diphenyl phosphate or
phates, phenol, or mixtures of alkylphenols, for example,
cresyl diphenyl phosphate. Of the trialkyl phosphate esters,
isobutylphenol and a mixture of t-butylphenols, are used as
tri-butyl phosphate is the most important of the synthetic
the starting materials. The equation below generically repre-
base stocks. Most are used in aircraft hydraulic fluids. Dibu-
sents the esterification reaction to form the phosphate es-
tyl phenyl phosphate, also used in an aircraft hydraulic fluid,
ters.
is the most important of the alkyl/aryl phosphate esters.
Products may be either mixtures of the phosphate esters re-
3ROH + POCl3 → 共RO兲3PO + 3HCl
sulting directly from the manufacturing process or are ob-
Although aromatic esters have excellent lubricating tained by post-blending with additives. The key properties of
properties, they have a low VI and suffer from poor hydro- these materials include excellent fire resistance, outstanding
lytic and thermal stability. The result is the formation of ac- antiwear properties, excellent oxidation stability, high resis-
ids, which can attack and corrode vital metal components. tance to shear-related viscosity loss, and low foaming ten-
This precludes their widespread use in synthetic lubricants. dency.
They also possess high solvency and, hence, are incompat- For aviation use, tert-butylated triphenyl phosphate is
ible with certain seal materials. Fluid degradation through the ester of choice. For most applications, water-based flame
hydrolysis and oxidation can be minimized by lowering the retardant fluids are used. However, these cannot be used in
water level to less than 1000 ppm, keeping the acid number systems where fluid temperature exceeds 60° C, or the pres-
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CHAPTER 3 䊏 SYNTHETIC AND BIOLOGICAL BASE STOCKS 73
making them practically nontoxic 共toxicity rating of 5兲. Tox- traditional lubricants will not suffice. PCTFE is used in hy-
icity of PCTFE—oil-based hydraulic fluid, with three parts draulic fluids for advanced aircraft and armored vehicle
PCTFE and one part oil, is believed to be due to the conver- turret-and-gun control system. CTFE-based polymers and
sion of the neutral chlorotrifluoroethylene 共CTFE兲 oligo- copolymers are also used in the synthesis of high perfor-
mers into the corresponding halogenated fatty acids. mance lubricants, plastics, and elastomers, which are mar-
Because of their resistance to chemicals, nonflammabil- keted by Allied Chemical under the trade name of Halar®
ity, high thermal stability, good lubricity, and low compress- 关140兴. Synthetic chlorotrifluoroethylene derived oils, which
ibility, these materials are used to lubricate equipment in in- can be used in rotary piston and rotary vane pumps, are mar-
dustries, such as aerospace, nuclear, and chemical, where keted under the trade name of Halovac™ fluids made by the
Halocarbon Corporation 关141兴. These are sold in three vis-
cosity grades, Halovac™ 100, 125, 190, as the cost effective
TABLE 3.12—ASTM slope values for poly„phe- alternative to PFPE fluids. Their listed attributes include
nyl ether…s †4‡. sealing and lubricity required by the mechanical vacuum
ASTM Slope pumps, low vapor pressure, and chemical stability up to
Poly„phenyl 230– 260° C, or 450– 500° F. CTFEs are also used in design-
ether… 38– 99° C 99– 205° C 205– 315° C 315– 370° C ing health-related chemicals, such as anesthetics, and are
pp-4P3E ¯ 0.78 0.85 0.96 used in telomerization with carbon tetrachloride or chloro-
mp-4P3E 0.86 0.81 0.89 1.01
form for use as inert fluids, hydraulic fluids, or lubricants
mm-4P3E 0.84 0.82 0.92 1.06
op-4P3E 0.88 0.87 0.94 1.11
关142兴.
mo-4P3E 0.95 0.88 0.96 1.13
oo-4P3E ¯ 0.95 0.98 1.22 Poly共phenyl ether兲s 关4兴
m-3P2E 0.90 1.09 1.25 Proper name for phenyl ether polymers is poly共phenyl
mm-4P3E 0.84 0.82 0.92 1.06 ether兲, or polyphenyl polyether but the name polyphenyl
mmm-5P4E 0.90 0.77 0.84 0.94 ether, 共PPE兲 is widely accepted. Poly共phenyl ether兲s contain
mmmm-6P5E 0.93 0.75 0.80 0.89 benzene rings that are joined through ether linkages, usually
mmmmm-7P6E 0.98 0.73 0.76 0.86 in the meta orientation. These materials are obtained by the
reaction of an alkali metal phenate with a halogenated ben-
zene in the presence of copper catalysts 共Ullman Ether Syn- ample, ASTM slope values for mp - 4P3E fall between those
thesis兲. Ullman Synthesis for a 3-ring PPE is shown in the of the pp - 4P3E and mm - 4P3E and the values for mo-3P4E
lower half of Fig. 3.40. PPEs of up to six phenyl rings are fall between those for mm - 4P3E and oo-4P3E. For
commercially available. They are characterized by indicat- m-substituted phenolic polyethers, shown on the right side
ing the substitution pattern of each ring, followed by the of the figure, the ASTM slope values decrease as the number
number of the phenyl rings and the number of the ether link- of phenolic groups increase. With respect to volatilities,
ages. Thus, the structure in Fig. 3.40 is identified as p-derivatives have the lowest volatilities and o-derivatives
pmm-5P4E, indicating a total of five rings and four ether have the highest volatilities. The opposite is true for the flash
linkages, the di-substituted rings having para, meta, and points and fire points. Spontaneous ignition temperatures of
meta orientation. Longer chain analogues with up to ten the poly共phenyl ether兲s lie between 550 and 595° C, alkyl
benzene rings are also available. As stated earlier, meta sub- substitution reduces this value by ⬃50° C. PPEs swell the
stitution of the aryl rings in these materials is the most com- common seal materials 关4兴.
mon. Oxidation stability of the unsubstituted derivatives is
Typical physical properties of poly共phenyl ether兲s are quite good, partly because they lack easily oxidizable
provided in Table 3.11 关143兴. The important attributes of carbon-hydrogen bonds. However, alkylated diphenyl oxides
these materials include their thermal and oxidative stability are highly susceptible to oxidation. Their decomposition
and the stability against ionizing radiation. However, they does not generate any residue or corrosive materials; there-
have the disadvantage of having high pour points; those con- fore their viscosity increase due to oxidation is minimal. Oxi-
taining two and three benzene rings are actually solids at dative stability of the alkylated derivatives can be improved
room temperatures. Their melting points are lowered if they by the use of the oxidation inhibitors. See Table 3.13 for the
contain more m-phenylene rings, alkyl groups, or are mix- stability data 关144兴. Thermal decomposition temperature, as
tures of isomers. PPEs that contain o- and p-substituted measured by the isoteniscope procedure is between 440 and
rings have the highest melting points. 465° C. This procedure, described as ANSI/ASTM Method
These fluids have excellent high temperature properties
and good oxidation and radiation stability. While the pres-
ence of the aromatic rings lowers their VT properties some-
what, they are still reasonable. Within the class, p-ethers are
the best, m-ethers are in the middle, and o-ethers are the
worst, with respect to the VT properties, as shown by the
ASTM slopes 关4兴. These data are provided in Table 3.12 and
plotted in Fig. 3.41. The ASTM slope is used to correlate vis-
cosity and temperature. High values indicate large viscosity
changes with temperature and low values indicate small vis-
cosity changes with temperature. The ASTM slope essen-
tially indicates the same parameter as the VI, but for tem-
perature ranges other than for 40 and 100° C, typically used
to define the VI. Lower slope values are better than the
higher slope values.
Data in the table and on the left side of the figure show
the ASTM slopes to increase with increasing molecular
weight; their value for the mixed ring substitutions falling
between those with uniform ring substitutions. For ex-
D2879, measures vapor pressures of liquids with vapor pres- Pennzane® X-1000, because of its excellent low-temperature
sures of 0.1 to 100 kilopascals 共kPa兲 共0.75 to 750 torr兲. Me- viscometrics is used to lubricate mechanisms with very low
thyl, ethyl, and isopropyl substituents reduce the decompo- starting torque, even at very low temperatures; however, its
sition temperatures to about 380° C and n-propyl and higher higher volatility precludes its use in many high vacuum ap-
alkyl groups drop the decomposition temperature to plications. Pennzane® X-3000, the highest viscosity product,
330– 350° C 关4兴. PPEs have high radiation resistance. Ioniz- offers superior wear protection, especially in applications
ing radiation, the same as in other cases, increases viscosity, that experience higher loads. Its high viscosity makes it suit-
acidity, evaporation loss, corrosivity, and coke formation. It able for use as a damping fluid to reduce noise and undesired
also lowers the PPEs’ flash and ignition points. Of all classes motion. Nye Lubricants, Inc. markets these products under
of synthetic lubricants, poly共phenyl ether兲s are the most ra- the name of Nye Synthetic oils 关150兴. Pennzane® hydrocar-
diation resistant. bons have a functional temperature range of
High-temperature lubricating properties of the −50° C to 125° C. Viscometric properties are typical for hy-
poly共phenyl ether兲s, measured in the laboratory at drocarbons and similar to those of the PAOs. The main dis-
200– 300° C, are comparable to those of the mineral oils and tinguishing characteristic of MACs is that they are essen-
synthetic esters, see Table 3.14 关144兴. Alkylsubstituted tially mono-disperse and their volatility is therefore
poly共phenyl ether兲s are somewhat better 关4兴. However, in substantially lower than that of the mineral oil or the PAO of
real life applications, their load-carrying capacity and wear similar viscosity. Viscosity and viscosity index can be ad-
resistance is inferior to those of the mineral oils 关4兴. justed by the appropriate selection of the chain length and
Poly共phenyl ether兲s are used as base oils for use in aviation the degree of branching of the alcohol raw material, and by
gas turbine lubricants, ultra-high vacuum diffusion pump the degree of substitution obtained. MACs are fully compat-
fluids, electronics lubricants, high-temperature and ible with conventional additives and many other types of
radiation-resistant hydraulic fluids, and lubricating greases base stocks. These materials have a high surface tension, ap-
关143–145兴. proximately 32 dynes/ cm, which makes them good lubri-
cants since they make more durable surface films. Their
Alkylated Cyclopentanes 关79兴 properties can be considerably improved by the use of the
Polyalkylated or multiply-alkylated cyclopentanes, or MACs, conventional additives, such as extreme pressure agents, an-
were developed recently for use in lubricants. They are made tiwear agents, and oxidation inhibitors. Comparative prop-
by the reaction of cyclopentadiene, in the form of dicyclo- erties of these lubricants with respect to their use in space
pentadiene, with an alcohol or an alkyl halide in the presence applications are discussed in a NASA report 关153兴. Pennzoil
of a strong base 关146兴. The resulting alkylated cyclopentadi- also markets Pennzane®-based synthetic engine oils. The
ene is catalytically hydrogenated to yield a mixture contain- claimed benefits of such oils include extra engine protection
ing di-, tri-, tetra-, and penta-alkylated cyclopentanes. Frac- against deposits and wear resulting from extreme driving
tionation of the mixture results in the isolation of the conditions, good broad-temperature performance, and low
components suitable for use as base oils 关147–151兴. The reac- oil consumption.
tion scheme for the synthesis of these hydrocarbons is pro-
vided in Fig. 3.42, along with the possible mechanism. It is Cyclohexane Derivatives 关79兴
important to note that while we stopped the mechanism at Unlike alkylated cyclopentanes, which were devised prima-
tri-alkylated cyclopentadiene, theoretically five alkyl sub- rily for use in high-temperature, high-vacuum applications,
stituents on cyclopentadiene ring are possible. cyclohexane derivatives were developed for use in automo-
A number of MACs have been developed, out of which tive and industrial transmission applications, requiring high
three have been commercialized under the trade name of traction. Previously, a number of products with this chemis-
Pannzane®. Pennzane® X-1000 has a viscosity of ⬃8 cSt at try were available, but today only 2,4-dicyclohexyl-2-
100° C, Pennzane® 2000 has 100° C viscosity of 14.5 cSt, and methylcyclopentane is commercially available 关74兴. It is
Pennzane® X-3000 has 100° C viscosity of 220 cSt. 关150兴. made by the catalytic hydrogenation of ␣-methylstyrene
Pennzane® X-1000 remains fluid between −50 and −60° C, dimer.
compared to Pennzane® X-2000’s low temperature rating of Most of the properties of this hydrocarbon are similar to
−45° C. While chemically Pennzane® X-2000 is a tri-2- those of the other hydrocarbon materials of analogous mo-
octyldodecyl substituted cyclopentane 关151兴, Pennzane® lecular weight, except that it exhibits high traction coeffi-
1000 is a dialkylated cyclopentane. cients under high pressures that occur during EHD contact.
MACs are synthetic hydrocarbons that combine excel-
lent wear protection and low vapor pressure, two of the most Petroleum Base Stocks Versus Synthetic Base
critical properties needed for lubricants to be used in space Fluids
and other vacuum environments 关152兴. Of the three, Typically, synthetic fluids are superior to petroleum-refined
Pennzane® 2000 is the oldest product, which has been exten- base oils with respect to thermal stability, oxidation resis-
sively used in satellites, space vehicles, and space suits 关153兴. tance, viscosity index, low-temperature fluidity—their pour
It has a vapor pressure of about 1 ⫻ 10−12 torr at 25° C. It is points are −40° C 共−50° F兲 or lower, coefficient of friction,
also used in the manufacture of the semiconductors, preci- and volatility. The advantages of synthetics are mostly real-
sion instruments, and other clean-room applications. Low ized at extreme temperatures. For example, low pour point
vapor pressure in vacuum applications is important so that gains importance at very low temperatures since the oil stays
the loss of lubricant due to out-gassing and possible con- fluid at these temperatures and provides adequate lubrica-
tamination of the nearby critical components, such as semi- tion. High viscosity index, low volatility, and high thermal
conductor wafers, sensors, and optics, is minimized. and oxidation resistance are important at high tempera-
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CHAPTER 3 䊏 SYNTHETIC AND BIOLOGICAL BASE STOCKS 77
tures. Oil maintains reasonable viscosity, to provide effective • Better low- and high-temperature properties, such as
lubrication, its volatility-related losses are low, and there is viscosity, pour point, viscosity index, and volatility.
minimum thermo-oxidative breakdown. An additional but • Good thermal and oxidative stability.
important advantage of the synthetic fluids is the flexibility • Low flammability or nonflammability.
to create structures that provide optimal performance in an • Ionizing radiation stability.
application. A number of other properties are also consid- • Improved lubricity, usually at very high and very low
ered while selecting a suitable fluid. These include demulsi- temperatures.
bility, lubricity, rust and corrosion protection, antiwear • Biocompatibility, i.e., reduced environmental impact,
properties, elastomer and other materials compatibility biodegradability, and reduced toxicity.
共seals and paints兲. The biggest drawback of synthetics is Base stocks are used either directly or as blends to for-
their high cost of production. As a result, synthetic-mineral mulate lubricants and their properties largely determine the
oil blends are often used as base fluids to formulate lubri- properties of the lubricant. A number of properties for some
cants for some applications. In this case, the idea is to take of the commonly used synthetic base stocks are listed in
advantage of the superior properties of the synthetics but at Table 3.15, along with the relative cost. The examination of
a reasonable cost. Of course, in such cases compatibility be- the data suggests that while some base stocks are better than
tween the fluids being mixed becomes an important issue the others in some aspects, none is perfect. Data from Table
since not all synthetics are compatible with one another or 3.15 are consolidated with additional data and presented in
with the mineral oils. Tables 3.15 and 3.16. Table 3.16 visually compares the over-
Modern mechanical equipment places increased de- all attributes of the synthetics among one another 关4兴. Table
mand on the lubricant because of the extreme operating en- 3.17 presents the physical properties of the common base
vironments. In some such applications, for example those stocks, both mineral and synthetic, which are a primary con-
pertaining to aviation, mineral oil-based lubricants are inca- sideration while selecting a base stock for formulating a lu-
pable of delivering the necessary performance, but synthetic bricant for a particular application. Information provided in
base stocks do. This is because synthetics possess a number these tables should facilitate the base stock selection process
of properties that are better than those of the mineral oils, or 关44,318兴. In terms of the cost and the overall performance,
are unique. Such properties include: mineral oil base stocks are the most attractive; however, in
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78 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
certain cases the cost is irrelevant and there is merit in using cosities at 40° C 共104° F兲 and 100° C 共212° F兲 are reported.
synthetic base stocks. Some of these applications are listed Historically, the temperatures of 100° F 共37.8° C兲 and 210° F
in Table 3.18. Incidentally, these tables contain data on some 共99° C兲 were of interest because the kinematic viscosities at
fluids that we did not include in our discussion either due to these temperatures were previously used to calculate the vis-
their use in very specialized applications or their low-volume cosity index. These temperatures were rounded up to 40° C
manufacture. In addition to the desirable base stock proper- and 100° C during transition to the metric system. Inciden-
ties discussed above, there are other base oil properties that tally, ISO grades for industrial lubricants have always been
must be considered when designing a lubricant for specialty based upon lubricant viscosity at 40° C. Previously, the oil’s
applications. VI range of between 0 and 100 was considered relevant, but
the VIs of today’s oils can be less than 0 and as high as 300,
Viscosity-temperature and Viscosity-pressure see Table 3.15. It is important to note that while the VI is a
Behavior good criterion for an oil’s viscosity-temperature relation-
Proper viscosity of a lubricant is critical to its ability to per- ship, it may or may not predict viscosity outside this range.
form the lubrication function. Typically, the lubricant vis- Ultimately, it is the viscosity of the oil at the operating tem-
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CHAPTER 3 䊏 SYNTHETIC AND BIOLOGICAL BASE STOCKS 79
TABLE 3.17—Physical properties of lubricant base stocks †44,318‡. Reprinted with permission from
Lubrizol Corporation.
Kinematic Viscosity, cSt
Dynamic Viscosity, Viscosity Pour Point COC Flash
Type 40° C 100° C at −40° C „cP… Index „°C… Point „°C…
„A… Mineral Oils
90 Neutral 17.40 3.68 Solid 92 −15 190
100 Neutral 20.39 4.11 Solid 101 −13 192
200 Neutral 40.74 6.23 Solid 99 −20 226
350 Neutral 65.59 8.39 Solid 97 −18 252
650 Neutral 117.90 12.43 Solid 96 −18 272
150 Bright Stock 438.00 29.46 Solid 95 −18 302
„B… Synthetic Base Stocks
Alkylated aromatics 26.84 4.99 9047 119 −18.3 224
Olefin oligomers 16.77 3.87 2371 126 −43.0 221
Dibasic acid esters 共Dioctyl sebacate兲 18.2 … 3450 176 −15.6 232
Trimethylolpropane esters 共C7 Acid兲 13.94 3.4 2360 … −18.3 232
Poly共alkylene glycol兲s 45.69 … … 150 … 177
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CHAPTER 3 䊏 SYNTHETIC AND BIOLOGICAL BASE STOCKS 81
perature that is of interest to a formulator, or a user. At high dentally, the lower temperature limit of −7 ° C is around the
temperatures, lubricant or base oil decomposition may oc- cloud point of napthenic oil ⫺14°C for paraffinic oil and
cur, thereby unexpectedly increasing or decreasing viscosity. ⫺23°C for the napthenic oil, as shown in Table 3.21. Synthet-
Also, it is important to note that the increase or decrease in ics also follow the Walther relationship but their extrapola-
the operating temperature in equipment may not be consis- tion range is −18° C to 175° C 共0 ° F to 347° F兲 关154兴. Since
tent or it may fluctuate, thereby making it difficult to predict the operating range of the synthetics is well beyond these
the viscometric requirements of the equipment. The same temperatures, extrapolation outside this range will yield er-
problem can be encountered if the system being lubricated roneous values. Table 3.20 provides extrapolation of viscosi-
dissipates heat at a different rate with a change in its operat- ties at high temperatures and Table 3.21 provides extrapola-
ing parameters. tion at low temperatures. Data in the tables indicate the
Most industrial mineral lubricating oils have a VI be- following:
tween 55 and 100, but VI can be up to 175 for the high VI oils. 1. Deviations from the measured values increase as the ex-
Viscosity Indices of various industrial oils are shown in Table trapolation temperature is further away from the ex-
3.19. A less arbitrary indication of the change in viscosity trapolation temperature range limit of −18 to 175° C.
with temperature is the viscosity temperature coefficient 2. At elevated temperatures, the discrepancy is small for
共VTC兲. For 40 to 100° C range, it can be calculated by the fol- mineral oil stocks.
lowing expression. 3. At low temperatures, the discrepancy is high for paraf-
finic mineral oils.
Viscosity at 40 ° C − Viscosity at 100 ° C
VTC = 4. Deviation for mineral oils at low temperatures is posi-
Viscosity at 40 ° C tive but for synthetic oils it is negative. This implies that
Viscosity at 100 ° C for the mineral oils, the Walther equation under-
=1− predicts viscosities and for the synthetics, it over-
Viscosity at 40 ° C
predicts them. Incidentally, silicones and poly共glycol
The lower the value of the coefficient, the higher is the VI. ether兲s, not included in the table, like mineral oils, have
The coefficient for mineral oils can vary by a factor of 10 de- measured viscosities that are higher than predicted.
pending on the temperatures. While formulating a lubricant, the influence of pressure
In Chapter 1 on Lubrication Fundamentals, we stated on viscosity is usually neglected. This is reasonable for low
that extrapolation of the viscosity-temperature curve out- pressures, but for pressures greater than 1000 psi 共68 atmo-
side of the 40° C and 100° C range is not advisable because of spheres, 6895 kPa兲, the absolute viscosity of a fluid may be a
the unexpected transitions that may occur. This is because strong function of pressure. Viscosity-pressure coefficient
viscosity index, as measured by ASTM D2270, is based upon 共VPC兲 measures the rate of viscosity-increase with increased
Walther plots 共ASTM D341兲, which allow extrapolation of load 共pressure兲. Viscosity increases with pressure because
viscosities based on two measured values. The extrapolation the molecules of the fluid come closer together, which in-
range for mineral oils is −7 ° C to 177° C 共20 to 350° F兲. Inci- creases their intermolecular van der Waals type interactions.
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82 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
Low-temperature Properties
TABLE 3.25—Low-temperature engine oil Pour point and cloud point are two commonly used mea-
requirements. sures of the low-temperature behavior of an oil. Pour point is
Cold-cranking the lowest temperature at which an oil will flow. This prop-
Viscosity Viscosity at erty is important for oils that involve the low-temperature
at −25° C, cP operation. The general guideline for selecting an oil is that it
Lubricant base oil 100° C, cSt „mPa-s… has a pour point of at least 10° C or 20° F lower than the low-
Mineral SN 100 3.8 1300
est anticipated ambient temperature. Cloud point is the tem-
Polyalphaolefin 3.9 500
perature at which the dissolved solids in oil, such as the par-
Polyol Ester 4.5 550
affin wax, begin to form crystals and separate from the oil.
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CHAPTER 3 䊏 SYNTHETIC AND BIOLOGICAL BASE STOCKS 83
Certain oils must be maintained at temperatures above the ⬍20,000 cP at −40° C and for MERCON® V type transmis-
cloud point to prevent plugging of filters and small orifices. sion fluids, Brookfield viscosity of ⬍13,000 cP at −40° C is
Cloud point is usually higher than the pour point, that is, on specified. Incidentally, MERCON® specification was retired
cooling, visible crystal formation occurs first and the oil in the year 2007 and all Ford transmissions will be serviced
ceases flow afterwards. Table 3.24 provides pour points of by the MERCON® V quality fluids. The GM, Ford, and
the commonly used synthetic fluids. For automotive lubri- Chrysler ATF specifications are provided in the Hydraulic
cants, three additional low-temperature measures are used. and Transmission Fluids chapter, Chapter 7. For gear oils,
For engine oils, they are low-temperature cranking and temperature at which the oil attains Brookfield viscosity of
pumping viscosities at prescribed temperatures and for 150 000 cP needs to be reported. For details, see SAE Stan-
transmission fluids and gear oils it is the Brookfield viscosity. dard J306 and consult Chapter 8 on Gear Lubricants. Syn-
Cold-cranking engine oil viscosity requirements are 6200 cP thetic fluids with low pour points and a lower tendency to
共−35° C兲 for 0W and 13 000 cP 共−10° C兲 for 25W. Complete thicken at low temperatures perform better than their min-
physical requirements are provided in the SAE Standard eral oil counterparts. This is demonstrated by the data in
J300 and in Chapter 5, the Combustion Engine Lubricants Table 3.25 for PAO and polyol ester with similar 100° C vis-
chapter. For DEXRON®, MERCON®, and Mopar® type auto- cosities as 100 solvent neutral mineral oil.
matic transmission fluids, Brookfield viscosity of
Volatility
Base fluid volatility is also an important parameter since it
will contribute to the volatility of the lubricant. High volatil-
ity is undesired because evaporation of the base fluid, espe-
cially in high-temperature applications, will not only require
constant topping up and replenishment but will also pose a
fire hazard. In engine oils, there is an additional concern re-
garding an increase in the undesired emissions. There are
two methods to measure volatility of the base oils: the ASTM
D1160 method and the NOACK Volatility Test. Similar to the
better low-temperature performance, the volatility of the
synthetics is in general better than that of the mineral oils.
This is shown by the ASTM distillation curves at 1 mm of Hg
共Figs. 3.43 and 3.44兲. Figure 3.43 compares the volatility of
the polyolefins and the alkylaromatic base stocks with that of
the mineral oils and Fig. 3.44 compares the volatility of the
ester base stocks with that of the mineral oils. Despite the
fact that the synthetic base stocks and the mineral oils under
consideration differ in viscosities, one can still draw conclu-
sions about the superior volatility of the synthetic base
stocks. A consideration of the distillation profiles suggests
that in terms of volatility:
Fig. 3.45—Typical Noack volatilities for base oil types versus speci- 1. Synthetics are better than mineral base stocks of a com-
fications 关157兴. parable or higher viscosity.
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84 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
2. Alkylaromatics are superior to polyolefins. der Waal also rated certain base oils and some additives with
3. Polyol esters are better than the diesters. respect to the nonpolarity index 关107兴. The data, graphically
Volatility of lubricants in general and of engine oils in presented in Fig. 3.46, suggest that base stocks, such as min-
particular is under scrutiny because it contributes to unde- eral oils and polyalphaolefins, with a higher nonpolarity in-
sirable emissions. Engine oil volatility limits are being de- dex 共⬎100兲, are less likely to interfere with the action of the
creased progressively. For passenger car engine oils, GF-2 EP agents than additives, such as detergents, that have a
NOACK volatility limit was 22 % but for GF-4, it is lowered to lower nonpolarity index 共⬍2兲. Esters with the nonpolarity
15 %. Further lowering of this limit is expected in the upcom- index of 50–100 fall in the middle 关107兴.
ing lubricant specifications. Part of the problem is the grow- The ability to dissolve additives, or solvency, of a base
ing trend to use low viscosity oils, which have good low- stock is a related problem. Most additives, except some vis-
temperature fluidity that contributes towards fuel economy. cosity improvers or some pour point depressants, contain
As the data in Fig. 3.45 show, the mineral oils of 100° C vis- hetero atoms, nitrogen, oxygen, sulfur, and phosphorus.
cosity of less than 5.5 cSt do not meet the ACEA A1/B1 and Their presence makes these additives highly polar in a man-
ILSAC GF-3 NOACK volatility limits 关157兴. ner similar to that of the esters and PAGs, therefore raising
the question of compatibility. While polar base stocks are
Fluid Compatibility and Additive Solubility quite compatible with the most classes of additives, PAOs
While intercompatibility of the mineral oil-derived lubri- sometimes have difficulty in keeping the additives dissolved.
cants is not a problem, the intercompatibility of the synthet- This is overcome by co-blending with either a mineral oil, an
ics is and so is their compatibility with the mineral oils. This ester, and or an alkylaromatic; the latter is believed to be the
is because not all synthetics are compatible with mineral oils case for the engine oil sold under the trade name of Mobil 1.
or with one another. This is because of the polarity difference
among them, as was stated earlier. Thermo-oxidative and Chemical Stability
Besides compatibility, the polarity of the base oil plays Synthetic fluids can lose their structural integrity via ther-
an important role in many other applications. For example, mal, oxidative, and chemical degradation. And of course,
blends of polar esters with nonpolar polyalphaolefins or par- this susceptibility relates to their chemical structure as well
affinic base oils have better viscometrics, as well as good lu- as composition. Chemical stability of a base fluid is one of
bricating ability. This is because in the hydrodynamic lubri- the key properties that determines the performance of a lu-
cation regime the nonpolar component is effective and in the bricant. While for hydrocarbon fluids, such as mineral oils
mixed or boundary lubrication regime, the polar ester com- and polyolefins, stability largely implies oxidative stability;
ponent forms a durable lubricating film. Of course, the for organic fluids with high oxygen content, such as ester flu-
greater surface affinity of the oil is one of the many proper- ids, thermal and hydrolytic stability are also important.
ties that makes it an effective lubricant under boundary lu- A number of factors can affect oxidation testing of or-
brication conditions. Despite this advantage, polar PAGs and ganic materials. These include exposure time, availability of
synthetic esters can overwhelm the surfaces, making it diffi- oxygen 共air兲, and the temperature. With respect to oxidation,
cult for the surface-active additives, such as extreme- base fluids that have low hydrogen content, such as perfluo-
pressure/antiwear additives and rust and corrosion inhibi- ropolyethers, fluoroesters, chlorofluorocarbons, poly共phe-
tors, to adsorb on the surface to perform their function. The nyl ether兲s and arylsilicones, have better stability than those
result is greater wear and increased corrosion when these that have high hydrogen content. This is because these are
base fluids are used without properly compensating for their the aliphatic carbon hydrogen bonds that react with the oxy-
affinity for the metal surfaces. We explained the concept of gen first, to form hydroperoxides, which are the oxidation
nonpolarity index under synthetic ester base stocks. G. van initiation species. See Chapter 4 on Additives and the section
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CHAPTER 3 䊏 SYNTHETIC AND BIOLOGICAL BASE STOCKS 85
Fig. 3.47—Thermal stability panel coker test; Panel temperature= 310° C; Sump temperature= 121° C; operation= 6 min splash/1.5 min bake;
Clean rating= 10 关71兴.
on Oxidation Inhibitors. Many oxidation tests are used to de- A number of other tests are used to evaluate the oxida-
termine the susceptibility of a base fluid towards oxidation. tion performance of the engine oils. These include ASTM
In fact, each application has its own specific tests that try to Rotating Pressure Vessel Oxidation Test 共Rotary Bomb Test,
simulate the operating conditions in that application, which ASTM D2272兲, Turbine Oil Oxidation Stability Test 共ASTM
is to observe their effect on lubricant oxidation. Pressure Dif- D943兲, Cigre Oxidation Test 共IP 280兲, Panel Coker 共FTM
ferential Scanning Calorimetry 共PDSC兲 is a useful technique 3462兲 and Wolf strip tests 共UK 359兲, Conradson Carbon Resi-
for discriminating fluids with good oxidation stability 关42, due 共ASTM D189兲, Coke Residue 共DIN 51 551兲, Pneurop Oxi-
116兴. The data in Table 3.5 give the oxidation onset tempera- dation Test 共DIN 51352-2兲, NOACK Volatility 共ASTM D5800兲,
ture 共OOT兲 of the hydrogen-rich oils. According to these and thermo-gravimetric analysis 共TGA兲.
data, untreated PAOs and mineral oils are equivalent but are Performance comparison in oxidation screen tests indi-
highly susceptible to oxidation. Diesters are better and cates synthetics to have better overall performance than
polyol esters are the best with respect to oxidation resis- mineral oils 关71兴. However, some synthetics, such as esters,
tance. The data also show that blending polyalphaolefins are better than others. It is possible that some esters, already
with ester base stocks increases their oxidation resistance being highly oxidized, have less affinity towards oxygen and
significantly. This is one of the strategies that is often used to are therefore less likely to undergo oxidative degradation. Al-
lower the cost of synthetics while achieving a reasonable oxi- ternatively, the oxidation screen tests measure thermo-
dation performance. Further support for this is obvious oxidative stability and not oxidative stability. The results of
from the OOT data for fully formulated oils; again the PAO/ the panel coker thermal stability test, depicted in Fig. 3.47
synthetic ester blends are better than the lubricants based on 关71兴, are consistent with this rationale. It is important to
mineral oils and hydrocarbon mixtures. point out that these tests were performed on fluids that were
devoid of additives. Fully formulated oils may reflect differ-
ent performance. With regard to the mechanical tests, the
PAO-based engine oils were equivalent in performance to
those that were mineral oil-based.
Oxidative stability measurement by MIL-L-9236A Gas
Lubricant °C °F °C °F
Petroleum oils 95–120 200–250 135–150 275–300
Super–refined petroleum oils 175–230 350–450 315–35 600–60
Synthetic hydrocarbons 175–230 350–450 350–345 600–650
Organic esters 175–190 350–375 220–230 425–450
Phosphate esters 95–175 200–350 135–230 275–450
Polyglycols 160–175 325–350 205–220 400–425
Poly共phenyl ether兲s 315–370 600–700 425–480 800–900
Silicate esters 190–220 375–425 260–290 500–550
Silicones 220–275 425–525 315–345 600–650
EP oils 60–80 140–175 65–85 150–185
a
Long term⬇ hundreds of hours.
b
Short term⬇ few hours.
Turbine Test, a real life test, that uses a temperature of 260° C cohol or mono-carboxylic acid derived esters. The life of an
and air blow rate of 5 L / h, led to a large viscosity increase oil at a particular temperature depends upon the amount
and acid build-up, showing esters to possess only poor to and the type of degradation that is acceptable. This in turn
mediocre stability. However, lowering the temperature to depends upon how much performance can be allowed to de-
200° C prolonged their oxidative life considerably 关72兴. teriorate during use.
These findings may appear contradictory to those noted Greater thermal and oxidative stability of the synthetics
above but it is important to state that petroleum-derived and are two of the primary reasons to choose synthetic base
nonester base stocks do even more poorly in this test and stocks over mineral oils. With respect to thermal stability, es-
that most turbine lubricants are of the ester type and contain ters are more stable than pure hydrocarbon base stocks,
a substantial amount of an oxidation inhibitor package. such as mineral oil and PAOs 共Table 3.16兲. Among esters,
Hydrolysis, molecular degradation due to water, is only polyol esters are three times more stable than monohydric
a problem in esters and not in mineral oils and PAOs. It is alcohol derived esters. The stability relates to the number of
usually catalyzed by strong acids and does not occur in their -hydrogens present in the alcohol portion of the molecule
absence. However, the presence of the residual acidity after 关72,158兴. The higher the number of -hydrogens, the lower is
manufacture or exposure to acidic materials and environ- the thermal stability. The absence of the -hydrogens in
ment during use can lead to hydrolytic cleavage of the ester polyol esters greatly enhances their thermal stability. The
functional group. Usually esters with steric crowding, such presence of the -hydrogens, as is the case in alkyl esters, fa-
as those derived from neo-alcohols or geminal dibranched cilitates thermal degradation via a six-membered transition
acids, hydrolyze much more slowly than the unbranched al- state. When the -hydrogens are absent, esters decompose
via a free radical mechanism that requires much higher en- cols, elastomer compatibility problems are more serious.
ergy 关158兴. That is why polyol esters have higher decomposi- The problems occur because of the fluid migrating into or
tion temperatures 共⬎300° C兲 than alkyl esters 共⬃200° C兲. The plasticizer moving out of the elastomer seal material. The
mechanisms for the pyrolysis of esters are depicted in Fig. former type of fluids, exemplified by esters and PAGs, will
3.27. cause excessive swelling of the seals and the latter types, ex-
Figure 3.48 gives an indication of the useful life versus emplified by the PAOs and the alkylaromatics, will cause
temperature for the formulated lubricants based on syn- shrinking and cracking of the seals. Material compatibility
thetic fluids. As expected, an increase in temperature de- of the synthetic base fluids is provided in Table 3.28 关161兴.
creases a lubricant’s useful life. Useful life presented here is
based on field experience in a range of applications 关79,159兴. Compressibility/Bulk Modulus
Table 3.26 subjectively provides volatility and deposit As stated earlier, bulk modulus expresses the resistance of a
forming tendencies of the various lubricants 关79兴. Materials fluid to compression, which is the reciprocal of compress-
with relatively higher polarity have a lower tendency to form ibility. This property of the fluid is significant for use in hy-
deposits than the low polarity mineral oil, PAOs, and alky- draulic and servo systems. Of all synthetics, silicones and
laromatics. This is partly due to their higher solvency, which perfluoropolyethers show a relatively low bulk modulus
keeps the polar deposit precursors in solution instead of al- 共high compressibility兲 based on a density correlation. Bulk
lowing them to separate out on the surfaces. These precur- modulus is a physical property of the base fluid which can-
sors on hot surfaces result in the formation of deposits. As not be changed significantly by additives.
mentioned earlier, volatility is a function of the molecular
Heat Transfer
weight; the low molecular weight materials have higher
A variety of industries employ heat transfer fluids. Those
volatility. A number of factors may be responsible for the
worth mentioning within the context of lubricants include
poor volatility characteristics of a base stock, the presence of
food processing, oil and gas industry 共natural gas compres-
the low boiling components being one. Both mineral oils and
sor engines and high-speed industrial stationary engines,
polymeric synthetic materials, such as unpurified polyole-
drilling equipment兲, petroleum and petroleum refining, met-
fins or poly共alkylene glycol兲s, with poly-dispersity index of
alworking and metal processing, and aerospace and military.
higher than 1, contain such components. However, all syn-
Lubricating advantage of a particular base fluid de-
thetic fluids undergo a rigorous purification step; hence,
pends on a number of factors. It depends upon its viscosity-
their poor volatility is related to their thermal depolymeriza-
temperature 共VT兲 and viscosity-pressure 共VP兲 behavior, its
tion or oxidative degradation to the lower boiling species.
affinity for the surface 共polarity兲, and the lubrication regime
This may be the primary reason for the higher volatility of
共hydrodynamic, elasto-hydrodynamic, mixed, or boundary兲.
the PIBs and PAGs above their threshold temperature, where
When used as lubricants in the vicinity of the high-
rapid degradation initiates. It is important to note that a
temperature environments, such as internal combustion en-
temperature of 250° C is quite high and in most cases is out-
gines, or where the machine elements generate a significant
side the recommended operating range of the most synthetic
amount of frictional heat, such as gears, the VT properties of
fluids. See the data in Table 3.27 关160兴.
the fluids are of primary importance. This is because a sub-
Hydrolytic Stability stantial viscosity loss due to heat will diminish their ability
Hydrolytic stability is an important consideration if the base to lubricate effectively. In addition, because of the high tem-
stock is to be used either in combination with water, such as peratures oxidative degradation of the lubricant and metal
in the case of water-based metalworking fluids, or has a corrosion due to acidic oxidation products will also increase.
chance to be exposed to water, such as in combustion engine This will result in shorter service life. In such situations,
lubricants. Under these circumstances, the oil must keep its lubricants/base fluids with good thermal capacity, or heat
integrity and must not hydrolyze. Hydrolysis is a primary transferring capability to dissipate heat, are useful. Heat
concern for silicate esters and phosphate esters and only a transfer directly affects equipment performance, fuel effi-
minor concern for carboxylate esters. High temperatures ciency, materials selection, emissions, and engine or equip-
and a trace amount of acidic impurities catalyze the hydro- ment life.
lytic breakdown of these base stocks. Heat capacity of a liquid/oil is the amount of heat it can
absorb or store before a change in its overall temperature oc-
Materials Compatibility curs. Thermal capacity of a fluid is defined as the amount of
Many applications employ plastics and elastomers. Hence energy required to raise the temperature of a sample by 1 ° C.
compatibility of the synthetic fluids with these materials is The value of this parameter can be calculated from the spe-
important. While compatibility of the synthetic base oils cific heat capacity at constant pressure, thermal conductiv-
with plastics is not a problem, except for esters and polygly- ity, density, viscosity, and the heat transfer coefficient of the
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88 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
better. The oil must be able to absorb heat, store it, and re-
lease it without ever compromising its own stability. The rate
at which this absorption, storage, and release occurs is
known as the heat transfer coefficient; higher values of this
parameter are highly desirable. In general, lubricants with
good heat transferring ability have good heat capacity, high
thermal conductivity, high density, and low working viscos-
ity.
An ideal heat transfer fluid must have superior thermal
conductivity, exceptional thermal stability 共resistance to
coking and oxidation up to 425° C兲, low pour point
共艋0 ° C兲, low vapor pressure at high temperatures, high boil-
ing point, long operating life, and the ability to be used over a
broad temperature range. In addition, it must be nonflam-
mable, nontoxic, and inexpensive. Commercial heat transfer
fluids 共HTFs兲 vary in performance. Polar materials have gen-
erally higher heat capacity than nonpolar materials. A rough
estimate of the heat storage ability of the polar synthetics is
around 10 % over that of the pure hydrocarbon fluids. Hy-
drocarbon fluids, especially petroleum oils, in addition, are
susceptible to accelerated oxidation at temperatures of
around 135° C 共275° F兲. They also suffer from the disadvan-
tage of high volatility and can evaporate at elevated tempera-
tures. Synthetic fluids used to make heat transfer lubricants
include organic esters and diesters, poly共alkylene glycol兲s
Fig. 3.49—Radiation resistance limits of various base fluids 关165兴. and water-glycol mixtures, and silicones. Current commer-
cial HTFs are derived either from hydrocarbons 共paraffinics
or alkylaromatics兲, poly共alkylene glycol兲s, silicones, or CFCs
lubricant components 关79兴. Specific heat capacity of a sub- 共only for closed systems兲. Some of these may even contain
stance is the amount of energy required to raise the tempera- water. Properties of some commercial heat transfer fluids
ture of one kilogram of the substance by 1 ° C 共1 ° K兲. Heat ca- are provided in Ref 关162兴. While many of these meet the
pacity can be measured by using calorimetry. The measuring above listed criteria for the ideal heat transfer fluid, the
unit of heat capacity is joule per kilogram Kelvin, J · kg−1 · K−1 search for better heat transfer fluids continues 关163兴.
or J/共kg·K兲, or BTU/lb °F. Higher values indicate higher heat
capacity. The specific heat can also be interpreted as a mea- Radiation Stability
sure of how well a substance maintains its temperature, i.e., Radiation affects all organic compounds, causing a change
“stores” heat. Thermal conductivity is a measure of the abil- in their properties. This is because radiation attacks the co-
ity of a material to conduct heat. Again, the higher values are valent bonds that are most prevalent in organic compounds.
Since the strength of these bonds differs among organic radiation on the viscosity of mineral oils. In one study, the
compounds, so does their stability under radiation, espe- performance of the PPE under the influence of
cially short-wavelength, highly energetic ionizing radiation, 1011 ergs/ gram of radiation at 99° C 共210° F兲 was compared
such as gamma rays, X rays, and subatomic charged par- with that of the aliphatic ester, aliphatic hydrocarbon, meth-
ticles. One result of ionization is that the organic molecules ylphenyl silicone, and chlorophenyl silicone 关164兴. PPE
disproportionate to form smaller hydrocarbon molecules as showed a viscosity increase of only 35 %, while all other flu-
well as larger hydrocarbons molecules. Smaller molecules ids showed a viscosity increase of 1700 % and gelled. In some
result from fragmentation and larger molecules result from lubricants, radiation also creates free radicals that can cause
their recombination, or polymerization. Other chemical re- corrosion. Radiation stability of the ortho-phosphoric acid
actions caused by radiation include oxidation and isomer- esters, not part of this study, is also reported as poor 关4兴. PPE-
ization. derived lubricants are therefore widely used in radiation en-
Lubricants as well as base fluids are primarily organic vironments. Radiation resistance of various base fluids is
molecules, hence their radiation stability is a concern when shown in Fig. 3.49 关165,166兴. From the figure it appears that
used in applications with a possibility of radiation exposure. the materials that are primarily aromatic in structure, such
Examples of such an environment include nuclear power as PPEs and polyphenyls, are the most radiation stable.
plants, space satellites, nuclear submarines, food steriliza- Their greater stability can be ascribed to the presence of the
tion equipment, radiation chemistry systems, and medical difficulty to ionize aromatic carbon hydrogen bonds. Radia-
imaging systems. Radiation stability of a lubricant is typi- tion properties of the fluids can be improved by the use of
cally assessed by an increase in its viscosity. Those additives. Among those tried, dialkyl selenide was found to
lubricants/base fluids that exhibit the lowest increase in vis- be the most effective 关165兴. This is shown in Fig. 3.50. With-
cosity under radiation are the most desirable in the above- out the selenide, phenylmethyl silicone shows a large viscos-
listed applications. Lubricants that contain a large number ity increase at 4 ⫻ 108 Rads, but the addition of dodecyl se-
of ionizable carbon-carbon and carbon-hydrogen bonds, lenide helps the fluid maintain its viscosity at a reasonable
such as petroleum base stocks 共mineral oils兲, have a lower level, even at higher radiation dosage. The effect in C16–18
stability than those that contain fewer such bonds. The ex- alkylbiphenyl, which maintains its viscosity well without the
amples of the latter type are poly共phenyl ether兲s 关PPE兴 and additive, the effect is a lot less dramatic. Other base fluids,
perfluoropolyethers 共PFPEs兲. Table 3.29 shows the effect of such as esters, also respond well to such additives 关165兴.
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90 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
Polymers used in finished lubricants as viscosity modifiers loss can interfere in the lubricant’s second critical function,
respond differently to radiation, as shown in Fig. 3.51. Poly- which is to form a durable lubricating film between surfaces
共alkyl acrylate兲 and polybutene lose their viscosity but poly- to prevent metal-to-metal contact. Situations that explicitly
styrene somewhat gains viscosity on irradiation. The ideal require effective lubrication primarily occur during the
fluid must do neither and by this criterion, finished fluid that start-up, slow down to stop, overheating, and overloading. In
contains poly 共␣-methylstyrene兲 is a good one. Please note such situations, the lubricating film is either not present or is
that all fluids depicted in the figure contain radiation stabil- ineffective. Lubricants derived from the polar base stocks,
ity additives. Viscosity increase is not the only consequence such as esters, have a greater affinity towards metal surfaces
of radiation exposure. Other radiological effects that are ob- than those derived from the mineral oil; hence they form
served in synthetic fluids are listed in Table 3.30. In addition more durable surface films under all situations. The film for-
to the base fluids and additives, there are other materials in mation capability in elasto-hydrodynamic contacts has been
modern machines that are also affected by radiation. Prime studied. The results indicate that the polar polyesters form
examples include elastomers that are used to make seals and thicker lubricating films that are maintained in highly
polymeric coatings. Radiation effects on these materials are loaded, high slip contacts. This was ascribed to their high
provided in Fig. 3.52 关165–167兴. Again, different materials
surface affinity.
have a varying degree of resistance to radiation exposure.
Low-temperature viscosity of a lubricant is also an im-
portant consideration. This is because during cold starts the
Lubrication
As mentioned in the earlier part of the discussion, the lubri- main cause of engine wear is the inability of the lubricant to
cating advantage of a particular base fluid depends upon a reach parts requiring lubrication. The lubricants that have
combination of factors. These include superior viscosity- poor low-temperature viscometrics take too long to reach
temperature 共VT兲 and viscosity-pressure 共VP兲 behavior and such parts. Lubricants, especially those for automotive use,
high affinity towards surfaces, also termed polarity. Of these, have low-temperature viscosity specifications. These are
a lubricant’s surface affinity has the most direct influence on provided in the section on low-temperature properties and
lubrication, the primary objectives of which are temperature for the engine oils in Chapter 5 on Combustion Engine Lu-
control and minimizing metal-to-metal contact to avoid bricants. As stated earlier, cranking and pumping viscosities
wear. The temperature control is critical since it can cause a are two of the most critical requirements for engine oils. En-
reduction in lubricant viscosity, facilitate its oxidative degra- gine lubricants derived from the PAOs and polyol esters have
dation, and promote metal corrosion due to the resulting much better cold-cranking viscosity than those derived from
acidic oxidation products. The temperature-related viscosity the mineral oils. Part of the advantage here is the absence of
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CHAPTER 3 䊏 SYNTHETIC AND BIOLOGICAL BASE STOCKS 91
the high molecular weight linear hydrocarbons, the paraffin drilling fluids, textile lubricants, and marine and aviation lu-
wax. Incidentally, lubrication characteristics of all base bricants 关169兴.
stocks can be improved by the use of the friction modifiers Biodegradability of the oils plays a predominant role in
and antiwear and extreme-pressure agents. Friction modifi- assessing the environmental compatibility of the lubricating
ers adsorb on metal surfaces and associate with the oil to oil, both in Europe and in the United States 共ASTM D6046兲.
keep it on the surface and extreme-pressure/antiwear agents There are a number of methods that are used to measure bio-
form more durable chemical films on metal surfaces via ther- degradability 关170兴. These include CEC-L-33-T-82, CEC-L-
mal reaction. 33-A-94, OECD 301B, and ASTM D5864. The biodegradabil-
ity results obtained by the use of different methods are
Environmental Compatibility compared in Table 3.31 关171兴. As one can see, not only that
Governmental regulatory agencies, such as the Environ- the extent of biodegradability differs across methods but it
mental Protection Agency 共EPA兲, National Marine Fisheries also differs within the same class, as indicated by the biode-
Service 共NMFS兲, U.S. Department of Agriculture 共USDA兲, gradability range. Results also differ if the sludge used in the
and European Environment Agency 共EEA兲, and many pri- test is obtained from a different source. Typically, linear hy-
vate organizations are established to monitor and control drocarbon materials and natural oils exhibit the highest de-
the release of harmful substances into air, water, and soil. gree of biodegradability. ASTM D6006 is a guide for assess-
Various countries have initiated the use of environmental la- ing the biodegradability of the hydraulic fluids and ASTM
bels, or eco-labels. The objective of the scheme is to promote
D6384 describes the terminology relating to the biodegrad-
products with a reduced environmental impact, compared
ability and eco-toxicity of the lubricants. For biodegradation
to other products in the same product group. Not all product
mechanism, see Ref 关172兴. From the data in Table 3.31 one
groups are amenable to eco-labeling. Those that are must
can see that the ester fluids, such as diesters and vegetable
meet the following criteria 关168兴:
oils, are highly biodegradable. Please consult Chapter 13 for
• They must represent a significant volume of sales and
further discussion on this topic.
trade in the domestic market.
When assessing toxicity, one considers environmental
• They must have a significant environmental impact.
fate 共photodegradation, stability in water, biodegradation,
• They must present a significant potential for affecting
environmental improvements through consumer fungicidal action兲, health effects 共acute toxicity, repeated-
choice. dose toxicity, genetic toxicity, and reproductive/
• A significant part of the sales volume must be sold for fi- developmental toxicity兲, and ecological effects 共harm to fish,
nal consumption or use. invertebrates, and algae兲. As one can see, biodegradability is
The reason for choosing these criteria is to convey the one of the many criteria that define environmental compat-
environmental characteristics of the product to the con- ibility. A fluid may be highly biodegradable but still may be
sumer. The hope is that the consumers will choose environ- harmful to life or the environment. Numerous toxicity test
mentally friendly products, due to a concern for the environ- methods have been available for years, and some of these
ment. This in turn will increase the demand for such have been used to evaluate lubricants. Some of the test meth-
products, which will motivate manufacturers to produce ods can be applied as such to determine lubricant toxicity
products that are environmentally compatible. Lubricants, but others need extensive modification. Some others may
new or used, not only meet the above listed criteria but their prove totally inadequate. This is because the traditional tox-
release into the environment is also a concern because of the icity test methods were devised for assessing toxicity of
accidental release of its precursor, petroleum, into the envi- aqueous specimens and not nonaqueous specimens, such as
ronment and its well publicized negative impact. Eco- lubricants. Most test methods attempt to determine the le-
labeling of lubricants in Europe uses four measures to select thal dose 共LD50兲 of an animal species being tested. An LD50
lubricants; these are biodegradability, aquatic toxicity, value is the amount of a solid or liquid material that it takes
health hazardness, and renewability. As of the year 2003, no to kill 50 % of the test animals in a single dose. This is closely
eco-labels have been used for automotive lubricants, which related to the LDLo value which is the lowest dosage reported
make up ⬃47 % of the total lubricant use, compressor oils, to have killed animals or humans. The species of animals
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92 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
claimed oils, and only about 24 % is truly recycled. The rest is biological in origin. Interestingly, a significant driver for the
either burned or disposed of illegally. industrial use of the vegetable oils is “green chemistry” ini-
Animal fats and vegetable oils occur in nature and are tiatives by the U.S. Government, under the auspices of the
therefore biodegradable 关106兴. As a result, the disposal of lu- 2002 Farm Bill which promote the development of the new
bricants containing them is of less concern. Interest in bio- bio-based products and processes. The objective of the bill is
degradable lubricants, such as those derived from the natu- to promote cooperation between agriculture and other in-
ral oils, has historically been in response to the
dustries to exploit homegrown biochemical resources. A va-
environmental concerns, particularly relating to the effects
riety of terms are used to designate products derived from
of the oil entering the soil and the fresh water. Therefore, the
the natural oils, many of which are used in adhesives, per-
lubricants used in agriculture, forestry, and marine applica-
tions are formulated by the use of biodegradable and sonal care products, and fuels and lubricants. Common
nontoxic synthetic and natural ester base stocks. Such terms for such products include renewable, bio-based,
lubricants include hydraulic oils, gear oils, and greases. Bio- green, environmentally sound, environmentally acceptable,
logically compatible or acceptable lubricants are particu- natural, and so on, portraying an environmentally conscious
larly popular in the northern European countries. Inciden- image. Vegetable oil-based products, such as those produced
tally, the U.S. EPA treats all oil spills alike and does not from canola, soybean, palm, and sunflower seed, are re-
distinguish them based on whether they are petroleum or ferred to as natural esters since they are used only after ex-
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94 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
base oils because of the presence of wax that is removed dur- Two ways to improve oxidation stability of these oils are
ing refining. The melting points of the oils of biological origin, the use of the traditional oxidation inhibitors, the same as
on the other hand, are not due to the presence of the remov- for mineral oils, and the structural modifications. Unfortu-
able impurities but are related to the fundamental structure nately, this further exacerbates their cost disadvantage rela-
of the organic compounds that make up their bulk. Since tive to the mineral oils. One approach that has been used to
these oils do not respond well to pour point depressants that improve oxidation stability is to lower their overall olefinic
are commonly used to improve the low-temperature proper- content 共unsaturation兲, either through selective breeding of
ties of the mineral oils, blending with fluids that have good the seed or the fruit-bearing plants by genetic manipulation
low-temperature fluidity is an option. Blending with some or by chemical means. Olefinic sites in the natural oil struc-
synthetic esters is quite effective and hydraulic fluids with ture are among those that are the most susceptible to oxida-
pour points of −32.8° F 共−36° C兲 have been developed 关177兴. tion. Selective breeding can result in genetic strains that can
If a high degree of biodegradability is to be maintained, bio- produce oils of up to 98 % oleic 共mono-unsaturate兲 content.
degradable synthetic esters must be used as diluents. Oils of high mono-unsaturate 共low poly-unsaturate兲 content
have superior oxidation stability than those of the low mono-
Oxidative Stability unsaturate content. This is demonstrated in Fig. 3.54 关178兴.
All hydrocarbon materials, irrespective of their origin, are One can see that as the mono-unsaturate content increases,
prone to oxidation. Autoxidation of organics is discussed in so does the oxidative stability. High oleic soybean, canola,
detail in the oxidation inhibitors section of Chapter 4 on Ad- rapeseed, and sunflower oils are now becoming standard
ditives. Atmospheric oxygen attacks the weaker portion of base oils for formulating biodegradable lubricants and
the molecule to form hydroperoxides. These materials can greases.
fall apart to form free radicals that start the oxidation chain Chemical modification involves partial hydrogenation
mechanism. Allylic and benzylic hydrogens, if present in a of the vegetable oil and the redistribution of the fatty acids.
molecule, are among those that are highly susceptible to oxi- While hydrogenating, it is important to stop at a point where
dative attack. Most natural oils are primarily glycerol esters an oil of reasonable oxidative stability is obtained, without
of unsaturated carboxylic acids, such as oleic acid, linoleic the loss of its fluidity. The low-temperature properties of the
acid, and linolenic acid. These compounds contain allylic vegetable oil are not great to start with and too much hydro-
hydrogens that oxidize readily and are the reason for the genation can convert the oil into a product that is semi-solid,
poor oxidative stability of the natural oils. Mineral oils, on with grease-like consistency even at room temperature.
the other hand, either do not contain such components or if Most genetically manipulated and chemically modified oils
they do, their oxidative susceptibility can be reduced retain high biodegradability in tests established by ASTM
through hydrogenation. There is no straight forward way to and OECD. Most vegetable oils show a biodegradability of
achieve this for the natural oils. better than 70 % in 28 days. Petroleum oils normally show a
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96 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
TABLE 3.35—Fatty acid composition of commonly used fats and oils in lubricant-related applica-
tions †179‡.
Saturated Mono-unsaturated Poly-unsaturated
ther by direct transesterification reaction or by first saponi- ters have excellent low- and high-temperature viscometrics,
fying the oil and then converting the isolated acid into an improved oxidation stability, and biodegradability. Although
ester by reacting it with a mono- or polyhydric alcohol. their biodegradability is somewhat lower, they still meet the
These reactions are depicted in Fig. 3.24, along with other biodegradability requirements to be labeled as biodegrad-
esters that possess biodegradability as well. Various proper- able. There are a few on the list, such as higher grades of
ties of the parent vegetable oils and these modified esters are PAOs, which have low biodegradability. As mentioned ear-
provided in Table 3.36 关180兴. As one can see, the modified es- lier, additives can negatively impact biodegradability and
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CHAPTER 3 䊏 SYNTHETIC AND BIOLOGICAL BASE STOCKS 99
nontoxicity of these base oils. Unfortunately, at this time, a rent engine tests 关180b兴. It appears that the performance de-
full array of nontoxic additives is not yet available to the for- ficiencies that exist may be overcome by the use of suitable
mulators. additives.
So far the biological base stocks have been used to for- Based on the discussion in this section, it is clear that all
mulate lubricants for hydraulics and other devices that are lubricant base stocks are not alike. In practice, many lubri-
utilized in natural settings. Industries that employ bio-based cant base oils are manufactured according to the market
lubricants include farming, forestry, construction, off-shore specifications, by blending base stocks of various physical
drilling, and maritime; and a substantial amount of data and chemical properties. Despite this effort to narrow their
supporting the benefits of these lubricants are available. structural and performance differences, lubricants devel-
However, data regarding their use in highly demanding auto- oped from the same additive package may have radically dif-
motive applications, such as engine oils, are either sparse or ferent performance. To minimize this problem, the API has
nonexistent. Interestingly, an article published in a recent is- classified base oils into five categories, Group I to Group V,
sue of Lubes and Greases magazine provides an insight into and has published guidelines relating to interchange of base
the expected performance of the bio-based engine oils in cur- oils.
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MNL59-EB/Mar. 2009
4
Lubricant Additives
IN THIS CHAPTER WE DESCRIBE THE CHEMISTRY, pressure or EP additive system, was found to be effec-
manufacture, and properties of the chemicals that are used tive. When GM in its 1937 models introduced hypoid
in lubricants as additives. The function of these chemicals axles, it tested and recommended the use of a number
is either to enhance the already existing properties of the of such lubricants.
base fluids or to impart new properties that they lack. Dis- 3. Complex calcium soap greases were invented in 1940,
cussion also includes the mechanism by which each addi- lithium soap greases were invented in 1942/1943, and
tive type performs its functions, multifunctional nature of barium greases were invented in the 1950s. These
some additives, and their impact on the environment. The greases retain their semi-solid morphology at much
need and the development of a new additive and the pro- higher temperatures than their sodium and calcium
cess by which it is approved for use in a particular appli- analogues. They contain sodium nitrite to inhibit cor-
cation are also explained. rosion and oxidation.
All mechanical equipment must be lubricated. The pri- 4. Until 1947, the performance of the engine oils was de-
mary purpose is to reduce friction and wear. If not con- fined solely by their viscosity grades, without due con-
trolled, these can lead to inefficiencies, damage, and ulti- sideration to the engine design, its operating environ-
mately to equipment seizure. ments, and the fuel type and quality. In 1947, API
Pictorial records depicting the use of lubricants date as introduced three performance categories, regular, pre-
far back as 1650 B.C. Analysis of the residue from chariot mium, and heavy-duty, based on the severity of service.
axle hubs suggests the use of animal fat as a lubricant, as Regular oils were straight mineral oils with or without
early as 1400 B.C. This practice continued until 1859 when viscosity modifiers and corresponded to oils defined
petroleum-based lubricants became available. While the previously by the viscosity grades. These oils were for
claimed use of additives in lubricants dates far back into both gasoline and diesel engines operating under mild
the 1860s, the modern history of lubricant additives began to moderate service conditions. Premium oils, de-
in the early 20th century, with the use of fatty oils and signed for somewhat more severe operating condi-
sulfur in mineral oils to improve lubrication under high tions, generally contained oxidation and corrosion in-
loads. The use of additives became common only after the hibitors, and, in some cases, mild detergents. Heavy-
1930s when more compact and faster engines were devel- duty oils possessed better oxidation and corrosion
oped and the OEMs started to specify oils for use in their resistance and detergency than the premium oils and
equipment 关181,182兴. However, these were the military were designed to withstand the most severe service.
needs during and after the Second World War that were the 5. In the early 1950s, multi-grade oils were an outcome of
major driving force behind the development of the lubri- the development of the viscosity modifiers. These were
cant additives as we know them today. This is because the made by dissolving polymeric materials to low viscos-
fast-running engines had a complex design, which placed a ity, or thin, oils.
heavy demand on the lubricants. At that time, besides the All of today’s lubricants contain additives, which im-
SAE viscosity classification system, there were no estab- part to the lubricants the necessary performance. The
lished performance criteria and the end-user had to de- amount of additives in a lubricant can range between 1 to
pend on the lubricant supplier’s claims regarding the suit- 25 %, and more. See Table 1.4 for typical additive concen-
ability of the lubricants 关182兴. Additives are not only trations for some commonly used lubricants. The largest
critical to the manufacture and use of automotive fuels and use of additives is in automotive lubricants, such as engine
lubricants; they are also extensively used in petroleum re- oils 共for gasoline and diesel engines兲, transmission fluids,
covery as drilling additives and refining as refinery chemi- gear oils, and greases. The primary role of the lubricants is
cals 关183兴. This was discussed in Chapter 2 on Mineral to provide protection for the metal surfaces against wear
Base Stocks. Some of the highlights of the additives devel- and corrosion. Lubricant additives for automotive lubri-
opment are as follows. cants are generally supplied as a performance package,
1. Sodium soap greases were developed in the 1930s. which is blended in base stocks or base oils to yield formu-
They did not suffer from water sensitivity and had bet- lated lubricants. These lubricants must meet the perfor-
ter resistance to high temperatures than the lime or mance requirements established by organizations such as
calcium soap 共calcium carboxylate兲 greases, the use of the SAE, API, U.S. Military, OEMs, and the end-users. The
which dates back to the 1880s. performance package contains many classes and types of
2. In 1937, the lubricants containing a lead soap-active additives 关184,185兴. While there are a number of ways to
sulfur additive combination, known as an extreme- classify additives, we have grouped them into stabilizers/
100
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CHAPTER 4 䊏 LUBRICANT ADDITIVES 101
deposit control agents, film-forming agents, polymeric ad- based hydraulic fluids and metalworking lubricants,
ditives, and miscellaneous others, based either upon their which employ such emulsions.
function or their structural characteristics. The primary Demulsifiers enhance water separation from the oil
functions of each type are briefly described below. A more contaminated with water.
detailed discussion on the chemistry and mode of their ac- Foam inhibitors prevent lubricant from forming persis-
tion will be provided in the subsequent discussion. tent foam.
• Stabilizers/Deposit Control Agents—minimize the • Miscellaneous Additives—perform miscellaneous other
amount of deposit formation. functions.
Oxidation inhibitors and metal deactivators control oxi- Seal swell agents swell elastomer seals.
dative decomposition of the lubricant and the Dyes are used to color code lubricants and fuels.
additives. Biocides prevent degradation of the high water-based
Dispersants keep normally insoluble contaminants dis- lubricants due to microbial attack.
persed in the lubricant.
Couplers help stabilize water-organic micro-emulsions.
Detergents prevent metal attack by acidic byproducts of
The evolution of the major classes of additives is pro-
combustion and oxidation by neutralizing and sus-
vided in Fig. 4.1. The world lubricant additives demand for
pending them, thereby keeping metal surfaces free of
the year 2006 is estimated at 3 million metric tons 共⬃6.6
deposits.
billion lb兲, which is expected to grow at an average rate of
• Film-forming Agents—either increase the durability of
less than 1 % per year, until the year 2010 关186兴. The addi-
the lubricant film or form chemical films on metal
tive growth rate in North America over the next five years is
surfaces.
Friction modifiers generally lower the coefficient of fric- predicted to remain flat; Europe, Middle East, and Africa
tion, thereby leading to improved fuel economy. will see a decline; Asia Pacific and Latin America will see
Antiwear and extreme pressure agents protect metal sur- an increase of 5 % and 2 %, respectively 关186兴. The U.S.
faces against wear and equipment seizure. consumption in 2006 was estimated to be about
Rust and corrosion inhibitors prevent corrosion and 862,000 metric tons 共1.9 billion lb兲, almost 29 % of the
rusting of the metal parts that come in contact with the world total. This volume reflects an average annual growth
lubricant. rate of around 2 % since 2002, which is primarily due to
• Polymeric Additives—alter physical properties, such as changing diesel engine oil specifications to meet stringent
viscosity and pour point, of the lubricants. environmetal standards and the demand for high-
Viscosity modifiers minimize the rate of viscosity de- performance industrial lubricants that meet the occupa-
crease with an increase in temperature. tional safety and health requirements, established by Occu-
Pour point depressants enable a lubricant to flow at low pational Safety and Health Administration 共OSHA兲. The
temperatures. increased use of synthetics, vegetable oils, and their blends,
Emulsifiers promote mixing of water and oil to form an which require higher additive treat rate levels, have also
emulsion. These additives are used to make water- contributed towards this growth.
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102 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
Estimated North American use for the year 2006 by deposit formation and acid-related corrosion damage will
application is depicted in Fig. 4.2 and by additive type is occur. Hence, engine lubricants are formulated with oxida-
provided in Fig. 4.3. As one can see, engine oils account for tion inhibitors, which control the formation of these spe-
63 % of the total additive use. Detergents and dispersants, cies, and dispersants and detergents that keep them away
that are classified as deposit control additives, and viscos- from the surfaces by neutralizing them or suspending them
ity modifiers account for 55 % of the total additive con- in the bulk lubricant. In addition, dispersants have the abil-
sumption. The engine lubricants are exposed to combus- ity to largely contain undesired particulate emissions 共PM兲
tion products in the form of blow-by that travel past the in the bulk oil. Hence, the large volume use of these classes
piston rings into the lubricant. In addition to containing of additives is consistent with the greater use of the engine
unburned and partially burned fuel, the blow-by contains lubricants. As will be discussed later, the use of detergents
reactive intermediates from fuel oxidation, such as perox- is expected to drop because of the incompatibility of the
ides and peroxy-free radicals, nitrogen oxides, resulting sulfonate detergents with particulate filtering devices
from the high-temperature reaction of nitrogen and oxygen 共DPFs兲, discussed in the Chapter 6, the Emissions Chapter.
from the air, soot, sulfur oxides, carbon monoxide, carbon As mentioned above, from 2006 to 2010, the growth of the
dioxide, and water. Peroxides and peroxy-free radicals ini- lubricant additives is expected to plateau. This is because
tiate lubricant oxidation to form deposit precursors and of the maturity of the North American lubricants market
acidic products. The formation and or separation of these and a variety of other factors, such as the growing con-
products on hot surfaces must be minimized; otherwise sumer interest in hybrid cars, extended service 共drain兲 in-
Fig. 4.3—Estimated additive use for 2006 by additive type, North America.
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CHAPTER 4 䊏 LUBRICANT ADDITIVES 103
tervals, low oil consumption engines, sealed-for-life com- seal compatibility, oxidation resistance, corrosivity, the
ponents, and the use of highly refined base oils that require viscosity-temperature relationship 共VI兲, low-temperature
lower additive treatment. Additive use data from the Fre- properties, such as cloud point and pour point, and high-
donia group for the 1989–2009 period, presented in Table temperature properties, such as volatility and flash point 关4兴.
4.1, aptly support this prediction. Examination of the data Other important properties include thermal expansion, bulk
reveals the following. modulus or compressibility, thermal conductivity, thermal
1. The growth of the additives for the 1989–99 period capacity, electrical conductivity, and surface tension. The
outpaced the growth of the lubricants, but for the knowledge of these properties is especially useful in design-
1999–2009 period, the two are almost equal. ing lubricants for specialty applications.
2. The additive use per gallon increased during the first The viscosity and viscosity-temperature relationship
decade, but has leveled off in the second decade. were discussed in the viscosity section of Chapter 1 on Lubri-
3. The strongest sustained growth occurred and will oc- cation Fundamentals. The interested reader may like to refer
cur in oxidation inhibitors, corrosion inhibitors, and back to that chapter. The high-temperature properties of the
foam inhibitors. base oil are governed by its distillation temperature, or its
Desirable Lubricant Properties boiling range. Volatility is important because it is an indica-
tion of the oil’s tendency to be lost during service due to va-
For lubricants to perform effectively, they must possess cer- porization, for example, in a hot engine. The methods used
tain specific properties, which include suitable viscosity, to determine volatility include distillation curves 共see Chap-
slipperiness, high film strength, low corrosivity, low pour ter 3 on Synthetic Base Fluids兲, thermo-gravimetric analysis,
point, good cleansing and dispersing ability, nontoxicity, and and NOACK volatility. Flash point is the lowest temperature
low flammability and volatility. In addition, the lubricant at which auto-ignition of the vapor above the heated sample
must not foam. It must also be capable of getting rid of air occurs. Flash point of an oil is important from a safety point
共oxygen兲 to minimize oxidation and maintaining its lubricat- of view and is used to classify flammable liquids into hazard
ing characteristics. As mentioned in the prior discussion, the grades. There are two methods to determine the flash point:
lubricants are formulated by blending base oils with addi- the closed cup method 共Pensky-Martens Closed Cup or
tives to meet a series of performance specifications. These PMCC兲 and the open cup method 共Cleveland Open Cup or
specifications relate to the physical and chemical properties COC兲 关4兴.
of the lubricant, when it is new and during use, and its ability Density is important because oils may be formulated by
to protect the equipment against damage during service. weight but measured by volume. Density is also used to iden-
Many of these properties were discussed under the lubricant tify an oil, or its fractions, and in calculating kinematic vis-
selection criteria in Chapter 1. Previously, we also stated that cosity from absolute or dynamic viscosity. Demulsibility is
the base fluid is the largest component in a lubricant and its the ability of an oil to separate water. Foaming characteris-
properties are likely to have the greatest effect on lubricant tics determine the tendency of the oil to form foam and the
properties. Hence, it is important to choose a base oil that by stability of the foam once it is formed. Seal compatibility of
and large has the properties that are desired in a lubricant. the oil is also important because the oil in most applications
Criteria For Suitable Base Stocks comes in contact with elastomer seals. If seals are damaged,
the equipment will be left unprotected since the lubricant
Although in a lubricant many of the base fluid’s proper- will be lost.
ties are modified or enhanced by the use of the additives, the Oxidation resistance of the base oil depends largely
knowledge of such properties is critical to the formulator. upon the structure of the hydrocarbons present. As men-
These properties deal with the base oil’s density, viscosity, tioned earlier, lubricants that do not contain aromatic struc-
both at low and high temperatures, foaming characteristics, tures or structures with unsaturation have better oxidative
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104 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
stability than those that do. Oxidation of the base oil results
in the formation of the polar compounds that are either cor-
rosive or lead to the formation of sludge and resin, both of
which can impair proper functioning of the equipment. Pre-
viously, the sulfur content of the base oils was used as an in-
dicator of their natural resistance to oxidation. This is be-
cause many naturally-occurring organo-sulfur compounds
in crude oils are moderately effective in destroying the or- Fig. 4.4—A general representation of a typical additive molecule
ganic peroxides and breaking the oxidation chain mecha- 关50兴.
nism. However, modern refining processes, which are used
to enhance the other desirable properties of the base oils, re- ropolyalkylethers, and fluorinated esters; all of which have
sult in the removal of these beneficial compounds. good electrical properties. At one time polychlorobiphenyls
Thermal expansion predicts an increase in volume of a 共PCBs兲 were extensively used as insulating oils in transform-
given mass of oil with an increase in temperature and is ac- ers. This was because of their low water solubility, excellent
companied by a decrease in density. The degree of expansion thermal stability, low volatility, and virtual inflammability.
is expressed as the coefficient of thermal expansion. The However, since the 1970s their use has declined almost to
knowledge of the oil’s thermal expansion is useful for deter- nothing because of their being persistent organic pollutants.
mining the size of the container needed when the oil is It is important to note that while clean, dry base oil has a low
heated. Its knowledge is also useful in assessing the lubrica- electrical conductivity, the used, wet, and contaminated oil
tion needs of the bearings since in elasto-hydrodynamic lu- can have a high conductivity. Hence, quality control of such
brication 共EHD兲 regime the thermal expansion of the oil re- oils is imperative.
sults in an increase in the hydraulic pressure. Surface tension is the surface energy between a liquid
As mentioned in Chapter 3, the bulk modulus expresses and its vapor, or air, or a metal surface. Surface tension is
the resistance of a fluid to a decrease in volume due to com- considered a factor in the ability of an oil to “wet” a surface,
pression and is accompanied by an increase in density. Com- stability of its emulsions, and the stability of its dispersions
pressibility is the reciprocal of the bulk modulus, or the ten- that contain solids. Of these, the first two phenomena are
dency to be compressed. In high-pressure hydraulic most relevant to the present discussion. This is because they
systems, a high bulk modulus, or low compressibility, is re- relate to surface affinity, a concept important in film-
quired to transmit power efficiently and dynamically. Min- forming 共surface-active兲 agents, and foaming tendency of
eral oils have low compressibility, but low-viscosity polysi- the oil. High surface tension fluids form more persistent
loxane fluids have high compressibility, or a low bulk foams. One way to correct this problem is by the use of sili-
modulus. cones, which reduce the surface tension of the bubbles,
Thermal conductivity is the rate of dissipation of heat hence help break foams.
through a material. A fluid with high thermal conductivity is The base oil must not contain components that promote
expected to lower the temperature of a bearing more quickly corrosion. Corrosion tests usually involve bringing the oil
than a fluid of low thermal conductivity. Most mineral oils sample in contact with a metal, such as copper or silver, un-
and hydrocarbon fluids, such as the polyperfluoroalkyl der controlled conditions. Discoloration of the metal,
ethers and PAOs, have very low thermal conductivity of changes in its surface condition, or weight loss reflects the
0.13 W / m K, or W m−1 K−1, relative to that of water and eth- corrosive tendency of the oil.
ylene glycol at 0.6 and 0.42 W / m K, respectively. However,
polyglycols and silicones with a little higher thermal conduc-
Performance Additives
tivities of 0.15 and 0.14 W / m K are slightly better than the It is always implied that the lubrication involves the use
hydrocarbon oils. The quick transfer of heat from a hot spot of lubricating oil, usually formulated by blending the appro-
in a bearing to the lubricant can control overheating of the priate quality lubricant base stock共s兲 and additives. Inciden-
bearing and minimize damage. tally, for some applications, such as automotive engine oils
Thermal capacity, or heat capacity, is the heat required and transmission fluids, the additives manufacturer sup-
to raise the temperature of a body by one unit of tempera- plies additives as a package that meets certain industry
ture, i.e., 1 ° K. Specific heat is the ratio of the thermal capac- specified testing criteria. In other cases, such as metalwork-
ity of the substance to that of water at 15° C. Specific heat is a ing fluids and greases, the additives supplier furnishes indi-
function of the fluid structure and the density. Higher values vidual additives, which the end-user adds to the base stock.
are better since they imply that the fluid can contain larger Most lubricant additives, except perhaps some viscosity
amounts of heat. With respect to this parameter, hydrocar- modifiers and pour point depressants comprise an oleo-
bon oils and polyglycols are better than silicone oils. In hy- philic 共lipophilic兲 hydrocarbon group and a polar functional
drodynamic lubrication, specific heat is used to calculate group, as shown in Figure 4.4 关50兴. The polar functional
heat transfer, temperature rise, and other thermal factors in group typically contains oxygen, nitrogen, sulfur, and or
an oil film. phosphorus. With respect to the polar group strength, the
Electrical conductivity is a measure of a material’s abil- oxygen-based additives are the most polar, which are fol-
ity to conduct an electric current. This property is important lowed by the nitrogen-based additives, sulfur-based addi-
for insulating oils, where low conductivity base stocks are tives, and phosphorus-based additives. The polarity of the
needed. A variety of base fluids are used for this application, various polar functional groups follows Pauling’s electrone-
including hydrotreated heavy paraffinics, silicones, perfluo- gativity scale—the electronegativities of oxygen, nitrogen,
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CHAPTER 4 䊏 LUBRICANT ADDITIVES 105
Oil Thickening
Oil thickening can result from the combination of the oxida-
tive degradation of the lubricant and the accumulation of the
insolubles 关194兴. Autoxidation of the lubricant, accelerated
near the oxidation inhibitor depletion stage, can lead to oxy-
genated products which, through polymerization, can cause
Fig. 4.10—Formation of deposit precursors. a viscosity increase 关192兴. Contaminant-related thickening
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CHAPTER 4 䊏 LUBRICANT ADDITIVES 109
Oxidation Inhibitors
Since both the base fluid and the additives that comprise the
lubricant are organic in nature, they are susceptible to oxida-
tion. There are base fluids that either do not contain any
carbon-hydrogen bonds, such as perfluoropolyethers, or
contain carbon-hydrogen bonds that are not easily oxidiz-
able as in the case of poly共phenyl ether兲s. They are used in
specialty applications involving extreme temperatures. See
Synthetic Fluids, Chapter 3, for the pertinent discussion. It is
obvious that with respect to oxidation not all base fluids are
alike. As stated previously, base fluids are mineral, synthetic,
Fig. 4.13—U.S. diesel piston designs—old versus current. or biological in origin. Each type has a stable threshold, be-
yond which the rate of oxidation increases rapidly and stabi-
lizers, or oxidation inhibitors, are needed to retard oxida-
ronmental 共emissions兲 concerns, there is a consolidated ef- tion. With respect to oxidative stability, synthetic oils are the
fort by the OEMs and the lubricant marketers in the United most stable and vegetable oils are the least stable, and min-
States, Europe, and Japan to minimize the formation and re- eral oils fall between the two.
lease of the particulates into the environment. One strategy Most lubrication applications expose lubricants to oxy-
to achieve this goal is by the use of a lower thickness oil film. gen in some manner, the exposure being more intensive
This strategy is quite effective except that beyond a certain when used to lubricate an internal combustion engine. This
limit, the oil film thickness is ineffective for proper lubrica- is because the engine’s lubrication environment contains all
tion and the ring/liner scuffing problem initiates. Lubricant the key elements that increase the rate of oxidation. These
volatility is another important factor responsible for the in- include the following:
creased oil consumption. Lighter base oils, used in formulat- 1. The presence of the ample amount of oxygen since the
ing multi-grade diesel oils, not only contribute to the forma- engine is open to the atmosphere, via the combustion
tion of a less effective lubricating film but can also readily chamber.
leak past the piston rings and burn 关195兴. The current piston 2. High ambient temperatures because of the close prox-
design has been developed to minimize the formation of the imity to the flame.
lubricant-related particulates in the diesel engine emissions. 3. The presence of NOX.
Top piston ring in these pistons drags less oil into the com- 4. The presence of metals and their ions.
bustion chamber. This is achieved by decreasing the “crevice These factors not only facilitate the attack of oxygen on
volume” between the piston and the cylinder liner. These pis- the hydrocarbon molecules that make up the lubricant, but
tons have less cut back crowns and smaller first lands. The they also exponentially increase the reaction rate. The reac-
older and current piston designs are shown in Fig. 4.13. tion sites in hydrocarbon molecules, in order of decreasing
ease of attack, are benzylic, allylic, tertiary alkyl, secondary
Ring Sticking alkyl, and primary alkyl hydrogens. The result is the forma-
The major cause of ring sticking is the formation of deposits tion of peroxy or other free radicals. The mechanism of oxi-
in the piston grooves. The consequence is a loss of oil seal dation is illustrated in Figs. 4.10–4.12 and Fig. 4.14. Oxida-
which not only favors blow-by but also leads to poor transfer tion proceeds in three stages: the initiation stage, the
of heat from the piston to the externally cooled cylinder wall. propagation stage, and the termination stage 关196兴. During
This is quite serious because this can cause nonuniform the initiation stage, oxygen reacts with the fuel and the lubri-
thermal expansion of the pistons, hence a loss of compres- cant to form alkyl free radicals, see Fig. 4.14, Eqs. 14 and 15.
sion and ultimately to engine seizure. During the propagation stage, these free radicals react with
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CHAPTER 4 䊏 LUBRICANT ADDITIVES 111
trolling action. The structures of the commonly used oxida- represented by alkyl sulfides and alkyl polysulfides, react
tion inhibitors are shown in Fig. 4.21. Common hydroperox- with hydroperoxides and are converted into alkyl sulfoxides,
ide decomposers include sulfur and phosphorus-containing alkyl thiosulfinates, and alkyl sulfones, as shown in Part 1 of
compounds, such as sulfides, dithiocarbamates, phosphites, Fig. 4.22. Sulfoxides and thiosulfenates may disproportion-
and dithiophosphates. The mechanism by which the hydro- ate or arrange thermo-oxidatively to form other sulfur-
peroxide decomposers perform is shown in Fig. 4.22. Hydro- containing compounds, such as sulfonic and sulfuric acids,
peroxide decomposers convert the chain-propagating hy- which are also hydroperoxide decomposers. Figure 4.23
droperoxides into alcohols while themselves getting shows the mechanism of formation of these products from
oxidized to the higher oxidation levels. Sulfur compounds, di-t-butyl sulfides. Organic sulfides used as oxidation inhibi-
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CHAPTER 4 䊏 LUBRICANT ADDITIVES 113
tors include phenol sulfides, sulfurized and phosphosulfur- carbamates are considered multipurpose additives since
ized fats, and alkyl dithiadiazoles. Many of these compounds they provide both the oxidation control and the antiwear/
are discussed in the subsequent sections. Organic sulfides extreme-pressure properties. While these compounds are
are usually made by the reaction of an organic halide with synergistic with alkylated diphenylamines, they are expen-
sodium sulfide and removing the resulting sodium halide sive and can cause copper and lead corrosion, under certain
salt. Organic polysulfides can be made either by the reaction circumstances.
of a sodium polysulfide with an organic halide or by sulfuriz- Phenol and nonhindered alkylphenols act as hydroper-
ing an olefin at high temperature with elemental sulfur. The oxide decomposers as well and in the process they get con-
synthesis of these compounds will be covered in the latter
part of the chapter while discussing antiwear and extreme-
pressure agents. Dilauryl selenide is another hydroperoxide
decomposer that is related to the organic sulfides on account
of the selenium belonging to the same group in the periodic
table as sulfur. Its mechanism to inhibit oxidation is also via
hydroperoxide decomposition. It is made by the reaction of
lauryl chloride with dimethyl selenide. It is used as an anti-
oxidant in greases and some synthetic fluids 关165兴. Molybde-
num compounds, such as molybdenum sulfide,
molybdenum-amine complexes, and molybdenum dithio-
Fig. 4.18—Effect of metals and metal coatings on oxidation stability of oxidation-inhibited synthetic ester-based hydraulic fluid 共ASTM
D2272兲 关115兴.
verted into poly-hydroxy compounds. The manner in which phosphites. Again, these methods will be discussed in some
they take part in making hydroperoxides innocuous is detail in the latter part of the chapter.
shown in Part 2 of the Fig. 4.22. The hydroperoxide decom- Dialkyl dithiophosphoric acid derivatives are the most
posing action of the phosphorus compounds is depicted in potent of the phosphorus-based inhibitors, primarily be-
Part 3 of the Fig. 4.22. Phosphines, rarely used as inhibitors cause they inhibit oxidation both by hydroperoxide decom-
because of their toxicity, are not as effective as other phos- position and free radical scavenging mechanisms. They de-
phorus derivatives. This is because they stoichiometrically compose hydroperoxides catalytically as well as by reacting
react with hydroperoxides to form phosphine oxides, which with them to form compounds that are peroxide decompos-
lack further oxidation-inhibiting ability. Alkyl phosphites ers in their own right. Various processes involved in the oxi-
are better inhibitors because during the process of decom-
posing hydroperoxides they are converted into phosphates,
which continue inhibiting oxidation by forming acidic mate-
rials, via thermal degradation or hydrolysis. Alkyl phosphi-
tes are made either by the reaction of alcohol with phos-
phorus trichloride or by the trans-esterification reaction
involving an alcohol and a lower alkyl phosphite or hydrogen
phosphite. Alkyl phosphates are analogously made by the re-
action of an alcohol with phosphorus oxychloride in the
presence of a base or by the oxidation of trialkyl or triaryl
Fig. 4.22—Hydroperoxide decomposers—Mode of their action. Fig. 4.23—Hydroperoxide decomposition by alkyl sulfides.
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116 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
Fig. 4.27—Radical scavengers and mode of their action. catalytic action, which is represented by the cyclic sequence
in the figure.
The oxidation-controlling action of an aromatic amine
transfer. Figures 4.26 and 4.27 illustrate the mechanism of is shown in Fig. 4.30 关207兴. Despite being from the obsolete D
their performance. Hindered phenol, represented by version of the ASTM Sequence III Test, the data are still use-
2,6-di-t-butyl-4-methylphenol in Fig. 4.26 transfers its phe- ful in demonstrating the effectiveness of an arylamine in
nolic hydrogen to the alkoxy free radical and converts it into controlling the oxidation-related viscosity increase. The
an alcohol. The phenoxy-free radical that results from this 10W-30 base formulation containing 8 % shear-stable poly-
process is incapable of propagating oxidation because of be- methacrylate viscosity modifier and 5 % performance pack-
ing sterically hindered. However, this free radical either rear- age shows a several hundred percent viscosity increase after
ranges to form the benzylic free radical 4, which dimerizes to 30 hours of the 64-hour test. However, when 0.5 % of the ary-
form the diphenoxyethane 5, or reacts with an alkylperoxy lamine oxidation inhibitor was added to the formulation, the
free radical to form the quinone methide 6. The diphenoxy- viscosity increase was only 90 %, which is well within the
ethane 5 still contains the hindered phenol functional group specified 375 % limit for the test 关207兴. Alkylated arylamines
and the benzylic hydrogens. Therefore, it can continue to act are synthesized by the reaction of an amine, such as diphe-
as an oxidation inhibitor. 2,6-Di-t-butyl-4-methylphenol, nylamine, with an olefin, in the presence of a Lewis acid—
also called butylated hydroxytoluene 共BHT兲, is made by the aluminum chloride being a common one. Alkylated phe-
reaction of p-cresol and isobutylene in the presence of a nothiazines are a related class of multifunctional oxidation
Lewis or a Brönsted acid 关203兴. The hindered phenol substi- inhibitors. In addition to being an arylamine, they contain a
tuted methyl propionate ester is prepared by the base- sulfide group, which imparts them the ability to inhibit oxi-
catalyzed reaction of 2,6-di-t-butylphenol with methyl acry- dation via hydroperoxide decomposition as well. However,
late. This can be converted into other esters by the base-
catalyzed trans-esterification reaction 关204,205兴. The
synthesis of these materials is shown in Fig. 4.28. Thioglycol
propionate ester in the figure contains both the hindered
phenol moiety and the sulfide functional group. This means
that it can act both as a hydroperoxide decomposer and a
free radical scavenger and there are claims to its superior
oxidation performance in engine oils 关206兴. Other additives
that perform via free radical scavenging are shown in Fig.
4.29.
The mechanism of oxidation inhibition by arylamines,
which inhibit oxidation by free radical scavenging, is pre-
sented in Fig. 4.27. The newly formed free radicals are
resonance-stabilized and hence cannot start the new oxida-
tion chains. However, they do react with hydroperoxides and
peroxy free radicals to form the nitroxy free radical 7, which
is also a potent inhibitor. This is because it has the ability to
terminate a large number of oxidation chains through a Fig. 4.29—Other commonly used oxidation inhibitors.
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118 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
refined oil 共Curve B兲, but observe its dramatic response to the
sulfur-phosphorus inhibitor as indicated by the slopes of the
Curves F and I. Metal deactivators, another class of oxida-
tion inhibitors, are used to control oxidation in the presence
of the metal ions. These inhibitors, commonly used in fuels,
Fig. 4.30—Oxidative viscosity control by an arylamine in ASTM se- perform by forming complexes with metal ions and taking
quence IIID Test 关207兴. them out of the chain reaction. Ethylenediaminetetraacetic
acid derivatives and N,N-disalicylidene-1,2-
propanediamine represent the most popular members of
their hydroperoxide decomposing action is limited since the
this class. Their structures are provided in Fig. 4.32. Other
sulfide group is aromatic and after reacting with two moles
derivatives that are used in this application include lecithin,
of hydroperoxides and getting converted into sulfone, its ac-
heterocycles, such as thiadiazole, imidazole, and pyrazole,
tivity subsides. This is because the aromatic sulfides and sul-
and citric and gluconic acid derivatives 关4兴.
fones lack the -hydrogen atoms, which enhance the activity
Copper ions promote oxidation just like the other transi-
of the aliphatic sulfides via -elimination, to form the further
tion metal ions. They do this by forming free radicals both
hydroperoxide decomposing sulfinic and sulfenic com-
directly and by delivering the molecular oxygen in a more re-
pounds. This is shown in Fig. 4.23. Alkyl phenothiazines are
active state. They in addition catalyze the decomposition of
made by the reaction of diphenylamine with sulfur, followed
hydroperoxides to free radicals. These reactions are shown
by alkylation.
in Eqs. 30–33 of Fig. 4.33. Copper ions also exhibit excellent
Transition metals can act both as oxidation initiators
oxidation-inhibiting ability 关208兴. They remove free radicals
共promoters兲 and oxidation inhibitors, depending upon their
by converting them into ions which do not have the ability to
oxidation state 关196兴. They act as promoters if they facilitate
take part in the oxidation process. The reactions leading to
the formation of the free radicals, and they act as inhibitors,
the free radical removal are represented in Eqs. 34–36 of Fig.
if they remove the free radicals from the oxidation process
4.33. The positive effect of copper stearate in diminishing
关208兴. For example, heavy metals, such as iron and lead, and
the rate of oxidation of tetralin catalyzed by iron stearate has
their salts are well known as oxidation promoters 关199,209兴;
been reported in Ref. 关198兴. Tetralin 共tetrahydronaphtha-
see Eq. 25 in Fig. 4.14. This is appropriately depicted in Fig.
lene兲 is a bicyclic hydrocarbon that contains an aromatic
4.31 关4兴. The presence of copper, iron, and even calcium ions
greatly increases the rate of the oxygen uptake to a varying
degree. Compare the slopes of the Curves C, D, and E, which
are for lubricants that contain metals, with the slope of the
Curves B and A, which are for metal-free oils. The difference
between Oil A and Oil B is the degree of refining. The use of
an efficient oxidation inhibitor, such as zinc dialkyl dithio-
phosphate, does help control the oxygen uptake. Compare
the slopes of the Curves G, H, and F, for oils that contain in-
hibitors, with those of the Curves C, D, and E, for oils that
contain only the metal ions. The figure also depicts the effect
of the degree of refining on the oxidation of the oil and its
response to oxidation inhibitors. Highly refined oil 共Curve A兲
takes up oxygen at a somewhat slower rate than the normally Fig. 4.32—Metal deactivators.
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CHAPTER 4 䊏 LUBRICANT ADDITIVES 119
Dispersants
Dispersants are metal-free additives that suspend oil-
insoluble resinous oxidation products and particulate con-
taminants in the bulk oil. By doing so, they minimize sludge
formation, particulate-related abrasive wear, lubricant vis-
cosity increase, and oxidation-related deposit formation.
Dispersants perform these functions by doing the following
关187兴:
• They include polar contaminants in their micelles.
• They associate with colloidal particles to prevent aggre-
gation to larger particles so as to prevent them from Fig. 4.39—Mechanism of soot-resin-additive interaction 关191兴.
separating out of oil.
• They suspend aggregates, if they form, in the bulk lubri-
combines with the oxygenated species, oil, and water 关191兴.
cant.
The local piston temperatures and the lubricant’s ash-
• They modify soot to minimize its aggregation and hence
producing tendency have a profound effect on the composi-
prevent soot-related oil thickening.
tion of the carbon deposits. High temperatures and the lubri-
• They lower the surface/interfacial energy of the polar cants with high metals content primarily produce deposits
products to decrease their tendency to adhere to with high residue and low organic content 关216–219兴. Metals
surfaces. are the main source of ash, which is a part of some deposits.
The undesirable polar materials, generically described Basic detergents contain metals and hence are considered to
as dirt, are a consequence of the oxidative degradation of the make a contribution. Zinc dialkyl dithiophosphates also
lubricant and or thermal decomposition of the thermally la- contribute towards deposits, but only slightly, because their
bile lubricant additives, such as extreme-pressure/antiwear amount in lubricants is much smaller than that of the deter-
agents; and the reaction of the resulting chemically reactive gents.
species, such as carboxylic acids, with the metal surfaces or Because of the low oil-solubility, resin tends to separate
wear debris in the engine. The lubricant consists of three out as amber lacquer on hot piston surfaces. If oil contains
components: the base fluid, the additives, and a viscosity soot, soot separates with resin to form “resin-coated soot par-
modifier, in the case of a multi-grade lubricant. On account ticles,” which appear as black lacquer. As the soot level in-
of being organic, all three are susceptible to attack by oxy- creases, more and more soot associates with the resin to
gen, resulting in the formation of the highly oxygenated po- form “soot-coated resin particles.” These events are shown in
lar materials. Parts A and B of Fig. 4.39. The size and the composition of
In gasoline-fueled engines, the formation of these mate- these particles do not allow them to adhere to metal sur-
rials is catalyzed by nitrogen oxides, or NOX. NOX results faces, but they have the propensity to collect in the areas of
when nitrogen and oxygen present in the air-fuel mixture re- the low oil flow, such as piston grooves, as deposits.
act at high temperatures 共1370° C兲. NOX can react with hy-
drocarbons of the fuel and the lubricant to form nitrate es- Deposit Control by Dispersants
ters 关192,215兴, shown in Fig. 4.11, which along with the As stated before, resin and soot are of low lubricant 共hydro-
hydroperoxides generated from the direct oxidation of the carbon兲 solubility, with a propensity to separate on surfaces
lubricant thermally decompose to form carbonyl com- and form varnish, lacquer, and carbon deposits. The separa-
pounds, such as aldehydes and ketones. In the presence of tion tendency of these materials is a consequence of their
bases or acids, these compounds undergo aldol-type con- particle size. Small particles are more likely to stay in oil
densation to form oligomeric or polymeric materials, which than large particles. Therefore, resin and soot particles,
further oxidize to form oxygenates. These high molecular which are the two essential components of all the deposit
weight oxygenates are of sticky consistency and the term forming species, must grow in size via agglomeration, prior
resin is often used to describe them. to separation. Growth occurs either because of the dipolar
In diesel-fueled engines, soot from the combustion interactions, as is the case in resin molecules, or due to the
chamber is the key component of the carbon and lacquer de- adsorbed polar impurities, such as water and oxygen, as is
posits, which occur on pistons, and sludge. As stated in an the case in soot particles. Alternatively, soot particles get
earlier part of this chapter, soot combines with resin to form caught in the sticky resin, which is shown in Parts A and B of
lacquer and carbon deposits. In general, lacquer is rich in Fig. 4.39.
resin, and carbon is rich in soot. Sludge results when soot Dispersants suppress the agglomeration of the resin and
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122 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
Dispersant Structure
A dispersant molecule consists of three distinct structural
features: a hydrocarbon group, a polar group, and a connect-
ing group, or a link. These are graphically depicted in Fig.
4.43. The hydrocarbon group is polymeric in nature and de-
pending upon its molecular weight, dispersants can be clas-
sified into polymeric dispersants and dispersant polymers.
Polymeric dispersants are of lower molecular weight than
the dispersant polymers. The molecular weight of polymeric
dispersants ranges between 3000 and 7000 g / mol as com-
pared to the dispersant polymers that have a molecular
weight of 25,000 g / mol and higher. While a variety of poly-
olefins, such as polyisobutylene, polypropylene, polyalpha-
olefins, and mixtures thereof, can be used to make polymeric
dispersants, polyisobutylene-derived dispersants are the
most common. The primary reasons for polyisobutylene to
be the olefin of choice are its thermal stability, large volume
availability in the proper molecular weight range, and its
relatively low cost. The desired number-average molecular
Fig. 4.42—The mechanism of electrostatic stabilization. 共A兲 by ion- weight 共Mn兲 of polyisobutylene to make polymeric dispers-
ized dispersant; 共B兲 by un-ionized dispersant.
ants ranges between 500 and 3000 g / mol, with an Mn of
1000– 2000 g / mol being typical 关220兴. In addition to the Mn,
breakdown, thereby losing its ability to associate with and other polyisobutylene parameters, such as molecular weight
suspend potentially harmful products. Poor oxidative stabil- distribution, the length and the degree of branching, and the
ity translates into the dispersant molecule contributing to- reactivity are also important in determining the overall ef-
wards deposit formation. Improved shear stability is impor- fectiveness of a dispersant. However, despite its strengths,
tant, especially in the case of high molecular weight the polyisobutylene use in dispersants has its limitations.
dispersant polymers, also called dispersant viscosity modifi- For example, achieving high-temperature viscosity without
ers. Improved low-temperature properties of a lubricant are adversely affecting the cold-cranking viscosity with poly-
desired for many reasons. These include the ease of cold isobutylene is a minor challenge. The other concern that is
cranking, good lubricant circulation, and fuel economy. driving the new dispersant research, including the use of the
Base oil suppliers have developed a number of ways to new olefins, is to develop technology that is chlorine free, has
achieve these properties. The methods they use include a lower cost, and meets or exceeds the ever-changing perfor-
isomerization of the base stock hydrocarbons via hydroc- mance specifications for the future engine oils. With respect
racking and the use of special synthetic oils as additives. Dis- to the use of the new olefins, any olefins that have the proper
persants must have no or low residual chlorine because of its molecular weight range and reasonable reactivity are at
role in dioxin formation, which has a negative effect on pub- present being explored. Incidentally, in the ensuing discus-
lic welfare. Noncorrosiveness to copper and lead is impor- sion the term dispersant pertains to polymeric dispersants.
tant because of the use of these metals in bushings, bearings, Substances that are obtained via a polymerization reac-
cam followers, and oil coolers in diesel engines. Standard tion, especially those made by the use of an acid catalyst or a
test methods ASTM D6594 and ASTM D5968 are used to de- free radical initiator, often contain molecules of different
termine diesel engine lubricant’s tendency to corrode alloys sizes. Molecular weight distribution, or the polydispersity
of lead and copper. Elastomer seal compatibility, especially index, is commonly used to assess the heterogeneity in the
those made from Viton®, is desired. Since dispersant is one molecular size. Polydispersity index is the ratio of the
form. However, if the hydrocarbon chain in the dispersant is conversion 关231,232兴. Trilene® is another hydrocarbon the
too small, the lubricant solubility greatly suffers. Because of use of which has been reported to introduce the hydrocar-
this, the low molecular weight components in polyisobuty- bon group in dispersants 关233,234兴. Trilene® is a liquid
lene are not desired. This is despite their higher reactivity. ethylene-propylene-diene rubber 共EPDM兲 that is available
These must be removed, which is achieved by distillation. Al- from Uniroyal Chemical Co.
ternatively, one can minimize the formation of these compo- As mentioned earlier, dispersant polymers are derived
nents by decreasing the amount of the catalyst or by lower- from ethylene-propylene copolymers, styrene-butadiene co-
ing the polymerization reaction temperature, or both. polymers, polyacrylates, polymethacrylates, and styrene-
A new class of dispersants derived from esters. Ethylene-propylene rubbers are synthesized by
ethylene/␣-olefin copolymer with a number-average molecu- Ziegler-Natta catalysis 关235兴. Styrene-butadiene rubbers are
lar weight 共Mn兲 of 300 to 20,000 g / mol has also been re- synthesized via anionic polymerization. Polyacrylates and
ported, primarily by the Exxon scientists 关229,230兴. Such polymethacrylates are synthesized via polymerization of the
dispersants are claimed to have superior low and high- monomers using the free radical initiators. Styrene esters
temperature viscometrics to those of the polyisobutylene- are made by the reaction of styrene-maleic anhydride co-
derived materials. Polyalphaolefin derived dispersants are polymer or styrene-maleic anhydride-alkyl acrylate terpoly-
also being explored, presumably because of their superior mer with alcohols, usually in the presence of a proton acid,
dispersancy, good low-temperature performance, and better such as sulfuric acid or methanesulfonic acid, catalyst. Since
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126 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
Fig. 4.49—New acylating groups for dispersants. Fig. 4.51—Amines and alcohols used to synthesize dispersants.
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128 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
polyamines contain piperazines as a by-product. If one ex- However, the tertiary amine can make a salt if there is free
amines the structures of the various amines, one can see that carboxylic acid functional group present in the molecule, as
they contain primary amino groups, secondary amino is the case in amide/carboxylic acid. These reactions are
groups, and tertiary amino groups. Each type of amino shown in Figure 4.53. New high molecular weight amines
group has different reactivity towards alkenylsuccinic anhy- derived from phosphoric acid catalyzed condensation of the
dride. Primary amino group reacts with the anhydride to polyhydroxy compounds, such as pentaerythritol, with poly-
form a cyclic imide, the secondary amino group reacts with alkylene polyamines, such as triethylenetetramine, are
the anhydride to form an amide/carboxylic acid, and the ter- known 关267兴. These amines are claimed to form high TBN
tiary amine does not react with the anhydride at all 关266兴. 共total base number兲 dispersants with low free amine content
and better engine test performance than dispersants made
from the conventional polyamines.
Polyhydric alcohols that are commonly used to make
dispersants include trimethylolpropane, tris共hydroxymethy-
l兲aminomethane, and pentaerythritol, all of which are base
catalyzed reaction products of formaldehyde, either with an-
other aldehyde or with nitromethane. Reaction mechanisms
for the formation of trimethylolpropane and pentaerythritol
were provided in Figs. 3.22 and 3.23 in the Synthetic Esters
section of the Synthetic and Biological Base Stocks chapter.
Hence, here we present only the synthetic sequence for tr-
is共hydroxymethyl兲aminomethane 共THAM兲, see Fig. 4.54.
The reaction mechanism in this case is analogous to that of
the trimethylolpropane formation. That is, it involves the
base-catalyzed addition of three moles of formaldehyde to
nitromethane. The resulting nitro derivative is then reduced
to the amino compound 关268兴.
Imide and ester dispersants are made by the reaction of
Fig. 4.53—Amine-anhydride reaction products. the polyamines and the polyhydric alcohols with alkenylsuc-
Dispersant Properties
Dispersant properties that define dispersant performance
include dispersancy, thermo-oxidative stability, viscosity
characteristics, and elastomer seal compatibility. These
properties in turn are a function of a dispersant’s structural
features—the hydrocarbon chain, the connecting group, and
the polar functional group; individually and in combination.
Please note that our primary interest is in assessing perfor-
mance of the dispersant in engine oils where they find major
use.
Dispersancy
Dispersancy pertains to a dispersant’s ability to suspend by-
products of combustion, such as soot, and of lubricant deg-
radation, such as resin, varnish, lacquer, and carbon depos-
its. Dispersancy of a dispersant depends upon all three of its
tional group, and in imide and ester dispersants, the succin- Thermal and Oxidative Stability
imide, succinate, and phosphonate functional groups, are All three components of the dispersant structure also deter-
polar, the same as the amine and the alcohol-derived portion mine its thermal and oxidative stability, the same as dispers-
of the molecule. The polarity is a consequence of the elec- ancy. The hydrocarbon group can oxidize in the same manner
tronegativity difference between carbon, oxygen, nitrogen, as the lubricant hydrocarbons to form oxidation products
and phosphorus atoms. The greater the electronegativity dif- that can contribute towards the deposit forming species
ference, the higher is the polarity. This implies that groups 关55,196兴. This was described earlier on the nature of deposits
that contain phosphorus oxygen bonds are more polar than and the mode of their formation. While the rate of oxidation
those containing carbon oxygen bonds, carbon nitrogen of largely paraffinic hydrocarbon groups, such as polyisobu-
bonds, and the carbon phosphorus bonds. The electronega- tyl group, is quite slow, those that contain multiple bonds,
tivity difference for such bonds is 1.4, 1.0, 0.5, and 0.4, re- such as polyisobutenyl, and the benzylic groups, it is quite
spectively 关299兴. However, since the dispersants have many high. The benzylic functional group is present in styrene-
butadiene and styrene-ester derived dispersant polymers,
bonds with various combinations of atoms, the overall polar-
and in Mannich dispersants. Purely paraffinic hydrocarbon
ity in a dispersant and its ability to associate with the polar
groups that contain tertiary hydrogen atoms, such as
materials is not easy to predict. Because some of the materi-
ethylene-propylene copolymers, oxidize at a faster rate than
als with which the dispersant associates are acidic, such as
those that contain only primary and secondary hydrogen at-
carboxylic acids derived from lubricant oxidation, the pres-
oms. Styrene-isoprene derived materials contain both ben-
ence of an amine nitrogen is an advantage because of its ba-
zylic and tertiary hydrogen atoms. This implies that highly
sic character. Therefore, in certain gasoline engine tests, the
branched alkyl groups, such as polyisobutyl and poly-
nitrogen dispersants are superior to the ester dispersants. isobutenyl, have a higher susceptibility towards oxidation
Ester dispersants, on the other hand, are usually superior in than linear or unbranched alkyl groups. Dispersant poly-
diesel engine tests because of their higher thermo-oxidative mers with built-in oxidation-inhibiting moieties are known
stability. Mannich dispersants are good low temperature dis- in the literature 关277,296兴. The polar moiety in a dispersant
persants; hence they are typically used in gasoline engine that is amine-derived is also likely to oxidize at a faster rate
oils. than the oxygen-derived moiety. This is because of the facile
As mentioned in the earlier part of the chapter, commer- formation of the amine oxide functional group on oxidation.
cial polyisobutylenes have a molecular weight distribution. Such groups are known to thermally undergo -elimination
This leads to dispersant structures of varying sizes, hence 关306兴, called the Cope Reaction, to form an olefin. These ole-
varying molecular weights. An optimum ratio between the fins can polymerize to form polymeric deposit precursors.
molecular weight of the hydrocarbon chain and that of the From a thermal stability perspective, the hydrocarbon
polar functional group 共nonpolar to polar ratio兲 is a prereq- group in the case of high molecular weight dispersant poly-
uisite for good dispersancy. If a dispersant composition has mers, such as those derived from OCPs, is more likely to frag-
an excessive amount of components with low molecular ment than the hydrocarbon groups present in the low mo-
weight 共short兲 hydrocarbon chains, its associating ability lecular weight polymers. Dispersants based upon
with the polar species increases but its oil solubility suffers. 1000 to 2000 g / mol molecular weight polyisobutylenes are
This is likely to deteriorate its dispersancy, especially after relatively stable, except at very high temperatures that are
associating with the polar impurities, which will increase its experienced in some engine parts, such as near the top of the
polar to non-polar ratio. Such structures in dispersants are piston 关21,23兴. Thermal breakdown of the oxidized amine
therefore undesired. These can be minimized either by using polar group was already mentioned in the previous para-
polyolefins of low polydispersity index 关300兴, controlling the graph.
formation of the low molecular weight components, remov- Chemical reactivity of certain dispersants towards wa-
ing such components via distillation, or post reacting with ter and other reactive chemicals present in the lubricant for-
mulation or generated during use is an additional concern.
another reagent, preferably with a large hydrocarbon group.
The most likely reaction site is the connecting group. The
Polyolefins of low polydispersity index 共艋2.0兲 are available
common connecting groups are amide and imide in amine-
from British Petroleum 共BP兲 and Exxon Chemical Company.
derived dispersants and ester in the alcohol-derived dispers-
Controlling the formation of the low molecular weight com-
ants. All three can hydrolyze in the presence of water 关307兴,
ponents is exemplified by the use of boron trifluoride cata-
but at different rates. Esters are easier to hydrolyze than
lyst for making alkylphenols instead of aluminum chloride amides and imides. The hydrolysis is facilitated by the pres-
that has the tendency to fragment polyisobutylene. Remov- ence of bases and acids. Basic detergents are the source of
ing the lower molecular weight components, although not the metal carbonate and metal hydroxide bases, which at
easy, is possible at the precursor stage, which is prior to re- high temperatures can cause saponification reaction or cata-
acting with the alcohol or the amine. A number of reagents lyze hydrolysis reaction. Additives, such as zinc dialkyl
can be used for the post reaction 关300兴. Hydrocarbon post- dithiophosphates, are a source of strong acids that result
treatment agents include polyepoxides 关302兴, poly- when these additives hydrolyze, thermally decompose, or
carboxylic acid 关303兴, alkylbenzenesulfonic acids 关304兴, and oxidize. The fate of the ester, amide, and imide type dispers-
alkenylnitriles 关305兴. Whenever post reacted dispersants are ant polymers, such as those derived from polyacrylates,
used in engine oils, improved dispersancy, viscosity index polymethacrylates, and styrene ester substrates, is the same.
credit, improved fluorocarbon elastomer compatibility, hy- Some OCP-derived dispersant polymers, such as those ob-
drolytic stability, and shear stability are often claimed. tained by grafting of the monomers, 2- or 4-vinylpyridine
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CHAPTER 4 䊏 LUBRICANT ADDITIVES 133
and 1-vinyl-2-pyrrolidinone 关276,280兴, do not suffer from • Choosing the optimum olefin to maleic anhydride molar
this problem since they do not contain easily hydrolyzable ratio 关311兴.
groups. Reactivity towards other chemicals present in the • Selecting the type and the amount of the polyamine
formulation is again prevalent in the case of the ester- used.
derived dispersants. Reaction with metal containing addi- In dispersant polymers, the viscosity balance can be
tives, such as detergents and zinc dialkyl dithiophosphates, achieved by selecting a polymer of the correct molecular
can occur after hydrolysis to form the metal salts. This can weight and branching, and a suitable pendent group. Dis-
destroy the polymeric structure of the dispersant and hence persant polymers derived from medium molecular weight,
its effectiveness. Some formulations contain amines or their highly branched structures and ester type pendent groups
salts as corrosion inhibitors or friction modifiers. Depending are best suited for use as additives. Examples include poly-
upon the molecular weight and the ambient temperature, acrylate, polymethacrylate, and styrene ester-derived dis-
these can displace the polyol or sometimes the polyamine, persants. These additives not only act as viscosity modifiers
thereby again altering the dispersant structure, hence the and dispersants; they also act as pour point depressants,
dispersant properties. thereby improving the low-temperature properties of the lu-
Viscosity Characteristics bricant.
The amount of dispersant in automotive engine oils typically A number of patents pertaining to dispersants with bal-
ranges between 3–7 % by weight 关279兴, making it the highest anced high-temperature viscosity and low-temperature
among additives. In addition, the dispersant is the highest properties have been reported in the patent literature 关312–
molecular weight component except the viscosity improver 315兴. A Mannich 共alkylphenol兲 dispersant, derived from
关308兴. Both these factors can alter some physical properties, ethylene/1-butene polymers of Mn 1500–7500, has been
such as viscosity, of the lubricant. A boost in the viscosity of a claimed to possess both improved dispersancy and the pour
lubricant at high temperatures is desired but at low tempera- point 关312兴. Another patent claiming the synthesis of a dis-
tures it is a disadvantage. At high temperatures, the lubri- persant with superior dispersancy and pour point depress-
cant loses some of its viscosity 关4兴, hence its film-forming ing properties has also been issued 关313兴. The dispersant in
ability, resulting in poor lubrication. Maintaining good high- this patent is based upon the reaction of the maleic
temperature viscosity in a lubricant is therefore imperative anhydride/lauryl methacrylate/stearyl methacrylate terpoly-
in order to minimize wear damage. This is usually achieved mer with dimethylaminopropylamine and a Mannich base,
by the use of the polymeric viscosity modifiers 关50,226兴. obtained by reacting N-aminoethylpiperazine, paraformal-
Some dispersants, especially those that are based on high dehyde, and 2,6-di-t-butyl phenol. A number of patents de-
molecular weight polyolefins which have been oversucci- scribe the use of ethylene/␣-olefin/diene inter-polymers to
nated also partly fulfill this need 关243兴. Hence, in this case the make dispersants 关314–316兴. These dispersants are claimed
amount of the polymeric viscosity modifier necessary to to possess excellent high-temperature and low-temperature
achieve specific high-temperature viscosity is reduced. Un- viscosities, as defined by VR1 / VR ratio. Here VR1 pertains to
fortunately, dispersants that provide a viscosity advantage the dispersant and VR pertains to the precursor, such as
lead to a viscosity increase at low temperatures also. The alkylphenol or alkenylsuccinic anhydride. VR1 is the ratio of
low-temperature viscosity requirements for engine oils have the −20° C cold cranking simulator 共CCS兲 viscosity 共cP兲 of a 2
two components: cranking viscosity and pumping viscosity % solution of the dispersant in a reference oil and the 100° C
关309兴. Cranking viscosity is an indication of how easily the kinematic viscosity 共cSt兲 of the dispersant. VR is the ratio of
engine will turn over in extreme cold weather conditions. the −20° C cold cranking simulator 共CCS兲 viscosity 共cP兲 of a 2
Pumping viscosity is the ability of the lubricant to be % solution of the precursor in the reference oil and the
pumped at low temperatures to reach the various parts of an 100° C kinematic viscosity 共cSt兲 of the precursor. The values
engine. For cold weather operation, low to moderate crank- of 2.0 to 3.9 for VR and VR1 and of less than 1.11 for the
ing and pumping viscosities are highly desirable. While VR1 / VR ratio are considered suitable for balanced low- and
pumping viscosity and the pour point can be lowered by the high-temperature viscosities.
use of additives, called the pour point depressants 关21,226兴, Seal Performance
lowering the cranking viscosity is not easy. The use of the Seals in automotive equipment are used for many purposes,
pour point depressants is only effective in paraffinic base the most prominent of which are to have an easy access to
stocks, where these additives help suspend wax in a finely the malfunctioning parts to perform repair and to minimize
crystalline form. Base oil manufacturers therefore use a contamination and the loss of lubricant. A variety of poly-
number of other strategies to develop base oils with good meric materials is used to make seals. These include fluo-
low-temperature properties. These include carefully blend- roelastomers, nitrile rubber, polyacrylates, and polysilox-
ing the selected base oils, isomerization via hydrocracking, anes 共silicones兲. Maintaining the integrity of the seals is
and the use of the special synthetic oils as additives. An ideal critical, otherwise the lubricant will be lost and wear damage
polymeric dispersant must provide high-temperature vis- and equipment failure will occur. Seals fail in a number of
cosity advantage, without adversely affecting the cold crank- ways. They can shrink, elongate, or become brittle and thus
ing viscosity of the lubricant. Dispersant polymers have the deteriorate. The damage to elastomer seals is assessed by
same requirement. Good high-temperature viscosity to soaking the elastomers in the lubricant for a prolonged pe-
cranking viscosity ratio in polymeric dispersants can be riod of time and examining the change in volume, hardness,
achieved by taking the following actions. and tensile strength; and the tendency to elongate and rup-
• Carefully balancing the type and the molecular weight of ture 关317兴. Two primary mechanisms by which the seal dam-
the hydrocarbon chain 关310兴. age can occur include abrasion due to particulate matter in
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134 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
the lubricant and the attack of the various lubricant compo- persants are used both in gasoline and diesel engine oils, but
nents on the seals. The lubricant-related damage can occur the use of the alkylphenol-derived dispersants, that is, of the
when some of its components diffuse into the seals. This will Mannich type, is limited to gasoline engine oils. Dispersant
either cause a change in the seal’s hardness, thereby leading polymers derived from ethylene-propylene rubbers, styrene-
to swelling and or elongation, or extract the plasticizer, an diene copolymers, and polymethacrylates are also used in
agent used to impart flexibility and strength to the polymeric both gasoline and diesel engine oils. Polymethacrylate and
materials. styrene ester-derived dispersant polymers are primarily used
Abrasive damage is not common since most equipment in automatic transmission fluids, power steering fluids, and,
has an installed lubricant filtration system. The lubricant- to a limited extent, in gear oils.
related damage, however, is of primary interest to us. The lu- As mentioned earlier, dispersant polymers lack suffi-
bricant is a blend of base stocks and an additive package. cient dispersancy to be used alone and hence they are used in
Certain base stocks, such as those of high aromatics content combination with the polymeric dispersants. In gasoline
or those that are of ester type, have the tendency to extract and diesel engine oils, the effectiveness of a dispersant is de-
the plasticizer because of their high polarity. Additives, on termined by its ability to disperse lamp black or used engine
the other hand, have the ability to diffuse into the seal mate- oil sludge. Laboratory screen tests, the ASTM Sequence VE/
rial and alter its properties as well as remove the plasticizer. VG, and the various diesel engine tests are used for this pur-
Among additives, dispersants are those that are most impli- pose. Figure 4.64 shows the effectiveness of a dispersant in
cated in causing the seal damage, especially to fluoroelas- controlling sludge in the Sequence VE Test 关318兴. The exhibit
tomer 共Viton®兲 seals. While in many cases, seal failure can be portrays the effect of the dispersant treat level at different
corrected by the use of additives, called the seal-swell agents, stages of the test. The treat level increases on going from left
it is wise to eliminate such damage via prevention. Elas- to right and the stages are determined by the number of
tomer compatibility requirements are a part of ACEA’s 共Asso- hours into the test. If one examines the degree of agglomera-
ciation des Consructeurs Européens de l’Automobile兲 2007 tion 共growth兲 of the dirt particles 共indicated by dark areas兲, it
standard for engine oils and worldwide automotive trans- is clear that the particle growth is higher when the dispers-
mission and tractor hydraulic fluid specifications 关318兴. ant treat level is low, compare the left most plates in the fig-
Damage to seals is prevalent in the case of nitrogen dispers- ure with the right most plates, and in the latter parts of the
ants. In general, the higher the nitrogen content, the greater test, compare the first row plates with the last row plates. The
the seal problems 关317兴. Rationally, these problems occur
most desirable performance is depicted by the right most
due to the presence of the low molecular weight molecules in
plate at the end of the test 共288 h兲, which signifies the dis-
the dispersant. These include free amine either as such or in
persant treat of 5 %. The data in the figure clearly demon-
a labile form, such as an alkylammonium salt, or low mo-
strate the importance of the dispersant quality and quantity
lecular weight succinimides and succinamides. These mol-
in providing sustainable performance.
ecules, because of their high polarity and smaller size, are
Additives manufacturers use a variety of laboratory
more likely to diffuse into the seal material and alter its
screen tests and engine tests to evaluate a dispersant’s effec-
physical and mechanical properties 关319兴. It is believed that
tiveness. Many of the screen tests are proprietary but all are
in the case of the Viton® seals, the loss of the fluoride ions is
developed around evaluating performance in terms of a dis-
responsible for seal deterioration. Removal of the free amine
persant’s ability to disperse lamp black or used engine oil
and of low molecular weight succinimides will improve seal
sludge. The laboratory engine tests are industry required
performance. Alternatively, one can post-treat dispersants
tests and include both the gasoline engine and the diesel en-
with reagents, such as boric acid and epoxides, which will
gine tests. These are listed in the ILSAC 共International Lubri-
either make such species innocuous or hinder their diffusion
cant Standardization and Approval Committee兲, API 共Ameri-
into the seal material. Many chemical treatments of dispers-
can Petroleum Institute兲, ACEA 2007, JASO 共Japanese
ants cited above claim to improve the seal performance of
Automobile Standards Organization兲, and BIS 共Bureau of
the dispersants and engine lubricants that use them. These
Indian Standards兲 standards. Some of these standards are
reagents react with the seal damaging amines and low mo-
listed in Chapter 5 on Combustion Engine Lubricants. It is
lecular weight succinimides to make them harmless. Strate-
important to note that the U.S. Military and the original
gies other than listed above are also reported in the patent
equipment manufacturers 共OEMs兲 have their own perfor-
literature 关320–324兴.
mance requirements, which are over and above those of the
Performance Testing API. While the details of the various tests are available in
Engine oils account for almost 80 % of the total dispersant these standards and elsewhere 关318兴, the important engine
use. It includes use in gasoline engine oils, heavy-duty and tests that possibly evaluate a dispersant’s performance are
railroad diesel engine oils, natural gas engine oils, and avia- listed in Tables 4.6–4.8.
tion piston engine oils. Other applications that use these ad- As mentioned earlier in the chapter, the soot-related vis-
ditives include automatic transmission fluids, power steer- cosity increase and deposit-related factors are the primary
ing fluids, gear lubricants, hydraulic fluids, and in refinery criteria for evaluating a dispersant’s performance. Moreover,
processes as antifoulants. The dispersants of a relatively it is important to note that the neutral detergents 共soaps兲 also
lower molecular weight are also used in fuels to control in- help control deposits, such as varnish, lacquer, sludge, and
jector and combustion chamber deposits 关325,326兴. Such carbon. Therefore, besides controlling the soot-related vis-
dispersants usually contain the polyether functional group cosity increase, which is the sole domain of the dispersants,
关327兴. the deposit control is the result of a joint performance of the
Succinimide and succinate ester type polymeric dis- oxidation inhibitor, the detergent, and the dispersant. How-
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CHAPTER 4 䊏 LUBRICANT ADDITIVES 135
Fig. 4.64—The effectiveness of a dispersant in the ASTM sequence VE test 关318b兴. Reprinted with permission from the Lubrizol Corporation.
ever, in this regard the oxidation inhibitor and the dispersant fluid’s oxidative stability. Polymeric dispersants are useful in
play a more prominent role. controlling the sludge build-up 关328兴. When friction modifi-
Besides engine oils, transmission fluids are the primary cation of the transmission fluid is the goal, either the dispers-
users of the dispersants. Certain parts of the transmission ants or their precursors, such as alkenylsuccinic acids or an-
see very high temperatures, which lead to extensive lubri- hydrides, are used in combination with metal sulfonates
cant oxidation. The oxidation products, such as sludge and 关329–333兴. In many such formulations, either the borated
varnish, appear on parts, for instance, clutch housing, clutch dispersant or the borated detergent 共metal sulfonate兲, or
piston, control valve body, and oil screen components. These both, are used.
can impair the functioning of these parts. Turbohydramatic Dispersants are used in gear oils to also improve their
Oxidation Test 共THOT兲 is used to determine a transmission properties. Gear oils usually contain thermally labile ex-
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136 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
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CHAPTER 4 䊏 LUBRICANT ADDITIVES 137
Detergent Substrates
Detergents are the metal salts of organic acids, which in-
clude alkylbenzenesulfonic acids; alkylnaphthalenesulfonic
acids 关340–343兴, alkylphenols 关344–348兴, long chain ali-
phatic carboxylic acids such as natural fatty carboxylic ac- Fig. 4.66—Common olefins used in detergents.
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138 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
alkylphenol to form another bridge, and so on. One side mentioned earlier, dioxins result from the reaction of
product that is undesirable is the hyform, which is polymeric chlorine/chlorine donors with organics in the environment
material with low oil solubility. It is shown in Fig. 4.72 as me- and are a concern. The use of the elemental sulfur to make
thylene bridged alkylphenol oligomer. Figure 4.73 shows the phenol sulfides does not “suffer” from this disadvantage.
formation of alkylphenol sulfides by the use of sulfur dichlo- However, one obtains di- and tri-sulfide bridged alkylphe-
ride and Fig. 4.74 shows the formation of alkylphenol sul- nols. They result from sulfur acting as an oxidizing agent, as
fides by the use of elemental sulfur. While sulfur dichloride shown in Fig. 4.74. The tri-sulfide bridged materials are not
has the advantage of stopping the reaction at a single sulfide desirable since they can separate reactive sulfur, which is
bridge stage, it results in chlorination of the alkylphenol by
chlorine, resulting from the disproportionation of sulfur
dichloride, as shown in the boxed portion of Fig. 4.73. As
Fig. 4.73—Alkylphenol sulfide formation by the use of sulfur Fig. 4.74—Possible mechanism for alkylphenol sulfide formation
dichloride. by the use of elemental sulfur.
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CHAPTER 4 䊏 LUBRICANT ADDITIVES 141
size alkenylphosphonic and thiophosphonic acids are diaminopropane, sulfurized C16–18 ␣-olefins, Propomeen®
shown in Fig. 4.77. Please note that in this scheme and in the T/12, t-dodecyl hydroxypropyl thioether, trioctylamine,
subsequent discussion, we represent phosphorus pentasul- Tergitol® 26L-5, and didodecyl ether of ethylene glycol pen-
fide as P2S5, although in reality the solid phosphorus penta- tamer 关382兴. The structures of some of these are shown in
sulfide exists as a dimer; that is, as P4S10 with an adaman- Fig. 4.79. Alkaline earth metal salts of cyclic alkenylsuccin-
tane type structure 关380兴, as is shown in Fig. 4.78. imide with good engine test performance have also been re-
In addition to the acidic detergent substrates discussed ported. Magnesium salt was made by the reaction of alkenyl-
so far, nonacidic substrates have also been used to make de- succinimide with magnesium methoxide 关240兴.
tergents 关381,382兴. These include tallow- and oleyl-
Neutral and Basic Detergent Synthesis
The acidic detergent substrates are reacted with a metal
base, such as a metal oxide, hydroxide, or carbonate, to form
a neutral salt or a basic or overbased material. Basic materi-
als are made by the overbasing process that allows entrain-
ment of a large amount of inorganic base in a detergent in a
soluble form. Neutral salts by analogy with traditional neu-
tral carboxylates are called soaps. The base that is normally
used is derived from an alkali metal, an alkaline earth metal,
or aluminum. In general, the reaction between the organic
acid and the inorganic base is not easy, because of the poor
contact between the two reactants. This is due to the base be-
ing highly polar and most times being a solid, and the sub-
strates being relatively nonpolar. To facilitate contact and
hence the reaction between the two, a number of com-
pounds, called promoters, are used both in salt formation as
well as during carbonation or a related reaction. Common
promoters include ammonium hydroxide, low molecular
Fig. 4.77—Polyisobutenyl-phosphonic acid substrates.
Detergent Parameters
Fig. 4.84—Synthesis of neutral and basic metal sulfonates. Chemically, detergents are described by the use of a number
of parameters. These include metal ratio, percent sulfated
ash, degree of overbasing or conversion, soap content, and
detergents have a much higher base reserve. They typically total base number 共TBN兲 关184兴.
have a TBN of 200 to 500 and the base is commonly present The metal ratio is defined as the total equivalents of
as a metal carbonate. metal per equivalent of acid. The percent sulfated ash is the
The calcium-based phenate detergents are easier to ash produced when the detergent is treated with sulfuric
make than the magnesium-based phenate detergents. This is acid and burned. All organic material in the detergent burns,
because the alkylphenols are weak acids and their reaction leaving behind the metal sulfate ash. Sulfate ash results from
with magnesium oxide, a weak base, is not facile. In order to the reaction of the metal compounds with sulfuric acid ei-
make the neutral salt, the alkylphenol must be reacted with a ther directly, as in the case of metal hydroxide and metal car-
strong base, such as magnesium alkoxide. This reagent can bonate, or through oxidative degradation of the metal sul-
be prepared by the reaction of magnesium metal with an ex- fonate. Detergents are not the only additives that produce
cess of highly reactive alcohol, such as methanol. However, sulfated ash due to the reaction with sulfuric acid. Other
this method is hazardous, because of the hydrogen gas by- metal containing additives in the lubricant also contribute
product, and costly, because of the price of the magnesium towards it. Such additives include metal carboxylates and
metal. Once the neutral salt or soap formation occurs, the ex- metal dialkyl dithiophosphates, such as zinc dialkyl dithio-
cess alcohol is exchanged with an inert solvent, such as tolu-
ene or mineral oil, prior to overbasing. Alternatively, one can
use the high-temperature overbasing procedure using a low
molecular alkylphenol as a promoter 关393兴. In the case of
methylene or sulfur bridged phenols that are more acidic
than the regular alkylphenols, the reactivity towards magne-
sium oxide is not a problem. And, these compounds form
neutral and overbased magnesium salts without difficulty.
Neutral and basic calcium phenates, bridged or unbridged,
are easy to make because calcium hydroxide is a strong base;
hence it readily reacts with alkylphenols. The other acids,
i.e., alkylsalicylic acids, fatty carboxylic acids, and alk-
enylphosphonic acids react with calcium and magnesium
bases without any problems.
The synthetic sequences that are used to make common
neutral and carbonate overbased detergents are outlined in
Figs. 4.84–4.89. Sulfonate, salicylate, and carboxylate deter-
gents are commercially available as calcium and magnesium
salts and phosphonates are available as calcium salts. Some
specialty sulfonates, for example NA-SUL® BSB, are also
available as barium salts. Phenate detergents are commonly
available as calcium salts and phosphonate detergents are
available as both calcium and barium salts. Fig. 4.86—Synthesis of neutral and basic bridged metal phenates.
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146 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
Fig. 4.92—Effect of detergent concentration on exhaust port blocking and piston cleanliness in a two-stroke cycle gasoline engine 关4兴.
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CHAPTER 4 䊏 LUBRICANT ADDITIVES 149
gine oils, transmission fluids, and tractor hydraulic fluids; all cants. Because the deposit control is the joint domain of the
of which are high-volume lubricants. Detergents have major detergents and the dispersants, the tests listed in Tables
use in engine lubricants. Gasoline and diesel engine oils ac- 4.6–4.8 are applicable to detergents as well. Thiosulfate over-
count for over 75 % of the total detergent consumption. De- based materials have been tested in gear oil tests, CRC L-37
tergent treatment levels in engine lubricant formulations are and L-42. They showed good EP/anti-wear performance
fairly high, with the marine diesel engine lubricants contain- 关387兴.
ing the highest detergent amounts. This is because marine
engines use high-sulfur diesel or residual fuel, which leads to Film-forming Agents
acidic combustion products 共sulfuric acid兲. Therefore, the
Lubrication is necessary to facilitate the countermovement
lubricants for these engines need the base reserve of the “ba-
of two sliding surfaces. This function, which is usually per-
sic” detergents for acid neutralization. Of the total detergent
formed by the base oil, can be enhanced by using high viscos-
market, basic calcium sulfonates make up almost 65 %, fol-
lowed by phenates at 31 %. At the end of the year 2008, the ity oils 关397兴. As shown in Fig. 4.94, a high lubricant viscosity
sulfonate use in heavy-duty diesel engine oils may see a de- has a positive effect on the load-carrying capacity of the
cline. This is because the new heavy-duty diesel engines gears, both at low temperatures and high temperatures.
come equipped with diesel particulate filters 共DPFs兲, some of However, beyond a certain threshold temperature, the lubri-
which are sulfur intolerant. Alkenylphosphonic and alk- cant fails to form an effective film, and the friction and wear
enylthiophosphonic acid detergents also have little use in can result. The lubricant’s film-forming ability under such
modern lubricants, primarily because of the negative effect circumstances can be made more efficient by using the film-
of phosphorus on catalytic converters. As mentioned earlier, forming agents. Such agents can interact with metal sur-
the development of the basic detergents that are not derived faces either through adsorption or the chemical reaction.
from the organic acids have been reported in the patent lit- Physical adsorption, or physisorption, is a weaker associa-
erature 关381,382兴. Substrates that were used to make such tion of the additive with the metal than chemical adsorption,
detergents include organic amines and polyamines, ethers, or chemisorption, which in turn is weaker than chemical re-
and organic sulfides 共see Fig. 4.79兲. However, only alkali action. During adsorption, an additive molecule generally
metal-derived overbased materials were reported. keeps its structural integrity. In a chemical reaction, how-
A variety of proprietary and industry established tests ever, it has the tendency to lose it because it gets converted
are used to determine a detergent’s effectiveness in lubri- into new molecules. The modes of interaction of addi-
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150 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
Fig. 4.94—Load-carrying capacity versus viscosity at 10,000 r / min gear speed 关397兴.
tivemolecules with the surface are depicted in Fig. 4.95 共CAFE兲 Standards for passenger cars and light trucks. The
关398,399兴. light truck category includes pickup trucks, minivans, and
sport utility vehicles 共SUVs兲 关401兴. The CAFE Standard for
Friction Modifiers the trucks for the Model Years 2008–2011 was introduced in
The United States is the major user and the importer of en-
March 29, 2006.
ergy 关400兴, and its usage and cost are escalating, see Fig. 4.96.
Typically, only about 15 % of the energy from the fuel is
Because of this and the energy’s importance to the U.S.
converted into useful work, for example, for motion down
economy and the national security, the U.S. Government has
the road or run useful accessories, such as air conditioning.
established a number of regulations and measures to save
The remaining 85 % of the energy is lost to engine and driv-
energy. These include Corporate Average Fuel Economy
eline inefficiencies and idling. Hence, there is a great deal of
potential to improve fuel efficiency. The vehicle manufactur-
ers are using a number of strategies to improve the fuel effi-
ciency, not only to meet CAFE requirements but to surpass
them 关402兴. These technologies include alternative fuel ve-
hicles, hybrid electric vehicles, diesel-fueled vehicles, and
the energy efficient technologies 关400兴.
Alternative fuel vehicles are those that use E85 共85 %
ethanol, 15 % gasoline兲, M85 共85 % methanol, 15 % gaso-
line兲, compressed natural gas 共CNG兲, or liquefied propane
gas 共LPG兲, or any combination of these fuels. Hybrid-electric
vehicles 共HEVs兲 combine the benefits of the gasoline engines
and the electric motors, and can be configured to improve
fuel economy, increase power, and provide additional auxil-
iary power for electronic devices and power tools. Pure elec-
tric vehicles based upon fuel cell technology are not expected
to become available for public use prior to the year 2010.
Diesel engines are inherently more fuel efficient, by about
30–35 %, than gasoline engines, primarily because they use
lean fuel-air mixtures. Their use in automobiles will save en-
ergy. Previously, the use of the diesel engines in automobiles
was not common because of the issues related to their per-
formance and efficiency, exhaust emissions, vibration, and
noise. However, modern diesel engines have overcome the
performance and efficiency issues through the use of fuel in-
jection and electronic engine control technologies; and that
of the exhaust emissions by the use of the low-sulfur diesel
Fig. 4.95—Modes of additive—surface interactions 共taken from and biodiesel. Low-sulfur diesel produces less particulate
Ref. 关399兴 and modified兲. matter and is the diesel particulate filter friendly. See Chap-
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CHAPTER 4 䊏 LUBRICANT ADDITIVES 151
ter 6 on Combustion Engine Emissions. In addition, the new resources, lubricants that can provide improved fuel
engine designs come equipped with noise- and vibration- economy are becoming increasingly desirable. As a matter of
dampening systems that make them quieter and smoother. fact, fuel economy is one of the factors that is driving the new
Cold-weather starting, another chronic problem in the specifications for automotive lubricants, such as engine oils
diesel-fueled engines, has also been improved. Energy- and transmission fluids. Catalyst compatibility of the lubri-
efficient technologies for the gasoline-fueled automobiles cant is another factor.
that are presently being marketed are listed in Table 4.9 The American Petroleum Institute 共API兲 designates en-
关400兴. gine oil “Energy Conserving,” if it shows fuel economy im-
While these technologies are all well and good with re- provement over that of the standard reference oil, in the
spect to containing the fuel costs and the efforts to conserve same engine operated under controlled conditions. While
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152 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
4. Sulfurized fats and hydrocarbons. of the friction modifiers with the metal surface and the lubri-
5. Organic polymers, such as PTFE. cant, both under steady-state condition and under the influ-
6. Layered inorganics, such as graphite and molybdenum ence of shear 关409兴. The adsorption of the additive on the
disulfide. metal is a function of the additive’s polar/nonpolar ratio and
Of these, the compounds belonging to the first four the intensity of its interaction with the surface depends upon
groups are among those that are used most often. The others its reactivity. Typically, materials with a high polar/nonpolar
are used in specialty applications. Organic friction modifiers ratio have greater affinity for the surface than those with a
are long-chain molecules with a polar end group and a non- medium or low polar/nonpolar ratio. This is demonstrated
polar linear hydrocarbon chain. The polar end groups either in Fig. 4.106 by the differential rates of absorption of more
physically adsorb onto the metal surface or chemically react polar stearic acid and less polar octadecyl alcohol on copper
with it while the hydrocarbon chains extend into the lubri- and the increased adsorption of the stearic acid over time 关4兴.
cant. These chains associate with one another and the lubri- As a general rule, within the same chemical class the longer
cant to form a strong lubricant film 关408兴. This is shown in the hydrocarbon portion of the friction modifier, the lower
Fig. 4.104. Figure 4.105 illustrates the manner of interaction the friction. This is shown in Fig. 4.107 关4兴. As the molecular
VIB Fuel Economy Test. Glycerol monooleate 共GMO兲 is a group. Long and linear-chain materials reduce friction more
commonly used friction modifier and Perfad® FM 3338 is effectively than short and branched-chain materials. Also,
Uniquema’s proprietary friction modifying additive 关410兴. As fatty acids are better than fatty amides, which in turn are bet-
one can see, both GMO and Perfad® have friction coeffi- ter than fatty alcohols. Saturated acids, containing a 13 to 18
cients lower than that of the baseline oil. Note the progres- carbon chain, are generally preferred. Lower molecular
sive increase in friction with an increase in temperature for weight fatty acids are avoided because of their corrosivity.
the two additives, which was previously ascribed to desorp- Fatty acid derivatives are the most commonly used friction
tion. Figure 4.110 shows the estimated fuel economy index modifiers.
of the two additives based on the fuel economy test 关410兴. Transition metals 共molybdenum and zinc兲 salts/
Perfad® friction modifier provided a fuel economy of 2.5 %, complexes of carboxylic acids, dialkyl dithiophosphoric ac-
compared to GMO at about 2.1 %, and the base oil slightly ids, dithiocarbamic acid, and dithiophenol have been used
over 1.9 %. Similar results were obtained when this additive as friction modifiers as well. Of these, molybdenum dithio-
was tested in a European fuel economy test 关410,411兴. carbamate 共Mo-DTC兲 is the most often used friction modifier
Perfad® has the added advantage of greater oxidation stabil- in lubricants. In reality, the compounds, such as Mo-DTC,
ity since unlike GMO and other oleic acid derivatives, it has that contain sulfur perform as multipurpose additives, that
no multiple bonds. Phosphoric acid and phosphorous acid is, as friction modifiers, antiwear agents, and oxidation in-
esters that are used as friction modifiers include linear or hibitors. Mo-DTCs are usually used in combination with
fatty alcohol derivatives. Because of the phosphorus limit in zinc dialkyl dithiophosphates. This results in the formation
engine oils, the use of the phosphorus compounds is limited of a mixed dithiocarbamate/dithiophosphate salt, via an ex-
primarily to nonengine lubricants, such as gear oils and hy- change reaction, which has superior friction reducing prop-
draulic fluids. The synthesis of these materials will be de- erties. Sulfurized fats and hydrocarbons, depending upon
scribed in the extreme pressure/antiwear section. For the the structure and the molecular weight, can also act as multi-
fatty alcohol and fatty acid families, the friction-modifying functional additives. These will also be addressed in the ex-
properties are a function of the length and the structure of treme pressure/antiwear additives section. Organic poly-
the hydrocarbon chain and the nature of the functional mers, such as PTFE, and layered inorganics, such as
graphite and molybdenum disulfide—often referred to as
solid lubricants, are also discussed in the latter part of this
chapter.
Mechanical losses due to friction in an engine are esti-
mated at 10 % of the total energy output. Of this, the bearings
consume 31 %, valve train consumes 8 %, and pistons and
rings consume 62 % 关412兴. This power consumption is based
upon normal operating temperature and typical oil sump
temperature of 190° F 共88° C兲. In a cold engine, the cold oil
leads to a greater power loss because of the less effective lu-
brication, primarily due to the higher lubricant viscosity.
Figure 4.111 shows the power loss in an engine with and
without a friction modifier; and at low and high tempera-
tures 关413兴. While examining the figure, please note that the
torque units in the right and left Y-scales are not the same.
The temperature changes viscosity, which alters the nature
of lubrication in different parts of the engine. At high tem-
Fig. 4.110—Fuel economy index 关410b兴. peratures, a decrease in viscosity increases frictional power
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CHAPTER 4 䊏 LUBRICANT ADDITIVES 157
loss in the power train but lowers such loss in bearings and against frictional damage but they also contribute towards
the piston assembly. This is because the power train operates fuel economy. For limited-slip axles, which contain friction
under boundary lubrication, where higher lubricant viscos- clutches and cones, friction-modified gear lubricants mini-
ity is beneficial in an effective film-formation. Either way, the mize noise arising from stick-slip. LFW-1 共Alfa Laval Load,
overall effect of the lower viscosity 5W-30 oil, which contains Friction, and Wear Test兲 and LVFA 共Low-Velocity Friction
a friction modifier, is a decrease in the power loss in all parts Apparatus兲 data for gear oils showing the effect of the fric-
of the engine. Also, it is important to note that at low crank- tion modifiers on friction 关415兴 are presented in Table 4.12.
case temperatures, the lubricant viscosity overwhelms any As can be seen from the table, friction modifiers de-
benefits that the friction modifier may have to offer. Con- crease static and dynamic coefficients of friction in both
versely, at high crankcase temperatures, where the low- single grade and multi-grade oils. In general, the friction-
lubricant viscosity increases boundary lubrication, the ben- modified gear oils show an increase in axle-efficiency rela-
efits of the friction modifier are more observable. This tive to normal gear oils. This is shown in Fig. 4.113 关210兴. The
explains the discrepancy observed in Part B of the figure, axle efficiency is better both for urban and highway driving.
where the lower viscosity oil containing the friction modifier Axle efficiency is believed to have a positive correlation with
shows a negative effect on the power loss. Figure 4.112 the fuel economy.
shows the positive effect of the friction modifier on the Under heavy loads, the EP agent replaces the friction
cranking torque 关414兴. As one can see, the torque required is modifier and takes over the function of preventing the wear
lower when the oil contains a friction modifier than if it does damage. As the load decreases, the friction modifiers again
not. come into action. Friction modifiers have a finite life, which
As described earlier, the frictional properties of the is related to their oxidative and thermal stability. This is one
transmission fluids and the hydraulic fluids are also impor- of the reasons behind fuel economy durability requirement
tant. The frictional compatibility of the fluid with the func- in the Sequence VIB test. These additives are commonly
tioning parts of the transmission and with wet brakes and used in gasoline engine oils, automatic transmission fluids,
wet clutches in tractors assures their smooth and noise-free tractor hydraulic fluids, power steering fluids, shock ab-
共chatter-free兲 operation. Frictional properties play an sorber fluids, and metalworking fluids. In passenger car ap-
equally important role in gear oils. In standard applications, plications, with Federal Government-mandated fuel
friction-modified gear oils not only protect gears and axles economy, lubricant suppliers use these additives as a com-
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158 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
petitive marketing tool. In ATFs and limited slip axle lubri- corrosive materials. Wear resulting from the surface-to-
cants, the friction modifiers are used to control clutch and surface contact is frictional or adhesive wear, from contact
band engagement. Anti-squawk additives, which are func- with foreign matter is abrasive wear, and from contact with
tionally similar to the friction modifiers, are used to reduce corrosive materials is corrosive wear. Fatigue wear is an ad-
objectionable mechanical noise, such as squawk and chatter. ditional type of wear that is common in equipment where the
Anti-squawk agents are primarily used in automatic trans- surfaces are not only in contact but also experience repeated
mission and tractor hydraulic fluids, automotive gear oils, stresses for prolonged periods. Abrasive wear can be pre-
and some industrial oils. vented by installing an efficient filtration mechanism to re-
The effectiveness of the friction modifiers and the anti- move the offending debris. Corrosive wear can be controlled
squawk agents is judged by the lubricant’s performance in by using additives which neutralize the reactive species that
LVFA and SAE #2 tests. Their load-carrying capacity is deter- attack the surface. The control of adhesive wear requires the
mined by the film strength tests, such as the Timken test. use of additives called antiwear and extreme pressure 共EP兲
agents.
Antiwear and Extreme Pressure Agents Under normal conditions of speed and load, two metal
Wear occurs in all equipment that has moving parts. Three surfaces are effectively separated by a lubricant film, a con-
conditions that can lead to wear are surface-to-surface con- dition identified as hydrodynamic lubrication. An increase
tact, surface contact with foreign matter, and erosion due to
Static Dynamic
GL-5 gear oil 共75W兲 0.070 0.052
GL-5 gear oil 共75W兲 + 1 % friction 0.050 0.042
modifier
GL-5 gear oil 共75W兲 + 1 % oleic acid 0.052 0.043
GL-5 gear oil 共75W兲 + 1 % Armeen HT 0.062 0.050 Fig. 4.113—The effect of a friction modifier on axle efficiency of
gear oil 关210兴.
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CHAPTER 4 䊏 LUBRICANT ADDITIVES 159
Secondary alkyl zinc dithiophosphates lose an olefin via than the aromatic derivatives. And among aliphatics, the
-elimination to form a product with the free dithiophos- secondary alcohol-derived are better than those that are pri-
phoric acid functional group. This product can further de- mary alcohol-derived.
compose by the loss of hydrogen sulfide or another olefin to Extreme Pressure Agents
form a thioanhydride and a variety of other products. Tri- Alkyl and aryl disulfides and polysulfides, dithiocarbamates,
alkyl tetrathiophosphate is again the major product. The chlorinated and sulfochlorinated hydrocarbons, dialkyl hy-
aromatic zinc dithiophosphates are believed to decompose drogen phosphites, and the salts of alkyl phosphoric acids
by a free radical mechanism to phenol and a number of are the common extreme pressure 共EP兲 agents.
phosphorus and sulfur-containing products. These mecha- Polysulfides are synthesized from olefins either by react-
nisms are shown in Fig. 4.118. Besides the thermal decom- ing with sulfur or sulfur halides, followed by dehydrohaloge-
position mechanism described above, these additives can nation. Sulfurization of olefins, fats and oils, or compounds
also decompose oxidatively to form products that are potent with active hydrogens, with elemental sulfur, or sulfur and
oxidation inhibitors in their own right. The details of their hydrogen sulfide, results in organic sulfides and polysulfides
oxidation-inhibiting properties were discussed in the oxida- 关421,422兴. Three issues that must be addressed in relation to
tion inhibitors section. It is important to note that the oxida- sulfurization using sulfur, especially of fats and oils, are
tion inhibiting action of these additives is independent of the color, odor and copper activity. Color is due to the presence
nature of the alkyl group, but their antiwear/extreme pres- of dithiolthione and conjugated thiophene structures, which
sure action is not. As indicated in Fig. 4.116, aliphatic zinc are shown in Fig. 4.119. Odor is either due to the presence of
dialkyl dithiophosphates have better antiwear performance the dissolved free sulfur; the mercaptans, which are the reac-
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162 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
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CHAPTER 4 䊏 LUBRICANT ADDITIVES 163
and higher temperatures will have extreme boundary lubri- 共Wear Volume兲共Hardness兲
cation situation. As shown in Fig. 4.126, there is a direct cor- k=
共Normal Load兲共Sliding Distance兲
relation between the conjunction temperature, the tempera-
ture of the two surfaces in contact, and the degree of the EP Table 4.17 provides friction coefficients, wear coeffi-
protection needed 关6兴. Generally, the higher the conjunction cients, and AWNs for various materials. As one can see, pure
temperature, the more difficult it is to achieve the desired hydrocarbon materials, which are low in aromatics, have
load-carrying capacity. Fig. 4.127 approximately correlates AWNs of around 7. Hence, they cannot provide a great deal
the antiwear numbers 共AWNs兲 with the need for EP/antiwear of EP/antiwear performance and there is a need for friction
performance and the ability of the hydrocarbon lubricant in modifiers and antiwear agents. Incidentally, if a medium has
achieving it. The antiwear number is inversely correlated an AWN of 6 or below, extensive wear will result. Table 4.18
with the wear coefficient 共k兲, which is defined by the follow- correlates various types of wear with wear coefficients and
ing relationship 关6兴. AWNs 关429兴. Comparison of the data in the two tables under-
Antiwear Number 共AWN兲 = − log10 k = log10共1/k兲,
where k = Wear Coefficient
scores the importance of lubrication on wear. Item 4 共C30 iso- as a function of load is shown in Figs. 4.128 and 4.129
paraffin兲 is equivalent to 4 centistokes PAO fluid with respect 关6,430兴. Figure 4.128 shows that nonlubricated equipment
to its molecular weight and has an AWN of 7. This implies experiences seizure at low loads and that the equipment’s
that it can minimize wear in most parts of the mechanical load-carrying capacity progressively increases, when lubri-
equipment. cated and film-forming additives, such as friction modifiers,
The equipment that operates at slow speeds and high anti-wear agents and EP agents are added to the lubricant
loads generally requires more EP protection than the equip- 关413兴. Figure 4.129 shows the same in the FZG test. As the
ment that operates at high speeds and low loads. This is be- load increases, the wear increases as well and the EP agents
cause the former generates higher temperatures as a conse- are needed to control wear 关6兴.
quence of the increased friction. The need for EP protection Disulfides and polysulfides decompose on metal sur-
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166 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
Fig. 4.127—Antiwear number versus wear control of steel-on-steel by hydrocarbon oils 关6兴.
faces at temperatures above 200° C to form a protective sul- make a metal phosphite or a metal phosphate protective
fide layer. The thickness of this layer depends on the quantity film. Such films form at a much higher temperature than
and the lability of sulfur in the additive. Sulfurized fatty oils those formed by the sulfur EP agents. Tricresyl phosphate is
and sulfurized olefins are the most commonly used products the best known phosphorus EP agent. Dialkyl hydrogen
in this class. phosphites 关431兴 and phosphonic and phosphoric acid salts
Chlorine-containing compounds provide protection un- are the other examples of such EP agents. The effectiveness
der boundary lubrication conditions, via the formation of a of these compounds as EP/antiwear agents is related to their
metal chloride film. A detrimental aspect of the chlorine- affinity for the surface, that is, their polar to nonpolar ratio,
based EP agents is the formation of the hydrogen chloride in and the chemical reactivity. Chemical reactivity is defined as
the presence of moisture, which can cause severe corrosion the rate of change of radius 共⌬r / min兲 in the hot wire method.
problems. Chlorinated paraffins with 40–70 % chlorine by As shown in Figure 4.130, trilauryl phosphate 共TLPA兲 and
weight were once popular. However, environmental con- lauryl acid phosphate 共LAP兲 show better EP/antiwear perfor-
cerns about the negative effects of chlorine are minimizing mance than trilauryl phosphite 共TLPI兲 and dilauryl hydro-
the use of these additives, especially in Europe. gen phosphite 共DLPH兲 关432兴. Of these, TLPI has the lowest
Phosphorus compounds react with the metal surface to reactivity, hence shows the least wear control, and DLPH is
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CHAPTER 4 䊏 LUBRICANT ADDITIVES 167
the most reactive and probably contributes towards the length additives and those that measure wear require
larger scar diameter due to corrosion. The smaller wear di- shorter carbon chain length additives 关431兴. The major chal-
ameter by TLTTP, which has similar chemical reactivity, is lenge for a formulator and the tribologist is to maximize the
likely to be due to sulfur. Sulfur-containing additives are equipment’s service life by understanding the factors listed
known to have smaller wear scar diameter in the Timken below 关434兴.
test. The negative effect of the additive corrosivity on the EP 1. Surface temperatures and pressures in the contact area.
performance is also demonstrated in Fig. 4.131 关433兴, where 2. Catalytic properties of the deformed metal and the
the chemically more reactive chlorine additive shows lower newly exposed surface.
load-carrying capacity then the less reactive sulfur additive. 3. Chemical reaction between the metal and the additive,
And the phosphorus EP agent with medium reactivity falls in its kinetics, and the role of oxygen in the reaction.
the middle. Load-carrying capacity is determined by the 4. Lubricant residence time in the contact zone.
Mean Hertz Load 共MHL兲 of the additive-containing lubri- 5. Optimal surface film thickness for maximum antiwear
cant relative to that of the additive-free oil. The chemical re- response.
activity is defined the same as for the data depicted in Fig. 6. Properties of the surface film that control its rheology,
4.130. The data also suggest the importance of the nature shear strength, and adherence to the metal.
and the durability of the resulting surface film, which will be As stated earlier, the EP mechanism involves two steps:
described later. Incidentally, the optimum carbon chain the adsorption of the EP agent onto the metal surface and
length in organophosphorus additives differs depending the chemical reaction of the acidic materials that result from
upon whether the test measures friction or measures wear. its thermal decomposition or hydrolysis due to moisture
Tests, which measure friction, require longer carbon chain with the metal. In the case of sulfur and phosphorus com-
Fig. 4.129—Effect of load on wear in FGZ Gear Test A, 2175 pinion speed 关430兴.
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168 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
film can expose fresh metal, and the film-forming process is across more than one lubrication regime and to benefit from
repeated. Each time the film is removed, a molecular layer of possible synergism 关436,439兴. Figure 4.138 shows the benefit
metal is removed with it. One way of looking at the process of from the combined effect of a fatty acid and an organic phos-
EP protection is the controlled wear of the rough surfaces, as phate EP agent 关440,441兴. Organic phosphate is less effective
shown in Fig. 4.137 关6兴. in lowering the wear rate than the fatty acid, which also be-
In general, the formulators use different types of EP comes effective somewhat earlier. A combination of the two
agents in combination because of the need for performance additives provides superior wear control than either of the
Fig. 4.133—Possible mechanism of load-carrying action of dialkyl hydrogen phosphites and amine phosphates 关431, adapted兴.
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170 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
Fig. 4.135—Modes of decomposition of polysulfides to form an Fig. 4.137—Controlled wear of asperities to produce submicron
extreme pressure 共EP兲 film 关438兴. debris 关6兴.
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CHAPTER 4 䊏 LUBRICANT ADDITIVES 171
ants. These components interfere with the EP mechanism ei- pounds are good as EP agents. Some of the tribological
ther by irreversibly adsorbing on the surface or by forming terms that are often used in discussing friction and wear are
complexes with the EP agents, thereby rendering them inac- listed in Table 4.20, along with the approximate related di-
tive 关444,445兴. This antagonism between a dispersant, a de- mensions 关6,446兴.
tergent, and a zinc dialkyl dithiophosphate 共ZnDTP兲 is de- EP-additive treat level in a lubricant can range from
picted in Fig. 4.142. Please note that while ZnDTP in the tenth of a percent to several percent. The precise amount de-
formulation alone is very effective in controlling the viscos- pends upon application, base oil quality, base oil type, other
ity of the oil, the presence of a dispersant or a sulfonate deter- additives, equipment configuration, and the desired perfor-
gent has a negative effect on its performance; magnesium mance. The presence of the other additives can lead to syner-
sulfonate causing more harm than calcium sulfonate. The gism, as shown in Fig. 4.141, or to antagonism as shown in
same is true of some highly polar base stocks that can over- Fig. 4.142, which will reduce the effectiveness of these addi-
whelm the surfaces because of their shear amount. This for tives. Synergism will reduce the treat level of these additives
ester lubricants was described in the Synthetic Base Stocks and antagonism will increase it, if similar performance is de-
chapter, Chapter 3. This type of antagonism is quite common sired. Applications that operate at high ambient tempera-
for some lubricants, such as gear oils, where the EP agents tures, such as automotive gear systems, deplete these addi-
form the core of the formulation. Many effective extreme tives faster than applications that operate under low
pressure and antiwear additives are corrosive to metals. ambient temperatures, such as automobile engines and au-
Therefore, the lubricants using them are typically formu- tomatic transmissions. While discussing the synthetic base
lated to optimize a balance between corrosivity and the ex- fluids, we commented on the polarity of certain base fluids.
treme pressure and antiwear protection. Highly polar base fluids, such as synthetic esters, compete
Table 4.19 compares the effectiveness of the various with the polar EP/antiwear agents for the surface. Because
base fluids and various classes of film-forming agents in con- of being present in a much larger amount, synthetic esters
trolling friction and wear 关440,442兴. Of the compounds overwhelm the surface, thereby preventing the absorption of
listed, natural oils and fats, long-chain fatty acids, amines, EP/antiwear agents on the surface. Other film-forming addi-
and alcohols, and organo-molybdenum compounds are tives, such as rust and corrosion inhibitors, also cause a
good for friction modification. Zinc dialkyl dithiophos- similar problem. Typically, this problem is overcome by us-
phates and phosphorus compounds are good as antiwear ing these additives in higher amounts. Table 4.21 provides a
agents and organosulfur and organophosphorus com- comparison between various classes of film-forming agents,
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172 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
Fig. 4.139—Wear—load diagram, the ASTM procedure, showing synergism between chlorine and sulfur extreme pressure 共EP兲 agents 关436兴.
along with their function and the performance mechanism able or ineffective. Examples include the following applica-
关440兴. Table 4.22 lists typical applications of organophos- tions.
phorus esters 关440兴. 1. There is a concern for contamination of the product or
There is always a concern regarding the addition of the the environment.
hetero-atom 共N, S, and P兲 containing additives to biodegrad- 2. Maintenance is either unlikely or impossible.
able base oils, with respect to whether it will diminish their 3. Extreme low and high ambient temperatures are experi-
biodegradability characteristics. It appears from the limited enced.
data presented in Table 4.23 that some of these additives are 4. Fluid lubricants are unsuitable because of the unique
highly biodegradable themselves; hence they are unlikely to environment, such as vacuum/space, and that involving
negatively impact the biodegradability properties of the base ionizing radiation or a high rate of oxidation, for ex-
oil 关447兴.
ample, foundry operations.
Solid Lubricants A variety of materials are used as solid lubricants. For a
The term solid lubricant refers to finely divided solid 共pow- material to function as a solid lubricant, it must possess cer-
der兲 or a thin film that protects surfaces against wear dam- tain specific properties. These include the ability to form sur-
age that are in contact and in motion. These lubricants are face films of low friction coefficient and low shear strength,
used in situations where fluid lubricants are either undesir- and to control wear 关448兴. Solid lubricants fall under the gen-
eral classes of the lamellar solids, metal salts, reaction films, higher, which is ascribed to the presence of the additional
soft metal films, diffusion coatings, polymeric coatings, or- stronger electronic interaction between atoms across layers
ganic polymers, and dispersions in oils and greases. than the weak van der Waals forces alone. Graphite has high
Lamellar solids are materials that have a layered struc- thermal stability, greater than 2000° C, but its oxidation sta-
ture, where the bond strength between the atoms within the bility is only around 500 to 600° C. While this is quite re-
layer or the plane 共intralamellar兲 is greater than between the spectable for most applications, the primary limitation is the
atoms across the layers 共interlamellar兲—possibly due to van necessity of the adsorbed vapors and gases to maintain low
der Waals type forces 关449兴. This provides these materials the friction. Gases desorb easier than water, which will be re-
ability to form films of low shear stability; one of the proper- moved around its boiling point of 100° C. Organic vapors,
ties desired in a good solid lubricant. Graphite and molybde- present as contaminants in the surrounding environment, or
num disulfide 共MoS2兲 are two materials that are most com- the material introduced deliberately into the graphite can
monly used as solid lubricants. The lamellar structure of the preserve its frictional properties at a higher temperature. In-
graphite is shown in Fig. 4.143. Graphite has low friction co- organic compounds, such as lead oxide 共PbO兲, cadmium ox-
efficient of 0.05 to 0.1, which is ascribed to its lamellar struc- ide 共CdO兲, sodium sulfate 共Na2SO4兲, and cadmium sulfate
ture and easy shear. During sliding, the basal planes orient 共CdSO4兲 added to graphite have all been shown to be effec-
themselves almost parallel to the surface and the movement tive on nickel alloy substrates to around 550° C 关448,449兴.
separates layers via shear, thereby lowering the friction. It is MoS2, like graphite, also has a lamellar structure but
important to note that the graphite has low friction only in with the difference that the interlamellar bonding is between
environments that contain water or gases, such as those sulfur atoms instead of being between carbon atoms. The
present in the air. In vacuum, its friction coefficient is much bonding is again of the van der Waals type and hence is fairly
TABLE 4.20—Tribology terms and related di- weak, see, Fig. 4.144. Unlike graphite, where adsorbed va-
mensions †6‡. pors decrease friction, in MoS2 the adsorbed vapors usually
increase friction, but the effects are relatively small. In the
Parameter Approximate Size Range 共m兲
oxidation-free environment, thermal stability of MoS2 is
Monomolecular layer 0.2– 2 ⫻ 10−3
Sliding wear debris 0.002–0.1
around 1100° C, but in the presence of air the stability drops
Boundary film 0.002–3 to around 350 to 400° C. The air-oxidation product is MoO3.
EHD film 0.01–5 One problem with MoS2 is the presence of the abrasive im-
Asperity height 0.01–5 purities, which can contribute to abrasive wear. Despite this,
Rolling wear debris 0.7–10 it is replacing graphite in metalworking lubrication and in
Asperity contact 0.7–10 electrical contacts. This is because of its consistent quality,
Hydrodynamic film 2–100 nondependence of low friction on the adsorbed vapors, low
Asperity tip radius 10–1000 friction in vacuum, and its superior load-carrying capacity.
Concentrated contact width 30–500
Boron nitride is a ceramic lubricant which is used in ap-
Engineered counterfomal radius 1 – 100⫻ 10−3
Engineered conformal radius 2 – 2500⫻ 10−6
plications where the use of graphite and MoS2 is less than
desired. It is extremely resistant to oxidation even at tem-
peratures of 1200° C and has high thermal conductivity.
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CHAPTER 4 䊏 LUBRICANT ADDITIVES 175
These make its use suitable in applications that require the friction coefficient in vacuum is higher than in air. In mo-
quick dissipation of heat and high temperatures that are out- lybdenum disulfide and tungsten disulfide, it is lower, which
side the realm of graphite and molybdenum disulfide. Boron makes them good lubricants for vacuum applications. Both
nitride is produced by the reaction of the boric acid with also tolerate higher loads better than the graphite. There are
urea at temperatures of 800– 2000° C. The result is the for- many other lamellar solids, but their use in lubricant appli-
mation of cubic boron nitride and hexagonal boron nitride. cations is limited.
It is the latter form that resembles the structure of graphite Numerous inorganic salts with the low shear strength
and is used in lubricant applications. See Fig. 4.144 for its and film-forming ability have shown promise as solid lubri-
lamellar structure 关449兴 and compare it with that of graphite cants. Those worth mentioning are lead oxide 共PbO兲 and cal-
shown in Fig. 4.143. The frictional properties of the com- cium fluoride 共CaF2兲. PbO is an effective thin film lubricant
monly used solid lubricants in air and vacuum are provided with an operating range from room temperature to about
in Table 4.24 关450兴. It is important to note that in all cases, 350° C, and upwards of 500° C. Between the two tempera-
except for the molybdenum disulfide and tungsten disulfide, tures, it oxidizes in air to Pb3O4, which has poor lubricating
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176 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
maximum wear life is 0.1 to 1 m, which is similar to that by weight and in greases is 20 % by weight. The use of MoS2
required to give minimum coefficient of friction 关448兴. in engine oils is known to reduce wear and improve fuel
Diffusion coating is an alternative to deposition of the economy 关454兴. It is important to note that the wear-
surface films for reducing friction and wear. The process in- reducing ability of MoS2 and graphite can be inhibited by de-
volves thermal diffusion of the atoms of dissimilar elements, tergents and that their presence can affect the oxidation sta-
such as C, N, S, Cu, and Sn, into the metal surface. This is bility of oils and greases. In applications, such as textile
achieved by surface treatment. The result is the increased machinery lubrication, which are adverse to the black color
wear resistance due to increased surface hardness; produc- of these two additives, phosphates, oxides, and hydroxides—
tion of low-shear strength surface films, which inhibit scuff- such as Zn2P2O7 and Ca共OH兲2, and PTFE are used. PTFE-
ing and seizure; and an increase in corrosion-resistance. thickened fluorocarbon greases are also effective lubricants
Typically, these coatings are approximately 2 to 25 m in in oxidizing environments that involve broad-temperature
thickness and are porous, which makes their surface ideal range 关455兴, such as rocket motors and space components.
for depositing solids. Without the use of the supplemental Solid lubricants are used to control friction and wear in
solid or liquid lubricants, these coatings do not provide pro- three types of applications: those that require thin-films,
tection against friction and wear 关448兴. those that require self-lubricating properties, and those that
A variety of organic polymers are also employed to re- require low-shear strengths films. Machines of various ge-
duce friction and wear. These are used in three forms: thin ometries are used to evaluate one or more of the properties
films, self-lubricating materials, or binders for lamellar sol- of the solid lubricants. Common machines include Four-
ids. Polytetrafluoroethylene 共PTFE兲 is a polymer of the gen- ball, hemisphere on disk, block on ring 共Timken, LFW1兲, re-
eral formula 关C2F4兴n which is quite effective in forming thin ciprocating pad on ring, Falex, Almen-Wieland 共journal
films of low coefficient of friction, in the order of ⬃0.03 to bearings兲, LFW-3 共thrust bearing兲 and LFW4 共press fit兲 关448兴.
0.1. In addition, it is effective over a broad temperature Figure 4.145 provides their geometries. Motion is indicated
range 共−200 to + 250° C兲, and is chemically inert. Its low fric- by circular arrow and load is indicated by straight arrow/s.
tion coefficient is attributed to its molecular profile and ori- Frictional properties of some solid lubricants, as determined
entation, which facilitate easy sliding of the coated surfaces. by the Thrust Fit Test, are provided in Table 4.25 关4兴. As one
PTFE films are obtained by spraying the surfaces with the can see that while all solid lubricants lower the friction of the
polymer and sintering at temperatures above 325° C. The base fluid, molybdenum disulfide and tungsten disulfide are
formation of PTFE films can also be achieved by the use of a the best performers.
synthetic resin, which lowers the curing temperature signifi-
cantly. Load-carrying capacity and durability of these films Rust and Corrosion Inhibitors
on metals are inferior to those of the MoS2 coatings and their Corrosion is a general term that is used to describe the de-
low thermal conductivity limits the maximum operating structive alteration of the metal by chemical or electro-
speed. PTFE coatings are therefore used only in applications chemical action of its environment. It primarily involves a
that involve moderate conditions of sliding, for example, the heterogeneous reaction which causes a metal to change
food processing and plastics molding equipment. The only from its nascent form 共metallic state兲 to an oxidized form
other polymers used as thin-film lubricants are polyimides 共ionic state兲. All metals, except noble metals, are thermody-
关451兴. While they can withstand higher temperatures namically unstable under atmospheric conditions and get
共⬃300° C兲 than the PTFE, their frictional properties are not converted into their oxidized form. Noble metals, such as
as good. They have a friction coefficient of 0.13 to 0.3, com- gold, platinum, iridium, and palladium, on the other hand,
pared to that of 0.03 to 0.1 for PTFE. The greatest use of poly- are resistant to attack by the environment and are therefore
mers is in self-lubricating composites as a replacement for found in nature in the free form.
the lubricated metals 关452,453兴. PTFE requires reinforce- There are many types of corrosion, but a lubricant for-
ment when used in bulk, to minimize viscoelastic deforma- mulator is primarily concerned with corrosion in the pres-
tion under load. This is done by the use of thermosetting res- ence of electrolytes 共electrochemical corrosion兲 and in the
ins, such as phenolics. The presence of the lamellar solids, absence of electrolytes 共chemical corrosion兲. Common elec-
such as PTFE and MoS2, in return is beneficial to the ther- trolytes that lead to electrochemical corrosion include water,
mosetting resins since they impart to resins lower friction acids, alkalis, and salts. Chemical substances that cause
and wear properties. Graphite, because of being fibrous, also chemical corrosion include acids, alkalis, and sulfur and its
increases the strength of the resulting polymer composites. compounds. In alloys, corrosion can be selective or nonse-
The use of oil dispersions as additives in oils and greases lective. It is selective if a particular metal is corroded in pref-
to lower friction and to reduce wear is quite common. erence to another. It is nonselective if all metals in the alloy
Graphite and MoS2 are among the most commonly used are corroded at the same rate.
lamellar solids. Because of their less than fluid nature, such Electrochemical corrosion involves the reaction of met-
dispersions are not suitable in applications that require hy- als in the presence of electrically conducting solutions, or
drodynamic or elastohydrodynamic lubrication. The con- electrolytes, and occurs in two steps: the anodic process and
centration of these additives ranges from 0.1 to 60 % by the cathodic process. In the anodic process, the metal goes
weight. The dispersions that contain high solids content are into the solution as ions with the extra electrons being left
pastes, which are used only in the component assembly op- over. The process can be considered oxidation. The cathodic
erations. Testing has shown that the use of MoS2 dispersions process involves the reaction of thus generated electrons
improves the load-carrying capacity, reduces wear, and pro- with water and oxygen to form the hydroxide ions. The pro-
longs the rolling bearing life. Typical treat level in oils is 3 % cess can be considered reduction. In solution, the metal ions
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178 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
combine with the hydroxide ions to form metal hydroxides, Factors that affect the corrosion rate include internal
or hydrated oxides. factors and external factors 关456兴. Internal factors are di-
Chemical corrosion, on the other hand, does not need an rectly related to the metal itself, and include its composition,
electrolyte and can occur both in aqueous and organic me- structure, surface condition, oxidation potential, and the
dia. It involves attack of the corrosive species, such as acids presence of stresses. External factors pertain to the environ-
and sulfur, on metals. The damage occurs when the resulting ment and include the nature of the oxide film, acidity, alka-
salts are removed. linity, the presence of a polar solvent such as water, the pres-
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CHAPTER 4 䊏 LUBRICANT ADDITIVES 179
ence of an electrolyte 共salts, acids, or bases兲, the presence tains iron 共Fe兲, copper 共Cu兲, lead 共Pb兲, chromium 共Cr兲, man-
and reactivity of aggressive species, and the temperature. ganese 共Mn兲, antimony 共Sb兲, aluminum 共Al兲, vanadium 共V兲,
While the role of these factors is considered elsewhere 关456兴, zinc 共Zn兲, nickel 共Ni兲, and tin 共Sn兲. Protecting four of these
we are especially interested in the oxidation potential of the elements against corrosion is of primary interest: iron,
various metals. which is the principal metal used to forge the engine and the
Oxidation potentials of the elements that make up the auxiliary equipment; copper, which is present in bearings
metallurgy of the modern mechanical equipment are pro- and seals; lead, which is also present in bearings; and alumi-
vided in Fig. 4.146 关457兴. The elements that are primarily num that is used in newer cars and trucks to make them
used to fabricate metal parts are shown by bold italic sym- lighter for better fuel economy.
bols; hence their corrosion control is the primary goal. The Protection against corrosion is necessary because it can
oxidation potentials reported in the table are relative to hy- lead to a loss of metal, thereby lowering the integrity of the
drogen with a value equal to 0. Positive values indicate ease equipment and resulting in its malfunction. In addition, cor-
of oxidation and negative values indicate resistance to oxida- rosion exposes fresh metal that can wear at an accelerated
tion. Because of hydrogen being the reference point, we can rate and result in metal ions that can act as oxidation pro-
directly compare these values to assess the relative oxidative moters.
tendency of the various metals. The higher the oxidation po- Corrosion of iron and its alloys, sometimes referred to
tential, the easier it is for the metal to oxidize. Metals in the as ferrous corrosion or rust, is primarily electrochemical in
left column of the table with the smaller values are therefore nature. It can occur both in the liquid phase and the vapor
less susceptible to oxidation, hence corrosion, than those in phase and needs water, electrolyte such as salt, and oxygen.
the right column. The values with a forward slash indicate a In an internal combustion engine, water results from the fuel
metal’s first and second oxidation potentials. For example, combustion, oxygen comes from the air, and electrolytes are
for iron, 0.44 represents the oxidation potential of the Fe0 to metal salts that form by the reaction of the metals and cer-
Fe+2 transition and 0.04 represents the oxidation potential of tain additives with the combustion and oxidation-derived
the Fe0 to Fe+3 transition. The same is true for copper. Of the acids. Ferrous corrosion mainly occurs in engines that are
metals of interest, aluminum is the easiest to oxidize, fol- run in short intermittent cycles 共stop-and-go driving兲. Rust
lowed by iron and lead. Copper with the negative values is initiates when water sets up a localized electrochemical re-
the most resistant of the metals listed in the table. action between the surface iron and the iron oxide layer. Na-
Of the external factors listed above, acidity, alkalinity, scent iron acts as the anode, and the iron oxide layer acts as
the presence of the reactive species and the temperature the cathode. Iron emits electrons and forms ferrous ions that
have the largest impact. The presence of the acids and bases are released into the medium. The electrons migrate to the
can accelerate corrosion. In lubricant applications, acids re- cathode 共oxide layer兲 and form the hydroxide ions by react-
sult from the oxidation of the fuel sulfur and the base stock. ing with oxygen and water. Ferrous ions and hydroxide ions
Lubricant contains additive derived components, both or- then combine to form ferrous hydroxide, which is subse-
ganic and inorganic, which are moderately basic and there- quently oxidized to ferric hydroxide, lose water, and become
fore pose little problem by themselves. However, the reac- rust 关207兴. The mechanism of the rust formation is depicted
tion between the acidic and the basic species results in salts in Part A of the Fig. 4.147 关207兴.
which because of being electrolytes can promote corrosion. Corrosion of copper and bronze 共the yellow metal corro-
The lubricant also contains additives that can lead to acidic sion兲 is chemical in nature and occurs by the attack of the
decomposition products. Some of these additives are sulfur aggressive species on metals. Such species result from the
and phosphorus compounds that are added to the lubricant oxidation and combustion of the hydrocarbon materials,
to improve its oxidative stability and antiwear performance. such as fuel, base oil, and sulfur-containing additives. Yellow
These can corrode metals either directly or by forming ag- metal corrosion results when the chemically reactive materi-
gressive chemical species via decomposition. Higher tem- als, such as acids or sulfur, attack copper or copper oxide.
peratures that are typically encountered in the internal com- The result is the formation of the ionic copper compounds
bustion engines can accelerate corrosion as well. that are removed, thereby causing the metal damage. This is
Metallurgy in automotive equipment commonly con- shown in Part A of the Fig. 4.148 关207兴.
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180 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
concentrations, zinc dialkyl dithiophosphates can also lead mineral oil have primary use in metalworking and hydraulic
to pitting of the some ferrous alloys. applications. To be effective, emulsions must possess a num-
Corrosion inhibitors have major uses in engine oils, gear ber of desirable properties. They must be stable over long pe-
oils, metalworking fluids, and greases. Thiadiazole and tria- riods of time, possess good lubricating properties, not attack
zole derivatives are especially useful in protecting against seals and metals, and be easy to demulsify for disposal.
nonferrous or yellow metal corrosion. In the presence of water, certain lubricant formulations
Metal corrosion is measured by a variety of tests, de- have an increased tendency to form emulsions. This is due to
pending upon the application. At present for engine oils, Se- the presence of the chemical additives which act as surfac-
quence VIII 关Unleaded L-38 Test 共copper/lead兲兴, Ball Rust tants. Demulsifiers are added to such formulations to en-
Test 共ASTM D6557兲, and High Temperature Corrosion hance water separation and suppress foam formation.
Bench Test 共ASTM D6594, copper/lead/tin兲, also called Cum- Emulsifiers and demulsifiers are essentially surfactants
mins Bench Corrosion Test, are used. For gear oils, CRC 共surface-active agents兲 that have the ability to adsorb onto
L-13, L-21, and L-33 Tests are used for rust and ASTM D130 surfaces to significantly alter them, as in the case of the film-
Test is used for copper corrosion. For industrial products, forming agents, or onto interfaces to change their interfacial
ASTM D665 Test is used for rust and ASTM D130 Test is used free energies. The term interface describes the boundary be-
for copper corrosion. For hydraulic and metalworking flu- tween any two immiscible phases, such as oil and water.
ids, a number of ASTM specified tests are utilized 关20兴. These additives are made up of hydrophilic and hydrophobic
moieties. The hydrophilic moiety is a hetero atom-derived
Emulsifiers and Demulsifiers polar functional group which is attached to a hydrophobic
Emulsifiers are chemical compounds that enable two im- hydrocarbon group. Common hetero atoms are atoms of the
miscible fluids to form an intimate mixture, known as an elements nitrogen, oxygen, sulfur, and phosphorus. The hy-
emulsion. Oil-water emulsions are often used as lubricants drophobic group is usually a hydrocarbon group of suffi-
in many industries and for a variety of applications. This is cient chain length to provide proper solubility or dispersibil-
because such lubricants are low cost, easier to dispose of, ity in the oil phase.
and have fire-retardant properties. Emulsions of water and Emulsifiers and demulsifiers can be classified as non-
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CHAPTER 4 䊏 LUBRICANT ADDITIVES 183
ionic or ionic, depending upon whether the polar part is un- emulsifiers and demulsifiers 关459兴 are given in Fig. 4.155.
charged or charged. Ionic compounds can be further subdi- It is important to note that only the charge on the func-
vided into cationic, if the charge is positive, and anionic, if tional group attached to the carbon chain is used in this clas-
the charge is negative 关458兴. Generalized structures for sification. The charge on the counter ion, which is usually in-
organic in origin, is ignored. The term amphoteric applies to HLB value of 3 to 6 are suitable for water-in-oil emulsions
a group of additives which contain both the cationic and the and those with an HLB value of 8 to 18 are suitable for oil-in-
anionic groups of organic origin, preferably within the same water emulsions. The manner in which these additives form
molecule. They possess the structural features and the prop- emulsions is shown in Fig. 4.156. Water-in-oil emulsions
erties of both the cationic and the anionic materials grouped form when these additives associate with water via their po-
together. lar ends and with oil and other additive molecules via the
Emulsifiers reduce the surface tension of water and, nonpolar ends. This is shown in Part A of the figure. The re-
therefore, facilitate thorough mixing of the oil and water to sult is water miscibility in oil, or water-in-oil emulsion. The
form an emulsion. The efficiency of an emulsifier depends mechanism of oil-in-water emulsion is similar, except that
upon its molecular weight, which is usually less than the additive molecules associate with oil in the reverse man-
2000 g / mol, its HLB 共hydrophile-lipophile balance兲 value, ner. This situation is shown in Part B of the figure. See Chap-
water pH and hardness, the nature of the oil, and the operat- ter 11 on Metalworking Fluids for further discussion on
ing conditions, such as temperature. Emulsifiers with an emulsifiers.
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186 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
Demulsifiers perform the opposite function and en- times avoided because their enhanced solubility in water
hance water separation. Structurally, most demulsifiers are does not allow their clean separation for disposal.
oligomers or polymers with a molecular weight of up to Poly共ethylene oxide兲 derivatives and salts of carboxylic
100,000 g / mol and contain 5–50 % polyethylene oxide in a and sulfonic acids are the most commonly used emulsifiers,
combined form. They are commonly block copolymers of primarily in metalworking fluids. Demulsifiers are used in
propylene oxide and or ethylene oxide and initiators such as applications where water contamination of the lubricant is a
phenol-formaldehyde resins, siloxanes, polyamines, and problem and quick separation of water is desired. Automatic
polyols 关460兴. For water-in-oil emulsions, polymers contain-
transmission fluids, hydraulic fluids, industrial gear oils,
ing 20–50 % ethylene oxide are suitable. These materials
and some engine oils, are examples of such lubricants.
concentrate at the water-oil interface and create low viscos-
Figure 4.157 shows a situation where water-in-oil emul-
ity zones, thereby promoting droplet coalescence and
gravity-driven phase separation. Low molecular weight ma- sion essentially plugged up the breather tube in the ASTM
terials, such as alkali metal or alkaline earth metal salts of Sequence IID, now obsolete, engine test. The problem was
dialkylbenzene- and dialkylnaphthalene-sulfonic acids, are solved by the use of a demulsifier. The results of the field test
also useful in some lubricant-related applications. are shown in Fig. 4.158 关461兴. As can be seen, the use of a
As a general rule, nonionic emulsifiers are used in metal- proper demulsifier led to a remarkable improvement in the
working fluids based on naphthenic stocks, and fatty acid emulsion performance of the lubricant. Parts that were to-
carboxylates are used in those based on paraffinic stocks. tally covered with emulsion became emulsion-free. Com-
Poly共alkylene glycol兲s, or hydroxyalkyl ethers, are some- pare the left half of the figure with the right half.
Polymeric Additives that contain hetero atoms in the backbone are not included
Materials with polymeric structures are the key components in this class.
in high-performance lubricants. They can be used as lubri- Branched polymers can have a comb-like structure or a
cant base stocks 共synthetic lubricants兲 or to enhance a lubri- star-shaped structure. Comb-like branched polymers consist
cant’s inherent properties, such as viscosity and pour point. of a long hydrocarbon chain as the backbone and short
They can also be used as starting materials to prepare certain chains as the pendent groups that appear like teeth on a
classes of additives, such as dispersants and detergents. comb. Star-shaped branched polymers, also called radial
The development of the synthetic hydrocarbon poly- polymers, have a center from which hydrocarbon chains ex-
mers started with Bakelite 共phenol-formaldehyde resin兲 in tend as rays. The molecular configurations of the different
1907, which was closely followed by the commercialization types of polymers 关462兴 are presented in Fig. 4.160.
of the synthetic rubber 共styrene-diene copolymer兲. Polysty- Polymers fall under two broad classes: homo-polymers
rene became commercial around 1930 in Germany and in and copolymers. Homo-polymers contain only one kind of
1937 in the United States. Since then, a large number of syn- repeating unit; that is, they are derived from a single mono-
thetic polymers have become commercially available. Over mer. Copolymers contain two or more kinds of fundamental
time, these materials have found extensive use in a wide vari- units; that is, they are derived from two or more monomers.
ety of consumer and industrial products, including lubri- If different kinds of units occur randomly, the polymer is
cants. The first use of the polymeric additives 共pour point de- called a random copolymer. If they occur in an alternating
pressants兲 to improve the low temperature properties 共flow兲 fashion, the polymer is called an alternating copolymer.
of lubricants dates back to the mid-1930s. By the 1940s, When the units occur in blocks, the polymer is called a block
other lubricant additives, including viscosity modifiers copolymer. Block polymers result from the sequential poly-
共VMs兲, were commercialized and by the 1950s their use in merization of two or more monomers. The polymerization
lubricants became a normal practice. Dispersants and foam of one monomer gives rise to one block and the polymeriza-
inhibitors are two other classes of polymeric additives that tion of the second monomer gives rise to the other block.
are commonly used in lubricants. Graft copolymers are polymers where already formed poly-
Dispersant polymers, or dispersant viscosity modifiers mer chains are extended by forming new blocks of new re-
共DVMs兲, are hydrocarbon polymers that have a dispersant peating units or by attaching another functional group.
These polymeric arrangements for linear copolymers
moiety attached to them. These materials are used as viscos-
关462,463兴 are depicted in Fig. 4.161. Such arrangements are
ity modifiers with added dispersancy. The molecular weights
also possible for branched and network polymers.
of these materials are in the 25,000 – 500,000 g / mol range.
The invention of the viscosity modifiers led to the introduc- Molecular Weight Averages and Distribution
tion of the multi-grade oils, which eliminated the need to use Most polymeric materials are compositions that consist of
low viscosity oils for winter and high viscosity oils for sum- the polymer chains of varying sizes. The bulk properties of
mer. Multi-grade oils contain polymers of suitable molecular these compositions depend upon the average molecular
weight and physical properties in a low viscosity oil. These weight of the polymer chains. As stated earlier, the molecular
oils are therefore suited for all-season use. Polymers have weights of polymeric materials are expressed as number-
been designed that have the viscosity-modifying ability and average, weight-average, z-average, 共z + 1兲 average, and vis-
dispersancy or antioxidancy, or both. In this book, the multi- cosity average molecular weights 关221–225,462–464兴. Of
functional polymers are identified by the use of the letters D these, the number-average 共Mn兲, weight-average 共Mw兲, and
and DA. They precede the abbreviation for the polymer type. z-average 共Mz兲 molecular weights are most often used to de-
For example, PMA-based viscosity modifiers are referred to scribe the polymer compositions. The mathematical func-
as DPMAs, if they are claimed to have additional dispersant tions representing these averages are given below. In these
action. Similarly, DAOCP refers to a polymer with both dis- equations, Mi is the molecular weight and ni is the number
persant and antioxidant properties. The timeline for the de- of moles of the component molecule i.
velopment of the different types of viscosity modifiers and
dispersant viscosity modifiers is shown in Fig. 4.159.
Number − average molecular weight: Mn =
兺 niMi
A polymer is a substance that is made up of large mol-
ecules containing repeating molecular units, derived from 兺 ni
the monomer. Polymer molecules can be linear, branched, or
network type, depending upon the arrangement of the
Weight − average molecular weight: Mw =
兺 niMi 2
The polymer chain can also contain a functional group To calculate Mn, Mw, and Mz of an equimolar polymer
at the end, which is denoted by the latter F in the structure. composition that consists of five components of molecular
Such polymers are called -functional polymers. The func- weights 8000, 9000, 10,000, 11,000, and 12,000 g / mol, the
tional end groups are usually introduced by terminating the following procedure can be employed. All values for the
homo-polymerization with a hetero atom 共O, N, S, or P兲 con- computation can be determined from ni and Mi. For a poly-
taining monomer. Polymers, such as poly共alkylene oxide兲s, mer composition that contains an equimolar mixture of the
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188 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
five components, these values are provided in Table 4.26. By 80003 90003 10,0003 11,0003
using the values in the table, Mn, Mw, and Mz values for such Mz = + + +
5.10 ⫻ 108 5.10 ⫻ 108 5.10 ⫻ 108 5.10 ⫻ 108
a polymer composition can be calculated as follows.
12,0003
+ = 1004 + 1429 + 1961 + 2610 + 3388
5.10 ⫻ 108
Mn =
兺 niMi = n1M1 + n2M2 + n3M3 + n4M4 + n5M5 = 10,392 g/mol
兺 ni 5 5 5 5 5
The values of ni and Mi necessary to compute the mo-
lecular weights for a nonequimolar polymer composition
are presented in Table 4.27. By using the ni and Mi values
50,000 8000 9000 10,000 11,000 12,000 from this table, Mn, Mw, and Mz for a nonequimolar poly-
Mn = = + + + +
5 5 5 5 5 5 mer composition can be computed as follows.
Mw =
兺 niMi = n1M1 + n2M2 + n3M3 + n4M4
2 2 2 2 2
+
n5M52 兺 niMi 50,500
50,000
Mz =
兺 niMi 3
=
5.3445 ⫻ 1012
Mw =
510,000,000 80002
= +
90002 10,0002 11,0002
+ + 兺 niMi 2 516,500,000 or 5.165 ⫻ 108
50,000 50,000 50,000 50,000 50,000
= 10,348 g/mol
12,0002
+ = 1280 + 1620 + 2000 + 2420 + 2880 The number-average molecular weight 共Mn兲 represents the
50,000
chemical stoichiometry and is useful in carrying out the
= 10,200 g/mol chemical reactions involving polymers. The weight-average
molecular weight 共Mw兲 correlates with the mechanical prop-
erties, such as tensile strength and modulus in plastics, films,
Mz =
兺 niMi 3
=
n1M13 n2M23 n3M33
and fibers, and the viscosity improving behavior of the poly-
mers. The z-average molecular weight 共Mz兲 largely influ-
8 + 8 +
兺 niMi 2 5.10 ⫻ 10 5.10 ⫻ 10 5.10 ⫻ 108 ences the polymer’s viscoelastic properties, such as the melt
elasticity.
n4M43 n5M53 5.30 ⫻ 1012 While a number of methods can be employed to mea-
+ 8 + 8 =
5.10 ⫻ 10 5.10 ⫻ 10 510,000,000 or 5.10 ⫻ 108 sure these averages, each technique has its limitations 关464兴.
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CHAPTER 4 䊏 LUBRICANT ADDITIVES 189
Solution osmometry is the primary method used to deter- size. The elution is monitored by the use of a detector, a dif-
mine the number-average molecular weight and light scat- ferential refractometer being the most common. This type of
tering is the primary method for determining the weight- detector measures the difference in the refractive index of
average molecular weight. Gel permeation chromatography the polymer solution and the pure solvent, the difference be-
共GPC兲, or size-exclusion chromatography 共SEC兲, although a ing proportional to the concentration of the polymer in solu-
secondary method, is extensively used for determining the tion. Figure 4.162 shows a schematic of how different mo-
polymer molecular weights. This technique is popular be- lecular weight fractions separate in a GPC column.
cause it allows the calculation of all three molecular weight- The GPC chromatogram, one presented in Fig. 4.163,
averages from a single elution curve 关223 225兴. shows a plot of the polymer concentration against the elu-
GPC makes use of a column packed with beads of po- tion or retention volume. To obtain meaningful data, the re-
rous cross-linked polystyrene gel, with an average pore size tention volume scale must be calibrated to the molecular
of 60 to 107 Angstrom. As the polymer solution passes weight scale by the use of standard polymers. For polymers
through the column, the polymer molecules enter the pores to be good standards, they must have narrow molecular
that are large enough to accept them. Since there are a larger weight distributions, and their molecular weights must be
number of pores for smaller molecules to enter and pass predetermined by the use of the primary methods, such as
through than for larger molecules, the larger molecules light scattering and membrane osmometry.
come out of the column 共elute兲 faster. The result is the sepa- While average molecular weight information is impor-
ration of the polymer molecules based on their molecular tant, it is the molecular weight distribution that is more use-
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190 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
ful in understanding the polymer properties. A number of the higher molecular weight fractions towards the molecu-
fractionation methods other than GPC are available for this lar weight. The relationship between different types of mo-
purpose 关465兴. The molecular weight distribution is mea- lecular weights is shown in Fig. 4.164 关224兴. It can be seen
sured by the polydispersity index or the heterogeneity index, from the figure that Mn is less than Mw, which in turn is less
which is the ratio of the weight-average molecular weight to than Mz. The viscosity-average molecular weight 共Mv兲,
the number-average molecular weight, or Mw/Mn. For which is easy and quick to determine from the intrinsic vis-
mono-disperse polymers, which contain molecules of essen- cosity of the polymer solution, is very close to Mw. Hence, it
tially the same chain length, the value of this index is close to is sometimes used to approximate the weight-average mo-
1 and for poly-disperse polymers, it is greater than 1. This is lecular weight 共Mw兲.
because in the latter case there is a greater contribution of The polydispersity index is a function of the polymeriza-
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CHAPTER 4 䊏 LUBRICANT ADDITIVES 191
tion method. It is closer to 1 for polymers derived from an- mers derived from polymerization using the coordination
ionic polymerization, 1.5–2.0 for polymers derived from step catalysts.
growth polymerization, between 2 and 5 for polymers de-
rived from free radical polymerization, and above 5 for poly-
cosity modifiers and are available both in semi-solid form weight analogues of the OCPs, are prepared by polymerizing
and as liquid concentrates in mineral oil. Typical concen- the ␣-olefins in the presence of a Lewis acid. See Chapter 3
trates contain between 10 to 15 % polymer and have 100° C on Synthetic and Natural Base Stocks. These polymers find
viscosity of between 500 to 1500 cP 共mPa· s−1兲. Typical use in lubricants, such as power steering pump and gear oils
viscosity-concentration relationship is provided in Fig. that require enhanced shear stability. The polyisobutylenes
4.170 关467兴. Generally, the higher the molecular weight of a 共PIBs兲 of the molecular weights of 2000 to 3000 g / mol are
polymer, the more prone it is to the mechanical degradation used as viscosity modifiers in gear lubricants, hydraulic flu-
under the forces of shear. This is true for the OCPs as well. ids, and industrial oils.
␣-Olefin 共alphaolefin兲 copolymers, the lower molecular OCPs are inferior to polymethacrylates with respect to
Fig. 4.170—Kinematic viscosity of 50 PSSI 共Permanent Shear Stability Index兲 OCP in 100 N mineral oil 关467兴.
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CHAPTER 4 䊏 LUBRICANT ADDITIVES 195
the engine oils that use dispersant-functionalized OCPs typi- smaller size alkyl group has low solubility in oil, especially at
cally need less ash-less dispersant to achieve an acceptable low temperatures, and it stays closely coiled. In other words,
level of engine cleanliness than those that use nonfunction- it occupies a small hydrodynamic volume; hence, it contrib-
alized OCPs. utes little, if any, to viscosity. This is a benefit with respect to
Styrene-diene polymers 共STDs兲 can be of the di-block or the pour point of the oil. However, as the oil temperature in-
random-block type and are produced by anionic polymeriza- creases, the polymer chains open up and their association
tion of styrene and butadiene, or isoprene. This type of poly- with the bulk lubricant increases, which increases the hy-
merization produces polymers with a narrower molecular drodynamic volume; hence the oil viscosity. The presence of
weight distribution than those obtained by the use of Ziegler the alkyl group of 8 to 13 carbon atoms increases the solubil-
and Friedel-Crafts catalysts, or the free radical initiators. ity of the polymer in the oil, both at low and high tempera-
That is, their Mw/Mn is closer to 1. Because of the narrow tures, and contributes towards an increase in viscosity. It is
molecular weight distribution, these polymers possess the important to note that the viscosity contribution at lower
best thickening power of the types discussed so far. However, temperatures is a lot less than at high temperatures, prima-
the presence of the aromatic rings and the double bonds rily because of the smaller hydrodynamic volume. The inclu-
makes these polymers more susceptible to oxidation. This sion of the alkyl group of 14 and more carbons imparts pour
problem is somewhat overcome by catalytically hydrogenat- point depressing properties to the polymer since the alkyl
ing the double bonds. Figure 4.171 schematically presents group interacts with the wax crystals, which are of similar
the synthesis of these types of polymers. carbon size, during their formation. Polymethacrylates that
Recently, a different type of polymer, labeled a “star” are used solely as pour point depressants use a mixture of
polymer 共Radial Isoprene兲, has become commercially avail- C8-C13 and C14 and higher carbon monomers.
able. It has thickening power similar to that of the styrene- The carbon-carbon double bond in the alkyl methacry-
diene type, but has better shear stability. A clustered poly- late monomer is very reactive because of the conjugation
anion prepared from divinylbenzene and styrene forms the with the ester carbonyl. This makes it amenable to addition
center of the star, and the rays are made up of the polymer- type polymerization reaction. The presence of the methyl
ized diene monomer units. substituent on the double bond introduces steric hindrance,
Ester Polymers which deters attack by chemicals, including water, on the es-
These polymers include polymethacrylates 共PMAs兲 and ter functional group. This imparts chemical resistance and
styrene-ester 共SE兲 polymers. Polymethacrylates 共PMAs兲 are hydrolytic stability to the polymer. The alkyl group in the
made by the polymerization of alkyl methacrylate mono- methacrylate ester functional group is introduced either by
mers. The alkyl group either contains 1 to 7 carbons, 8 to 13 direct esterification of the methacrylic acid or by transesteri-
carbons, or 14 or more carbons 关469兴. The size of each alkyl fication. Direct esterification is commonly employed for
groups affects the polymer properties differently. The short chain alkyl methacrylates. The process involves the re-
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CHAPTER 4 䊏 LUBRICANT ADDITIVES 197
action of an alcohol with methacrylic acid in the presence of to lower their viscosity to a managing level, both during poly-
an acid catalyst and removing the reaction water. On the merization and afterwards. The solvent to be used must be
other hand, transesterification is the method of choice for nonreactive, have low volatility, avoid chain transfer reac-
making long-chain alkyl methacrylates. This method in- tion during polymerization, and be suitable for use in the fi-
volves the reaction of methyl methacrylate with an appropri- nal application. For the lubricant-related applications, min-
ate alcohol, usually in the presence of a basic catalyst. The eral oil with high saturates content is quite suitable.
reaction by-product, methanol, is removed to shift the equi- Depending upon the application, one can choose oils of
librium towards the product side. Both these reactions are 40° C kinematic viscosity between 2.7 cSt and 24 cSt. One
depicted in Fig. 4.172. The methacrylic acid itself is synthe- can also use a volatile solvent with the above-listed attributes
sized from acetone via its cyanohydrin, followed by hydroly- and exchange it with the desired oil 关469兴. The amount of oil
sis and esterification. An alternative method is via the oxida- or the solvent used is typically between 30 to 80 %; the exact
tion of butylene, hydrolysis, and esterification 关469兴. amount depends upon the molecular weight of the polymer.
Depending upon the polymer composition intended, ei- The purpose is to facilitate handling and pumping.
ther a single monomer or a mixture of monomers is treated Polymethacrylate based dispersant viscosity modifiers
with a free radical polymerization initiator, such as perox- 共DVMs兲 are also commercially available. As stated before,
ide, hydroperoxide, or a per-ester. The initiator free radical DVMs provide both the viscosity improvement and the dis-
attacks the terminal carbon of the double bond of the alkyl persancy. The dispersant moiety in PMAs is introduced both
methacrylate molecule, forming a tertiary carbon free radi- by co-polymerization 关187,285兴 and grafting 关276–294兴. Co-
cal, which reacts with another molecule. The process contin- polymerization usually involves nitrogen-containing meth-
ues until the process is terminated, which is done by the use acrylate monomers, such as dimethylaminoethyl methacry-
of a free radical transfer agent, such as an alkyl mercaptan. late, as shown in Figure 4.61. Grafting involves the use of
The use of the chain transfer agents is necessary to control either a nitrogen-containing monomer, such as N-vinyl-
the molecular weight of the resulting polymer, so that it has pyrrolidinone, directly, or via the incorporation of a func-
proper viscometrics and shear stability. The chain transfer tionalizable moiety, such as succinic anhydride, followed by
agent terminates polymerization by transferring hydrogen the reaction of the resulting polymer with a polyamine
to the polymer and in the process forms a new free radical, 关238,259,288–294兴. Grafting has the advantage of incorpo-
which is not reactive enough to take part in the polymeriza- rating monomers that have different reactivity than meth-
tion reaction. Polymerization temperature is typically be- acrylates and hence are not copolymerizable.
tween 60– 140° C, and requires selecting an initiator which Polymethacrylates are chemically inert molecules that
has a reasonable half life in this temperature range. Higher do not easily react with most chemicals. However, the reac-
temperatures usually result in polymers of lower molecular tions that they do undergo are depolymerization, oxidation,
weight and lower temperatures result in polymers of higher and hydrolysis. Depolymerization is the reverse of polymer-
molecular weight. This is because at higher temperatures, ization that occurs at high temperatures. The result is the
the initiator-derived free radical formation is rapid; result- formation of the high concentration of the original mono-
ing in many free radicals and hence many polymer chains. mers. The temperatures that cause depolymerization, typi-
See Fig. 4.173 for the polymerization mechanism using ben- cally around 235° C, are not normally encountered in
zoyl peroxide as initiator. Its half life is one to ten hours, de- lubricant-related applications 关235,470,471兴. Another ther-
pending upon the temperature. Commercial polymethacry- mal reaction PMAs undergo is the thermal decomposition at
lates have molecular weights between 20,000 and ⬃250° C, involving the alkyl group of the ester functional
750,000 g / mol. Higher molecular weight polymethacrylates group. The result is the formation of an olefin and a carboxy-
are almost always prepared in a solvent, which is necessary lic acid group, which can react with an adjacent carboxylate
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198 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
functional group to form a cyclic anhydride, by losing a mol- dium to large hydrocarbon chains, typically present in PMAs
ecule of water or the alcohol. Thermal decomposition of the used in lubricants, makes hydrolysis reaction even less likely
esters was described while discussing synthetic esters in the because of the general hydrophobic nature of such PMAs.
Chapter 3 on Synthetic and Natural Base Stocks. The ulti- Despite good overall thermal and chemical stability,
mate result of the thermal reactions is the generation of the PMAs are susceptible to mechanical shear, the same as OCPs
volatile materials and the loss of the polymer’s viscosity im- and other polymers. Mechanical shearing not only decreases
proving and pour point depressing properties. the size of the polymer chains but it also generates the free
Like other hydrocarbon materials, polymethacrylates radicals. In lubricants, the free radicals are quickly
are also susceptible to oxidation. The result is the polymer quenched by the hydrogens of the hydrocarbon oil or by the
chain scission to lower molecular weight polymeric frag- oxidation inhibitor, if present. However, the formation of
ments 关469,470兴. This lowers the thickening power of the smaller polymer fragments is a concern because of their di-
polymer because of the drop in the molecular size. While all minished effect on viscosity. As mentioned while discussing
carbon hydrogen bonds are prone to oxidative attack, poly- other polymers, shear stability of a polymer is related to its
methacrylate structure does not contain any benzylic, al- molecular weight, or more specifically to its linear size, and
lylic, and tertiary hydrogens that have the highest reactivity not the overall structure 关472兴.
towards oxygen. See the oxidation inhibitor section of this Since the polymethacrylates 共PMAs兲 are produced by
chapter. Consequently, oxidative scission of the polymer is the free radical polymerization of alkyl methacrylates, the
not a concern. polymer has a relatively broad molecular weight distribu-
Polymethacrylates are quite stable to hydrolysis reac- tion. Because of this, PMAs have low thickening efficiency
tions since the hydrolyzable ester functional group is well and hence only moderate viscosity-improving ability. Since
surrounded by various groups, which hinder the approach this ability depends upon the polymer’s molecular weight,
of water towards the ester carbonyl. The presence of the me- different polymers must be compared on an equal molecular
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CHAPTER 4 䊏 LUBRICANT ADDITIVES 199
weight basis. As mentioned above, there is flexibility to alter General structures of the various commercially available
the alkyl group in the ester portion of the polymer to obtain polymers along with their structural types are presented in
products that have the best oil solubility and the optimum Table 4.30.
viscosity-improving properties. In addition, these polymers Thickening Efficiency
have good compatibility with a large number of refined and Thickening efficiency and shear stability are two important
synthetic base stocks and are superior to olefin copolymers, considerations for selecting a polymer for use as a viscosity
both in oxidative and thermal stability and the low- modifier. Thickening efficiency is a direct function of the
temperature properties. Because of these attributes, PMAs polymer’s molecular weight. More specifically, it is the func-
find extensive use in a number of lubricants. Such lubricants tion of the length of the polymer backbone as shown in Fig.
include automotive engine oils, gear oils, automatic trans- 4.175. On an equal weight basis, a high molecular weight
mission fluids, hydraulic fluids, industrial oils, and greases. polymer provides higher viscosity than a low molecular
Styrene-ester polymers are prepared by first copolymer- weight polymer, as long as the structural features, such as
izing styrene and maleic anhydride and then esterifying the branching, are similar. For a given molecular weight, the
intermediate alternating copolymer using a mixture of alco- OCPs and PIBs have greater thickening power than styrene-
hols. Normally, the esterification step is taken to about 90 % diene polymers, which in turn have greater thickening
or more, followed by post-neutralization using a bifunc- power than poly共vinyl ether兲s and polymethacrylates. In this
tional or polyfunctional amine. Because of the presence of regard, styrene ester polymers are the least effective among
the basic nitrogen, these polymers function both as a dis- viscosity-modified polymers.
persant and as a viscosity modifier. Shear-related Viscosity Loss
Figure 4.174 summarizes the methods of synthesis for The viscosity loss in a viscosity-modified lubricant can result
polymethacrylate and styrene ester type viscosity modifiers. from mechanical, thermal, and oxidative degradation of the
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200 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
polymer. Unlike mineral oils, which primarily exhibit New- when the stress is removed, it is termed as temporary viscos-
tonian rheology, the polymer-thickened oils exhibit vis- ity loss. This type of loss is due to the reversible deformation
coelastic rheology. That is, their viscosity depends upon the of the polymer under the influence of the shear forces, which
degree of mechanical stress 共shear兲. When oils containing minimizes the association between the polymer and the lu-
the viscosity modifiers are subjected to moderate shear bricant. Temporary viscosity loss, shown in Fig. 4.177 关235兴
stress, viscosity decreases until it approaches the viscosity of and Fig. 4.178, is desired in lubricants because it decreases
the polymer-free oil. The mechanical or shear viscosity loss the viscous drag at low temperatures and hence could con-
is generally encountered in those equipment parts that inter- tribute towards fuel economy.
mesh. Journal bearings, vane pumps, and gear pumps are ex- The viscosity loss is considered permanent if after the
amples of such parts. The speed of the moving surfaces also shear forces are removed, the viscosity does not revert to its
influences the shear rate and hence viscosity. The viscosity prior value 关473兴. Permanent viscosity loss occurs when the
loss of a lubricant is directly proportional to the applied polymer in the viscosity-modified oil breaks down to the
shear rate, as shown in Fig. 4.176 关50兴. The higher the shear lower molecular weight fragments under the influence of
rate, the greater is the loss in viscosity. Piston rings experi- shear, as depicted in Fig. 4.179 关235兴. This type of viscosity
ence low shear rates; hence, the lubricant in this region expe- loss is not desired because a formulated lubricant will not
riences a low viscosity loss. Conversely, rod bearings are a stay in its viscosity grade. Whether temporary or permanent,
high shear environment; hence the lubricant undergoes a the viscosity loss depends upon the shear stability of the
high viscosity loss. The viscosity loss in the regions of the polymeric viscosity modifier used, which is a function of its
main bearings and cylinder walls that have intermediate molecular weight; more specifically it is the function of the
shear rates falls in between. size of the polymer backbone. This relationship, which holds
The viscosity loss can be temporary or permanent. If the true within a polymer type, is shown in Fig. 4.180.
viscosity bounces back to the original viscosity or close to it, High molecular weight polymers generally lose viscos-
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CHAPTER 4 䊏 LUBRICANT ADDITIVES 201
ity at a higher rate under shear than the low molecular Shear stability requirements for different applications
weight polymers. Hence, the lubricants thickened with low parallel the severity of the lubricating environment. Engine
molecular weight polymers are more likely to maintain their lubrication is mostly hydrodynamic in nature; hence, the lu-
viscosity in the desired viscosity range than the lubricants bricants of low shear stability are adequate. Gear lubrica-
thickened with high molecular weight polymers. Figures tion, on the other hand, is boundary in nature and therefore
4.181 and 4.182 depict the temporary and the permanent vis- requires lubricants of high shear stability. Transmission and
cosity loss in oils containing viscosity modifiers of two differ- hydraulic fluids fall in between the two in terms of these re-
ent molecular weights 关473兴. As can be seen, in both cases, quirements. This is shown in Fig. 4.183 关235兴.
the lower molecular weight polymer experiences a lower vis- The relationship between the polymer’s molecular
cosity loss. weight and its viscosity-improving effect, and the relation-
The problem of viscosity loss due to shear can be allevi- ship between the polymer’s molecular weight and its shear
ated by preshearing the high molecular weight polymer, stability are presented in Fig. 4.184 关4兴. Specific viscosity
prior to blending, or by choosing a more shear-stable poly- sp / c can be used as a measure of a polymer’s molecular
mer. Shear stability, which can be defined as the ability of a weight since the solution viscosity of the polymer-thickened
lubricant to resist viscosity loss under the influence of shear, lubricant is directly related to the molecular weight of the
primarily relates to the permanent viscosity loss. polymer. Specific viscosity is the fractional increase in vis-
cosity over that of the pure solvent caused by the addition of tive degradation occurs when the weak carbon hydrogen
the polymer. As depicted in the figure, both the polymer’s bonds in the polymer molecules react with oxygen to form
viscosity-improving ability and the shear sensitivity increase hydroperoxides and peroxy free radicals. These species can
with an increase with its molecular weight 共an increase in disproportionate to form a number of lower molecular
the specific viscosity兲. Higher shear sensitivity implies lower weight oxygenated compounds. This type of degradation not
shear stability. only causes a loss in viscosity but the resulting polar com-
A number of tests are available to measure the viscosity pounds also form varnish and coke deposits in a manner
improving properties and the shear stability of polymers in similar to that of the lubricants. The mechanism of oxidative
lubricants. The shear stability of a lubricant is measured by degradation of polymers is shown in Fig. 4.186.
the CRC L-38 Test, FZG Shear Test, Sonic Shear Test, Or- Table 4.31 compares the properties of interest between
bahn Shear Test, Bosch Injector Test, and the Tapered Bear- various classes of polymers. The data indicate OCPs to be the
ing Simulator Test. In terms of severity, the Tapered Bearing cheapest but in terms of the overall performance, styrene-
Test is the most severe, followed by the FZG Test, Orbahn diene types 共SB and SI polymers兲 are the best. OCP-g-PMA is
Test, and the CRC L-38 Test. the best choice if both cost and performance are considered,
Viscosity Loss Due to Polymer Degradation which is most often the case. These polymers result from the
In addition to mechanical breakdown 共shear兲, polymers can grafting of the alkyl methacrylates onto the OCPs.
also undergo thermal and oxidative degradation. Thermal
degradation occurs when the polymerization process is re- Dispersant Viscosity Modifiers 共DVMs兲
versed under the influence of heat. Polymers break down via Dispersant viscosity modifiers 共DVMs兲 based on poly-
chain scission to form the lower molecular-weight frag- methacrylates and OCPs are also commercially available. A
ments. The consequence is a permanent loss in viscosity. new class of DVMs, made from PMA/OCP mixtures, was in-
This type of degradation, which is more prevalent in aro- troduced in the 1990s. Dispersancy in these polymers is ob-
matic polymers due to their ability to form more stable al- tained by including the basic nitrogen or the surfactant type
lylic and benzylic free radicals, is shown in Fig. 4.185. Oxida- oxygen-containing monomers during the polymerization
process. The monomers that are commonly used for this two ways. Grafting is common in the case of OCP and SD
purpose are shown in Fig. 4.63. The dispersant functional type polymers but for PMAs, copolymerization is more
group is introduced either by grafting or through copolymer- prevalent.
ization. Grafting and copolymerization with a nitrogen- Commercially available DVMs contain two distinct
containing monomer, such as 2- or 4-vinylpyridine, imparts functional groups: a polymeric backbone 共the VM portion兲
the dispersancy directly. Grafting of maleic anhydride, on and the dispersant moiety. Thus, their physical, mechanical,
the other hand, leads to a succinic anhydride or succinic acid and chemical properties will depend upon either the inher-
that must be reacted with alkylene-polyamines to form a dis- ent properties of the VM portion of the molecule, the dispers-
persant functional group. At present, no commercial prod- ant functional group, or both. When the properties are deter-
ucts made in this manner appear to be on the market. Anti- mined by both, a possibility of synergism or antagonism
oxidant functional group can also be added in either of these exists. The properties that relate to the VM portion of the
molecule are thickening efficiency, shear performance, ther-
mal and oxidative stability, and low-temperature properties;
and those pertaining to the dispersant portion are oxidative
and chemical stability, and dispersancy. For a detailed dis-
cussion on the role of DVM structural features on various
properties, please refer to the topic of dispersants, especially
the dispersant polymers.
Considering the theorized mechanism of the dispersant
action, it is reasonable to assume that the dispersancy will
relate to both the basicity and the molecular weight of the
DVMs. Based on the pKa values of the different functional
groups, one would expect dimethylamino group to be more
basic than pyridyl group, which in turn is expected to be
more basic than 2-keto pyrrolidinyl group. Hence, one
would anticipate dispersancy to follow the same order. Typi-
cally, formulations containing DVMs require an additional
amount of dispersant since some applications, such as en-
gine oils, need certain level of nitrogen to appropriately per-
form the function of suspending deposit precursors, depos-
its, and soot. It is generally believed that the multifunctional
Fig. 4.180—Shear stability as a function of polymer molecular additives, such as DVMs, perform better than the combina-
weight. tion of additives of the two types because both moieties are
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204 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
concurrently present where they are needed. Data reported and the desirable presence of wax due to its high VI charac-
in Table 4.32 support this notion. The test is Sequence VG ter 关50兴. For mineral oils to function effectively at low tem-
engine test that uses the SAE 5W-30 API SG quality oil 关469兴. peratures, the additives called the pour point depressants
The formulations contain analogous ingredients, except the are used. Current practice favors mild dewaxing in combina-
viscosity modifier. tion with the use of the pour point depressants. Incidentally,
wax is only a problem in the API Group I oils and not in
Pour Point Depressants Group II or III oils.
The pour point is the lowest temperature at which a fuel or
A good pour point depressant can lower the pour point
mineral oil will pour when cooled under defined conditions.
of a lubricant by as much as 40° C. These additives are com-
At low temperatures, the wax tends to separate as crystals
monly used in mineral oil-based lubricants that are designed
with a lattice type structure. These crystals can trap a sub-
for applications with operating temperatures usually below
stantial amount of oil via association, thereby inhibiting the
0 ° C. Pour point depressants have virtually no effect on the
oil flow and ultimately hindering proper lubrication of the
critical equipment parts. temperature where the wax crystals start to precipitate
Base oil suppliers remove most of the wax during petro- 共cloud point兲 or the amount of wax that separates. They es-
leum refining. However, complete dewaxing of base oils is sentially act as the wax-crystal modifiers and function by al-
not practical because of the process limitations, economics, tering the crystal size. They do this either by absorption onto
the surface of the newly formed crystals or by co-
crystallizing with the precipitating wax. Both mechanisms
inhibit lateral crystal growth and keep the bulk oil fluid. Of
the commercial pour point depressants, alkylaromatics are
believed to perform via the absorption mechanism and the
aliphatic polymers via co-crystallization 关308兴.
The molecular weight and the structure of the polymeric
pour point depressants enable them to be effective over a
wider range than their low molecular weight counterparts.
The extended range of performance in the case of polymers
is believed to be due to their limited solubility in the petro-
leum fractions. As the temperature decreases, different poly-
mer segments become successively co-crystallizable.
A good pour point depressant must possess one or more
of the following structural features.
1. Polymeric structure.
2. Waxy and nonwaxy components.
3. Comb structure—Comb structure means a short back-
Fig. 4.182—Permanent viscosity loss due to shear 关473兴. bone with long pendent groups. This is in contrast to the
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CHAPTER 4 䊏 LUBRICANT ADDITIVES 205
structure of the viscosity modifiers where the backbone late derivatives can act both as viscosity modifiers and pour
is relatively long and the pendent groups, if present, are point depressants; hence when this chemistry is used for vis-
short. cosity improvement, the need for a pour point depressant is
4. Broad molecular weight distribution. minimized.
Most commercial pour point depressants are organic Pour point depressants are used at treatment levels of
polymers, although some nonpolymeric substances have 1 % or lower. In nearly all cases, there is an optimum concen-
been shown to be effective. Tetra 共long-chain兲 alkyl silicates, tration above and below which the pour point depressants
phenyltristearyloxysilane, and pentaerythritol tetra-stearate become less effective. The essential structural difference be-
are examples of the nonpolymeric type. Commercial pour tween the pour point depressants and the viscosity improv-
point depressants include alkylated naphthalenes, poly共alkyl ers of the same class is that the viscosity improvers consist of
methacrylate兲s, poly共alkyl fumarate兲s, styrene esters, oligo- long backbones with short pendent groups and the pour
merized alkylphenols, phthalic acid esters, ethylene-vinyl point depressants consist of short backbones with large pen-
acetate copolymers, and other mixed hydrocarbon poly- dent groups. This difference is depicted in Fig. 4.188. Figure
mers. 4.189 shows a pour point’s ability to change wax crystal mor-
Figure 4.187 contains the structures of the poly共alkyl phology and permit flow.
methacrylate兲s, alkylaromatics, and styrene-ester polymers, Pour point depressants are used in engine oils, auto-
which are the most commonly used chemical types. The matic and power transmission fluids, automotive gear oils,
alkyl chains on these additives are largely linear and of differ- tractor and industrial hydraulic fluids, and circulating oils,
ent carbon number, from C1 to C24, or higher. Carbon distri- especially those intended for use in cold climates. The need
bution prevents them from crystallizing out of the oil at for these additives is likely to decrease due to a general shift
room temperature. At low temperatures, fatty carbon chains away from the API Groups I oils towards Group II and III
共艌C12兲 interact with the wax and interfere in the formation oils, where the iso-dewaxing technology alters the linearity
of the crystalline networks. For PMAs with pour point de- of the wax-forming components. The performance of a pour
pressant properties, the molecular weight ranges between point depressant is determined in a base stock and the lubri-
200 and 3000 g / mol. High molecular weight polymethacry- cant by one or more of the following tests.
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206 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
Fig. 4.184—Effect of specific viscosity on oil viscosity and shear stability 关4兴.
1. ASTM D97—Pour point of petroleum oil cult to break. The presence of the surface-active materials,
2. ASTM D3829—Borderline pumping test such as dispersants and detergents, further increases the lu-
3. ASTM D2602—Apparent viscosity at low temperature bricant’s tendency to foam.
using cold-cranking simulator Foam inhibitors control the foam formation by altering
the surface tension of the oil and by facilitating the separa-
Foam Inhibitors tion of air bubbles from the oil phase. In general, these addi-
Gases are soluble in mineral oils to a limited amount. The tives have limited solubility in oil; hence they are added as
amount varies with the type of gas and the oil temperature. very fine dispersions. Foam inhibitors are effective at very
For example, 8 to 9 % of air by volume is soluble in mineral low treatment levels, 3 to 150 parts per million.
oil at room temperature. Dissolved gases affect a number of Silicones 共polysiloxanes兲, poly共alkyl acrylate兲s, and
oil properties, such as viscosity, bulk modulus, heat transfer, poly共alkyl methacrylate兲s are the commonly used foam in-
oxidation, boundary lubrication, and the foaming tendency.
hibitors, with silicones being the more popular. ASTM D892
The amount of the soluble gas in oil is measured by the
Test is used to assess a lubricant’s foaming tendency. The
ASTM D2780 Test. When the amount of a gas in oil exceeds
structures of the three common types of additives are shown
saturation, small gas bubbles are slow to come out and the
in Fig. 4.190.
oil appears hazy for a period of time. This phenomenon is
called entrainment. Foam forms when a large amount of gas,
for example, air is entrained in a liquid. While foaming is de- Other Additives
sirable in certain applications, such as flotation, washing, In addition to the major classes of additives described so far
and cleaning, it is undesirable in others, such as distillation in this chapter, lubricants contain a number of other addi-
and pumping of fluids. In lubricant-related applications, tives. These include seal-swell agents, dyes, biocides, and cou-
foam can act as an impediment and must be controlled. Al- plers.
most every lubricant application involves some kind of agita- Seals are used in modern machinery for a variety of rea-
tion which encourages foam formation through air entrain- sons. In lubrication systems, their functions are as follows.
ment. Excessive foaming will result in ineffective lubrication 1. Isolate various lubrication environments from harmful
due to the formation of the noncontinuous lubricating film, elements.
thereby leading to metal-to-metal contact; and, over time, 2. Help maintain hydraulic pressure.
will cause oxidative degradation of the lubricant. Additional 3. Allow removal and replacement of the malfunctioning
problems due to foaming include over-filling of the sumps, parts without the need to totally dismantle the equip-
loss of oil out of the vents, and poor performance in hydrau- ment.
lic systems. The foaming characteristics of an oil are mea- 4. Minimize contamination and the loss of lubricant.
sured by the ASTM D892 Test. The viscosity and the surface Seals are commonly made from polymeric materials
tension of a lubricant determine the stability of the foam. such as fluoroelastomers, nitrile rubber, polyacrylates, and
Low-viscosity oils produce foams with large bubbles, which silicones. Structures of these materials are provided in Fig.
tend to break quickly. On the other hand, high-viscosity oils 4.191. Lubricants containing certain base stocks and addi-
generate stable foams that contain fine bubbles and are diffi- tive systems can cause shrinkage, brittleness, and deteriora-
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CHAPTER 4 䊏 LUBRICANT ADDITIVES 207
tion of the seals and impair the performance of the lubricat- These include alkalinity buffers, odor masks, and anti-
ing system. misting agents. Alkalinity agents and odor masks are used to
Seal-swell agents are additives which maintain the integ- control acidity and odor in water-based systems. Acidity and
rity of these seals. Additives belonging to this class include odor result from the decomposition of the oil and the addi-
polyesters, some phosphorus derivatives, and proprietary tives due to bacterial and fungal attack. Amines and inor-
chemicals. Seal-swell agents are commonly used in trans- ganic bases are used to control acidity and natural and syn-
mission and hydraulic fluids. thetic aromatic materials are used to control odor. Anti-
Dyes are used to color-code lubricants to ensure their misting agents are used to suppress mist formation,
use in the proper application and as a leak detection aid for primarily in oil-based fluids, which if not controlled can be
the consumer. ATFs contain a red dye, and two-stroke cycle harmful to workers. Polymers of various types are used for
oils contain a blue or a purple dye. These dyes are oil-soluble this purpose. Chapter 11 on Metalworking Fluids contains a
organic compounds, mostly with an azo structure. To a lim- more detailed discussion on these additives.
ited extent, dyes are also used as a marketing tool to impart
color, or the fluorescence, to lubricants that was historically Multifunctional Nature of Additives
perceived to indicate good performance. This is because to- A number of additives perform more than one function. Zinc
day’s refining processes remove compounds that impart this dialkyl dithiophosphates, known mainly for their antiwear
characteristic. action, are also potent oxidation and corrosion inhibitors.
In general, the mineral oil-based lubricants resist mi- Styrene-ester polymers and functionalized polymethacry-
crobial attack because of their high-temperature operation lates and can act as viscosity modifiers, dispersants, and
and the presence of the additives, many of which have bio- pour point depressants. Basic sulfonates, in addition to act-
cidal action. High water-based lubricants, such as certain ing as detergents, perform as rust and corrosion inhibitors.
metalworking fluids and hydraulic fluids, are easily attacked They do so by forming protective surface films and by neu-
by microbes and fungi. The control of bacterial and fungal tralizing acids that arise from fuel combustion, lubricant
growth is essential to minimizing product deterioration and oxidation, and additive degradation.
possible health hazards. This is done by the use of the water-
soluble triazine, morpholine, imidazoline, and thiazoline Environmental Impact of Additives
derivatives, which possess biocidal properties. Triazines, ATC 共the Technical Committee of Petroleum Additive Manu-
which owe their biocidal action to their formaldehyde- facturers in Europe兲 in the early 1990s carried out a study
releasing ability, find extensive use in this application. The that traced engine oil additives across 19 OECD 共Organiza-
interested reader may refer to Chapter 11 on Metalworking tion for Economic Co-Operation and Development兲 coun-
Fluids for a more detailed discussion on biocides. tries with cradle to grave perspective. The objective was to as-
Couplers are additives that are used in water-based lu- sess the impact of additives on the consumer and the
bricants to help stabilize micro-emulsions. Glycol and its de- environment. The report 关474兴 reviews the nature, develop-
rivatives are commonly used for this purpose. ment, health and safety aspects, benefits to the consumer,
Metalworking fluids use a number of other additives. and the ultimate fate of the engine lubricant additives. An ac-
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208 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
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CHAPTER 4 䊏 LUBRICANT ADDITIVES 209
the equipment under development. To fulfill this need, vari- Newly developed additives are blended with other addi-
ous organizations, such as SAE, API, ASTM, AGMA, and tives in the customer’s base oil and are screened in a number
OEMs, initiate the development of new performance specifi- of proprietary bench tests. Bench tests are accelerated tests
cations and the test methods. A flowchart leading to the de- which are devised to closely simulate the conditions the lu-
velopment of a new category, exemplified by the develop- bricant is likely to experience in actual service. This kind of
ment of ILSAC GF3, is depicted in Fig. 4.192 关476兴. Additive testing is quite common because it allows the evaluation of a
companies, either alone or in collaboration with a lubricant large number of additives quickly and inexpensively.
supplier, try to satisfy the performance requirements estab- Once a lubricant satisfies the performance criteria of the
lished for the new product/category. If the additive company bench tests, full-fledged testing using actual equipment is
is unable to develop an additive system using their existing carried out. This may be done in a laboratory or in collabora-
technology base, they initiate a project to develop and test a tion with an end-user. For additives used in automotive
new additive. products, field trials may also be necessary. The costs associ-
Fig. 4.189—The mechanism of the pour point depressant performance 关318兴. Reprinted with permission from the Lubrizol Corporation.
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210 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
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CHAPTER 4 䊏 LUBRICANT ADDITIVES 211
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MNL59-EB/Mar. 2005
5
Combustion Engine Lubricants
DISCUSSION IN THIS CHAPTER PERTAINS TO walls, or travel past piston rings as part of the blow-by
combustion engine lubricants. The chemistry and technol- and enter the crankcase. This typically occurs in cold
ogy of these lubricants are presented along with United weather or short distance driving because the engine
States and European performance specifications and the and the lubricant are not hot enough for water to be
process of establishing them. In order to facilitate under- removed via evaporation. Water can initiate rust and,
standing, various types of internal combustion engines and in the presence of the acidic materials resulting from
their operation are described. The chapter also addresses the lubricant oxidation and additive decomposition,
the current topics of fuel economy, emissions control, and can cause corrosion.
extended service intervals. The chapter is concluded by cit- 6. Keep Engine Parts Clean: Partial fuel combustion prod-
ing examples of several engine oil formulations. ucts, such as free radicals, soot, sulfur, and nitrogen
Engine lubricants, or engine oils, are designed for use oxides, enter the crankcase as the blow-by and react/
in internal combustion engines. Modern engines operate interact with the lubricant to form highly polar deposit
on a wide variety of fuels and in environments that involve precursors and corrosive materials. These species have
temperature extremes; hence their lubrication is quite the tendency to separate on the hot surfaces to form
complex. A combustion engine lubricant must possess at- deposits and to lead to corrosion. Engine lubricants
tributes to help it perform the following functions effec- are designed to prevent the formation of these species
tively. or keep them from separating on the surfaces by sus-
1. Permit Easy Starting: It must have low viscosity at low pending them in the bulk lubricant, or both.
temperatures and be pumpable, so as to instanta- 7. Cool Engine Parts: Cooling of the engine parts is cru-
neously reach the engine parts that need lubrication. cial to its trouble-free operation. Parts that must be
This is an important attribute since most of the engine cooled include cylinder heads, cylinder walls, valves,
wear occurs during the start-up, primarily due to lu- crankshaft, main and connecting rod bearings, timing
bricant starvation. gears, pistons, and others. Certain parts of the engine
2. Maintain Adequate Viscosity at High Temperatures: This can be cooled by the use of a coolant, which is typi-
is important because most oils experience a decrease cally a mixture of water and ethylene glycol. Other
in viscosity at high temperatures, such as those in and parts cannot be effectively cooled by the coolant, either
around the combustion engine. If the viscosity of the because of their vicinity, or the part temperature is ex-
oil drops too far, the lubricant loses its ability to form tremely high, which leads to the rapid evaporation of
the lubricating film of the appropriate thickness, water. In such situations, the lubricant acts as a cool-
which will permit metal-to-metal contact and wear will ant.
ensue. 8. Seal Combustion Pressures: Surfaces of piston rings,
3. Lubricate and Prevent Wear: This translates into the oil ring grooves, and cylinder walls do not have an ideal
forming a lubricating film of appropriate thickness to fit, primarily because of the machining limitations. It
prevent metal surfaces from contacting each other and is important that these parts act as a good seal to pre-
experiencing wear. For most engine parts the surfaces vent the loss of the high combustion and compression
are well separated, which makes lubrication easier. pressures, which are needed for the efficient engine
However, there are parts such as the piston rings and operation. A loss into the low pressure area of the
cam lobes, which are designed to have metal-to-metal crankcase would result in a reduction of the engine
contact and the function of the lubricant is to mini- power and efficiency. Engine oils therefore improve
mize wear by making chemical surface films. the seal by filling spaces in the above-listed parts. Typi-
4. Reduce Friction: The formation of the lubricant film of cally the oil film that acts as a seal is only 0.025-mm
proper thickness on surfaces and its maintenance will thick; hence it is ineffective in filling spaces that are
reduce friction and the accompanied wear. This is es- larger because of the intensive wear. Incidentally, the
pecially true during the start-up and idle, when the oil consumption in a new engine is high until the sur-
lubrication is inadequate and the frictional losses oc- faces in these parts become smoother due to wear for
cur. Therefore, controlling friction will improve the the oil to form a better seal.
fuel economy. 9. Control Foam: Foaming of the engine oil due to air
5. Protect Against Rust and Corrosion: Water resulting entrainment occurs because of the rapidly moving en-
from the fuel combustion, while meant to escape gine parts which create turbulence. The result is the
through the exhaust, can condense on the cylinder formation of the air bubbles, which normally rise to
212
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CHAPTER 5 䊏 COMBUSTION ENGINE LUBRICANTS 213
the surface of the oil and break. However, the presence fueled engines, a spark plug. Intake valves allow the intake of
of water and additives, many of which have surfactant air or of the air-fuel mixture and exhaust valves help remove
properties, slows down this process. Foam in the en- the products of combustion. Pistons are attached to a crank-
gine oil is undesired because of its poor cooling ability shaft by the connecting rods and their motion rotates the
and noncontinuous film formation, which will result in crankshaft, which is connected to a drive mechanism by
excessive engine wear. suitable gearing. Such engines can be either four-stroke
While a good quality engine oil can perform these cycle or two-stroke cycle, depending upon the number of
functions adequately, the continuing efforts of the OEMs to strokes by the piston in one full turn, or cycle, of the crank-
improve emissions quality by recycling partial combustion shaft.
products from the exhaust and venting the volatiles from Reciprocating piston engines, based upon the mode of
the fuel system and the bulk lubricant 共positive crankcase ignition, can be divided into spark-ignition 共SI兲 and
ventilation兲 into the combustion chamber place additional compression-ignition 共CI兲 types. While there are a number of
demands on the lubricant. This strategy is effective in low- differences between the two types, the primary difference
ering the partial combustion products, such as the un- lies in the combustion system. The SI engines use a homoge-
burned or partially burned hydrocarbons and carbon mon- neous air-fuel mixture, obtained by premixing the two either
oxide, but at the expense of enriching the combustion in a carburetor or the intake port. Combustion is initiated by
mixture in NOx 共nitrogen oxides兲, a potent oxidant. This a spark, and the combustion rate is primarily controlled by
will be discussed further in Chapter 6 dealing with Emis- the shape of the combustion chamber. The CI engines, on the
sions in an Internal Combustion Engine. other hand, burn a heterogeneous mixture since the air is
Types Of Engines And Mode Of Their compressed first and then the fuel is introduced. Combus-
Operation tion occurs via self-ignition due to the heat generated from
the compression process. Incidentally, in some CI engines, a
Engines are devices that help produce motion. The energy glow plug is used to facilitate ignition. The rates of ignition
used to drive engines comes from a number of sources, but and combustion in these engines are largely controlled by in-
chemical sources, such as petroleum products, are the most jection timing and the injection rate.
prevalent. Engines where fossil fuels are burned to convert A graphic representation of the operation of the four-
the fuel’s latent energy into heat to do the work are called the stroke cycle engine is shown in Fig. 5.1. The four strokes are
combustion engines. They can be of external combustion intake, compression, ignition and power, and exhaust. Dur-
type, such as steam and Stirling engines, or of the internal ing the intake stroke, the rotating crankshaft moves the pis-
combustion type 关477兴, such as gasoline and diesel-fueled ton down, creating a partial vacuum which facilitates the in-
engines. In an external combustion engine, the fuel is troduction of the air-fuel mixture into the cylinder through
burned in a furnace that is not an integral part of the engine. the open intake port. During the compression stroke, both
The generated energy is used to heat a fluid, water or air, intake and exhaust valves are closed and the mixture is com-
which does the actual work. In an internal combustion en- pressed by the piston moving up. During the ignition and
gine, the fuel is burned inside the engine itself, and the com- power stroke, ignition of the fuel-air mixture occurs and hot,
bustion products are used to drive the mechanisms that per- expanding gases result that force the piston down and rotate
form the work. Based upon the mode of combustion and the the crankshaft, thereby producing power. During the ex-
manner in which the energy is transformed into work, the haust stroke, the by-products of combustion are vented
internal combustion engines can be further classified into through the exhaust valve/s. After the exhaust stroke, the
reciprocating-piston engines, rotary engines, and cycle starts again with the intake stroke. At the beginning of
continuous-combustion gas turbine engines 关23兴. the intake stroke and the ignition and power stroke, the pis-
Reciprocating-piston Engines ton is at the top of the cylinder. At the beginning of the com-
These engines are used most widely and contain pistons that pression and the exhaust strokes, it is at the bottom. The
move up and down in cylinders; hence, the name reciprocat- number of crankshaft revolutions per minute represents the
ing piston. The top of the cylinder is closed by a metal cover, engine speed.
called the head, which contains valves and, in gasoline- Unlike the four-stroke cycle engines that produce one
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214 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
power stroke for every four strokes 共two crankshaft revolu- When the piston reaches the top dead center, ignition is
tions兲; the two-stroke cycle engines require only two strokes induced either by spraying the fuel into the hot compressed
共one crankshaft revolution兲 for each power stroke. This is air 共CI兲 or by spark-igniting the air-fuel mixture 共SI兲; thereby
achieved by combining the compression and the ignition in starting the power stroke. When the piston moves below the
the first stroke and the exhaust and the intake in the second exhaust Port B, most of the exhaust is displaced. Soon after,
stroke. However, the two operations in each stroke are timed the intake Port A is uncovered and either air or an air-fuel
to achieve a higher degree of efficiency. All operations are mixture is introduced into the cylinder. If the intake port and
controlled by the upper and lower edges of the pistons. The the exhaust port are situated across from each other, as
operation of a two-stroke cycle engine is shown in Fig. 5.2. shown in Part A of Fig. 5.3, a portion of the intake can escape
with the exhaust. This situation, termed cross-scavenging, Face B is starting to compress the air-fuel mixture. Rotor
can be minimized by using deflectors on the top of the pis- Face C is at the end of the power phase and is starting to ex-
tons. Another way to minimize cross-scavenging is by loop haust the combustion products. As the rotor moves counter-
scavenging. In this arrangement, the intake and the exhaust clockwise, as shown in Part 2, both the intake and the ex-
are placed nearby instead of across from each other 共Fig. 5.3, haust ports are open, and intake, compression, and exhaust
Part B兲. This forces the intake to pass through a complete occur simultaneously. As the rotor continues to move, these
“loop” before reaching the exhaust port. Part C of Fig. 5.3 three functions are almost near completion, as shown in Part
shows the arrangement where a combination of the exhaust 3 of the figure. At this time, the ignition takes place and the
valves in the head and the intake ports in the cylinder are power is generated. Further rotation leads to completion of
used to achieve through or uniflow scavenging. the exhaust phase, the power phase, and the intake phase, as
The rotary engine, or a Wankel engine, is also a four- shown in Part 4 of the figure. At this stage, the cycle starts
stroke cycle internal combustion engine, but it differs radi- again. The key features of the Wankel engine are its configu-
cally from the conventional reciprocating piston engines. ration and the rotary motion. These not only facilitate de-
The cylinders and the pistons are replaced by working cham- signing of the advanced pollution control devices for such
bers and rotors encased in a stationary housing with ports. engines easy, but also help them achieve higher engine
The working chamber and the rotor parallel the functions speeds than those ordinarily possible by the reciprocating
performed by the cylinder and the piston, the ports in the piston engines.
housing act as valves, and the phases take the place of The continuous-combustion gas turbine engines, the one
strokes. The position of the rotor subdivides the working shown in Fig. 5.5, contain a compressor, turbine, and com-
chamber into sections, each of which performs a specific bustion chamber 关23,479兴. Air is pulled into the compressor
function. However, unlike the piston engine where each ac- and compressed. The compressed air is split into two
tion 共intake, compression, ignition, and exhaust兲 takes place streams. One stream is passed into the combustion chamber
sequentially, in the rotary engine, several actions take place where it is mixed with the fuel and the air-fuel mixture is ig-
simultaneously. nited. The second stream of air is mixed with the combustion
The working of the Wankel engine is depicted in Fig. 5.4 products downstream and the mixture is passed through a
关478兴. In such engines, simultaneous functions are possible narrow nozzle ring to decrease pressure, hence increase ve-
because of the radial location of the rotor. When the rotor is locity. The high-velocity gases are used to turn a turbine
in the position shown in Part 1 of the figure, both the intake wheel, which is connected to a compressor by a shaft. Due to
and the exhaust ports are closed by Face A, and the rotor the continuous flow of gases, these engines achieve much
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216 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
higher speeds than those possible by the other types of com- engine parts clean, minimizing combustion chamber depos-
bustion engines. its, cooling engine parts, and sealing combustion pressures.
Most engines used in transport and industry today are of In the United States, performance specifications for en-
the internal combustion type. The prime reasons for the gine lubricants are established by the collaborative efforts of
popularity of such engines are their high thermal efficiency a number of organizations, including the Society of Automo-
and their light weight in relation to power capability. Four- tive Engineers 共SAE兲, American Petroleum Institute 共API兲,
stroke SI and CI engines are used in most automotive appli- ASTM International 共ASTM兲, American Automobile Manu-
cations. Depending upon the cylinder arrangement, four- facturers Association 共AAMA兲, Engine Manufacturers Asso-
stroke cycle engines can be further classified into in-line, V ciation 共EMA兲, and Chemical Manufacturers Association
共Vee兲, opposed-piston, and the radial types 关23兴. Two-stroke 共CMA兲 关480兴. The history of development of the North Ameri-
cycle SI engines are commonly used in lightweight applica- can performance standard for engine oils and other lubri-
tions 共outboard motors, mopeds, motor scooters, motor cants is described in Ref 关33兴. In a number of cases, the U.S.
cycles, snowmobiles, and chain saws兲, and two-stroke cycle Original Equipment Manufacturers 共OEMs兲 and the U.S.
CI engines find use in on-highway trucks, city buses, slow- Military have additional specifications. In Europe, ACEA
speed marine, and some railroad diesel applications. 共Association des Constructeurs Européens de
The manufacturers of the internal combustion engines l’Automobiles兲, CEC 共Conseil Européens de Coordination
are implementing design changes in their equipment so as to pour les Developments des Essais de Performance des Lubri-
meet national and international emissions standards. Some fiants et des Combustibles pour Moteurs兲, ATC 共Technical
of these are addressed in the Chapter 6 dealing with the In- Committee of Petroleum Additive Manufacturers兲, and
ternal Combustion Engine Emissions. ATIEL 共Association Techniqué de l’Industries Européenne
des lubrifiants兲 have collaborated in a manner similar to
Lubricant Specifications and Classifications
their American counterparts to come up with their own en-
The automobile industry by far is the largest user of lu- gine oil classification system, called the European Engine
bricants. Of the total lubricant use for the year 2006, esti- Lubricant Quality Management System 共EELQMS兲. The
mated at 38 million metric tons, about 57 % is for the auto- system does include some individual OEM requirements.
motive applications and over two thirds of it is for Prior to December 1995, Comité des Constructeurs
automotive engine oils. Engine oil demand is slowly declin- d’Automobiles du Marché Commun 共CCMC兲 helped ensure
ing because of the OEMs’ on-going efforts to improve engine the availability of the lubricants that met the performance
designs, with the intent to reduce weight, increase fuel requirements of the European vehicles. In Japan and India,
economy, increase power output, and meet environmental the Japanese Automobile Standards Organization 共JASO兲
emissions guidelines. A number of other power train tech- and the Bureau of Indian Standards perform these func-
nologies, which are either already being marketed, such as tions. Japanese vehicle manufacturers generally recom-
hybrids, or are on the horizon, such as those involving the mend engine oils for service-fill based upon the API Classifi-
fuel cell, are likely to have additional negative impact on the cation System.
demand of engine oils. The American Automobile Manufacturers Association
As mentioned earlier, engine oils are designed to per- of the United States 共AAMA兲 and the Japan Automobile
form a number of diverse functions in an engine. The perfor- Manufacturers Association 共JAMA兲 have collaborated to
mance of engine oils is primarily judged on their ability to form the International Lubricant Standardization and Ap-
reduce friction, resist oxidation, minimize deposit forma- proval Committee 共ILSAC兲. ILSAC has developed and ap-
tion, and prevent corrosion and wear. However, there are ad- proved its minimum performance standards GF-1 to GF-4
ditional requirements that relate to, for example, good visco- for passenger car engine oils 关481兴, starting with GF-1 in
metrics to permit easy starting at low temperatures and 1992. GF-2, GF-3, and GF-4 went into effect in the year 1996,
provide adequate lubrication at high temperatures, keeping 2001, and 2004, respectively. The work has already started
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CHAPTER 5 䊏 COMBUSTION ENGINE LUBRICANTS 217
on the ILSAC GF-5 standard, which is slated to go into effect vice life. At this stage, the lubricant viscosity will see an
in the year 2009 关482兴. ILSAC GF-4, the most recent standard abrupt increase. Base oil viscosity increase as a consequence
that is currently in effect consists of three sections dealing of oxidation was described in Lubricant Additives, Chapter
with physical and performance properties of the lubricant, 4.
while the fourth section cites documents applicable to the Viscosity is not the only lubricant parameter that is
standard 关481兴. The first section deals with viscosity and uses likely to change with oxidation; its Total Acid Number 共TAN兲
the SAE viscosity classification standard, SAE J300. This will increase as well as the deposit-forming tendency. The
section also includes an ASTM Test, D5133, which measures former is due to the oxidation-derived acids and the latter is
the low temperature, low shear rate viscosity in terms of the due to the formation of the highly oxygenated materials of
gelation index and the temperature at which gelation occurs. low oil solubility and aldehydes and ketones that can react
Gelation index represents the maximum rate of viscosity in- with each other to form polymeric materials. The mecha-
crease. The second section deals with the performance re- nism of formation of the deposit precursors was explained in
quirements and primarily uses the API SM performance cri- the section on Oxidation Inhibitors in Chapter 4. It is impor-
teria. The third section contains specifications for a number tant to control the formation of both these species otherwise
of physical bench test performance parameters. These in- proper engine performance will be compromised due to in-
clude catalyst compatibility, wear, volatility, high tempera- creased corrosion and deposits. Typically oxidation-derived
ture deposits, filterability, foaming tendency, high- acids are neutralized by the use of the basic detergents.
temperature high-shear rate viscosity, homogeneity and Therefore, to achieve the objective of extending the service
miscibility, and the rusting tendency. interval, one must have the base oils, hence the lubricants,
An important feature of the ILSAC standards is that fleet that are oxidatively more stable and additives, such as oxida-
testing of the lubricant to demonstrate performance is not tion inhibitors, detergents, and dispersants that are longer
necessary. Meeting the performance requirements in the lasting. The topic of drain interval is discussed further to-
specified engine sequence tests is considered sufficient. This wards the end of this chapter.
is done to minimize testing time and costs. An analogous The topic of fuel economy was dealt with in some detail
standard for diesel engine oils may be forthcoming. While in the Friction Modifiers Section of the Additives Chapter 4;
the standards established by each country are important, hence we will be brief here. Many nations in the world are
ACEA and ILSAC standards for gasoline engine oils and the interested in preserving the quality of their environment, es-
API standard for diesel engine oils are global in impact. Glo- pecially the air quality. Carbon dioxide 共CO2兲 is one of the
bal specifications are also in place for heavy-duty diesel en- combustion-related gases that are being scrutinized. More
gine lubricants, DHD-1, and the proposed DHD-2. specifically, the drive is to decrease the vehicle-related emis-
sions of CO2 by lowering the use of gasoline in cars and die-
Trends Impacting the New Performance Standards sel in trucks. This is precisely the objective of the Corporate
New performance standards are developed in response to Average Fuel Economy 共CAFE兲 program in the United
equipment changes implemented by the OEMs as a result of States. Since the OEMs have little choice but to meet the
changing consumer needs or by the legislative action of the CAFÉ requirements, they are implementing engine design
governmental organizations, such as the EPA. Examples of changes to meet them. And of course, the lubricant manu-
changing consumer needs are more power and low fuel use facturers are helping them achieve this objective by formu-
共fuel economy兲 and examples of the governmental actions lating lubricants that provide efficient fuel economy. Such
are low emissions and high corporate average fuel economy lubricants are low viscosity oils 共SAE 5W-30 and SAE 5W-20兲
共CAFE兲 legislations. New lubricant development process with good low temperature fluidity that are supplemented
generally starts prior to commercialization of the new equip- with the friction-reducing additives. The realized fuel
ment because of the time and the resources involved. economy benefit by the use of these lubricants is 1.5 to 2.0 %.
Lubricants for modern gasoline engines place a major Soot control is one of the primary reasons for design
emphasis on greater oxidative stability, improved fuel changes in the heavy-duty diesel engines. Two strategies that
economy, catalyst compatibility, and reduced emissions and are presently in place to avoid exiting soot into the environ-
those for heavy-duty engines place a major emphasis on soot ment are directing it into the oil and installation of the Diesel
handling capability, reduced emissions, and compatibility Particulate Filters 共DPFs兲 on the engine’s exhaust system.
with particulate filters 共DPFs兲 关483兴. The drive for greater The first strategy depends upon the dispersant additives to
oxidative stability is a consequence of the desire to prolong keep soot suspended in oil until the next service when it is
the service life of the lubricant. At present for passenger cars removed with the used lubricant. The second strategy is to
in the United States, the service interval is about three pass the soot that escapes the first strategy through a filter,
months and in Europe, it is about six months to two years. prior to allowing the exit of the exhaust gases into the atmo-
Operating temperatures in modern gasoline engines are up sphere. The topic of soot control is discussed in detail in
to 130 ° C at the sump 共under heavy loads兲 and 250 ° C, or Chapter 6 on Emissions Control.
higher, at the pistons 关483兴. At these temperatures, the rate of Regulations pertaining to a vehicle’s exhaust emissions
the lubricant oxidation is quite high. If one intends to pro- are progressively becoming more stringent. One of the ways
long the service interval, which appears to be the case at this to meet the exhaust emissions requirements is by the use of
time, the lubricant must possess excellent oxidative stability the after-treatment devices, such as catalytic converters or
so as to maintain its viscosity/fluidity and the lubrication particulate filters, discussed in the previous paragraph.
properties over the intended period. While the presence of Since they are described in detail in Chapter 6 on Combus-
the oxidation inhbitors greatly helps, they have a finite ser- tion Engine Emissions, we will briefly comment on these
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218 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
here. The devices that are used to treat exhaust emissions, as ASTM Standards D5293 and D4684 describe methods to
in the case of gasoline engines, or capture them, as in the measure the cranking and pumping viscosities, respectively.
case of diesel engines, contain noble metal catalysts. These The ASTM Standard D445 is used to determine minimum
lose their activity by elements such as sulfur and phos- and maximum viscosities at 100 ° C and the ASTM test pro-
phorus, which may be present in fuels and finished lubri- cedures D4683 and D4741 are used to determine the HTHS
cants as additives. Because of the potential damage to the viscosity. The “W” or the winter grade requirements to be
after-treatment devices, the use of such elements in fuels and pumpable at low temperatures, and the non-“W” grade re-
lubricants is being controlled. quirement to have sufficient viscosity at high temperatures
ensure proper lubrication and the protection of the engine
U.S. Standards parts during all-season operation. The viscosity require-
Physical characteristics of the engine lubricants for the ments relating to the different API/SAE grades are summa-
North American use are defined by the SAE viscosity classifi- rized in Table 5.1. Multi-grade oils should satisfy the appro-
cations and the performance characteristics are defined by priate requirements of both the “W” and the non-“W” grades,
the API service classifications. As stated before, a lubricant as is shown in Fig. 5.6.
must have specific viscosity characteristics to ensure easy The U.S. Military uses eight viscosity grades for engine
starting at low temperatures and adequate lubrication at oils, which are identified in three U.S. Military specifications
high temperatures. The viscosity classification system helps 关484兴, see Table 5.2. Military uses three single grades—10W,
select lubricants by taking into account the equipment’s op- 30, and 40, and five multi-grades—0W-30, 5W-30, 10W-20,
erating temperature range. The service classifications, on 10W-30, and 15W-40. Viscosity grade 10W requires the
the other hand, assure the user that the lubricant meets the cranking viscosity of 艌6600 cP at −30 ° C and 艋7000 cP at
performance requirements of the equipment manufacturer. −25° C and pumping viscosity of 艋30,000 cP at −30° C.
Until very recently, the SAE, ASTM, and API were the three Single grades 30 and 40 have minimum and maximum kine-
key organizations responsible for developing such specifica- matic viscosity requirements at 100 ° C and require a mini-
tions. The SAE defined the need for the service category, the mum VI of 80. Multi-grades must meet the minimum and
ASTM developed or selected the testing techniques, and the maximum cranking viscosity requirements at
API developed the user language to define the category. How- −35 to − 20° C; the maximum pumping viscosity require-
ever, in view of the time delays in developing new perfor- ments at −40 to − 25° C, depending upon the grade, and the
mance categories and testing constraints, a number of other HTHS viscosity requirements. Military oils, in addition,
organizations, such as ILSAC, CMA, AAMA and EMA, are have specifications related to pour point, stable pour point,
now actively involved in the process 关309兴. Other countries flash point, evaporative loss, phosphorus content, and the
have similar organizations that establish the performance sulfated ash 关484兴. Physical requirements for the military
criteria for engine oils used in their countries. As mentioned grades are provided in Table 5.3.
earlier, the U.S. Military and the original equipment manu- The SAE Standard J1536 describes the miscibility and
facturers 共OEMs兲 have their own performance require- fluidity grades for the two-stroke cycle engine oils 关485兴. It
ments, which are over and above those of the API. defines four grades, ranging from SAE-1 to SAE-4. These
grades reflect a lubricant’s ability to mix with the fuel at pre-
Viscosity Classification scribed temperatures. A low-temperature viscosity require-
The importance of viscosity was recognized in the earlier ment is associated with each of these grades. Two-stroke
part of this century when in 1911 the SAE established the cycle SI engines do not usually have an oil sump, and the lu-
first engine oil classification system based on viscosity. Since bricant is mixed with the fuel in the fuel tank. The miscibility
then, the system has been revised many times 关33兴. At and fluidity specifications ensure that the lubricant is mis-
present, the viscosity classification systems for engine oils cible with the fuel and that the blend meets the low-
are described by the SAE Standards J300 and J1536 temperature viscosity requirements of the desired perfor-
关309,485兴. The SAE Standard J300 deals with the viscosity of mance category. The SAE categories, along with the
the lubricants for four-stroke cycle engines 共both CI and SI matching requirements, are presented in Table 5.4.
types兲 and two-stroke cycle CI engines. The SAE Standard
J1536 specifies viscosity of oils for the two-stroke cycle SI en- API and SAE Service Classifications
gines only. The basic viscosity grade categories for engine The API and SAE engine oil performance requirements for
oils are determined by the Crankcase Classification System North America are based on the standard tests and are de-
devised by the SAE, which uses the test methods approved scribed by the API Engine Service Classification System,
by the ASTM. which was first introduced in 1969/ 1970 关33兴. The API ser-
The most recent SAE Standard J300 has eleven viscosity vice symbol, “Donut,” was established in 1983 and is pre-
grades, six “W” grades and five regular grades. The “W” sented in Fig. 5.7. This symbol, although originally designed
grades range from 0W to 25W, and regular grades range to cover the entire lid of a round full-seal quart or a litre con-
from 20 to 60. Each viscosity grade must meet a number of tainer, can be applied in a prominent position on a variety of
requirements. Single grade viscosity oils with the letter “W” other packages. The significance of the symbol is to commu-
共winter兲 must meet the maximum low-temperature cranking nicate the engine oil quality and performance to the general
and pumping viscosities at the prescribed temperatures and public and to help them select oils that meet manufacturers’
the minimum kinematic viscosity at 100 ° C. Single grade recommendations for use in the intended application. The
oils without the letter “W” must meet the minimum and the upper part of the symbol displays the API service category,
maximum viscosities at 100 ° C and the high-temperature, the center part displays the SAE viscosity grade, and the bot-
high-shear 共HTHS兲 viscosity at 150 ° C and 106 s−1. The tom part displays the energy conserving feature, if claimed.
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CHAPTER 5 䊏 COMBUSTION ENGINE LUBRICANTS 219
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220 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
SJ, SL, and SM, and by ILSAC GF-2, GF-3, and GF-4, which chemical properties of the publicly marketed oils. Both these
are designed for the most severe operation. The API SM and organizations have installed a number of measures to dis-
ILSAC GF-4 qualified oils are designed to have superior oxi- courage the illegal use of the API and the ILSAC symbols. De-
dation resistance 共less oil thickening兲, protection against de- spite the efforts of these organizations to manage oil quality,
posits, wear protection, and low-temperature performance many oils in the marketplace have lower quality than
than oils qualified under the previous performance catego- claimed by the suppliers of these lubricants.
ries. In addition, these oils have improved environmental For diesel engine oils, the API CF, CF-2, CF-4, CG-4,
compatibility since they extend the life of the emissions sys- CH-4, CI-4, and CJ-4 categories are presently active. API CJ-4
tem and conserve energy. As mentioned earlier, fuel is the newest engine oil category that was introduced to ser-
economy and emissions system compatibility are the pri- vice the 2007 model heavy-duty diesel trucks fitted with die-
mary factors responsible for the gasoline engine design sel particulate filters 共DPFs兲. API CF-2 is for severe-duty two-
changes and the new oils are developed to lubricate them. stroke cycle engines. API CF is for four-stroke cycle engines
The “Starburst” symbol, shown in Fig. 5.8, is intended to be that are either turbocharged or use high sulfur fuel. Such en-
used for oils that meet the ILSAC performance requirements gines are often for off-highway use. API CF-4 and CG-4,
关481兴. The timeline for the development of the gasoline en- CH-4, CI-4, and CJ-4 categories are for four-stroke cycle en-
gine oil categories is depicted in Fig. 5.9. gines for on-highway use. These engine oils are formulated
The licensing of both the “Donut” symbol and the “Star- for use in low-emissions engines of the model years 1991,
burst” symbol is administered by the API. The objective of 1994, 1998, 2004, and 2007. Emissions control is the major
these labels is to protect the public against products that do driving force that is causing new improvements in engine de-
not meet the appropriate performance requirements. SAE sign and each major change requires the development of a
has a similar Oil Labeling Assessment Program 共OLAP兲 lubricant that is suitable to lubricate the new engine. API
which is sponsored by the U.S. Army and the petroleum and CJ-4 category is designed to qualify oils for the low-
automotive industries. SAE monitors the viscosity and the emissions 2007 engines that use low-sulfur diesel fuel. These
listed in Table 5.7 and the parameters that the diesel tests
measure are listed in Table 5.8. These tests are devised to
measure protection against rust, varnish, deposits, sludge,
wear, high-temperature oil-thickening, and ring sticking.
The minimum and maximum performance limits for each
parameter for various gasoline and diesel engine tests are
given in Table 5.9–5.14 关487兴.
Figure 5.11–5.13 identify the parts of a four-stroke cycle
engine that are commonly rated. Figure 5.11 shows a cross-
sectional view of an in-line six-cylinder engine, and Fig. 5.12
shows a cross-sectional view of a V-8 engine. Figure 5.13
shows the various other parts of the engine that are rated. As
mentioned earlier, only certain parts of the engine encounter
Fig. 5.7—API “Donut” service symbols 关480兴.
boundary lubrication and hence experience adhesive wear
damage. These are the valve train, cylinder bores, and piston
lubricants must have elemental composition that will not rings. Figure 5.14 shows the valve train arrangements and
impair the functioning of the diesel particulate filters. See the type of wear damage due to lubrication failure at differ-
Chapter 6 on Emissions Control for a detailed discussion. ent points 关488兴. Pitting and scuffing are the main types of
Other factors that are either important or gaining impor- surface damage experienced by these parts. The damage is
tance are the fuel economy and the extended service inter- more prevalent on the working face of the follower and on
vals. The primary objective is to control the downtime costs. the nose and flanks of the cam.
API SJ/SL/SM and CH-4/CI-4/CJ-4, the most recently in-
troduced categories, are designed for the most severe opera- U.S. Military and OEM Specifications
tions 关486兴. The new interim categories for the next genera- U.S. Military equipment needs differ from those of the com-
tion heavy-duty diesel engine oils are forthcoming. Again, mercial equipment. The military operates large and diversi-
the emphasis in the new categories is likely to be on emis- fied fleets of vehicles containing both two- and four-stroke
sions and fuel economy. The progression of the U.S. heavy- cycle engines, air-cooled and liquid-cooled, ranging from 2
duty diesel specifications with time is provided in Fig. 5.10. to over 1000-hp. U.S. Military specifications, designated by
In general, oils meeting the higher service requirements are the prefix MIL, have performance requirements similar to
suitable for use in the lower service class in the same cat- those of the API service designations. However, it is impor-
egory. tant to note that the development of the military specifica-
Engine test requirements for each active gasoline en- tions does not usually follow but parallels the development
gine oil category are given in Table 5.5 and those for diesel of the API categories, as depicted in Fig. 5.10. Incidentally,
engine oil categories are provided in Table 5.6. Current en- afte1997 the MIL-L-2104 upgrades for engine oils were re-
gine tests and the parameters the gasoline tests measure are named as MIL-PRF-2104.
Most OEMs accept the performance requirements es-
tablished by the API categories. However, certain OEMs
have additional requirements to qualify oils for use in their
equipment. Mack EO-M, Cummins CES20078, and Caterpil-
lar’s upcoming ECF-2 and ECF-3 specifications are examples
of such requirements. It appears that in the future such OEM
specifications are going to become more prevalent as the
heavy-duty engine builders require performance above that
established by the accepted industry standards, as defined by
the API categories 关489兴.
The National Marine Manufacturers Association
共NMMA兲 has its own performance requirements for the two-
stroke cycle engine oils. TC quality oils are the most specified
Fig. 5.8—ILSAC Starburst symbol 关480兴. oils for the air-cooled engines and TC-W3® specified oils are
the most recommended oils for use in the modern water- All engine performance testing data to show compliance
cooled outboard engines. with the ACEA test sequences must be generated according
The API performance classification system, the SAE vis- to the European Engine Lubricants Quality Management
cosity grades, and the OEM performance requirements to- System 共EELQMS兲. This system is described in the ATIEL
gether help design engine oils well suited for the specific end- Code of Practice. It addresses product development testing
use applications. New demands placed on the lubricants due and product performance documentation, involves the reg-
to the changing technology and the governmental regula- istration of all candidate and reference oil testing, and de-
tions require continual revisions and upgrading of the per- fines the compliance process. Compliance with the ATIEL
formance specifications. Code of Practice is mandatory to claim meeting the require-
ments of the ACEA 2007 关490兴.
European Standards A number of changes have been implemented in the
As mentioned earlier, European standards for automotive ACEA 2007 Engine Oil Sequences relative to those of the
engine oils prior to December 1995 were established by the ACEA 2002 and 2004. These are listed below 关487,490兴.
CCMC. Subsequently, ACEA assumed the responsibility of
defining the lubricant quality. ACEA standards recognize Light Duty Engine Sequences
that European engines differ from those in the United States, 1. The A 共gasoline兲 and B 共diesel兲 sequences were replaced
both in design and the operating conditions; hence they by the combined A/B sequences, which contain both
place different demands on the lubricant. This implies that gasoline and diesel engine performance tests.
the oils used in the European engines are unique and hence 2. New C sequences were introduced, which again com-
require classification system that is different from that of the bine the gasoline and diesel engine performance, and
API and includes European engine tests. In addition, some also include the chemical limits.
ACEA standards must take into account the effect of the oil 3. There are four combined A/B categories 共A1/B1, A3/B3,
on the engine emissions and emissions control systems. This A3/B4, and A5/B5兲. The requirements are based upon
is critical for engines that must meet the much tighter Euro 4 the previous A and B category requirements.
emissions standards. 4. There is no new category based upon A2 and B2.
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CHAPTER 5 䊏 COMBUSTION ENGINE LUBRICANTS 223
TABLE 5.5—Tests associated with current U.S. gasoline engine oil classifications
5. There are no chemical limits besides the sulfated ash in 3. E6 is based on the previous E4 category with the follow-
the A/B sequences. ing changes.
6. Sulfur, phosphorus, and chlorine levels must be re- • Chemical limits were introduced for sulfur and
ported. phosphorus and reduced for sulfated ash.
7. Sulfated ash levels are based upon the previous levels, a. Shear stability requirements have been in-
and where the A and B levels were different, the higher creased to passing after 90 cycles in the Kurt-
limit has been used. Orbahn test.
8. There are four new C categories 共C1, C2, C3, and C4兲. b. The Mack T-10/T-12 is now required.
9. C1 defines a “low SAPS,” low viscosity oil of A5/B5 per- 4. E7 is based upon the previous E5 category with the fol-
formance level. SAPS is the acronym for sulfated ash, lowing changes.
phosphorus, and sulfur. • Shear stability requirements have been increased to
10. C2 defines a “mid SAPS,” low viscosity oil of A5/B5 per-
passing after 90 cycles in the Kurt-Orbahn test.
formance level.
a. The Mack T-9 test is replaced by the Mack T-10/
11. C3 defines a “mid SAPS,” normal viscosity oil with a per-
T-12 test.
formance level aligned with the DaimlerChrysler
b. Cummins M11 is replaced by Cummins ISM.
p229.31 specification.
12. C4 defines normal viscosity “low SAPS” oils aligned with ACEA 2007 European Oil Sequences for Service-fill Oils
the Renault Long Drain specification. consist of the test sequences for gasoline engines, light-duty
13. There is no change to the engine test requirements in the diesel engines, and for engines that are equipped with the
A/B or C sequences, except in C4 which was introduced after-treatment devices. Within each group, there are catego-
in 2007. ries which reflect different performance requirements; A1/
14. The XUD11BTE is obsolete. B1, A3/B3, A3/B4, and A5/B5 for gasoline and light-duty die-
15. The DV4 test was developed to replace the XUD11BTE. sel engines and C1, C2, C3, and C4 for low sulfated ash,
phosphorus, and sulfur oils 共SAPS兲 for engines that are
Heavy Duty Diesel Engine Sequences equipped with after-treatment devices.
1. The E3 and E5 categories have been deleted, and the two In these designations, the letter represents the class and
new categories, E6 and E7 are defined. the number represents the category. These are to help the
2. The requirements for E2 and E4 remain unchanged. consumer select oils that are suitable for use in the intended
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224 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
TABLE 5.6—U.S. engine oil classification system for current automotive heavy-duty diesel
engine services.
equipment. Each category also has a two-digit number that identifies oils for use in both gasoline engines and light-duty
identifies the implementation year and is for the benefit of diesel engines. The nomenclature and the description used
the industry. For example, the combined designation for various 2007 ACEA categories are summarized below.
A1 / B1−04 indicates that it was issued in the year 2004 and 1. A / B—gasoline 共petrol兲 and diesel engine oils. A indicates
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CHAPTER 5 䊏 COMBUSTION ENGINE LUBRICANTS 225
oil for a gasoline engine and B indicates oil for a light- 9. Other classes may be added in the future if, for example,
duty diesel engine. the need arises to separately issue specifications for
2. A1 / B1—Oils intended for use in gasoline and diesel car natural gas engines.
and light commercial vehicles, specifically capable of 10. E—Heavy-duty diesel engine oils.
using low friction, low viscosity oils with high 11. E2—General purpose oil for naturally aspirated and tur-
temperature/high shear characteristics. bocharged heavy-duty diesel engines, medium to heavy
3. A3 / B3—Oils for use in high performance gasoline and duty cycles and mostly normal oil drain intervals.
diesel cars and light commercial vehicles where ex- 12. E4, E6, and E7—Stable, stay-in-grade oil for highly
tended drain intervals are specified by the vehicle manu- rated diesel engines meeting Euro 1, Euro 2, Euro 3, and
facturer and for year-round use of the low viscosity oils Euro 4 emissions requirements and running under very
and for use in severe operating conditions, or a combi- severe conditions, such as significantly extended oil
nation thereof, as defined by the vehicle manufacturer. drain intervals. These oils are designed to provide excel-
4. A3 / B4—Oils for use in high performance gasoline and lent control of piston cleanliness, wear, soot handling,
direct injection diesel engines. Includes oils suitable for and lubricant stability and are suitable for engines with-
applications described under B3. out particulate filters, for some EGR engines, and some
5. A5 / B5—Oils for use at extended oil drain intervals in engines fitted with SCR 共selective catalytic reduction兲
high performance car and light commercial gasoline NOx reduction systems. E7 oils in addition provide ef-
and diesel engines designed for low viscosity oils. fective control with respect to piston bore polishing. E6
6. C—Catalyst compatible oils for gasoline and diesel en- oils are the oils of choice for engines fitted with particu-
gines with after-treatment devices. late filters and operate on low sulfur diesel fuel 共max
7. C1, C2 and C3—Oils for use in high performance car 50 ppm兲. However, the recommendations may differ be-
and light commercial gasoline and diesel engines, tween engine manufacturers.
equipped with diesel particulate filter, three-way cata- In addition to the engine oil test sequences for gasoline
lyst, and requiring low viscosity, low friction, catalyst engine oils, light-duty diesel engine oils, and heavy-duty die-
compatible oils, or both sel engine oils, ACEA Standard contains physical require-
8. C4—Oils of normal viscosity suitable for use in engines ments that parallel those for the U.S. engine oils. ACEA uses
that follow Renault Long Drain Specification. These oils the SAE viscosity classification system, described in SAE
have low sulfated ash, phosphorus, and sulfur 共SAPS兲 J300 关309兴, to define the viscosity grades. It has additional re-
limits. quirements relating to shear stability, evaporation loss, elas-
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226 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
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CHAPTER 5 䊏 COMBUSTION ENGINE LUBRICANTS 227
TABLE 5.9—API SM/ILSAC GF-4 gasoline engine oil classifications for 2006 †487‡.
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228 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
TABLE 5.10—API SJ/ILSAC GF-2 and SL/ILSAC GF-3 gasoline engine oil classifications 2006
†487‡.
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CHAPTER 5 䊏 COMBUSTION ENGINE LUBRICANTS 229
TABLE 5.11—API CJ-4 heavy-duty diesel engine oil classification 2007 †487‡.
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230 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
TABLE 5.12—API CI-4/CI-4 plus heavy-duty diesel engine oil classifications 2006 †487‡.
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CHAPTER 5 䊏 COMBUSTION ENGINE LUBRICANTS 231
tomer compatibility, sulfated ash, foaming tendency, and are listed in Table 5.19 and the specifications limits are pro-
changes in viscosity due to high shear and high temperature. vided in Table 5.20 关492兴. The required engine tests and the
Special laboratory test procedures are used to determine if a specifications limits for the heavy-duty diesel standard are
lubricant meets the desired performance requirements in provided in Tables 5.21 and 5.22. Details of the standard can
these areas. These procedures are described in the SAE be accessed at JAMA’s website 关493兴.
J2227 report 关491兴. ACEA specifies the use of the tests devel-
oped by the ASTM and CEC to assess the lubricant’s ability to Japanese Standards
meet these requirements. The engine test requirements un- The Japanese Automobile Standards Organization 共JASO兲
der ACEA 2007 are provided in Table 5.15 along with the pa- also publishes oil standards. JASO tests use small Japanese
rameters they measure and the test methods. Tables engines, and their ratings use more stringent valve train
5.16–5.18 list the actual pass/fail criteria and the test meth- wear standards than those used by the other countries. Japa-
ods 关490兴. nese vehicle manufacturers use SAE Viscosity Classification
As stated earlier that ACEA has developed global perfor- System, described in SAE J300 关309兴, and API Classification
mance standards for light-duty diesel engine oils and heavy- System to recommend engine oils for service-fill applica-
duty engine oils, by collaborating with the members of the tions 关491兴. Some of the Japanese engine tests, such as Nis-
Alliance of Automobile Manufacturers, Engine Manufactur- san KA-24E, Nissan TD25, and Mitsubishi 4D34T4, are in-
ers Association 共EMA兲, and Japan Automobile Manufactur- cluded in the new API, ILSAC, and ACEA specifications.
ers Association, Inc. 共JAMA兲. The objective of the specifica- While Japanese manufacturers recommend API/ILSAC and
tions is to identify/develop oils with consistent performance ACEA approved oils for use in their equipment, they also
in high-speed, four-stroke cycle light-duty and heavy-duty have their own “in-house” test procedures and performance
diesel engines used worldwide and provide the engine manu- requirements. For service-fill oils, JASO helps in coordinat-
facturers the option to recommend these oils for use in their ing these additional procedures and requirements. JASO
equipment. The oils for the light-duty diesel engines are de- comprises Japanese automobile and truck manufacturers,
signed to meet the year 2000 and newer exhaust emissions oil and additive companies, and government authorities.
standards worldwide and those for the heavy-duty diesel en- SAE Publication J2227 describes these procedures 关491兴.
gines are designed to meet 1998 and newer emissions stan- Current Japanese engine tests for lubricants, along with the
dards. These oils are also compatible with certain older en- evaluation criteria, are described in Table 5.23.
gines. In April 2001, the Society of Automotive Engineers of
The global light-duty diesel engine oil standard consists Japan, Inc., in collaboration with the Japan Automobile
of three specifications: DLD-1, DLD-2, and DLD-3 关492兴. The Manufacturers Association, Inc., the Petroleum Association
heavy-duty diesel engine oil standard has only one specifica- of Japan, and other organizations, specified the JASO DH-1
tion, DHD-1. These specifications identify engine oils for use standard for engines made in Japan. The quality of JASO
in applications/environment that necessitate wear control, DH-1 diesel lubricants for four-stroke cycle diesel engines is
high-temperature stability, soot handling properties, protec- specified under the Japanese Standard JASO M 355:2000.
tion against oil-thickening due to oxidation and insolubles, JASO DH-1 engine oil provides higher performance in wear
aeration control, and minimal shear-related viscosity loss. and corrosion prevention, high-temperature oxidation sta-
The required engine tests for the light-duty diesel standard bility, and piston deposit and soot control than the conven-
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232 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
TABLE 5.13—API CH-4 heavy-duty diesel engine oil classifications 2006 †487‡.
tional API CD quality oil, which is widely used in Japan. In into effect. Test parameters and performance criteria for
addition, JASO DH-1 specifies performance related to im- JASO DH-1 specification are provided in Table 5.24.
proved piston detergency, high-temperature deposits, foam-
ing, oil consumption due to volatility, viscosity after shear- Indian Standards
ing, and seal compatibility. Although JASO DH-1 was Bureau of Indian Standards 共BIS兲 has developed engine oil
developed for new engines meeting stringent exhaust emis- specifications to qualify lubricants for use in local vehicles.
sions regulations, it can also be applied to engines manufac- Physical requirements for engine oils include viscosity, pour
tured before the new exhaust emissions regulations went point, flash point, evaporation loss, and foaming tendency.
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CHAPTER 5 䊏 COMBUSTION ENGINE LUBRICANTS 233
TABLE 5.14—API CG-4/CF/CF2 heavy-duty diesel engine oil classifications 2006 †487‡.
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234 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
Again, the SAE viscosity classification system 关309兴 is the ba- Industrial Standards Organization 共JIS兲 are involved in the
sis for the Indian viscosity grades. To measure other param- process.
eters, BIS presently employs a combination of international
test procedures which it plans to replace with national pro- Diesel Engine Oils
cedures when they are developed. API, ACEA, and OEMs are the three key organizations which
are involved in defining these oils. The oils for North Ameri-
Engine Oil Classification Based on End-use can use are defined by the API Service Classifications, by the
Engine lubricants can be divided into the following end-use OEMs, or both. The U.S. Military also plays a role in setting
categories: specifications for these oils. In the United States, API CI-4
1. Gasoline engine oils and CJ-4 designated oils deliver the top performance and are
2. Diesel engine oils suitable for use in most modern engines. API CF-2 oils are
䊊 Automotive diesel oils designated for use in supercharged two-stroke cycle engines.
䊊 Stationary diesel oils ACEA categories E7−04 and C4−07 are designed to deliver top
䊊 Railroad diesel oils performance in the European engines.
䊊 Marine diesel oils The present specification-establishing process is re-
3. Stationary gas engine oils gional and involves the development of base requirements
4. Aviation engine oils relating to wear, deposits, corrosion, sludge, and oxidation,
5. Small engine oils which are established by industry organizations; such as the
API, ACEA, and JASO. To these, the OEMs add stricter lim-
Gasoline Engine Oils its, in-house tests, and field tests to bring up the oil perfor-
Gasoline engine 共passenger car兲 oils for North American use mance for use in their equipment. The future trend is to-
are primarily defined by the API Service Classification Sys- wards de-emphasizing the role of the industry organizations
tem. As mentioned under specifications, API SM and ILSAC in defining lubricant quality and the OEM performance re-
GF-4 qualified oils are suitable for use in the newest cars and quirements playing the major role. These trends make for-
that for Europe, ACEA, and for Japan, JASO and Japanese mulating universal lubricants a challenge since invariably
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CHAPTER 5 䊏 COMBUSTION ENGINE LUBRICANTS 235
conflicts are likely to arise due to differing performance re- 2. Minimize deposit formation on critical parts; such as
quirements across various OEMs. There is also a trend to- cylinder ports, pistons, piston rings, ring grooves, under
wards global specifications, which again allow a greater par- pistons and in general keep engine surfaces clean.
ticipation of the OEMs in the specification-establishing 3. Lower the wear rates of the cylinders and the piston
process 关494兴. Many of the OEMs are concerned about the rings.
number of worldwide heavy-duty diesel lubricant standards. 4. Be compatible with common elastomers used to make
However, the standards of North America and Europe are al- oil seals.
ready converging and the development of the global specifi- These oils are usually SAE 30, 40, or 50 mono-grades
cations is another indication that the worldwide conver- and are of API CF, CF2, or higher quality, depending upon if
gence is on the way 关495兴. the engine is four-stroke cycle or two-stroke cycle. They typi-
Stationary Diesel Engine Oils cally have a high base reserve 共TBN兲, high flash points, low
A stationary diesel engine implies any compression-ignition pour points especially if the outdoor winter use is intended,
internal combustion engine, except combustion turbines, and provide excellent wear protection, soot control, oil-
that converts heat energy into mechanical work and is not thickening, and bearing corrosion protection. In April 2006,
mobile. Such engines are commonly employed in industries, the emissions standard for stationary engines went into ef-
such as off-highway construction, earth moving and mining, fect; hence the lubricants must not contribute to emissions,
agriculture, oil and gas exploration, chemical processing, but instead help control them 关401兴.
paper-making, and for generating power to drive pumps, Railroad Diesel Engine Oils
compressors, drilling equipment, and other auxiliary ma- Railroad diesel engines are two-stroke cycle and four-stroke
chinery. Some of these engines burn residual fuels of high cycle, naturally aspirated or turbocharged, medium-speed
sulfur content 共1 to 4.0 %兲 and operate at high pressures, engines. Engines of similar type are also used in stationary
high temperatures, and have long strokes. Lubricants used and marine applications; hence some of their lubrication re-
in these applications are blends of highly refined base oils quirements overlap. Railroad diesel engine oils are formu-
that have the ability to effectively perform the following lated to provide year-round lubrication and typically are
functions. SAE 40 viscosity grade for single grade oils and 20W-40
1. Neutralize corrosive acids that result from the use of grade for multi-grade oils. These oils are derived from paraf-
high sulfur fuels. finic and naphthenic base oil blends and have a sufficient
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236 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
TABLE 5.15—Engine tests associated with current ACEA 2007 sequences for service-fill au-
tomotive oils.
case. A cross-sectional view of a cross-head marine diesel en- ability will not suffer in the case of the water contamination.
gine is shown in Fig. 5.16 关497兴. Table 5.28 summarizes marine diesel engine oil require-
The cylinder oil lubricates piston skirts and cylinders, ments 关318兴. Lubricants with API CF and CF2 quality are
and handles corrosive combustion products derived from commonly used in this application.
the heavy fuel. It therefore provides wear protection and en- At present, there are no emissions regulations on the
gine cleanliness. The crankcase oil, also called the systems open seas. Hence, ocean-going freighters and tankers use the
oil, lubricates bearings, gears, and other engine compo- lowest cost and the lowest quality fuel possible and do not
nents. worry about the resulting emissions. However, in coastal ar-
Marine cylinder lubricants are typically SAE 50 viscos- eas, environmental regulations do apply 关401兴 and hence fer-
ity grade and have a suitable base reserve 共TBN between 60 ries, tug boats, and cruise ships use higher quality distillate
and 100; typically 70兲 to neutralize the acidic combustion
fuels. But smaller oil sumps designed to make room for more
products arising from sulfur 共2–5 %兲 in the fuel. Cylinder oils
cargo, along with emissions control devices, severely stress
are once-through lubricants because they are injected into
the lubricant.
the cylinder and burned with the fuel. Crankcase oils are
SAE 30 viscosity grade and are formulated to handle rust,
Stationary Gas Engine Oils
oxidation, deposits, and wear. They typically have a TBN of 5
to 10. Stationary engines typically operate on natural gas. Natural
Medium-speed, trunk-piston engines have a single lu- gas engines can be a two-stroke or four-stroke cycle, natu-
bricating system and run on distillate or heavy fuels. They rally aspirated or turbocharged. These engines are mainly
use a lubricating oil of SAE 30 or SAE 40 viscosity grade and used in stationary applications in the natural gas industry, in
have a TBN of 12 to 40, depending on the fuel quality. Lubri- petroleum refining, for power generation, and in agricul-
cants that are suitable for use in these engines must possess tural irrigation service. Primary advantages of the natural
superior extreme pressure/antiwear performance, high- gas engines over diesel engines include lower NOx, CO, and
temperature stability, oxidation resistance, detergency, and particulate matter 共PM兲 emissions and the lower fuel costs.
dispersancy. Again, the base reserve is necessary to neutral- Stationary gas engines are available in various configu-
ize the acidic combustion products due to the fuel sulfur. rations and sizes. Engine characteristics include the follow-
For marine lubricants, water tolerance is an additional ing 关498兴:
desirable property. This is to ensure that their lubricating 1. Two- or four-stroke cycle design.
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238 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
TABLE 5.16—ACEA 2007 European oil sequence for service-fill oils for gasoline and diesel
engines †487‡.
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CHAPTER 5 䊏 COMBUSTION ENGINE LUBRICANTS 239
2. Less than 100 hp to 16,000 hp; 800 to 1500 hp being charge 共usually natural gas兲 is introduced under high pres-
most common. sure.
3. 1–20 Power cylinders. In the low-pressure gas engines, gas and air charge is
4. Oil sump capacities of 14 to 6000 liters; 300 to premixed either in an intake air manifold or in a precham-
800 liters, or 80 to 200 U.S. gallons, being the most com- ber, prior to entry into the cylinder. Pilot fuel is then injected
mon. to initiate combustion of the air-gas mixture. These engines
5. Engine speeds of 300 r / min 共slow-speed兲 to 2000 r / min use either stoichiometric or lean air-fuel mixtures. Engines
共high-speed兲; mostly between 3.5 to 1200 r / min. that use stoichiometric mixtures are equipped with a three-
6. Piston bores of 22.5 in. 共572 mm兲 in slow-speed engines way catalyst system to meet HC, CO, and NOx emissions re-
to bores of 3.5 to 9.45 in. 共89 to 240 mm兲 in high-speed quirements. Lean burn engines, on the other hand, do not
engines. need a catalyst system. High air 共oxygen兲 content of the lean
7. Naturally aspirated or turbo-charged; newer engines mixtures leads to more efficient combustion and lower com-
are mostly turbo-charged. bustion temperatures, which translate into lower HC, CO,
8. Burn stoichiometric air-fuel ratio 共14 parts air and 1 and NOx emissions. Fuels used in such engines include natu-
part fuel兲 or lean air-fuel ratio 共greater than 14 parts air ral gas 共85 % methane兲, city gas 共high in hydrogen兲, high sul-
and 1 part fuel兲. The latter ratio will result in lower NOx fur sour gas 共contains up to 8000 ppm hydrogen sulfide兲,
emissions. sewage gas 共also contains hydrogen sulfide兲, and landfill gas
9. Engines and compressor units separate or joined end- 共contains corrosive organic halides兲. The sewage gas and the
to-end. In the latter case, they are coupled at the crank- landfill gas are poor fuels since their methane content is only
shaft by a coupling. around 50 %. Because of the nature of the fuel and the diver-
Stationary gas engines are of three types: spark-ignited, sity of the impurities, it is critical to select an engine oil that
low-pressure gas engines; pilot-fuel ignited, low-pressure is not only an effective lubricant but also has the ability to
gas engines; and pilot-fuel ignited, high-pressure gas en- protect against products resulting from the combustion of
gines. While the spark-ignition engines are equipped with a impurities.
spark plug, the pilot-fuel ignited engines use a small charge Lubricants for natural gas engines are formulated dif-
of the distillate fuel, approximately of 5 % of the total, to start ferently than those for diesel and gasoline engines. This is
the ignition process 关318兴. In high-pressure gas engines, pilot because natural gas engines burn cleaner, do not cause fuel
fuel is injected by the use of a fuel valve when the piston is dilution because the fuel is gas, and the soot contamination
top center. Once the ignition starts, the remaining fuel of the oil; hence, they require less detergency/dispersancy,
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240 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
TABLE 5.17—ACEA 2007 European oil sequence for service-fill oils for gasoline and diesel
engines with after-treatment devices †490‡.
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CHAPTER 5 䊏 COMBUSTION ENGINE LUBRICANTS 241
which allows these lubricants to be formulated at lower ash. generation applications have the only two published ap-
However, gas burns hotter than diesel; hence these engines proval lists for the commercial brands of oils 关499兴. Sulfated
have exhaust temperatures of 165 to 235 ° C 共300 to 400° F兲 ash level is another criterion that is often used by the OEMs
higher than those of the diesel engines. This factor alone to recommend oils for their equipment, with a preference for
generates a greater amount of oxidation- and nitration- oils that produce ash levels of 0.5 % or lower. Oils that pro-
related oil decomposition products and deposits. In addi- duce an ash level of less than 0.1 % are designated as ash-
tion, these engines operate at constant speed, which makes less. Those that produce 0.4–0.6 % ash are designated as low
them retain deposits. ash; those that produce 0.7–1.0 % ash are designated as me-
Natural gas engine oils are available both in mono dium ash; and those that produce greater than 1.0 % ash are
grades and multi-grades. SAE 30 and SAE 40 are the com- designated as high ash oils 关318兴. Ash primarily originates
mon mono grades and 15W-40 is the common multi-grade. from the metal-containing additives, such as basic deter-
Multi-grade oils are useful in situations where frequent low- gents, which are added to the lubricant to neutralize acids
temperature start-ups are expected or sump heaters are ei- and suspend deposit precursors in oil. Basic detergents also
ther unavailable or unreliable, or both. Multi-grades not protect the exhaust valves against recession by forming a
only provide easy low-temperature starting but they also sacrificial protective layer of ash. Ash results when the lubri-
have reduced oil consumption, means lower emissions, and cant residue on various parts of the engine burns, leaving be-
improved fuel economy. However, because of the higher op- hind a whitish-gray deposit. While the presence of the ash-
erating temperatures, the polymer in the multi-grade oil may forming additives in the lubricant is beneficial, the presence
undergo extensive thermo-oxidative degradation and may of more than the optimal amount can cause excessive depos-
not be suitable for use in engines from some manufacturers. its on various parts, which can result in reduced heat trans-
Performance specifications for natural gas engine oils fer, preignition or detonation, or both, ring sticking or break-
are generally established by the OEMs, who use various cri- ing, plug fouling, and valve burning.
teria to specify oils for use in their equipment. Some equip- In general, two-stroke cycle engine manufacturers pre-
ment manufacturers refer to older API “CC” or “CD” diesel fer oils that produce no ash 共ash-less兲 and four-stroke cycle
engine oil designations to try to establish a minimum perfor- engine manufacturers prefer low ash-producing oils. This is
mance level, but the use of the diesel engine oil performance because the two-stroke cycle natural gas engines do not have
specifications to classify natural gas engine oils is not ac- intake or exhaust valves, but instead have oil injection ports
cepted by many. This is because of the different characteris- that feed oil directly into each cylinder and a high ash-
tics of the natural gas engines that were listed in the previous producing oil can cause exhaust port blockage. Higher ash-
paragraph. Other OEMs have developed their own natural producing oils are necessary when severe fuels, such as those
gas engine tests, but for the most part, the performance is derived from landfill or sewage, are used. Older Waukesha
measured by field testing. Dresser-Rand and Waukesha co- four-stroke engines are the only engines that require high
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242 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
TABLE 5.18—ACEA 2007 European oil sequence for service-fill oils for heavy-duty diesel
engines †490‡.
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CHAPTER 5 䊏 COMBUSTION ENGINE LUBRICANTS 243
ash oils, which is due to the high valve angles that were used. 8. Good TBN retention, which will allow the use of such
Besides ash, other parameters for these oils include their oils in engines that are fueled by sour gas or fuel gas that
phosphorus content and resistance to oxidation and nitra- contains up to 0.3 % sulfur as hydrogen sulfide and
tion. Phosphorus limit is to minimize catalyst poisoning in small amounts of organic halides such as chlorides.
converters used to control emissions. More specifically, the 9. Reduced wear of pistons, rings, liners, cylinder walls,
performance of these oils is assessed in terms of the follow- valve train, and bearings.
ing performance criteria: 10. Good volatility characteristics 共low oil consumption兲.
1. Improved oxidation and nitration stability and anti-
11. Rapid circulation and pumpability at low temperatures.
coking characteristics.
12. Shear stability to stay in grade over the oil drain interval.
2. Control of valve recession and torching 共guttering兲.
13. Low foaming tendency.
3. Piston groove, land, and skirt cleanliness and reduction
in piston ring sticking. 14. CF and CF-2 credentials for use in modern engines.
4. Reduced port deposits and port plugging. Table 5.29 summarizes the engine builders’ preferences
5. Reduced bearing corrosion. in defining lubricant quality for their equipment 关318兴. SAE
6. Minimized combustion chamber ash accumulation and has recognized the need for new service categories to define
plug fouling. the performance of these oils and has requested API and
7. Catalytic converter compatibility. ASTM to define such categories and write the user language.
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244 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
TABLE 5.20—Global engine oil service specification DLD-1, DLD-2, DLD-3 †492‡.
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CHAPTER 5 䊏 COMBUSTION ENGINE LUBRICANTS 245
Aviation Engine Oils cSt兲 and possess improved thermal and oxidation stability
Aviation engine oils are of two types: Those that are used in properties. The specifications for 5 cSt viscosity oils are de-
piston engines and those that are used in turbine engines. scribed in U.S. MIL-PRF-23699F Specification and the U.K.
Aircraft piston engines use engine oils to lubricate the crank- Military Specification DEF STAN 91-102/2 共DERD 2499兲.
shaft, connecting rods, pistons, rings, bearings, and other Testing requirements of these specifications are listed in
moving parts. These oils are designed to prevent wear by ap- Tables 5.30–5.32 关503,504兴. The required tests in these stan-
propriately lubricating the engine parts, keep deposit- dards relate to lubricant and engine parameters that include
forming materials and abrasives in suspension, dissipate the following:
heat, and inhibit entry of the blow-by gases into the crank- 1. Low-temperature properties, such as low-temperature
case. They must especially perform these functions under viscosity and pour point, to assure low-temperature per-
extreme operating conditions. Piston engine oils are usually formance both on ground and at high altitudes.
SAE 30 to SAE 60 viscosity grade, are mineral oil-based, and 2. High-temperature properties, such as flash point to as-
contain nonash-producing 共metal-free兲 additives. These oils sess ignitability and evaporation loss of the lubricant
contain oxidation inhibitors that impart oxidation stability fractions at high temperatures and low atmospheric
and dispersants that impart dispersancy. Because of the pressures that exist at high altitudes.
presence of these additives, the piston engine oils inhibit the 3. Vapor phase deposits resulting from the contact of the
formation of oxidation-initiated deposit precursors and sus- oil mist and the vapors with hot engine surfaces.
pend them in oil, if they form; thereby preventing their sepa- 4. Load-carrying capacity, so as to prolong the life of the
ration from the oil and on hot engine parts to form varnish, bearings, gears, and other highly loaded parts.
sludge, and piston deposits. The suspended contaminants 5. Cleanliness, to minimize the formation of varnish and
and abrasive particles, if present, are removed during the oil or sludge deposits.
change. SAE J1899 specification, which replaced the U.S. 6. Oxidation stability, to inhibit oxidation-related lubri-
Military Specification MIL-L-22851D, defines the quality of cant degradation.
these oils. 7. Compatibility with metals, elastomers, carbon seals,
Jet turbine engine oils are formulated using synthetic and other lubricants.
base stocks, usually of polyol ester and aliphatic ester types It is important to note that MIL-PRF-23699F Specifica-
关500兴. These oils are used to lubricate metal surfaces ap- tion has two versions: the STD 共Standard兲 version and the
proaching temperatures of up to 675 ° C and their main HTS 共High Thermal Stability兲 version. The difference be-
function is to control deposit formation on the hot surfaces. tween the two primarily relates to the high-temperature per-
A mineral oil-based lubricant will not provide the satisfac- formance. The STD class oils are intended for use in normal
tory performance at these high temperatures due to insuffi- performance turbo equipment, where ferrous material
cient stability of the mineral base oils. U.S. Military Specifi- 共gears and bearings兲 corrosion induced from extended peri-
cations MIL-PRF-7808L and MIL-PRF-23699F are used to ods of nonoperation in a moist environment is not a concern.
select lubricants for use in this application 关501–504兴. The HTS class oils are for use in hot running engine designs
MIL-PRF-7808 specification defines lubricant quality of where evidence of oil coking or oil degradation, or both, is
the low viscosity 共3 cSt at 100 ° C or 210° F兲 aircraft turbine observed. While the two lubricant classes are interchange-
lubricants for use in equipment employed by the U.S. Air able and fully compatible with each other, mixing the two
Force. These oils are also used in commercial helicopter will diminish the added benefits provided by the HTS oils
turbo shaft engines and in certain jet aircraft equipment/ and the mixture will revert to the STD level of performance.
accessories that operate in extreme low-temperatures envi- Lubricants meeting MIL-PRF-23699F HTS credentials must
ronments. Aviation engine oils for most of the newer high- meet the additional requirements relating to thermal stabil-
performance jet engines are of higher 100 ° C viscosity 共5 ity and corrosivity at 274 ° C 共FED-STD-791, 3411兲, corro-
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246 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
TABLE 5.22—Global heavy-duty diesel engine oil service specification DHD-1 †493‡.
sion and oxidative stability at 204° C 共FED-STD-791, 5308兲, tion, and foaming, and to provide good high temperature
and sediment formation 共FED-STD-791, 3010兲. performance and load-carrying ability. The performance of
Most commercial aircrafts require engine oils that have these oils is defined by the U.K. Military Specification DEF
a 100 ° C viscosity of 7.5 cSt. These oils are formulated using STAN 91-98/1 共DERD 2487兲, which is summarized in Table
synthetic base stocks and additives that inhibit wear, oxida- 5.33 关501兴. There are additional military standards for avia-
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CHAPTER 5 䊏 COMBUSTION ENGINE LUBRICANTS 247
tion engine oils, some of which are available in the Air BP needs. It is important to note that the use of engine oils de-
Lubricants brochures posted at BP’s website 关501–504兴. signed for four-stroke cycle and two-stroke cycle automotive
engines in small engines is not appropriate. This is because
Small Engine Oils regular engine oils contain additives, such as detergents,
Besides gasoline and diesel engines that are used in large au- which are metal salts of organic acids. These on combustion
tomotive applications, such as passenger cars and heavy with the fuel form ash which deposits on the spark plugs and
trucks and buses, many applications use small engines.
forms residues in the combustion chambers. Two-stroke
These include outboard marine engines; personal watercraft
cycle engine oils, on the other hand, are designed to mini-
and jet skis; scooters, mopeds, and all-terrain vehicles; chain
mize spark plug fouling and residue formation. They also re-
saws, lawn mowers, and other portable equipment; and mo-
duce preignition, ring sticking, scuffing, carbon formation,
tor cycles. These devices use two-stroke cycle and four-
and the crankcase sludge. The quality of these oils is assessed
stroke cycle engines, both air-cooled and water-cooled.
on the basis of their miscibility and fluidity characteristics
Specifications of lubricants for these engines are established
and performance in a number of industry tests, as defined by
by organizations, such as the API, JASO, ISO, TISI 共Thai In-
dustrial Institute兲, and NMMA 共National Marine Manufac- JASO/ISO two-cycle index and NMMA’s TC-W specifications.
turer’s Association兲. These engines have separate perfor- Miscibility/fluidity classification, provided in Table 5.4, is
mance specifications because they have unique lubrication important because the two-stroke cycle engine oils must be
mixed with the fuel, prior to use. Typical gasoline to lubri-
cant ratios are 12: 1, 16: 1, 24: 1, 32: 1, 50: 1, and 100: 1, de-
TABLE 5.23—Current Japanese engine tests. pending upon the engine manufacturer’s recommendation.
Incidentally, the higher the amount of the oil in the mixture,
Engine Test Engine Type Evaluation Criteria
the higher is its smoking tendency, see Fig. 5.17 关4兴. As one
Four-cylinder
Toyota 3A Overhead Valve train wear
can see, to attain low smoking tendency, the oil must contain
Cam 共OHC兲 engine smoke-suppressing additives. Without their presence a sig-
Piston deposits, nificant amount of visible smoke results, even at the fuel to
Six-cylinder double sludge, varnish, oil ratio of 100: 1 共1 % oil兲. The oil’s performance is deter-
Toyota 1G-FE
OHC engine wear, and viscosity mined by an engine test that evaluates three parameters: the
increase anti-scuff characteristics, ring sticking and engine cleanli-
Nissan VG-20E V-6 single OHC Piston deposits, ness, and preignition.
engine sludge, varnish,
Lubricant performance categories for air-cooled en-
and wear
Four-cylinder
gines are provided in Table 5.34. Of these, TA, TB, and TC are
Nissan KA-24E single Valve train wear the oldest performance categories, but API TC is still the
OHC engine most predominant and most demanded category since it en-
Four-cylinder Piston deposits, compasses the two-stroke cycle engine performance re-
Nissan TD25
Overhead sludge, varnish, quirements covered by TA and TB categories. In 1994, JASO
共JASO 336-97兲
Valve Engine and wear 共Japan Automobile Standards Organization兲 proposed a per-
Mitsubishi 4D34T4 Four-cylinder Camshaft, lifter, formance specification for low-ash engine oils for two-stroke
共JASO M354:1999兲 manual cylinder, piston cycle air-cooled engines. Prior to this time, metal-free 共ash-
transmission ring, and bearing
less兲 oils were commonly recommended for these engines.
wear
One of the reasons for issuing the new specification was that
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248 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
the ash-less oils started to experience ring-sticking, which 3. Inhibit deposit formation
can be corrected by the use of the low-ash oils. JASO specifi- 4. Reduce scuffing
cation has three performance categories: FA, FB, and FC; 5. Resist spark plug fouling
which assess the lubricant’s detergency, lubricity, and ex- The primary goal of the JASO specification is to improve
haust port blocking and smoking tendency. In all cases, per- the air quality by controlling smoke in Asian cities, most of
formance of the candidate oil is compared to that of a refer- which use two-stroke cycle engine vehicles for transporta-
ence oil. In terms of the engine performance, these lubricant tion. International Standardization Organization 共ISO兲 has
properties must accomplish the following: also established a two-stroke cycle engine oil specification.
1. Resist combustion chamber deposit-induced pre- Two of the categories in the two specifications overlap except
ignition FA in the JASO specification and GD in ISO specification. GD
2. Prevent ring sticking category represents the highest level of performance for the
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CHAPTER 5 䊏 COMBUSTION ENGINE LUBRICANTS 249
TABLE 5.25—Railroad diesel engine perfor- TABLE 5.27—Marine diesel engine operating
mance designations †318‡. Reprinted with parameters.
permission from the Lubrizol Corporation. Type Speed „r/min… Bore size „mm…
Detergent Level Slow Speed 65–150 260–1000
Designation Dispersant Level „TBN-ASTM D2896… Medium Speed 230–750 300–650
Generation 1 0 4 to 5 Medium High Speed 600–1500 200–400
Generation 2 Moderate 7 High Speed 600–2250 100–200
Generation 3 Moderate 10
Generation 4 High 13
Generation 5 High 13 and over
gines. The primary reason for considering the use of the
OEM Evaluation Tests
Bench EMD Silver Corrosion and Oxidation Test
four-stroke cycle engines in the outboard market is to reduce
GE Oxidation Test the exhaust emissions. The required tests are listed in Table
Bronze Friction Test 5.38. The details and pass/fail criteria are available in NMMA
Engine 25-h EMD 2-567 Certification Procedure Manual 关507兴.
750-h GE 7FDL Figure 5.18 shows a cross-sectional view of a liquid-
Fieldb 480-h Caterpillar IG2a cooled, two-stroke cycle engine 关508兴. Pistons, spark plugs,
3 to 10 late model locomotives and exhaust port are the parts that are usually rated for mal-
1 year and 100,000 miles function. As mentioned in the preceding discussion, the per-
a
This test is obsolete and in many cases is replaced by Caterpillar formance criteria for such engines include the lubricant’s
1M-PC. ability to provide protection against ring sticking, piston var-
b
Approval for field testing is granted by the OEM after the candi- nish, plug fouling, exhaust port blocking, and piston scuff-
date oil has completed bench and engine tests. ing.
two-stroke cycle engine oils. JASO and ISO specifications Lubricant-related Causes of Engine Malfunction
are presented in Table 5.35. Most of the problems associated with the internal combus-
Water-cooled engines radically differ from the air- tion engine lubrication are related to the by-products of
cooled two-stroke cycle engines; hence they have their own combustion, their entry into the crankcase as the blow-by,
specifications. Table 5.36 compares characteristics of the and the subsequent lubricant decomposition. This suggests
two types of engines 关505兴. Performance specifications of that the quality of the fuel, thermal and oxidative stability of
water-cooled engines, which are mainly used in out-board the lubricant, and the efficiency of combustion all play an
applications, are established primarily by the National Ma- important role. The major causes of the engine malfunction
rine Manufacturers Association 共NMMA兲. Originally, there due to lubricant quality are deposit formation, lubricant
were three categories: TC-W, TC-WII® TC-W3®. Of these, the contamination, oil thickening, oil consumption, ring stick-
first two are obsolete and only TC-W3® is in effect. TC-W® ing, corrosion, and wear.
qualified oils, the same as the TC oils for air-cooled engines, While discussing deposit control in the chapter on Addi-
must prevent ring sticking, deposit-induced preignition, and tives 共Chapter 4兲, we described the mechanisms which result
piston scuffing. The difference is that the tests used are dif- in the formation of the engine deposits, see Figs. 4.6 to 4.12
ferent. SAE service classifications and performance criteria of the Additives chapter. The deposit precursors are highly
for the two-stroke cycle gasoline engine oils are described in oxygenated, polar organic compounds, which have the ten-
the SAE Standard J2116 关506兴. Test requirements for NMMA dency to separate out of the oil and onto the surfaces as resin,
TC-W3®, the most recent category, along with the primary a sticky substance. Its deposition on surfaces that have high
performance criteria are given in Table 5.37 关318兴. In the year ambient temperatures, such as piston crowns, rings, and
2004, NMMA introduced FC-W™ engine oil specifications skirt, leads to dehydration or further chemistry to form var-
for four-stroke cycle, water-cooled outboard gasoline en- nish, lacquer, and carbon deposits. In addition to the deposit
TABLE 5.26—Railroad engine builder lubricant requirements †318‡. Reprinted with permission from
the Lubrizol Corporation.
Zinc Content
TBN „ASTM Sulfated Ash API
Engine Builder SAE Grade D2896… „% mass… max max min Classification Road Test Requirement
General Motors 40 or 20W-40 10–20 … 10 ppm … … 3 locomotives, 1 year
EMD
General Electric, U.S. 40 or 20W-40 13–20 … … … … 3 locomotives, 100,000 miles
M.T.U. 30 … 1.5 … 0.05 % SE/CC, SE/CD Required
40 … 1.5 … 0.05 % SE/CD Required
15W-40 … 1.8 … 0.05 % SE/CD Required
G.E. Locomotive Canada 40 7–13 … … … CD …
共Alco 251 Engines兲
Sulzer 40 … … … … CD Required
SEMT Pielstick 40 10 min … … … CD Required
S.A.C.M. 40 10 min … … … CD Required
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250 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
and the ASTM. Engine parts that are commonly rated for the
most recent gasoline and diesel engine tests are listed in
Table 5.39 and the test parts from some of the engines with
PASS/FAIL results are shown in Figs. 5.19–5.35
关318,513,514兴.
Figure 5.19 shows pistons and copper/lead/tin bearings
from Sequence L-38 test 共ASTM D5119兲. Piston is evaluated
for varnish deposits and the connecting rod bearing is evalu-
ated for discoloration and weight loss. In the figure, FAIL
piston shows a significant amount of varnish and fail bear-
ing shows visible discoloration. Figure 5.20 shows pistons
from Sequence IIIF and IIIG engines. Pistons are rated for
varnish, deposits, and stuck rings, and the cam and lifter are
rated for wear. These ratings are in addition to measuring
the oxidation-related viscosity increase, oil consumption,
and oil screen plugging. In the figure, PASS pistons have less
varnish and carbon deposits than the FAIL pistons. Figure
5.21 shows the test camshafts from Sequence IVA engine test
共ASTM D6891兲. This test measures the camshaft lobe wear in
an overhead camshaft engine. Camshaft lobes shown in the
Fig. 5.15—Comparison between crosshead and trunk-piston en- left half of the figure have less wear, and are rated a PASS,
gines 关496兴. than those shown on the right half of the figure, which are
rated a FAIL. Figure 5.22 shows oil pans, baffles, and rocker
precursors, lubricant also gets contaminated by the partial arm covers from Sequence VE test 共ASTM D5302兲. In the fig-
combustion products, for example, soot and acidic combus- ure, cleaner pan, baffle, and rocker arm covers are rated a
tion products that include the sulfur and nitrogen oxides and PASS while those with a lot of varnish and sludge are rated a
the derived acids. Soot leads to an increase in oil viscosity, FAIL. The test in addition rates:
which adversely affects the oil’s ability to lubricate, thereby 1. Sludge deposits on other parts of the engine as well,
causing increased wear. Sulfur and nitrogen oxides take part which include valve deck, front seal housing, and cylin-
in oxidative and thermal degradation of the lubricant and in der block.
the presence of water the derived acids lead to corrosion. 2. Varnish deposits on piston skirts, rocker arm cover, cam
The lubricant performance is assessed by analyzing baffle, cylinder walls, and oil pan.
various lubricant parameters for change and by inspecting 3. “Hot” stuck piston compression rings.
various engine parts for damage. In a four-stroke cycle en- 4. Clogging of oil pump screen, piston oil rings, and cam-
gine, lubricant-related parameters include viscosity increase shaft oil feed holes.
due to oxidation or soot, sludge formation, filter plugging, The test also measures cam lobe wear and weight loss of
fuel efficiency, and foaming. Engine parts inspected include the follower arms. Figure 5.23 shows test pistons and baffles
bearings for rust and corrosion; valve train components for from Sequence VG engine test 共ASTM D6593兲. Again, the
wear; pistons for deposits, wear, and oil consumption; and cleaner parts have a PASS rating and those with heavier de-
cylinder liners and piston rings for wear. These parts are posits have a FAIL rating. This test in addition rates sludge
identified in Figs. 5.11–5.14 and the qualifying limits for deposits on rocker arm covers, cam baffles, timing chain
these parameters are listed in Tables 5.9–5.14, 5.16–5.18, cover, oil pan and valve decks, and the varnish deposits on
5.20, 5.22, and 5.24. As mentioned earlier, in two-stroke cycle cam baffles. It also inspects for “hot” and “cold” stuck piston
and four-stroke cycle SI engines, the parameters examined compression rings, clogging of the oil pump screen and pis-
include exhaust smoke, exhaust system blocking, pre- ton oil rings, and measures the roller follower pin wear and
ignition, stuck rings, and piston varnish and deposits. ring gap increase. Figure 5.24 shows the connecting rod
bearing from Sequence VIII engine test. Like the L-38 test,
Rating of Engine Parts this test evaluates a lubricant’s ability to protect the copper/
Rating is a process that is used to describe the condition of lead/tin bearing against corrosion. However, unlike L-38,
the test components. Most lubricant and additive suppliers which uses leaded fuel, this test uses unleaded fuel.
use one of the following methods for this purpose. Figures 5.25–5.29 show the appearance of the PASS and
1. Coordinating Research Council 共CRC兲 Method FAIL pistons from the various Caterpillar diesel engine tests.
2. Coordinating European Council 共CEC兲 Method In all cases, the emphasis is on piston cleanliness and FAIL
3. Institute of Petroleum 共IP兲 Method pistons have more carbon deposits on top lands and top
While all three methods use similar basic principles, there grooves. Additional factors in the Caterpillar tests relate to
are many differences. At present, nationally organized bod- oil consumption, change in side clearance, piston, ring, or
ies are attempting to arrive at a uniform method. Uniformity liner distress 共scuffing兲, and stuck rings. Figure 5.30 shows
in ratings is important in conveying meaningful information crossheads from the Cummins M-11 EGR engine test. While
to the users. Rating is performed by qualified raters who are the PASS/FAIL decision in this case is primarily based upon
trained by a self-policing industry-supported group. Guide- wear-related weight loss, other parameters such as oil filter
lines for rating engine parts are regularly published by CRC plugging, engine sludge, and top ring weight loss also play a
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CHAPTER 5 䊏 COMBUSTION ENGINE LUBRICANTS 251
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252 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
role. Two new Cummins engine test procedures, Cummins test procedure is used to evaluate a crankcase lubricant’s
ISM and Cummins ISB, are a part of the new API CJ-4 heavy- ability to reduce camshaft lobe and valve train wear. The test
duty diesel engine oil specification. The ISM test procedure is carried out using a Cummins ISB, common rail fuel sys-
is used to evaluate a lubricant’s effectiveness at reducing tem engine equipped with EGR. Both procedures use PC-10
soot-related wear of overhead components, sludge, and oil fuel. Parts from this test are shown in Fig. 5.32. In both these
filter plugging. The engine parts from this test are shown in figures, the parts on the left reflect less than exemplary per-
Fig. 5.31. The procedure uses a Cummins ISM engine formance.
equipped with EGR and is intended to be a replacement pro- Four Mack tests are also included in the current heavy-
cedure for the M-11 EGR, using newer hardware. The ISB duty specifications. These tests are Mack T-8, Mack T-10,
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CHAPTER 5 䊏 COMBUSTION ENGINE LUBRICANTS 253
TABLE 5.30—U.S. Military Specification MIL-PRF-7808L Grade 3 for aviation engine oils
†503‡.
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254 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
Mack T-11, and the newest Mack T-12, which is part of the matics, sulfur, and nitrogen compounds. Severely hydropro-
most recently introduced CJ-4 heavy-duty diesel category. cessed oils, the same as hydrocracked oils, are made by hy-
Mack T-8, T-8E, and T-11 evaluate soot handling capability of drotreating under severe conditions 关425– 480 ° C
an oil with regard to viscosity, oil filter plugging, and oil con- 共800 to 900° F兲 and 1500 to 3000 psi pressure兴. In addition
sumption. Mack T-10 evaluates an oil’s ability to minimize to hydrogenating aromatics and removing sulfur and nitro-
cylinder liner wear and piston ring and bearing wear in en- gen compounds, the process involves molecular reconstruc-
gines equipped with exhaust gas recirculation 共EGR兲. Top tion, such as converting the linear hydrocarbons into
ring weight loss limit for Mack T-10 is 140 mg maximum, but branched hydrocarbons. Hydrocracking/hydroiso-
for Mack EON-PP, it is 12 mg maximum. Mack T-12 evalu- merization enables the refineries to produce oils that not
ates piston ring wear, cylinder liner wear, lead bearing corro- only have excellent low-temperature properties, but also
sion, oil consumption, and oxidation. very high viscosity indices. Such oils are designated as VHVI
Figure 5.33 shows parts from the roller follower test. In or X-HVI paraffinic base stocks. These oils are comparable
this case, the wear on roller follower axles is the primary de- to synthetic base fluids in performance.
terminant in the PASS/FAIL decision. The wear limit for Engine oil formulations use both mineral oils and syn-
CG-4 oils is 11.4 microns 共0.45 mils兲 and for CH-4 and CI-4 thetic fluids. However, because of the increasing demands of
oils is 7.6 microns 共0.30 mils兲. a modern combustion engine on the lubricant, the conven-
Parts of the natural gas engines that are examined for tional solvent-refined oils are not very suitable. This is be-
varnish, deposits, or damage include pistons, piston liners, cause of their meager low-temperature fluidity, mediocre
cylinder heads, valves, valve deck, connecting rod bearing, viscosity indices, fair volatility characteristics, and border-
and oil pan. These for a natural gas engine oil of a suitable line thermo-oxidative stability. Hydroprocessed and hydroi-
quality are shown in Fig. 5.34 关498,514兴. Pistons from vari- somerized oils are better since they have good color, good
ous two-stroke cycle engines are shown in Fig. 5.35 关318兴. low-temperature fluidity, uniform composition hence low
Notice the heavy deposit build-up on pistons that are unac- volatility, and excellent thermo-oxidative stability because of
ceptable. being free from aromatics. These base oils are grouped un-
der API Group II and Group III categories, which are pro-
Formulating Engine Oils vided in Table 5.40 along with their sulfur and saturates con-
Engine oils must possess a number of attributes to perform tent and viscosity indices 关515兴. One of the major drawbacks
effectively in the tests summarized in the above-listed perfor- of removing aromatics from the mineral oil composition to
mance specifications. Typically an engine lubricant contains improve its properties is that the new oil lacks good solvency.
70 % or more base oil depending upon the application, and That is, it has diminished ability to dissolve additives many
the additives make up the balance. Base stocks manufactur- of which are polar in character. The same issue must be ad-
ers classify base stocks into four broad groups: conventional, dressed while selecting nonpolar synthetics such as PAOs as
hydroprocessed, severely hydroprocessed, and synthetics. base fluids since their structure is analogous to that of the
Conventional base stocks, commonly referred to as mineral modified mineral oils. One way the formulators overcome
oils, are derived from petroleum refining. Hydro-processed the solvency problem is to add back some of the polars, such
oils are highly refined mineral oils, which are made from as an alkylnaphthalene, a synthetic ester, or both. Despite the
mineral oil stocks by hydrogen treatment under mild condi- fact that the aromatics removed from mineral oil via hydro-
tions 关400 ° C 共750° F兲 and 500 psi pressure兴. Base oils thus processing are being replaced with an alkylnaphthalene, an-
obtained are of similar quality as those traditionally made by other aromatic, the new composition has superior proper-
sulfuric acid treatment, neutralizing, and clay filtration, but ties since alkylnaphthalene is oxidatively more stable than
without generating any waste. These oils have low aromatics the removed aromatics. If the alkylnaphthalene contains a
content and lighter color, which is due to the removal of aro- tertiary alkyl group, which lacks easily oxidizable benzylic
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CHAPTER 5 䊏 COMBUSTION ENGINE LUBRICANTS 255
TABLE 5.31—U.S. Military Specification MIL-PRF-23699F for aviation engine oils †504‡.
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256 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
TABLE 5.32—U.K. Military Specification DEF STAN 91-101/2 „replaces DERD 2499… for avia-
tion engine oils †504‡.
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CHAPTER 5 䊏 COMBUSTION ENGINE LUBRICANTS 257
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258 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
TABLE 5.33—U.K. Military Specification DEF STAN 91-98/1 „DERD 2487… for aviation engine
oils †501‡.
hydrogens, the composition will have even better oxidation bon oils shown in Table 5.41, the API Group V oils are even
stability 关516兴. more expensive than the PAOs, which are grouped under API
The major advantage of the API categories is that they Group IV. For example, the polyesters base stocks are ten to
minimize a marketer’s retesting costs when blending li- fifteen times more expansive than conventional or hydropro-
censed engine oils from base oils manufactured differently. cessed base oils. Semi-synthetic base stocks are a compro-
The higher API category typically represents a higher level of mise where the cheaper hydrocarbon oils are mixed with
performance, and so does the cost. Various properties of the PAOs and polyesters to take advantage of their superior
API Group I to API Group IV base stocks of similar 100 ° C properties at a reasonable cost. The proportion of the se-
viscosity are shown in Table 5.41 关517兴. API Group V cat- verely hydroprocessed PAOs or synthetic base stocks in
egory in Table 5.40 includes base stocks that contain oxygen, semi-synthetic oils is usually between 10 and 25 %.
phosphorus, chlorine, fluorine, etc. The only exception to Additives that are used to formulate engine oils are
the list is the alkylated aromatics, which are pure hydrocar- listed below, along with the functions they perform.
bons. Of the API Group V base stocks, diesters, polyol esters, 1. Oxidation Inhibitors—Maintain oil stability over the
and alkylated aromatics are used to develop automotive and service interval. Keep the formation of oxygenates in
aircraft engine oils. Compared to the cost of the hydrocar- control, thereby minimizing an increase in the lubricant
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CHAPTER 5 䊏 COMBUSTION ENGINE LUBRICANTS 259
first portion contains polymeric additives, such as viscosity The automakers’ drive to protect pollution control de-
improver/s and pour-point depressant/s. The second portion, vices is critical in meeting the increasingly stringent air
called detergent inhibitor or DI for short, contains additives emissions regulations. Automakers want to make sure that
that include dispersants, detergents, oxidation inhibitors, the emissions control systems on their vehicles continue to
antiwear agents, corrosion inhibitors, foam inhibitors, and perform over the vehicle’s lifetime. Therefore, they demand
friction modifiers. In the case of the passenger car oils, the engine oils to have lower levels of sulfur, phosphorus, and
polymeric portion of the additive package accounts for ap- metal compounds—elements the automakers believe dete-
proximately 30 % of the total additive volume, approxi- riorate the performance of the exhaust system catalysts.
mately 6 % of the finished oil. Polymethacrylates, styrene- While oil and additive companies do not fully agree with the
isoprene polymers, and ethylene-propylene and ethylene- automakers, they have little choice but to attempt to remove
propylene-diene polymers are used to impart to the oil the these elements from passenger car engine oils. The com-
ability to maintain appropriate viscosity across a broad tem- pounds that are especially being targeted for replacement
perature range. The use of the highly refined base oils, which are zinc dialkyl dithiophosphates, which have been used for
have high viscosity indices and low pour points, greatly many years as extremely cost-effective multipurpose addi-
helps in meeting this objective. The DI portion of the addi- tives for controlling lubricant oxidation, wear, and corro-
tive package makes up the remaining 70 % of the total addi- sion. These additives contain all three elements to which the
tive volume, or 14 % of the finished oil. The DI portion com- automakers object. Incidentally, a statistical study on the ef-
prises approximately 60+ % dispersant, 20+ % detergents, fects of the oil phosphorus on emissions control systems ap-
10+ % antiwear agents, and the balance is the rest of the ad- pears to agree with the automakers’ concern regarding the
ditives. Dispersants are typically the alkenylsuccinimide effects of phosphorus. The study concluded that phosphorus
type and detergents are typically alkaline-earth metal salicy- has a statistically significant effect on HC and CO emissions
late, sulfonate, and or phenate. Antiwear agents are usually and the emissions degradation factors. The authors also sug-
of the zinc dialkyl dithiophosphates type. However, there are gested that calcium detergents may mitigate the detrimental
changes on the horizon with respect to the use of antiwear effect of phosphorus 关518兴. ILSAC GF-4 and forthcoming
agents, corrosion inhibitors, oxidation inhibitors, and the specifications favor increasing the use of oxidation inhibi-
friction modifiers. This is because automotive engine tech- tors, many of which contain sulfur. This forced GF-4 formu-
nologies are constantly being upgraded and it is critical that lators to use even more expensive arylamine and hindered
the new lubricants are compatible with the new changes in phenol type oxidation inhibitors.
engine design or operation. Passenger car technologies are Engine oils for heavy-duty trucks have compositions
driven by fuel economy and maintaining catalytic converter similar to those of the passenger car engine oils but they
efficiency and heavy-duty diesel technologies are being must conform to their own environmental regulations—
driven by emissions control via exhaust gas recirculation most notably new limits on soot emissions. In the United
共EGR兲, fuel economy, and lowering the operating costs States, it is reflected by the new heavy-duty engine oil specifi-
through extended service intervals. cation, API CJ-4, which is designed to cope with higher levels
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CHAPTER 5 䊏 COMBUSTION ENGINE LUBRICANTS 261
of crankcase soot. This surfaced the undesirability of certain TABLE 5.36—Two-cycle engine operating con-
elements in heavy-duty diesel engine oils as well. Sulfur is ditions †505‡.
the main element whose presence in these oils is no longer
Parameter Outboard Air-cooled
welcome because of its negative effect on diesel particulate
Speed Constant Variable
filters and the related devices. That is why the EPA has man- Physical Use Smooth Active
dated the use of ultra-low sulfur diesel, S15, in on-highway Average Piston Temperature Moderate Low
model year 2007 heavy-duty vehicles, which is going to be ex- Peak Piston Temperature Moderate High
tended to the nonroad use by the year 2010 and to locomo-
tive and marine engines by the year 2012. Theoretically, the
lubricant sulfur should not have any effect on emissions, but TABLE 5.37—TC-W3® tests †318‡. Reprinted
it does since part of the lubricant in the internal combustion with permission from the Lubrizol
engine travels past the piston rings into the combustion Corporation.
chamber and burns with the lubricant. This implies that the
Test Pass/Fail Criteria
formulators will have to formulate with additives that are ei-
Compatibility Homogeneous after being
ther sulfur-free or have low sulfur. The major class of addi- mixed separately with each
tives that is of concern is detergents. Basic, or overbased, reference oil and stored
metal sulfonates have been used to both neutralize acidic by- 48 hours
products, resulting from the high-sulfur fuel combustion Brookfield 共Fluidity兲 共cP兲 at ⬍7500
and lubricant decomposition, and to suspend deposit pre- −25° C
cursors in oil, thereby controlling the deposit formation. De- Miscibility at −25° C No more than 10 % more
tergents are especially useful in formulating lubricants for inversions than reference
Rust 共%兲 Equal to or better than
rail-road diesel and marine diesel engines that burn high-
reference
sulfur residual fuels. Sulfonate technology is relatively inex- Filterability Decrease in flow not greater
pensive because alkylbenzenesulfonates are used in many than 20 %
consumer products as surfactants. Under the present sce- OMC 40-hp 共98 h兲 Average piston varnish and
nario, these must be replaced with more expensive carboxy- top ring stick ratings not
late and phenate detergents. In addition to cost, there are lower than 0.6 below same
health and environment concerns regarding the endocrine ratings of reference
mimicking ability 共hormone disruption兲 of alkylphenols, es- OMC 70-hp 共100 h兲 Average piston deposits and
pecially of octylphenol and nonylphenol. Hormone disrup- second ring stick ratings equal
to or better than same ratings
tor is a chemical that interferes with an animal’s natural hor-
of reference
mone function. The endocrine mimicking ability of certain
Mercury 15-hp 共100 h兲 No stuck rings; reference run
alkylphenols can be explained by their conformational simi- Scuffing 共%兲 every 5 candidate runs 30 max
larity to natural hormones 关519兴, see Fig. 5.36. Although Bearing Stickiness Needles must fall easily from
alkylphenols are on EPA’s general list of endocrine disrupt- Compression Loss 共psi兲 max wrist pin 20
ing industrial chemicals 关520兴, endocrine mimicking data on Yamaha CE50S Torque drop equal to or
dodecylphenol, 2,6-di-t-butylphenol, and their derivatives better than reference within
Tightening/Lubricity
that are commonly used in lubricant applications, are either 90 % confidence level
inconclusive or negative 关521兴. Yamaha CE50S
Preignition 共100 h兲 Major preignitions equal to or
Table 5.42 qualitatively shows the effect of various addi-
better than reference
tives on engine performance. The table is useful since some
additives are multifunctional and provide benefits in differ-
ent areas. Other additives are performance specific and may
not perform the other functions well. Information in the salt and a basic salt, is extremely effective in taking care of
table shows that the dispersant is excellent in controlling de- the fuel sulfur-derived acids. Zinc dialkyl dithiophosphate is
posit formation in the gasoline engines, controlling soot in extremely potent as an oxidation inhibitor and as a wear and
diesel engines, and does not contribute to the lubricant ash. corrosion control agent in gasoline engine oils. Information
Low-ash oils are important in diesel applications since they in this table is invaluable to a formulator to help select
contribute less to the formation of the carbon deposits. Basic proper additives.
detergents are great on gasoline engine rust and in taking
care of the fuel sulfur; both because of the base reserve. This Fuel Economy
becomes evident when one compares the performance of the This topic was considered in detail while discussing friction
high base detergents with that of the low base detergents in modifiers in the Additives chapter. To summarize, automak-
these areas. If the deposit control in the diesel engines is an ers must meet the U.S. Government’s Corporate Average
objective, which is of course true, a combination of the low Fuel Economy 共CAFE兲 requirements for passenger cars and
base detergents and the phenate is most beneficial. This is for light trucks, which include pickup trucks, minivans, and
because of the potential synergy between the two types of ad- sport utility vehicles 共SUVs兲 关401兴. The objective of the fuel
ditives: the phenate controls the formation of deposit precur- economy legislation is being met by the combined efforts of
sors by providing high-temperature oxidation control, and the automobile manufacturers, who are implementing a
the high soap in the low base detergent keeps any that form number of design changes to their equipment, and the en-
in the bulk lubricant. Phenate, being basic, both as a neutral gine oil formulators, who are developing energy-conserving
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262 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
oils by the use of the low-viscosity base fluids and the gines include altering fuel composition and properties,
friction-reducing additives. These oils must meet Sequence changing engine designs and operating variables, and the
VIB fuel economy requirements of ILSAC GF-3/GF-4 specifi- use of on-board diagnostics and after-treatment devices.
cation. These oils must also demonstrate fuel economy dura- Emissions control in diesel engines uses both prevention
bility. and correction strategies, the same as in gasoline engines.
Prevention strategies include better fuel quality and delivery,
Emissions Control increased injector and cylinder pressures, advanced com-
The topic of emissions control in engines is discussed in de- bustion chamber and piston designs, and advanced timing.
tail in Chapter 6, titled Emissions in an Internal Combustion Correction strategies include a greater use of EGR, develop-
Engine. To summarize, government-mandated emissions ment of NOx reduction catalysts, and more effective particu-
standards for both gasoline and diesel engines are met by the late filters. Of course, lubricant also plays a role in lowering
combined strategies of the fuel manufacturers, the OEMs, engine exhaust emissions by being compatible with the
and the lubricant designers. The strategies for gasoline en- emissions control system and after-treatment devices, such
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CHAPTER 5 䊏 COMBUSTION ENGINE LUBRICANTS 263
as catalytic converters and diesel particulate filters, and by sel engines are recommended by the OEMs. For North
suspending species such as soot in oil for the duration of the America, GM and Ford recommends oil service for passen-
service interval. The compatibility of the lubricants with the ger cars every 3000 to 7500 miles and Chrysler recommends
emissions control devices was addressed in the previous sec- service every 6000 miles. However, the typical service inter-
tion. val for GM vehicles is 6000 miles and for Ford vehicles it is
5000 miles. To be used in new cars, the oils must be of ILSAC
Extended Service Intervals „Extended Oil Drains… GF-3 or GF-4 quality. Typical OEM service interval recom-
As mentioned earlier, the OEMs and the end-users, espe- mendations for use in Europe is between 9000
cially diesel equipment operators, are greatly interested in to 18,000 miles, with 10,000 miles being typical. For heavy-
extending the service intervals because it lowers their oper- duty diesel engine oils of CH-4/CI-4 quality, Caterpillar rec-
ating costs by reducing the downtime. There is an additional ommends service every 200– 250 hours of operation; Mack
incentive and that is to lower the lubricant use so that mil- recommends service every 25,000 miles, which it down-
lions of gallons less of used oil would require reprocessing or graded from 40,000 for the pre-EGR engines; Cummins rec-
disposal, or both. Every organization that is involved in the ommends service every 25,000 miles, or after 300 hours of
design, service, or use has their own interpretation of the op- operation; and Detroit Diesel recommends service every
timal service interval. However, oil drain intervals have been 22,500 miles, or after 300 hours of operation.
increasing in the light of the significant advances in the lu- The lubricant suppliers tend to recommend longer inter-
bricant technology—both in the additive components and vals. This is partly to distinguish their product from that of
the base oils. the competition. The service companies, on the other hand,
Service intervals for passenger cars and heavy-duty die- recommend a shorter interval, which is to sell their service
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264 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
determining the oil drain intervals can vary by as much as the engine components, leading to serious damage. It is
30 %. therefore imperative that the engine service interval is not
Higher quality oils maintain their performance for an extended beyond the oil’s capacity to effectively suspend
extended period; hence service intervals for such oils are soot.
generally longer. As exemplified in Fig. 5.37, an improve- Bearing life is reduced by factors such as fuel dilution,
ment in the oil quality is accompanied by an increase in the coolant leaks, abrasive wear, and corrosion. Extending the
oil drain interval. This is because each oil upgrade approxi- service interval increases the chances of accumulation of
mately imparts 10 to 20 % improvement over the previous these undesirables in oil. Fuel and coolant dilution of the oil
performance category, which makes the oil last longer. Fac- deteriorates its ability to form an effective boundary lubrica-
tors other than oil quality that affect oil drain intervals in- tion film between the bearing and the shaft, which results in
clude engine-related factors that are addressed below. the removal of the soft metal bearing overlay and causes
1. Increased piston deposits damage to the bearing linings. Bearing overlay performs a
2. Increased oil soot levels leading to an increase oil viscos- number of important functions, which include conformity,
ity and wear. embedding capacity, seizure resistance, and corrosion resis-
3. Reduced bearing life due to corrosion/seizure, resulting tance. Damage to the bearing overlay will ultimately lead to
from increased level of abrasives, fuel, and the coolant the bearing failure.
in the oil. Another concern with respect to extending the drain in-
4. No allowance for a missed drain, which is likely to result terval is that a scheduled service cannot be missed. This is
in catastrophic damage to the engine. because the OEM recommended intervals are conservative,
5. Increased accumulation of the wear metals in the oil, which is to promote maximum engine durability. Extending
causing increased abrasive wear and oil oxidation. the drain intervals to the lubricant’s ultimate performance
6. Elastomer seal damage due to particle accumulation at limit does not allow for missing a service; otherwise cata-
the seal lip. strophic damage to the engine will occur.
7. Loss of fuel economy, especially in passenger cars. Extending the oil drain interval leads to greater accu-
The critical question that needs to be answered is “What mulation of the wear metals in oil, the amounts of which are
is the optimal length of the extended service interval?” To an- directly related to the miles driven. The presence of in-
swer this question, besides lubricant quality and the factors creased metal debris in oil with a long service leads to a rapid
listed above, there are additional factors that need to be con- increase in engine wear, which is shown in Fig. 5.39 关522兴.
sidered. These include the rate of the fuel use, oil consump- The base number, on the other hand, is inversely related to
tion, and the engine sump size 关522兴. The OEMs use these pa- the miles driven: it decreases with an increase in miles, as is
rameters to determine the oil service interval, see Fig. 5.38 shown in Fig. 5.40 关522兴. If the base reserve of the oil drops
关522兴. In the figure, MPQ represents oil consumption per too low, the oil can lose its acid-neutralizing ability, which
quart. For an engine with a sump size of eleven gallons, fuel will be evidenced by the corrosive wear of the rings, liner,
consumption rate of 5.5 miles per gallon, and oil consump- and the bearings. It is imperative that the oil’s base number
tion of one quart for every 1000 miles, the recommended ser- does not drop below 3.0, as measured by ASTM D2896, or
vice interval is 19,250 miles. On the other hand, for an en- 1.5, as measured by ASTM D4739. The rate of the base num-
gine of the same oil consumption and the same sump size ber loss depends upon the fuel sulfur as well as oil consump-
that has a lower fuel consumption rate, that is, travels tion; high sulfur fuel and low oil consumption increases this
6.5 miles per gallon, the service interval extends to rate and low sulfur fuel and high oil consumption decreases
23,000 miles. The reason for this advantage is that an engine this rate. This is shown in Fig. 5.41 关522兴.
with lower fuel consumption generates less heat, which re- As mentioned earlier, extending the oil drain interval
sults in lower oil oxidation, hence extends the oil’s useful life, leads to an increase in oil contamination, which in conjunc-
and has lower piston deposits. Similarly, the service interval tion with the loss in the oil’s base reserve can result in engine
can be extended for engines that consume less oil. On the power loss. This is shown in Fig. 5.42 关522兴. As one can see,
chart this is exemplified for the engine that has a fuel con- extending the oil drain interval from 12,000 miles to 25,000
sumption rate of 5.5 miles per gallon and a high oil con- resulted in a significant power loss, which is believed to be
sumption rate of 600 miles per quart. In this case, the service due to the increased ring wear that increases the blow-by
interval extends to 22,000 miles. Here the advantage is due 关522兴. Data plotted in the figure are from field testing, using
to the constant replenishment with fresh oil and additives. the 430 hp engines.
The presence of high levels of soot in the oil not only Extending the service interval may result in the forma-
leads to a viscosity increase but also causes wear of the valve tion of increased deposits that can result in stuck compres-
train components and a loss in fuel economy. Once the oil sion rings, which will cause an increase in the blow-by and
loses its ability to suspend soot, which is likely to occur if the hence the loss of power. Stuck rings are the consequence of
service interval is too long, the additional soot will be re- the depletion of the oxidation inhibitors and detergents that
leased into the environment. As a general rule of thumb, minimize deposit formation. If this problem is to be avoided,
doubling the service interval will double the amount of soot it is necessary to replenish these additives by periodically
in the oil 关522兴. Typically, an oil filter is used to remove par- adding fresh oil. Crankshaft seal leakage is a potential prob-
ticulates and metal debris to prevent abrasive wear, but if the lem that may occur if the oil drain intervals are extended.
soot level in the oil is too high, it will form sludge on the filter, This is due to particle accumulation at the seal lip, which can
rocker covers, and cylinder head deck. Once the filter is accelerate wear between the seal and the crankshaft.
clogged, the oil will by-pass the filter and cause wear of all of As depicted in Fig. 5.40, extending the service interval
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266 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
Fig. 5.23—Sequence VG engine test parts 关513兴. Fig. 5.25—Caterpillar 1M-PC engine test pistons 关513兴.
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CHAPTER 5 䊏 COMBUSTION ENGINE LUBRICANTS 267
can cause a drop in the lubricant’s base number to danger- precisely this and in an ingenious fashion. This system is an
ously low levels. At this time, the lubricant’s acid- embedded system that extends oil change intervals on elec-
neutralizing ability will diminish, which will be reflected by tronically controlled diesel engines by periodically removing
the corrosive wear of the rings, liner, and bearings and the a small amount of the used oil from the engine’s crankcase
increased deposit formation. Replenishing the lubricant’s and replacing it with the fresh oil. The used oil is sent to the
base reserve may help correct these problems. The Cummins engine’s fuel tank, where it is blended with the fuel and
Centinel Advanced Oil Management System accomplishes burned during the normal combustion. The periodic addi-
tion of the fresh oil not only replenishes the depleted base re-
serve but also introduces more dispersant into the oil. The
combined effect is the control of soot in oil as well as a de-
crease in the soot-related wear and the acid-initiated corro-
sion. The effects of the oil-replacing strategy are shown in
Figs. 5.43 and 5.44 关523–525兴.
Fig. 5.27—Caterpillar 1P engine test pistons 关513兴. Fig. 5.28—Caterpillar 1R engine test pistons 关513兴.
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268 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
Fig. 5.32—Cummins ISB engine test parts 关513兴. Fig. 5.33—Engine test parts from the roller-follower test 关513兴.
methacrylate viscosity modifier, and 30 ppm methylsilicone the balance is base oil 共formulation extracted from Ref 528兲.
foam inhibitor—the balance is the base oil. Stationary Diesel Engine Oil: Formulations analogous
Automotive Diesel Engine Oil: 5.5 % High-molecular to those of the automotive diesel engine oil.
weight alkenylsuccinimide dispersant, 1.4 % mixture of ba-
sic calcium and magnesium sulfonate detergents, 0.85 % Railroad Engine Oils
methylene-bridged calcium phenate,1.3 % primary and sec- These oils are formulated to possess oxidation resistance,
ondary alcohol-derived zinc dialkyl dithiophosphates mix- protect rings and liners against scuffing, deposit control,
ture antiwear agent, 1.6 % alkylated hindered phenol, 0.2 % rust and corrosion protection, and cold weather startability.
polymethacrylate pour point depressant, 6.5 % olefin co- They must also be zinc-free to minimize corrosion of the sil-
polymer or polymethacrylate viscosity modifier, and 80 ppm ver 共silver-steel alloy兲 bushings or bearings that are used in
methylsilicone foam inhibitor, 0.35 % alkenylsuccinic acid the high-performance engine designs. These lubricants have
rust inhibitor, 0.15 % polyethoxylated phenol demulsifier— a high TBN 共13 or 17兲, to counter the acid resulting from the
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CHAPTER 5 䊏 COMBUSTION ENGINE LUBRICANTS 271
or basic metal sulfonate and a phenate or a salicylate. How- Jet Turbine Oil: 1.0–3.0 % Tricresyl phosphate and a pro-
ever, in natural gas engine oils metal phenate is preferred prietary additive mixture antiwear agent, 1.0–3.0 % hin-
over metal sulfonate because of its superior ability to control dered phenol oxidation inhibitor, and 0.5–1.0 % quinizarin
lubricant oxidation and deposit control. However, its acid metal deactivator. The balance is the synthetic ester base
neutralizing ability and hence rust and corrosion control is stock.
not very good. In most cases, the use of a rust inhibitor is re- Ashless Piston-engine Oil: 2.0–3.0 % Polymethacrylate-
quired. Metal salicylate, in view of having phenol functional based dispersant, 0.5–1.0 % tricresyl phosphate antiwear
group, has excellent oxidation control. It also has a basic car- agent, and 0.3–0.5 % hindered phenol oxidation inhibitor.
boxylate functional group, which greatly helps in controlling The balance is the base oil.
rust and corrosion. Phenol and carboxylate functionalities
are next to each other; that is, they have ortho orientation, Small Engine Oils
which provides salicylate with great complexing ability that Small engines are both the two-stroke cycle and the four-
assists in good deposit control 关532兴. Examples of the sta- stroke cycle types. Two-stroke cycle engine oils are formu-
tionary gas engine oil formulations are provided below. lated to reduce smoke, prevent ring sticking, and improve
Ashless Stationary Gas Engine Oils: 3.5 % Alkenylsuc- cleanliness and lubricity. These oils are mineral oil-based
cinimide dispersant, 0.5–1.0 % tricresyl phosphate antiwear and contain additives, such as dispersants, oxidation inhibi-
agent, 0.3–0.5 % arylamine oxidation inhibitor 共NOx- tors, antiwear agents, and corrosion inhibitors. Four-stroke
inhibiting agent兲, 0.5–0.8 % triazole metal deactivator, and cycle engine oils are formulated to improve cleanliness,
5 ppm silicone foam inhibitor. The balance is the base oil. wear, corrosion, oxidation stability, and the clutch friction
Ash-producing Stationary Gas Engine Oil: 3.0–3.5 % performance. These lubricants are formulated using deter-
Alkenylsuccinimide dispersant, 4.0–5.0 % calcium sulfonate gents, dispersants, rust inhibitors, and oxidation inhibitors.
and phenate mixture detergent, 0.2 % tricresyl phosphate The functions performed by these additives are provided in
antiwear agent, 0.4–0.5 % arylamine oxidation inhibitor, Table 5.44 关533兴. Representative formulation examples for
0.5–0.6 % triazole metal deactivator, and 5 ppm silicone these oils are provided below.
foam inhibitor. The balance is the base oil. Ashless Two-stroke Cycle Engine Oil: 3.0–5.0 % Alkenyl-
Aviation Engine Oils succinimide dispersant, 0.1–0.2 % sulfurized fat antiwear
These lubricants fall under two general categories: lubri- agent, 0.2–1.0 % hindered phenol oxidation inhibitor, 0.5–
cants for jet turbine engines and lubricants for aircraft piston 1.0 % fatty acid and alkenylsuccinic acid-based corrosion in-
engines. Jet turbine oils possess excellent thermal and oxida- hibitor, 0.1–0.2 % long-chain alcohol coupler or emulsifier,
tive stability, load-carrying capacity, deposit control, and 2.0–2.5 % Stoddard solvent, and 0.01–0.05 % blue or purple
anti-corrosion protection. They are based upon synthetic es- dye. Stoddard solvent is added to the formulation to enhance
ter base stocks and contain oxidation inhibitors, antiwear fuel compatibility. Sometimes the formulation contains high
agents, and corrosion control additives. Piston engine lubri- molecular weight amines that act cleanliness aids. The bal-
cants are designed to prevent wear of the engine parts, keep ance is the base oil.
abrasives and deposit-forming materials in suspension, dis- Ash-producing Two-stroke Cycle Engine Oil: 1.0–1.5 %
sipate heat, and seal off blow-by of the combustion chamber Neutral calcium sulfonate or fatty acid-based corrosion in-
gases into the crankcase. These oils are based upon highly hibitor, 0.1–0.2 % long-chain alcohol coupler or emulsifier,
refined mineral oils, synthetics, or semi-synthetics and con- 1.5–2.0 % Stoddard solvent, and 0.01–0.05 % blue or purple
tain dispersants, antioxidants, antiwear agents, and rust and dye. The balance is the base oil.
corrosion inhibitors. Esters are superior to mineral oil- Low-ash Two-stroke Cycle Engine Oil: 4.75 % Alkenyl-
containing formulations with respect to low temperature succinimide dispersant, 3.0–4.5 % alkylphenol—alkaline
viscometrics, viscosity index, volatility, and the Ryder gear earth metal alkylsalicylate mixture detergent, 0.25 %
test 共EP兲 performance 关214兴. For turbo-propeller use, viscos- sulfur-free organo-molybdenum derivative friction
ity modified diesters are used. However, for turbofan and tur- modifier/detergent, 3 % polyisobutylene lubricity agent,
bojet applications, polyol esters without the viscosity modi- 0.5 % fatty acid imidazoline, 0.2 % long-chain alcohol cou-
fiers are preferred. Turbofan lubricants employ high pler or emulsifier, 2.0–2.5 % kerosine, and 0.01–0.05 % blue
viscosity esters and turbojet lubricants employ low to me- or purple dye. The balance is the base oil. Kerosine is added
dium viscosity esters. Representative formulations for the to the formulation to enhance fuel compatibility 共formula-
aviation engine oils are provided below. tion extracted from Ref 534兲.
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MNL59-EB/Mar. 2009
6
Emissions in an Internal Combustion Engine
UNDESIRABLE EMISSIONS IN INTERNAL COMBUS- also of concern because of their indirect threat to the envi-
tion engines are of major concern beause of their negative ronment. In the United States, mobile sources are the larg-
impact on air quality, human health, and global warming. est contributor to the air toxics. Air toxics consist of pollut-
Therefore, there is a concerted effort by most governments ants that are either known or the suspected carcinogens, or
to control them. Undesirable emissions include unburned are a serious hazard to the public health or the environ-
hydrocarbons 共HC兲, carbon monoxide 共CO兲, nitrogen ox- ment. These include materials, such as benzene and form-
ides 共NOx兲, and particulate matter 共PM兲. In this chapter, we aldehyde, and greenhouse gases, such as carbon dioxide
present the U.S. and European emissions standards, both 共CO2兲, that trap heat in the Earth’s atmosphere, thereby
for gasoline and diesel operated engines, and strategies to leading to the global climate change.
control the undesirable emissions. The role of engine de- Carbon monoxide is a colorless, odorless, poisonous
sign, vehicle operating variables, fuel quality, and emission gas that is a major air pollutant in most urban areas. It
control devices in minimizing the above-listed pollutants results from the incomplete combustion of the hydrocar-
are also detailed in this chapter. bon fuel. According to the EPA studies, up to 95 % of the
“Emissions” is a collective term that is used to describe carbon monoxide is due to vehicle emissions. Hydrocar-
the undesired gases and particles which are released into bons are another serious air pollutant. It is not only a com-
the air or emitted by various sources. Its amount and the ponent of the smog, but it also contributes to the formation
type change with a change in the industrial activity, tech- of the ground-level ozone by reacting with nitrogen oxides
nology, and a number of other factors, such as air pollution in the presence of sunlight. Hydrocarbon emissions result
regulations and emissions controls 关535兴. from the incomplete combustion of the fuel as well its
The U.S. Environmental Protection Agency 共EPA兲 is evaporation from the tank and other fuel supply compo-
primarily concerned with emissions that are or can be nents. Nitrogen oxides result from the reaction of nitrogen
harmful to the public at large. EPA considers carbon mon- and oxygen in the air at high combustion temperatures,
oxide 共CO兲, lead 共Pb兲, nitrogen dioxide 共NO2兲, ozone 共O3兲, such as those present in an internal combustion engine.
particulate matter 共PM兲, and sulfur dioxide 共SO2兲 as the More than half of all nitrogen oxide emissions come from
pollutants of primary concern, called the Criteria Pollut- the mobile sources, both on-road and non-road vehicles.
ants. These pollutants originate from the following four Particulate matter is a term used to describe solid or liquid
types of sources. particles found in the air. Some particles are quite large,
1. Point sources, which include facilities such as factories around ⬃10 micron共兲 or more in size, or are dark enough
and electric power plants. to be seen as soot or smoke, or both. While the particles of
2. Mobile sources, which include cars and trucks but also this size can lead to irritation of the nose and throat and
lawn mowers, airplanes, and anything else that moves coughing, it is the particles of the smaller size, which are
and releases pollutants into the air. generally invisible to the naked eye, that have serious
3. Biogenic sources, which include trees and vegetation, health effects. Mobile sources, both on-road and non-road,
gas seeps, and microbial activity. of particulate emissions consist mainly of particles that
4. Area sources, which consist of smaller stationary have a size of 2.5 or less. This is especially true of the
sources such as dry cleaners and degreasing diesel-powered vehicles, which are responsible for more
operations. than 50 % of the mobile source particulate emissions. The
The primary drivers that are used to maintain or im- particulate matter of the diameter 2.5 or less 共PM2.5兲 can
prove the country’s air quality include the Clean Air Act travel deep into the lungs and cause chronic lung prob-
共CAA兲, Office of Air and Radiation 共OAR兲 Rules, and Air lems, such as asthma, difficulty in breathing, bronchitis,
Toxics Rules. We will primarily focus on pollutants result- and sometimes even cancer. Fine particulates can also
ing from the mobile sources since they are most pertinent cause haze, thereby reducing visibility.
to our discussion 关536兴. Mobile source air toxics 共MSATs兲, also known as haz-
Air pollution from the mobile sources occurs through ardous air pollutants, are also of concern since these
two processes: combustion and fuel evaporation. The pol- chemicals are known or suspected to cause cancer or other
lutants that are considered a significant threat to human serious health effects, such as reproductive problems or
health and the environment are carbon monoxide 共CO兲, hy- birth defects. These chemicals enter the atmosphere either
drocarbons 共HC兲, nitrogen oxides 共NOx兲, and particulate by direct evaporation of the fuel, or its passage through the
matter 共PM兲. In addition to these, there are other air pol- engine via combustion. These components may also be
lutants, such as air toxics and greenhouse gases, which are present in the fuel as additives, result during combustion,
273
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274 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
or the atmospheric oxidation. Examples of such chemicals emissions. Hence, the EPA is proposing to limit the ben-
include formaldehyde and acetaldehyde. Some air toxics, zene content of the gasoline to an annual average of 0.62 %
such as metals, can result from engine wear or from impu- by volume, beginning in the year 2011. The EPA is also
rities in the oil or the fuel. A detailed list of the compounds proposing to limit the exhaust emissions of hydrocarbons
emitted from the mobile sources and their cancer and non- from the passenger vehicles, when they are operated at
cancer risk to the regional and national population is listed cold temperatures. This standard will be phased in during
in the Integrated Risk Information System 共IRIS兲 database the 2010 to 2015 period. Further proposals involve the
关537兴 and the EPA February 28, 2006 proposed rule docu- evaporative emissions standards for passenger vehicles,
ment, titled “Control of Hazardous Air Pollutants from Mo- which are equivalent to those in California, and hydrocar-
bile Sources” 关538兴. Among the national- and regional-scale bon emissions standard for gas cans beginning in 2009.
cancer and non-cancer risk drivers identified in the 1999 This standard will reduce evaporation and spillage of the
NATA, seven compounds have significant contributions gasoline from these containers. These controls will signifi-
from the mobile sources. These include benzene, 1,3- cantly reduce emissions of benzene and other MSATs, such
butadiene, formaldehyde, acrolein 共acrylaldehyde兲, polycy- as 1,3-butadiene, formaldehyde, acetaldehyde, acrolein,
clic organic matter 共POM兲, naphthalene, diesel particulate and naphthalene. In addition, these standards will signifi-
matter 共PM兲, and diesel exhaust organic gases. These air cantly reduce emissions of the particulate matter from pas-
toxics can cause a variety of cancer and non-cancer health senger vehicles, thereby offering substantial benefits to the
effects. Non-cancer health effects include neurological, car- public health. In the absence of these and other existing
diovascular, liver, kidney, and respiratory effects as well as antipollution measures, the pollution is expected to in-
effects on the immune and reproductive systems. Table 6.1 crease significantly in the future, as shown in Fig. 6.2 关539兴.
provides mobile source contribution to the 1999 NATA risk The figure shows contribution of the source categories to
drivers 关539兴. the air toxics emissions from 1990 to 2020, not including
These projected risks were estimated using the same the diesel particulate matter. The dashed line represents
tools and methods as the 1999 NATA 共National-Scale Air the projected emissions without the controls enacted by
Toxics Assessment兲. NATA assesses human health impacts the Clean Air Act. If the diesel PM emissions were added to
from the chronic inhalation exposures to the outdoor the mobile source total, mobile sources would account for
sources of the air toxics. It assesses lifetime risks assuming 48 % of the total 5,398,000 tons in 1999. Figure 6.3 sum-
continuous exposure to levels of the air toxics estimated at marizes the trend in the diesel PM between 1999 and 2020,
a particular point in time. The most recent NATA was car- by source category 关540兴. Diesel PM emissions will be re-
ried out for the year 1999 关539兴. Figure 6.1 summarizes the duced from 368,000 tons in 1999 to 114,000 tons in 2020, a
changes in average population inhalation cancer risk for decrease of 70 %. As the controls on highway diesel engines
the MSATs listed in Table 6.1 关539兴. Despite significant re- and non-road diesel engines phase in, the diesel-powered
ductions in risk from these pollutants, average inhalation locomotives and commercial marine vessels increase from
cancer risks are expected to remain well above 1 in 11 % of the inventory in 1999 to 27 % in 2020.
100,000. According to the EPA, the emissions reductions
from the February 28, 2006 proposed standards for the mo- Exhaust Emissions Of Concern
tor vehicles and their fuels, combined with the standards
already in place, represent the maximum achievable reduc- As mentioned earlier, emissions in an internal combustion
tions of emissions from motor vehicles by the application engine are of two types: evaporative and combustion-
of technology that is or will be available. These standards related. Fuel system and crankcase are the sources of the
propose controls on gasoline-fueled passenger vehicles, evaporative emissions. These emissions are hydrocarbon in
and portable gasoline containers 共gas cans兲. Among nature and can enter the environment directly. Combustion-
MSATs, benzene is a known human carcinogen, and mo- related emissions, on the other hand, arise from the oxida-
bile sources are responsible for the majority of the benzene tion of the hydrocarbon material that is the source of the
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CHAPTER 6 䊏 EMISSIONS IN AN INTERNAL COMBUSTION ENGINE 275
Fig. 6.1—Trends in nationwide average population cancer risk from inhalation exposure to outdoor sources of mobile source air toxics,
1999 to 2030 关539兴.
chemical energy, which through combustion gets converted 共H2O兲. Incomplete combustion, however, leads to the forma-
into thermal energy, and ultimately into mechanical work. tion of the partially oxidized products, such as carbon or par-
Complete combustion results in the formation of the fully ticulate matter 共PM兲, carbon monoxide 共CO兲, aldehydes
oxidized products, such as carbon dioxide 共CO2兲 and water 共CnHmCHO兲, ketones 关共CnHm兲2CO兴, and carboxylic acids
Fig. 6.2—Contribution of source categories to air toxic emissions, 1990 to 2020 共not including diesel particulate matter兲 关539兴.
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276 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
Fig. 6.3—Contribution of mobile source categories to diesel particulate matter emissions 1999 to 2020 关540兴.
共CnHmCOOH兲. Fuel components that escape combustion coming more stringent, combining of all these strategies will
become part of the exhaust as the unburned hydrocarbons be necessary to meet them. The OEMs’ efforts in this regard
共HC兲. The exhaust, in addition, contains small amounts of pertain to engine designs that minimize the formation of the
hydrogen, ethylene, acetylene, and polycyclics that result undesirable emissions and developing effective emissions
from thermal cracking of the hydrocarbons in the fuel. Sul- control systems, which are primarily based upon after-
fur oxides 共SO2 and SO3兲 and NOx, also present in the ex- treatment devices that convert undesirables into innocuous
haust, are produced from the reaction of oxygen with the products.
fuel sulfur and from the reaction of oxygen and nitrogen, Before considering the emissions control strategies, in-
both of which are present in the air. NOx is primarily a mix- dividual emissions, their properties, and their sources must
ture of nitric oxide 共NO兲 and nitrogen dioxide 共NO2兲. NOx be carefully examined. After that we will discuss general per-
formation requires temperatures of about 1370 ° C. formance of the internal combustion engines, which will be
Combustion-related emissions of concern comprise un- followed by the emissions standards, both for gasoline and
burned hydrocarbons 共HC兲, carbon monoxide 共CO兲, nitro- diesel engines, and the strategies to control emissions. And
gen oxides 共NOx兲, aldehydes, and particulate matter 共PM兲. in this regard, the impact of the fuel properties, engine oper-
The amount of pollutants in the exhaust gas depends ating conditions, and the engine design changes will be con-
upon the type and the quality of the fuel, the composition of sidered.
the air-fuel mixture, combustion quality, the type of ignition
共spark versus compression兲, engine operating conditions, Unburned Hydrocarbons „HC…
and the presence or absence of the emissions-control de- HC is a collective term that is used to describe all hydrocar-
vices. Emissions of concern in gasoline engines primarily bon material present in the exhaust gas. In the presence of
consist of HC, CO, NOx, and CO2, and for diesel engines, sunlight and NOx, these compounds can form oxidants,
they, in addition, include aldehydes, PM, and odor constitu- such as organic peroxides, ozone, and peroxy-acetyl nitrates,
ents. some of which may cause irritation of the mucous mem-
Besides water and carbon dioxide, which are the essen- brane. Polycyclic hydrocarbons, if present, are also of con-
tial products of combustion, all others are considered unde- cern, due to their carcinogenic activity.
sirable. Public concern towards emissions is growing at a Besides evaporation, these emissions in a four-stroke
rapid rate and their control is being mandated by various cycle engine arise from two sources, incomplete combustion
government organizations and a number of legislations in of the fuel and wall quenching. In a two-stroke cycle engine,
the United States and other countries exist to control their the additional source is exhaust scavenging of the fresh in-
release into the atmosphere. Even the amount of CO2 is be- coming mixture. Incomplete combustion is a consequence
ing scrutinized because of its contribution to the greenhouse of the ineffective flame propagation that can result when the
effect. However, its control is difficult because of the wide- fuel-air mixture is too rich, too lean, or is highly diluted by
spread use of the fossil fuels. the exhaust gas. This problem is more prevalent during the
There are a number of ways to reduce undesirables in warm-up and deceleration when the fuel-air mixture is of
the exhaust. These include fuel reformulation, changing en- improper composition for efficient combustion. This is
gine operating conditions, and modifying engine designs. sometimes indicated by misfiring. Under these conditions,
Since the future emissions standards are progressively be- the amount of HC is very high. As mentioned earlier, wall
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CHAPTER 6 䊏 EMISSIONS IN AN INTERNAL COMBUSTION ENGINE 277
quenching is the process where free radicals, essential to stable nitrogen pentoxide 共N2O5兲. With respect to engine
combustion, become inactive 共quench兲 after colliding with emissions, we are primarily concerned with the formation of
the wall, and the wall temperature is too low to support com- the nitric oxide 共NO兲 and nitrogen dioxide 共NO2兲. Nitric ox-
bustion. Scavenging-related hydrocarbon emissions occur ide is a colorless, odorless gas that, at least in principle, can
because of the tendency of the unburned fuel-air mixture to result from the direct reaction of nitrogen and oxygen that
escape directly into the exhaust. The amount of HC emis- constitute air. NO2, a reddish-brown gas with a penetrating
sions in the cross-scavenged two-stroke cycle engines is the odor, which can cause irritation of the mucous membranes,
highest. results when the NO oxidizes further. The mechanism of
NOx formation is shown by the chemical equations given be-
Carbon Monoxide „CO… low.
This pollutant results when the temperature and the oxygen
N2 + O2 2NO
content of the fuel-air mixture are not high enough to affect
complete combustion. The low-temperature situation typi-
2NO + O2 2NO2
cally exists between the lean flame region and the lean flame-
out region, usually at the onset of combustion and at low The rate of NO formation by this mechanism is slow
loads. Figure 6.4 identifies the various flame regions. The 关542兴; hence the equilibrium quantities produced at peak
situation changes as the combustion process proceeds. The temperatures and pressures in the cylinders cannot be
CO formation under high loads is not a problem since they reached. Zeldovich proposed an alternative mechanism
require richer fuel-air mixtures, which translates into high based upon atomic oxygen as the initiating species 关543兴.
reaction temperatures that facilitate its oxidation to CO2. Lavoie et al. 关544兴 extended it by including the reaction with
However, too rich a combustion mixture can increase CO by hydroxyl free radicals 共·OH兲 derived from the oxidation of
making the combustion less efficient which is due to the in- the fuel. See the oxidation inhibitors section in Chapter 4 on
adequate oxygen content. The problem can be corrected by Additives. The combined mechanism is shown by the chemi-
using close to stoichiometric combustion mixtures and by cal equations below.
ensuring homogeneous mixing of the fuel and air.
Carbon monoxide 共CO兲, a colorless, odorless gas, is O2 2O
highly toxic. Inhalation of air contaminated with 0.3 volume
percent carbon monoxide can cause death within N2 + O NO + N
30 minutes. The toxicity of the CO is related to its ability to
permanently block hemoglobin’s oxygen-complexing site, N 2 + O N 2O
thereby leading to asphyxiation. Its concentration in the ex-
haust gas from the spark-ignition engines is the highest at N + O2 NO + O
idle speed and in colder months.
N + · OH NO + H·
Nitrogen Oxides „NOx…
NOx is a collective term used for the oxides of nitrogen that H · + N2O N2 + · OH
are many. These are nitrous oxide 共N2O兲, nitric oxide 共NO兲,
nitrogen dioxide 共NO2兲, dinitrogen trioxide 共N2O3兲, and un- O + N 2O N 2 + O 2
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278 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
O + N2O 2NO
Empirical data 关545兴 suggest that the rate of NO forma-
tion is higher for the fuel-rich mixtures than for the stoichio-
metric or the lean mixtures. This is not surprising since rich
mixtures result in higher temperatures and pressures, both
of which facilitate the reaction of the nitrogen and oxygen to
NOx. NOx is also affected by the air-fuel 共A/F兲 ratio and by
the engine design factors that influence the temperature,
such as compression ratio, spark timing, and the cooling sys-
tem performance. Combustion chamber deposits are gener- Particulate Matter „PM…
ally believed to have a modest insulating effect, thus raising Particulates 共particulate matter or PM兲 are defined as sub-
the combustion temperatures and increasing the NOx emis- stances that are present in the exhaust gases in a solid 共ash,
sions slightly. While the original air quality standard was carbon兲 or a semi-solid form. Particulate matter is com-
implemented to control the release of nitrogen dioxide posed of different size particles. Some are as big as 10 mi-
共NO2兲 into the atmosphere, the concern for NO is equally crons 共PM10兲 in size; the others are 2.5 microns 共PM2.5兲 or
valid since it oxidizes in the air to form NO2. NOx emissions smaller. According to the EPA estimate, less than 2% of the
primarily result from the motor vehicles and the industrial total PM10 is attributable to on-road and off-road engines.
and commercial industries that burn fossil fuels. NO is non- Vehicle exhaust-related PM10 includes both the primary car-
toxic, but contributes to ozone formation. However, NO2, its bon particles, mainly from the diesel fuel, and the secondary
oxidation product, is quite toxic and in the worst case can sulfate and nitrate aerosols, formed by the reactions of SO2
cause lung damage. and NOx in the atmosphere. Both the EPA and California
have established the PM10 standards. PM2.5, on the other
hand, poses a much serious health threat since it is small
Ground Level Ozone enough to travel far into the lungs and may contain other as-
Ozone is an indirect contaminant, that is, it is not part of the sociated materials that may also be harmful.
exhaust emissions but results as a consequence of these Particulates are not a serious problem in gasoline en-
emissions. Ozone is a colorless gas that is the chief compo- gines but they are in diesel engines. Diesel particulates are of
nent of the urban smog. It is formed by the interaction of the two types: liquid particulates and soot. Liquid particulates,
reactive organic gases, also called volatile organic carbon which appear as white smoke, result during cold starting
共VOC兲, with the oxides of nitrogen 共NOx兲 in the presence of and idling, and at low loads. These usually consist of the fuel
sunlight. Most hydrocarbon emissions 共HC兲 are VOCs. That and the low boiling fractions of the lubricating oil that es-
is why there are on-going efforts to reduce them. Not all hy- cape combustion. The white smoke tends to cease as the load
drocarbons contribute equally to ozone formation. Olefins increases. Soot, or black smoke, which results from the in-
and aromatics are more likely to take part in ozone forma- complete combustion, is much more persistent and is the
tion than the paraffinic hydrocarbons. Ozone’s health effects cause of great concern.
include damage to the lung tissue, reduced lung function, Soot is primarily made up of fine carbon particles in an
and the sensitization of lungs to other irritants. agglomerated form and results from the stripping of the hy-
drogen atoms from the hydrocarbon molecules of the fuel or
Sulfur Dioxide the lubricant. Soot at low loads forms during the initial stage
Sulfur dioxide 共SO2兲 results from the combustion of fuels of combustion and both in the lean flame zone and the spray
that contain sulfur. On-road and off-road engine fuels are es- core, see Fig. 6.4. It goes away as the combustion proceeds.
timated to contribute less than 3 % towards the total SO2 However, soot formation in the spray core at high loads is
emissions. SO2 is a moderate lung irritant and it along with persistent and is primarily a consequence of the pyrolysis re-
NOx are the major contributors towards acid rain, most of actions that occur due to oxygen deficiency. Fuel deposition
which occurs in and around the highly industrialized cities. on the cylinder walls can also result in soot and for the same
reason.
Aldehydes
Aldehydes occur in emissions of both the CI 共compression Odor
ignition兲 and the SI 共spark ignition兲 engines. The mechanism Kerosine type odor of the diesel fuel, while not of primary
by which they result parallels that of the CO formation and concern, arises from the aromatic organic compounds, such
the combustion temperature and oxygen content of the com- as alkylbenzenes, naphthalenes, indenes and their partially
bustion mixture affect their formation in an analogous man- hydrogenated derivatives that escape combustion. Odor in-
ner. These pollutants are produced in the combustion cham- tensity increases at high loads where the combustion is inef-
ber during the preflame stage when the temperature is low ficient. Strategies that improve combustion also reduce
and only partial oxidation of the hydrocarbon fuel takes odor.
place. Aldehydes also form in air-injected exhaust systems. The governments of many world nations, including that
Two common aldehydes that are found in emissions are of the United States are aware of the impact of these pollut-
formaldehyde and acrylaldehyde, or acrolein. See structures ants on the health and welfare of their populations and have
below. Data show formaldehyde formation to precede knock installed measures to control their release into the environ-
in the gasoline engines 关546兴, suggesting thereby that partial ment. These measures are continuously being revised to stay
oxidation may be the cause of auto-ignition. abreast of this problem. In the United States, the Environ-
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CHAPTER 6 䊏 EMISSIONS IN AN INTERNAL COMBUSTION ENGINE 279
mental Protection Agency 共EPA兲 is assigned to monitor, con- the use of the richer than stoichiometric mixtures. The use of
trol, and or improve the nation’s ambient air quality. Present the higher amounts of fuel to boost the engine performance
U.S. ambient air quality standards are provided in Table 6.2 is impractical for two reasons. First, the amount of fuel in a
关540, 541兴. mixture can be increased until a maximum is reached; be-
yond which there is not enough air in the combustion mix-
General Engine Performance Considerations ture to ensure efficient combustion 关23兴. As a consequence,
there is both a loss of the generated power and an increase in
Traditionally, three key parameters were used to evalu-
HC emissions. Second, at low air-fuel ratios, the cost of the
ate engine performance: power, fuel consumption 共thermal
fuel becomes an issue. Fuel consumption is expressed in
efficiency兲, and driveability 关23,547兴. In recent years, an-
terms of specific fuel consumption 共SFC兲. A minimum SFC is
other measure, namely emissions control, has been added to
reached when all fuel in the cylinder is consumed most effec-
the list. Engines that produce more power, consume less
tively. To increase fuel economy, leaner mixtures are prefer-
fuel, and generate little or no undesirable emissions are
able. However, such mixtures generate less power because
highly desired. All of the listed parameters relate to combus-
they tend to burn slowly. A minimum is reached beyond
tion, hence improving combustion efficiency is one of the
which the flame is difficult to maintain 关23兴.
ways to improve the engine performance.
The effect of the air-fuel composition on MEP and SFC
Fuel requires a certain amount of oxygen, or air, to burn
in an SI engine 共compression ratio= 10兲 at a specific speed is
completely. The air-fuel ratio, denoted by AF, indicates the
shown in Fig. 6.7 关23兴. The data show that as we progres-
relative proportion of air and the fuel in the combustion mix-
ture. The term fuel-air ratio, FA, which is also used, is the re- sively move from the stoichiometric mixture towards rich
ciprocal of the air-fuel ratio. The exact amount of air neces- mixtures, MEP increases 共top curve兲 until it reaches its maxi-
sary to convert the fuel into completely oxidized products is mum at AF of 13: 1. Conversely, moving towards lean mix-
called theoretical or stoichiometric amount 关23,479兴. This tures decreases the SFC 共bottom curve兲 until a minimum is
amount equals 14.7 parts by weight of air for one part by reached at AF of ⬃16: 1, after which it increases. Because
weight of the hydrocarbon fuel, that is, an AF of 14.7: 1, MEP and SFC are inversely related, achieving both simulta-
which is also called a stoichiometric air-fuel mixture. Air- neously is not an easy task. Since the low MEP generation is
fuel mixtures with ratios less than this are labeled rich and ascribed to lean mixtures burning slowly, increasing their
those greater than this are labeled lean. This is shown in Fig. combustion efficiency can help correct this problem. The
6.5 关479兴. Rich and lean pertain to the amount of fuel present easiest way to obtain high efficiency is to use a high octane
in such mixtures. While nitrogen does not take part in the fuel in a stoichiometric air-fuel ratio, employ optimized
combustion process itself, it does oxidize to form nitrogen spark timing, and operate at temperatures that will ensure
oxides, which constitute undesirable emissions. Equiva- the complete combustion. In general, the higher the gasoline
lence ratio , a ratio of AF stoichiometric and AF actual, is octane, the higher is the MEP. This can be seen in the figure
another term used to describe the composition of the com- by relating the MEP values to the fuel octane numbers. This
bustion mixtures 关23兴. The value of equals one for the stoi- strategy works as indicated by the lower amount of HC and
chiometric case. In this chapter, all three ratios will be used, CO in emissions. However, it increases the amount of NOx
depending upon the concepts being explained. formation, as shown in Fig. 6.6, which is a consequence of
While it is possible to operate an internal combustion the higher temperatures that result from the complete com-
engine by the use of the air-fuel mixtures of varying composi- bustion. As mentioned earlier, HC in the SI engines primarily
tion, the maximum combustion temperature, hence the results from wall quenching, incomplete combustion, and
maximum mechanical efficiency, is obtained when the air- inefficient scavenging 关547兴. Wall quenching, a situation
to-fuel ratio is 14.7 to 1, which is indicated by the ideal air where a flame does not propagate well in the vicinity of a
air-fuel mixture in Fig. 6.5 关479兴. However, the combustion wall, occurs for two reasons: 共1兲 the lower wall temperatures
products from such a mixture contain substantial amounts promote fuel deposition, mainly the high boiling fractions,
of unburned hydrocarbons 共HC兲, carbon monoxide 共CO兲, hence poor combustion; and 共2兲 free radicals that are re-
and nitrogen oxides 共NOx兲. Figure 6.6 shows the effect of the sponsible for combustion terminate at the wall, thereby
air-fuel mixtures of varying composition on emissions 关479兴. slowing down the combustion chain reaction. Wall quench-
As we can see, burning of the leaner mixtures 共air-to-fuel ra- ing is the primary source of the unburned hydrocarbons in
tios of ⬎14.7兲, in general, tends to lower the HC and CO the four-stroke cycle engines. These factors will be revisited
emissions and increases the NOx emissions. However, when in the latter section of the discussion.
the mixtures become ultra lean, the situation is reversed. Combustion efficiency, hence emissions quality, also de-
Lean mixtures are also preferable because of the fuel pends upon engine design. In general, the emissions from
economy. Nonetheless, the power generation often requires the piston engines have higher amounts of pollutants than
burning rich mixtures, which produce higher HC and CO those from the gas turbine engines. Data for NOx levels in
emissions. emissions from the various types of engines are graphically
Combustion efficiency depends upon the composition presented in Fig. 6.8 关479兴. As can be seen, gasoline and die-
of the combustion mixture as well as the engine type. Since sel engines emit the highest amount of NOx and gas turbine
torque and mean effective pressure 共MEP兲 are directly re- engines emit the lowest amount. The amount of NOx in
lated, the combustion mixtures that result in maximum emissions from the piston engines fluctuates because of the
MEP result in maximum torque at a given speed. Maximum design differences, such as revolutions per minute, fuel in-
MEP is reached at each engine speed when all of the air in jection method, etc.
the cylinder is effectively consumed. This can be achieved by There are two main reasons for the presence of a lower
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CHAPTER 6 䊏 EMISSIONS IN AN INTERNAL COMBUSTION ENGINE 281
Fig. 6.7—The effect of air-fuel ratio on MEP and SFC in an SI engine 关23兴.
of work 共grams/brake horsepower-hour—g/bhp-h兲, which al- but it also can do more work. The emissions of the gasoline-
lows the use of a single standard for engines of all sizes. A powered vehicles are also expressed as weight per unit of
larger engine generates a higher volume of exhaust and a work, but the units are grams per mile 共g/mile兲. This measure
higher absolute amount of emissions than a smaller engine, of emissions is not suitable for use for diesel emissions stan-
dards because the diesel emissions are tested in an engine gasoline-powered cars, starting with the 1968 model year.
that is stationary and is not in a vehicle. Also, there is more These first limits applied to CO and hydrocarbons 共HC兲 emis-
variation in the sizes and loads of the diesel vehicles than is sions, the limits for NOx were added starting with the 1973
in the gasoline vehicles. model year. The emissions limit data for these pollutants up
Gasoline Engine Standards to the year 2003 are presented in Figs. 6.12–6.14 关548兴. Ex-
Acting on the provisions of the Clean Air Act, the EPA set amination of the plotted data underscores the effectiveness
standards, or limits, for exhaust emissions from the of the EPA emissions standards in lowering HC, NOx, CO,
Fig. 6.11—The effect of air-fuel ratio on MEP and SFC in a CI engine 关23兴.
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284 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
Fig. 6.12—Evolution of U.S. Federal passenger car hydrocarbon 共HC兲 and nitrogen oxides 共NOX兲 exhaust emission standards.
and PM exhaust emissions from the gasoline-fueled vehicles. the year 2004. Tier 1 standards apply to new light-duty ve-
Federal Standards hicles 共LDV兲, such as passenger cars, light-duty trucks, sport
For light-duty vehicles, there are two sets of standards: Tier 1 utility vehicles 共SUV兲, minivans, and pick-up trucks. The
and Tier 2. Tier 1 standards were fully implemented in the LDV category includes all vehicles of less than 8500 lb gross
year 1997 and Tier 2 standards were phased in beginning in vehicle weight rating, or GVWR. These standards apply to
Fig. 6.13—Evolution of U.S. Federal passenger car carbon monoxide 共CO兲 exhaust emission standards.
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CHAPTER 6 䊏 EMISSIONS IN AN INTERNAL COMBUSTION ENGINE 285
Fig. 6.14—Evolution of U.S. Federal passenger car particulate matter 共PM兲 exhaust emission standards.
the full useful life of the vehicle, which is considered to be to lighter vehicles and does not include Heavy Light-duty
100,000 miles. The standards also provide limits that must Truck 关HLDT, gross vehicle weight 共GVW兲 ⬎6000 lb兴 ve-
be met at 50, 000 miles. Car and light truck emissions are hicles.
measured by using the Federal Test Procedure 共FTP兲 75 and Tier 2 standards are provided in Table 6.4 关401兴. In addi-
the results are expressed in g/mile. In addition, a Supple- tion to the lower limits than those of the Tier 1, the limits ap-
mental Federal Test Procedure 共SFTP兲 has also been phased ply equally to all vehicle weight categories, i.e., cars, mini-
in between the years 2000 and 2004. The SFTP includes test vans, light-duty trucks, and SUVs, irrespective of if they
cycles that measure emissions during aggressive highway operate on gasoline, diesel, or the alternate fuel. This means
driving and urban driving while the vehicle’s air condition-
that the large engines, such as those used in light trucks or
ing system is being used. Tier 1 standards are provided in
SUVs, will need more advanced emissions control technolo-
Table 6.3 关401兴.
gies than that used in cars. The standard also applies to
National Low Emissions Vehicle 共NLEV兲 Program is a
voluntary program, under which the northeastern states and “Medium-Duty Passenger Vehicles” 共MDPV兲 that are used
the auto manufacturers agreed to follow the more stringent for personal transportation, with GVWR between 8500 and
emissions standards between the year 1997, when Tier 1 10, 000 lb.
standards were implemented, and the year 2004, when Tier 2 The Tier 2 regulation introduces new requirements for
standards went into effect. Northeastern states in the model the fuel quality. Newer fuels must be compatible with the ad-
year 1999 and the states across the nation in the model year vanced emissions after-treatment devices, for example, cata-
2001 followed such a standard. The standard is similar to lysts that are needed to meet these and upcoming regula-
that used by California for its low emissions vehicle pro- tions. Lower sulfur level in gasoline is one such requirement.
gram; see Table 6.5. The National LEV program extends only Beginning in the year 2004, the average gasoline sulfur level
TABLE 6.3—EPA Tier 1 emission standards for passenger cars and light-duty trucks, FTP 75, g/mile
†401‡.
50,000 miles/ 5 years 100,000 miles/ 10 yearsa
was lowered to 120– 300 ppm, which has dropped further to 4. Super Ultra Low Emissions Vehicles 共SULEV兲
30– 80 ppm. 5. Zero Emissions Vehicles 共ZEV兲
California Standards Table 6.5 summarizes the California ARB standards for
Tier 1/LEV California emissions standards were in effect the new light-duty vehicles and Table 6.6 summarizes the
through the year 2003. In the year 2004, LEV II regulations standards for the medium-duty vehicles 关401兴. After the year
went into effect. The current California emissions standards 2003, Tier 1 and TLEV standards were eliminated. The same
are defined through the following emissions categories: standards apply to gaseous pollutants for the diesel- and
Tier 1
gasoline-fueled vehicles. PM standards apply to diesel ve-
1. Transitional Low Emissions Vehicles 共TLEV兲
hicles only. Emissions are measured using the FTP 75 test
2. Low Emissions Vehicles 共LEV兲
3. Ultra Low Emissions Vehicles 共ULEV兲 and the results are expressed in g/mile. The additional SFTP
procedure was implemented in California between the years sions standards. Medium-duty vehicles above 8500 lb gross
2001 and 2005. weight 共old MDV4 and MDV5兲 will still certify to the
Low Emissions Vehicle II 共LEV II兲 standards, provided medium-duty vehicle standard; see the second half of Table
in Table 6.7 关401兴, apply to the model years 2004 to 2010. In 6.7. Under this standard, the same limits apply to both gaso-
this regulation, light-duty truck and medium-duty vehicle line and diesel vehicles, including the PM standard.
categories of below 8500 lb gross weight were reclassified by California—Greenhouse Gas Emissions for Cars
in the year 2007. At present, most pick-up trucks and sport As mentioned earlier, there is a concern towards the increase
utility vehicles are required to meet the passenger car emis- of the greenhouse gases, such as carbon dioxide, in the atmo-
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288 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
sphere because of their global warming effect. In order to 15.5 g / bhp-h over the span of the last 20 or so years. Figure
offset this, the California Air Resources Board 共CARB兲 has 6.16 is visually more apt in reflecting the chronology and
implemented the greenhouse gases 共GHG兲 emissions stan- tightening of the emissions standards over this time span
dard that became effective on January 1, 2006. The standard 关549兴.
is to be phased in over the 2009 to 2016 period, as shown in The following emissions standards apply to the new die-
Table 6.8 关401兴. The implementation of these standards is ex- sel 共compression-ignition兲 engines used in the heavy-duty
pected to result in an average decrease in greenhouse gases highway vehicles. Heavy-duty vehicles are the vehicles of
of about 22 % in the year 2012 and about 30 % in the year GVWR 共gross vehicle weight rating兲 of above 8500 lb in the
2016, relative to the level of GHG emissions in the year 2004. federal jurisdiction and above 14, 000 lb in California
The GHG standards are part of the California low emis- 共model year 1995 and later兲. Diesel engines used in the
sions vehicle 共LEV兲 legislation. There are two fleet average heavy-duty vehicles are further divided into service classes
GHG requirements. One is for the passenger car/light-duty by GVWR, which are described below.
truck 1 共PC/LDT1兲 category, which includes all passenger • Light heavy-duty diesel engines: 8500⬍ LHDDE
cars and light-duty trucks below 3750 lb equivalent test ⬍ 19, 500 共14, 000⬍ LHDDE⬍ 19, 500 in California,
weight 共ETW兲. The other is for the light-duty truck 2 共LDT2兲
1995+兲
category, including light trucks between 3751 lb ETW and
• Medium heavy-duty diesel engines: 19, 500艋 MHDDE
8500 lb gross vehicle weight 共GVW兲. Medium-duty passen-
艋 33, 000
ger vehicles 共MDPVs兲 from 8500 to 10,000 lb GVW are in-
• Heavy heavy-duty diesel engines 共including urban bus兲:
cluded in the LDT2 category.
HHDDE⬎ 33, 000
Diesel Emissions Standards 关401兴 Under the Federal light-duty Tier 2 regulation, phased in
Emissions standards for the diesel engines relate to the con- beginning in 2004, the vehicles of GVWR up to 10,000 lb
trol of CO, HC, NOx, and the particulates. EPA emissions used for personal transportation have been reclassified as
standards call for progressively lower NOx and particulate “medium-duty passenger vehicles” 共MDPV—primarily
emissions. This is evident from Fig. 6.15. In this figure, we larger SUVs and passenger vans兲 and are subject to the light-
did not include the CO emissions since they were constant at duty vehicle legislation. For the model years 1988 to 2003,
U.S. Federal 共EPA兲 and California 共ARB兲 emissions stan- of the two options. The Federal 2004 standards for highway
dards for the heavy-duty diesel truck and bus engines are trucks are harmonized with California standards. However,
summarized in Table 6.9 关401兴. The certification fuel sulfur California certifications for the model years 2005 to 2007 re-
content for the year 1994 and the following years have been quire the Supplemental Emissions Test and NTE 共Not-to-
established at 500 ppm by weight. Compliance with the exceed兲 limits of 1.25 times the FTP standards. California
emissions standards must be demonstrated over the useful also has more stringent standards for the 2004 to 2006 model
life of the engine, which is defined as follows. year engines for the public urban bus fleets. For the model
1. LHDDE—10 years/ 110, 000 miles 共whichever occurs year 2007 and later heavy-duty highway diesel engines, the
first兲 regulation consists of two components: 共1兲 emissions stan-
2. MHDDE—10 years/ 185, 000 miles dards and 共2兲 diesel fuel regulation.
3. HHDDE—10 years/ 435, 000 miles/ 22, 000 hours The standard for the 2004 model year engines combines
4. Emissions warranty—5 years/ 100,000 miles the non-methane hydrocarbons 共NMHC兲 and NOx together,
Voluntary Clean Fuel Fleet 共CFF兲 emissions standard is instead of considering them separately. This makes sense
the federal standard that applies to the 1998 to 2003 model since both these pollutants are of concern because of their
year engines, both CI and SI, over 8500 lb GVWR, see Table role in the generation of ozone. The concern about carbon
6.10 关401兴. Vehicles must meet this standard as well as other dioxide emissions and their relationship to global warming
applicable conventional standards for other pollutants. The is leading to a serious consideration of using diesel engines
emissions standards for the model year 2004 and beyond are in light-duty trucks, vans, sport utility vehicles, and U.S. pas-
provided in Table 6.11 关401兴. For the year 2004, manufactur- senger cars. The inherent fuel efficiency of the diesel engine
ers have the flexibility to certify their engines by using either relative to that of the gasoline engine results in substantially
lower emissions of CO2 per driven mile. However, there may to lower NOx and particulate matter 共PM兲. The objective of
be emissions control challenges for such vehicles to meet the the study was to determine if the EPA’s 2007 emissions stan-
EPA standards. While the Federal 2004 standards for high- dards for heavy-duty diesel engines pertaining to lower NOx
way trucks are harmonized with the California standards, and PM emissions were achievable. The study employed
California certification for the model years 2005–2007 addi- compression ignition, direct injection 共CIDI兲 diesel-cycle ve-
tionally requires the Supplemental Emissions Test 共SET兲 hicles and four emissions control systems, which were as fol-
and not to exceed 共NTE兲 limits of 1.25 times the FTP 共Federal lows:
test procedure兲 standards. California standards for the 1. Diesel Oxidation Catalysts 共DOCs兲
model years 2004 to 2006 engines for the public urban bus 2. Lean-NOx Catalysts 共LNCs兲
fleets are more stringent than the EPA standards. 3. NOx Adsorber Catalysts 共NACs兲
The EPA is also limiting the diesel fuel sulfur content for 4. Diesel Particulate Filters 共DPFs兲—two types were used:
on-highway diesel fuel to 15 ppm by weight, down from the continuously regenerating DPF 共CR-DPF兲 and a cata-
previous limit of 500 ppm. Ultra low sulfur diesel 共ULSD兲 lyzed DPF 共CDPF兲.
fuel has been introduced as a “technology enabler” to pave The key findings of the study are summarized below.
the way for advanced, sulfur-intolerant exhaust emissions 1. Diesel oxidation catalyst 共DOC兲 did not control PM emis-
control technologies, such as catalytic diesel particulate fil- sions well enough to meet the EPA’s 2007 standards. The
ters and NOx catalysts. Such technologies were necessary to DOC may be effective when used in combination with
meet the 2007 emissions standards. Since the designation selective catalytic reduction 共SCR兲 technology, either as
ULSD may refer to different maximum sulfur content in a pre-catalyst for converting NO to NO2 or as a post-
other parts of the world, it is advisable to use the designa- catalyst to control ammonia slip. Ammonia slip is the
tions S15, S500, and S5000 to describe diesel fuels that meet unwanted ammonia, which is a by-product of the NOx
15 ppm, 500 ppm, and 5000 ppm maximum sulfur content, reduction processes, such as SCR. Ammonia slip must
respectively; as defined in the ASTM Standard D975. In be controlled to minimize its downstream impacts, such
North America 共U.S. and Canada兲, ULSD and S15 are often as corrosion, fouling, and undesirable emissions.
used interchangeably. 2. Lean-NOx catalyst had limited reduction efficiency,
Ultra Low Sulfur Diesel—ULSD 共S15兲 regulation is about ⬃20 %; hence it did not meet the EPA’s 2007 emis-
based upon U.S. Diesel Emissions Control–Sulfur Effects sions standards. However, it did meet the 2004 emis-
共DECSE兲 Project. The project was a joint effort of the U.S. sions regulations for light- and heavy-duty diesel en-
Department of Energy, two national laboratories, and the gines. A DOC may be used to clean up HC slip when this
manufacturers of the heavy-duty compression ignition en- approach is used. HC slip is the amount of HC 共hydro-
gines and of the emissions control systems 关550兴. Research- carbon兲 that is in excess of the amount needed to reduce
ers conducted tests to determine the effects of the various NOx, which is exhausted into the air.
levels of the fuel sulfur on emissions exhaust control systems 3. NOx adsorber catalyst may prove promising for meeting
TABLE 6.11—Emissions standards for the model year 2004 and later
†401‡.
EPA Emission Standards EPA and CARB Emission
Pollutant for MY 2004 Standards for MY 2007 and Latera
Option 1 Option 2
NMHC+ NOX 共g/bhp-h兲 2.4 2.5 —
NMHC 共g/bhp-h兲 n/a 0.5 0.14
PM 共g/bhp-h兲 — — 0.01
NOX 共g/bhp-h兲 – – 0.20
a
The PM emission standard took full effect in the 2007 heavy-duty engine model year. The NOx
and NMHC standards will be phased in for diesel engines between 2007 and 2010. The phase-in
would be on a percent-of-sales basis: 50 % from 2007 to 2009 and 100 % in 2010 共gasoline
engines are subject to these standards based on a phase-in requiring 50 % compliance in 2008
and 100 % compliance in 2009兲.
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CHAPTER 6 䊏 EMISSIONS IN AN INTERNAL COMBUSTION ENGINE 291
will also identify the properties of the fuels and vehicle sys-
tems that could lead to even lower emissions beyond the year
2010 关550兴. The project selected two emissions control tech-
nology systems for further study.
1. Selective Catalytic Reduction 共SCR兲/Diesel Particulate
Filter 共DPF兲—The SCR is an emissions reduction device
that, combined with a DPF and advanced fuel formula-
tions, may reduce regulated 共especially NOx兲, unregu-
lated, and toxic emissions. Two types of SCR-based cata-
lysts are being evaluated in combination with DPFs and
possibly DOCs.
2. NOx Adsorber Catalyst/Diesel Particulate Filter—The
NOx adsorber may significantly reduce NOx, HC, and
CO emissions from the diesel engine exhaust. Combined
with a DPF, the NOx adsorber can also effectively oxi-
Fig. 6.17—Engine-out and post-DPF emissions of total PM and dize the PM and other unregulated emissions from the
components versus fuel sulfur level for the OICA cycle 共with 95% diesel exhaust. Two systems are being evaluated on
confidence intervals on estimated PM兲 关550兴. light-, medium-, and heavy-duty engines; and light- and
medium-duty vehicles.
future NOx standards. However, more study is needed to The EPA has mandated the use of the S15 fuel beginning
investigate the frequency of desulfurization and ther- June 2006 and of high-efficiency catalyst exhaust emissions
mal degradation associated with the high-temperature devices, or comparably effective technology, in the diesel-
desulfurization. More studies are also needed to address operated model year 2007 vehicles. The EPA considers that
the long-term operation of the NOx adsorber catalyst, these actions will help vehicles meet the future nitrous oxide
the durability of the engine and the catalyst, and other 共NOx兲 and particulate matter 共PM兲 emissions standards as
exhaust constituents, such as smoke levels during re- well. It is important to note that the lowering of the diesel
generation and its reduction and control. sulfur will impact its lubricity, cetane number, and the en-
4. Diesel particulate filter, when used in combination with ergy content. Lubricity is the diesel fuel’s ability to protect
the low-sulfur fuel, is capable of meeting future PM various parts of the engine’s fuel injection system against
standards. Research is needed to demonstrate DPFs’ ef- wear. The process required to reduce sulfur is likely to re-
fectiveness in combination with SCR and a NOx ad- move the naturally-occurring lubricity agents in the diesel
sorber. Additional research on measurements for PM fuel; which, if not replaced, can increase wear of the engine’s
mass, size, and composition, as well as for air toxics fuel delivery system. The sulfur-removal process reduces the
must also be conducted. aromatics content as well, which negatively impacts fuel
The effect of the fuel sulfur on PM emissions is provided economy, only slightly, but boosts the cetane number. The
in Fig. 6.17 关550兴. As one can see, at a fuel sulfur level of less American Society for Testing and Materials 共ASTM Interna-
than 30 ppm, particulate emissions primarily consist of sul- tional兲 has established a lubricity specification that is de-
fates. This was confirmed by a repeat test after 400 hours of fined in its standard ASTM D975, which has been in effect
operation. since January 1, 2005.
The results and the test experiences from the DECSE While our discussion so far has been limited to the gaso-
project are being used by its successor, the Advanced Petro- line engines and on-highway heavy-duty diesel engines, it is
leum Based Fuels–Diesel Emissions Control 共APBF-DEC兲 important to note that the emissions standards for non-road,
Project. The goal of the project is to identify the optimal marine, and recreational engines also exist. Table 6.12 pro-
combinations of fuels, lubricants, diesel engines, and emis- vides Tier 2 marine emissions standards 关401兴. There exists a
sions control systems which will meet the projected EPA voluntary “Blue Sky Series” program, which permits the
emissions standards for the years 2008 to 2010. APBF-DEC manufacturers to certify their engines to these more strin-
TABLE 6.13—“Blue Sky Series” voluntary TABLE 6.16—Proposed 20° F FTP exhaust
emission standards †401‡. emission standards †538‡.
Displacement „D… NOx + THC PM NMHC Sales-Weighted Fleet
dm3 per cylinder g/kWh g/kWh Average
Power 艌37 kW & D ⬍ 0.9 4.0 0.24 Vehicle GVWR and Category Standard „grams/mile…
0.9艋 D ⬍ 1.2 4.0 0.18 艋6000 lb: Light-duty vehicles 0.3
1.2艋 D ⬍ 2.5 4.0 0.12 共LDV兲 and Light light-duty
2.5艋 D ⬍ 5.0 5.0 0.12 trucks 共LLDT兲
5.0艋 D ⬍ 15 5.0 0.16 ⬎6000 lb: Heavy light-duty 0.5
15艋 D ⬍ 20 and Power ⬍3300 kW 5.2 0.30 trucks 共HLDT兲 up to 8500
15艋 D ⬍ 20 and Power 艌3300 kW 5.9 0.30 lbs and Medium-duty
20艋 D ⬍ 25 5.9 0.30 passenger vehicles 共MDPV兲 up
25艋 D ⬍ 30 6.6 0.30 to 10,000 lb
gent emissions standards. The qualifying emissions limits Essentially, the EPA is proposing controls on gasoline, pas-
for this program are listed in Table 6.13 关401兴. The Blue Sky senger vehicles, and portable gasoline containers 共gas cans兲
program begins upon the publication of the rule and extends to significantly reduce emissions of benzene and other haz-
up to the year 2010. ardous air pollutants, called mobile source air toxics
Some recreational vessel standards became effective at 共MSATs兲. The proposal consists of the three sets of stan-
the beginning of the year 2006. Others will become effective dards, which are as follows.
in the years that will be specified later. The phase-in sched- 1. Light-Duty Vehicle Emissions Standards propose con-
ule, listed in Table 6.14, depends on the size of the engine trol of both the exhaust and the evaporative emissions
关401兴. Recreational engines are also subject to not-to-exceed from passenger vehicles. These will significantly reduce
limits. There are no smoke requirements for the recreational nonmethane hydrocarbon 共NMHC兲 emissions from pas-
marine diesel engines. Similar to the commercial vessels, senger vehicles at cold temperatures. These hydrocar-
voluntary “Blue Sky Series” limits exist for the recreational bons include many mobile source air toxics, including
vessels also, which are based on a 45 % emissions reduction benzene and VOC.
beyond the mandatory standards. 2. Gasoline Fuel Standards to limit the benzene content of
Useful life and warranty periods for marine engines are all gasoline, both reformulated and conventional.
listed in Table 6.15 关401兴. The periods are specified in operat- 3. Portable Gasoline Container 共Gas Can兲 Controls to re-
ing hours and in years, whichever occurs first. The relatively duce the hydrocarbon emissions from evaporation, per-
short useful life period for Category 3 engines is based on the meation, and spillage.
time the engines operate before being rebuilt for the first Light-Duty Vehicle Cold Temperature Emissions
time. For non-road diesel standards, please check out Ref Standards
关401兴. These standards apply to Tier 2 gasoline-fueled vehicles and
will achieve proportional NMHC control from the 75 ° F Tier
Proposed New Emissions Standards 2 standards to the 20 ° F test point. The purpose of these
In February 2006, the EPA proposed new standards to con- standards, which are provided in Table 6.16 关538兴, is to
trol hazardous air pollutants, especially benzene, from mo- achieve the maximum hydrocarbon emissions reductions,
bile sources to further improve the nation’s air quality 关538兴. by utilizing the current emissions control hardware. These
standards are expected to reduce PM resulting from the cold-
temperature operation as well. The implementation of these
TABLE 6.14—Recreational marine diesel en- standards is proposed to begin in the 2010 model year for
gines standards †401‡. LDVs/LLDTs and 2012 model year for HLDTs/MDPVs.
Displacement „D… CO NOx + HC PM Evaporative Emissions Standards
dm3 per cylinder g/kWh g/kWh g/kWh Date These standards apply to all light-duty vehicles, light-trucks,
0.5艋 D ⬍ 0.9 5.0 7.5 0.40 2007 and medium-duty passenger vehicles. The proposed stan-
0.9艋 D ⬍ 1.2 5.0 7.2 0.30 2006 dards are equivalent to California’s LEV II standards and are
1.2艋 D ⬍ 2.5 5.0 7.2 0.20 2006 shown in Table 6.17 关538兴. Theses standards are expected to
D 艌 2.5 5.0 7.2 0.20 2009 lead to a 20 to 50 % reduction in evaporative emissions, de-
pending upon the vehicle weight class and the type of test,
relative to the Tier 2 standards that will be in effect in the
TABLE 6.15—Useful life and emission war- years immediately preceding the implementation of the
ranty periods †401‡. presently proposed standards. The implementation of these
Useful Life Warranty Period standards is proposed in the model year 2009 for LDVs/
LLDTs and the model year 2010 for HLDTs/MDPVs.
Category hours years hours years Gasoline Benzene Control Program
Category 3 10,000 3 10,000 3 The standard is proposed to be implemented on January 1,
Category 2 20,000 10 10,000 5
2011. The refiners are expected to meet an average gasoline
Category 1 10,000 10 5000 5
benzene content of 0.62 % by volume on the gasolines, both
Recreational 1000 10 500 3
reformulated and conventional, that they produce. The
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CHAPTER 6 䊏 EMISSIONS IN AN INTERNAL COMBUSTION ENGINE 293
implementation will result in the largest feasible overall re- the year 2005, and become mandatory from the year
ductions in benzene. 2009.
Proposed Emissions Control Program for Gas Emissions standards for passenger cars and light com-
Cans mercial vehicles, vehicle categories M1 and N1, respectively,
The purpose of this standard is to minimize the entry of the are summarized in Tables 6.18 and 6.19 关401兴. Please note
volatile organic compounds 共VOCs兲 into the atmosphere, that Euro 2 imposes limits for diesel engines that differ from
since they are ozone precursors, and the VOC-based toxics, those for the gasoline engines. Diesel engines have more
such as benzene and toluene. Gas cans are to meet a maxi- stringent CO standards but are allowed higher NOx. Gaso-
mum of 0.3 grams per gallon per day 共g/gal/day兲 of HC as line vehicles are exempt from PM standards through Euro 4.
evaporative and permeation losses, as measured over a diur- Euro 5 proposes PM standards for lean-burning gasoline
nal test cycle. The cans would be tested as a system with their cars. Values listed in the tables are the new approval emis-
spouts attached. The test is to be carried out by placing the sions limits, unless stated otherwise. Vehicles must stay in
cans in an environmental chamber which simulates sum- compliance with emissions standards for a vehicle’s useful
mertime ambient temperature conditions and cycling the life, i.e., emissions durability, which for regulation purposes
cans through the 24-hour temperature profile 共72– 96 ° F兲. is defined as follows.
The test procedures would ensure that gas cans meet the 1. Euro 3 stage—80,000 km or five years, whichever oc-
emissions standard over a range of in-use conditions, such curs first. Instead of an actual run, the manufacturers
as different temperatures, different fuels, and taking into may use the following deterioration factors: 1.2 for CO,
consideration factors affecting durability. As an aspect of HC, and NOx for gasoline or 1.1 for CO, NOx, HC + NOx,
considering the proposed standard’s technological feasibil- and 1.2 for PM for diesel.
ity, EPA is proposing to require manufacturers to meet the
standard beginning January 1, 2009. TABLE 6.18—EU emission standards for pas-
senger cars „Category M1a…, g/km †401‡.
Emissions Standards—European Union Tier Date CO HC HC + NOx NOx PM
European emissions regulations for new heavy-duty diesel Diesel
engines are commonly referred to as Euro I to Euro V. Arabic Euro 1a 1992.07 2.72 — 0.97 — 0.14
numerals are also used 共Euro 1 to Euro 5兲. In the discussion 共3.16兲 共1.13兲 共0.18兲
that follows, the Roman numerals are used in heavy-duty en- Euro 2, IDI 1996.01 1.0 — 0.7 — 0.08
gine standards, and the Arabic numerals are used for light- Euro 2, DI 1996.01d 1.0 — 0.9 — 0.10
duty vehicle standards. Euro 3 2000.01 0.64 — 0.56 0.50 0.05
Euro 4 2005.01 0.50 — 0.30 0.25 0.025
Emissions Regulations for New Light Duty Euro 5c mid-2008 0.50 — 0.25 0.20 0.005
Vehicles Petrol 共Gasoline兲
These regulations cover cars and light commercial vehicles, Euro 1b 1992.07 2.72 — 0.97 — —
共3.16兲 共1.13兲
as specified in the Directive 70/220/EEC. The chronology of
Euro 2 1996.01 2.2 — 0.5 — —
the standards that were implemented is provided below.
Euro 3 2000.01 2.30 0.20 — 0.15 —
1. Euro 1 standards 共also known as EC 93兲. Euro 4 2005.01 1.0 0.10 — 0.08 —
2. Euro 2 standards 共EC 96兲. Euro 5c mid-2008 1.0 0.075 — 0.06 0.005e
3. Euro 3 / 4 standards 共2000/2005兲. These standards in- a
Before Euro 5, passenger vehicles ⬎2500 kg were type approved
cluded minimum diesel cetane number of 51 共year
as Category N1 vehicles.
2000兲, maximum diesel sulfur content of 350 ppm in the b
Values in brackets are conformity of production 共COP兲 limits.
year 2000 and 50 ppm in the year 2005, and maximum c
Proposed.
petrol 共gasoline兲 sulfur content of 150 ppm in the year d
Until 1999.09.30 共after that date DI engines must meet the IDI
2000 and 50 ppm in the year 2005. “Sulfur-free” diesel limits兲.
and gasoline fuels 共艋10 ppm S兲 must be available from e
Applicable only to vehicles using lean burn DI engines.
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294 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
2. Euro 4 stage—100,000 km or five years, whichever oc- clude emissions requirements for on-board diagnostics
curs first. 共OBD兲 equipped vehicles and for a low temperature emis-
3. Euro 5 共draft proposal兲—160,000 km or five years, sions test 共−7 ° C兲 for gasoline vehicles, effective year 2002.
whichever occurs first. The limits for cars are 15 g / km for CO and 1.8 g / km for HC,
The year 2000/2005 regulations had provisions to in- measured over the urban part of the test only.
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CHAPTER 6 䊏 EMISSIONS IN AN INTERNAL COMBUSTION ENGINE 295
TABLE 6.20—European OBD threshold limits, TABLE 6.22—Emission standards for diesel
g/km †401‡. and gas engines, ETC Test, g/kWh †401‡.
Category Class Tiea Date CO HC NOx PM Tier Date Test CO NMHC CH4a NOx PMb
Diesel Euro III 1999.10, EEVs only ETC 3.0 0.40 0.65 2.0 0.02
M1 EU 3 2003 3.20 0.40 1.20 0.18 2000.10 ETC 5.45 0.78 1.6 5.0 0.16
EU 4 2005 3.20 0.40 1.20 0.18 0.21c
N1 I EU 3 2005 3.20 0.40 1.20 0.18 Euro IV 2005.10 4.0 0.55 1.1 3.5 0.03
EU 4 2005 3.20 0.40 1.20 0.18 Euro V 2008.10 4.0 0.55 1.1 2.0 0.03
II EU 3 2006 4.00 0.50 1.60 0.23 a
For natural gas engines only.
EU 4 2006 4.00 0.50 1.60 0.23 b
Not applicable for gas fueled engines at the year 2000 and 2005
III EU 3 2006 4.80 0.60 1.90 0.28
stages.
EU 4 2006 4.80 0.60 1.90 0.28 c
For engines of less than 0.75 dm3 swept volume per cylinder and
Petrol 共Gasoline兲
a rated power speed of more than 3000 min−1.
M1 EU 3 2000 3.20 0.40 0.60 …
EU 4 2005 1.90 0.30 0.53 …
N1 I EU 3 2000 3.20 0.40 0.60 …
1996. These applied to both truck engines and urban
EU 4 2005 1.90 0.30 0.53 …
II EU 3 2001 5.80 0.50 0.70 … buses; the urban bus standards, however, were volun-
EU 4 2005 3.44 0.38 0.62 … tary.
III EU 3 2001 7.30 0.60 0.80 … 2. Euro III standards were introduced in the year 2000, fol-
EU 4 2005 4.35 0.47 0.70 … lowed by the introduction of Euro IV standards in the
a
Euro 4 threshold limits are proposed values, still under discussion. year 2005. Euro V is slated to go into effect for the model
Note: Passenger cars category M1 ⬎ 2500 kg or with more than six year 2008 vehicles. The standards have the voluntary
seats meet OBD requirements for Category N1. compliance of stricter emissions limits for extra low
emissions vehicles, known as “enhanced environmen-
tally friendly vehicles,” or EEVs.
Starting from the Euro 3, vehicles are required to be
The European Commission has submitted a proposal
equipped with an on-board diagnostic system for emissions
for Euro VI emissions standards in the year 2007, which in
control. The proposed emissions limits for such vehicles are
addition to having more stringent emissions limits may in-
provided in Table 6.20 关401兴. The thresholds are based on the
clude new standards for pollutants that are as yet unregu-
NEDC 共cold start ECE+ EUDC兲 test. NEDC is an abbrevia-
lated. The standard is expected to become effective for heavy
tion for New European Driving Cycle and ECDE is an abbre-
duty engines for the model year 2013. The unregulated pol-
viation for Extra Urban Driving Cycle. To distinguish from
luatants this standard plans to limit may result from the use
the U.S. OBD, the European limits are also referred to as the
of the alternative fuels or additive-based emissions control
EOBD 共European OBD兲.
systems, or both. The commission may also assess the need
European Heavy-duty Diesel Truck and Bus to instill additional limits on particle levels and size. Table
Engine Emissions Standards 6.21 contains a summary of the emissions standards and
The emissions standards provided in this section are from their implementation dates 关401兴. Dates in the tables refer to
consolidated European Directive 05/55/EC and apply to all the new approvals; the dates for all type approvals are in
motor vehicles with a “technically permissible maximum most cases one year later 共EU type approvals are valid longer
laden mass” over 3500 kg 共⬃7700 lb兲, equipped with com- than one year兲.
pression ignition engines, or positive ignition natural gas or Engine test change in Euro III Standard was made in the
LPG engines. The chronology and highlights of the Euro year 2000—the old steady-state engine test cycle ECE R-49
emissions standards for this type of equipment are as fol- was replaced by two cycles: the European Stationary Cycle
lows. 共ESC兲 and the European Transient Cycle 共ETC兲. Smoke
1. Euro I standards were introduced in the year 1992, fol- opacity is measured on the European Load Response 共ELR兲
lowed by the introduction of the Euro II standards in test. For approval of new diesel vehicles with engines accord-
porized with the assistance of air flow. This is an attempt to Fuel volatility can affect engine performance in many
duplicate the evaporation in an engine where the fuel is va- ways. Ignition requires the air-fuel ratio between 6 : 1 共rich
porized under the influence of the intake air. In this method, mixture兲 and 20: 1 共lean mixture兲, with 14.5: 1 being optimal.
air and liquid fuel are supplied at a steady rate to an open During cold starting, the temperature is too low for proper
system that is maintained at a specific temperature. Percent fuel evaporation which necessitates the use of a rich mix-
fuel evaporated is calculated by taking into account the total ture. This, in a carbureted engine, is achieved by the use of a
fuel introduced and the amount of fuel that passes through choke to reduce the air supply. One would expect the higher
the apparatus. The results are shown as temperatures plot- fuel volatility to favor the cold starts, which is indeed the
ted against percent vaporized fuel. While in principle these case when the ambient temperature is ⬍20 °F 共−6.7 ° C兲. At
charts can be used to calculate the air-vapor ratios, the re- higher temperatures, however, the volatility has little or no
sults do not parallel those found in the actual engine because effect. The effect of volatility during the warm-up and the ac-
of the geometrical differences and the non-equilibrium con- celeration, on the other hand, is quite large. A correlation ex-
ditions.
ists between the warm-up performance and the temperature
at which 50 % evaporation occurs. Ambient temperature
TABLE 6.25—Boiling ranges versus also affects this performance. In general, the lower the ambi-
performance. ent temperature, the higher is the difficulty to achieve
Boiling Percent smooth acceleration. This may be partly related to the rate of
Range „°C… Evaporated Performance Parameter the choke opening. A slow opening choke is likely to provide
⬃30– 70 0–20 Ease of starting smooth running at low temperatures but can lead to higher
⬃71– 150 21–80 Driving in cold weather, HC emissions. A fast opening choke may lead to rough run-
especially during warm- ning at low ambient temperatures but will provide better
up, and fuel economy fuel economy and improved HC emissions.
⬃151– 215 81–100 Driveability after warm-up, High fuel volatility may lead to icing problems in cars
fouling and deposit-
equipped with carburetors. Icing occurs in and below the
forming tendency
venturi and is a consequence of evaporation of the low boil-
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298 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
ing components of the fuel. Icing could result in inefficient perature, compression ratio, spark advance, and the coolant
running and stalling of the engine, primarily at idle engine temperature. The higher the value of these parameters, the
speeds. Vapor lock is also related to high volatility. It occurs greater is the engine’s tendency to knock. Near stoichio-
when at high temperatures the pressure build-up due to fuel metric air-fuel mixtures also result in knock. While one can
vapors equals that of the pressure in the fuel system. This im- use reformulated gasoline to control knock, it is usually con-
pairs the fuel flow and the engine loses its ability to run. The trolled by the use of the antiknock additives, or the octane
ASTM 10 % distillation point and RVP correlate with a fuel’s boosters.
tendency to vapor lock. Other problems associated with fuel Engine knock is also a function of an engine’s compres-
volatility include evaporation losses, primarily from the fuel sion ratio, or CR. CR is defined as the ratio of the volume of
tank and the carburetor, and the engine lubricant dilution. gases in the cylinder at the beginning of the compression
Fuel loss from the tank relates to the ASTM distillation tem- stroke and the volume of gases at the end of the compression
perature around 71 ° C 共160 ° F兲 and from the carburetor re- stroke. Mathematically, it can be represented by the equa-
lates to the RVP, measured at ⬃38 ° C 共100 ° F兲. Fuel dilution tion below, where VD is the displaced volume, or the swept
of the lubricant relates to the high boiling fraction or the volume, that is, the volume swept by the piston in one stroke
back end, the components in the 90 % distillation tempera- and equals the volume of the cylinder; and VC is the volume
ture range, of the ASTM distillation curve. of the compressed gases when the ignition takes places, that
The newer gasoline vehicles come equipped with injec- is, the volume of the combustion chamber.
tors instead of carburetors. Fuel injection systems belong to
three general groups. If the injector is installed in the throttle VD + VC
body on top of the air intake manifold, it is called a throttle CR =
VC
body injection 共TBI兲 system. A port fuel injector system 共PFI兲
uses an injector at the intake port of each cylinder. It sprays The usual compression ratio ranges for the gasoline engines
fuel on the intake valves. A central port fuel injection system are from 8 : 1 to 11: 1, and for the diesel engines are from
uses a central distribution valve connected to spring-loaded 15: 1 to 25: 1.
poppet nozzles that spray fuel on the intake valves of each As mentioned above, the octane rating of the fuel deter-
cylinder. Fuel injectors are more precise in their fuel delivery mines the engine’s ability to run knock-free. Higher com-
than the carburetors; hence they provide better emissions pression ratios are desired because of the higher thermal ef-
control. ficiency, but the fuel octane rating is the limiting factor. If the
Antiknock quality is the primary determinant of the igni- octane rating of the fuel is not appropriate, high compres-
tion quality in a gasoline engine. Knock is an audible noise sion engines will tend to knock. For example, for a 6.5 CR
that results from spontaneous ignition 共detonation兲 of the engine, a fuel with an octane rating of 60 is fine; but for a 10
end gases at high loads and slow speeds. This type of ignition CR engine, a fuel with a minimum octane rating of 95 is nec-
is undesired because it not only results in the loss of power essary. After the onset of knock, thermal efficiency drops rap-
and the fuel economy but it can also lead to mechanical dam- idly. However, an increase in the compression ratio results in
age. Engine knock relates to a fuel’s octane rating. Fuel with higher cycle temperatures, which increase the formation of
a high octane rating has a lower tendency to knock than the NOx.
one with a low octane rating. The factors that influence an Deposits can form in the intake system as well as in the
engine’s tendency to knock include intake pressure and tem- combustion chamber. These are undesired because they not
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CHAPTER 6 䊏 EMISSIONS IN AN INTERNAL COMBUSTION ENGINE 299
only have an adverse effect on driveability, power, and fuel parameters are somewhat less effective in controlling emis-
consumption, but they also lead to an increase in undesir- sions.
able emissions due to inefficient combustion. Therefore, it is Deposits as a problem is universally recognized by most
important that the injectors, intake valves, and combustion OEMs, who recommend the use of fuels that contain deposit
chamber are deposit-free. Both the fuel composition and the control additives. Such additives improve emissions, in-
additives, such as octane boosters, can affect deposit forma- crease power, and lead to better fuel economy 关555兴. They do
tion. A variety of deposit control additives are commercially so by minimizing deposit formation and by cleaning the al-
available. These will be discussed in the section dealing with ready formed deposits. Because of the described benefits,
the fuel additives. many OEMs have their own standards for intake system
cleanliness.
Formulated Gasoline
Attempts have been made to optimize gasoline performance
Reformulated Gasolines „RFGs…
Acting on the above relationships, the EPA and the Califor-
with respect to the air quality. These include controlling its
nia Air Resources Board have established a number of regu-
chemical composition and using additives. A number of
lations that control the gasoline properties to reduce emis-
gasoline components negatively impact emissions. These in-
sions from the gasoline-fueled vehicles. Table 6.27 shows the
clude oxygenates, aromatics, olefins, sulfur, heavy metals,
chronology of the EPA-mandated changes to the gasoline
and the high boiling fractions. The decision to remove lead composition 关548兴. Reformulated gasoline 共RFG兲 is a gaso-
from the gasoline emphasized the need for alternative oc- line whose composition is optimized to meet the specified
tane boosters. Alcohols and ethers are among the most com- emissions requirements. RFG is either Simple Model or
monly used octane boosters. While these additives control Complex Model. Incidentally, the terms simple model and
CO, like other oxygenates in gasoline, they result in in- complex model to describe gasoline are used only in the
creased deposit formation that adversely affects the other United States.
emissions 关554兴. Hence, their amount in gasoline must also Simple Model gasoline, introduced in 1995, was de-
be controlled. Table 6.26 shows the effect of changes in the signed to decrease the volatile organic carbon 共VOC兲 in gaso-
gasoline composition on emissions. The data suggest that a line by 15 % and no NOx change relative to the 1990 baseline
gasoline which has low volatility, contains low levels of sul- fuel. Simple model gasoline contains minimum 2 weight
fur, and is treated with ethers and cleanliness additives re- percent oxygen and maximum 1 volume percent benzene
sults in the lowest amount of undesirable emissions. Other and has an RVP of 7.2 for Class B and 8.1 for Class C gasoline.
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300 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
Load or Power Level lead to substantial dilution of the combustion mixture, com-
In most engines, load has no effect on HC and CO emissions, bustion enhancement occurs, thereby lowering the HC emis-
if the speed and the mixture composition are unchanged and sions. This is because the tail end exhaust gases, primarily
the spark timing is adjusted to obtain the best torque. How- responsible for the back pressure, are rich in HC and burn
ever, some engines show an increase in HC with load, which with the fresh charge. If, however, the back pressure is high
primarily relates to a shorter residence time for HC in the ex- and charge dilution occurs, inefficient combustion will re-
haust for the oxidation chemistry to complete. sult, which will lead to higher HC emissions. The charge di-
lution, on the other hand, will decrease the amount of NOx.
Engine Speed
HC emissions decrease with increasing engine speed. This is Valve Overlap
attributed to improved combustion because of the increased Opening and closing of the intake and exhaust valves in an
turbulence. Higher speeds also cause higher turbulence in internal combustion engine is timed to obtain the maximum
the exhaust system, thereby leading to a more effective oxi- power and on a continuous basis. Conceptually, the intake
dation of HC to water and carbon dioxide. Carbon monoxide valve should open when the piston is top center and close
共CO兲, on the other hand, is not affected by speed. when the piston is bottom center. The exhaust valve, on the
The effect of engine speed on NOx depends upon the AF other hand, should open when the piston is bottom center
ratio of the combustion mixture. Increasing engine speeds and close when it is top center. For high-speed engines, the
lead to an increase in NOx, if rich mixtures are burned, and closing of the exhaust valve and opening of the intake valve is
to a decrease in NOx, if lean mixtures are burned. This is be- overlapped to obtain a higher output. Overlapping involves
cause higher speeds increase the rate of combustion due to two valves to be open simultaneously. This strategy takes the
increased turbulence and by reducing heat losses per cycle, advantage of fluid dynamics to scavenge the residual gases
both of which increase compression hence combustion tem- more effectively, which allows a greater amount of fresh
peratures and pressures. However, the difference in the rate charge to enter the cylinder, therefore resulting in increased
of NOx formation between rich and lean mixtures is due to output.
the different rates of combustion. Rich mixtures, which The degree of overlap varies among engines and its ef-
burn faster, result in higher temperatures and pressures than fect on emissions is analogous to that of the exhaust back
the lean mixtures that burn slower. The amount of NOx in pressure; that is, it primarily affects HC emissions. It lowers
the former case is therefore higher. them at very low overlap 共2°兲, beyond which they increase. It
has no effect on CO emissions, unless the combustion mix-
Ignition Timing ture becomes richer at which time it leads to increased emis-
In an internal combustion engine, work is performed by the
sions.
expanding combustion gases. Combustion of the fuel-air
mixture at maximum compression, i.e., when the piston is at Intake Manifold Pressure
top dead center, help attain maximum work. The problem is The function of the intake manifold is to uniformly distrib-
that combustion is not instantaneous and in an SI engine ute the air-fuel mixture to all cylinders. This is a difficult task,
takes 1 – 2 milliseconds to complete. This is overcome by ini- especially when the fuel in the combustion mixture is not in
tiating combustion before as well as after the piston is at top a fully vaporized state. Intake manifold pressure that facili-
dead center. Initiating ignition before piston is top dead cen- tates proper distribution to cylinders varies with the load
ter is called advanced ignition timing and after top dead cen- and is a function of the throttle opening. While intake mani-
ter is called delayed ignition timing. If ignition is initiated too fold pressure varies over a wide range, the values between 9
early, the pressure buildup precedes completion of combus- and 20 mm of mercury are the best for low HC and CO emis-
tion, which will lead to an increase in temperature and the sions. Both tend to be higher outside this range.
fuel-air mixture’s tendency to auto-ignite 共knock兲. Also, the The lower the manifold pressure, the lower is the
effect of high temperature on emissions will be the forma- amount of NOx formation. This is because the lower pres-
tion of a greater amount of NOx at all speeds and loads. The sures decrease the temperature and increase the amount of
delayed ignition timing, on the other hand, will lower the re- the residual gases, thereby leading to a greater ignition delay
lease of maximum pressure that in turn will lower the engine and reducing the rate of combustion. Both decrease the
efficiency. It is also likely to form the higher amounts of the amount of the NOx formation.
partial combustion products, such as HC and CO. However,
this strategy transfers part of the energy into the exhaust sys- Combustion Chamber Deposit 共CCD兲 Buildup
tem where it facilitates reactions that lower HC and NOx. CCDs are irregular in shape and porous in texture. Their
The overall effect is the reduction of emissions, but at the ex- shape increases a combustion chamber’s surface area,
pense of fuel economy. Ordinarily, the effect of the delayed thereby leading to more quenching, and their texture makes
timing on CO alone is not as striking and little, if any, im- them trap high boiling fuel fractions that are released during
provement is observed. Too much retard can lead to higher the next cycle. Both these factors contribute towards an in-
CO emissions by not allowing sufficient time for CO to oxi- crease in HC emissions. Again, CCDs have little or no effect
dize to CO2. on CO emissions.
ment, volumetric efficiency, and the need for effective lubri- bustion, when the piston is well down the cylinder, at which
cation. time the s/v ratio is much lower than when the piston is top
center. Similarly, the air-fuel ratio change and any design
Surface-to-volume Ratio 共s/v兲 change that will slow the combustion process will have an
HC emissions primarily result from quenching; hence the
analogous effect. The downside of the spark retardation is a
combustion chamber designs with lower surface area
decrease in power.
should improve emissions. Surface-to-volume ratio, or s/v, is
HC emissions comprise hydrocarbons that survive oxi-
one of the measures that can be used to assess the effective-
dation, which occurs during combustion and in the exhaust
ness of the combustion chamber design on emissions. En-
system. Henein and Patterson 关547兴 summarize the effect of
gines with low s/v ratios are better on HC emissions than
various engine parameters on HC during their passage from
those with high s/v ratios. Carbon monoxide 共CO兲 emissions,
the combustion chamber to the exhaust.
on the other hand, are insensitive to these ratios.
Controlled Auto-ignition Combustion
Combustion Chamber Design This technology, at present at the conceptual stage, is analo-
In general, the lower the surface area of a combustion cham-
gous to homogeneous charge compression ignition 共HCCI兲
ber, the lower are the HC emissions. For the same clearance
technology in a diesel engine. The perceived benefits of this
volume, the double hemisphere design was found to be supe-
technology are fuel economy and exhaust emissions control.
rior to others.
The technology involves compressing an air-fuel mixture to a
Stroke-to-bore Ratio 共s/b兲 high enough temperature to initiate auto-ignition. This type
This parameter is related to surface-to-volume ratio 共s/v ra- of auto-ignition differs from that produced from knocking
tio兲. Engines with long strokes and small bores have low s/v combustion in that it is controlled and occurs at a slower
ratio, hence they result in lower HC emissions. Modern en- rate, except at high loads where its control is difficult.
gines, however, do not favor this design because such en-
gines tend to be large, costly, low in fuel efficiency, and have
Effect of Coolant Temperature
The coolant’s influence on the amount of HC, CO, and NOx
low peak power.
arises from its ability to affect combustion temperature by
Displacement per Cylinder way of the combustion mixture. High coolant temperatures
Everything else being constant 共compression ratio and s/b lead to lower HC and CO emissions but higher NOx. Low
ratio兲, an increase in the displacement of a cylinder will coolant temperatures, on the other hand, will cool the cylin-
lower its s/v ratio and hence HC emissions. The reason for der walls and the combustion mixture more effectively than
this is described earlier while discussing surface-to-volume the high coolant temperatures; hence they will result in
ratio. lower NOx.
tios, the engine performance is less than desired. Since NOx quality, effective fuel delivery to minimize the undesirable
occurs at very high temperatures, lowering the combustion emissions, fuel’s evaporative control, effective exhaust gas
temperature should help minimize its formation. Exhaust recirculation, and proper functioning of the emissions con-
gas recirculation 共EGR兲 and introducing water vapor or an trol systems. The engine components that are monitored in-
inert gas, such as CO2, into the combustion mixture help clude the catalytic converter, oxygen sensor, spark plugs,
achieve this. The drop in temperature is due to the dilution of EGR system, coolant system, and evaporative emissions
the combustion mixture which reduces the flame speed and control system. The OBD system contains an electronic con-
the ensuing temperatures. The principle of EGR is fairly trol module 共ECM兲, which has the ability to correct the
simple. It involves introducing part of the exhaust gas into above-listed problems, if they surface, by electronic optimi-
the intake manifold 共recirculation兲, where it gets mixed with zation of the engine’s operating parameters. Such param-
air and the fuel. When the mixture burns, the combustion eters comprise fuel and spark requirements, metering of the
temperature is not as high as in the absence of the EGR. Be- fuel, consistency of the intake manifold pressure and tem-
cause the NOx formation is an exponential function of the perature with the vehicle’s operation, ignition control 共elec-
combustion temperature, a small decrease in this tempera- tronic spark timing兲 to minimize the engine knock, EGR ad-
ture will greatly reduce its amount. A 16 % drop in peak tem- justment, control of the idle speed, and optimization of the
perature is estimated to drop the amount of NOx by as much in-cylinder charge, such as heating and cooling of the intake
as 85 % 关558兴. EGR also decreases the amount of HC and CO air and adjustment of the air-fuel ratio.
emissions, if present in the exhaust, via re-entry into the
combustion chamber and facilitating their oxidation to H2O Emerging New Engine Technologies
and CO2. The impetus behind the development of these technologies
While the NOx-lowering potential of the EGR can not be is to improve fuel economy or lower emissions, or both.
refuted, it has a negative effect on power and fuel economy. These technologies come under two general classes:
In general, the higher the amount of the EGR, the higher is hydrocarbon-fueled technologies and petroleum-free tech-
the specific fuel consumption and the lower is the brake nologies. Direct fuel injection 共DFI兲 vehicles and hybrid
power. In addition, after 15 % EGR, NOx reduction tends to gasoline-electric vehicles belong to the former class and the
level off. However, this is not a problem because at 15 % EGR fuel cell technology and the electric vehicles belong to the
the amount of NOx is lowered by 88 % while the power loss latter class. Vehicles equipped with DFI technology and hy-
and the fuel consumption increase is only 16 % and 14 %, brid cars are already being marketed.
respectively. The negative effect of the EGR on power and the Direct fuel injection technology was already discussed.
fuel consumption can be offset by ignition advance and ma- Hybrid vehicles are either already available or are being de-
nipulation of the air-fuel ratio. However, these parameters veloped for introduction into the marketplace. A hybrid
have an adverse impact on NOx and after all the adjustments power train combines a gasoline 共or diesel兲 internal combus-
the realized benefit is only 60 % reduction, which is quite re- tion engine with an electric motor, a generator, and a storage
spectable 关558兴. battery. There are two types of hybrid drive systems, series
and parallel. In the series configuration, a gasoline engine
Effect of Turbo-Charging drives a generator that provides the electrical energy for the
Turbo-charging has no significant effect on HC and CO emis- storage batteries and the electric motor, but only the electric
sions. It is the process in which a compressor, driven by an motor drives the vehicle. In the parallel configuration, the
exhaust gas turbine, forces compressed air into the intake of gasoline engine drives a generator and the vehicle under low-
an engine. This increases the flow of the fuel and hence re- load conditions, and the electric motor is used to provide the
sults in a gain in power output. Turbo-charging, therefore, additional power for driving the vehicle under higher-load
makes it possible to obtain a higher output from smaller and conditions. Both types of systems recover the energy that is
lighter compact engines. In addition, because turbo- normally lost during decelerations and braking and use it to
charging is on demand, engines fitted with turbochargers charge the storage batteries. The hybrids being offered today
usually have better overall fuel economy. Turbo-charging re- and those under development are typically parallel configu-
sults in higher pressures and temperatures that can lead to ration hybrids.
self-ignition or knock in the SI engines and a corresponding Gasoline hybrids are likely to be replaced with the fuel
increase in NOx. Inter-cooling is an option where the intake cell electric vehicles in the future, when the fuel cell technol-
air is cooled in an effort to lower the combustion tempera- ogy becomes commercially viable. This is because this tech-
tures. However, this option is rarely used. Instead, knock is nology is expected to have extremely high efficiency in gener-
usually controlled by using higher octane fuels, rich mix- ating electrical energy from the fuel and generate the lowest
tures, or by retarding ignition timing, or both. Unfortu- amount of emissions. Fuel cell technology generates power
nately, all of these strategies partially offset the mechanical in the form of electricity and heat by converting hydrogen,
efficiency gained through turbo-charging. obtained from the fuel by the use of on-board reformers, and
oxygen into water. It essentially converts chemical energy of
On-Board Diagnostics 共OBD兲 the fuel into electricity. There are two fuel options: hydrocar-
Most modern vehicles come equipped with on-board diag- bon fuel and methanol. At present, the hydrocarbon fuel is
nostic systems 共OBDs兲. These are designed to constantly preferred because of the existence of the infrastructure for
monitor the performance of a variety of components and its delivery, production, cost, etc. In a fuel is cell, hydrogen is
systems in a vehicle, including those dealing with the emis- the reactant on the anode side, oxygen is the reactant on the
sions control. The emissions control performance relates cathode side, and water is their final reaction product. Typi-
primarily to the catalyst system efficiency, improved ignition cally, the reactants flow in and the reaction product共s兲 flow
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304 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
out. In principle, virtually continuous long-term operation is the hydrogen is catalytically converted into hydrogen ions
feasible as long as these flows are maintained. 共protons兲 and electrons. This oxidation half-cell reaction is
Chemically, the fuel cell is a hydrogen cell, which like represented by the equation below.
any other cell consists of an anode and a cathode that are
H2 → 2H+ + 2e− Eo = 0 V
separated by a polymer electrolyte membrane, see Fig. 6.19
关559兴. A stream of hydrogen is delivered to the anode side of The newly formed protons permeate through the polymer
the membrane-electrode assembly 共MEA兲. At the anode side, electrolyte membrane to the cathode side. However, the elec-
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CHAPTER 6 䊏 EMISSIONS IN AN INTERNAL COMBUSTION ENGINE 305
trons travel along an external load circuit to the cathode side and also when the injected fuel hits the compressed air.
of the MEA, thus creating the electric current output of the There are pockets of fuel-rich zones and air-rich zones,
fuel cell. In the meantime, a stream of oxygen is delivered to which makes the combustion nonuniform. Efficient com-
the cathode side of the MEA. At the cathode side, the oxygen bustion occurs only in zones which have the fuel-air ratio
molecules react with the protons permeating through the within a certain range. The zones where this ratio is too low
polymer electrolyte membrane and the electrons arriving or too high, the combustion either does not occur or is ineffi-
through the external circuit to form the water molecules. cient and the result is higher CO, HC, and PM emissions. It is
This reduction half-cell reaction is represented by the fol- important to note that NOx 共NO and NO2兲, HC, CO, and PM
lowing equation. result under different conditions and via different mecha-
nisms.
4H+ + 4e− + O2 → 2H2O Eo = 1.229 V
NOx forms in the stoichiometric and slightly lean fuel-
Besides a fuel cell stack that converts hydrogen into air mixture regions, where the ambient temperature and the
electrical energy, a fuel cell powertrain consists of an electri- concentration of oxygen are high. HC results in regions
cal motor/generator drive unit, storage battery, and hydro- where the temperatures are low or oxygen is insufficient to
gen fuel storage—with high-pressure liquid, or hydride op- initiate and propagate combustion. The upper cylinder walls
tions. Alternatively, an on-board fuel reformer fed by the and regions around the top of the piston edge are examples
liquid hydrocarbon fuels might be used to produce the hy- of the low temperature regions. As mentioned earlier, in die-
drogen. Because of the many hurdles that need to be over- sel engines HC and CO emissions are not a major problem
come, the timing of use of the fuel cell technology in com- since they tend to operate on lean fuel-air ratio. Particulate
mercial vehicles is hard to forecast. matter 共PM兲 results from fuel droplets that do not vaporize,
Table 6.29 summarizes the effect of various design and hence do not burn properly. PM results mainly from oxida-
operating variables on emissions. tion of the fuel during preignition stage and not combustion.
Diesel Engine Emissions Control Oxidation essentially strips fuel hydrocarbons, partially or
fully, of hydrogen leaving behind soot, which is the primary
Control of the exhaust emissions from a diesel engine is component of the diesel exhaust. The formation of soot com-
a challenge. Two major components of the diesel engine ex- monly occurs when the last portion of the fuel enters the cyl-
haust are NOx and particulates 共PM兲, both of which are a se- inder where the combustion has already ensued, or the en-
rious health hazard. Of the two, NOx is invisible and PM can gine is being operated at high load and or high speed. In the
be visible 共smoke兲 or invisible, depending upon its particle former situation, the fuel gets oxidized prior to hitting the
size. Contrary to the exhaust of the gasoline engines, which combustion zone; and in the latter situation, the fuel is being
contains large amounts of unburned or partially burned hy- pumped into the cylinder at a faster rate than the combus-
drocarbons 共HC兲 and carbon monoxide 共CO兲, their amount tion rate. Additional contribution to soot comes from the lu-
in the diesel exhaust is minimal. The formation of NOx and bricant that travels past the piston rings, either by design or
PM is related to the mechanism of the diesel combustion. In inadvertently, and burns partially.
a diesel engine, the fuel at high pressure is injected into the A number of strategies have been used to control emis-
cylinder that contains compressed air. Because of the design, sions from the diesel engines. Those that deal with manipu-
the fuel-air ratio in different parts of the cylinder is different lating the operational parameters are described below.
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306 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
• Increasing injection pressures—The result is better at- Because of the stringency of the modern emissions con-
omization of the fuel, hence improved combustion. trol regulations, strategies discussed so far are not sufficient.
• Directional injection—Control of the position and the In order to meet the present and future government-
angle of the injector in the cylinder head and better mandated requirements, additional steps are necessary.
nozzle design to deliver fuel in the optimal combustion These involve installation of devices that either remove ex-
zone. haust pollutants or treat them to make them innocuous.
• Fuel charge control—Controlling the rate of fuel entry Those worth mentioning include particulate filters and cata-
during injection to increase the combustion efficiency. lytic converters. Diesel particulate filters 共DPFs兲 are devices
In some cases, a small amount of fuel is charged first 共pi- installed on the diesel engine vehicles that collect particulate
lot injection兲, which initiates the combustion. This is fol- matter from the exhaust without obstructing the flow of the
lowed by the main injection. exhaust gases or damaging the vehicle, or both. Figure 6.20
• Generating turbulence—Cylinder head, air intake valve, shows a conceptual diagram of the functioning of a DPF
and piston head are designed to improve fuel-air mixing. 关561兴. If desired, a number of technologies can be installed in
• Charge cooling 共inter-cooling兲—Most diesel engines em- conjunction with a DPF to reduce the amount of harmful ex-
ploy supercharging or turbo-charging to increase power. haust gases expelled into the atmosphere.
The strategy is to introduce more air 共oxygen兲 into the Several types of diesel particulate filters, also known as
engine, which improves the combustion efficiency, trap oxidizers, are either commercially available or are un-
hence power. These engines have a mechanically-driven der development. Wall-flow ceramic cordierite, woven fiber
共supercharging兲 or an exhaust-driven 共turbo-charging兲 cartridges, and temperature resistant paper 共disposable兲 are
pump that compresses or pressurizes the intake air. the three types of filters that are currently in commercial use.
Since compression increases the intake air temperature, These filters have collection efficiencies ranging from 50 to
the NOx formation tends to increase as well. This prob- 90 %. In addition, noble-metal catalyzed, fuel additive cata-
lem can be overcome by cooling the intake air by passing lyzed, and externally regenerated filter systems are also
it through a heat exchanger, prior to allowing it to enter available, with filter efficiencies well over 90 %. The PM re-
the cylinder. A key advantage of the turbochargers is that moval process involves the passage of the exhaust gases
they increase the engine power with only a slight in- through a porous cell, which removes the particulate matter.
crease in weight. After some period, such filters reach their limit and need to
• Lower oil consumption—All engines have the tendency be replaced, if disposable, or regenerated. The regeneration
to burn the lubricant that travels past piston rings into is usually carried out by burning, i.e., the oxidation of the
the combustion chamber. This contributes to exhaust PM, which is primarily carbon. Some designs have built-in
emissions. New diesel engines use piston designs with burners or electrical resistance heaters that raise the trap’s
low crevice volume. Such pistons minimize lubricant internal temperature to burn off the particulates as soon as
travel into the combustion chamber, thereby controlling they reach the device. Figure 6.21 shows the schematic of a
the lubricant-related contribution to emissions. regular filter and a continuously regenerating filter 关550兴. In
• Exhaust gas recirculation 共EGR兲—As mentioned earlier, addition to removing more than 90 % of the PM, DPFs also
NOx formation increases at high temperatures. The tem- destroy the soluble organic fraction 共SOF兲 of the PM, the car-
peratures can be decreased by diluting the reaction mix- bon particles, CO, HC, and the toxic emissions, such as alde-
ture with an inert gas, which effectively decreases the hydes, from the diesel engines. EPA describes changes in en-
temperature of the combustion mixture. Exhaust gas is gine performance that can occur when retrofitting this
an ideal option since it is essentially inert and the engine program 关560兴. These include the following:
does not need an additional source of such a gas. The 1. Possible back pressure increase above the manufacturer
EGR process directs a portion of the exhaust gas into the specifications, which can lead to a decrease in power.
air intake manifold. It is important to note that while 2. A slight increase in fuel consumption.
this strategy reduces the NOx formation, a small loss of 3. Noise attenuation and muffler warranty—in almost all
power does result. cases, retrofitting with a DPF will require replacement
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CHAPTER 6 䊏 EMISSIONS IN AN INTERNAL COMBUSTION ENGINE 307
Diesel Combustion
Hydrocarbons 共HC兲 and CO in the exhaust of a diesel engine
are lower than those present in the exhaust of a gasoline en-
gine, except at low operating temperatures and high loads.
This is because diesel engines burn lean combustion mix-
Fig. 6.21—Diagram of catalyzed diesel particulate filter 共CDPF兲 tures, i.e., they operate on excess air 共 ⬎ 1兲. The main con-
and continuously regenerating diesel particulate filter 共CR-DPF兲 cern is NOx, smoke, and aldehydes. Even the NOx levels for
关550兴. the CI engines are lower than those for the SI engines. Major
problem in the diesel engines is smoke, especially gray or
black smoke that contains soot particles, or PM.
of the existing muffler. In this case, the noise attenuation Emissions in a diesel engine largely relate to the use of a
for the replacement muffler will be the same as with the heterogeneous combustion mixture and the diesel fuel’s
stock muffler. higher boiling range 共150 to 380° C兲. As a result, diesel en-
Catalytic converters remove pollutants by altering their gines are always run on combustion mixtures with excess air
structure, primarily through oxidation. Oxidation catalysts 共 ⬎ 1兲. Otherwise, combustion will be incomplete and large
that are used to treat diesel exhaust are similar to those used amounts of HC, CO, and particulates, such as soot, will re-
for the gasoline engines. They oxidize unburned hydrocar- sult. Spraying of the diesel fuel into the swirling air intro-
bons 共HC兲 and carbon monoxide 共CO兲 to carbon dioxide and duces heterogeneity and results in zones of varying combus-
water. However, diesel catalytic converters suffer from a tibility. Henein and Patterson suggest a combustion
number of problems. These include deactivation due to fuel efficiency model to explain the formation of undesirable
sulfur; particulate build up on the catalyst, thereby impair- emissions in diesel engines 关547兴. They classify combustion
ing the flow of gases; and lower catalyst efficiency on ac- zones of high, medium, and low flammability. Moving away
count of the diesel engine exhaust being cooler than the from the injector nozzle, there is a spray zone with a spray
gasoline engine exhaust. Since catalytic converters prima- core and a spray tail 共and after injection兲, and near and far
rily address HC and CO emissions, the quantity of which in edges of the nonspray zone. Figure 6.4 shows these zones in
diesel engine exhaust is low, catalytic after treatment is not the fuel spray from a diesel injector 关23兴.
generally needed. As mentioned earlier, the removal of NOx The spray core has fuel droplets of good size and there is
from the diesel engines is the real challenge. While lowering enough oxygen to have complete combustion, which is true
NOx levels by the use of the EGR is possible, its complete re- under part load. This results in high combustion tempera-
moval from the exhaust is not highly likely. The reason is that tures that facilitate NOx formation. However, if the tempera-
it will involve reduction conditions, which in diesel engine ture and the oxygen content of the fuel-air mixture are not
exhaust do not exist. As a matter of fact, the environment in high enough to cause complete oxidation, CO and aldehydes
diesel exhaust is oxidizing because of the presence of an ex- will result. This situation exists between the lean flame re-
cess amount of air 共oxygen兲 in the air-fuel mixture. However, gion and the lean flame-out region at the onset of combus-
this problem can be overcome by the use of selective cata- tion and at low loads. Incomplete oxidation is more likely
lytic reduction 共SCR兲 technology. In this approach, a nitro- under high loads when the core becomes more fuel rich and
gen compound with N-H bonds, such as ammonia or urea, is the combustion becomes relatively inefficient. This leads to
injected into the exhaust gas in an amount proportional to the increased formation of CO, aldehydes, and carbon. The
the NOx present. Nitrogen oxides 共NOx兲 get reduced to nitro- spray tail is the last part of the fuel that is injected and be-
gen and water, and ammonia and urea gets oxidized to nitro- cause of the low pressure it has poor penetration and mixing
gen, water, and carbon dioxide, as is shown in the reaction with air. The result is the formation of large droplets with in-
scheme in Fig. 6.22. Mercedes-Benz is one company that is ability to burn effectively. Therefore, they act as a source of
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308 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
HC, CO, carbon, and oxygenates. After-injection occurs un- poor penetration arising from the low fuel injector pres-
der medium and high load conditions when a small amount sures. If the deposited fuel can evaporate, because of the
of fuel bleeds after the main injection and has similar conse- high velocity of the surrounding gas and high wall tempera-
quences. The situation changes as the combustion process tures, and there is ample oxygen for the vapors to burn, there
proceeds. Carbon monoxide 共CO兲 formation under high is little problem. However, if the volatility of the deposited
loads is not a problem since such loads require richer fuel-air hydrocarbon components is low and the wall temperature
mixtures. This translates into high reaction temperatures and the velocity of the surrounding gas are not suitable for
that facilitate oxidation of CO to CO2. However, too rich a efficient combustion, HC, partial oxidation products, and
combustion mixture can increase CO by making the com- carbon particles result.
bustion less efficient because of the inadequate oxygen con-
tent. Diesel Fuel Properties
The near edge of the nonspray zone, called the lean Fuel-related parameters that impact diesel vehicle emissions
flame region, has a reasonable amount of fuel vapor to un- include the fuel’s cetane number/Index, density, volatility,
dergo combustion. However, there are only pockets of fuel- distillation range, viscosity, the amount of aromatics and
air mixture that are appropriate for combustion. Once the sulfur, and the additive usage. An inadequate cetane number
ignition occurs, the flame spreads throughout the region, leads to less efficient combustion, hence higher HC and CO
generating NOx. The far edge of the nonspray zone, called emissions.
the lean flame-out region, is fuel lean and therefore can not
support efficient combustion and is primarily responsible Cetane Number
for the HC emissions. Wall quenching also leads to poor Cetane number measures the ignition quality of a diesel fuel.
combustion and is another source of HC, partial oxidation The number is based upon a scale of zero to 100; where
products, and carbon. ␣-methylnaphthalene has a cetane number of 0 and cetane
In addition to the above discussed spray-related factors, 共hexadecane兲 has a cetane number of 100. Low cetane num-
fuel deposited on the cylinder walls is another factor that bers lead to misfiring, engine deposits, and rough running.
plays a role in determining the quality of the exhaust emis- Increasing the cetane number improves fuel combustion
sions. Fuel deposition occurs because of the shorter spray and hence reduces NOx and PM emissions. The cetane num-
path, as in the case of small diesel engines, or because of ber effects are not linear, unlike the fuel sulfur effects, and
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CHAPTER 6 䊏 EMISSIONS IN AN INTERNAL COMBUSTION ENGINE 309
Volatility
A typical diesel fuel volatility curve is depicted in Fig. 6.25
关551兴. Various boiling fractions affect different performance
parameters, except the cetane quality, which is a function of
the whole boiling range. Front-end volatility affects the flash
Fig. 6.24—Predicted effect of cetane difference on NOx for heavy- point; mid-range volatility affects the ease of starting and
duty highway engines 关563兴. white smoking tendency; and back-end volatility affects the
yield/price of the fuel and its cold flow properties. T95 is the
temperature at which 95 % of a particular diesel fuel distills
cetane number improvers do most good if the starting fuel in a standardized distillation test 共ASTM D86兲. Reducing T95
has a low cetane number, see Fig. 6.24 关563兴. In the figure, decreases NOx emissions slightly, but increases the hydro-
fuel A, with low natural cetane number, has the smallest re- carbon and CO emissions, and without affecting PM10.
sponse to cetane-improving additives and fuel C, with a high
natural cetane number, has the lowest response. The EPA Diesel Sulfur
has established a minimum cetane index of 40 and a maxi- The sulfur content of the diesel fuel affects PM emissions be-
mum aromatics content of 35 %. The California Clean Air cause some of the sulfur in the fuel is converted into sulfate
Act of 1993 requires the use of a reformulated diesel fuel that particles in the exhaust. There is a direct correlation between
contains no more than 0.05 % sulfur and 10 % aromatics, or the fuel sulfur and the PM emissions; hence diesel sulfur
TABLE 6.32—Diesel fuel properties versus TABLE 6.33—Low-sulfur diesel versus Biodie-
emissions. sel „B100…—Properties comparison †564‡.
Light-duty Engines Heavy-duty Engines Low-sulfur
Parameter Biodiesel Diesel ASTM D975
Emission Type HC CO NOX PM HC CO NOX PM Property „typical… „typical… Specification
Cetane No. Increase ⫹ ⫹ ⫽ ⫺ ⫹ ⫹ ⫽ ⫽ Flash Point, °C 100 60 52 min
Density Reduction ⫹ ⫹ ⫺ ⫹ ⫺ ⫹ ⫹ ⫹ Viscosity, 40 ° C, cSt 4.7 3.2 1.9–4.1
Polyaromatic Reduction ⫺ ⫺ ⫹ ⫹ ⫹ ⫽ ⫹ ⫹ Sulfur, % mass ⬍0.01 0.03 0.05 max
T95 Reduction ⫽ ⫽ ⫺ ⫹ ⫺ ⫺ ⫹ ⫽ Cetane Number 48–52 45 40 min
Note: +Positive benefit; −Negative benefit; =No benefit. Heating Value net, Btu/gal 128,000 130,000 ¯
Relative Density, 15 ° C 0.88 0.83-0.86 ¯
high sulfur diesel fuel. CARB has also limited the aromatics
content for on-road diesel to 10 % by volume, maximum. Al-
CO, and PM emissions than the petroleum-derived diesel.
ternative formulations with higher aromatics contents are
Pure biodiesel has good lubricity properties and is devoid of
allowed, if they achieve the same or lower emissions in a
sulfur or aromatics. However, its higher pour point limits its
standardized engine test than the reference fuel with 10 %
use in cold climates. Bio-diesel is highly biodegradable, and
aromatics. In these formulations, five properties are exam-
hence is prone to attack by microorganisms, which can be-
ined, which are the sulfur content, nitrogen content, aromat-
come an issue during storage. Since the structure of its com-
ics content, polycyclic aromatics content, and the cetane
ponents contains unsaturation, its oxidation stability is
number. If a candidate formulation passes the emissions test
lower than that of the petroleum diesel as well. Its major dis-
and receives the CARB approval, commercial formulations
advantage is its higher cost; hence its widespread use in the
based on these credentials must not exceed the sulfur, nitro-
United States in the very near future is not likely. However,
gen, aromatics, and polycyclic aromatics contents of the ap-
its use is gaining popularity in Europe because of its poten-
proved formulation.
tial environmental benefits.
Biodiesel
Recently, biodiesel has been getting a lot of publicity as a PuriNOx™ Technology
possible alternative to the petroleum-derived diesel. The Recently, another pollution-reducing diesel fuel technology
main incentive for this interest is that the biodiesel can be 共PuriNOx™兲 was commercialized by Lubrizol. The product
obtained from sources that can be replenished and the envi- is a well-blended, safe-to-use, “water-in-diesel” fuel emul-
ronmental compatibility. In the United States, soybean oil is sion, which is made from normal diesel fuel, purified water,
the largest source of biodiesel, although oils from other bio- and proprietary PuriNOx™ additive chemistry. The Puri-
logical sources may also be used. Biodiesel is a mixture of NOx™ fuel reduces NOx emissions up to 30 % and particu-
fatty methyl carboxylates, which can be obtained from cata- late matter 共PM兲 emissions up to 65 %, compared to the con-
lyzed trans-esterification reaction of triglycerides 共oils and ventional No. 2 diesel fuel. The beneficial effect of water on
fats兲 with methanol. The chemistry involved is depicted in diesel combustion has been known for many years, except its
Fig. 6.26. This methyl ester mixture has properties that are method of delivery into the combustion chamber was a chal-
comparable to those of the conventional diesel fuel hence it lenge until recently.
is considered a good substitute. See Table 6.33 for compari-
son of the typical properties 关564兴. Diesel Engine Design and Operating Variables
While diesel engines can run on 100 % biodiesel, Biodie- Design and operating variables that impact diesel emissions
sel B100, most of the testing in the United States was carried include the following:
out on 20: 80 blend with low sulfur diesel, Biodiesel B20. • Fuel-air Ratio/Air-fuel Ratio
Limited testing has shown this fuel to produce lower HC, • Cetane Number
ing explored to overcome the waiting period for the con- facilitate its reductive reaction to nitrogen and water. The
verter to become operational. Close coupled catalytic con- process involves three steps: adsorption of pollutants on the
verters are used in most modern ultra-low emissions catalyst surface at low temperatures, oxidation and reduc-
vehicles 共ULEV兲. Close coupled means closer to the engine, tion of pollutants to innocuous products, and desorption of
thus faster heating. Electrically heated catalysts are not in these products at high temperatures.
commercial use yet. The exhaust gas contains oxygen in varying amounts. Its
Catalytic converters are of three types, oxidation cata- amount can be correlated with the quantity of air in the air-
lytic converters, reduction catalytic converters, and dual- fuel mixture. A three-way or selective catalytic converterwith a
bed catalytic converters. Oxidation catalytic converters oxi- lambda closed-loop control system is the most advanced of
dize CO to CO2 and HC 共VOC兲 to CO2 and water. Lean the converters. The system helps in precisely controlling the
mixtures have enough air to complete the oxidation but rich composition of the fuel-air mixture to near stoichiometric. A
mixtures require excess air through a secondary air injec- lambda sensor is an electronic device that measures the
tion. In air-injected exhaust systems, the air is injected into amount of oxygen in the exhaust. It generates an electronic
each exhaust port, downstream from the exhaust valve/s, by signal based on the oxygen level in the exhaust and sends it to
the use of an air pump 关558兴. High exhaust gas temperatures the engine’s electronic unit. The unit makes adjustments to
catalyze oxidation of HC and CO to innocuous water and car- the air-fuel mixture composition if is different from 1. The
bon dioxide. The effectiveness of this strategy depends upon lambda closed-loop control system interconnects the
a number of factors including the composition of the air-fuel lambda sensor, the electronic control unit, the engine, and
mixture, the amount of the air injected, and the injection the fuel metering system 关558兴. It signals adjustments to the
pressure. While the amount of both HC and CO decreases fuel metering system. Such sensors can also be used to deter-
with air injection, the effect is more pronounced in the case mine the catalyst activity. This is accomplished by installing
of rich fuel-air mixtures, with the magnitude of HC reduc- one sensor before and one after the catalyst system. These
tion being larger than that of the CO. An increase in the sensors have a threshold operating temperature of ⬎280 ° C
amount of air injected and the injection pressure also reduce and a maximum temperature of ⬃850 ° C, beyond which
the amount of these pollutants. However, the HC decrease their electrodes get damaged. Hence, they, like catalytic con-
with injected air levels off at about 20 % of the engine air verters, are installed close enough to the engine to benefit
flow. Reduction catalytic converters, used to lower NOx, oper- from the combustion heat to attain activation temperatures
ate with little or no air. The chemistry in this case involves quickly but far enough to minimize damage due to sintering
the use of the unburned hydrocarbons in the engine exhaust in case of extensive heat. This problem can be overcome by
as the chemical reducing agent, which translates into a installing the unit farther away from the engine but using a
higher fuel consumption 共 = 0.9兲. Because the oxidation heater for the sensor to achieve its operating temperature.
type converters lower HC and CO and the reduction type The converter catalysts get deactivated by lead and phos-
converters lower NOx, in a dual-bed converter the two types phorus that block the active sites, a situation referred to as
are combined in a series. poisoning.
Three-way Catalytic Converter Exhaust
Treatment Emissions Control via Engine Design Changes
The purpose of the treatment is to achieve oxidation and re- Minimizing harmful emissions by manipulating fuel com-
duction within one converter, i.e., oxidize CO to CO2, HC to position and engine operating parameters obviously has its
H2O and CO2, and reduce NOx to N2. Ordinarily, these reac- limits, so has the use of deposit control/cleanliness additives
tions are sluggish. However, their rates can be increased by to improve combustion efficiency via a uniform flow. The
the use of the noble metals catalysts, such as platinum and OEMs realize the challenges of meeting the future emissions
rhodium. Platinum is a good oxidation catalyst and rhodium standards by the use of these strategies and are actively in-
is a good reduction catalyst. Their reactivity is the highest volved in designing new engines that have better combustion
when the fuel-air mixture is stoichiometric or rich. Since the efficiency, improved fuel economy, and lower exhaust emis-
two metals in combination remove all three pollutants, a sions. They plan to achieve these goals through engine modi-
catalyst system containing both is called a three-way catalyst fications, electronics/fuel management, and exhaust treat-
system. Because the reactions occur in a gas phase, an adsor- ment 关558兴. New technologies will be discussed for the
bent surface, commonly provided by the inert alumina gasoline engines first, followed by those for the diesel en-
共Al2O3兲, is necessary. Catalyst metals are imbedded in the gines. It is important to note that the emissions control chal-
surface as very fine particles to provide a large surface area. lenges are resulting in a loss of distinction between tradi-
A minimum exhaust temperature of 250– 300 ° C is required tional gasoline and diesel engine technologies and they are
for the reactions to occur. Typical exhaust temperatures are merging together. The key requirement of the technologies is
300– 400 ° C at idle and up to 900 ° C at full load. The normal that it must work. In other words, every known technique is
operating range of the catalytic converters is 400– 800 ° C. being considered to improve emissions from the internal
Below this range, they are not very effective and above this combustion engines.
range, they lose their activity due to sintering.
For converters to be effective over an extended period, Gasoline Engines
the engine must operate at very close to stoichiometric 共AF For gasoline engines, the prevention technologies include
= 14.7; = 1兲 or at slightly richer 共AF= 14.48– 14.62兲 air-fuel more efficient delivery systems, on-board diagnostics, and
ratios. This is because at high loads when the exhaust con- new combustion chamber designs. Correction technologies
tains high amounts of NOx, unburned hydrocarbons 共HC兲 include a greater use of exhaust gas circulation 共EGR兲 and
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CHAPTER 6 䊏 EMISSIONS IN AN INTERNAL COMBUSTION ENGINE 315
exhaust gas after-treatment, both of which were briefly 1.1 is optimal for fuel economy, and at heavy loads, ⬍ 0.9 is
touched on during the preceding discussion. needed to maintain smooth engine operation. Hence, the de-
Efficient Fuel Delivery livery of the combustion mixture with the right amount of
Gasoline engines are designed to burn premixed air-fuel air is imperative to minimizing emissions while maintaining
mixtures that are prepared either through carburetion or by proper engine operation and fuel economy. In modern cars,
fuel injection. Modern automobiles favor fuel injection be- on-board diagnostics help achieve this. They measure a
cause it results in more efficient combustion, hence maxi- number of parameters, such as engine speed, manifold pres-
mum output. The fuel is usually injected into the intake sure, and ignition timing, and use them to formulate air-fuel
manifold rather than directly into the cylinder. This is to mixtures that will lead to optimum output and low emis-
avoid combustion deposit buildup and high-temperature sions. The diagnostics also include knock sensors and oxy-
damage to injectors. However, the direct-injection engines gen sensors. A knock sensor detects the onset of the engine
are better for fuel economy. This is because direct injection vibration resulting from knock and adjusts the ignition tim-
uses stratified charge and also results in better homogeneity ing by taking into account the fuel density and the octane rat-
due to turbulence, hence more complete combustion. OEMs ing. An oxygen sensor 共Lambda sensor兲 measures the ex-
are pursuing this technology primarily because of the fuel haust oxygen level to determine the air-fuel ratio and adjusts
economy benefit. The use of the high pressure swirl injectors it to within 1 % of the stoichiometric ratio. This leads to
and the invention of effective deposit control additives do maximum power, fuel economy, and low emissions.
help preclude deposit formation on the injector tips. Deposit New Combustion Chamber Designs
infested injectors increase both the fuel consumption and Engine torque, power output, and fuel consumption are a
the amount of pollutants 共HC, CO, and NOx兲. The amount of function of an engine’s compression ratio, the shape of the
these emissions varies among engines and depends upon the combustion chamber and piston crown, the number and the
air-fuel ratio of the combustion mixture; the engine’s operat- size of the intake and exhaust valves, and the position of the
ing variables, such as ignition timing, load, and speed; and spark plug. Both thermal efficiency, hence fuel economy, and
the presence of the deposit control additives. Since rich fuel- power output can be increased by raising the compression
air mixtures result in CO and HC due to partial combustion ratio and minimizing the combustion time. However, raising
and in NOx on complete combustion, the use of lean com- the compression ratio not only results in higher NOx but is
bustion mixtures should minimize their formation. How- also limited by the onset of knock. The latter can be cor-
ever, lean mixtures result in lower power, therefore other rected by the use of the high octane fuels. An alternative way
strategies, such as the use of catalytic converters and ther- to increase fuel economy and output is by the use of high tur-
mal reactors as the after-treatment devices are often pre- bulence, lean burn, and compact combustion chamber en-
ferred. Strategies to burn lean mixtures without losing gines.
power are described below. Good combustion chamber designs are those that syn-
The use of additional valves results in better turbulence chronize intake and exhaust with the engine’s operation, al-
and fuel-air mixture control, which translates into more low thorough mixing of the fuel and air, and burn the charge
complete combustion. This, in conjunction with the use of rapidly and smoothly. Design features that meet these re-
the high pressure swirl injectors, electronic swirl control quirements include low surface-to-volume ratio 共s/v ratio兲,
valves, and intelligent variable valve timing, can improve the adequate swirl to allow proper mixing of the fuel and air,
combustion efficiency and lower undesirable emissions. squish zones to create turbulence, little or no preignition, the
Variable valve timing controls the amount of the air intake. It highest possible compression ratio without promoting deto-
can also minimize the need for the valve overlap to achieve nation, short flame travel distance, a centrally located spark
smooth engine performance. Extensive valve overlap has a plug, and adequate number of valves to make efficient charg-
tendency to increase HC and CO emissions due to the escape ing of the combustion mixture and the removal of the
of the raw fuel into the exhaust 共scavenging兲. Most modern burned gases 关558兴. Most of these features increase the com-
vehicles are equipped with an electronic control module bustion rate, which translates into lower HC emissions.
共ECM兲, which facilitates variable valve timing that is ad- Lean or Fast Burn Combustion Chamber
justed to the engine’s operating conditions. Technology
On-board Diagnostics Most pollutants result from incomplete combustion. If the
As mentioned earlier, combustion mixture composition and combustion is complete, the formation of these pollutants is
ignition timing are the two key parameters that largely con- minimized. Lean burn technology will allow complete or
tribute towards emissions and fuel consumption. Typically, near complete combustion, thereby reducing the pollutants
combustion mixtures are defined in terms of the fuel-air ra- and increasing the fuel economy. The SI engines require AF
tio. However, it is the amount of air that is critical to engine ratio of 12.5– 13.5: 1 for maximum power, which leads to
performance and emissions. The use of the excess air factor, higher HC and CO emissions, and AF ratio of 15.5– 16.5: 1
, is therefore more appropriate. We know that rich mixtures for fuel economy, which will result in high NOx levels al-
共 ⬍ 1兲 lead to higher HC, CO, and NOx because of the high though HC and CO emissions decrease. Therefore, there is a
combustion temperatures, and lean mixtures 共 ⬎ 1兲 lead to trade-off between decreasing NOx and decreasing HC and
lower emissions and good fuel economy. We also know that CO. Combustion chamber design research has produced en-
the amount of air required for proper combustion depends gines that can operate consistently with lean combustion
upon the engine operation. For example, at idle, of 0.9–1.05 mixtures, that is, air-fuel ratios of 18: 1 and 19: 1. These pro-
is necessary to minimize misfire, which will lead to an in- duce lower NOx but increase HC only slightly. The main
crease in HC emissions. At low loads and high speeds, of problem is that engines equipped with such combustion
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316 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
Fig. 6.31—DB OM616 injector nozzle coking test for diesel fuel Test engine—4-cylinder, 2.4 litre; test duration—3 h.
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CHAPTER 6 䊏 EMISSIONS IN AN INTERNAL COMBUSTION ENGINE 319
TDC position, that is, between −10 and 0°, to initiate com- regulates and times the gas flow 共right loop兲. The purpose of
bustion, which is followed by the main fuel charge at be- the EGR cooler, also called the intercooler, is to lower the
tween 0 and 10°. The flow in the rate-shaping fuel injector is temperature of the exhaust gases prior to their mixing with
controlled by adjusting the needle valve lift. This type of flow the intake air 共left loop兲 and their entry into the engine. De-
has the advantage of being continuous and therefore the en- spite the benefits, EGR has its limitations. These include the
gine experiences less hesitation and noise. following:
Exhaust Gas Recirculation 共EGR兲 1. Increased soot accumulation in the lubricant, as re-
EGR recirculates a portion of the engine exhaust gases back flected by the viscosity increase.
into the engine. Intermixing of the incoming air with the re- 2. Soot-derived wear.
circulated exhaust gases dilutes the combustion mixture in 3. Increased engine temperatures, which causes higher lu-
the engine with the inert gas. This lowers the peak combus- bricant oxidation and possible loss of some lubricant
tion temperatures and the amount of excess oxygen, thereby components through volatilization.
reducing the generation of NOx. However, this is achieved at 4. Increased corrosion because of condensation and the
the expense of an increase in particulates. higher amount of acid formation.
Figure 6.32 shows the flow of the intake air and the ex- Increase in acid formation with the increased EGR is
haust gases through a turbocharged engine, by the use of ar- shown in Fig. 6.33 and increased wear and lubricant viscos-
rows 关573兴. A portion of the exhaust from the engine is di- ity data are provided in Table 6.34 关574兴. It appears that ap-
rected back into the engine by the use of an EGR valve, which proximately 100 h of EGR is the upper time limit, after
treatment devices, whose primary role is to lower particulate tain phosphorus and sulfur compounds present in the en-
and nitrogen oxide emissions from the model year 2007 on- gine oil, react with metals. This can deposit in the DPF and
road engines. closing its pores, which will lead to plugging. Extensive filter
As mentioned in the earlier part of the discussion, DPFs blockage can lead to back pressure and improper function-
remove particulates from the diesel exhaust, prior to its dis- ing of the engine, which will be reflected by increased fuel
charge into the atmosphere. The collected particulates can consumption and a loss in power. Ash deposits on the sur-
either be burned externally 共disposable DPFs兲 or internally faces of the catalysts can deactivate them since they can no
in the device itself 共catalyzed DPFs or CDFs兲. DPFs of the lat- longer facilitate oxidation chemistry. Phosphorus-derived
ter type are either precatalyzed, or can use fuel additives as ash is particularly detrimental to noble metals as they block
catalysts. A precatalyzed DPF uses noble metal catalysts, their active sites, a process referred to as poisoning. Sulfur in
such as platinum, palladium, and rhodium, to reduce the the form of sulfur trioxide 共SO3兲, on the other hand, blocks
temperature necessary for the particulate burn off. the NOx storage sites or the reaction sites of the NACs and
Fuel additive-catalyzed filters lower the temperature re- LNCs, thereby reducing the efficiency of these catalysts to
quired for soot burning, but the ash from the additive/s re- convert NOx into nitrogen. In addition, since all catalysts in-
mains in the filter after the burn off, which creates the prob- volve oxidation, sulfur will be converted into metal sulfates
lem of the ash build-up. This problem is overcome in the by way of its oxidation to sulfur trioxide. As a result, exces-
continuously regenerating DPF 共CR-DPF兲, which contains a sive amount of sulfur will show up in the form of the in-
diesel oxidation catalyst 共DOC兲 upstream of the diesel par- creased particulate emissions. Sulfur is also detrimental to
ticulate filter. This catalyst oxidizes the oxides of nitrogen the selective catalyst reduction 共SCR兲 technology because
other than NO2 to NO2 before the exhaust enters the DPF. the catalyst can be fouled by sulfates, especially ammonium
The NO2 lowers the temperature required to oxidize or burn sulfate, which forms at low exhaust temperatures. Because
off the particulates, thereby allowing the CDPF to continu- of these reasons, the EPA mandated the use of ultra-low sul-
ously clear itself of the trapped particulates. DOCs are plati- fur diesel 共SD15兲 in 2007 model year heavy-duty trucks,
num or palladium compounds that catalyze the oxidation of which are equipped with the emissions reducing technolo-
the organic particulates from the unburned fuel and the oil, gies discussed in this section. Please note that these tech-
hydrocarbons, and carbon monoxide to carbon dioxide nologies can affect fuel consumption: SCR improves fuel
共CO2兲 and water. Besides DOCs, there are two other catalyst economy but DPF, NAC, and LNC result in a fuel penalty.
technologies that are worth mentioning. These are lean-NOx Turbo-charging—Inter-cooling
catalysts 共LNCs兲, which are capable of converting NOx into Power output in an engine is proportional to the amount of
nitrogen 共N2兲 in the presence of oxygen, and NOx adsorber air it takes in. In general, the greater the amount of air, the
catalysts 共NACs兲, which first store 共adsorb兲 NOx and then re- greater is the power output. Two ways to introduce a greater
duce it under fuel-rich conditions. amount of air is through turbo-charging or supercharging.
In an ideal situation, soot and other organic matter col- Either technique increases the density of air or the air-fuel
lected in the DPF is burned as stated. However, engine oils mixture, via compression. This allows the introduction of a
contain a number of metal-containing additives that do not greater mass of charge into the cylinder under pressure. The
burn completely, leaving behind ash. Ash forms when cer- consequence is a more efficient combustion; hence lower HC
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322 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
Fuel Additives
Fuel properties during manufacture are carefully moni-
tored so as to ascertain their proper performance during use.
In the earlier part of this chapter, we presented data showing
the effects of various fuel parameters on the deposit forma-
tion, see Tables 6.26 and 6.30. A number of specifications
dealing with these properties exist 关576兴. A variety of chemi-
cals, listed in Table 6.35, are added to fuels to correct fuel de-
ficiencies and enhance performance 关551兴. These chemicals
can be broadly classified into performance additives, distri-
bution additives, and those that maintain fuel quality. The
treatment levels of these additives are usually very low, in
parts per billion to parts per million. The use of fuel additives
is growing fast, primarily because of a concern for emissions
and the OEM endorsement who are interested in the long- Fig. 6.36—Location and performance effects of engine deposits
term durability of their equipment. 关556兴.
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CHAPTER 6 䊏 EMISSIONS IN AN INTERNAL COMBUSTION ENGINE 323
decrease the combustion efficiency, hence decrease power, and in the combustion chamber has similar effects. Deposits
degrade driveability, lower fuel economy, and increase unde- on these parts also form because of the high ambient tem-
sirable exhaust emissions. Deposits can cause similar prob- peratures. Deposits not only increase the undesirable ex-
lems in the older carbureted engines because they block nar- haust emissions by impairing the proper functioning of the
row channels and orifices in the carburetor that meter the parts 关577兴, but they also cause part damage, e.g., valve stick-
fuel. Figure 6.37 shows a close up of the deposits in the me- ing and burned valves. The magnitude of the emissions in-
tering holes of a gasoline injector tip 关556兴. crease can be substantial. This not only decreases the com-
The formation of deposits on the intake valves, ports, bustion efficiency but also decreases the efficiency of the
catalytic converter. Figure 6.38 shows different levels of the
intake valve deposits common in today’s engines 关556兴 and
Fig. 6.39 depicts the effect of the intake valve deposits 共IVDs兲
on emissions. As the figure shows, the cleaner valves produce
lower emissions than the valves with deposits. In Fig. 6.38
LAC detergency rating corresponds to detergency resulting
from the lowest additive concentration.
The development of the cleanliness/deposit-control
agents is the most active area of fuel’s research. As men-
tioned earlier, deposits can form on many surfaces that see
high temperatures, but the fuel additive supplier is primarily
concerned with the intake system deposits 共primarily IVDs兲
Fig. 6.38—Typical intake valve deposits 关556兴.
Fig. 6.39—Effect of additives on exhaust emissions in a BMW 1.8 litre 4-cylinder engine.
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324 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
One tankful of gasoline treated with these additives can de- rived amines are prepared by the reaction of polyisobutylene
crease ORI by 30 to 40 %. Subsequent periodic treatments or polyisobutenyl-succinic anhydride with a polyamine.
with deposit control additives are necessary to maintain the Mannich types are the reaction products of polyisobutylphe-
deposit-free combustion chambers, otherwise the deposits nol, formaldehyde, and a polyamine. The methods of their
will reappear and ONR will revert to its previous equilibrium synthesis were described under dispersants in Chapter 4, the
level. Lubricant Additive chapter.
Two CCD-related problems that occur in some engines Figure 6.45 shows the effect of the cleanliness additive
are chamber deposit interference 共CCDI兲 and combustion on intake valve deposits. The greater the level of the additive,
chamber deposit flaking 共CCDF兲. The former results from the lower is the amount of deposits. An effective deposit con-
the physical contact of the piston top deposits and the cylin- trol additive must pass a number of performance standards,
der head deposits. The contact produces a loud, metallic including those that are listed below. The first four were de-
banging sound. This problem normally occurs in engines veloped by four automobile manufacturers 共BMW, General
that are designed to have minimal clearances to reduce emis-
sions. Combustion chamber deposit flaking can lead to low
compression pressures, if the flakes end up between the
valve face and the valve seat, thereby resulting in a poor seal.
Difficulties in starting and rough running, when the engine
is cold, indicate a CCDF problem.
Fig. 6.46—Fuel spray pattern—clean versus the one with deposits 关570兴.
Cetane Improvers „Diesel Ignition Improvers… increase in cetane number from 2-ethylhexyl nitrate de-
These additives enhance ignitability of the diesel, a low vola- pends upon its concentration and the quality of the diesel
tility fuel, reduce combustion noise, and smoke. The magni- fuel. If the diesel fuel being treated has high initial cetane
tude of the benefits depends upon the engine design and the number, the benefit from the additive is high, as is shown in
operating mode. A variety of thermally unstable compounds Fig. 6.52 关584兴. The boost in cetane number gets progres-
are used for this purpose including alkyl nitrites and ni-
sively smaller as the amount of 2-ethylehxyl nitrate is in-
trates, nitro and nitroso compounds, organic peroxides, and
creased. Typically, ethylhexyl nitrate concentration in diesel
a number of other oxidizing agents. Of these, 2-ethylhexyl ni-
trate, sometimes called the octyl nitrate, is the most often fuel ranges 0.05 % by weight to 0.4 % by weight. This usually
used cetane improver because of it being the most effective. leads to a cetane number increase of 3 to 8 units. Di-tertiary
See Fig. 6.51 for chemical structures. These materials ther- butyl peroxide has been a recent addition to the family of the
mally decompose at high temperatures in the combustion commercial cetane number improvers.
chamber to form species that facilitate fuel combustion. The
Fig. 6.50—Modified BOCLE wear versus additive concentration in a Class II diesel fuel.
Combustion Modifiers/Smoke Suppressants expected from this class of additives are provided in Table
These additives improve combustion efficiency of the diesel 6.38 关570兴.
fuel, thereby minimizing undesirable smoke emissions.
These are primarily calcium, cerium, platinum, manganese,
Flow Improvers/Wax Modifiers
iron, and copper containing organic compounds. While pre-
viously the use of these additives was discontinued, there is a At low temperatures the diesel fuel separates wax which can
possibility of a comeback due to their ability to lower the impede its flow as well as lead to filter plugging by wax crys-
auto-ignition temperature of soot. It is important to note tals. These additives modify crystal growth so that only fine
that while these additives are used in other parts of the crystals result and include ethylene-vinyl acetate polymers
world, they have not yet been approved by the EPA for use in and polyolefins. These usually work in conjunction with the
the United States, which may be due to their ash-forming low-temperature operability additives.
tendency. See the discussion on DPFs. Just the same, such
additives are often used in vehicles equipped with diesel par-
ticulate filters to further improve emissions control.
TABLE 6.38—Typical performance of low-
Low-temperature Operability Additives
temperature operability additives †570‡.
These additives are used to lower the diesel fuel’s pour point
共gel point兲, cloud point, and improve its cold flow properties.
These additives are analogous to pour-point depressants that
are used to improve the low-temperature properties of the
mineral oils. They are polymeric additives that interact with
wax crystals that form in the diesel fuel at low temperatures.
Different classes of additives affect various fuels differently;
hence the best additive and the treat rate for a particular fuel
must be determined experimentally. The benefits that can be
Foam Inhibitors plastic and elastomeric parts are replacing metals in the fuel
Some diesel fuels foam during pumping into the vehicle systems. Furthermore, the service station systems and op-
tanks, which can hinder complete filling of the tank or may erations are designed to prevent free water from entering a
even result in a spill. This can be precluded by the use of the vehicle’s fuel tank. The fuel treat level with these additives is
polysiloxane type of foam inhibitors. They are added to the 5 to 15 ppm.
fuel at concentrations of 10 ppm or lower. The mechanism by which these additives perform in-
volves their adsorption on the metal surface via their polar
Corrosion Inhibitors end and associating with the fuel via their non-polar end
These additives minimize corrosion of tanks, fuel lines, in- 共Fig. 6.53, Part B兲. This results in the formation of a film that
jectors, and pumps that primarily results from rusting be- acts as a barrier against surface attack by the corrosive spe-
cause of the contamination of the fuel with water. The pres- cies. Figure 6.53, Part A depicts the mechanism of rust inhi-
ence of the dissimilar metals in the vehicle’s fuel system is bition by alkenylsuccinic acids.
partly responsible for the rust, a form of electrochemical cor-
rosion. Rust starts at sites of the manufacturing faults, such Demulsifiers
as pinholes in the fuel tank. The presence of the oxygenates Typically, fuel and water do not stay mixed. However, emul-
in gasoline leads to chemical corrosion of the tank’s lead lin- sion can result from the contamination of the fuel with water
ing. If not controlled, corrosion can lead to blockage of the and passage through high-shear portion of a centrifugal
filters as well as deterioration of the automobile’s fuel sys- pump. The presence of the polar materials, such as additives
tem, thereby creating a fire hazard. that are present in the fuel, further exacerbates this problem.
Most corrosion inhibitors are metal-free surface active If not controlled, the emulsion will not only lead to the exten-
materials that function by making surface films that keep sive corrosion of the various metal parts but also will cause
corrosive materials away. See the corrosion inhibitor section filter plugging. Demulsifiers facilitate water separation from
of Chapter 4 on Lubricant Additives. The presence of the the emulsions, if they form, and therefore prevent filter plug-
oxygenates in gasoline warrants a higher additive treatment ging and also make it easy to siphon off the separated water.
level. This is because oxygenates, also being surface active, Demulsifiers are added to the fuel in very small amounts, at a
compete with the corrosion inhibitors for the surface. Car- concentration ⬃5 to 30 ppm. They are usually nonionic
boxylic acids and organic derivatives of the phosphoric acids compounds with a long chain hydrophobic group and at
and sulfonic acids are among those commonly used. These least one polar or the hydrophilic group. Polyethoxylated al-
additives are also used in refineries, tanks, and pipelines to cohols 共polyglycols兲, phenols, and amines are the common
protect equipment, which is typically constructed of un- types used.
coated steel. Rust in pipelines can cause reduced flow rates
and suspended particles that can result in blocked filters. Biocides
Once the fuel is in the vehicle, corrosion control is not as While high temperatures during refinery processing to make
critical since the metal parts in the fuel systems of today’s ve- fuels effectively sterilize them, they can quickly get contami-
hicles are made of corrosion-resistant alloys or of steel nated with microorganisms that are present in air or water.
coated with corrosion-resistant coatings. More and more These microorganisms include bacteria and fungi, such as
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332 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
yeasts and molds. Bacterial growth in the water-organic mix- ard and must be controlled. Antistatic agents are chromium
tures is common and leads to the formation of slime and un- based materials that are added to the fuel at few ppm levels
desirable odor. Most microorganisms grow at the fuel-water to control static.
interface, when one exists. Higher ambient temperatures
also favor growth. Microorganism growth must be con- Drag Reducers
trolled since it results in the acidic by-products, which will These are high-molecular-weight polymeric additives that
accelerate metal corrosion, and slime that will plug filters. improve the flow characteristics of the low-viscosity petro-
Static equipment is more amenable to microbial growth leum products. Their use lowers the energy required to
than that in constant use. The best approach to limit micro- pump fuels through the pipelines. They reduce the frictional
bial growth is prevention, which can be easily achieved by drag between the flowing fuel and the walls of the pipe and
eliminating water from the fuel storage tanks. Biocides must turbulence during pumping. The result is an increase in the
be used when microorganism growth becomes evident. fuel flow rate of 20% to 40%. Typical use concentration of
These are chemicals that discourage microbial attack and these additives is below 15 ppm.
stop their growth. The best biocides are those that are
soluble both in water and fuel, so that they can counteract Dyes and Markers
microbes in both phases. Typical use concentration of these Dyes are primarily colored aromatic compounds with azo or
additives is in the 200 ppm to 600 ppm range. Organobo- quinonoid structures that are used in fuels to visually differ-
rates, nickel-amine complexes, glycol ethers, and quaternary entiate batches, grades, or applications of the gasoline prod-
salts of salicylic acid are among the most commonly used ucts. For example, gasoline for general aviation, which is
biocides. manufactured to different and more exacting requirements,
is dyed blue to distinguish it from motor gasoline for safety
Antistatic Agents
An electrostatic charge develops during the fast pumping of
the fuel, an operation commonly used for loading and un-
loading large quantities. The charge poses an explosion haz-
Fig. 6.54—Commonly used fuel oxidation inhibitors. Fig. 6.55—Amine stabilizer for diesel fuel.
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CHAPTER 6 䊏 EMISSIONS IN AN INTERNAL COMBUSTION ENGINE 333
reasons, and they are used to indicate sulfur level in off- use concentration for these additives is between
highway diesel fuel. Markers, on the other hand, do not color 10 ppm to 80 ppm.
the fuel and their presence can only be detected by chemical Fuels contain certain components that get converted
or spectroscopic means. A refiner may use a marker in gaso- into high molecular weight species with little or no solubility
line to identify its movement through the distribution sys- in the fuel. These include nitrogen- or sulfur-containing
tem. Furfural and diphenylamine are among those used of- compounds, or both, organic acids, and reactive olefins.
ten. While the formation of the polymeric species primarily in-
volves oxidation, the acid catalysis can also result in their
Oxidation Inhibitors/Stabilizers formation. One way to minimize their formation is to con-
These additives minimize color degradation, control high- trol the fuel acidity. This is achieved by the use of strongly
temperature deposit formation, improve long-term fuel stor- basic stabilizers, such as amines. One such stabilizer is N,
age stability, and lower fuel filter plugging tendency. Most of N-Dimethylcyclohexylamine, whose structure is provided in
these problems relate to the attack of the atmospheric oxy-
Fig. 6.55. The typical treat level of the stabilizers ranges from
gen on fuel to form peroxides and gums. Peroxides degrade
50 ppm to 150 ppm. They react with weakly acidic com-
the antiknock quality, cause fuel pump wear, and attack plas-
pounds to form products that are fuel soluble.
tic and elastomeric fuel system parts. Soluble gums can lead
to engine deposits and insoluble gums can plug fuel filters or
the fuel injection system. Inhibiting oxidation is important Metal Deactivators
for fuels designed for use in modern fuel-injected vehicles, as Trace amounts of metals and metal ions can catalyze oxida-
their fuel recirculation design may subject fuel to higher tive degradation of the hydrocarbon materials, such as the
temperatures and increased oxygen exposure. Fuels of high fuels, which can lead to problems of all sorts. These additives
olefinic and aromatic content are more susceptible to oxida- chelate with the metal ions, such as those of copper and zinc,
tive attack than those of the high paraffinic content. The and make them ineffective as oxidation catalysts. N,
classes of materials that are commonly used as inhibitors in- N⬘-Disalicylidene-1,2-propanediamine is an example of
clude alkyl/aryl substituted amines and phenylene- such an additive. They are typically used in the concentra-
diamines, alkylphenols, and alkylaminophenols. Structures tion range of 1 ppm to 15 ppm. Figure 6.56 shows this deac-
of the two common inhibitors are given in Fig. 6.54. Typical tivator both in the free form and in the complexed form.
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MNL59-EB/Mar. 2009
7
Hydraulic and Transmission Fluids
IN THIS CHAPTER WE PRESENT TECHNOLOGY Compressibility is the rate of decrease in the ßuid vol-
relating to hydraulic and transmission ßuids. Under the ume with an increase in pressure. Below 1000 bars, the vol-
topic of hydraulic ßuids, we describe ßuids both for ume decrease is approximately 0.5 % per 100 bars at 20 ¡ C
tractor-type equipment and industrial hydraulics. We list and it is approximately 0.7 % per 100 bars at 80 ¡ C. At higher
the performance requirements of various equipment pressures, the volume decrease per 100 bars pressure be-
manufacturers and teach the formulating of an appropriate comes progressively smaller 关4兴. The decrease in volume due
ßuid. Under the topic of transmission ßuids, we describe to compression is because of an increase in density. A related
ßuid requirements for automatic transmissions, power concern in high-pressure hydraulic systems is an increase in
transmissions, and continuously variable transmissions. air entrainment, which is undesired since it can lead to a va-
We conclude the chapter by citing formulation examples riety of problems, including the possibility of cavitation
for each type of ßuid. damage. Solubility coefÞcients for different gases at tem-
Hydraulic Fluids peratures of 0 Ð 100 ¡ C are provided in Table 7.1 关4兴. These
coefÞcients are valid up to approximately 300 bars, above
Hydraulics is a branch of science that deals with mechanical which the solubility of gases decreases. Dissolved air is no
properties of ßuids, usually liquids, and the hydraulic ma- problem if it stays dissolved. However, when the pressure is
chinery. The latter comprises machines and tools which use eased off, the entrained air comes out as bubbles in pipes and
the ßuid power to perform work. Many industries employ cavities or forms surface foam in valves, pumps, and storage
these devices. Common examples of such machines include tanks. When the pressure is reapplied, cavitation can occur.
bulldozers, excavators, industrial cranes, harvesters, trac- For petroleum oils, compressibility is estimated to be 0.5 %
tors, and aircrafts; examples of the tools that employ hydrau- for each 1000 psi pressure increase up to 4000 psi 关585,586兴.
lics include backhoes and automotive brakes and transmis- Heat in hydraulic systems is a normal occurrence and
sions; and examples of industries that use these devices arises from the following sources 关587兴:
include agriculture, transport, construction, excavation, for- 1. Friction between the moving parts of the pump and or
estry, iron and steel, paper, food processing, and mining. the hydraulic motor.
The principle of hydraulic power is simple. It is based 2. FluidÕs interaction with surfaces of valves, pipes, and
upon the knowledge that a force applied on a small area can other devices.
result in a much larger force by a larger area due to hydro- 3. Heat release due to compression of the ßuid.
static pressure, and a large amount of energy can be carried Thermal conductivity and speciÞc heat of a ßuid indi-
by a small ßow of a highly pressurized ßuid. In hydraulic ma- cate its ability to absorb heat. ASTM D2717 and ASTM
chines, an almost incompressible ßuid 共the hydraulic ßuid兲 D2766 Test Methods are used to measure these parameters.
at a high pressure is transmitted through small tubes and In view of the fact that friction of one kind or another is the
ßexible hoses to various parts that perform the actual work. primary source of heat, a lubricant with the ability to reduce
While the primary function of the hydraulic ßuid is to friction, hence wear, will be extremely beneÞcial as a hydrau-
transfer power, it must also perform the functions that are lic ßuid. For discussion pertaining to various lubricant-
typical of all lubricants, which are to reduce friction, reduce related parameters, such as the viscosity and Þlm-forming
wear, and remove heat. The pump is the central component ability, that enhance lubrication, refer to the Lubrication
in most hydraulic systems, whose function is to collect the Fundamentals and Additives chapters, Chapters 1 and 4, re-
ßuid from a reservoir, pressurize it, and transfer it to various spectively.
system parts that perform the work. Most of the components
of the hydraulic system operate at high speeds, high pres-
sures, and high temperatures. Hence these parts require lu- TABLE 7.1—Solubility of different gases in
brication and effective cooling to extend the equipmentÕs medium viscosity mineral oil †4‡.
useful life. Bunsen Coefficient ␣a
Incompressibility, or low compressibility, is one of the
Gas 0 ŠC 50 Š C 100 Š C
key requirements for an efÞcient power transfer medium,
Air 0.092 0.091 0.091
because this permits maximum transfer of the generated
Oxygen 0.150 0.137 0.130
power. Bulk modulus of a ßuid, which is the reverse of com- Nitrogen 0.081 0.088 0.090
pressibility, is the change in ßuid volume as a function of the Hydrogen 0.047 0.053 0.067
applied pressure. The bulk modulus can be estimated from a Carbon Dioxide 1.0 ¯ ¯
lubricantÕs viscosity and density 关154,585,586兴. A high bulk a
With low-viscosity Ðuids, ␣ values are higher
modulus implies minimum compressibility.
334MNL
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CHAPTER 7 䊏 HYDRAULIC AND TRANSMISSION FLUIDS 335
The same as the other lubricants, hydraulic fluids are application and based upon composition. Application-based
blends of base stocks/fluids and additives. The term hydrau- classification includes tractor hydraulic fluids, industrial hy-
lic is a composed word with its origin in the Greek language: draulic fluids, transmission fluids, brake fluids, shock ab-
hydor meaning water and aulos meaning pipe. So, the term sorber fluids, and power steering fluids.
hydraulic fluid represents water 共or a water-based fluid兲 that
travels through a pipe from one point to another point. De- Tractor Hydraulic Fluids
spite the origin of the name hydraulic, modern hydraulic flu- Tractor hydraulic fluids 共THFs兲 are multipurpose lubricants
ids are derived from many other incompressible liquids, that are used to lubricate tractor transmissions, final drives,
which are the basis for their composition based classifica- hydraulic systems, wet brakes, and wet clutches 关588–590兴.
tion. Common base stocks used to formulate hydraulic fluids To perform these functions properly, THFs must combine
include the following: hydraulic and transmission properties with extreme-
1. Solvent-refined paraffinic base oils 共API Group I兲. pressure properties. Their function as a transmission fluid
2. Severely hydrotreated naphthenic base oils. and as a lubricant for wet brakes and wet clutches requires
3. Mildly hydrotreated paraffinic base oils 共API Group II兲. them to possess proper frictional characteristics. A sche-
4. Severely hydrotreated paraffinic base oils 共API Group matic representation of a tractor’s lubrication requirements
III兲. is provided in Fig. 7.1. Tractors use a wide variety of fluids to
5. Synthetic base stocks, such as polyalphaolefins 共PAOs, lubricate various parts. The list is provided in Table 7.3
API Group IV兲. 关588,591兴.
6. Other synthetic base stocks 共API Group V兲. Tractor hydraulic fluids differ widely in performance re-
• Synthetic esters quirements because the OEMs cannot agree on common
• Poly共alkylene glycol兲s specifications for a universal tractor hydraulic fluid. The
• Organophosphate esters specifications for these fluids, in general, deal with extreme
• Silicones pressure 共EP兲 and antiwear properties, and with matching
7. Natural base stocks, such as canola oil and castor oil. the frictional requirements of the equipment. The quality of
Mineral base stocks 共Items 1–4兲 are used most often to these fluids is assessed on the basis of their ability to meet
formulate hydraulic fluids. Synthetic fluids and natural oils individual OEM specifications, as well as API GL-4 for EP
are used only for specialized applications. For a detailed dis- and Allison C-4 for friction, oxidation, and wear perfor-
cussion on their manufacture or properties, please refer to mance requirements. Physical characteristics of these fluids
Chapters 2 and 3. are described in Table 7.4 and their performance specifica-
Like most commercial lubricants, hydraulic fluids need tions are described in Tables 7.5 and 7.6, respectively 关318兴.
additives that enhance their performance. Table 7.2 lists the There are eight major OEM specifications, and most
commonly used lubricant additives along with their func- tractor fluids are formulated to meet them. These specifica-
tions, mechanism of performance, and the test methods tions are:
used to determine their effectiveness. For further details on • JI Case MS1207
additives, please refer to Chapter 4. • John Deere J20C/D, and J27
The typical additive treatment rate for hydraulic fluids • New Holland FNHA-2-C-201.00 and M2C159B/C
ranges between 0.5 and 10 % and in the case of multi-grade • AGCO Massey-Ferguson M1135, M1139, and M1141
hydraulic fluids, the amount of the viscosity modifier is addi- In addition to a hydraulic fluid, farm tractors and re-
tional. Hydraulic fluids for use in tractors contain additives lated equipment need an engine oil and a transmission fluid.
in the amount of 6–9 % and for those to be used in industrial In order to reduce the number of lubricants handled by the
applications, the additives treatment is between 0.5 and 2.0 farmer, the concepts of Universal Tractor Transmission Oil
%. In transmission fluids, the additive treatment rate is in 共UTTO兲 and Super Tractor Oil Universal 共STOU兲 were devel-
the vicinity of 6–12 % and that of the viscosity modifier is oped. UTTOs have the ability to lubricate transmissions, wet
3–14 %. The additives used in these applications may be the brakes, and hydraulic systems. STOUs have the additional
same or different. Additives that are typically used in indus- ability to be used as engine oils and meet major performance
trial hydraulics include the following: criteria of the leading equipment manufacturers. Tables 7.7
1. Oxidation Inhibitors and 7.8 provide a list of the performance requirements of
2. Anti-wear Agents these lubricants 关318兴.
3. Extreme-pressure 共EP兲 Agents
4. Rust and Corrosion Inhibitors Industrial Hydraulic Fluids
5. Foam Inhibitors These fluids are used in industries, such as automotive,
6. Demulsifiers manufacturing, material handling, construction, chemical,
7. Metal Passivators mining, textile, food, rubber, and agriculture.
In some formulations, other types of additives may also As mentioned earlier, the pump is the central compo-
be present. For example, the emulsion-type hydraulic fluids nent in an industrial hydraulic system. Pumps create both
contain emulsifiers and biocides and the multi-grades con- the flow and the pressure necessary for the hydraulic system
tain viscosity modifiers. In addition to many of the additive to work. Common pump designs used in hydraulic systems
listed above, tractor hydraulic fluids contain a detergent, include piston pumps, vane pumps, and gear pumps. Each
friction modifier, pour point depressant, and viscosity modi- type has unique lubrication needs because of design. Piston
fier. pumps primarily operate under hydrodynamic lubrication;
Hydraulic fluids are classified in two ways: based upon hence fluids for them do not need the antiwear additives for
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CHAPTER 7 䊏 HYDRAULIC AND TRANSMISSION FLUIDS 337
good performance. Typically, oils containing oxidation and used in dirty environments, such as steel mills and mining
rust inhibitors, R&O oils, are satisfactory and so are the operations. R&O oils provide the necessary performance in
Denison HF-0 quality fluids that contain thermally stable these pumps 关591,592兴.
zinc dialkyl dithiophosphate 共ZDTP兲 antiwear agents. Ther- Primary functions that industrial hydraulic fluids per-
mal stability of the ZDTP is important since these pumps form include the following:
contain bronze piston shoes and the hydraulic systems con- 1. Power transmission
tain copper and brass. The acidic decomposition products 2. Pressure transmission
from thermally unstable ZDTP can lead to serious corrosion 3. Heat removal
of these parts. Nonzinc antiwear agents, based on sulfur- 4. Corrosion protection
phosphorus chemistry, are also acceptable for use in these 5. Elastomer compatibility
pumps. Vane pumps, on the other hand, operate under 6. Wear reduction
boundary lubrication and there is extensive continuous For a hydraulic fluid to perform these functions effec-
metal-to-metal contact. Therefore, hydraulic fluids for these tively, they must possess proper viscometrics 共viscosity, vis-
pumps contain antiwear agents to control wear. For low- cosity index, and low temperature fluidity兲, excellent EP
pressure applications, those involving less than 500 psi, properties, low compressibility, high heat capacity and ther-
R&O fluids work quite well but for high pressure applica- mal conductivity, low flammability, good oxidation resis-
tions, antiwear agents are necessary for satisfactory perfor- tance 共aging stability兲, low foaming tendency, good demulsi-
mance. Gear pumps operate under either full film 共hydrody- bility 共the ability to shed water quickly兲, high
namic兲 or mixed film lubrication and typically under mild to biodegradability, and noncorrosivity. A variety of chemicals
medium loads. There is little or no metal-to-metal contact are added to the base fluids of various kinds to enhance or
between the drive and the idler gears. Unlike vane pumps impart these properties. The performance requirements of
that require fluid cleanliness, axial piston and radial piston the finished fluids are described in major industry manufac-
pumps are not contamination-sensitive. Hence, they can be turers’ specifications; such as Denison HF-0, HF-1, HF-2;
Eaton-Vickers M-2950-S, 1-286-S; Cincinnati Lamb Landis 4. ASTM D2272, Rotary Pressure Vessel Oxidation Test–
P-68, P-69, P-70; General Motors 共1S2兲 1H-03-1, 1H-04-1, RPVOT 共Formerly Rotary Bomb Test, RBOT兲.
1H-06-1; DIN 51524, Part 2; and U.S. Steel 127. While in the 5. IP 280 and DIN 51 352, Cigre and Pneurop Oxidation
United States, the original equipment manufacturers Tests.
共OEMs兲 primarily establish the product requirements; in Besides the use of the oxidation inhibitors, which act to
Europe, the major country standards organizations set the prevent the formation of sludge and deposits, one can also
requirements 关592兴. In other nations, even governmental use detergents/dispersants that act as corrective additives.
agencies get involved in setting such standards. The stan- They suspend the deposit-forming species in the bulk fluid in
dards for the United States and Europe are provided in a soluble form and do not allow them to separate on surfaces
Tables 7.9 and 7.10 关592兴. The desired properties that are to form deposits. Detergents are neutral and basic alkaline
listed in the table are evaluated by using standardized and earth metal 共calcium and magnesium兲 salts of alkylphenols
nonstandardized tests. These are briefly described below. and alkylsalicylic and sulfonic acids. Dispersants are metal-
free derivatives of alkylphenol-derived amines and alkenyl-
Oxidation/thermal Stability succinimides. See the Additives chapter, Chapter 4, for fur-
The ability of a hydraulic fluid to withstand high tempera- ther details.
tures is extremely critical. This is because hydraulic fluid is
designed to act as a heat transfer medium. The resulting high Wear Control
temperatures can cause hydraulic fluids to rapidly react with Friction reduction and wear prevention are the basic func-
oxygen to form polar products that can cause thickening of tions of all lubricants. Both these objectives can be attained
the fluid, formation of acidic by-products, and deposit for- by the use of a fluid with suitable viscosity and the use of the
mation. Fluids that are designed for use in high temperature film-forming additives, such as friction modifiers and EP/
environments contain oxidation inhibitors, such as zinc di- antiwear agents. Fluid viscosity is of extreme importance in
alkyl dithiophosphate and hindered phenol, which retard hydraulic applications; hence a match with the equipment’s
the fluid break down. The tests that are commonly used to operating requirements is critical. A fluid of too low a viscos-
assess fluid stability include the following: ity will cause low volumetric efficiency, fluid overheating,
1. ASTM D943, Standard Test Method for Oxidation Char- and increased pump wear; and a fluid of too high a viscosity
acteristics of Inhibited Mineral Oils 共also known as the will cause poor mechanical efficiency, difficulty in starting,
Turbine Oil Oxidation Stability Test-TOST兲. and wear due to insufficient fluid flow 关593兴. Since viscosity
2. ASTM D4310, Test Method for Determination of the is a function of temperature, the temperature operating win-
Sludging Tendencies of Inhibited Mineral Oils. dow for a particular viscosity grade must be considered. In-
3. ASTM D2070, Standard Test Method for Thermal Sta- cidentally, hydraulic fluid viscosity is expressed in terms of
bility of Hydraulic Oils. International Standardization Organization 共ISO兲 viscosity
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CHAPTER 7 䊏 HYDRAULIC AND TRANSMISSION FLUIDS 339
grades and the older Seconds Saybolt Universal 共SSU兲 vis- regarding the functioning of these additives are provided in
cosity grades. ISO viscosity grades are based upon midpoint Chapter 4, the Additives chapter. The tests commonly used to
viscosity of the fluid at 40 ° C. Common ISO viscosity grades assess the wear control properties of a hydraulic fluid in-
共ISO VG兲 along with corresponding SSU grades are provided clude the following:
in Table 7.11. Figure 7.2 shows the effective viscosity range 1. ASTM D2782, Standard Test Method for Measurement
of ISO VG fluids, as defined by ASTM D2422, Classification of Extreme-pressure Properties of Lubricant Fluids
of Industrial Fluid Lubricants by Viscosity System 关594兴. For 共Timken Method兲.
example, ISO VG 32 hydraulic oil will provide satisfactory 2. ASTM D2783, Standard Test Method for Measurement
performance over −8 to 64 ° C temperature range. Viscosity
of Extreme-Pressure Properties of Lubricating Fluids
of hydraulic fluids is measured according to ASTM D445,
共Four-Ball Method兲.
Standard Test Method for Kinematic Viscosity of Transpar-
3. ASTM D4172, Standard Test Method for Wear Preven-
ent and Opaque Liquids.
In high-pressure hydraulic applications, the nature of tive Characteristics of Lubricating Fluids 共Four-Ball
lubrication changes from being hydrodynamic to mixed- Method兲.
film and boundary. This allows metal-to-metal contact and 4. ASTM D5182, Standard Test Method for Evaluating the
the wear can ensue. Additives used to control wear in hy- Scuffing 共Scoring兲 Load Capacity of Oils 共the FZG Test兲.
draulic systems include zinc dialkyl dithiophosphates 5. DIN 51 354, Part 2—Four-square Gear Test Rig 共FZG
共ZDTP兲, tricresyl phosphate 共TCP兲, sulfur compounds, Test兲.
amine phosphates, dithiocarbamates, and chlorinated 6. ASTM D2882, Standard Test Method for Indicating the
phosphorus/sulfur and molybdenum compounds. Details Wear Characteristics of Petroleum and Non-petroleum
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340 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
TABLE 7.5—J. I. Case and John Deere tractor hydraulic specifications †318‡. Reprinted with
permission from the Lubrizol Corporation.
Hydraulic Fluids in a Constant Volume Vane Pump Water Content and Hydrolytic Stability
共Vickers 104C兲. In many hydraulic systems, the fluid either contains water or
7. ASTM D2271, Standard Test Method for Preliminary is susceptible to contamination with water. In water-free flu-
Examination of Hydraulic Fluids 共Wear Test兲. ids, contamination with water can lead to a drop in lubricity,
8. Vickers V-104C and 35VQ25 Vane Pump Tests for increased corrosion, additive degradation, filter plugging,
screening hydraulic fluid wear performance for higher and cavitation. Hence, OEMs attempt to limit the amount of
pressure and mobile applications. water that enters their hydraulic systems and the fluid for-
9. Denison T6HZOC Piston Vane Pump Test. mulators try to design hydraulic fluids that resist chemical
10. Komatsu HPV35⫹35 Twin-pistons Pump Test using degradation and or hydrolysis in the presence of water. Hy-
cycled pressure for biodegradable vegetable oil-based drolytic stability is the key factor in the wet filterability be-
hydraulic fluids. havior of the hydraulic fluids 关595兴. There are no specific ad-
11. The Sundstrand Series 90 Piston Pump 共water stability兲 ditives that can improve hydrolytic stability of a fluid; it is
Test to determine the effect of water contamination on the selection of the stable components that results in a hy-
mineral oil hydraulic performance and yellow metal drolytically stable hydraulic fluid. Methods used to assess
corrosion. water content and hydrolytic stability of the hydraulic fluids
12. Three-stage Piston Pump Test based on the Bruening- include the following:
haus A4VSO piston pump, proposed by Rexroth 关592兴. 1. ASTM D95, Standard Test Method for Water in Petro-
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CHAPTER 7 䊏 HYDRAULIC AND TRANSMISSION FLUIDS 341
TABLE 7.6—New Holland and AGCO Massey-Ferguson tractor hydraulic specifications †318‡. Re-
printed with permission from the Lubrizol Corporation.
New Holland AGCO Massey-Ferguson
leum Products and Bituminous Materials by Distilla- tension of the oil-water interface, which facilitates separa-
tion. tion, and include alkylphenol ethers and low to medium mo-
2. ASTM D96, Standard Test Method for Water and Sedi- lecular weight synthetic metal sulfonates. Demulsibility in a
ment in Crude Oil by Centrifuge Method. hydraulic fluid is measured by ASTM D1401, Standard Test
3. ASTM D1744, Standard Test Method for Determination Method for Water Separability of Petroleum Oils and Syn-
of Water in Liquid Petroleum Products by Karl Fischer thetic Fluids and ASTM D2711, Demulsibility Characteris-
Reagent. tics of Lubricating Oils 共Wheeling Steel Demulsibility兲.
4. ASTM D2619, Standard Test Method for Hydrolytic Sta-
bility of Hydraulic Fluids 共Beverage Bottle Method兲. Aeration and Foam
The presence of air in a hydraulic fluid is quite common. Its
Demulsibility amount depends upon the fluid’s viscosity and polarity and
Demulsibility is the term used to describe a fluid’s ability to the ambient temperature and pressure. Low viscosity fluids
separate from water. As discussed in the previous section, contain a higher amount of air than those with higher viscos-
water contamination can lead to deterioration of the fluid as ity, but they also lose it quicker, if the other factors do not
well as it can affect equipment durability. It is therefore de- change. Fluids with higher polarity, such as synthetic esters
sirable for a hydraulic fluid to shed water as quickly as pos- and water-based fluids, are likely to have a higher amount of
sible, so that it settles to the bottom of the reservoir and it can dissolved air than the less polar mineral oils. Higher tem-
be drained off, if desired. For fluids with poor demulsibility peratures and lower pressures decrease the amount and the
characteristics, the separation is either very slow or unlikely. lower temperatures and higher pressures increase it. In ad-
To improve the properties of such fluids, chemicals called dition, the fluid circulation through the hydraulic system
demulsifiers, are added. These additives alter the surface may result in additional introduction of air into the hydrau-
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342 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
lic fluid, especially if the reservoir size, which is the case in of the fluid兲, reduced thermal conductivity and dielectric
the new equipment, or the design does not allow sufficient properties, and fluid degradation. While cavitation com-
residence time for air separation to occur. Aeration is a prob- monly occurs at the pump, it can occur anywhere within the
lem because it will result in foam formation, which under hydraulic system. Cavitation damage leads to metal erosion,
pressure can cause cavitation damage 关596兴. Cavitation is thereby causing physical damage to hydraulic system com-
the process where the bubbles resulting from the air entrain- ponents and contaminating the fluid. In extreme cases, it can
ment of the fluid implode under compression. In addition to even cause catastrophic failure of the hydraulic pumps, con-
cavitation, other reasons that make aeration and foam for- trol valves, and motors. Sometimes an air-ignitable mixture
mation in a hydraulic fluid undesirable include vibration, is present within the bubble, which will ignite due to a rise in
noise, sluggish component response 共due to spongy behavior temperature that accompanies compression. Although the
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CHAPTER 7 䊏 HYDRAULIC AND TRANSMISSION FLUIDS 343
TABLE 7.9—Original equipment manufacturers „OEM… viscosity guidelines for hydraulic fluids
†592‡. Reprinted with permission from the Lubrizol Corporation.
Operating Viscosity
„cSt…
Max Start-Up Viscosity Optimum
Manufacture Equipment Min Max Under Load „cSt… Viscosity „cSt…
Bosch
Form No. S/106 US FA;RA;K 15 216 864 26–45
Q; Q-6; SV-10, 15,20,25; VPV 16, 25, 32 21 216 864 32–54
SV-40, 80, 100; VPV 45, 63 32 216 864 43–64
Radial Piston 共SECO兲 10 65 162 21–54
Axial & RKP Piston 14 450 647 32–65
Commercial lntertech Roller & Sleeve Bearing Gear Pumps 10 1600 20
Sauer Danfoss All 10 … 1618 21–39
Denison Piston Pumps 13 … … 24–31
Bulletin 440 Vane Pumps 10 107 860a 30
Dynex/Rivett PF4200 series 1.5 372 372 20–70
Axial Piston Pumps PF2006/8, PF/PV4000, PF/PV6000 Series 2.3 413 413 20–70
PF1000, PF2000, PF3000 Series 3.5 342 342 20–70
Eaton Heavy-duty Piston Pumps & Motors, 6 … 2158 10–39
Medium-duty Piston Pumps & Motors,
Charged Systems, Light-duty Pumps
Medium-duty Piston Pumps & Motors, 6 … 432 10–39
Uncharged Systems
Gear Pumps, Motors & Cylinders 6 … 2158 10–43
Eaton-Vickers Mobile Piston Pumps 10 200 860 16–40
Industrial Piston Pumps 13 54 220 16–40
Mobile Vane Pumps 9 54 860 16–40
Industrial Vane Pumps 13 54 860 16–40
Eaton-Char-Lynn J, R & S Series Motors & Disk Valve Motors 13 … 2158 20–43
A & H Series Motors 20 … 2158 20–43
Haldex Barnes W Series Gear Pumps 11 … 750 21
Kawasaki Staffa Radial Piston Motors 25 150 2000 共no led兲 50
P-969-0026
P-969-0190 K3V/G Axial Piston Pumps 10 200 1000
Linde All 10 80 1000 15–30
Rexroth V3, V4, V5, V7 Pumps 25 … 800 25–160
V2 Pumps 16 160 800 25–160
R4 Radial Piston Pumps 10 200 … 25–160
G2, G3, G4 Pumps & Motors, G8, G9, G10 10 300 1000 25–160
Pumps
Parker Hannifin Gerotor Motors 8 … … 12–60
PGH. D/H/M Series Gear Pumps … … 1000 17–180
Hydraulic Steering 8 … … 12–60
PFVH/PFVI Vane Pumps … … 1000 17–180
Series T1 10 … 1000 10–400
VCR2 Series 13 … 1000 …
LSHT Motors 10 … … …
Variable-Volume Piston Pumps … … 1000 17–180
PVP & PVAC … … 1000 17–180
Axial Fixed Piston Pumps … … 850 12–100
Variable-Volume Vane—PW … … 440 16–110
Poclain Hydraulics H & S Series Motors 9 1500 20–100
Sauer-Sundstrand All 6.4 … 1600 13
USA
Sauer-Sundstrand Series 10 & 20 RMF Hydrostatic Motor 7 … 1000 12–60
GmbH Series 15 Open Circuit 12 … 860 12–60
Series 40. 42. 51 & 90 CW S-8 Hydrostatic 7 … 1600 12–60
Motor
Series 45 9 … 1000 12–60
Series 60LPM Hydrostatic Motor 9 … 1600 12–60
Gear Pumps & Motors 10 … 1000 12–60
a
Low speed and pressure.
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344 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
TABLE 7.10—Major hydraulic fluid specifications †592‡. Reprinted with permission from the
Lubrizol Corporation.
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CHAPTER 7 䊏 HYDRAULIC AND TRANSMISSION FLUIDS 345
process is of brief duration, lasting only nanoseconds, the lo- the fluid contains 1300 to 2500 particles larger than 4 m,
cal temperatures can be as high as 2012 ° F 共1100 ° C兲, or 320 to 640 particles larger than 6 m and 40 to 80 particles
higher, which will lead to thermal and oxidative degradation larger than 14 m 关597兴. Typical cleanliness rating to meet
of the fluid, resulting in varnish and sludge formation. This Denison HF-0 and Cincinnati Lamb requirements is
will be discussed later. Foam-inhibiting additives, such as 17/ 15/ 11 关598兴, to meet GM LS-2 requirement is 19/ 16/ 13
polydimethylsiloxanes and poly共alkyl acrylate兲s are used to 关599兴, and to meet Rexroth requirement is 20/ 18/ 15 关600兴.
break the foam bubbles. The tests used to evaluate these fluid Table 7.12 lists the ISO 4406:1999 cleanliness codes 关597兴.
parameters include the following: SAE AS 4059 is an Aerospace Standard 共AS兲 that defines
1. ASTM D892, Standard Test Method for Foaming Char- cleanliness classes for particulate contamination of hydrau-
acteristics of Lubricating Oils. lic fluids and includes methods of reporting the related data.
2. ASTM D3519, Standard Test Method for Foam in Aque- The contamination classes selected are based on the widely
ous Media 共Blender Test兲. accepted NAS 1638 cleanliness classes. The SAE Standard
3. IP 313, DIN 51381 or ASTM D3427, Standard Test has been revised five times, with the E version being intro-
Method for Air Release Properties of Petroleum Oils.
duced in May of 2005. SAE AS 4059 offers significant advan-
tages over NAS 1638, which include the following 关601兴:
Filterability
Proper fluid selection and fluid maintenance are important 1. It uses ISO 11171 for calibration of the automatic par-
in achieving reliability and durability of the hydraulic equip- ticle counters 共APCs兲, which provides increased preci-
ment. Fluid maintenance includes assuring fluid cleanliness sion and improved repeatability and reproducibility.
and filtration. Fluid should easily flow through the filter, with 2. It presents data in terms of cumulative counts
minimum pressure drop and little or no depletion of addi- 共⬎Xm ; ⬎ Y m兲 rather than range mode 共X-Y m兲.
tives. ISO 4406-99, Fluid Cleanliness Code, and SAE AS 4059 This is the manner in which particle counters generate
are the most widely used methods for determining particle the data.
counts in turbine oils and hydraulic lubricants. ISO 4406 3. It introduces a new cleanest class, 000.
uses a three-range number system. The first number corre- 4. It extends the size range to smaller sizes 关⬎4 m共c兲兴 for
sponds to particles larger than 4 m; the second number increased sensitivity,
corresponds to particles larger than 6 m; and the third The SAE AS 4059E Standard is presented in Tables
number corresponds to particles larger than 14 m. An ISO 7.13A and 7.13B. Part A of the table provides cleanliness
code of 18/ 16/ 13 for a hydraulic fluid indicates that 1 mL of classes for cumulative particle counts and Part B of the table
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346 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
TABLE 7.11—ISO viscosity grades. TABLE 7.12—ISO 4406, SAE J2472 fluid clean-
Kinematic Saybolt liness codes number of particles per mL †597‡.
ISO Viscosity Viscosity at 40 ° C Viscosity at 100 °F ISO More Up to and ISO More Up to and
Gradea „cSt… „SSU… Code Than Including Code Than Including
2 1.98–2.42 32 1 0.01 0.02 15 160 320
3 2.88–3.52 36 2 0.02 0.04 16 320 640
5 4.14–5.06 40 3 0.04 0.08 17 640 1300
7 6.12–7.48 50 4 0.08 0.16 18 1300 2500
10 9–11 60 5 0.16 0.32 19 2500 5000
15 13.5–16.5 75 6 0.32 0.64 20 5000 10,000
22 19.8–24.2 105 7 0.64 1.3 21 10,000 20,000
32 28.8–35.2 150 8 1.3 2.5 22 20,000 40,000
46 41.4–50.6 215 9 2.5 5.0 23 40,000 80,000
68 61.2–74.8 315 10 5.0 10.0 24 80,000 160,000
100 90–110 465 11 10.0 20.0 25 160,000 320,000
150 135–165 700 12 20.0 40.0 26 320,000 640,000
220 198–242 1000 13 40.0 80.0 27 640,000 1,300,000
320 288–352 1500 14 80.0 160.0 28 1,300,000 2,500,000
460 414–506 2150
a
Viscosity grade numbers of the ISO are the same as those of
ASTM 共The American Society of Testing and Materials兲 and BSI • 62 particles in ⬎25 m size= 3D
共British Standards Institution兲, with the difference that the viscosi- • 1241 particles in ⬎5 m size= 3B
ties for the ISO grades are measured at 40 ° C, while those of the • 12 particles in ⬎50 m size= 3E
ASTM and BSI are measured at 100 ° F 共37.8 ° C兲. Lubricants of a • 6 particles in ⬎100 m size= 5F
given ASTM or BSI grade are slightly more viscous than lubricants For hydraulic fluids that are likely to encounter filtra-
of the corresponding ISO grade. tion problems because of the environment or the chemistry,
high molecular weight alkenylsuccinimide and Mannich
provides cleanliness classes for differential particle counts. dispersant additives are used. These additives keep particu-
Please note that contrary to Part A that uses individual par- lates suspended in the fluid, thereby preventing their deposi-
ticle sizes to assign a class, in Part B particle size ranges are tion on the filter. Filterability of the hydraulic fluid is as-
used for this purpose. Part B is analogous to the NAS 1638 sessed by tests that consist of filtering a specified quantity of
Cleanliness specification. fluid, with or without water, through a standard medium
Data below are presented for a hypothetical fluid that while monitoring changes in flow rate. The use of water is
employed Method 1 to determine the sizes and the number based upon the fact that in many hydraulic fluids, its pres-
of particles. Cumulative class rating for such a fluid accord- ence usually makes filterability worse, which is a conse-
ing to 4059E Standard will be 2A/3B/2C/3D/3E/5F. Please quence of the hydrolysis and the interaction of some of the
note that ISO Code is based on the number of particles per additives. Denison TP 02100 Test, Pall Filterability Test, and
milliliter 共mL兲 but SAE 4059 is based on number of particles AFNOR Filterability Test are used to assess filterability of the
per 100 mL. hydraulic fluids.
• 2563 particles in ⬎1 m size= 2A
• 162 particles in ⬎15 m size= 2C Corrosion Protection
Corrosion-causing species, such as acids, originate from the
oxidation of the fluid or oxidation and decomposition of the
additives. These materials, if present, can attack metal com-
ponents and cause corrosion. Ferrous metal corrosion, pri-
marily rust, is often due to water contamination, while cor-
rosion of copper and its alloys 共yellow metals兲 is due to sulfur
compounds or acidic species that are either present in the
fluid or result from the high temperature degradation of the
fluid and its components. For a discussion on rust inhibitors
and the mechanism of rusting, please refer to Chapter 4 on
Additives. Ferrous metal corrosion control in hydraulic sys-
tems is achieved by the use of acid-neutralizing and film-
forming agents, such as neutral and basic arylsulfonates,
alkenylsuccinic acid derivatives, and fatty amines. Yellow
metal corrosion, on the other hand, is controlled by the use
of soluble sulfur and nitrogen-containing heterocyclic com-
pounds, such as tolyltriazole and dimercaptothiadiazole
共DMTD兲. The ASTM methods used for evaluating corrosion
inhibition properties of hydraulic fluids include the follow-
ing:
Fig. 7.2—Operating temperature ranges of ISO viscosity grades 1. ASTM D665, Rust-Preventing Characteristics of Inhib-
关594兴. ited Mineral Oil in the Presence of Water.
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CHAPTER 7 䊏 HYDRAULIC AND TRANSMISSION FLUIDS 347
2. ASTM D5534, Test Method for Vapor-Phase Rust- per Strip Tarnish Test. Copper strip rating criteria are
Preventing Characteristics of Hydraulic Fluids. provided in Table 7.14 关594兴.
3. ASTM D3603 is the Horizontal Disk Method for Rust-
Preventing Characteristics of Steam Turbine Oils in the Seal Compatibility
Presence of Water. Hydraulic systems contain a variety of seals whose function
4. ASTM D6547, Test Method for Corrosiveness of a Lubri- is to maintain hydraulic pressure, isolate sections to facili-
cating Fluid to a Bi-Metallic Couple. tate removal and replacement of the malfunctioning parts,
5. ASTM D2070, Standard Test Method for Thermal Sta- and isolate the fluid from harmful elements. Hydraulic fluids
bility of Hydraulic Oils 共Cincinnati Thermal Stability at high temperatures and high pressures can interact with
Test兲. rubber and elastomer seals causing them to swell, shrink,
6. ASTM D130, Standard Test Method for Detection of harden, or crack, depending upon whether the fluid travels
Copper Corrosion from Petroleum Products by the Cop- into or the plasticizer is removed out of the elastomer mate-
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CHAPTER 7 䊏 HYDRAULIC AND TRANSMISSION FLUIDS 349
TABLE 7.17—Water solubilities for organo- TABLE 7.18—Thermal conductivity and spe-
phosphate ester hydraulic fluid components cific heat data for materials †4.154‡.
†604‡. Thermal Conductivity Specific Heat
Water W/m·K at 373 ° K J/kg·K 293 K
Solubility Material „Btu/ h / ft2 / F / Ft at 212 ° F… „Btu/lb °F · 68 ° F…
Chemical Name „mg/L… Steel 46.7 共27兲 460 共0.11兲
1. Triphenyl phosphate 1.9 Oil 0.14 共0.08兲 1966 共0.47兲
2. Tricresyl phosphate, mixed isomers 0.36 Water 0.67 共0.39兲 4184 共1.0兲
3. Trixylenyl phosphate, mixed isomers 0.89
4. Isopropylphenyl diphenyl phosphate, mixed 2.2
isomers
5. Nonylphenyl diphenyl phosphate, mixed isomers 0.77 mended use temperature, they thermally decompose to form
6. Cumylphenyl diphenyl phosphate, mixed isomers 0.063 harmful compounds. Phosphate ester fluids are susceptible
7. t-Butylphenyl diphenyl phosphate, mixed isomers 3.2 to hydrolysis, which is further facilitated by their affinity for
8. 2-Ethylhexyl diphenyl phosphate 1.9 water. The rate of water absorption and the rate of hydrolysis
9. Tributyl phosphate 280.0 are a function of the organic moiety. When the alky group is
10. Dibutyl phenyl phosphate 280.0 hindered, both rates are slow, which is highly desirable. One
way to assess water affinity of a material is to consider its wa-
ter solubility. Materials with low water solubility will be the
upon their unique properties, i.e., antiwear fluids, fire- best for use in hydraulic fluids. Table 7.17 provides water
resistant fluids, and biodegradable fluids. solubility data for various phosphate esters 关604兴. Data sug-
As shown in Fig. 7.3, hydraulic fluids belong to the gen- gest that while items 1–8 are better than items 9 and 10,
eral classes of petroleum-based, synthetic-based, and water- items 2, 3, 5, and 6 are the best. The lubricity characteristics
based fluids. Water is the oldest hydraulic fluid known to of these fluids are comparable to those of the petroleum-
man and despite the fact that its use in modern applications based hydraulic fluids and hence they can be used in most
has diminished; it is still in use in some systems. This is be- commercial hydraulic pumps. These materials are very ag-
cause of its inherent advantages, which include extremely gressive to packings, seals, paints, and pipe joint com-
low cost, relative abundance, high-viscosity index 共main- pounds. However, butyl, silicone, Viton, and PTFE 共Teflon®兲
tains its viscosity with an increase in temperature兲, high seals are okay to use with these fluids. These fluids are usu-
compressibility 共least affected by pressure兲, high cooling ally compatible with all metals that are normally used in hy-
ability, and compatibility with all sealing materials, except draulic systems and can be filtered through most types of fil-
leather and the porous cellular type. The primary limitations ters. However, they must be handled with care and
resulting in its declining use are: prolonged exposure and repeated skin contact must be
1. Its narrow operating range of 3 ° C to about 50 ° C. avoided. In general, phosphate esters are considered to have
2. Its freezing point of 0 ° C and boiling point of 100 ° C. excellent fire resistance and their fire resistance is an inher-
3. Its rate of evaporation above 60 ° C to be too high to con- ent chemical property and not a property provided by an out-
tain it in the hydraulic system without difficulties. side agent such as water. Sometimes mineral oil blends with
4. Its inability to provide protection against rust and corro- esters, such as phosphates esters, are used as hydraulic flu-
sion. ids. This is done to lower the cost and improve the hydrolytic
5. Its low lubricity and susceptibility to bacterial growth, stability of the phosphate esters, and hence decrease their
after being contaminated with organic material. corrosivity.
Despite the disadvantages, a renewed interest in the use Another class of fire-resistant fluids that are used in hy-
of water in hydraulic fluids/systems has been developing. draulic applications comprises emulsions. Soluble oils are
This is being facilitated by new formulating concepts and excellent coolants and extremely fire resistant since they
new pump designs. contain 80 to 95 % water, but their use is extremely limited
Petroleum-based fluids are also low cost, respond well because of the low lubricity and poor additive solubility. The
to additives, have a broad operating range of about cooling ability of these fluids is due to the presence of water
−40 to 100 ° C, and provide excellent lubricity, except that which has high thermal conductivity and specific heat rela-
they lack adequate fire resistance. Synthetic fluids have a tive to mineral oil. Comparative data in Table 7.18 关154兴 indi-
higher cost, but are preferred in many applications because cate the advantage of water over all other fluids with respect
of the much broader operating range than that of the petro- to heat dissipation. High values of both parameters are bet-
leum base fluids. Synthetics that are used to formulate hy- ter with respect to cooling ability. Water-in-oil emulsions
draulic fluids include PAOs, diesters, silicones, and phos- based upon petroleum oil are generally preferred. While
phate esters. Some of these base stocks exhibit a high degree these fluids can have any amount of oil in the composition,
of fire resistance, which is useful, but many are incompatible typically these emulsions contain 55 to 65 % oil and the bal-
with packings, paints, and finishes that are used in hydraulic ance water and additives. Because of the higher oil content,
systems. Incompatibility with certain metals may also be a these fluids have good lubricity, and since they contain func-
problem, especially with ester-type fluids that in the pres- tional additives, they have good rust and corrosion and anti-
ence of water will hydrolyze to generate corrosive acids. wear properties as well. Their lubricity is suitable under
Phosphate ester fluids and phosphate ester-mineral oil many conditions and for many pumps. Their fire resistance
blends are often used as nonaqueous fire-resistant fluids. is due to their high-water content. In addition, these fluids
They have high flash and fire point, but above the recom- are compatible with most conventional packing and sealing
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CHAPTER 7 䊏 HYDRAULIC AND TRANSMISSION FLUIDS 351
ity, compatibility with most common metals, except lead, forming additives, similar to those used in automatic trans-
zinc, and cadmium, and with common filter construction mission fluids. As a matter of fact, many of the coupler and
materials. converter mechanisms use ATFs.
Relative to the mineral oils, triaryl phosphates have su- HR type fluids are HL fluids that contain viscosity modi-
perior VT properties, lower vapor pressure, lower compress- fiers, which improve their viscosity, giving them broad-
ibility, and higher shear strength. However, they may be temperature performance capability. Also see description
harmful to some seal materials, such as acrylonitrile- under HV oils below.
butadiene rubbers and butyl and ethylene/propylene elas- HV type fluids contain the same chemistry as HM fluids,
tomers, depending upon the temperature. Overall, the except that they contain the additional viscosity index 共VI兲
fluoro-hydrocarbon elastomers have proven to be the most improver. Viscosity improvers make these fluids multi-
resistant materials. A compatibility test with the fluid is grades. These fluids are produced by adding a polymer to a
therefore recommended with each polymer type. low viscosity fluid. The polymer increases the viscosity of the
HG type fluids are for slide way use. These are formu- oil more at high temperatures than at low temperatures. The
lated using a variety of base stocks to have good frictional result is easy flow at low temperatures and the ability to
and antiwear performance and metal cutting fluid compat- counter heat-related viscosity loss at high temperatures.
ibility. This is because slide ways are often used in metal cut- This improves the fluid’s performance at both low and high
ting operations. temperatures 关611兴. See Chapter 4 on Additives for a more
HH type fluids are mineral oils without additives. They detailed discussion. A wide variety of polymers are used to
are suitable for use in air-over-oil hydraulic systems, such as achieve this.
those used in car lifts at automotive service centers, manual HS type fluids are petroleum oil-based fluids that have
hydraulic pumps, jacks, and other low-pressure hydraulic good water stability, low aeration and foaming tendency,
systems. While these fluids are effective in transmitting suitable low and high temperature viscometrics, good oxida-
power, they lack the high temperature performance and tion resistance, good materials compatibility, and excellent
have limited lubricity. protection against rust. Many HLP and HVLP fluids 共HV
type fluids with improved rust and oxidation inhibition and
HL type fluids are also mineral oil-based, but they con-
anti-wear properties兲, engine oils, and automatic transmis-
tain rust and oxidation inhibitors to extend the life of the hy-
sion fluids fulfill these requirements.
draulic fluid and protect equipment against water-promoted
Tractor Fluids, ATF, and Engine Oils form a miscella-
rust damage. These fluids, also known as R & O oils, are rec-
neous group, which besides ATFs 共HA兲 are not directly classi-
ommended for use in machine tool applications, where sys-
fied under ISO classification for hydraulic fluids, but they are
tem pressures are ⱖ2000 psi, and for some piston pump ap-
often used as hydraulic oils. Groups of oils used as tractor
plications, such as Denison piston pumps 关610兴, where the
hydraulic fluids were discussed in the earlier part of this
zinc dialkyl dithiophosphate containing oils may not be suit-
chapter, ATFs are discussed below, and engine oils were dis-
able, due to being aggressive to yellow metal 共brass and
cussed in Chapter 5; hence discussing them here will be re-
bronze兲 and silver alloyed components. Typically, rust in-
dundant.
hibitors used in these fluids are alkenylsuccinic acid deriva-
Four classes of fluids that are of special interest are R&O
tives 关226兴, which are not always compatible with the basic
oils, fire resistant fluids, antiwear fluids, and biodegradable
metal sulfonate or phenate rust inhibitors and zinc dialkyl
fluids.
dithiophosphates that are used in many antiwear hydraulic
fluids. The metals from these additives react with the alk- R&O Oils
enylsuccinic acid to form oil insoluble metal succinates, For simple applications, the fluids essentially have no perfor-
which can cause hydraulic valve sticking and filter plugging mance requirements and refined mineral oils are often used.
problems 关611兴. HLP fluids are HL type fluids with improved R&O oils, on the other hand, have many requirements. Table
antiwear properties and HLPD fluids are HLP fluids that 7.20 lists the requirements of HL and HLP type hydraulic flu-
contain a detergent additive. Please note that HLP and ids specified in DIN 51 524, Part 1 关4兴. As stated earlier, HL
HLPD are not part of the ISO 6743/4 共1999兲 Hydraulic Fluid fluids are straight R&O oils and HLP fluids are oils that con-
Standard. tain additional antiwear additives. These oils are mineral oil-
HM type fluids contain antiwear additives in addition to based that are used in high-pressure hydraulic systems
the rust and oxidation inhibitors used in HL fluids. HL fluids which operate at high temperatures and require extended
are the most widely used mineral oil-based hydraulic fluids, service life. The service life of these fluids is measured by the
since they possess the antiwear performance necessary in standard industry tests, such as ASTM D943 and Cigre and
most high-pressure hydraulic applications and have the Pneurop oxidation tests 共IP 280 and DIN 51 352兲. Newer hy-
thermal stability necessary for their use in piston pumps. draulic pumps produce higher temperatures than the older
Zinc dialkyl dithiophosphate is the most widely used anti- pumps and hence they require additives that will provide
wear additive for hydraulic applications. Because of the re- oxidation and corrosion protection at elevated tempera-
cent interest in removing the heavy metals from lubricants, tures. These fluids contain oxidation inhibitors, rust and cor-
due to their impact on the environment, zinc-free 共ash-less兲 rosion inhibitors, and possibly demulsifiers and foam inhibi-
technology has been developed to replace zinc dialkyl dithio- tors. HL hydraulic fluids are used in systems that demand
phosphates. The new technology is based upon the sulfur/ greater thermal and oxidative stability and protection
phosphorus chemistry. against corrosion from the fluid, as well as longer service life.
HN type fluids are used for hydraulic couplers and con- HLP fluids are used in applications that in addition demand
verters. They are usually light mineral oil-based with film- the antiwear protection. Good demulsifying properties are
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CHAPTER 7 䊏 HYDRAULIC AND TRANSMISSION FLUIDS 353
TABLE 7.20—Requirements for hydraulic oils according to DIN 51 524, Part 1 †4‡.
required for both classes since in some applications the fluid machinery. Instead of these oils, one can use engine oils that
is exposed to water due to water leak, condensation, or con- in most cases provide satisfactory performance. Table 7.21
tamination; for example, by the water-based metalworking provides viscometrics and temperature limits of engine oils
fluids. The hydraulic fluid is expected to separate water for use as hydraulic fluids 关4兴. It is important to note that en-
quickly. HLPD hydraulic fluids are modified HLP fluids that gine oils are not designed for use in hydraulic systems; hence
contain detergents in applications that require reserve base,
they may not meet all the performance requirements.
for example, for mobile hydraulic systems in road building
TABLE 7.21—Typical temperature limits for the use of motor oils as hydraulic oils †4‡.
Approximate Temperature „°C… for a Max. Approximate Temperature „°C… for
Start-up Viscosity of a Working Viscosity of Approximate Temperature „°C…
for Limiting Viscosity
SAE Grade 2000 mm2 / s 1000 mm2 / s 500 mm2 / s 25 mm2 / s 15 mm2 / s 10 mm2 / s
l0W −15 −8 0 55 65 80
20 −10 0 8 62 78 95
30 0 8 15 75 90 107
15W–40 −7 2 12 82 96 115
10W–30 −10 0 8 68 87 103
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354 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
Fire-resistant Fluids of their high water content, their properties are influenced
Fire-resistant fluids are produced either by the use of the by the properties of water. Table 7.22 lists the typical proper-
synthetic base stocks or are water-based. While mineral oil- ties of the aqueous fire-resistant hydraulic fluids 关4兴. As
based fluids have most of the properties necessary in a hy- shown in the table, the operating range for emulsions is
draulic liquid, they are flammable under normal conditions 2 to 60 ° C. Below 2 ° C, they freeze and above 60 ° C the wa-
and can cause explosion under the influence of high pres- ter evaporation rate is too high for their use. The same is true
sures and high temperatures. Nonflammable synthetic liq- for the HFC fluids, although they have much lower freezing
uids have been developed for use in hydraulic systems where points that permit their use in most low-temperature appli-
the fire hazards exist. Fire-resistant hydraulic fluids are for- cations. The use of the aqueous fluids above 60 to 65 ° C can
mulated using materials with lower BTU content than the result in cavitation-related damage. Type HFA emulsions
mineral oils, such as polyol esters, phosphate esters, and have very low viscosities, ⬃1.5 mm2 / s at 20 ° C and
water-glycol solutions. Hence, when they burn, less heat is ⬃0.5 mm2 / s at 80 ° C, and hence they have high leakage
generated. Water-based fluids are largely nonflammable, but rates. This is corrected by making clearances in the equip-
synthetic ester-based fluids, such as phosphate esters type, ment narrower than those intended for use with more vis-
will burn, if sufficient heat and flame are applied; but they do cous fluids. This in turn will create a greater need for filtra-
not support combustion. These fluids include soluble oils, tion to remove the dirt particles which can cause jamming
invert emulsions, water-glycol mixtures, and those based and wear of the mobile parts.
upon phosphate esters and polyol esters. The major draw-
All aqueous hydraulic fluids have VT characteristics in-
backs of these fluids include their deleterious effect on paints
ferior to those of the mineral oils and so is the compressibil-
and adhesives, insulations used in electrical cables, and
ity. These fluids reflect poor wear control relative to mineral
many gasket and seal materials. Industrial uses of these flu-
oil-based fluids, because of the lack of appropriate lubricity.
ids include hydraulic environments that are in close proxim-
HFC fluids are somewhat better in controlling wear since
ity to flame or high temperatures, such as foundries, steel
mill operations, furnace hydraulics, aircraft systems, and their viscosity relative to HFA fluids is higher. Aqueous flu-
turbines for generating power. Fire hazard occurs, if a flam- ids, especially of the HFA type, suffer from corrosion prob-
mable hydraulic fluid leaks on hot surfaces due to damage to lems and are highly susceptible to bacterial attack. Soluble
the hydraulic systems during operation, or if overheating of oils, another class of aqueous fire-resistant fluids, also suffer
the pressurized hydraulic system causes leakage and self- from the same problems. These problems are corrected by
ignition of the fluid. The use of the fire-resistant hydraulic the use of the rust and corrosion inhibitors and biocides and
fluids minimizes this hazard. The fire resistance of the fluid fungicides.
is assessed not by a single test but a battery of tests which The DIN 24 320 specification demands good emulsion
attempt to simulate different hazard situations. One of the stability, good corrosion protection, low metal attack, and a
tests even deals with slow leaks on hot pipelines and is also pH of 6.5 to 8.5. If the emulsion is designed to be biodegrad-
capable of distinguishing between different kinds of hydrau- able, the emulsifier共s兲 and the base fluid used must have a
lic fluids. These tests are listed below under the section on high degree of biodegradability. HFB type fluids, which are
fire-resistant hydraulic fluids. The ISO classification for water-in-oil emulsions, are used less often. Their need for the
these fluids, shown in Table 7.19, is summarized below: rust-inhibiting additives and bactericides is much less.
1. HFAE—Oil-in-water emulsions, typically containing Polymer-thickened HFC fluids are mixtures of glycol, water-
⬎ 80% water. soluble glycol ethers, and polyglycols with oxidation inhibi-
2. HFAS—Chemical solutions in water, typically tors and rust control agents. Their water content is 35 %, or
containing⬎ 80% water. more, which imparts to them the desired fire resistance.
3. HFB—Water-in-oil emulsions containing approxi- Emulsions require continuous quality control and purifica-
mately 45 % water. tion 共filtration兲 to maintain stability.
4. HFC—Water-polymer solutions containing approxi-
mately 45 % of water. Nonaqueous Fire-resistant Hydraulic Fluids
5. HFDR—Synthetic fluids containing no water and con- These fluids are used in extremely high temperature and
sisting of phosphate esters. high pressure environments and hence they must possess
6. HFDU—Synthetic fluids containing no water and of good thermal stability, excellent boundary lubrication prop-
other compositions. erties, low volatility, fire resistance, and moderate hydrolytic
stability. These fluids include polysiloxanes 共silicones兲, poly-
Water-Miscible 共Aqueous兲 Fire-Resistant
chlorinated biphenyls 共PCBs兲 containing 35–50 % chlorine,
Hydraulic Fluids
Aqueous fire-resistant hydraulic fluids fall under three cat- and phosphoric acid esters. PCBs only see a limited use, and
egories: HFA, HFB, and HFC. These categories include only in military applications, because of the chlorine’s role in
emulsions and solution type fluids that contain large carcinogenic dioxin formation. Some high boiling and high
amounts of water. The majority of the water-based fluids are flash oleic acid esters and polyglycols are also used in these
either the oil-in-water-type, HFAE, or the polymer-thickened applications, but with limited effectiveness. For large vol-
aqueous solutions, HFC. Their high water content is respon- ume use, silicones are not considered because of their high
sible for their low flammability. Additional advantages in- cost and poor lubrication characteristics. These fluids use
clude their lower cost and greater compatibility with the en- specialized tests to assess their fire resistance. These tests are
vironment, compared to the nonaqueous fluids. These listed below, along with some of the specifications that in-
attributes are important if there is leakage or a spill. Because clude these tests 关4兴.
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CHAPTER 7 䊏 HYDRAULIC AND TRANSMISSION FLUIDS 355
Fire Resistance Fluid Tests oxidation of these materials generate acidic products with
1. Determination of the flammability of the fluid, atomized the ability to further catalyze hydrolysis, continuous filtra-
under pressure. tion of the fluid through bleaching clay is normally em-
2. Determination of flame propagation in a mixture of coal ployed to remove these deleterious materials. Table 7.23 con-
dust and fluid. tains some of the relevant properties of the polychlorinated
3. Determination of flammability of atomized fluid. biphenyls and a phosphoric acid ester 关4兴 and Table 7.24
a. Wick test compares the various characteristics of all classes of fire-
b. B13C flash test resistant fluids that are commonly used 关613兴. Phosphoric
4. Test with hot metal surface 共Hot Manifold Test兲. acid ester type fire-resistant fluids are not compatible with
5. Test with molten light alloy. the mineral oil-based fluids, and mixing will cause a drop in
6. Self-ignition temperature. their resistance and an increase in their oxidation suscepti-
7. Ignition temperature. bility. They also harm some elastomers, such as Buna-N or
nitrile, PVC coatings, and paints.
Fire Resistant Fluid Specifications The U.S. Military, especially the U.S. Navy, is one of the
1. Luxemburg Report 共Community of Six兲, Part III 3.1
principle users of the fire-resistant hydraulic fluids. The
2. Luxemburg Report 共Community of Six兲, Part III 3.2
standards for various fluids used by the U.S. Navy and their
3. Luxemburg Report 共Great Britain兲, Part VI 6.15 NCB
properties are provided in Table 7.25. We previously dis-
570/ 1270
cussed the hydrolytic stability issues of the phosphate esters
4. Luxemburg Report 共Great Britain兲, Part VI 6.16 NCB
and concluded that the phosphates that are hydrolytically
570/ 1270
stable will be the base fluids of choice. This is borne out by
5. DIN 51 515-2
examining the U.S. Military Standards, provided in Table
6. SAE AMS 350
7.26, where specifications MIL-H-19457B and MIL-H-
7. BBC Flash Test 共BBC ZLC 2-4-3兲
19457C that employ phosphate esters use the hydrolytically
8. ASTM D2155, DIN 51 794 Requirements
stable aryl esters 关604兴.
a. No flash appears, or flame must not reach screen.
b. Flame must not exceed arithmetic mean value of Antiwear Hydraulic Fluids
10 cm 共propagation兲. These fluids contain additives that impart them antiwear
c. Atomized jet must not continue to burn for more properties and, as stated earlier, these are the most com-
than 30 s after removal of igniter flame. monly used hydraulic fluids. Metal dialkyl dithiophos-
d. Mean duration of burning must not exceed 60 s. phates, which are often used as oxidation inhibitors, for ex-
e. “Self-extinguishing” 共duration of burning ⬍5 s兲, no ample in R&O oils, also act as antiwear agents to control
flash or short flash only at 704 ° C. wear that results from metal-to-metal contact in hydraulic
The oxidation stability of the phosphoric acid tri-esters pumps and the related equipment. Zinc dialkyl dithiophos-
is satisfactory and is comparable to that of the mineral oils, phates are shown to be good in cases of steel-to-steel contact,
but their hydrolytic stability is of concern. Aryl esters and but not in the case of copper and bronze. This is because
short-chain alcohol esters hydrolyze more rapidly than the most zinc dialkyl dithiophosphates suffer from inadequate
long-chain esters. Sterically hindered aryl and alkyl groups thermal stability, leading to the formation of products that
diminish the rate of hydrolysis. Since the hydrolysis and the are aggressive to yellow metals.
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356 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
Zinc dialkyl dithiophosphates 共ZnDTP兲 have been in use ment of the fluids for use specifically in hydraulics. Zinc di-
since the 1950s. First, they were used as antiwear/ alkyl dithiophosphates were used in these fluids as well. Un-
antioxidant component of the mono-grade engine oils that like vane pumps, piston pumps do not need the antiwear
were used at that time as hydraulic fluids. Later, the industry protection of the zinc dialkyl dithiophosphates. As a matter
discovered that some components of the engine oils, such as of fact, their presence in fluids caused extensive wear of the
dispersants and detergents, had a detrimental effect on copper components used in pumps, piston shoes, and cylin-
pump performance because they prevented the oil from der liners. The development of the stabilized ZnDTP chemis-
separating water readily 共demulsification兲. Good demulsibil- try changed all that and almost all hydraulic fluids used to-
ity properties were necessary for hydraulic fluids used in in- day contain ZnDTP and the stabilized ZnDTP additives.
dustrial applications since many of them are exposed to wa- The primary incentive for using the dialkyl dithiophos-
ter, which contributed to the formation of sediment, phate chemistry in hydraulic fluids is its performance, both
deposits, and other undesirables. This led to the develop- as an antiwear agent and as an oxidation inhibitor, which ex-
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358 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
TABLE 7.28—Typical oxidation and thermal stability performance of various antiwear hy-
draulic fluids †198‡
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CHAPTER 7 䊏 HYDRAULIC AND TRANSMISSION FLUIDS 359
ent tests that are used worldwide to determine biodegrad- define than environmentally friendly since physical tests to
ability and they all provide different estimates. There is a determine biodegradability exist. One interpretation of envi-
move by the United States and the European standard devel- ronmentally friendly is that the technology is nontoxic,
oping organizations to distinguish between environmentally which means to life, and hence is biodegradable. The ques-
friendly and biodegradability. Biodegradability is easier to tion is which organisms should be used in the fundamental
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360 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
tests to clearly arrive at the conclusion. Another interpreta- ral salts and activated sewage sludge sample 共bacteria兲 to the
tion of the term is that the technology has no adverse effects test sample and water. The sample is considered biodegrad-
on the environment. This involves assessing the impact on able if 70 % of the oil is consumed in 21 days. EPA
the environment, isolating various components to deter- 560/ 6-82-003 Test is a 28-day test that involves shaking a
mine the cause and effect relationship, and then eliminating mixture of the sample, water, sewage sample, and oil. The
the harmful or potentially harmful component/s from the sample is considered biodegradable if in 28 days 60 % of the
formulation. The term environmentally acceptable implies sample is converted into carbon dioxide. OECD 301B Test,
that the formulation does not contain chemicals that are also a 28-day test, is used for water-insoluble oil samples.
known to be harmful to life and the environment and may be The sample is considered biodegradable if over the period of
more appropriate to use. Either way, it is important to ques- 28 days 60 % of the sample is converted into carbon dioxide.
tion the manufacturer about the label used and what tests Of the fluids listed in the table, vegetable oils and synthetic
were carried out to arrive at the conclusion. fluids have a high degree of biodegradability, but others are
Environmentally acceptable hydraulic fluids are used in not as good. Incidentally, PAGs 关poly共alkylene glycol兲s兴, that
hydraulic applications where there is risk of fluid leaks and are derived from ethylene oxide have higher degree of biode-
spills entering the environment, especially waterways, and gradability than those derived from propylene oxide. Biode-
affecting aquatic and terrestrial life. Examples of such appli- gradability of the PAGs derived from ethylene oxide/
cations include forestry, construction, locks and dams,
propylene oxide mixtures varies, depending upon their
heavy-duty lawn equipment, amusement parks/
ethylene oxide content. This suggests that if one is seeking a
entertainment industry, off-shore drilling, and maritime.
hydraulic fluid with high biodegradability, one must use veg-
These fluids must be nontoxic to aquatic life and possess
etable oil or a carboxylate ester as the base fluid.
aerobic biodegradability. Organizations such as the Organi-
While selecting a biodegradable lubricant one must also
zation for Economic Co-operation and Development
consider other performance criteria, such as oxidation sta-
共OECD兲, the Coordinating European Council 共CEC兲, and the
bility, antiwear protection, hydrolytic stability, viscosity-
U.S. Environmental Protection Agency 共EPA兲 have devel-
oped standard test methods to determine the toxicity and the temperature properties and the cost. Biodegradable lubri-
biodegradability of substances. ASTM and ISO have also de- cants use biodegradable base stocks, such as vegetable oils
veloped Guide for Assessing Biodegradability of Hydraulic and synthetics, and biodegradable additives, where possible.
Fluids 共ASTM D6006兲, Classification of Hydraulic Fluids for While the base fluid makes up the major proportion of the
Environmental Impact 共ASTM D6046兲, and ISO environ-
mental hydraulic fluid classifications based upon the above
organizations’ methods. ISO Environmental Hydraulic TABLE 7.31—Biodegradability of various base
Fluid Classifications are shown in Table 7.30 关115,616兴 and fluids according to CEC-L-22-T-82 biodegrad-
are described in the subsequent paragraphs. ISO, in collabo- ability test.
ration with regional environmental organizations, also Fluid % Biodegradability
awards Eco Labels 关168,169兴, such as German Blue Angel, Mineral Oil 15–35
Nordic Swan, and Japanese EcoMark. White OIl 25–45
The biodegradability estimates of various base fluids are Polyalphaolefin 共PAO兲 5–30
provided in Table 7.31. Three of the tests that are used to de- Polyisobutylene 共PIB兲 0–25
termine biodegradability are CEC-L-33-T-82; EPA Polyethers 0–25
Phthalate and Trimellitate Esters 5–80
560/ 6-82-003, “Shake Flask” Test; and OECD 301B, “Modi-
Polyol and Diesters 55–100
fied Sturm” Test. CEC-L-33-T-82 Test is 21-day test, which is
Natural and Vegetable Oil 70–100
used for oil-based substances. The test involves adding natu-
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CHAPTER 7 䊏 HYDRAULIC AND TRANSMISSION FLUIDS 361
fluid, the nonbiodegradable additives may significantly these oils have performance deficiencies, such as poor ther-
harm its biodegradability. mal, hydrolytic, and oxidation stability, and high pour point.
HETG type fluids are based on naturally occurring veg- They do have the advantages of good lubrication ability,
etable oils or triglyceride esters. Without the addition of a good surfactancy, and high viscosity indices. Some of the
thickener, vegetable oils are limited to a narrow viscosity new natural oil sources use genetically engineered strains to
range between that of ISO 32 and 46. While HETG fluids bio- provide oils with superior thermo-oxidative properties. Mix-
degrade rapidly, have excellent natural lubricity, and have a ing vegetable oils with synthetic diesters help maintain their
natural VI in excess of 200, they are unsuitable for use at biodegradability as well as improve their low-temperature
high and low temperature extremes. This is because they viscometrics and oxidative stability.
tend to gel at low temperatures and oxidize quickly at high
temperatures. The practical temperature limits for using Formulating a Hydraulic Fluid
HETG fluids is −25 ° F to 165 ° F 共−32 ° C to 74 ° C兲 关594兴. For a hydraulic fluid to function properly, it must transfer
HEES type fluids are based on unsaturated to fully satu- fluid power throughout the hydraulic system, act as heat
rated synthetic esters. Common ester chemistries utilized in transfer medium to remove heat from the system, lubricate
hydraulic fluids consist of TMP oleates, neopentyl glycol and all moving parts, provide internal seals, remain stable in
pentaerythritol ester-based HEES fluids adipate esters, and most environments, and be compatible with all components
complex esters. The synthetic esters-based HEES fluids have of the system. While hydraulic fluids have changed little over
better performance than the HETG type hydraulic fluids, the years, there are changes on the horizon, because the op-
with respect to broader operating temperature ranges, erating environment of these fluids is changing due to a drive
greater number of ISO viscosity grades, and better oxidation towards more compact systems. This translates into higher
stability while still maintaining biodegradability 关594兴. pressures, smaller lines, smaller reservoirs, and higher tem-
HEPG type fluids are poly共ethylene glycol兲s 共PEGs兲, peratures due to less cooling of the fluid. While the system
which possess good oxidation stability and low temperature requirements depend upon design and the application in-
flow characteristics. At molecular weights of up to volved, the most desirable hydraulic fluid properties are
600– 800 g / mol, HEPG type fluids are ecotoxicologically listed below:
harmless and readily biodegradable 共⬎90 % in 21 days兲 1. Good flow properties over a broad temperature range
关615,616兴. Some disadvantages of this class of fluids include 共proper low and high temperature viscometrics, high
miscibility with water, incompatibility with mineral oils, viscosity index, low pour point, shear stability, etc.兲.
and aggressiveness toward some types of elastomer seal ma- 2. Good film-forming and friction-reducing ability.
terials. 3. Ability to inhibit corrosion.
HEPR type fluids are polyalphaolefins 共PAO兲, or synthe- 4. Good mechanical, thermal, and chemical stability.
sized hydrocarbon 共SHC兲 based fluids, which have signifi- 5. High bulk modulus, or low compressibility.
cantly better viscometric properties over a broader range of 6. Low foaming tendency and air entrainment properties,
temperatures than mineral base fluids with the same stan- i.e., rapid deaeration and demulsification.
dard viscosity classification. Some low viscosity PAOs have 7. Low specific gravity and low vapor pressure.
shown acceptable primary biodegradability, though not as 8. Low coefficient of thermal expansion.
rapid as vegetable or synthetic ester base fluids. Additional 9. High heat-transfer rate 共high heat capacity and thermal
advantages claimed for synthetic lubricants over compa- conductivity兲.
rable petroleum-based fluids include improved thermal and 10. Adequate fire resistance.
oxidative stability, superior volatility characteristics, and 11. Material compatibility with system materials, such as
preferred frictional properties 关594兴. paint, metals, plastics, and elastomers.
The major worldwide performance specifications for 12. Biodegradability, environmental compatibility, and
biodegradable fluids are listed below: nontoxicity, both when new and after use and upon de-
1. ISO/CD15380 composition.
2. German VDMA 24568, 24569, 24570 13. Low cost and easy availability.
3. Swedish Standard 155434 A hydraulic fluid with suitable properties will help fulfill
4. German RAL-UZ 79 Blue Angel the equipment manufacturers’ requirements, which are
5. Nordic White Swan 0002/ 3.1 summarized in Tables 7.9 and 7.10. Many of the properties in
6. Austrian Onorm C 2027 a hydraulic fluid, for example 1, 2, 5, 7, 8, and 9 in the above
7. Netherlands Vamil list, can be achieved by the use of the appropriate base fluid/
8. Caterpillar BF-1 s. Achieving other properties in most cases requires the use
9. MIL-PRF-32073 of the performance-enhancing chemicals, or additives. A list
10. ASTM D6046 of additives that are commonly used along with their func-
11. Canadian ECP-05-94 tion and the mechanism by which they perform is presented
12. Komatsu BO in Table 7.2. Different types of fluids contain different types
13. Rexroth RE 90221 of additives.
14. Vickers Guidelines Modern hydraulic fluids last longer, provide greater pro-
Vegetable oils that are commonly used for formulating tection, and perform better than their predecessors. As men-
hydraulic fluids, or other biodegradable lubricants, include tioned earlier, the need for durable fluids of superior quality
corn oil, soybean oil, rapeseed 共canola兲 oil, sunflower seed arose because of the modern hydraulic equipment becoming
oil, peanut oil, olive oil, and others. In their natural form, smaller and more efficient with respect to higher speeds,
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362 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
TABLE 7.32—Typical temperature limits for ISO VG grades for hydraulic oils †4‡.
Approximate Temperature „°C… for a Approximate Temperature „°C… for Approximate Temperature
Maximum Start-up Viscosity ofb a Working Viscosity of „°C… for Limiting Viscosityb
ISO Viscosity Viscosity
Gradec Index 2000 mm2 / s 1000 mm2 / s 500 mm2 / s 25 mm2 / s 15 mm2 / s 10 mm2 / s
10 50 −39.0 ±2.0 −33.5 ±2.0 −27.0 ±2.0 16.5 ±3.0 28.5 ±3.0 40.0 ±3.0
100 −44.0 ±2.5 −38.0 ±2.5 −31.5 ±2.5 14.5 ±3.0 27.5 ±3.0 40.0 ±3.0
150 −50.0 ±2.5 −44.0 ±2.5 −37.0 ±2.5 12.5 ±3.0 26.5 ±3.0 40.0 ±3.5
15 50 −30.5 ±2.0 −26.5 ±2.0 −16.0 ±2.0 27.0 ±2.5 40.0 ±2.5 52.0 ±3.0
100 −34.5 ±2.0 −28.5 ±2.0 −21.5 ±2.0 26.5 ±3.0 40.0 ±3.0 52.5 ±3.0
150 −41.0 ±2.0 −34.5 ±2.0 −27.0 ±2.5 25.0 ±3.0 40.0 ±3.0 53.0 ±3.5
22 50 −23.0 ±2.0 −17.0 ±2.0 −10.0 ±2.0 36.5 ±2.5 52.0 ±3.0 62.0 ±3.0
100 −28.5 ±2.0 −20.0 ±2.0 −13.0 ±2.0 36.0 ±3.0 53.0 ±3.5 64.0 ±3.5
150 −35.0 ±2.0 −26.0 ±2.0 −18.0 ±2.0 35.5 ±3.5 54.5 ±4.0 66.0 ±4.5
32 50 −15.0 ±2.0 −9.0 ±2.0 −2.0 ±2.0 45.5 ±2.0 59.0 ±2.0 71.0 ±2.5
100 −19.5 ±2.0 −13.0 ±2.0 −7.0 ±2.0 46.0 ±2.5 60.5 ±2.5 74.0 ±2.5
150 −25.5 ±1.5 −18.5 ±1.5 −10.0 ±2.0 47.0 ±3.0 63.0 ±3.0 78.0 ±3.5
46 50 −9.0 ±1.5 −2.5 ±1.5 +5.0 ±1.5 53.0 ±2.0 66.5 ±2.0 79.5 ±2.0
100 −13.5 ±1.5 −6.5 ±1.5 −1.5 ±2.0 54.5 ±2.5 69.5 ±2.5 83.5 ±2.5
150 −20.0 ±1.5 −12.0 ±1.5 −3.5 ±2.0 56.5 ±2.5 74.0 ±3.0 90.0 ±3.5
68 50 −2.5 ±1.5 4.0 ±1.5 11.0 ±1.5 61.0 ±2.0 75.0 ±2.0 88.0 ±2.0
100 −7.5 ±1.5 0 ±1.5 8.0 ±1.5 64.0 ±2.5 79.5 ±2.5 94.5 ±2.5
150 −14.0 ±1.5 −6.0 ±1.5 3.5 ±1.5 67.5 ±3.0 86.0 ±3.0 103.0 ±3.5
100 50 3.0 ±1.5 9.5 ±1.3 17.5 ±1.5 67.0 ±2.0 83.0 ±2.0 96.5 ±2.0
100 −2.0 ±1.5 6.0 ±1.5 14.5 ±1.5 70.5 ±2.5 89.5 ±2.5 105.0 ±3.0
150 −8.0 ±1.5 0.5 ±1.5 10.0 ±2.0 76.0 ±3.0 98.5 ±3.0 107.0 ±4.0
a
For oils with Newtonian characteristics at low temperatures and sufficiently low cloud and pour points; temperature tolerances refer to
upper and lower ISO viscosity range.
b
Wear-free operation can generally be expected above 10 mm2 / s
c
Includes ISO viscosity tolerance of ±10 %.
higher operating pressures, and smaller sump reservoirs. above the ambient temperature. At this temperature, the hy-
The increase in operating temperatures causes fluids to de- draulic fluid must have a working viscosity of 13– 16 mm2 / s
grade rapidly. This requires the use of longer lasting anti- 共13– 16 cSt兲, which must not drop below 10 mm2 / s, so as to
wear additives, oxidation inhibitors, rust and corrosion in- avoid wear. However, in high-pressure systems 共above
hibitors, foam inhibitors, demulsibility additives, and other 400 bars兲, the working temperature is higher by about 10 ° C
chemical components. Conventional additives lack the abil- than that in the low pressure-systems; hence the working vis-
ity to retain performance over the duration of the intended cosity of about 25 mm2 / s is recommended. Since the re-
service. This is because the established hydraulic fluid speci- quired viscosity range is also a function of the pump used;
fications are not enough to ensure adequate protection of the the gear pumps usually require a working viscosity of at least
equipment during use, since they define the lubricant’s mini- 20 mm2 / s. It may even be necessary to install a cooling unit
mum performance quality. That is why the industry gener- to minimize the heat-related viscosity loss and maintain the
ally requires tests that are more consistent with the modern viscosity in the optimal range. Consideration of maximum
equipment’s performance needs. Some fluids suppliers use viscosity is also important since the start-up temperature af-
modified industry tests and proprietary tests to assess the ter prolonged inactivity is quite low and the fluid will have
quality of their fluids. These tests deal with the fluid’s much higher viscosity than at higher operating tempera-
thermo-oxidative properties, foaming, and air entrainment tures. Maximum intake 共start-up兲 viscosity guidelines are as
tendency 关592兴. follows:
One way is to design fluids whose viscosity matches the 1. Gear pumps—2000 mm2 / s 共2000 cSt兲
viscosity needs of the hydraulic components. This is critical 2. Piston pumps—1000 mm2 / s 共1000 cSt兲
because the viscosity changes with the operating tempera- 3. Vane pumps—500– 700 mm2 / s 共500– 700 cSt兲
ture and the fluid must provide proper lubrication over the The start-up and the working viscosities of the hydraulic
operating temperature range of the equipment. Therefore, it fluids belonging to different ISO viscosity grades and having
must meet both the minimum and the maximum tempera- different viscosity-temperature 共VI兲 characteristics are
ture needs of the hydraulic system components. Otherwise, shown in Table 7.32 关4兴. Commercial mineral oil fluids have
wear will ensue. The other way is to test the durability of the VIs of about 100. Hence, the working viscosity between 10
fluid by extending the duration of the current standard and 25 cSt in the 20 to 80 ° C temperature range and maxi-
pump tests and or run the tests at higher temperatures 关614兴. mum start-up viscosity of between 500 to 2000 cSt are of in-
The viscosity requirements of a hydraulic fluid depend terest. Considering the data presented in Table 7.32, ISO VG
upon a number of factors. For conventional systems, these 15 has the limiting working viscosity of 10 cSt around 54 ° C
include the working temperatures and the type of pump be- and working viscosity of 25 cSt 28 ° C; ISO VG 22 has these
ing used. The working temperature of a stationary hydraulic between 38 and 66 ° C, ISO VG 32 has these between 48 and
system for low or moderate pressures is usually 40 to 50 ° C 75 ° C, and ISO VG 46 has these between 56 and 85 ° C. Of
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CHAPTER 7 䊏 HYDRAULIC AND TRANSMISSION FLUIDS 363
course, none of these grades exceed the maximum viscosity provers, used to make the multi-grades, can hinder air sepa-
requirements, except at very low temperatures. Hence, for ration from the fluid. In addition, the viscosity-improving
most applications, ISO VG 32 and ISO VG 46 work well. polymers can lose their efficiency over time due to the high
However, for very low-temperature operations, the lower vis- shear rates and turbulent flow conditions that are often
cosity grades are better, and for very high temperature appli- present in hydraulic systems. A guideline for selecting a high
cations, higher viscosity grades are better. Since the higher VI or multi-grade fluid is to increase the hydraulic compo-
viscosity indices expand the operating temperature range, nent manufacturers’ minimum permissible viscosity values
the use of the very high VI oils and or the viscosity modified by 30 %, which is to compensate for the viscosity improver’s
oils can be beneficial in some applications. shear-related viscosity loss. If the hydraulic system has a nar-
It is important to recognize that under high pressures, row operating temperature range, choosing the optimum
the oils decrease their volume, hence increase their viscosity; fluid viscosity based upon mono-grade oil will work.
the viscosity increase being greater for naphthenic oils than
for paraffinic oils. However, the pressure must be greater Formulation Examples
than 200 bars, below which its effect on viscosity is minimal.
This implies that in high pressure applications, naphthenic Tractor Hydraulic Fluid: 4.0–6.0 % Basic metal sul-
oils will offset the temperature-related viscosity loss by gain- fonate detergent, 0.5–1.5 % zinc dialkyl dithiophosphate an-
ing viscosity because of the high pressures. In addition, the tiwear agent, 0.5–1.5 % hindered phenol oxidation inhibitor,
naphthenic oils have good low temperature properties 共low 0.3–0.5 % benzotriazole metal deactivator, 0.3–0.5 % long-
pour points兲, which permit their use in applications where chain organic acid derivative friction modifier, 0.1–0.5 %
the paraffinic oils that have higher pour point cannot be polymethacrylate pour point depressant, 200– 250 ppm me-
used. thyl silicone foam inhibitor, and 0–4.0 % olefin copolymer
Tables 7.33 and 7.34 provide minimum permissible viscosity modifier. The balance is the mineral base oil.
needs and minimum optimal needs of the various hydraulic Mineral Oil Hydraulic Fluid 共Ash-producing兲: 0.3–0.8 %
components 关613,614兴. The selection of correct fluid viscos- Primary alkyl and aryl zinc dialkyl dithiophosphate anti-
ity requires the knowledge of the equipment’s lowest operat- wear agent, 0.25 % hindered phenol oxidation inhibitor, 0.2–
ing temperature and the highest operating temperature. If 0.5 % calcium sulfonate corrosion inhibitor, 0.02–0.03 %
the operation is in winter-like conditions, the use of a multi- benzotriazole metal deactivator, and 50– 100 ppm methyl
grade oil is appropriate. This will permit flow at freezing silicone or 500– 1000 ppm polyacrylate foam inhibitor. The
temperatures and ensure maintenance of suitable viscosity balance is mineral cabe oil.
at high temperatures, to provide proper lubrication. Optimal Mineral Oil Hydraulic Fluid 共Ash-producing兲: 0.3–0.8 %
viscosity range for the all-temperature operation is between Stabilized zinc dialkyl dithiophosphate antiwear agent,
25 and 36 cSt. While the use of the multi-grades may reduce 0.01–0.12 % basic metal sulfonate detergent, 0.01–0.1 % neu-
the power consumption, the presence of the viscosity im- tral calcium sulfonate demulsifier, 0.1 to 0.25 % hindered
phenol oxidation inhibitor, 0.2–0.5 % calcium sulfonate cor-
rosion inhibitor, 0.02 to 0.08 % alkenylsuccinimide dispers-
TABLE 7.34—Typical minimum viscosity values ant, 0.02–0.08 % benzotriazole metal deactivator, and
for hydraulic components †614‡. 50– 100 ppm methyl silicone or 500– 2000 ppm polyacrylate
Minimum Permissible Minimum Optimum foam inhibitor. The balance is mineral base oil.
Component Viscosity „cSt… Viscosity „cSt… Mineral Oil Hydraulic Fluid 共Ash-free兲: 0.5–0.8 %
Vane 25 25 Sulfur-phosphorus antiwear agents, 0.01–0.1 % polyethoxy-
External Gear 10 25 lated phenol demulsifier, 0.1 to 0.25 % hindered phenol oxi-
Internal Gear 20 25
dation inhibitor, 0.1–0.2 % alkylated diphenylamine oxida-
Radial Piston 18 30
tion inhibitor, 0.2–0.5 % fatty amine corrosion inhibitor, 0.02
Axial Piston 10 16
to 0.08 % alkenylsuccinimide dispersant, 0.02–0.08 % ben-
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364 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
zotriazole metal deactivator, and 50– 100 ppm methyl sili- 7. Particle count
cone or 500– 2000 ppm polyacrylate foam inhibitor. 8. Mineral oil content
Mineral Oil Hydraulic Fluid 共Ash-free R&O plus Anti- 9. Electrical resistivity
wear Performance兲: 0.3–0.5 % Trialkyl or triaryl thiophos- 10. Elemental spectroscopy
phate 共phosphorothionate兲, 0.2–0.4 % trialkyl mixed ester of 11. Foaming
dithiophosphoric acid, 0.02–0.05 % ethoxylated fatty amine 12. Air release properties
salt of dialkyl dithiophosphoric acid, 0.1 % Arylamine anti- If a parameter is trending out of specification, it is pru-
oxidant 0.5 % phenolic antioxidant, 0.1 % benzotriazole dent to take corrective action. Stabilizing the acid number
metal deactivator, 0.05 % DMTD type of metal deactivator, 共Total Acid Number, TAN兲, with its hydrolysis catalyzing ef-
and 0.05–0.1 % imidazoline or alkenylsuccinate type rust in- fect, is the most critical requirement in the ester fluids. Most
hibitor. The balance is water 共formulation extracted from turbine manufacturers allow a maximum TAN limit of
Ref 关617兴兲. 0.20 mg KOH/g in the phosphate ester fluid. Obviously, the
Oil-in-Water Type Water-based Hydraulic Fluid: 1.17 % hydrolysis of the ester fluids can also be controlled by con-
Polyisobutenyl succinic ester amide dispersing agent, 0.9 % trolling the amount of water, which is of course a challenge.
phosphate-modified diethanolamine stearic/oleic acid Controlling the water content is not only important to mini-
amide, 0.38 % zinc dialkyl dithiophosphate or metal dialky- mize the fluid degradation but also to control rusting and
ldithiocarbamate EP agent, 0.5 % ether glycol emulsifier, corrosion of the metal components of the hydraulic system.
4.8–12.5 % polyglycol thickener, 0.5 % diethylethanolamine Hence, it is important to maintain the moisture levels as low
rust inhibitor, 0.06 % benzotriazole metal deactivator and as is reasonably achievable. Some fluids are more tolerant of
silicone foam inhibitor 共formulation extracted from Ref water than others. Moisture control devices for industrial
关618兴兲. hydraulic systems are also available.
Soluble-oil Hydraulic Fluid: 0.15 % Sulfurized fat anti- Particles, if present in a fluid, not only clog small orifices
wear agent, 0.25 % alkanolamines corrosion inhibitor, 0.1 % 共which impairs flow兲 but they can also cause abrasive wear.
triazole metal deactivator, 0.02 % methyl silicone foam in- Most turbine OEMs recommend fluid ISO 4406 cleanliness
hibitor, 0.05 % triazine biocide, and 0.25 % petroleum sul- levels of 18/ 16/ 13 or NAS 1638 cleanliness level of 7. Par-
fonate emulsifier. The balance is water. ticles in the hydraulic systems originate from the usual
sources of machining debris, common in the newly ma-
Condition-Monitoring of Hydraulic Fluids chined equipment, dirt and dust from the environment, and
All hydraulic fluids must be condition-monitored to ascer- the wear metals. In antiwear hydraulic fluids, the particles
tain that there is no deterioration in properties. Otherwise, also arise from the hydrolysis-related acid corrosion and the
the fluid will lose its effectiveness and the equipment dam- interaction of the hydrolysis acids with the detergent addi-
age or failure will occur. Table 7.35 lists the fluid parameters tives, if present. In the present context, an increase in the
for various types of hydraulic fluids that must be monitored particle count is indicative of the fluid break down. However,
关613兴. Condition monitoring of the phosphate ester-derived it is important to develop effective sampling, collection, and
fluids is especially important since they are extremely expen- analysis procedures that provide meaningful data with as
sive and the loss of their structural integrity will result in a little variability as possible. Ways to remove particles in-
loss of many of their desirable properties. Hydrolysis and clude filtration and magnetic devices. Obviously, these de-
thermal degradation of the phosphate esters, two of the com- vices will need periodic cleaning or filter replacement to re-
mon problems with these fluids, result in acidic products vive them.
that catalyze further fluid degradation. With proper mainte- Transmission Fluids
nance, they can remain in service for 15 years, or more.
Condition monitoring of the phosphate ester fluids is Transmission fluids are mineral oil or synthetic-based
carried out by the use of tests that are similar to those recom- hydraulic fluids with special properties. The key functions of
mended for the mineral oil fluid condition monitoring. The these fluids are lubrication and wear control, cooling, and to
following parameters are typically examined 关619兴: act as a hydraulic medium to transmit power. These fluids
1. Color are of three types: Automatic transmission fluids, manual
2. Appearance transmission fluids, and power transmission fluids. There is
3. Viscosity no official API classification system for these fluids. Perfor-
4. Acidity/acid number/neutralization number mance requirements for transmission fluids are primarily
5. Chlorine content established by the OEMs 关620兴. The most important features
6. Water content of these fluids are their frictional consistency 共durability兲
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CHAPTER 7 䊏 HYDRAULIC AND TRANSMISSION FLUIDS 365
and frictional compatibility with the transmission’s compo- such lubricants, widely available engine oils and mineral oils
nents. In automatic transmissions, such components in- were used. This practice continued until 1949 when GM in-
clude clutches and bands, and in manual transmissions and troduced its first specification for these fluids 关181–183兴. Re-
manual transaxles, they include cone or plate type synchro- cently, another type of transmission is being introduced in
nizers. Unlike automatic transmissions, which use transmis- the market place. These transmissions are called Continu-
sion fluids recommended only by the OEMs, manual trans- ously Variable Transmissions, or CVTs. Despite the advan-
missions use a wide variety of fluids. Such fluids include tages of the CVTs, the Hydra-Matic transmissions still oc-
automatic transmission fluids, engine oils 共5W-30兲, some cupy the largest share in the U.S. cars and SUVs.
gear lubricants, and a variety of specialty fluids. In addition
to frictional properties, certain OEMs require transmission Automatic Transmission Fluids
fluids for their equipment to have improved shear stability, Generally, the performance of these fluids is defined by
low-temperature fluidity, and other specific characteristics. service-fill specifications of the passenger car and commer-
Passenger car automatic transmissions were intro- cial vehicle transmission manufacturers. As stated earlier,
duced in the United States in 1939. Although special lubri- the frictional compatibility of the automatic transmission
cant needs were realized as early as 1937, in the absence of fluids 共ATFs兲 with the transmission’s clutch and band system
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366 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
is their most important feature. Over the years, the ATFs MERCON® V and MERCON® LV are not interchangeable
have evolved along with the evolution of the automatic trans- 关624兴.
missions. For the present transmission fluid specifications In Table 7.37 we present physical properties and perfor-
and their suggested use, see Table 7.36 关621兴. mance requirements for DEXRON®-III and MERCON®-V
DEXRON® and MERCON® are the two major types of fluids. GM’s 2005 upgraded specification for factory-fill/
automatic transmission fluids that are presently in use in the service-fill DEXRON®-VI automatic transmission fluids is
United States DEXRON® fluids meet General Motors’ per- superior to DEXRON®-III and DEXRON®-III共H兲 regarding
formance specifications and are primarily designed for use low temperature viscosity/fluidity, oxidation resistance,
in its transmissions. MERCON® fluids meet Ford’s perfor- wear performance, and frictional durability. The new speci-
mance requirements and are used in its transmissions. fication also contains volatility, cold cranking viscosity, and
DEXRON-III®, DEXRON®-VI, and MERCON-V® fluids are shear stability requirements that were not part of the previ-
the most current specifications for the transmission fluids. ous specifications. Data in Table 7.38 provides a comparison
In response to a growing need for better fuel economy between the three DEXRON® specifications 关625兴. In addi-
and improved emissions, GM in the 1990s designed a new tion to the properties listed in these tables, some OEMs, such
transmission 关622兴. This transmission required a lubricant as Mercedes-Benz, Ford International, and certain Japanese
that had superior performance with respect to low- auto makers, require ATFs with even higher shear stability
temperature properties, oxidative stability, antiwear charac- and better low-temperature fluidity.
teristics, shift-feel smoothness, and frictional durability. As is evident from the data in the two tables, suitable
DEXRON®-III/III 共H兲 specification was introduced to frictional properties, oxidation resistance, and antiwear
qualify fluids to service these transmissions. In 2006, GM is- characteristics are the key performance parameters for
sued DEXRON®-VI specification for a new automatic trans- ATFs. These fluids must not only possess the proper fric-
mission fluid for its 2006 and later model year cars and tional characteristics but must also maintain them for a cer-
trucks equipped with Hydra-Matic transmissions. This tain number of cycles 共frictional durability兲. The frictional
specification is an advance over the other major existing ATF suitability is determined by the use of the SAE #2 Friction
specifications with respect to performance, requiring run- Test. Figure 7.4 shows a schematic diagram of the SAE #2
ning the fleet tests, and demonstrating new chemistries to be test rig.
The test consists of repeated starting and stopping of a
compatible with those that were previously approved. This
clutch pack through 20,000 or more cycles and determining
fluid upgrade over DEXRON®-III 共H兲 is to accommodate the
the degree of change in the fluid’s frictional properties. The
needs of Hydra-Matic 6L80, GM’s first six-speed automatic
clutch pack consists of multiple composite and steel disks or
transmission. The viscosity profile of this fluid is such that it
plates that alternate in a sandwich-type arrangement. Typi-
would perform more consistently in extreme conditions and
cal modern composites include Kevlar®, graphite, and paper
would degrade less over time. These fluids have better oxida-
type materials. The steel disks are splined externally and are
tive and shear stability, foam performance, and protection
held stationary in the clutch head. Composite disks are
against pitting. GM considers DEXRON®-VI to deliver more
splined internally and can be rotated by an electric motor.
than twice the durability and stability in friction tests than
The clutch pack is spun at 3600 r / min and the hydraulic
do the other existing fluids 关623兴.
pressure is applied. This pressure is generated by the use of a
MERCON® specification of 1987 was introduced by
piston. As soon as the clutch pack engages, the motor is
Ford Motor Company to meet the lubrication requirements turned off and the transferred power is recorded by the use
of the 4L60 transmissions. MERCON® fluids were required of a computer. The engagement occurs when the rotating
to have better thermal stability and improved performance composite disks are pushed against the stationary steel
in the plate clutch and cycling tests than the Ford’s previ- disks. This process is repeated the desired number of times
ously specified Type F and Type H fluids 关622兴. This specifica- 共cycles兲 over a 100 to 200-hour test period. The fluid tem-
tion underwent several revisions, the most recent of which perature is as prescribed, usually 135 or 140 ° C, and the air
occurred in 1994. Ford released MERCON® V upgrade for is blown into the clutch head at a rate of 50 mL/ minute. The
use in 1996 and later model year vehicles. The fluids meeting data generated are plotted as an XY graph, where X-axis rep-
this specification must have better shear stability, antiwear resents the lock-up time in seconds and the Y-axis represents
performance, low-temperature fluidity, oxidation resis- the torque in Newton-meters. Examples of three such graphs
tance, friction retention, and anti-shudder durability than are shown in Fig. 7.5.
that of the MERCON® qualified fluids. Previously, The parameters of interest are midpoint dynamic
MERCON® V fluids were not recommended for use in older torque, end torque, maximum torque, delta torque, and the
cars because of the backward compatibility issues. The use stop time.
of the MERCON® quality fluids was recommended for cars 1. Midpoint torque is the torque value centered half way
produced between 1981 and 1993, but for cars produced between the start of the clutch engagement and the
prior to 1981 Ford Type F fluids were to be used. It appears lockup.
that Ford has solved the backward compatibility issue since 2. End torque is calculated using the north-east corner
as of July 1, 2007, production and licensing of the torque.
MERCON® fluids have stopped and MERCON® V will ser- 3. Maximum torque is the torque value between 500 r / min
vice transmissions that previously required the use of the and the clutch lockup.
MERCON® fluids 关624兴. Recently, Ford introduced a new 4. Delta torque is maximum torque minus the midpoint
transmission fluid, MERCON® LV, intended for fill-for-life. dynamic torque.
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CHAPTER 7 䊏 HYDRAULIC AND TRANSMISSION FLUIDS 367
5. Stop time is the elapsed time between the start of the eters. Graph 共A兲 represents the ideal torque trace. Graph 共B兲
clutch engagement and the complete clutch lockup. is the torque trace of a lubricant that does not possess the
Each OEM has its own specifications for these param- proper frictional characteristics. The engagement time is
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368 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
short and the shifting is jerky, as indicated by the abrupt in- mission fluid are assessed by examining the sun gear and the
crease in torque 共rooster tail兲 prior to the clutch engagement. vane pump parts.
Graph 共C兲 represents a friction-modified lubricant. While Turbo-Hydramatic Oxidation Test 共THOT兲 is the test
the midpoint torque and the lockup time are close to what is used to determine a transmission fluid’s oxidative stability. If
desired 兵compare with graph 共A兲其, the clutch engagement is adequate oxidative resistance is lacking, the oxidation of the
sluggish indicating too much slippage. fluid over its extended use will result in products that can
The frictional characteristics of the lubricant, deter- cause corrosion as well as lead to the formation of sludge
mined by the use of SAE #2 test, simulate smooth engage- and varnish. The sludge and varnish are likely to adhere to
ment and disengagement of the clutch and proper function- the forward clutch housing, clutch piston, control valve
ing of the band and the input drum in the actual body, and oil screen components and impair their function.
transmission. The ultimate test of a transmission fluid’s fric- Figure 7.9 compares the performance of a fluid with good
tional properties is the “Shift-feel Test,” where a qualified op- oxidative stability against one with poor oxidative stability
erator judges the lubricant’s suitability under the actual ser- 关626兴.
vice conditions. The use of the ATFs is not limited to automatic transmis-
Figure 7.6 shows a cross-sectional view of a Hydra- sions. A significant amount of the total 共⬃50 % 兲 is used in
Matic transmission and Figs. 7.7 and 7.8 show the parts that nonautomotive applications, thereby making these fluids
are commonly rated. The antiwear properties of the trans- highly versatile lubricants. Nonautomotive applications in-
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CHAPTER 7 䊏 HYDRAULIC AND TRANSMISSION FLUIDS 369
clude use in power shift transmissions in off-highway con- TO-4 friction tests. Fluids meeting the Allison C-4 require-
struction, agriculture, mining equipment, automotive, in- ments are designed for equipment that has both the torque
dustrial, mobile, and marine hydraulic systems, power conversion and the automatic transmission features. Many
steering fluids, and rotary screw compressors. engine oils meeting API’s most recent service requirements
are formulated to also meet Allison C-4 and Caterpillar TO-4
Power Transmission Fluids specifications, so that they can be used both in the engine
Power transmission fluids 共PTFs兲 are used in heavy-duty au- and the transmission 共See MIL-PRF-2104H specification in
tomatic transmissions and the torque converters in off- Table 5.6兲. Allison C-4 and Caterpillar TO-4 specifications
highway equipment. Such equipment is commonly used in were introduced to address the demands placed on the PTFs
agriculture and construction industries. Viscosity and fric- due to changes in the transmission design. Caterpillar re-
tional properties of these fluids are critical to their perfor- quires the use of the straight grade fluids for its transmis-
mance. Just like the ATFs, the SAE and OEM performance sions, wet disk brakes, and final drives. Fluids meeting this
specifications are used to describe these fluids 关626兴. specification provide superior frictional properties and wear
Power transmission fluids 共PTFs兲 have a viscosity range protection. Allison C-4 specifications are presented in Table
between the SAE 5W and the SAE 50 and are classified on the 7.39 and Caterpillar TO-4 requirements are presented in
basis of their performance in Allison C-4 and Caterpillar Table 7.40.
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370 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
filled-for-life fluids. To be approved for the listing, the fluid and bearings. Frictional properties of an ATF are not only to
must meet GM’s Type A Suffix A, DEXRON®-IID, and reduce friction, which is to minimize wear, but also to in-
DEXRON®-III requirements, as well as well as the test re- crease it so as to promote engagement of clutches during op-
quirements of DaimlerChrysler. eration. Most OEMs use proprietary frictional materials;
hence each ATF type is usually designed to meet the perfor-
Transmission Fluid Composition and Testing mance requirements of the transmissions from a specific
As mentioned earlier, automatic transmission fluids perform manufacturer. In addition, ATFs must be compatible with all
many functions, which include lubrication and wear con- transmission components, operate at both low and high
trol, cooling, and to act as a hydraulic medium to transmit temperature extremes, and maintain consistent perfor-
power. Wear and frictional heat in the transmission occurs mance for extended periods. Most ATFs can withstand nor-
due to metal-to-metal contact of the friction plates, gears, mal operating temperatures of around 200 ° F 共⬃94 ° C兲 and
for tens of thousands of miles. But if the temperature of the Table 7.45 关628兴. The objective is to realize the most effective
fluid rises above 220 ° F 共105 ° C兲, the fluid starts to break formulation at a minimal cost.
down quickly. Standard ASTM tests used to analyze and test transmis-
To meet the OEM established performance require- sion fluids are listed in the SAE International Surface Ve-
ments, the transmission fluids are formulated by the use of hicle Information Report, SAE J311. Some of these are listed
mineral and synthetic base stocks of suitable viscosity and a in Table 7.46. Additives used in transmission fluids are
number of additives. Synthetic oils have superior thermo- briefly described below:
oxidative properties than mineral oil-based lubricants, but 1. Viscosity improvers to reduce the rate of change of vis-
both types need additives to attain and maintain the desired cosity with temperature. It is important to maintain the
frictional properties, minimize wear, impart oxidation resis- viscosity in-grade at high temperatures to provide
tance, and provide corrosion inhibition to the transmission proper lubrication. Styrene ester and poly共alkyl meth-
components. Synthetic transmission fluids can be designed acrylate兲 type polymers are commonly used.
by the use of the PAOs or the PAO/ester blends. Both stan- 2. Pour point depressants to improve the low temperature
dardized and the OEM tests are used to test various lubricant fluidity, especially for use in cold climate countries of
parameters. The advantage of using a synthetic fluid, such as North America and Northern Europe. Although the low
PAO, in the ATF over that of the mineral oil is demonstrated viscosity base stocks work pretty well in this regard, to
by data presented in Fig. 7.10 关87兴. The superior oxidative attain the required Brookfield viscosity at −40 ° C, min-
stability is reflected by almost no viscosity increase for PAO eral oil 共API Group I oil兲 derived ATFs are treated with
under the test conditions. On the other hand, mineral oil af- pour point depressants, such as alkylated naphthalene,
ter 16 hours experiences a sharp viscosity increase as a con- alkylated phenols, and poly共alkyl methacrylate兲s that
sequence of oxidation. THOT 共Turbo-Hydramatic Oxidation contain fatty alkyl groups.
Test兲 and ABOT 共Aluminum Beaker Oxidation Test兲 data sug- 3. Oxidation inhibitors to slow down the lubricant degra-
gest that synthetic ATFs last twice as long as the mineral oil- dation due to oxidation. Hindered phenol and its deriva-
based ATFs 关87, 627兴. Suitability of the various synthetic- tives and arylamines help minimize oxidative break-
base stocks in formulating ATFs with respect to the down of the transmission fluid.
commonly sought ATF properties are listed in Table 7.44 4. Dispersants to keep deposit precursors suspended in the
关628兴. It is important to note that besides the listed proper- bulk lubricant, to prevent their separation on hot sur-
ties, there are other factors which must also be considered faces to form sludge and varnish. Polyisobutenylsuccin-
while selecting a suitable synthetic base stock for use in the imides and polyisobutenylsuccinate esters are used to
ATFs. Those worth additional consideration are listed in accomplish this.
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CHAPTER 7 䊏 HYDRAULIC AND TRANSMISSION FLUIDS 373
Fig. 7.9—Valve body and oil screen from transmission oxidation test 关626兴.
5. Antiwear agents to protect planetary gears, bushings, 8. Seal swell agents to minimize deformation of the elas-
and thrust washers against wear. It is important for the tomer seals. These materials, usually alkylaromatics,
wear rates to remain low so that excessive loss of mate- protect elastomers seals against damage due to lubri-
rial does not cause the shift characteristics to deterio- cant attack.
rate. Common antiwear agents used include metal and 9. Foam inhibitors to facilitate the collapse of foam, when
amine salts of dialkyl dithiophosphoric acids, alkyl it forms. These additives are usually polysiloxanes 共sili-
phosphoric acids, and dialkyldithiocarbamic acids. cones兲 and alkyl acrylate polymers.
6. Friction modifiers to match the lubricant’s frictional 10. Red dye for identification purposes.
characteristics with those of the clutch plates and the
band. A poor match is reflected by the generation of Continuously Variable Transmissions „CVTs…
shudder, or vibration. Long-chain fatty materials; such Use of Continuously Variable Transmissions 共CVTs兲 in auto-
as oleic acid esters, amides, and imidazolines are used mobiles is a recent development, although the first CVT
to meet the frictional requirements of the ATFs. How- equipped car was introduced in 1958 by DAF of The Nether-
ever, too much friction reduction will cause the trans- lands. Subaru offered a CVT transmission in the Justy in
mission components not to engage. 1989, Saturn in the VUE in 2002, and Ford in the European
7. Corrosion inhibitors to protect the metal parts against version of the Fiesta in 2004. Honda also uses CVT for cer-
rust and corrosion due to acidic and oxygenated prod- tain Civic models, so does Nissan in Japan.
ucts from the lubricant oxidation, thermal degradation, A continuously variable transmission 共CVT兲 is a type of
or the sulfur-active additives. Fatty amines, alkenylsuc- automatic transmission that can change the “gear ratio” to
cinic acid derivatives, and metal salts of arylsulfonic ac- any arbitrary setting within the limits. CVTs achieve this by
ids are used to protect against rust and DMTD and triaz- the use a flexible metal belt and pulleys to constantly shift the
ole derivatives are used to protect against the yellow gear ratios. The metal belts are composed of several 共typi-
metal corrosion. cally 9 or 12兲 thin bands of steel that hold together high-
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374 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
strength, bow tie-shaped pieces of metal. These belts do not software, especially at slow speeds. This is primarily to
slip and are highly durable, reliable, and efficient, enabling please the drivers. 关629兴.
the CVTs to handle a substantial amount of torque from the CVT transmissions have been refined over the years and
engine. Incidentally, the metal belt-driven CVTs are quieter are much improved from their originals. Compared to the
than the rubber-belt-driven older CVTs. Unlike typical auto- hydraulic automatic transmissions, which at present are
motive transmissions that are constrained to a small num- used in ⬎90 % of the cars and trucks sold in the United
ber of gear ratios, such as the 4 to 6 forward ratios, CVTs do States, CVTs can smoothly compensate for changing vehicle
not suffer from this constraint. This is because they do not speeds, allowing the engine speed to remain at its level of
generally have gears and the term “gear ratio” refers to the peak efficiency. This and their smaller size and lighter weight
ratio of the engine shaft speed to the driveshaft speed. improves both the fuel economy and the engine exhaust
CVTs have a much smoother operation than the conven- emissions. The fuel efficiency advantage is between 10 and
tional automatic transmissions, which gives a perception of 20 % over the commonly used four-speed Hydra-Matic auto-
low power to many drivers who expect a jerk when they be- matic transmissions. Most CVTs are simple to build and re-
gin to move the vehicle. The jerk indicates the changing of pair. For friction-driven CVTs, their torque handling capabil-
gears and in CVTs is simulated by the use of the CVT control ity is limited by the strength of the belt or the chain and by
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CHAPTER 7 䊏 HYDRAULIC AND TRANSMISSION FLUIDS 375
their ability to withstand frictional wear between the torque its traction coefficient 共friction coefficient兲. Rolling elements
source and the transmission medium. Hence, their use was involve high contact pressures, which will flatten the sur-
confined to the low-powered cars. However, more advanced faces in the contact zone, thereby leading to adhesion and
IVTs 共Infinitely Variable Transmissions兲 that use advanced seizure. The presence of a lubricating film in the contact
lubricants can handle torque in production vehicles, such as zone prevents this from happening. The film under these ex-
buses, heavy trucks, and earth moving equipment. treme pressures becomes solid, elastically deforming metal,
Because of the size, weight, and the cost advantages, and minimizing metal-to-metal contact. However, if the fric-
and because they are easier to build and install than the tra- tion coefficient is too low, slip will occur and as a result
ditional stick-shift and automatic transmissions, CVTs are power transfer will be inefficient. The capability of transfer-
being considered as transmissions of choice for automotive ring power is described as the traction coefficient. There is a
use by many OEMs. However, the technology is still evolv- proportional relationship between the traction force and the
ing. A cross-sectional view of a CVT showing its essential traction coefficient. As a result, to increase the traction force,
parts is presented in Fig. 7.11 关629兴. a larger traction coefficient is required. CVTs require fluids
that have the highest possible traction coefficient. Such flu-
Lubricants for the Continuously Variable ids are called the traction fluids.
Transmissions „CVTs… Traction coefficient of a fluid is determined by the use of
All CVTs are considered traction drives. Traction is the fric- a twin-disc machine that uses high-speed rolling contact un-
tion between a drive member and the surface it moves upon, der high pressure of at least 300,000 psi 关630兴. Figure 7.11
where the friction is used to provide motion. Traction is ex- shows a plot of the traction coefficients of six fluids 关630兴.
emplified by a wheel moving on the road surface. In CVTs, High traction coefficient is desired since it correlates with
motion is created by the use of the pulleys and the belt or a the fluid’s ability to form an effective EHD film. Cy-
chain, or by the use of rotating rollers, as in the case of Nis- cloaliphatic hydrocarbons, such as naphthenics, are the best
san’s extroid transmission. Additional transmission parts in- and PAOs, almost linear, are the worst with respect to the
clude a vane pump, bearings, a differential gear, an oil pan, EHD film-forming ability. This is not too surprising since we
and an enclosure for these parts. already know that naphthenics and aromatics rich mineral
Traction occurs at the contact between the roller and the oils have the best and the paraffinics have the worst
shaft, a cone and a ring, between a ball and a disk, or between pressure-viscosity relationship. The paraffinic mineral oil
a toroidal element and a roller. Because of the materials in- has the next best traction coefficient, which is due to its mi-
volved and the various types of contacts the working ele- nor but significant naphthenic and aromatic content. In the
ments experience, the use of a suitable lubricant is critical to Synthetic and Natural Fluids Chapter, Chapter 3, we dis-
minimizing wear. CVTs are subjected to all lubrication re- cussed a group of hydrocarbon synthetics called multiply
gimes: hydrodynamic, elasto-hydrodynamic, mixed-film, alkylated cyclopentanes and bridged cyclohexanes. These
and boundary. Critical areas of contact include pulley- base stocks, because of their high cyclic content, are likely to
sheave contact, nutating cone/control point, and traction have even higher traction coefficients 关631兴. The finished lu-
drive/roller. A lubricant designed for use in CVTs must pos- bricant based upon these cycloaliphatic hydrocarbons did
sess the following properties: not experience a negative effect on their traction coefficients
1. Ability to control rolling and sliding friction. due to the presence of the additives. In addition, these lubri-
2. Suitable viscosity to provide hydrodynamic and elasto- cants showed excellent performance as bearings lubricants
hydrodynamic lubrication. 关630兴. These base fluids are commercially available under
3. Thermo-oxidative resistance. the trade names of Penzane® and Santotrac®. Other base
4. Foaming resistance. stocks that are extensively covered in the patent literature to
5. Corrosion protection. formulate CVT lubricants are polysiloxanes 关631–635兴. Inci-
6. Low-temperature fluidity. dentally, the traction coefficient of a DEXRON®-III fluid is
7. Extreme-pressure properties to protect against wear. only 0.03, which implies that it is not suitable for use as a lu-
8. Protection against fatigue wear, if possible. bricant in CVTs 关630兴.
9. Elastomer compatibility. The data presented in Fig. 7.12 have an important bear-
Since CVTs involve a number of rolling elements, lubri- ing in formulating lubricants for CVTs. This is because while
cants that provide elasto-hydrodynamic 共EHD兲 lubrication cycloaliphatic hydrocarbons have superior traction proper-
are greatly desired. The ability of a lubricant to form an EHD ties and low pour points, they have low viscosity indices and
film of suitable thickness can be determined by measuring inferior oxidation resistance. This implies a higher treat-
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CHAPTER 7 䊏 HYDRAULIC AND TRANSMISSION FLUIDS 377
TABLE 7.43—DaimlerChrysler listing of approved ATFs †318‡. Reprinted with permission from the
Lubrizol Corporation.
Application 236.2 236.3 236.6 236.7 236.8 236.1 236.81 236.9
Passenger Cars
Transfer Case 共4 Matic兲 ✓
Mechanical Steering Lo75 Z ✓
Power Steering ✓
Manual Transmission ✓ ✓
Automatic MB Transmission ✓ ✓ ✓ ✓ ✓
Cross Country Vehicles
Mechanical Steering ✓
Power Steering ✓ ✓ ✓
Manual MB Transmission ✓
Automatic MB Transmission ✓ ✓ ✓ ✓ ✓
Commercial Vehicles
Mechanical Steering ✓ ✓
Allison Transmission ✓ ✓ ✓ ✓ ✓
Voith, ZF Automatic Transmission ✓ ✓ ✓ ✓ ✓
W4 B035 ✓
Power Steering ✓ ✓ ✓
Hydraulic Fan Drive For Auxiliary ✓ ✓ ✓
Radiator
MB Automatic Transmission ✓ ✓
UNIMOG, MB-Trac ✓ ✓
Differential Lock ✓ ✓
Power Steering ✓
Fig. 7.10—ATF hot oil oxidation test 200 ° C—PAO versus mineral oil 关87兴.
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380 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
TABLE 7.47—Viscosities and boiling points of brake fluids based on polyglycols, required by dif-
ferent specifications.
SAE J1702f SAE J1703
Property „Arctic… Jan. 80 DOTa 3 DOTa 4 DOTa 5 ISO 4925
Kinematic Viscosity at −55 ° C 共mm2 / s兲, max. 1500 … — — 900 —
Kinematic Viscosity at −40 ° C 共mm2 / s兲, max. — 1800 1500 1300 — 1500
Kinematic Viscosity at 50 ° C 共mm2 / s兲, min. — — 4.2 4.2 — —
Kinematic Viscosity at 100 ° C 共mm2 / s兲, min. 3.5 1.5 1.5 1.5 1.5 1.5
Boiling Point according to ASTM D1120 共fresh 150 205 205 230 260 205
brake fluid兲, °C, min.
Boiling Point according to ISO 4925 — — 140 155 180 140
共“moistened” brake fluid兲, °C, min.
Ignition point, °C, min. — — 82 100 —
pH — — 7.0 to 11.5 7.0 to 11.5 — —
a
DOT= U.S. Department of Transportation.
a drop in the boiling point; see the top curve in Fig. 7.14, and blue polyglycol brake fluids since they can not be used to-
an increase in corrosive attack on metals 关4兴. Hence, occa- gether.
sional replacement of the fluid is warranted. The operating
temperature in the brake systems depends upon many fac- Shock Absorber Fluids
tors, such as vehicle design, weight, operation, and the type These fluids are used in hydraulic systems that are utilized in
of brakes. Temperatures can reach up to 150 ° C during nor- vehicles, machinery, and equipment to dampen the vibra-
mal operation and up to 180 ° C during mountain driving. tion. Such devices include shock absorbers for wheels and
They can even reach higher under high-speed driving. The dampeners for steering systems. These fluids must possess
temperatures reached in the disk brakes are lower than those good VT characteristics, proper frictional properties, ther-
reached in the drum brakes. This is because the disk brakes mal and oxidative stability, rust control, and good antiwear
are largely open and have the opportunity to be cooled by air. properties and elastomer compatibility. These fluids are ex-
Under the influence of heat, the fluid that contains water will posed to temperatures between 60 to 150 ° C, depending
lead to vapor lock due to bubble formation, the result being upon the load. The heat from these fluids is removed by the
spongy braking. As shown by the bottom curve in Fig. 7.13, air stream of the moving vehicle. Since some of the devices
for a fluid with high water content, the bubble formation oc- operate at low ambient temperatures, they must also have
curs in the normal operating temperature range, but for a good low-temperature properties. Some ATFs meet these
fluid of low water content it occurs at temperatures that are criteria and can be used in this application. The shock ab-
well outside this range. Silicone fluids are well suited for use sorber producer and the OEMs jointly establish perfor-
in brake systems because they are chemically inert, have ex- mance criteria for these fluids.
cellent viscosity-temperature properties, and good oxidation Typical properties of the shock absorber fluids of vari-
stability and elastomer compatibility. Silicone fluids are ous viscosities are provided in Table 7.48 关4兴. These fluids
marked with a different dye so as not to mix them with the employ naphthenic oils because they have good low-
Fig. 7.13—Effect of water content on the low-temperature viscosity of polyglycol brake fluids 共DOT 3兲 关4兴.
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CHAPTER 7 䊏 HYDRAULIC AND TRANSMISSION FLUIDS 381
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MNL59-EB/Mar. 2009
8
Gear Lubricants
IN THIS CHAPTER WE DISCUSS GEAR LUBRICANT machinery, blowers, feeders, rubber and plastics processing
technology. We deal with the topics of gear types, gear met- equipment, sugar manufacture, rolling mills, food industry,
allurgy, and types of gear damage. An understanding of all elevators, conveyors, compressors, and others. However,
these subjects is important to formulating a suitable gear since the load in these gears is transmitted through a helix,
lubricant. Performance standards and testing of the gear the generated thrust along the axis of the gear must be
lubricants, both automotive and industrial, are also de- handled by the use of the appropriate thrust bearings. A
scribed. The chapter concludes with a number of formula- double helical gear, commonly known as herring bone gear,
tion examples. has two opposed helices and the end thrust is therefore bal-
The primary functions of a gear oil are to reduce fric- anced. With this arrangement, one of the gears must be free
tion between the gear surfaces in contact, dissipate heat, to move axially to align the two helices. Double helical gears
and provide extreme pressure protection to gears and axles have greater load-carrying capacity because at any one time
against fatigue, scoring, and wear damage, under bound- a greater number of teeth are in contact. Spur and helical
ary lubrication conditions 关12兴. In automotive applications, gears can take several forms. They can be external or inter-
the gear lubricant must also minimize shock and the noise nal, depending if the teeth are inside or outside the gear di-
resulting from the motion of the meshed gears in the rear ameter. Most planetary gear sets use a combination of inter-
axles, thereby providing a smooth and quiet operation dur- nal and external gears, as is shown in the figure of the
ing acceleration. internal spur gears. Spur and helical gears generally operate
on parallel shafts, as shown in the figure of the helical gear.
Gear Types Bevel gears are cut to produce teeth as truncated cones.
Gears are mechanical devices that help transfer rotating mo- The shafts in bevel gears are not parallel but intersect. While
tion and power from one part of a machine to another. In me- bevel gears are made for any included angle between the
chanical equipment, gears are used for increasing and de- shafts, the most common shaft angle is 90 degrees. The teeth
creasing torque, changing speed, or changing direction of on bevel gears can be straight, helical, or spiral. In straight or
movement. When two gears mesh or run together, the larger simple bevel gears, the teeth are straight and radiate from
gear is called the ring gear and the smaller gear is called the the points of the cones. The gears in these gear sets are of
pinion gear. Because of the differences in design, each gear equal size. A helical bevel gear is a toothed gear in an angular
type places different demands on the lubricant. Different design. Spiral bevel gears have spiral angles, which results in
kind of gears and gear arrangements that are used in auto- certain performance improvements. The contact between
mobiles and industry are shown in Fig. 8.1 关12兴. the teeth starts at one end of the gear and then spreads across
Spur gears, shown in the top part of the figure, are the the whole tooth. In all types of bevel gears, the shaft must be
simplest. They are of three types: external, internal, and rack perpendicular to each other and be in the same plane. Since
and pinion. All have straight teeth that are cut parallel to the spiral bevel gears have curved teeth that are at an angle to the
axis on a cylindrical surface. Because only one set of teeth is radial lines, the area of contact increases, which also in-
in contact at any one time, the load-carrying capacity of creases their load-carrying capability. In addition, these
these gears is limited. They are most commonly used in in- gears are quieter in operation at all speeds. Bevel gears are
dustrial machines that operate at moderate speeds and used in locomotives, marine equipment, automobiles, print-
loads. Applications include construction equipment, ma- ing presses, power plants, and steel plants. Spiral bevel gears
chine tools, indexing equipment, multi-spindle drives, roller can handle high speeds, high loads, and an extremely large
feeds, and conveyors. They are not used in automobiles be- number of load cycles and are used in rotorcraft drive sys-
cause they produce sound when the teeth of the two gears tems to redirect the shaft from the horizontal gas turbine en-
move against each other, which also increases stress on the gine to the vertical rotor. They are also used in power win-
gear teeth. dows and power seats. They are used where speed and
Helical gears are a modification of the spur gears in that strength are desirable, along with the change in angle of the
the teeth are cut at an angle to the axis of rotation, i.e., they power flow.
are twisted in a helix. This allows more than two teeth to be Worm gears are used where the shafts are at right angles
in contact at a time, thereby increasing their load-carrying and have maximum offset. The long gear is the worm, or the
capacity. Because of this and the fact that they run smoothly pinion gear, and the round gear is the wheel gear. The wheel
and quietly, even at high speeds, and are durable, helical gear has a large number of teeth, typically 359 or 360, which
gears are extensively used in high speed transmissions. Po- mesh with a single tooth, spirally wrapped around the worm
tential industrial uses of these types of gears are in textile gear face. For one full rotation of the worm, the gear will ro-
382
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CHAPTER 8 䊏 GEAR LUBRICANTS 383
tate 1 / 359 共or 1 / 360兲 of a revolution and thus drive the right characteristics of both the spiral bevel gears and the worm
ascension axle the same amount. The worm gear is always gears. However, their pinion, or the axle, is offset so that its
used as the input gear. The worm gear and the worm shaft axis does not intersect the gear axis. This design provides
are supported by antifriction roller bearings. The torque is these gears with very high load-carrying capacity and qui-
applied to the input end of the worm shaft by a driven eter operation. The axle offset permits the lowering of the
sprocket or an electric motor and the resulting motion drives drive shaft, which promotes their use in automotive applica-
the ring gear. Because the concave faces of the worm gear tions. Tooth-contact conditions of the hypoid gears are con-
tooth fit the curvature of the worm gear, it provides a line siderably more severe than those of the spur, bevel, and heli-
contact, instead of a point contact. These gears can provide a cal gears in that the offset of the axes introduces additional
high angular velocity between nonintersecting shafts at right sliding between teeth. This, along with the high loads attain-
angles and are capable of transmitting high tooth loads. able, creates an extreme lubrication environment. Because
Hence, they provide the ultimate power ratio. Their main of the increased areas of contact and sliding, these gears are
disadvantage is that they experience high friction due to the difficult to lubricate. Worm gears, described earlier, can be
maximum sliding and extensive contact. Their use in high- considered an extreme type of hypoid gear since they have
torque applications results in extensive wear of the gear the maximum offset possible. Because of this, they have even
teeth and erosion of the restraining surface. Proper lubrica- greater contact and sliding and are therefore more difficult
tion of these gears is therefore a challenge. Worm gears are to lubricate than the hypoid gears.
widely used in packaging machinery, material handling, ma-
chine tools, indexing, and food processing. They are also Gear Metallurgy
used in Torsen® differentials that are used in some high-
performance cars and trucks. Modern gears are made from a variety of materials rang-
Hypoid gears resemble spiral bevel gears and have the ing from steel to plastics. For gears used for power transmis-
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384 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
sion, steel is often the best material, since it is strong and such as bronze, which is 90 % copper and 10 % tin, is the
relatively inexpensive. Any deficiencies, if they emerge, are most commonly used nonferrous alloy. The desirability of
corrected by the use an effective lubricant. However, for bronze as gear material is due to its excellent corrosion resis-
some types of gears, such as worm gears, where extensive tance and the ability to withstand high sliding loads. Hence,
metal-to-metal contact results in extensive wear, the main it is quite useful in making wheel gear in worm gear set that
goal is to use material that is largely wear resistant since a predominantly involves sliding motion. Other nonferrous al-
lubricant may not provide the necessary protection. loys are also employed in forming gears through die-casting.
If steel is being used to manufacture gears, it is impor- Such gears are used in small mechanisms where only moder-
tant to consider its carbon content since it determines the ate power-transmitting capacity and life are desired.
steel’s hardness. The best steel has the carbon content of 0.8 Nonmetallic gears are used in systems where low noise
%. It provides maximum hardness after heating and quench- is desired. Noise is a consequence of the inaccuracies in
ing. Small quantities of steel alloying elements, such as chro- tooth profile and spacing. Low-modulus materials, such as
mium, manganese, nickel, and molybdenum, are added to polyethylene, polystyrene, Nylon® and Teflon® are used to
modify the steel’s response to heat treatment. Since ex- make these gears. In many cases, it is possible to obtain load
tremely hard metals are not easy to machine, many times it is capacity that is comparable to that of the metallic gears. The
desirable to form the part, in this case the gear, from ductile load capacity is even higher for nonmetallic gears that mesh
metal and then heat treating or chemical treating it to with metallic gears and most of these require little or no lu-
achieve the desired degree of hardness. However, it is impor- brication.
tant to note that unhardened steels may work harden, de- Surface finish and the surface coating, while not directly
pending on their chemical composition. Chemical composi- related to the topic being discussed here, do influence the
tion also influences the wear properties. For example, wear properties of the finished gears. A number of methods
stainless steel and nickel-alloyed steel gears show poor scor- are available for the finishing step and include grinding,
ing properties, but the presence of chromium and molybde- shaving, hobbing, broaching, and casting. With respect to
num appears to improve them. Nitriding also appears to finish, grinding is the most accurate and casting is the least
help. Nitriding is a surface-hardening heat treatment that in- accurate. Selection of a finishing method depends upon the
volves introducing nitrogen into the surface of the steel at a objective. Too high a surface roughness will lead to scoring
temperature of 500– 550 ° C or 930– 1020 ° F. The use of the and wear damage, at least initially, but after the break-in, the
hardened-steel gears is predominant since hardening does surface finish becomes the same, irrespective of the initial
improve wear resistance. For a maximum benefit, it is im- finish. In the worm gear sets, where different materials are
portant to harden both the gear and the pinion to achieve a used for the ring gear and the worm gear, the use of harder
similar degree of hardness, although sometimes hardening and finely finished worm gear prolongs the life of the gear
the pinion only provides the best wear results. Cast iron, set. Another technique that is used to improve wear and scor-
which is also used to produce gears, has a carbon content of ing resistance of the gears is surface coating. Easily remov-
2.5 to 4.0 %. Some of the carbon is in the free form and the able sacrificial coatings, whether of soft metal or hard
rest is in the combined form. Free carbon, which is in graph- chemical, produced by physical or chemical means, have
ite form, reduces the metal’s strength, ductility, and elastic- been attempted. There is some evidence in favor of their
ity, but imparts cast iron the abilities to self-lubricate and short-term effectiveness, but their long-term effectiveness is
dampen vibration. Sintered-iron gears are formed from iron doubtful. This is not too surprising since such surface films
powder by compacting in a die, then heating in a furnace to quickly wear off during service. Table 8.1 shows surface
fuse the particles together. Copper powder is often mixed in roughness as a function of the machining technique.
to improve the bonding of the iron particles. This technique Lubrication requirements for different types of gears
is usually used to make small spur gears by the use of a die. are related to their load-carrying capacity, which in turn de-
The advantages are the ability to make gears with good wear pends upon the area of contact. The higher the area of con-
resistance and to mix in a solid lubricant to make them self- tact, the higher is the load-carrying capacity, and hence the
lubricating. more demanding the lubrication requirements. Spur gears,
Gears are also made from nonferrous metals. Copper is with the lowest load-carrying capacity, are at the one ex-
too soft a material to be used to make gears, but its alloys, treme and the hypoid gears, with the highest load-carrying
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CHAPTER 8 䊏 GEAR LUBRICANTS 385
capacity, are at the other extreme, with respect to the lubri- ther due to abrasive particles in the oil or rubbing of the sur-
cation requirements. The lubrication requirements for other faces with the scuffing-derived transferred material.
types of gears fall in between. Continual wear of tooth roots weakens the gear until it
breaks. Wear typically occurs under boundary and mixed lu-
Gear Failure brication conditions, where the lubricant film thickness is
not suitable to separate the tooth surfaces. The presence of
Gear Failure Modes the antiwear additives will help prevent this type of damage,
Metal gears fail for a number of reasons. Some are related to by forming a durable chemical protective film.
gear design and manufacture and others are due to service-
related factors. Common gear failure modes are fatigue
共bending and Hertzian兲, pitting and micro-pitting, scuffing, Gear Diagnostics
and wear 关640兴. Assessing in-service performance of gears has its challenges
Fatigue-related failure results in the development of since it is not always practical to stop the equipment to ex-
cracks, which under extreme situations may result in the amine the condition of gears. However, this difficulty must
separation of the tooth from the body of the gear. Pitting, not preclude the importance of determining the in-service
sometimes referred to as macropitting to distinguish it from gear condition. This is because many times corrective mea-
micropitting, is surface damage that results from the cyclic sures can be implemented if the problem is lubricant-related
contact stresses being transmitted through the lubricant or service-related. The objective of the exercise is to prevent
film which is in or near elasto-hydrodynamic lubrication re- or delay gear failure. This is because gear failure will cause
gime. Pitting is one of the most common causes of gear fail- an unexpected shut down of the machine which is both in-
ure as well as of other machine components, such as antifric- convenient and expensive. A gear system fails when it ceases
tion bearings and cams, which experience rolling/sliding to efficiently perform the function for which it was designed.
contact under heavy loads. Pitting starts with small surface This can be the result of a single catastrophic event or an ac-
or subsurface cracks that grow under repeated contact load- cumulation of the initially undetected and rather innocuous
ing. When such cracks reach the tooth surface and intersect, events that may have occurred in the gear system. As stated
a small amount of material is lost from the surface, leaving previously, common modes of gear failure are macropitting,
behind a pit. If pitting damage is significant, vibrations and micropitting, scuffing, tooth wear, and breakage.
noise will be evident. This type of failure occurs in both Gear diagnostics is a set of new techniques, the objective
through-hardened and surface-hardened gears. Micropit- of which is to identify factors and events, which may appear
ting, a related type of failure, is the formation of the much innocuous or are hard to detect, or both. Once they are iden-
smaller craters on the tooth surface than those observed tified, attempts are made to correct the damage or slow
from pitting. In both cases, the removed material can cause down its rate to prevent or delay catastrophic failure. An en-
abrasive wear. However, the abrasive wear more often ac- gineer has many options to choose a diagnostic technique,
companies micropitting than macropitting. As a conse- such as thermal imaging, oil analysis, wear metal analysis,
quence, engineers incorrectly identify micropitting damage vibration analysis, etc. Of these, vibration and noise mea-
as abrasive wear. Micropitting is tooth surface or subsurface surement and analysis, alternatively called mechanical sig-
damage resulting from rolling/sliding contact fatigue, where nature analysis, is one of the most common techniques used
fatigue arises from repeated normal and tangential loads in a 关641,642兴. Mechanical signature analysis is a process of
boundary or mixed-film lubrication regime. monitoring the vibration signatures of the operating equip-
Scuffing, sometimes called scoring, is a severe type of ment or its components to determine their condition. The
adhesive wear, which damages the tooth surfaces that are in technique may also be used to diagnose the cause of a prob-
relative motion. Scuffing welds unprotected surfaces that lem. Signature deviation of the various parts of the equip-
are in metal-to-metal contact together. Due to motion, metal ment is compared to a baseline signature in the observed do-
particles detach and transfer from one or both meshing main, to identify a potential problem. Many statistical
teeth. During successive rotations, these particles can techniques help facilitate the collected data analysis and in-
scratch teeth flanks in the sliding direction. This type of terpretation. These are listed in Refs 关643,644兴. It is impor-
damage generally occurs in areas of high contact pressure tant to note that vibration harmonics-based diagnostic-
and sliding velocity that are far from the pitch surface. This methods for fault detection in gear-type couplings with
is because the conditions in these areas do not allow effective defects and slow-speed gears do not always work satisfacto-
lubricant film formation to prevent the direct metal-to-metal rily 关645兴.
contact. Protective film may either be a thick oil film 共greater In addition to vibrational analysis, other techniques
than the surface roughness兲 as a consequence of high lubri- used to assess in-service gear performance include monitor-
cant viscosity or an adsorbed or chemically formed film es- ing temperature 关646兴 and identifying wear metals in oil and
tablished by the lubricant additives. Scuffing damage is re- on oil filters 关647兴. A greater than expected temperature rise
lated to lubricant and lubricating conditions and not to and the presence of wear metals are also indicative of either
material strength. Scuffing commonly occurs when the a potential or a real problem. Depending upon the results
gears are new and hence tooth surfaces are not well run-in. from these techniques, one can either decide to continue
The risk of scuffing also goes up as the lubricant degrades running the equipment, or stop it to analyze surface damage
over time or becomes contaminated with metal particles or to gears and identify its cause. The latter objective is
water 关640兴. achieved by examining the gear alignment and gear tooth
Wear is a continuous, abrasive process where the mate- contact patterns and surface condition. Combining these
rial is removed from the mating gear teeth. This occurs ei- techniques with other surface analysis techniques, such as
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386 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
Scanning Electron Microscopy 共SEM兲 关648兴, will help clarify Mechanical Factors
the nature and root causes of the gear damage. Besides com- These factors relate to metallurgy, forging, cutting, grinding,
mon gear failure modes discussed above, another mode of and finishing of the gears. Many advances have been made in
gear failures which is worth mentioning is the gear overload. gear design, manufacturing capabilities, and materials tech-
Gear geometry data assist in estimating tooth bending nology. These pertain especially to very large gear sets and to
stress, contact stress, lubricant film thickness, and gear technology related to the improved steel hardness
tooth contact temperature, based on the transmitted loads. 关640,651,652兴. The result is an increase in durability of 100
Typical values can be calculated according to ANSI/AGMA %, or higher, and an increase in strength of over 50 % 关653兴.
2001 and AGMA 925 standards. These can be compared with Similarly, greater tooth accuracy of the pinions and gears is
AGMA’s allowable values to help determine risks of bending significantly improved. In this regard, the positive influence
of the American National Standards Institute/American
fatigue, micropitting, macropitting, wear, and scuffing.
Gear Manufacturers Association 共ANSI/AGMA兲 rating stan-
Light microscope is also useful for confirming the failure
dards, such as ANSI/AGMA 1103-H07 and ANSI/AGMA
mode, identifying the origin of a fatigue crack or disclosing a
1003-H-07 cannot be underestimated 关654兴.
material flaw such as a nonmetallic inclusion 关649兴. If neces-
sary, SEM may also be used. SEM uses energy dispersive Operation-related Factors
X-ray which helps in identifying corrosion, contamination, Figure 8.2 shows the effects of load 共torque兲 and speed on the
and inclusions 关648兴. Other nondestructive tests that can be types of gear failures 共wear, scoring, pitting, fatigue spalling,
used to detect material or manufacturing defects include the and tooth breakage or fracture兲 identified above. The exhibit
following: identifies the load-speed combinations leading to these types
1. Measuring surface hardness and roughness of gear damage 关647,655兴.
2. Looking for magnetic particles Wear and scoring are two forms of adhesive wear. Wear
3. Determining gear tooth accuracy reduces the tooth thickness and can change the contour of
Destructive tests include: the teeth. Wear initiates at slow equipment speed and low
1. SEM microscopy to study fracture surfaces torque and progressively increases with an increase in load,
2. Determination of nonmetallic inclusions as is shown to the left of the overload wear curve in the slow
3. Micro-hardness survey speed section of the figure. At slow speeds, the formation of a
4. Micro-structural determination using acid etches continuous lubricant film is difficult because only a small
5. Determination of grain size amount of the lubricant is available in the contact zone.
Data from these evaluations ought to provide reason- However, higher speeds facilitate the formation of partial,
able insight into the probable mode of the gear failure. mixed, or full lubricant film, i.e., there is partial metal-to-
metal contact or the film is thick enough to prevent metal-to-
metal contact; which will minimize wear. Viscosity and tem-
Causes of Gear Failure perature, with its effect on viscosity, are two additional
Durability, reliability, efficiency, and in-service performance variables that determine the integrity of the lubricant film
of a mechanical drive system, such as gears, depend on a and hence should be taken into account. High equipment
number of factors. These include factors such as design, speed, high oil viscosity, and low operating temperatures,
metallurgy, and mechanical integrity when they are new; op- which facilitate hydrodynamic film formation, increase the
erating variables such as speed and load; and the lubricant load that a gear set can handle without failure. In other
quality 关639,649,650兴. words, these factors increase both the slope of the wear line
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CHAPTER 8 䊏 GEAR LUBRICANTS 387
and the dimensions of the no-wear region. The use of the rience these types of failure decreases. This is shown in the
extreme-pressure additives produces the same effect. This figure by the gentle drop in the slope of the pitting and break-
type of wear is apt to occur in high-ratio gear sets, such as age lines with increasing speed. While improved gear design
worm gears, that operate at slow speeds. An increase in and material hardness are used to minimize this kind of
speed will shift the wear regime to the right of the scoring or wear damage, chemical additives also help to some degree.
the scuffing line. Scoring, or scuffing is the wear damage to
gear surfaces at high equipment speeds, shown in the high Lubrication-related Factors
speed region of the figure, and is a consequence of the oil- Gear lubricants are designed to perform in all three types of
film failure due to high temperatures that arise from sliding lubrication environments, that is, boundary, mixed film, and
of the tooth surfaces across the oil film. This causes tooth full film. Boundary lubrication occurs when the gear sets
surfaces of the two mating gears to rub against each other start or stop. When the gears are operating at slow speeds,
and weld. It is the shearing of the welds at high equipment they are in mixed lubrication regime and when they are oper-
speeds that leads to scoring. Since scoring roughens the ating at high speeds, they are in full film lubrication regime.
tooth surfaces, it further increases the wear rate. The regions Of course, the introduction of pressure or load into this
of the gear teeth affected are between the pitch line and both equation alters the nature of the lubrication. For example,
the gear root and tip. Scoring usually causes damage to high loads on gears operating in full film regime will change
many teeth simultaneously, which results in a large volume the lubrication regime to mixed film and the higher loads for
of wear debris. Because of the thermal origin of scuffing, oxi- those operating in the mixed film regime will alter the regime
dation of the metal surfaces to metal oxides also takes place. to boundary, see Fig. 8.3. For a detailed discussion on lubri-
The degree of oxidation depends upon the lubricant and the cation regimes, refer to the Chapter 4 on Additives.
severity of scuffing. Since high speeds generate greater heat, The fluid film under boundary conditions is negligible
the load required to initiate the scoring failure is lower than and the metal-to-metal contact is extensive. If the gears are
that to initiate wear failure. Scoring can be minimized by im- operated under these conditions for extended periods, with-
proving the gear design and by using high viscosity lubri- out adequate protection, rapid and severe wear damage will
cants and chemical additives, such as friction modifiers and occur. Protection in this type of environment is provided by
extreme-pressure agents. the extreme-pressure/antiwear additives. These are ther-
Above the pitting and fatigue spalling line, wear prima- mally labile organo-sulfur and organo-phosphorus com-
rily depends upon the strength of the gear material and not pounds that form protective chemical films on metal sur-
because the lubricant film is inadequate. In reality, the wear faces. These films protect the metal surfaces against the
damage occurs due to the load being transmitted through scoring damage. In mixed film lubrication environment,
the oil film, and if the load is high, fatigue particles result there are zones of metal-to-metal contact and zones where
from the gear pitch line. However, if the load is excessive, metal surfaces are well separated by a lubricant film of ad-
tooth breakage may occur. The quality of the lubricant has equate thickness. Friction resulting from the contacting as-
little effect, if any, since this event primarily depends upon perities not only induces wear directly but also indirectly.
the gear material and load 关647兴. Pitting, spalling, and tooth This is because the frictional heat leads to a drop in lubricant
breakage are gear fatigue failures that occur at fairly high viscosity, which impairs the lubricant’s ability to form an ef-
loads and across all speeds. However, the load for breakage fective lubricating film. In the mixed-film regime, wear will
failure is higher than that required for pitting. Nonetheless, occur at a slower rate than in the boundary regime. The addi-
as the speed increases, the susceptibility of the gears to expe- tives that are effective in controlling the wear damage are lu-
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388 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
Fig. 8.4—Brookfield viscosity versus temperature of typical automotive gear lubricants 关656兴.
bricity agents, which are natural or synthetic fatty materials, of hydrodynamic lubrication is called elasto-hydrodynamic
and antiwear agents, which are derivatives of dialkyl dithio- 共EHD兲 lubrication. The elasto-hydrodynamic 共EHD兲 oil film
phosphoric acids and dialkyldithiocarbamic acids. Fatty is at least two to three times as thick as the composite surface
materials increase the durability of the lubricating film via roughness. The lubricant viscosity and the nature of the base
physical association or a weak chemical reaction. Antiwear fluid used to formulate the gear lubricant affect the lubri-
agents form protective chemical films in a manner analo- cant’s ability to provide this type of lubrication. Base fluids of
gous to that of the extreme-pressure agents, i.e., through high pressure-viscosity relationship, such as alkylaromatics
chemical reaction, with the difference that they do so at a or naphthenics, are the most effective. Incidentally, lubri-
lower temperature than the EP agents. cant viscosity also affects other lubrication regimes. While
Full-film, or hydrodynamic lubrication, is the optimal the high-viscosity lubricants will invariably form more du-
type of lubrication. In this case, the fluid film is thicker than rable lubricating films, they will have lower fluidity at low
the asperities of the surfaces. The result is that the film is temperatures. This will make it more difficult to deliver the
thick enough to keep the surfaces well apart, with no metal- lubricant to gears, which will experience increased wear due
to-metal contact whatsoever. However, in gear systems, this to lubricant starvation. This is especially the case in equip-
type of lubrication is not very common because of the gear ment that is operated in cold wintry environment, such as
design and the intended function of efficiently transmitting that of North America and Northern Europe. That is why,
power. Attempting to keep surfaces apart to achieve hydro- due care must be taken to select automotive lubricants with
dynamic lubrication will lower their power transferring effi- proper low temperature and high temperature viscometrics.
ciency. Effective transfer of power requires the gear teeth of Low-temperature viscosity of the gear oils is determined
one gear to mesh with those of the other gear in the gear set. by the use of Brookfield viscosity measurement 共ASTM
This produces boundary and mixed-film lubrication envi- D2983兲. Maximum temperature to attain a viscosity of
ronment when the gears are static or when they are moving 150,000 cP is reported. Figure 8.4 shows Brookfield viscosi-
slowly. However, when the gears are moving at high speeds, ties of viscosity grades that are often used in automotive gear
the lubricant is pulled into the contact zone and under pres- lubricants 关656兴. As the figure shows, the lower winter 共W兲
sure, especially in the case of heavy loaded gears, it gains vis- grades reach the required viscosity at a lower temperature
cosity to become semisolid 共grease like兲 in behavior. The than the higher winter grades. Straight grade, such as the
semisolid lubricant is quite effective in minimizing extensive SAE 140, as shown in the figure, attains the required viscos-
metal-to-metal contact; hence in minimizing wear. This type ity of 150, 000 cP at −12 ° C. It is also important to note that
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CHAPTER 8 䊏 GEAR LUBRICANTS 389
TABLE 8.2—SAE J306 and MIL-PRF-2105E „SAE J2360… viscosity classifications for automotive
gear lubricants.
when a viscosity modifier is added to a low viscosity winter the tooth surface of the hypoid gears. Pitting is the damage
grade oil, there is an increase in temperature at which the reflected by the appearance of the small irregular cavities in
required low-temperature viscosity is attained. In general, the tooth surface. These result from the removal of the small
the broader the viscosity grade, the larger is the discrepancy. areas of the surface metal. Spalling can be the last stage of
This is obvious when one compares the viscosity- pitting or it can occur without previous pitting, as in case-
temperature curves for 85W-90 and 85W-140 multi-grades. hardened gears. In the latter situation, spalling failure is sub-
The 85W-140 multi-grade attains the required viscosity at surface in origin. Pitting and spalling are a consequence of
−15 ° C to − 16 ° C and 85W-90 attains it at −18 ° C to surface fatigue and occur after an extended operation. Scor-
− 24 ° C. Compare these with the temperature of −24 ° C for ing is the displacement of the metal from one tooth surface
the straight winter grade 85W. Please note that the Brook- to another, resulting in the development of a matte 共dull兲 sur-
field viscosity 共ASTM D2983兲 requirement is for multi- face.
grades and not for single grades, see Table 8.2. In the case of Rolling, peening, rippling, and ridging arise from plastic
the mineral oil-derived gear lubricants, it is often necessary flow. Plastic flow results from overloading of the gear beyond
to add pour point-depressants to the multi-grades as well. its yield stress. Rolling and peening damage, shown in the fig-
Most commonly used automotive gear oils are of 75W-90, ure, usually occurs in gears that are made of soft materials.
80W-90, and 85W-140 viscosity grades. Rippling, also an indication of the excessive loads, is caused
While abrasion, corrosion, fatigue, and adhesion all can by shearing stresses at the metal surface and can be rem-
cause gear damage, fatigue and adhesive wear play the edied by the use of a lubricant with a lower coefficient of fric-
prominent roles. Figure 8.5 depicts the kinds of surface dam- tion. Ridging occurs when the high spots plow the contacting
age that can occur in gears as a result of inappropriate lubri- surface.
cation 关657兴. Protection against wear depends upon the quality of the
Scratching is the alteration of the tooth surface in the lubricating film. This film can be physical or chemical in na-
form of scratches of random length in the direction of slid- ture. Physical films, somewhat temporary in nature, result
ing. It either results from the hard particles that are lodged from the wetting ability of the lubricant, with or without a
between the moving surfaces or by rubbing of the asperities friction modifier. Chemical films, somewhat more perma-
of one surface against the other surface. Corrosive wear can nent, result from the reaction of the metal surfaces with
cause pitting or polishing of the metal surface and results chemicals that are present in the lubricant. Viscosity of a
from the attack of the metal surface by water or the lubri- gear oil is directly related to its film-forming ability, hence
cant. Rippling is an alteration of the tooth surface to give an load-carrying capacity; the higher the load-carrying capacity
appearance of a more or less regular pattern resembling of the fluid, the greater the protection against wear. Conse-
ripples on water, or fish scales. Ridging is the alteration of the quently, high viscosity oils minimize wear. For example, SAE
gear tooth to give a series of parallel raised and polished 140 viscosity grade lubricants allow less wear than SAE 90
ridges running diagonally in the direction of the sliding mo- viscosity grade oils 关658兴. Figure 4.96 shows the effect of tem-
tion. These ridges run either partially or completely across perature on the load-carrying capacity of a lubricant. As the
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390 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
viscosity of the lubricant drops as a consequence of the manner that facilitates explanation. In reality, though, bulk
higher temperature, its load-carrying capacity also drops metals consist of positively charged ions 共nuclei兲 immersed
and correlates with the lubricant’s film-forming ability 关397兴. in a sea of electrons 关399兴, as depicted in Fig. 8.7. That is why,
As mentioned earlier, fatigue and adhesive wear are the metals have good thermal and electrical conductivity. Dur-
two primary causes of gear failure. Adhesive wear can be ing adhesion, some of the intrafacial bonds are replaced by
considered to take place in two stages: adhesion and weld- interfacial bonds. The intrafacial bonds are coordination
ing. A representation of the two processes for ferrous 共iron兲 bonds between atoms of the same surface, and interfacial
surfaces is given in Fig. 8.6. Iron forms body-centered crys- bonds are bonds between the atoms of one surface and the
tals which are shown as two crystal lattices, each represent- other. This situation is presented in the middle part of Fig.
ing a metal surface. The bonds between the metal atoms are 8.6, where the dotted bonds show adhesion. It is important
based on coordination and are shown in the exhibit in a to note that the bond formation in metals is different from
method depends upon the tangential speed in m/s 共metres/ 2. Lubricating grease is not suitable for use under high
second兲 and the rotating speed in r/min 共revolutions per load and continuous operation. This is because the cool-
minute兲. At slow operating speeds, grease lubrication is a ing effect of grease is not as good as that of the lubricat-
good choice. For medium and high speed operation, splash ing oil and the gear sets may run at higher temperatures,
lubrication and forced circulation lubrication are more ap- which can lead to extensive wear damage.
propriate. Of course, there are exceptions. Sometimes, for 3. The amount of grease must be sufficient to ensure
maintenance reasons, a grease lubricant is used even for proper lubrication. Too little will allow wear damage to
high speed operations. Table 8.3 lists suitable lubrication occur and too much may impair proper functioning of
methods for various gear speeds 关662兴. the gears due to viscous drag and the accompanying
Grease lubrication is suitable for any gear system that is power loss.
open or enclosed, as long as it runs at slow speed. However, Splash lubrication is commonly used in an enclosed sys-
there are three considerations before selecting grease to lu- tem. The rotating gears splash the lubricant onto the gear
bricate gears. These are listed below 关662兴.
system and the bearings. For effective lubrication, a mini-
1. Grease must have a suitable viscosity, especially when
mum tangential speed of 3 m / s is required. Splash lubrica-
used to lubricate the enclosed gear systems which re-
tion suffers from several problems, two of which are oil level
quire good lubricant fluidity.
and temperature limitations. Too high an oil level will result
in excessive agitation losses and too low an oil level will not
deliver an effective amount of lubricant to lubricate and cool
the gear system. It is therefore important to monitor the oil
level during the operation to make sure that the oil level is
suitable. This is because the oil level will drop when the gears
are in motion. This problem may be corrected by raising the
static level of lubricant or by installing an oil pan 关662兴. The
temperature of a gear system may rise because of the friction
increase in gears and bearings and due to lubricant agita-
tion. Rising temperature may cause lowering of the lubri-
cant viscosity, acceleration of lubricant degradation due to
oxidation, and deformation of the housing, gears and shafts.
Fig. 8.11—Cold welding versus metallurgical welding 关660兴.
High-performance gear lubricants typically endure tem-
peratures up to 80 to 90 ° C. If the lubricant’s temperature is
expected to exceed this limit, cooling fins must be added to
TABLE 8.3—Lubrication method versus gear the gear box, or a cooling fan incorporated into the system
speed †662‡. 关662兴.
Lubrication Spur and Bevel Gears Worm Gears Forced circulation lubrication supplies lubricant to the
Method Tangential Speed „m/s… Sliding Speed „m/s… contact portion of the gear teeth by means of an oil pump.
Grease 0.1 to 6 0.1 to 4 The lubricant is delivered into the contact zone in the form of
Splash 4 to 15 3 to 10
a drop, spray, or an oil mist using compressed air. The oil
Forced Circulation 13 to ⬎25 8 to ⬎25
mist method is especially suitable for high-speed gearing.
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CHAPTER 8 䊏 GEAR LUBRICANTS 393
Forced circulation system is considered the best way to lu- these applications, the low-viscosity oils are usually ad-
bricate gears. equate. In contrast, slow speeds are associated with high
loads and long contact times. These conditions require
Selection of a Gear Lubricant higher-viscosity oils. EP additives may also be required, if
For a gear lubricant to be effective, it must not only have suit- the loads are very high 关663兴.
able viscosity but also a variety of other properties, some of Ambient and operating temperatures also influence the
which are listed in Table 8.4 关662兴. selection of a gear lubricant. Normal gear oil operating tem-
Improper lubricant use will contributes towards gear perature ranges from 50 to 55 ° C 共90 to 100 ° F兲 above am-
failure. Lubricant-related failures stem from contamina- bient temperatures. Oils operating at high temperatures re-
tion, oil film collapse, additive depletion and use of a lubri- quire good viscosity and high resistance to oxidation and
cant that is unsuitable for the application. The most com- foaming. High operating temperatures are also indicative of
mon failure is due to particle contamination of the lubricant. oils that are too viscous for the application, which was men-
Dust and wear particles are highly abrasive and can pen- tioned earlier, excess oil in the housing, or an overloaded
etrate through the oil film, causing “plowing” wear or ridg- condition. Oils for gears operating at low ambient tempera-
ing on metal surfaces. Water contamination can cause rust tures must be able to flow easily and provide adequate vis-
on working surfaces of metallic gears and eventually destroy cosity. Therefore, these gear oils must possess high viscosity
their structural integrity. indices and low pour points.
Oil film collapse will result in pitting which is due to
tooth surface and subsurface fatigue cracks resulting from Gear Lubricant Classification
metal-to-metal contact of asperities or defects. High-speed Traditionally, gear lubricants are classified into two broad
gears with smooth surfaces and good film thickness may ex- groups: automotive gear oils and industrial gear oils. This
perience pitting due to subsurface cracks. Pits are formed classification distinguishes between the types of gear sys-
when these cracks break through the tooth surface and tems they lubricate and the system’s operating environ-
cause material separation. When several pits join, a larger ments. Automotive gear oils primarily lubricate spiral-bevel
pit, or a spall, is formed. Another possible cause of pitting is gears in on-highway and off-highway truck axles, and hy-
hydrogen embrittlement of the metal due to water contami- poid gears in vehicles that include trucks and passenger cars.
nation of the lubricant. Pitting can also be caused by foreign Conversely, industrial gear oils are used to lubricate gear sys-
particles being present in the lubricant. tems in nonautomotive applications. These are predomi-
Proper oil viscosity will ensure quiet operation by keep- nantly used in industries engaged in manufacturing of one
ing the surfaces well apart and dampening the noise. If the kind or another. We will discuss the automotive gear oils
oil viscosity is too high, drag-related power losses and a tem- first, which will be followed by the discussion on the indus-
perature rise will occur. The latter will lead to increased deg- trial gear oils.
radation of the lubricant. In cold climates gear lubricants Automotive Gear Oils
must flow at low temperatures. Typically, gear oils must have Automotive gear oils are classified in a manner similar to
a minimum pour point of 5 ° C 共9 ° F兲 lower than the lowest that of the engine oils, i.e., through the SAE viscosity grades
expected temperature. The pour point for mineral gear oil is 关664兴, API service designations 关665, 666兴, U.S. Military
typically −7 ° C 共20 ° F兲 关663兴. When lower pour points are re- specifications, and the OEM performance requirements.
quired, synthetic gear oils with pour points of −40° C 共40 ° F兲 However, it is important to note that the SAE viscosity
are usually used. Gear speed is also a consideration while se- grades for gear oils are different from the SAE viscosity
lecting lubricant viscosity. High velocities are generally asso- grades for engine oils and are independent of each other, see
ciated with light loads and very short contact times. For Fig. 1.15. A numerical comparison may therefore be mis-
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394 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
thermal oxidation stability, antiwear, and seal compatibility fill oils are defined by the major car and truck manufactur-
requirements of the API specification MT-1. The new specifi- ers. Such oils have performance characteristics that are
cation defines lubricants for nonsynchronized manual critical to the satisfactory operation of a particular drive
transmissions used in buses and heavy-duty trucks. Factory- train and may include break-in, bearing preload, and limited
TABLE 8.6—Bench and axle test requirements for gear oil categories †670‡.
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396 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
TABLE 8.7—Automotive gear oil performance criteria for API GL-4, GL-5, and MT-1
categories.
slip durability. The majority of passenger cars now use a These fluids have excellent thermal stability and carefully
transaxle drive train arrangement, reducing the need for the tailored frictional characteristics to provide smooth syn-
rear axle lubricants. These vehicles are filled for life at the chronization and good shift quality. A performance area not
factory. Conventional API GL-4 lubricants are being re- addressed by the industry specifications is limited slip. Be-
placed by more specialized manual transmission fluids. cause of the hardware differences among the various
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CHAPTER 8 䊏 GEAR LUBRICANTS 397
limited-slip differentials, no standard industry-wide test is bevel axles and API GL-3 and GL-4 lubricants for cars and
available to evaluate a lubricant’s ability to prevent chatter in trucks equipped with manual transmissions. As stated
this application. Lubricant requirements, therefore, are above, most modern cars no longer need rear axle lubri-
based on performance in an individual manufacturer’s test cants.
rig or vehicle. The European OEMs use API GL-5 and MIL-L- Gear oils are tested according to methods established by
2105D to define minimum performance requirements for the American Coordinating Research Council 共CRC兲 and in
oils used in their equipment. They have the additional re- specified axles. Table 8.5 presents the API service designa-
quirements pertaining to surface fatigue, component clean- tions and Table 8.6 lists the affiliated bench and axle tests
liness, synchromesh durability, and viscometrics, depending 关670兴. Table 8.7 describes the performance criteria for GL-4,
upon their specific needs. Japanese OEMs recommend API GL-5, MIL-PRF-2105G, and MT-1 service categories. As
GL-5 lubricants for vehicles fitted with hypoid and spiral mentioned earlier, the API GL-4 quality lubricants are used
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398 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
severity applications. Greases are used when the ambient sized units, where speeds are low and the temperatures
temperatures are high and leakage is a problem. Low viscos- are normal 共30– 40 ° C兲.
ity greases are also used in some high-temperature enclosed 3. ISO 460 and 680 for gears and bearings operating in
gear applications and for the same reasons. large units, having heavy loads and moderate speeds.
Enclosed gear lubricants are used for enclosed gear sys- These can also be used in smaller units where tempera-
tems which involve long and continuous periods of opera- tures exceed 40 ° C.
tion with severe stirring and agitation of the lubricant. These
gears operate over a wide range of loads, speeds, and tem- Composition-based Classes
peratures; hence the lubricants chosen must have proper vis- R & O oils are mineral oils that contain rust and oxidation
cosity and the EP characteristics. Enclosed systems have the inhibitors to control lubricant’s oxidative break down under
advantages of low lubricant loss and the ability to use a high operating temperatures and protect the metal surfaces
wider variety of lubrication methods. These include splash, against corrosion, resulting from the attack of the metal by
spray, and oil mists. For large operations, such in steel mills, aggressive chemical species. Such species are either present
the use of a circulating oil system is more economical. Fluid in the environment or the lubricant, or result from the ther-
lubricants of medium viscosity can fulfill the needs of the mal and oxidative decomposition of the lubricant. These oils
most gear applications. For high-speed applications, heat re- in addition contain foam inhibitors and antiwear additives.
moval and flow properties of the lubricant are important. R&O oils are commonly used to lubricate high-speed single
Fluid gear lubricants are made from base oil/s of suitable vis- helical, herringbone reduction gear sets in applications
cosity and one or more additives to improve service life and that experience light to moderate loads. The effective
suitability under various operating conditions. Because of temperature range of these lubricants is −5 °F to 250 °F
the relationship of the viscosity to the load-carrying capacity 共−15 ° C to 121 ° C兲.
as well as pumpability, gear lubricant must have good low- Extreme pressure oils contain additives that provide pro-
temperature fluidity as well as a high viscosity index, to pro- tection to gears under extreme pressure, or the boundary lu-
vide protection under high-load high-temperature condi- brication conditions. These additives are usually blends of
tions. At low temperatures, the oils may be too viscous to highly surface-active sulfur and phosphorus compounds
flow, leading to lubricant starvation in certain parts, leading that reduce friction and control wear damage to the gears.
to extensive wear. This is typically a problem when the con- These lubricants may also contain inorganic solids, such as
ventionally refined mineral oil base stocks are used to formu- graphite, molybdenum disulfide, and potassium tri-borate,
late lubricants. This is because such base stocks contain as a colloidal suspension. Ideal particle size of the suspended
straight long-chain molecules, which wax out at low tem- solids must be no more than 0.5 microns. Otherwise, they
peratures to form crystalline networks. The wax networks will have the tendency to separate from the bulk lubricant.
absorb most of the oil, thereby impairing its fluidity. This These materials make physical protective films rather than
problem can be overcome by the use of the pour point de- chemical protective films and further improve the gear lubri-
pressants, as stated in the Additives chapter. The use of the cant’s load-carrying capabilities. EP oils are used to lubricate
multi-grades, which are made by adding a polymeric viscos- spur, straight bevel, spiral-bevel, and helical gears, where the
ity modifier to a low viscosity oil in automotive gear oils is loads are too high and sliding conditions moderate to high
quite common, but not in industrial gear oils. Enclosed gear for R&O oils to provide adequate protection. Some EP oils
lubricants contain other additives to improve oxidation, EP are supplemented with dispersants and detergents, which
properties, foaming, corrosion, demulsibility, and so on. make them suitable for use in hypoid axles that are exposed
Typical viscosity grades for these lubricants range from ISO to heavy loads or shock loading. Shock loading occurs when
46 to ISO 1500, but for selecting a lubricant for use, the low- heavy acceleration is followed by quick deceleration. It pro-
est viscosity permitted by the gear manufacturer should be motes scoring damage to the gear surfaces. While typical op-
used since it will minimize the energy consumption. Typical erating range for EP oils is between −20 and 120° C
viscosity grade recommendations are as follows: 共−4 to 250°F兲, some oils can perform adequately even over
1. ISO 68, 100 and 150 for gears and bearings in small, −54 to 170° C 共−65 to 338 °F兲 range. This is especially true
high-speed gear reducers and larger units where the of the oils that are based on synthetic base fluids.
temperatures are less than 10 ° C. Compounded oils contain fat, tallow, or synthetic fatty
2. ISO 220 and 320 for gears and bearings in medium- materials as lubricity agents. These materials are added to
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CHAPTER 8 䊏 GEAR LUBRICANTS 401
TABLE 8.11—Types of gear lubricants used with various gear applications †649‡.
Gear Types
the heavy cylinder oil base stocks to reduce friction. Com- earlier. Essentially, these are materials that are used to lubri-
pounded oils are suitable for use in worm gear drives, where cate large gear sets that operate at slow speeds. These lubri-
high sliding speeds between the gear teeth requires lubricity cants are supplemented with tackifiers to make the lubricant
additives to reduce friction and improve torque efficiency. adhere to gears and resist easy removal. Typical operating
Typical effective temperature for these oils is between 5 and range for these lubricants is 5 to 120° C 共40 to 250 °F兲. Be-
82° C 共40 to 180°F兲. Because of the extensive contact be-
cause of their low fluidity, these lubricants cannot act as
tween the worm gear and the wheel gear, the lubricant gets
coolants.
constantly removed; hence the need for relubrication is con-
Greases were also commented upon earlier. The primary
stant. Most worm gear drives normally require an ISO 460 or
680 compounded oil, and in some cases ISO 1000 oil. The advantage of a grease as a lubricant is that it stays in place.
viscosity grade required depends upon the worm gear drive’s The use of lubricating greases is restricted to gears that oper-
speed and operating temperature. Generally, the lower the ate at slow speeds and under light loads. Greases are ideal
worm gear’s speed, the higher is the required viscosity grade. lubricants for small gear boxes used in household appli-
Open gear compounds were already commented upon ances. Operating temperatures range for greases is
−30 to 120 ° C, depending upon the base oil and the soap 关318兴. The tests included in these specifications are de-
used. scribed in the books on the ASTM Standards, which the
Table 8.11 summarizes the various types of gear lubri- ASTM publishes annually, and elsewhere.
cants and their application 关649兴. As one can see from the
table that for applications that involve heavy loads and or Gear Oil Formulation
high speeds, the EP oils are the best and for light loads, com-
pounded oils deliver reasonable performance. For most au- The primary functions of a gear lubricant are to reduce
tomotive applications that use hypoid gears, EP oils are the friction, remove heat, control wear, suspend contaminants,
most suitable gear lubricants. Gear lubricant viscometrics and protect against rust and corrosion. In addition, they
and additives technology used will be addressed later. must not foam and readily separate water. In order to meet
Industrial Gear Oils Specifications and Tests—As men- these performance objectives, the gear oils are formulated
tioned earlier, the performance of the industrial gear oils is by adding antiwear and extreme pressure additives, oxida-
established by the OEMs and industrial organizations. Like tion inhibitors, rust inhibitors, and foam inhibitors to a min-
other lubricants, industrial gear oils have viscosity grades as eral oil, synthetic fluid, or a vegetable oil.
well as performance classifications. AGMA viscosity grades
along with the ISO viscosity grades for these lubricants are Base Fluids
provided in Table 8.12 关649兴. These grades apply to R&O oils, As mentioned earlier, gear oils for most applications are for-
EP gear lubricants, and synthetic industrial gear lubricants. mulated by the use of the mineral oils. This is because of
In the table, for the R&O oils, the designation either has no their reasonable cost and adequate performance. However,
suffix attached or it has the suffix Comp. No suffix indicates for some automotive applications, gear oils with good low
that the lubricants contain R&O additives only and suffix temperature fluidity and high temperature thermo-oxidative
Comp indicates that the lubricants in addition contain fatty stability are required. Such oils are formulated by the use of
or synthetic fatty oils. The suffix EP indicates that the lubri- the synthetic base fluids. For automotive gear oils, the nor-
cants are supplemented with the extreme pressure additives mal 100 ° C viscosity range is between 4.1 cSt 共SAE 70W兲
and the suffix S indicates these lubricants to be synthetic in and 41 cSt 共SAE 250兲 and for industrial gear oils, it is be-
nature. Table 8.13 lists the minimum physical and perfor- tween 4.5 cSt to well over 200 cSt, or a 40 ° C viscosity of be-
mance specifications for inhibited and compounded gear lu- tween 28 cSt and over 7500 cSt, see Tables 8.2 and 8.12, and
bricants and Table 8.14 provides the same for the EP lubri- Fig. 1.15. Because of the need for high viscosity lubricants,
cants 关649兴. The two most common performance gear oils use medium to heavy base stocks. Physical proper-
specifications for industrial gear oils are AISE 224 and ties of the common mineral oil and synthetic base stocks are
AGMA 9005. These along with the other major industrial provided in Table 3.17 关318兴. For gear oils, blends of heavy
gear oil specifications and tests are provided in Table 8.15 neutral and synthetic base stocks are most useful since aro-
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CHAPTER 8 䊏 GEAR LUBRICANTS 403
TABLE 8.14—Minimum physical and performance specifications for EP gear lubricants †649‡.
matic and naphthenic components in such oils have different applications are depicted in Fig. 8.18 关469兴. Note
viscosity-pressure relationship that is much superior to that that within each application, the SSI values increase with
of the paraffinic oils. Note the lower pour points of synthet- the increasing molecular weight 共MW兲 of the polymer, indi-
ics and their high viscosity indices, both of which are of great cating a decrease in its shear stability. Across applications,
benefit for developing gear oils with the broad-temperature the SSI-MW lines are steeper for gear oils and hydraulic flu-
performance. ids, which are used for high shear applications, than for au-
High viscosity in gear oils, both for automotive and in- tomatic transmission fluids 共ATFs兲 and engine oils. Shear-
dustrial applications, is needed not only to improve their related viscosity loss in polymer-thickened lubricants is
film-forming ability under heavy loads, which will protect determined by the use of many tests. These include KRL
the gears against failure, but also to muffle the noise from Shear Stability Test 共CEC L-45-A-99兲, ASTM D6278, DIN 51
the meshing gear teeth. The final gear lubricant viscosity is 382, and ASTM D3945. To minimize the shear-related viscos-
achieved either by the use of a mixture of base fluids of differ- ity loss and to keep the lubricant within grade during its ser-
ent viscosities and or by the use of a viscosity modifier. The vice life, gear lubricants often use low molecular weight vis-
former strategy is used to develop narrow viscosity range cosity modifiers. However, because of the low thickening
multi-grades, such as 75W-90, and the latter strategy is often efficiency of the low molecular weight polymers, the lubri-
used to develop broad-viscosity range multi-grades, such as cant treatment level with these additives is quite high. It is
85W-140. Such multi-grades are primarily for automotive between 25 to 35 % for automotive gear oils and 2 to 12 % for
use. Because of the high shear forces experienced by the lu- industrial gear oils, depending upon the viscosity grade. The
bricant in the contact zone, high molecular weight poly- high levels of polymer are important so that even after shear-
meric viscosity modifiers are often less effective than low ing during service, the reduced viscosity is within the desired
molecular weight viscosity modifiers. This is because of the range to form the lubricant film of suitable thickness to pre-
propensity of the high molecular weight polymers to de- vent premature equipment failure. As mentioned earlier, the
grade rapidly under shear, a parameter that is measured by a multi-grade lubricants meet both the low-temperature vis-
polymer’s shear stability index 共SSI兲; low values are desired cosity and the high-temperature viscosity requirements of
in gear type applications. The SSIs of a number of alkyl the gear systems, which not only help prevent wear but also
methacrylate polymers of varying molecular weights used in improve the fuel economy, shiftability, and service life. Com-
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404 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
TABLE 8.15—Major industrial gear oil specifications and tests †318‡. Reprinted with permis-
sion from the Lubrizol Corporation.
mon types of polymers used in gear lubricants include sty- 1. Heat resistance 共thermal and oxidative stability兲 and
rene esters and alkyl methacrylate polymers. hence a lower tendency to form residues and deposits.
While additives can improve many of the properties of 2. Film strength 共high viscosity indices兲.
the mineral oils, there is a limit to this improvement. Syn- 3. Low temperature fluidity 共pour point and pumpability兲.
thetic gear oils are used to extend this limit. Synthetic lubri- 4. Volatility 共flash point and evaporation loss兲.
cants have an advantage over those based upon mineral oils 5. Lubricity 共at temperatures greater than 185 ° C, or
in applications where the operating temperatures are either 365 °F兲.
very low or very high; the loads are extremely high; and the Synthetics, such as esters and PAGs, also prevent the
volatility and flammability are a concern. Synthetic gear oils start-up gear wear, because of their greater surface affinity
surpass mineral oil-based lubricants with respect to the fol- which causes them to leave a residual lubricant film at shut
lowing properties. down. They also reach the critical surfaces quickly due to
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CHAPTER 8 䊏 GEAR LUBRICANTS 405
Fig. 8.18—Poly共alkyl methacrylate兲 viscosity modifier—molecular weight versus shear stability index 关469兴.
materials and may be supplemented with rust and oxidation 280, which makes it possible to use a lower initial viscosity
inhibitors. EP oils of low additive treatment level also work grade. This minimizes the energy usage at low temperatures,
well. Such oils are useful for gears operating under high because of easy flow, and at the same time providing ad-
pressure/high temperature conditions, where the EP agents equate film-forming ability at high temperatures. As stated
form the chemical protective films. However, the additives earlier, most PAGs possess inherent EP/antiwear properties
must be free of active sulfur, which is to minimize corrosion and hence do not need any EP additives. However, open gear
of the bronze ring gear. In this application, the PAO and PAG sets require high viscosity lubricants that contain extreme-
derived synthetic gear lubricants are also used. PAO-based pressure and antiwear additives. These oils belong to AGMA
lubricants have good low and high temperature properties, viscosity grades 7 and 8. Besides cost, they have the disad-
are elastomer compatible, and are miscible with the mineral vantages of incompatibility with the other fluids and aggres-
oils. They are usually supplemented with a small amount of siveness to paints, elastomer seals, and polycarbonate which
synthetic esters or the antiwear additives to improve their is used as a sight glass.
boundary lubrication ability. PAG-based lubricants are supe- Running-in gear oils are another class of lubricants that
rior to those based on mineral oils because they are not only are used to improve the surface finish of the new gears
better coolants, but they also possess good low and high tem- chemically and increase their load-carrying capacity. Oils
perature properties and control friction and wear more ef- containing sulfur-phosphorus additives and chlorinated par-
fectively. PAGs also have high viscosity indices, approaching affins are suitable for use as running-in gear oils. Sulfur-
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CHAPTER 8 䊏 GEAR LUBRICANTS 407
phosphorus additives, which have both running-in and a lubricant’s ability to perform effectively in the intended
normal-service characteristics, are used for automotive hy- equipment. These tests comprise both bench tests, lab tests,
poid axles. Chlorinated paraffins containing 40 % chlorine and field performance tests. Tests used for gear lubricants
are often used for the industrial gears. These oils need to be are listed below.
replaced with normal oils at the end of the running-in pe-
riod. The major problem associated with these oils is that Physical Tests
they are very corrosive, which can be controlled by the use of 1. API Gravity 共ASTM D287兲
inhibitors. Chlorinated paraffins function by reacting with 2. Kinematic Viscosity 共ASTM D445兲
the metal to form ferrous chloride at points where sufficient 3. Viscosity Index 共ASTM D2270兲
temperatures are generated due to frictional heat to cause a 4. Shear Stability CEC-L45-T-93
chemical reaction. The resulting iron 共II兲 chloride, with a 5. Low Temperature Brookfield Viscosity 共ASTM D2983兲
melting point of 677 ° C, has lower shear strength than the 6. Pour Point 共ASTM D97兲
metal itself and hence gets removed easily. This help smooth 7. Cold Crank Simulator 共ASTM D5293兲
surfaces to some degree. 8. Channel Point FTM 3456
Most industrial gear oils can be defined as extreme pres- 9. Flash and Fire Points by Cleveland Open Cup 共ASTM
sure 共EP兲 gear oils and contain the same sulfur-phosphorus D92兲
EP additives that are used to formulate the automotive gear 10. Precipitation Number 共ASTM D91兲
oils, but at a lower treat level. A typical automotive gear lu-
bricant treat level is 6 % EP additive, while the industrial EP
Analytical Tests
gear oils usually contain about 2 % additive. Industrial gear
1. Elemental Content ASTM D4951
oils contain some components that are not present in the au-
2. Elemental Analysis of Lubricants by WDXRF 共ASTM
tomotive gear oils, for example, a demulsifier. However,
D6443兲
compounded industrial gear oils do not contain sulfur/
3. Chlorine Level 共ASTM D808兲
phosphorus EP additives but contain a less active and less
4. Phosphorus Level 共ASTM D1091兲
corrosive additive, such as a fatty acid derivative. These oils
5. Sulfur Level 共ASTM D1552兲
are often used to lubricate bronze-on-steel worm gears
6. Nitrogen Level—Kjeldahl Method 共ASTM D3228兲
where darkening or corrosion of the yellow metal is a con-
7. Acid Number 共ASTM D664兲
cern. Typical properties of the gear oils for various gear sets
8. Base Number 共ASTM D4739兲
are provided in Table 8.17.
9. Water Content 共ASTM D1744兲
While gear oils perform many important functions, the
10. Insolubles in Used Oils 共ASTM D893兲
primary criteria to assess their effectiveness pertain to their
ability to form low friction physical or chemical films to pro-
tect gears against wear and seizure damage. Figure 8.19 Performance Tests
demonstrates the performance of properly formulated gear
lubricants in the FZG Test 关4兴. Oil a is a plain gear oil that EP/Antiwear Tests
contains no EP additives. It fails at Stage 8 due to scoring. Oil 1. Four-Ball EP 共ASTM D2783兲
b, which contains an EP additive, even at a low treatment 2. Four-Ball Wear Test 共ASTM D4172兲
level goes to Stage 11, prior to failing due to pitting. How- 3. Falex Continuous Load 共ASTM D3233兲
ever, oils c, d, and e, which have the proper viscometrics and 4. FZG 共ASTM D5182, DIN 51 354兲
a higher amount of EP additive treatment achieve perfor- 5. Timken EP Test 共ASTM D2782兲
mance up to 12th Stage. 6. Cyclic Durability Test 共ASTM D5579兲 关Automotive Gear
Oils兴
Gear Lubricant Tests 7. L-37 Low Speed High Torque Hypoid Test 共ASTM
D6121兲 关Automotive Gear Oils兴
Gear lubricants are subjected to a wide variety of tests to 8. Gear Scoring Test L-42 共Automotive Gear Oils兲
evaluate their properties. Some are physical and analytical 9. Synchronizer SSP 180 Test 共Automotive Manual Trans-
tests that determine physical and chemical properties of mission Test兲
these lubricants. Others are performance tests that evaluate 10. FZG Pits C i80 TS共Automotive Gear Oils兲
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408 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
Fig. 8.19—Effect of gear oil quality on FZG wear test 共A/8.3/90兲 performance 关4兴.
Demulsibility/Water Separability Tests Automotive Gear Oil 共low phosphorus兲: 4.0 to 8.0 % Sul-
1. Water Separability Characteristics of Petroleum and furized isobutylene or sulfurized polyisobutylene 共primarily
Synthetic Fluids 共ASTM D1401兲 tri-isobutylene兲 EP agent, 0.6 % secondary alcohol-derived
2. Demulsibility Characteristics of Lubricating Oils zinc dialkyl dithiophosphate antiwear agent, 3 % ethylene
共ASTM D2711兲 carbonate treated bis-succinimide dispersant, 1 % low TBN
calcium sulfonate detergent, 2.4 % high TBN calcium phen-
Rust and Corrosion Tests ate detergent, 0.5 % diphenylamine oxidation inhibitor,
1. Copper Strip Corrosion 共tarnish兲 Test 共ASTM D130兲
0.04 to 1.0 wt. % in terms of boron content of an alkali-
2. Turbine Oil Rust Test 共ASTM D665兲
metal borate, 0.1 to 0.8 % copper corrosion inhibitor; 0.01 to
3. Gear Corrosion Test L-33 共Automotive Gear Oils兲
0.1 % foam inhibitor; 0.01 to 0.1 % rust inhibitor, and a vis-
Foaming/Air Release Tests cosity index improver 关poly共alkyl methacrylate兲兴. The rest is
1. Foaming Characteristics of Lubricating Oils Test API Group II mineral oil of viscosity range suitable for use as
共ASTM D892兲 a gear lubricant 共formulation extracted from Ref 关676兴兲.
2. High Temperature Foam Inhibition 共ASTM D6082兲 Automotive Gear Oil: 4.4 % Di-alkyl polysulfide and 0.9
3. Storage Solubility of Gear Lubricants 共FTM 3440兲 % alkyl phosphates/phosphites EP/Antiwear agents, 1.14 %
4. Air Release 共ASTM D3427 or DIN 51 381兲 alkylamine rust inhibitor, 0.76 % alkenylsuccinimide and
0.38 % borated alkenylsuccinimide dispersants, 0.1% bis共di-
Oxidation Tests
alkylthio兲dimercaptothiadiazole corrosion inhibitor, 0.1 %
1. Oxidation of EP Oils ASTM D2893 共S-200兲
poly共butyl acryl ate兲 foam inhibitor, 1 % pour point depres-
2. Thermal and Oxidation Stability 共L-60-1兲 共ASTM
D5704兲 关Automotive Gear Oils兴 sant. The rest is mineral oil of viscosity range suitable for use
3. GFC Oxidation as a gear lubricant 共formulation extracted from Ref 关677兴兲.
Automotive Gear Oil for Manual Transmissions: 0.35 %
Material Compatibility Tests of an amine phosphate extreme pressure agent, 0.2 % of
1. Dynamic Seals Test nonylated diphenylamine oxidation inhibitor, 0.7 to 3.0 % by
2. Seal Compatibility 共ASTM D5662兲 weight overbased magnesium sulfonate, 0.15 % dimercap-
3. Compatibility of Gear Lubricants 关FTM 3430 共Automo- tothiadiazole derivative metal deactivator, 2.0 % borated alk-
tive Gear Oils兲兴 enylsuccinimide dispersant, 0.2 % of oleylamine friction
Formulation Examples modifier, 4.67 % of an olefin copolymer viscosity modifier
150 ppm of poly共alkyl acrylate兲 and 60 ppm of silicone foam
Automotive Gear Oil: 4.0–6.0 % Sulfurized isobutylene inhibitors. The balance is hydrogenated polyalphaolefin
and alkyl phosphite/phosphate EP agents, 0.25–0.5 % phe- 共PAO 6兲 共formulation extracted from Ref 关678兴兲.
nolic oxidation inhibitor, 0.3–0.4 % triazole metal deactiva- Automotive Gear Oil: 2.3 to 2.5 % Sulfurized isobuty-
tor, 0.6–1.0 % fatty amine friction modifier 共anti-squawk lene, 0.24 % dibutyl hydrogen phosphite, and 0.65 %
agent兲, 0.1–0.5 % poly共alkyl methacrylate兲 type pour point 2-ethylhexyl acid phosphate EP agents; 1.08 % ash-less di-
depressant, and 0.05–0.1 % poly共alkyl methacrylate兲 foam alkyl dithiophosphoric acid ester antiwear agent/oxidation
inhibitor. The rest is mineral oil of viscosity range suitable inhibitor; 0.30 to 0.35 % t-alkylamine rust inhibitor; 0.165 %
for use as a gear lubricant. 2,5-dimercapto-1,3,4-thiadiazole metal deactivator; 0.04 %
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CHAPTER 8 䊏 GEAR LUBRICANTS 409
poly共alkyl acrylate兲 foam inhibitor; and 0.04 % caprylic acid. use as a gear lubricant 共formulation extracted from Ref
The balance is mineral oil of viscosity range suitable for use 关679兴兲.
as a gear lubricant. Industrial Gear Oil: 1.0–2.0 % Sulfurized olefin and alkyl
Industrial Gear Oil:: 0.9 to 1.0 % Sulfurized isobutylene, phosphite/ phosphate EP agents, 0.08–0.2 % phenolic oxida-
0.10 % dibutyl hydrogen phosphite, and 0.025 % tion inhibitor, 0.1–0.13 % triazole metal deactivator, 0.2–0.3
2-ethylhexyl acid phosphate EP agents; 0.0422 % ash-less di-
% fatty amine friction modifier 共anti-squawk agent兲, 0.03–
alkyl dithiophosphoric acid ester antiwear agent/oxidation
0.2 % poly共alkyl methacrylate兲 type pour point depressant,
inhibitor; 0.12 % t-alkylamine rust inhibitor; 0.0645 % 2,5-
dimercapto-1,3,4-thiadiazole metal deactivator; 0.015 % and 0.02–0.03 % poly共alkyl methacrylate兲 foam inhibitor.
poly共alkyl acrylate兲 foam inhibitor; and 0.016 % caprylic The rest is mineral oil of viscosity range suitable for use as a
acid. The balance is mineral oil of viscosity range suitable for gear lubricant.
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MNL59-EB/Mar. 2009
9
Miscellaneous Industrial Lubricants
DISCUSSION IN THIS CHAPTER DEALS WITH Types Of Industrial Oils
lubricants that are used in various industrial applications.
The lubricants described include turbine lubricants, com- Industrial lubricants are classified either based on applica-
pressor and refrigeration oils, food grade lubricants, and a tion or function. Application-based classes include hydrau-
variety of others. For each type of lubricant, criteria for lic fluids, gear oils, turbine oils, metalworking fluids, and
selection, performance requirements, and testing are con- greases. Of these, hydraulic fluids and gear oils were de-
sidered. The chapter is concluded by presenting represen- scribed in Chapters 7 and 8, respectively. Others are being
tative formulations for some of these lubricant types. discussed in this chapter and the subsequent chapter.
The lubricant market is divided into two major seg- Function-based classes are many, but those that are of pri-
ments: Automotive and industrial. Automotive lubricants mary interest to us include rust and oxidation 共R&O兲 oils, EP
include engine oils, transmission fluids, automotive gear oils, circulating oils, compounded oils, and fire-resistant flu-
oils, tractor hydraulic fluids, and automotive greases. In- ids.
dustrial lubricants are used to lubricate industrial equip- As stated earlier, most modern lubricants are based
ment which help produce a variety of materials and prod- upon either mineral oil or a synthetic fluid, whose properties
ucts for the consumer use. Such lubricants include are enhanced by the use of additives. Synthetic fluids are
metalworking fluids, general machine oils, slide way lubri- used where the performance of mineral oils have reached
cants, industrial gear oils, hydraulic fluids, turbine lubri- their upper limit. Table 9.1 shows a comparison of the vari-
cants, rust prevention oils, compressor oils, refrigeration ous base stocks with respect to some of the desirable proper-
oils, industrial greases, and miscellaneous others. Distinc- ties 关447兴. For further details regarding the chemistry and
tion between the two lubricant segments is not clear cut performance of the synthetic fluids, please refer to Chapter 3
since some applications can be included in either of the on Synthetic Fluids. Figure 9.1 shows the operating tem-
two groups. For example, aviation turbines, marine en- perature advantage of the synthetics over mineral oil 关447兴.
gines, and railroad engines are considered by some as in- Temperature advantage is important, especially for formu-
dustrial applications and not automotive. Worldwide share lating lubricants for use in extreme temperature applica-
of industrial lubricants is around 45 % of the total lubri- tions. Please note that the finished lubricant properties may
cant market. Physical properties of these lubricants are improve or deteriorate somewhat, depending upon the type,
usually specified by ISO viscosity grades, and their perfor- the quality, and the quantity of the additives used.
mance requirements are established by the U.S. Military, Synthetic lubricants provide the industry a means to in-
OEMs, and end-users. crease productivity, efficiency, and energy conservation. The
410
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CHAPTER 9 䊏 MISCELLANEOUS INDUSTRIAL LUBRICANTS 411
selection of a proper synthetic lubricant for a specific appli- Turbines are usually coupled with alternators for elec-
cation is based upon the tribological needs of the equipment; tricity generation or to a pump, compressor, or fan which
operating conditions, such as temperature, speed, load, performs the work. For steam, gas, and wind turbines, there
sealed-for-life; and the operating environment. may be a need to install a reduction gear between the turbine
and the driven equipment, if the speed of the turbine is too
Turbine Lubricants high. Aero-engine gas turbines are not directly coupled to
other equipment, but are stand alone units, which use the
Turbine Types energy of the expanding gas to provide the forward motion.
Turbines are devices that convert kinetic energy of a fluid In some cases, the main turbine is used to drive a second tur-
into mechanical energy. Turbines employ a variety of fluids bine, called a power turbine, which is attached to an alterna-
to produce power. These include steam, gas, water, and tor or compressor. In each class, turbines are subdivided
wind. Steam turbine is a mechanical device that extracts based upon size, output, and application. Some of the infor-
thermal energy from pressurized steam, and converts it into mation on turbines is available from Refs 关214,680兴.
mechanical work. Gas turbine, also called a combustion tur-
bine, is a rotary engine that extracts energy from the flow of Lubrication Requirements
combustion gases resulting from the combustion of the air- The primary function of a turbine oil is to lubricate the tur-
fuel mixture. These gases are directed through a nozzle over bine and the generator bearings. However, it must also per-
the turbine’s blades, spinning the turbine that does the work. form the additional functions and possess the attributes
These types of turbines are used to power aircraft, trains, listed below.
ships, generators, and even tanks. Turbines for nonaircraft • Act as a hydraulic medium for hydraulic cylinders, accu-
use are usually of rugged construction and involve on-site mulators, servo valves, high-pressure pumps, and
maintenance. Such turbines are used in power generation, torque converters.
pipeline, and petrochemical applications. In the petro- • Lubricate the reduction gear, if used, and the coupling
chemical industry, they are used to drive pumps and com- between the turbine and the alternator.
pressors. • Lubricate bearings, gearing, and gas seals and must also
Water turbine, or hydro turbine, is a rotary engine that act as a heat transfer fluid 共coolant兲 and remove heat
takes energy from the moving water. Water turbines are one from these devices and the other hot surfaces.
of the oldest types and have been used to produce power for • Act as a shaft seal for hydrogen-cooled generators.
industrial use. Today, they are used to generate hydro- • Minimize friction and wear.
electric power. A wind turbine converts the kinetic energy of • Control rust and corrosion of the metal parts.
the wind into mechanical energy. If the mechanical energy is • Be compatible with the materials that are used in con-
used directly by the machinery, such as a pump or grinding structing turbines.
stones, the wind turbine is usually called a windmill. If the • Be fire resistant, if used in applications that pose a fire
mechanical energy is then converted into electricity, the tur- hazard, and also be easy to recondition.
bine is called a wind generator. Water and wind turbines are • Easily gets rid of contaminants, such as air and water,
most environmentally compatible since they use clean and and is filterable.
renewable energy sources. However, their operation is a • Possess all the properties necessary for trouble-free stor-
function of the weather. age and use, such as stability, viscosity, viscosity index,
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412 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
specific gravity, specific heat, thermal conductivity, pour thermal breakdown, the lubricant’s thermo-oxidative stabil-
point, and ignition temperature. ity will have an influence on its useful life.
• Has a reasonable cost and long service life. Fluid maintenance and system maintenance can have
Almost all of these functions are the same across most an indirect effect on fluid quality. For example, minimizing
turbine lubricants, irrespective of the turbine size or type. air and water entry into the lubricant can considerably pro-
Lubricant systems, except for some military aviation appli- long its service life. Aeration of the lubricant can directly in-
cations, are closed systems consisting of a reservoir; a pump crease its oxidation rate by increasing its oxygen content,
train with main, auxiliary, and emergency pumps; filters; a which is one of the factors that promote hydrocarbon lubri-
cooler; and may be a centrifuge or a purifier to remove the cant oxidation; the others being temperature and metals and
excess water and dirt 关214兴. Most turbines employ combined metal salts. Aeration and foaming cause additional prob-
lubricating and hydraulic oil systems, which normally use lems, which include poor lubrication, loss of fluidity, and
cavitation, if the aerated fluid is used as a hydraulic fluid.
mineral lubricating oil, with the lubricating oil supply pres-
Top-up rate is the rate at which the fresh fluid is added to the
sure of 1 – 2 bars and the hydraulic oil pressure of 3 – 4 bars.
fluid in the equipment. Typical top-up rates are 3–10 % per
Some turbines use separate hydraulic systems where the
year for steam turbines, up to 33 % for industrial gas tur-
pressure is as high as 160 bars.
bines that use mineral oils, and 0.25 L / h for aero engines.
In large steam turbines, the temperatures reach 600 ° C
Top-up rates influence lubricant quality since they help re-
共1112 ° F兲 and the presence of the mineral oil in the hydraulic
plenish used additives to the lubricant in service. High
system poses a fire hazard. To eliminate this, such turbines top-up rates reflect a loss of lubricant or its components due
are designed with separate hydraulic system that uses a fire- to evaporation or misting. In industrial operations, the oil
resistant fluid. The use of two different lubricants helps con- consumption can be lowered by the use of efficient oil demis-
tain the overall cost. We described the various classes of hy- ters.
draulic fluids in Chapter 7. Because of the extreme operating Previously, the OEMs recommended the lubricant ser-
temperatures of turbines, fire-resistant fluids based upon tri- vice by establishing acidity, water, viscosity increase, and
aryl phosphates are the most appropriate. Incidentally, a contamination limits. However, modern filtration devices
phosphate ester fluid that can be used both as a hydraulic greatly reduce the level of contaminants such as water and
fluid and a main bearing lubricant for steam turbines of up the particulates. This, combined with the practice of replen-
to 1000 MW output is commercially available. ishing the depleted additives, has helped in prolonging the
Aero-derivative gas turbines use synthetic ester-based lubricant service life greatly. The depleted additives can be
fluids because mineral oils do not possess the low- identified by the use of the modern analytical and spectro-
temperature properties and the high-temperature stability scopic techniques. Useful lubricant life for steam turbines,
required for use in modern turbine engines, see Fig. 9.1. Syn- both for mineral oil and synthetic hydrocarbon types, is be-
thetic esters are used both for aviation and industrial appli- tween 2 and 25 years. For industrial gas turbines, it is be-
cations where they function as a hydraulic fluid as well as a tween 1.5 and 6 years and for new generation combined
lubricant. Mineral oils still find use in older and smaller aero cycle gas turbines, it is between 4 and 5 years. For aviation
gas turbines used in military aviation and in industrial appli- gas turbines, the synthetic ester-based oil is continually
cations, where thermo-oxidative stresses are low. In some topped up and the whole charge is almost never replaced. In
aero-derivative units, both mineral oil lubricants and syn- industrial turbines, the lubricant is changed annually, or af-
thetic lubricants are used; a turbine engine is lubricated by ter 8000 hours of service. The service life of the fire-resistant
the ester lubricant and the driven equipment is lubricated by hydraulic fluids and lubricants is between 5 and 20 plus
the mineral oil, again to contain the overall cost. years, depending upon the type of in situ conditioning or pu-
Selection of a suitable lubricant requires consideration rification 关214兴.
of a number of factors, which include system design, duty
Lubricant Performance Specifications
cycle 共continuous versus intermittent兲, lubricant stability,
Turbine oils are classified by ISO viscosity grades and by ISO
system maintenance, and the rate of the lubricant top-up.
Standard 6743-5, Class L 共Lubricants兲 and Family T 共Tur-
The first three factors determine the thermal and oxidative
bines兲. ISO viscosity grades need not be addressed here since
stresses to which the lubricant is exposed and the last two they were already discussed in Chapters 7 and 8 on Hydrau-
deal with maintaining the quality and the effectiveness of the lic Fluids and Gear Oils, respectively. ISO Standard 6743-5
lubricant. The operating temperatures of bearings in large classifies turbine lubricants based on turbine type and the
steam turbines reach 320 ° C 共608 ° F兲 and for the gas tur- type of service they provide. The standard is duplicated in
bines, they reach 115– 149 ° C 共239– 302 ° F兲 for plain bear- Table 9.2 关440兴. As one can see, the standard broadly classi-
ings and 300 ° C 共572 ° F兲 for roller bearings. For aero- fies turbine lubricants into five groups, which are lubricants
derivative gas turbines, the lubricant comes in direct contact for steam turbines, lubricants for gas turbines, control sys-
with the metal surfaces that have temperatures ranging from tem fluids, aircraft turbine lubricants, and hydraulic oils.
204 to 316 ° C 共400 to 600 ° F兲. The sump lube oil tempera- The first two classes are subdivided to identify lubricants for
tures may range from 71 to 121 ° C 共160 to 250 ° F兲. The applications with specialized lubrication needs. Turbine oils
duty cycle is important because the intermittent operation is for steam and gas turbines, which are used in marine and
less demanding on the lubricant than a continuous opera- stationary applications, are designed to lubricate parts, such
tion over extended periods, if all other factors are assumed to as sealed electric motors, sintered bearings, plain and anti-
be the same. Since both the high temperatures and the con- friction bearings, fans, compressors, and gears. Circulating
tinuous operation promote faster lubricant oxidation and oils are turbine lubricants that are used in turbines equipped
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CHAPTER 9 䊏 MISCELLANEOUS INDUSTRIAL LUBRICANTS 413
TABLE 9.2—ISO classification for turbine lubricants „ISO Standard 6743-5… †214‡.
with circulating oil systems. Such systems are installed to fa- Some applications, such as the load equipment, operate at
cilitate quick removal of the large quantities of heat or where high speeds and high loads and hence need both EP and anti-
heavy contamination of oil is a concern. As a rule, all lubrica- wear protection. Addition of 2 % tricresyl phosphate or zinc
tion and hydraulic functions are satisfied by the circulating dialkyl dithiophosphate to a mineral oil lubricant helps in
oil. The exception is water turbines, where the lubrication controlling gear wear in such applications. However, these
and heat control systems are separate because the same vis- additives can be corrosive and increase sludge formation,
cosity grade lubricant cannot satisfy the needs of both. Con- hence they must be used only when a real need exists. Fire-
trol system fluids are highly fire-resistant phosphate ester flu- resistant fluids are used in operations that pose a potential
ids, which have the ability to endure extreme hot fire hazard, such as in turbines used for pumping oil and gas.
temperatures and high oil pressures in large-scale turbine Originally, chlorinated biphenyls were used in these turbines
hydraulic control systems. Aircraft lubricants are for lubri- but for the environmental reasons they are being replaced by
cating turbines used in the jet engines. Hydraulic fluids are triaryl phosphates.
used to lubricate the mechanisms that are used to operate U.S. Military and OEM specifications are used to deter-
the turbine’s peripheral equipment. For details pertaining to mine the quality of the turbine oils. These specifications per-
the function and the properties of these fluids, refer to the tain to the fluid’s oxidation resistance, thermal stability, rust
Chapter 7 on Hydraulic Fluids. and corrosion inhibition, demulsibility, yellow metal protec-
Turbine oils, in a manner analogous to that of the hy- tion, foam inhibition, air release characteristics, seal com-
draulic fluids, are available in ISO viscosity grades and are patibility, low-temperature fluidity, and volatility. The EP/
classified as R&O oils, non-EP oils, EP oils, and the fire- antiwear performance is usually demonstrated by the use of
resistant fluids. R&O oils are formulated to provide rust and the 4-Ball EP, Falex, and Ryder gear tests.
oxidation protection and EP oils are formulated to provide The United States and European OEM performance
EP protection, depending upon the intended end use. EP oils specifications for R&O, EP, and non-EP turbine oils are pro-
contain R&O packages enhanced with antiwear additives. vided in Tables 9.3 and 9.4, respectively 关318兴. R&O turbine
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414 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
oils inhibit rust and oxidation and are used in high-speed −40° C to + 60° C for a period of three years. ASTM D97 is
and heavy-duty steam and gas turbines. These oils are also used to determine the pour point.
used in light-duty or non-antiwear industrial hydraulic and
gear systems. Several specifications covering R&O and tur- Volatility
In some military aviation applications, a 3 cSt 共low viscosity
bine oils have been issued by the equipment builders, users,
oil兲 is used in a high temperature environment. Hence, there
military, and the technical societies in the United States and
is a concern for volatility, which is determined by the use of
Europe. An exhaustive list of national and international
ASTM D972, Standard Test Method for Evaporation Loss of
specifications is provided in Ref. 关214兴. Table 9.5 compares
Lubricating Greases and Oils.
the specific technical requirements for steam/industrial gas
turbine oils, air-derivative turbine oils, and fire-resistant hy- Acidity
draulic fluids. Please note that the air-derivative turbine oil Acidity in a lubricant, whether from manufacture or the
requirements are based on the U.S. MIL-PRF-23699F speci- presence of the acidic additives and fluid degradation prod-
fication. ucts, is not desirable. This is because it is likely to lead to
problems during storage and use, for example, extensive
Desirable Turbine Oil Properties foaming 共ASTM D892兲 and poor air release 共ASTM D3427兲. It
The desired properties in a turbine fluid include proper low may even cause corrosion 共ASTM D665兲 and promote oxida-
and high temperature viscometrics, volatility, acidity, oxida- tion 共ASTM D2272兲. For phosphate ester lubricants, it will
tion resistance, water and chlorine content, fire resistance, increase the rate of hydrolysis, which will destroy the integ-
thermal stability, lubrication and wear prevention, rust and rity of the lubricant. Acidity in lubricants is monitored by the
corrosion inhibition, water separation and demulsibility, use of ASTM D974 and ASTM D664 standards. For aviation
foam inhibition, air release characteristics, and seal and ma- lubricants, MIL-PRF-23699F includes a potentiometric
terials compatibility 关214兴. While some of these properties method. ASTM D943 uses an acidity limit which indicates
can be attained by the use of a proper base stock, others need the rate of the lubricant breakdown due to oxidation. Two
the help of additives. Additives that are commonly used in other ASTM standards 共D3339 and D5770兲 are also used to
turbine oils include the following: determine acidity, but during the test rather than at the end
1. Oxidation inhibitors of the test.
2. Rust and corrosion inhibitors
3. Detergents/dispersants Oxidation Resistance
4. EP/antiwear agents Heat reduces turbine oil life due to increased oxidation. For
5. Foam inhibitors every 10 ° C 共18 ° F兲 rise in temperature above 60° C 共140° F兲,
6. Demulsifiers the oxidation rate of hydrocarbon materials doubles. A con-
ventional mineral oil will start to rapidly oxidize at tempera-
Viscometrics tures above 180 ° F 共82 ° C兲. Most tin-Babbitt journal bear-
Each lubricant is designed to possess viscosity characteris- ings begin to fail at 121 ° C 共250 ° F兲, which is well above the
tics that are consistent with the equipment needs under all temperature limit of the conventional turbine oils. High-
operating conditions, so do these fluids. Kinematic viscosi- quality oxidation inhibitors can delay oxidation, but excess
ties of turbine lubricants at 40° C and 100 ° C are measured heat and water must be minimized to gain long turbine oil
by using ASTM D445 test method and are converted into vis- life.
cosity index according to the ASTM D2270 procedure. An- As mentioned in the Additives chapter, the function of
other ASTM method, D2532, measures viscosity changes on the oxidation inhibitors is to slow down the oxidative degra-
prolonged exposure to low temperatures. Figure 9.2 shows dation of the lubricant; hence control viscosity increase, the
such a plot for VT behavior, a surrogate of VI, of a number of formation of the harmful deposit precursors, and the
fluids below 40° C 关440兴. Please note that the slopes of the corrosion-causing acids. They achieve this by facilitating the
viscosity-temperature lines in this temperature range are in hydroperoxide decomposition to innocuous materials and
agreement with the VIs of the different fluids. ASTM D2422 quenching the reactivity of the peroxides. Sulfur-containing
and ISO 3448 standards for industrial lubricants classify lu- compounds, such as sulfides and polysulfides and dialkyl
bricants according to their viscosity at 40° C. For industrial dithiophosphoric acid and dithiocarbamic derivatives, be-
steam and gas turbine oils, ISO VG 32 and 46 and for aero long to the first group and hindered phenols and alkylated
turbines, and ISO VG 10 and 22 are the most commonly used diphenylamines belong to the second group. The combined
viscosity grades. use of the additives of the two types allows a formulator to
benefit from synergy, if it exists. However, the use of addi-
Low-temperature Properties tives that contain both types of functionalities within their
It is critical that a lubricant flows and pumps at low tempera- structure is often more advantageous than the use of two
tures, otherwise operating problems will set in. Unlike min- mono-functional additives.
eral base oils 共API Group I oils兲 that have poor low tempera- While zinc dialkyl dithiophosphates are excellent oxida-
ture performance because of the presence of the waxy tion inhibitors and antiwear agents, their use in turbine oils
components, synthetic fluids do not usually suffer from this is not preferred because of their tendency to hydrolyze in the
disadvantage. However, synthetic esters, when wet, become presence of water to form zinc oxide/hydroxide. Because of
turbid at low temperatures and also gain viscosity on stor- this, some turbine makers have imposed a limit on the
age. Therefore, aviation gas turbine oils, which employ ester- amount of zinc in lubricants for use in their equipment. For
derived lubricants, are tested for extended storage stability. metal-free 共ash-less兲 turbine lubricants, hindered phenols
MIL-PRF-23699F, for example, requires storage stability at and arylamines are used, either solely or in combination.
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CHAPTER 9 䊏 MISCELLANEOUS INDUSTRIAL LUBRICANTS 415
TABLE 9.3—Typical U.S. and European R&O specifications †318‡. Reprinted with permission
from the Lubrizol Corporation.
One of the most preferred phenol is 2,6-dibutyl-4- which contains only a diester sulfide, has very poor perfor-
methylphenol 共butylated hydroxytoluene, or BHT兲, because mance, but Fluid 3, which contains a synergistic combina-
of its lower cost and high efficiency. In some turbine formu- tion of the two inhibitors, has a much superior performance.
lations, it is being replaced by higher molecular weight ana- The structures of the phenolic and aminic inhibitors used
logues that have lower volatility. are provided in Fig. 9.3. While in general arylamines are
Turbine oil performance data by the use of various oxi- more effective than hindered phenols across a wide range of
dation inhibitors are provided in Table 9.6 关214兴. Data in Part conditions, they are costlier than phenols and impart color
A pertain to two phenolic inhibitors in a solvent neutral oil to the lubricant. It is important to note that the different base
共API Group I oil兲 and a hydrotreated oil 共API Group II oil兲. stocks respond differently to these additives. API Group I
The data demonstrate superior performance of the bi- oils, which have some aromatic and sulfur content, usually
functional inhibitor 1 to that of the mono-functional inhibi- respond better to hindered phenols and API Group II and
tor 2, and a better response of both in solvent neutral oil than Group III oils that are devoid of aromatics and sulfur re-
in the hydrotreated oil. The somewhat inferior performance spond better to arylamines. Alkylated aromatic amines are
in the latter case is due to the absence of the additional sulfur the inhibitors of choice in aviation gas turbine oils, which is
which is present in the solvent neutral mineral oil. Data in primarily due to their superior effectiveness at high tem-
Part B pertain to alkylated diphenylamine in API Group I oil. peratures.
Fluid 1, which contains only the alkylated diphenylamine, The effectiveness of the oxidation inhibitors is assessed
has a reasonably good oxidation performance. Fluid 2, by monitoring the lubricant’s viscosity increase and acidity,
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416 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
TABLE 9.4—Typical U.S. and European turbine oil requirements †318‡. Reprinted with per-
mission from the Lubrizol Corporation.
and by the formation of sludge. Two major tests that are used Water Content
to measure oxidative stability of the inhibited turbine oils Water in a lubricant is undesirable, both in dissolved and dis-
are ASTM D2272 and ASTM D943. ASTM D943, also known persed form. Solubility of water in mineral oils is very low
as TOST 共turbine oil stability test兲, is a very long test, hence 共about 30– 100 mg/ kg兲; hence its presence can be easily de-
some specifications, such as MIL-L-17331, has placed a time tected in mineral turbine lubricants as turbidity. However,
limit of 1000 hours but have added limits on the metal con- water solubility in polar ester lubricants at ambient tem-
tent and sludge 关214兴. ASTM D4310, which also uses the peratures is much higher 共2000– 2500 mg/ kg兲; hence ana-
D943 apparatus, measures the amount of sludge formed af- lytical methods must be used to measure its amount. The
ter 1000 hours. Another oxidation test, the Universal Oxida- common method used for this purpose is Karl-Fischer re-
tion Test 共ASTM D5846兲, measures the acidity and sludge agent 共ASTM D1744兲. While a small amount of water in tur-
when the acid number reaches 0.5 mg/ g or the level of bine oils is not a problem, large amounts will cause a drop in
sludge becomes unacceptable. The sludge rating is some- viscosity, hydrolysis of the additives, and even of the ester
times improved by the use of detergents and dispersants, base fluids.
which keep surfaces clean by suspending the contaminants
in the lubricant. Density
The stability testing of the aero turbine oils typically in- The knowledge of density, or specific gravity, of a lubricant is
volves higher temperatures than for steam turbine oils and important to a user since it indicates the energy required to
uses variations of FED-STD-791, Method 5308. ASTM pump it. Phosphate esters have densities ⬃30 % higher than
D4636 was later issued that combined the 5307 and 5308 those of the mineral oils, 1.17 versus 0.9 for an ISO VG 32
methods offering three alternative procedures. In the 5308 fluid, and hence they require more power to circulate. Fluids
procedure, the fluid viscosity and catalyst coupons are evalu- of higher density also hold more insolubles in suspension,
ated at the end of the test, but in the 5307 procedure, the fluid which necessitates the use of an efficient filtration system.
samples are monitored for viscosity and acidity increase dur- ASTM D1298 and D5002 are used for determining density.
ing the test. Variations of 5308 differ from each other in the Although values are usually determined at 15 and 20 ° C,
OEM specified test temperatures and the test duration 关214兴. they can be extrapolated to other temperatures. API gravity
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CHAPTER 9 䊏 MISCELLANEOUS INDUSTRIAL LUBRICANTS 417
TABLE 9.5—Technical requirements for turbine oils and fire-resistant hydraulic fluids.
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418 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
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CHAPTER 9 䊏 MISCELLANEOUS INDUSTRIAL LUBRICANTS 419
Fig. 9.4—Turbine oil air release rates as a function of temperature 共adapted from Ref 关214兴兲.
tives of tolyltriazole or dimercaptothiadiazole 共DMTD兲. the foam occurs on the surface of the liquid and consists of
ASTM D130 copper strip test is used to assess a lubricant’s air bubbles surrounded by a thin film of oil and the dispersed
copper protecting ability. Turbine oil specifications require air is present within the bulk fluid and a thick film of oil sepa-
Cu strip rating of 1b or better. rates the bubbles. A number of factors affect these properties
The function of the foam inhibitors in turbine oils is to and include circulation rates, fluid viscosity and fluid sur-
inhibit foam formation and facilitate quick collapse of the face tension, polar impurities, and the fluid temperature.
foam, if it forms. This is important since foam can lead to Tests used to measure a lubricant’s foaming tendency in-
improper lubrication and increased lubricant oxidation. clude ASTM D892 and the dynamic foam test, FED-STD 791-
Foam inhibitors are added to the lubricant in a very small 3214 test method. Air-release properties are assessed by the
amount, i.e., at ppm level. At a higher level, these additives use of the ASTM D3427 共ISO 9120, IP 313, and DIN 51 381兲
are harmful since they adversely affect air release properties test method. While this method is designed specifically for
of the turbine oil. Besides silicones 共polysiloxane兲s, poly共gly- mineral-based oils, it can be used for some synthetic fluids as
col ether兲s and poly共vinyl ether兲s are used for controlling well. Figure 9.4 shows the air release properties of the vari-
foam. However, they are not as effective as silicones and are ous turbine fluids and at different temperatures 关214兴. Inci-
needed in a larger amount. ASTM D892 共ISO 6247兲 is the dentally, 50 ° C is the normal recommended temperature for
common method to test a lubricant’s foam-forming ten- the test. While the temperature effect on air release is not
dency. possible to interpret, the data in the figure do indicate that
Turbine oils, such as those used in steam turbines and the air release from hydrocarbon oils is slow but from syn-
hydro turbines, get contaminated with water. Water con- thetic fluids it is fast.
tamination can lead to many problems in addition to reduc-
ing the oxidation life of the lubricant and promoting rust for- Water Separability and Demulsibility
mation. These problems were stated while discussing water Steam turbine oils often get contaminated by water, prima-
contamination. It is therefore imperative that water be re- rily via steam penetration through seals, coolant leaks, and
moved as quickly as possible. Demulsifiers are additive that condensed water dripping into the hydraulic actuators
facilitate water separation and removal. Common chemical 关214兴. Water in turbine oils leads to rusting, emulsion forma-
types include alkaline earth metal salts of aromatic sulfonic tion, additive hydrolysis, and bacterial growth. Hence it is
acids and block copolymers of propylene oxide or ethylene important to remove water from the lubricant as quickly as
oxide with a polyhydric alcohol, such as glycerol, as an ini- possible. Emulsion formation, which mainly occurs due to
tiator. ASTM D1401 Standard is used to determine the the presence of the polar additives, such as detergents, must
demulsibility characteristics of the turbine oils. be minimized or emulsions broken to facilitate water sepa-
ration. ASTM D1401 is the common test used to evaluate
Foaming and Air Release emulsion forming tendency of the lubricant and additives
All turbine oils contain air, either in dissolved form or as dis- called demulsifiers are used to quickly break emulsions.
persed bubbles. Dissolved air is not a concern, except in the
reduced pressure environment where it can instantaneously Compatibility with System Materials
come out, causing cavitation. Dispersed or entrained air, on It is imperative that the selected fluid is compatible with the
the other hand, is a problem since it can result in a loss of system’s constructional materials. These include seal and
compressibility, increased oxidation, and even poor lubrica- gasket materials and paints used to cover various system
tion. The difference between foam and dispersed air is that parts. Incompatibility or poor compatibility may cause
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CHAPTER 9 䊏 MISCELLANEOUS INDUSTRIAL LUBRICANTS 421
swelling, softening, or cracking of the elastomer seals, lead- creases the operating life of the lubricant up to 50,000 hours.
ing to a fluid leak. Fluid can attack paint causing flaking, In steam turbines, mineral hydraulic oil is completely re-
which can lead to filter blockage or expose metal surfaces to placed by triaryl phosphate type fire-resistant fluids to re-
harsh chemical environments. Highly refined mineral oils duce the fire hazard. Table 9.8 provides typical operating
共API Group III oils兲 and synthetic hydrocarbons, such as conditions that a turbine oil encounters 关214兴. Let us con-
PAOs, lead to seal shrinkage. Hence, they are supplemented sider the individual lubricant parameters listed in the table.
with carboxylate esters or aromatic compounds to improve Higher lubricant system capacity implies availability of a
their elastomer compatibility. Phosphate esters are usually higher amount of lubricant to cool the bearings and the
aggressive towards paints and some metals. The extreme higher circulation rate implies a higher rate of cooling. Effi-
temperature operating environment, for example, that expe- ciency of cooling depends upon the combined effect of both
rienced by aviation gas turbine lubricants, requires highly these parameters and is reflected by the remaining lubricant
resistant fluorocarbon and perfluoro-elastomer seals. For parameters in the table, the bulk lubricant temperature and
nonaerospace applications, turbine oils are tested by using the bearing oil return temperature. The differential between
the ISO 6072 procedure. For testing aero-gas turbine oils, the values of these parameters indicates the efficiency of the
FED-STD-791 methods 3604 and 3433 or procedures listed lubricant to cool the bearings; the greater the differential,
by the equipment manufacturers are used. No standard the higher the effectiveness of cooling. Based on this, we
methods in turbine oil specifications are known for evaluat-
conclude that with respect to the thermal stress on the lubri-
ing paint compatibility and one must follow the recommen-
cant, the turbine types follow the order shown in Fig. 9.5. Of
dations of the paint manufacturer 关214兴. Elastomer compat-
these, the industrial turbines, marine turbines, and aviation
ibilities of the various tubrine oils and fluids are provided in
turbines have the highest bulk lubricant temperature and
Table 9.7.
the bearing oil return temperatures; hence the lubricants in
Turbine Oil Formulation these turbine applications are expected to experience the
Turbine oils are based upon both the solvent-refined paraf- greatest degree of thermo-oxidative degradation. For these
finic mineral oils and the hydrocracked oils. For industrial applications, either heavily inhibited mineral oils are needed
gas turbines and the combined cycle units that have high op- or the use of the thermally stable synthetic lubricants will be
erating temperatures, the use of the hydrocracked oils in- beneficial.
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422 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
conditions, such as contact with hot surfaces. Esters are not cies, which include their low viscosity indices, which greatly
compatible with neoprene seals. Table 9.11 lists specifica- diminish their lubricating ability at high temperatures; their
tions and the tests required for the fire-resistant fluids 关214兴. high density, which requires more power for circulation;
Triaryl phosphates are produced by the reaction of alky- sensitivity to moisture; and aggressiveness towards materi-
lphenols with phosphorus oxychloride, or phosphoryl chlo- als, such as paints, coatings, and elastomers.
ride. Alkylphenols are either petroleum in origin or synthetic We commented earlier that polyol esters are promoted
in origin. Petroleum-derived alkylphenols are obtained from as low flammability lubricants. Table 9.14 compares the fire
the crude oil through distillation and are mixtures of cresols resistant properties of two esters with each other and with
and xylenols, commonly known as cresylic acids. The phos- the mineral oil 关214兴. The data indicate phosphate esters to
phates derived from them are also mixtures that contain tric- be the best, polyol esters to be the next best, and the mineral
resyl phosphate and trixylyl phosphate in varying ratios, oil to be the worst. The superiority of the phosphate esters
which depend upon the composition of the cresylic acids over polyol esters as fire-resistant fluid is demonstrated by its
starting materials. Synthetic alkylphenols are made by alky- excellent performance in the hot manifold ignition test, wick
lating phenol with propylene, butylene, or its oligomers. See ignition test, and the compression ignition test. Since polyol
Fig. 9.6 for the synthetic sequence. Please note that although esters meets all the requirements listed in the table, except
in the figure only a single structure for each alkylphenol is that of the wick test, for most applications, the polyol esters
provided, many other isomers exist. All aryl phosphates are may do an adequate job and at a lower cost. Since all phos-
not alike and they differ in properties, which are listed in phate esters are fire resistant, there are additional properties
Table 9.12 关214兴. As one can see, trixylyl derivative, which that help select the right phosphate ester for the right appli-
contains two methyl groups, outperforms others in most cation. For example, in steam turbine applications, where
properties. Properties of phosphate esters are compared contact with water is most likely, hydrolytically more stable
with those of the mineral oil of similar viscosity in Table 9.13 tri-xylyl phosphate ester may be more suitable, and in gas
关214兴. The data indicate phosphate esters to be better than turbines where superior oxidative stability is important, the
mineral oils in all properties, except water content and rust use of tri-t-butyl phosphate may be warranted, see Table 9.12
prevention. Phosphate esters also possess excellent antiwear 关214兴. It is important to note that like most organic materials
performance, as indicated by the hydraulic pump test phosphate esters are not completely nonflammable. They
共ASTM D2882兲. Phosphate esters have a number of deficien- will burn if enough energy is supplied, resulting in the for-
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CHAPTER 9 䊏 MISCELLANEOUS INDUSTRIAL LUBRICANTS 425
ture of the many types of chemicals. The compressors that ciprocating type compressors are equipped with cooling
move gas are located in ships and drilling fields, in chemical jackets and water or water-glycol refrigerant is circulated
and process plants, and in the maze of pipes that make up the through them. Despite this, the lubricant for these types of
distribution network to bring gas to the market in a pure, compressors must perform the function of a coolant as well.
useable form. For transportation and storage, natural gas The reciprocating type compressors contain two sets of
must be compressed to save space. parts: The cylinder parts and the running parts 关682兴. The
Compressors can be classified into two basic categories: cylinder parts include pistons, piston rings, cylinder liners,
Reciprocating and rotary. Reciprocating compressors are cylinder packing, and valves. The running parts include
used for compressing air, natural gases, and other process cross-head guides, the main bearing, and the wristpin,
gases when the gas flow rates are low and the desired pres- crankpin, and cross-head pin bearings. Although in some
sures are high. These compressors compress gas to increase cases, it is possible to use the cylinder lubricant to cool both
pressure by physically reducing the volume of the gas con- types of parts, in other cases different lubricants are used for
tained in a cylinder by the use of a piston. The piston may be each type. This is to avoid exposure of the cylinder lubricant
driven by a crankshaft. The compressors can be stationary or to the compressed gas at high temperatures.
portable, can be single or multi-staged, and can be driven by The screw type compressors are either dry or wet 共oil-
electric motors or the internal combustion engines. Rotary flooded兲. Dry screw type compressors have rotors that run
compressors use two meshed rotating positive-displacement inside a stator, without a lubricant 共or a coolant兲. For the oil-
helical screws to force the gas into a smaller space. These are flooded type, the lubricant is injected into the gas that is
usually for continuous, commercial, and industrial applica- trapped inside of the stator. The ambient temperature that
tions, both stationary and portable. They are commonly the lubricant is exposed to is 80 to 115 ° C 共180 to 240° F兲.
used by the roadside repair crews for powering their air The lubricant and the gas mixture from the compressor dis-
tools. This type of compressors is also used in many automo- charge line goes into a gas/lubricant separator where the
bile engine super-chargers because of the ease in matching compressed gas is separated from the lubricant. After sepa-
the induction capacity of the piston engine. Rotary compres- ration, the lubricant is cooled and filtered, then pumped
sors are further classified into positive displacement and the back into the compressor housing and bearings. The func-
dynamic types. A positive displacement compressor utilizes tion of the lubricant is to cool, seal, and lubricate. Unlike the
gas volume reduction to increase the gas pressure. Examples reciprocating type compressors, which are once through, ro-
of this type of compressors include rotary screw, lobe, and tary compressors, such as the screw compressor, continu-
the vane types 关682兴. ously recirculate the lubricant-gas mixture to facilitate gas
There are many options to power a compressor. These cooling and separation 关683兴. Lubrication of the rotary vane
include the use of gas turbines 共jet engines兲, steam turbines, compressors is also once through and the lubricant injected
or water turbines for large compressors; electric motors for into the compressor exits with the compressed gas and is not
static compressors; and alternating current, diesel engines recirculated.
or gas engines for portable compressors and for compres- Table 9.15 shows the operating temperatures of the vari-
sors used for super-charging and turbo-charging. Super- ous types of compressors and the associated lubrication-
charging uses the crankshaft power and turbo-charging uses related problems 关682兴. It is obvious that the compressor lu-
the exhaust gas energy. bricants must possess excellent thermal and oxidative
As mentioned earlier, the compression process causes stability.
an increase in temperature. This is due to the release of the
kinetic energy of the air or the gas molecules as their motion Compressor Lubricants
is confined to a small space. Most of this heat must be re- Compressor lubricant must be selected based upon the
moved by means other than the lubricant since the extreme equipment’s lubrication and cooling needs which are defined
temperature will cause rapid degradation of lubricant, both by the compressor design, pressures involved, operating
thermally and due to oxidation. Hence, cylinders in the re- temperatures, and the gas being compressed. Piston com-
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426 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
pressors generate the highest gas pressures; hence have the same lubricant as that used in the power unit which is driv-
highest ambient temperatures. Their needs are usually met ing the compressor. Hence, a compressor driven by a gaso-
by the use of the R&O oils. Vane type compressors have ex- line engine will be lubricated with an engine oil and a com-
tensive metal-to-metal contact; hence they need good EP pressor driven by a natural gas engine will be lubricated by a
protection. If the lubricant selected for a particular compres- natural gas engine oil. Industrial compressors, on the other
sor is not appropriate, the following problems will surface. hand, use R&O oils and antiwear hydraulic fluids but the
1. Increase in oil viscosity and total acidity ideal choice is that recommended by the compressor manu-
2. Copper corrosion facturer. Centrifugal compressors, often called dynamic or
3. Sludge deposits kinetic compressors, are driven by a high-speed impeller or
4. Substantial oil entrainment in discharge gas 共air兲 due to bladed rotor turning inside a close fitting shroud. These are
decreased efficiency of the demister element used in applications, such as in a steel mill, where high air
5. Oil strainer plugging volumes are required. Gear drive type compressors use anti-
6. Bearing failure wear oils and direct drive compressors use R&O oils. Recip-
Desirable properties in a compressor lubricant are al- rocating compressors, which operate under fixed condi-
most analogous to those of the other industrial lubricants, tions, due to sliding friction of the piston have even higher
such as hydraulic fluids and turbine oils, discussed so far operating temperatures. This can cause a build up of the
and include the following 关685–687兴. carbon-like deposits on the upper cylinder heads, which can
1. Oxidation resistance cause fire and explosion. R&O or anti-wear oils are normally
2. Thermal stability recommended for use in these compressors. These lubri-
3. Suitable low and high-temperature viscosity cants are often formulated from naphthenic base oils be-
4. Low pour point and good low-temperature pumpability cause they produce softer deposits on the cylinder heads,
5. High viscosity index which lowers the maintenance and operating costs.
6. Low volatility/high flash point Rotary sliding vane compressors involve boundary lu-
7. Superior antiwear performance brication conditions in addition to the high temperatures;
8. Good demulsibility hence they require lubricants that possess oxidation stability
9. Rust and corrosion inhibition as well as antiwear performance. As mentioned earlier,
10. Good hydrolytic stability screw compressors are either of the “dry” type or of the
11. Materials compatibility “flooded or wet” type. In dry compressors, screws do not con-
12. No sludge formation tact and hence they do not need a lubricant and the com-
13. Low foaming tendency pressed gas is delivered oil-free. However, these compressors
14. Good cooling ability do need gear oils. In a “wet” screw compressor, the incoming
15. Nontoxicity and environmental compatibility air is mixed with the lubricating oil, which helps cool the
Compressor lubricants are usually formulated by the compressed air and provides a seal between the rotating
use of low viscosity base stocks so as to facilitate lubrication screws. The oil is separated from the compressed air, cooled,
through narrow valve and piston clearances and tight fitting and recycled. Synthetic lubricants that have greater thermo-
vanes. These oils generally possess good thermal stability oxidative stability are often used in these compressors.
and oxidation and corrosion resistance. Compressors use a Compressor lubricants are formulated by the use of the
variety of lubricants, including engine oils, hydraulic fluids, mineral oils, both solvent-neutral and hydrotreated. Naph-
and automatic transmission fluids 共ATFs兲. In most cases, the thenic oils are often preferred because of their superior
OEMs recommend custom formulated fluids for their sys- pressure-viscosity relationship and good low temperature
tems and because of this the compressor lubricants lack the properties. These base stocks are supplemented with oxida-
standard performance tests. Most specifications define only tion inhibitors to improve their oxidation performance and
physical characteristics, such as viscosity, flash and fire the sludge forming tendency, foam inhibitors, rust and cor-
points, and pour point; but none defines parameters such as rosion inhibitors, demulsifiers, and EP/antiwear additives
oxidation life, corrosion protection, or the pump perfor- 关688,689兴. ISO lubricant classification for oil-lubricated air
mance. compressors is provided in Table 9.16 关682兴.
Mobile compressors are generally lubricated with the As mentioned before, some applications require perfor-
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CHAPTER 9 䊏 MISCELLANEOUS INDUSTRIAL LUBRICANTS 427
TABLE 9.16—ISO 6743, Part 3A—Family D compressor lubricant classification for oil-
lubricated air compressors †682‡.
mance that is outside the limits of the mineral oils, necessi- have high VIs, they can depolymerize at temperatures over
tating the use of the synthetic base stocks which are superior 200 ° C 关690兴; hence their use in applications with an ambi-
to mineral base oils in many respects. Common synthetic ent temperature above this must be avoided. PAG-based lu-
base stocks that are used to formulate compressor oils in- bricants work well in compressors used for natural gas, ni-
clude poly共alkylene glycol兲s 共PAGs兲, carboxylate esters, trogen, carbon dioxide, hydrogen, helium, and ethylene
phosphate esters, polyalphaolefins 共PAOs兲, silicones, fluoro- 关697兴. PAOs combine the strengths of the mineral oils, such
carbons, and alkylbenzenes 关690兴. While choosing a lubri- as low gas reactivity and materials compatibility, with good
cant, it is important to consider its reactivity towards the gas viscosity indices, excellent thermal and oxidative stability,
being compressed as well. Some of the gases, such as methyl and hydrolytic stability. Also, their cost is the lowest among
chloride, sulfur dioxide, hydrochloric acid, and ammonia, the synthetic base fluids. Hence, they are used extensively in
are quite reactive towards some of the base stocks, especially formulating rotary screw compressor lubricants 关695兴. For
those that are not of hydrocarbon types 关694兴. compressors used in the food industry, the food-grade com-
PAG-based compressor lubricants are often used in hy- pressor lubricants must be used, which are based on white
drocarbon gas compression applications because of their re- mineral oil 关698兴 or food-grade PAOs 关700兴. The topic of food
sistance to dilution by hydrocarbons 关695,696兴. This is be- grade lubricants is discussed in latter part of the chapter.
cause of the poor solubility of the hydrocarbon gases in these Ester base stocks used in compressor oil formulations
base stocks, which also prevents washing away of the lubri- include diesters, polyol esters, alkyl phthalates, and alkyl tri-
cant from the lubricated surfaces that will result in metal-to- mellitates 关699兴. Esters have excellent oxidative resistance,
metal contact, referred to as dry running 关690兴. However, this high-temperature stability, and solvency; hence they are of-
can lead to a build up of the condensed gases due to high op- ten used as cylinder lubricants for the reciprocating com-
erating pressures in the tank as a separate layer. While PAGs pressors. In addition, the use of the esters minimizes deposit
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428 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
Refrigeration Lubricants
Refrigeration is the process of removing heat from an en-
closed space or from a substance, by lowering its tempera-
ture and maintaining the lower temperature. The removed
heat is rejected elsewhere. The most widely used current ap-
plications of refrigeration are the air-conditioning of private
homes and public buildings and the refrigeration of food-
stuffs in homes, restaurants, and large storage warehouses.
Refrigeration is also used to liquefy gases, such as oxygen,
nitrogen, propane and methane, and in oil refineries, chemi-
cal manufacturing, and petrochemical plants. In petro-
chemical plants, it is used to maintain certain processes at
their required low temperatures, such as alkylation of
butenes and butane to produce a high octane gasoline com-
ponent.
Fig. 9.8—Effect of hydrocarbon gas dilution on viscosity of ISO 220
poly共propylene oxide兲 关682兴.
Typical air conditioning 共A/C兲 and refrigeration systems
operate under elasto-hydrodynamic and boundary lubrica-
tion regimes. This requires the lubricant to form physical or
a. 4-Ball EP and Wear Test 共Test Methods ASTM chemical films to reduce friction and wear. Other lubricant
D2783 and D4172 and IP 239兲 functions include the transfer of heat from one region to an-
b. FZG Visual Method 共ASTM D5182兲 other; to act as a sealant, especially in pressurized systems;
20. Compressor Tests protect surfaces from corrosion; and to suspend system de-
a. Broomwade 2050H Compressor Rig Test 关685兴 bris. In many cases, refrigeration lubricants are required to
b. Reavell VHP 15 Compressor Rig Test 关685兴 be compatible with the refrigerant with respect to solubility,
c. Coalescer Blocking Tendency 共CBT兲 Test 关702兴 miscibility, and chemical interaction 关703兴. The solubility of
21. Gas Solubility into the Lubricant gases in various lubricants and its effect on viscosity was al-
a. Gas Solubility in Petroleum Oils at Atmospheric ready addressed while discussing compressor lubricants.
Pressure 共ASTM D2779兲 The compatibility issue is important because many of the lu-
b. Estimation of Gas Solubility in Petroleum and bricants that were previously used with chlorofluorocar-
Other Organic Liquids 共ASTM D3827兲 bons, such as CCl3F, CCl2F2, and CHClF2, are no longer us-
c. Experimental Determination of Gas Solubility in able with new hydrofluorocarbon 共HFCs兲 refrigerants. This
Liquids 共ASTM D2780兲 is because of the incompatibility of the HFCs with the min-
d. Viscosity of Gas/Liquid Mixtures Under Pressure eral oils and the different lubricating characteristics of the
e. Absorption of the Lubricant into the Gas Phase nonmineral lubricants. Hence new lubricants need additives
关685兴 to improve their lubricity and antiwear properties. These ad-
22. Heat Transfer Efficiency ditives are especially useful in instances where the lubricant
Fig. 9.10—Viscosity decrease due to methane at 50 ° C—PAG versus petroleum oil 关682兴.
viscosity drops due to gas dilution and during shut down and system in an automobile and its high-temperature operating
start-up operations. Since the new lubricants, such as polyol environments, these lubricants require even higher thermal
esters and PAGs are highly polar, they have affinity for water. stability and better seal performance and other materials
This can cause the formation of insolubles via hydrolysis of compatibility. Unfortunately at present no standard tests
some of the base stocks and additives and the cross reaction specific to this application exist.
of the resulting products. The newly formed products can
cause plugging of the capillary tubes and the other expan- Refrigeration Lubricant Selection and
sion devices through deposition, resulting in a loss of perfor- Composition
mance 关704兴. Other properties that are desirable in refrigera- The quality of a refrigeration lubricant, like other lubricants,
tion lubricants include foaming tendency and the effect of is defined by its ability to meet the equipment’s operational
foam on lubrication, on inlet ports of the compressors, and requirements, as stipulated by the OEMs. These require-
the lubricant carry-over during start-up 关705兴. Polysiloxanes ments are translated into lubricant specific parameters and
that modify the surface tension of the bubbles can correct the related tests, which will help the lubricant perform its
this problem. function as desired. Major factors that govern lubricant se-
The initial decision of the industry to use poly共alkylene lection include the refrigerant 共whether CFCs, HFCs, CO2, or
glycol兲s 共PAGs兲 and polyol esters 共POEs兲 as lubricants with ammonia兲, compressor’s low- and high-temperature viscos-
the new HFC refrigerants was based on the assumption that ity requirements, and lubricant-refrigerant compatibility.
mutual solubility and miscibility of the POEs and HFCs due Refrigeration lubricants are formulated by the use of
to similar polarity will facilitate lubricant circulation and both the mineral oils and synthetic base stocks. Of mineral
compressor operation. However, this has been proven incor- oils, paraffinic base stocks are preferred because of their
rect by recent lubricant circulation studies 关706,707兴. high viscosity indices. However, because of a concern for
Automotive air-conditioning lubricants face the same wax crystallization on the expansion valve, capillary line
issues as the home and industrial refrigeration lubricants. plugging, and oil trapping in the evaporators, only paraffinic
These are to find a lubricant that is compatible with the re- oils of low wax content are selected. Naphthenic oils, which
frigerant and has suitable lubricity to provide long life to the are almost wax-free and hence have more favorable pour
pump. Because of the compactness of the air conditioning points, are also used.
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CHAPTER 9 䊏 MISCELLANEOUS INDUSTRIAL LUBRICANTS 431
EP performance. However, the products of reaction of some 1. H1 lubricants: Those that are used in food-processing
of these additives with metal surfaces produce materials of environments where there is a possibility of incidental
low lubricant solubility, which can impair the function of the food contact.
capillaries and the expansion devices due to deposition. Re- 2. H2 lubricants: Nonfood-grade lubricants that are used
action of tricresyl phosphate with polyol esters in the pres- on equipment and machine parts in locations where
ence of water also produces materials that after reaction there is no possibility of food contact.
with metals lead to similar problems. This necessities the 3. H3 lubricants: Food-grade lubricants, typically edible
need to install filter driers and the control of moisture to oils, which are used to prevent rust on hooks, trolleys,
overcome this problem. Moisture content of the lubricant is and similar equipment.
determined by the use of the ASTM Standards E203 and Base fluids and additives allowed for H1 lubricants are
D6304. Typical treatment level of EP/antiwear additives is identified in Federal Government issued CFR 178.3570 Stan-
between 1.0 and 3.0 %. The performance of these additives is dard 关713兴. National Science Foundation 共NSF兲 oversees the
evaluated by the use of the ASTM D3233 test. registration of the new products and maintains records of
Acid Scavengers Class H1 approved lubricants. For an inventory of the Effec-
These compounds are basic materials that are used to neu- tive Food Contact Substance Notifications see Ref 关714兴. For
tralize acids that may form in polyol esters and poly共alkylene further discussion of this topic, please see the food process-
glycol兲s due to the absorption of water or the decomposition ing section of Chapter 10 on Lubricating Greases.
of the EP/antiwear additives. Alkanolamines, long chain
amides and imines, carbonates, and epoxides are among the Transformer Oils
most often used acid scavengers. Typical use concentration A transformer is an electrical device that transfers energy
of these additives is 0.1 to 0.5 %. The major drawback per- from one circuit to another by a magnetic coupling with no
taining to the use of these additives is their reactivity to- moving parts. A transformer comprises two or more coupled
wards other additives, such as the antiwear agents, which windings, or a single tapped winding and, in most cases, a
decreases their effectiveness. ASTM Standards D664, magnetic core to concentrate the magnetic flux. An alternat-
D2896, and D4739 are used to determine the effectiveness of ing current in one winding creates a time-varying magnetic
these additives. flux in the core, which induces a voltage in the other wind-
Foam Inhibitors ings. Transformers are used to convert between high and low
In refrigeration systems, foaming results from mechanical voltages and to provide electrical isolation between circuits.
mixing of the lubricant and the refrigerant and by the sud- Large transformers generate a substantial amount of
den release of the low boiling refrigerant from the lubricant heat and need to be cooled. Power transformers, rated up to
at reduced pressures. While such foam in CFC-mineral oil a few kilowatts, are cooled by natural air convection but for
systems is persistent and does not collapse easily, in HFC- cooling transformers of higher power, a number of alterna-
synthetic lubricant systems it collapses readily. Foam con- tive methods are employed. These include fan cooling, cool-
trol agents that are used in these lubricants are polydimeth- ing by nitrogen or sulfur hexafluoride gas, or by the use of a
ylsiloxanes 共silicones兲 and polyacrylates. Their typical transformer oil 关715兴. This oil is a highly-refined mineral oil
treatment level is 100 to 1000 ppm. ASTM D892 Standard is that is stable at high temperatures. Large transformers, in-
used to determine the foaming tendency of the lubricants. tended for use indoors must use a nonflammable liquid. Pre-
viously, polychlorinated biphenyls 共PCBs兲 were used for this
Miscellaneous Industrial Applications purpose because of their fire resistance and thermo-
Other uses of industrial lubricants are in applications listed
oxidative stability. However, due to their tendency to accu-
below along with their performance requirements.
mulate in the environment and the negative impact, PCBs
Food-grade Lubricants are no longer used in the new equipment. They are replaced
These lubricants are used in machinery that is used in food by highly stable nontoxic silicone-based oils or fluorinated
and beverage production and processing and the manufac- hydrocarbons. Other less flammable fluids, such as canola
ture of food packaging. Machines employed in these opera- oil, may also be used.
tions have many moving parts that require lubricants to op- The function of the oil is to cool the transformer and act
erate reliably and efficiently. Food and beverage as an electrical insulation between the internal electrically
contamination can occur from drips off the chains, hydrau- active parts. Hence, it must be stable at high temperatures so
lic hose failure, oil leaks from seals and gearboxes, or a re- that a small short or arc will not cause a breakdown or fire. A
lease of compressed air containing an oil mist. The use of number of methods are used to keep the oil temperature
nonfood-grade industrial oils and greases is therefore inap- down and include convection cooling, cooling fans, oil
propriate in these settings. If a plant uses a nonfood-grade pumps, and even water via the heat exchangers. Oil-filled
lubricant, the U.S. Food and Drug Administration 共USDA兲 transformers undergo prolonged drying processes to make
allows zero amount of lubricant to come into contact with sure that the oil is free of water. This helps in preventing the
the food. If the lubricant accidentally comes into contact electrical breakdown under load.
with food, the batch must be discarded. Conversely, if the Specifications for the insulating oils for general applica-
plant uses food-grade lubricants, which are nontoxic, odor- tion, based primarily on naphthenic base stocks are pro-
less, colorless, and tasteless, the USDA allows lubricant con- vided in Table 9.18 关716兴. These specifications may also apply
tamination of up to 10 parts per million 关711兴. The USDA to paraffinic oils, with the exception of the aniline point re-
groups food-grade lubricants into three general classes quirement and performance at low temperatures. Uninhib-
关712兴, which are: ited oils do not contain any additives. Inhibited oils are
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CHAPTER 9 䊏 MISCELLANEOUS INDUSTRIAL LUBRICANTS 433
supplemented with either 2,6-di-tertiary-butylphenol, 1. Aniline Point 共ASTM D611兲—measures the oil’s total
2,6-di-tertiary-butyl-p-cresol 共BHT兲, or any other specified aromatic content, which relates to the solvency of the oil
and acceptable oxidation inhibitor. They do not contain any for materials in contact with the oil. The lower the
other additives. The tests performed on these oils include the aniline point, the greater is the solvency effect.
following 关716兴. 2. Carbon Composition 共ASTM D2140兲—the test deter-
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434 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
mines the aromatic, naphthenic, and paraffinic content veloped by the Doble Engineering Company, measures
of the oil. A change in composition can affect oil’s prop- the power factor of an oil while it is being aged at 95 ° C
erties, such as oxidation stability, low-temperature flu- in the presence of copper and air. It indicates the
idity, and the viscosity-temperature relationship 共VI兲. dielectric-loss characteristics of the insulating oil on ag-
3. Color 共ASTM D1500兲—reflects oil quality in the new oil ing.
and the deterioration level of the oil in service. 16. Oxidation Stability 共acid/sludge兲 共ASTM D2440兲—this
4. Corrosive Sulfur 共ASTM D1275兲—measures the test measures the oxidation resistance of an oil by deter-
amounts of the dissolved elemental and thermally un- mining the amount of acid/sludge formed under pre-
stable sulfur, which causes corrosion of the nonferrous scribed conditions.
transformer metals, such as copper and silver. 17. Oxidation Stability 共ASTM D2112兲—this test evaluates
5. Dielectric Breakdown 共ASTM D877 and D1816兲—this the oxidation stability of the new inhibited insulating
problem occurs due to the electrical flashover in an oil. oils. Good oxidation stability is a principal requirement
These tests measure the ability of the oil to withstand for long service life of the transformer oils.
electrical stress at power frequencies without failure. A 18. Gassing under Electrical Stress 共ASTM D2300兲—
low value for the breakdown voltage indicates the pres- gassing tendency is the rate of gas evolved or absorbed
ence of contaminants, such as water, dirt, and other con- by an insulating oil when subjected to electrical stress of
ducting impurities in the oil. sufficient intensity to cause ionization. This characteris-
6. Water Content 共ASTM D1533兲—measures the water tic is positive if gas is evolved and negative if gas is ab-
content in the lubricant. Low water content is necessary sorbed.
for acceptable electrical strength and low dielectric 19. Polychlorinated Biphenyls 共ASTM D4059兲—today’s
losses in the insulation systems. regulations prohibit the presence or the use of the poly-
7. Flash Point 共ASTM D92兲—high flash point minimizes chlorinated biphenyls 共PCBs兲. PCB contamination lev-
the formation of the combustible air-oil mixture except els must be monitored to ensure their absence.
at very high temperatures. 20. Viscosity 共ASTM D445兲—viscosity of an oil affects its
8. Furan Compounds 共ASTM D5837兲—these compounds flow, its cooling ability, and the speed of moving parts in
are generated as by-products of degradation of the cellu- tap changers and circuit breakers. High viscosity oils
are less desirable, especially in cold climates.
losic materials, such as insulating paper, pressboard,
Details of these tests are available from ASTM Stan-
and wood. The presence of these compounds is indica-
dards Books, published by ASTM International.
tive of the insulation degradation.
9. Impulse Breakdown Voltage 共ASTM D3300兲—indicates Lubricants for Air Tools 共Pneumatics兲
the oil’s ability to handle electrical flashover under im- Air tools are devices that are used to accomplish diverse me-
pulse conditions, such as those caused by the nearby chanical processes, such as drilling, hammering, grinding,
lightning strikes and high-voltage switching surges. sanding, and spraying. These tools use compressed air as the
10. Interfacial Tension 共ASTM D971兲—this parameter mea- source of power, which is generated by the use of air com-
sures the ease of rupture of the oil film at the oil-water pressors. Common tools include drills, ratchets, impact
interface. This is related to the foam formation; the wrenches, hammers, grinders, sanders, and sprayers. Air
lower the surface tension, which occurs due to the pres- tools are portable, versatile, convenient, and relatively light
ence of soaps, paints, varnishes, and oxidation prod- weight, and provide the power and speed to accomplish the
ucts; the easier the foam formation. An increase in sur- intended operations quickly and efficiently.
face tension during service indicates an increase in the Air tools employ cylinders and valves that require lubri-
formation of the oxidation products that can attack the cation. The cylinders are used to convert the air pressure into
insulation and interfere in the cooling of the trans- mechanical energy, which is used to perform linear move-
former windings. ment, such as lifting or moving tools and work pieces. The
11. Neutralization Number 共ASTM D974兲—this oil param- valves control the starts, stops, direction, and pressures to
eter measures the amount of acidic or alkaline materi- ensure that the pressurized air follows the intended path.
als. During service, the acidity and hence acid neutral- Lubricants for air tools must possess many of the following
ization number of the oil increases. This indicates the properties.
presence of materials that can attack metals used in 1. Suitable viscosity, consistent with the operating tem-
transformers peratures of approximately ⫺30°C to ⫹50°C.
12. Power Factor 共ASTM D924兲—the power factor of the in- 2. Protection at extreme operating temperatures.
sulating oil indicates the dielectric loss in an oil. A high 3. Lubricate the valves, pistons, and the other tool compo-
power factor suggests the presence of the contaminants nents to protect them against friction and wear.
or deterioration products. 4. Varnish, carbon, sludge, and deposit control 共high deter-
13. Specific Gravity 共ASTM D1298兲—specific gravity of the gency兲.
mineral oil influences its heat transfer rates. Oils of 5. Elastomer seal and O-ring compatibility.
vastly different specific gravities may not mix well. 6. Rust and corrosion protection of the tool’s internal
14. Oxidation Inhibitor Content 共ASTM D2668 and parts.
D4760兲—reflects the amount of oxidation inhibitor left 7. Demulsibility.
in an inhibited oil and can affect service life of the inhib- 8. Reduce icing.
ited insulating oils. 9. Noise reduction.
15. Power Factor Valued Oxidation 共PFVO兲—this test, de- 10. Environmental compatibility.
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CHAPTER 9 䊏 MISCELLANEOUS INDUSTRIAL LUBRICANTS 435
off the chain during the operation. These lubricants also furnace to be shaped by pressing, blowing, pressing and
contain EP/antiwear agents, solid film-forming agents, or blowing, drawing, rolling, or floating to produce the desired
solid lubricants to minimize wear. Because of the extensive products. Pressing and blowing are performed mechani-
use of these devices in natural environments, high biode- cally, using blank molds and glass cut into sections 共gobs兲 by
gradability of the lubricant is a desired trait. Hence, these lu- a set of shears. In the drawing process, molten glass is drawn
bricants use highly biodegradable vegetable oils and syn- upward in a sheet through rollers, with thickness of the sheet
thetic esters. The typical viscosity range for these lubricants determined by the speed of the draw and the configuration of
is from ISO VG 46 to ISO VG 100. the draw bar. The rolling process is similar to the drawing
process except that the glass is drawn horizontally on plain
Lubricants for Concrete Molds or patterned rollers and, for plate glass, requires grinding
Concrete is the most commonly used building material, and polishing. In the float process, the molten glass from the
which is used both for construction and to add decorative refiner moves to the molten tin bath over which the glass is
qualities to buildings and on structures. Whether it is precast drawn and formed into a finely finished surface requiring no
or poured on-site, concrete is shaped with shuttering or grinding or polishing. The end product undergoes finishing
molds. After the concrete has set, it must be possible to re- 共decorating or coating兲 and annealing 共removing unwanted
move the shuttering or mold, without damaging the set con- stress areas in the glass兲 as required, and it is then inspected
crete. The surface of the concrete must have a smooth finish
and prepared for shipment to market. Any damaged or
as well as accurately duplicate the shape of the mold. Mold-
undesirable glass is transferred back to the batch plant to
release agents are therefore indispensable for casting con-
be used as cullet 关Ref. www.epa.gov/ttn/chief/ap42/ch11/
crete or cement.
final/c11s15.pdf兴
In concrete molds, the mold release agents or form oils,
Glass manufacture employs a lubricant at many stages
are used to minimize the tendency of the concrete to stick to
and since it is a high-temperature operation, the mineral oil-
surfaces in contact. These oils are applied to formers and
based lubricants with low thermo-oxidative stability are not
shutters, needed to support the curing concrete. These lubri-
appropriate. This is because such lubricants on burning will
cants are of two types: oil-solvent systems and emulsifiable
generate carbon and ash in scoops and troughs, thereby ad-
oils. Oil-solvent systems use naphthenic oils that contain
versely affecting loading, clarity, and the quality of the glass.
fatty acids, which react with calcium in the concrete to form
Hence, synthetic oils, natural oils, or solid lubricants, such
soaps that provide the needed separation properties and rust
as graphite, are commonly used. Solid lubricant is used as a
protection to the metal shutters. Emulsifiable oils are water-
suspension in a carrier fluid which burns cleanly leaving be-
in-oil emulsions 共invert emulsions兲.
hind a film of the solid lubricant. For example, in order to
Continuing interest in environmentally compatible lu-
bricants, especially in Europe, has led to the development lubricate shears that are used to cut the stream of the molten
and marketing of the bio-based mold-release fluids. Most of glass into gobs 共temperature ⬃900°C兲, a lard oil-based lubri-
them are soy-based, although any natural oil can be used to cant is used which provides both lubrication and cooling.
formulate them 关717兴. In order to maintain a high degree of The next stage requiring lubrication is the blank mold,
biodegradability, many are formulated with highly biode- where the gob obtained from the first stage is transformed
gradable corrosion inhibitors and viscosity-reducing addi- into a hollow container. The lubricants for this stage, called
tives. the swabbing agents, contain wax thickeners and suspend-
ing agents, which although wax-like melt when stirred or
Glass Molding Lubricants rubbed into the swab. The waxes have the advantage of burn-
Commercially produced glass belongs to five broad classes, ing without residue or color. Besides swabbing agents,
which are soda-lime glass, lead glass, fused silica glass, boro- water-based or cured thermoset polysiloxane coatings con-
silicate glass, and 96% silica glass. Of these, soda-lime glass taining graphite are another way to coat the molds. These
accounts for 77 percent of the total glass production and is are applied by spraying and form hard durable coating on
manufactured from sand, limestone, soda ash, and cullet curing. Low concentration graphite and sulfer suspensions
共broken glass兲. Glass production involves four steps: 共1兲 in oil are also used as the oven chain lubricants and lubri-
preparation of raw material, 共2兲 melting in a furnace, 共3兲 cants for conveyers, rollers, hinge pins, and bearings 关592兴.
forming, and 共4兲 finishing. The final products made from When applied to a hot metal surface the oil vehicle boils off
soda-lime glass are flat glass, container glass, and pressed cleanly to leave behind a silvery-black solid lubricant film.
and blown glass. Crushed sand, limestone, and soda ash raw All lubricants in glass production must be environmentally
materials are mixed with cullet, to ensure homogeneous friendly as well as have excellent water separating ability.
melting, and the mixture is conveyed to a batch storage bin
where it is held until dropped into the feeder to the melting Paper Mill/Paper Machine Oils
furnace. The furnace most commonly used is a continuous Paper mill lubricants include greases, gear oils, and hydrau-
regenerative furnace capable of producing between 45 and lic fluids. The dryer sections of the mill experience extreme
272 megagrams 共50 and 300 tons兲 of glass per day. As the ma- temperatures of the superheated steam. In this section, there
terial enters the melting furnace through the feeder, it floats are a large number of roller bearings that require lubrica-
on the top of the molten glass already present in the furnace tion. Lubricants for these bearings must possess excellent
and as is melts, it passes to the front of the melter and eventu- thermo-oxidative stability, rust performance, detergency,
ally flows through a throat leading to the refiner. In the re- demulsibility, and long service life. Premium quality anti-
finer, the molten glass is heat-conditioned for delivery to the wear hydraulic oils and EP gear oils provide the needed per-
forming process. After refining, the molten glass leaves the formance in this application. There is a growing preference
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CHAPTER 9 䊏 MISCELLANEOUS INDUSTRIAL LUBRICANTS 437
for oils that have the ability to simultaneously provide anti- Lubricants for Textile Mills
wear and the extreme-pressure protection. Lubricants used in the fiber and textile industries are either
used for the lubrication of the textile machinery or are used
Lubricants for Rock Crushers as process oils. Process oils are used for processing the natu-
Rock crushers are devices that help reduce the size of rocks ral fibers, the production and processing of the synthetic fi-
that contain minerals. A rock crusher requires several lubri- bers, and for dressing or finishing of the intermediate or final
cants to lubricate hydraulics, gears, bearings, etc. 关592兴. En- products obtained from these fibers. Since these oils are
gine oils are usually of 5W-40 viscosity grade. For gears and close to or in contact with the fibers, yarns, and fabrics, there
bearings, the EP gear oils having USS 224, AGMA 250.04, is a concern for contamination of these materials by the oil
and DIN 51 254, Part 2 performance are used. OEMs recom- in the form of oily residue and non-removable stains, which
mend oils both for gears and hydraulics to have good oxida- may hinder their dying.
tion stability, EP/antiwear performance, rust and corrosion Textile mill lubricants are used to lubricate various parts
inhibition, demulsibility, and low foaming tendency. Gear of the textile machinery and include R&O type oils of ISO
viscosity grade 22. They are formulated with light-colored
oils are of ISO viscosity grades 150 to 680 共SAE 80W to 140兲
base oils or highly-refined technical white oils so as not to
and hydraulic fluids are of ISO viscosity grades 46 to 68 with
mar the fiber and/or the fabric. Some operations need fric-
ATF type performance.
tion reduction and wear control; hence these oils are formu-
lated with fatty oils to offer wear protection under high
Rock Drill Lubricants
speed, start-up conditions. Other oils, such as the coning lu-
These lubricants are used for percussion air tools, which in-
bricants, are formulated with emulsifiers and antistatic
clude rock drills, jackhammers, stoppers, drifters, wagon agents to reduce snagging and pulling of the yarn when it
drills, pavement breakers, pneumatic pile drivers, ballast comes off the cone 关592兴. For fast-running textile machinery
tampers, and chipper hammers. The moving parts in rock medium to high-viscosity lubricants of ISO viscosity grade
drills are lubricated by the oil mist which is carried through 68 and higher are used. This is to minimize their spattering
the drill by the passing air. These lubricants must possess on the fiber and the fabric by spindles rotating at speeds of
good thermal and oxidative stability, provide good EP/ up to 15,000 rpm. Sometimes tackifiers are added to improve
antiwear performance, inhibit rust, corrosion, and foam, adhesion properties of these oils. Some formulations con-
and possess emulsifying properties to absorb the excess wa- tain aging inhibitors that insure prolonged service of up to
ter that may be present in the air that is passing through the 5000 h and facilitate the removal of the oils by washing, even
system 关592兴. In addition, these lubricants must be compat- when they have been in prolonged use. Premium products
ible with steel, copper, and alloy parts, and have low odor also contain additives that facilitate the removal of the oil
and be non-toxic. Non-toxicity is important while drilling in stains from the fabrics.
confined spaces because of the fine oil mist that is emitted For hard-to-process fibers, as those of jute, oil-in-water
along with the exhaust. Viscosity grades for these lubricants emulsions are used to improve working. Such emulsions are
are between ISO VG 46 and ISO VG 320. While selecting a based upon low-viscosity, lightly-colored spindle oils of low
viscosity grade, it is important to take into consideration the odor that contain oleic acid to facilitate emulsion formation
ambient temperature since the air exiting the tool cools the with alkaline water, which is responsible for softening the fi-
lubricant. These lubricants are usually formulated using bers. In the manufacture of some synthetic fibers the thread
high VI paraffinic base oils, tackiness agents, and select addi- that leaves the nozzle is coated with a fine film of a colorless
tives to provide rust and corrosion inhibition, resistance to petroleum fraction of 260 to 330°C boiling point to permit
foaming, excellent oxidation stability, and superior load- further processing. While this oil is designed to evaporate
carrying ability. during the subsequent steps, sometimes an oily residue re-
mains which may lead to yellow discoloration of the prod-
Slide Way Lubricants ucts. This yellow color may be hard to remove if the oil has
A slide way is a track upon which a machine tool slides back inferior ant-aging characteristics. Staple fibers are treated
and forth during certain manufacturing processes. Slide after spinning with white-oil based formulations 共winding
ways are also found in lumber mills, on the saws and car- oils兲, in order to give the thread or yarn favorable processing
riages used to produce lumber. Slide way lubricants help characteristics. An important role of the mineral oil compo-
provide smooth tool movement and eliminate sticking and nent is to lubricate the thread so that the fiber experiences a
uniform pulling force. This is achieved by the use of the
chatter. Heavy loads squeeze the lubricant film out, thereby
tackifiers. Another group of lubricants that is used is called
producing boundary lubrication conditions 关592兴. These oils
“tearing oils,” which are light-colored mineral oils that con-
must perform at extreme temperatures, high loads, in the
tain friction-reducing additives. Their function is to prevent
presence of moisture, and in poor ambient air quality envi-
tearing of the used yarns and threads during re-spinning to
ronment. Hence, they must possess EP activity and rust and
obtain better quality yarns with long fibers.
corrosion-inhibiting properties. Slide way lubricants there-
fore contain EP/antiwear agents and rust and corrosion in- Vacuum Pump Fluids
hibitors. For use in vertical slide ways, the lubricants are Vacuum pumps reduce pressure of an environment below
supplemented with tackifiers that minimize run-off. Viscos- atmospheric and in effect are compressors working in a re-
ity range for these lubricants is between ISO VG 46 and ISO verse manner. Vacuum pumps are of three functional types:
VG 100. For more information on these lubricants, please re- mechanical, diffusion, and ejector. Mechanical type includes
fer to Chapter 11 on Metalworking and Machining Fluids. reciprocating, rotary, and dynamic units which are identical
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438 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
to compressors of the corresponding type. In general, the lu- wire ropes are made from high carbon steel for strength, ver-
brication requirements of mechanical vacuum pumps are satility, resilience, availability, and cost. Wire ropes may be
similar to those of their compressor counterparts. These are uncoated or galvanized.
lubricated with mineral oil, turbine oils, or other high qual- Lubricating wire ropes is not easy, irrespective of their
ity R&O circulating oils. Mineral oil-based lubricants cool, construction and material. The ropes with fiber cores are
lubricate, and provide a seal in piston and rotary vane air somewhat easier to lubricate than those made exclusively
vacuum pumps. The lubricant must have low vapor pres- from steel. Wire rope lubricants are used to reduce friction,
sures for maximum vacuum efficiency. ISO viscosity grades as the individual wires move against one another and other
of these lubricants range from ISO VG 32 to ISO VG 100. For surfaces, and rust and corrosion protection. These lubri-
pumps that handle moisture, 3 to 7 % fatty oil may be added cants are of two types: those that penetrate and those that
to counteract the effect of water condensing on the cylinder coat. Penetrating lubricants contain a petroleum solvent
walls. High vacuum rotary oil-sealed pumps may be lubri- that carries the lubricant into the core of the wire rope and
cated with ISO viscosity grade 68 straight mineral oils. then evaporates, leaving behind a heavy lubricating film to
Chemical stability and low-vapor pressure of the diesters protect and lubricate each strand. Coating lubricants pen-
and the phosphate esters make them good candidates for ap- etrate slightly and seal the outside of the cable against mois-
plications in cases where petroleum-based oils are not suit- ture and harmful elements. This reduces rust, wear, and fret-
able 关592,719兴. Diffusion pumps and ejector pumps have no ting corrosion of the external surfaces. Since most wire
moving parts to be lubricated. Diffusion pumps utilize a high ropes fail from the inside, it is important to make sure that
velocity vapor stream to entrain and remove the molecules the center core receives sufficient lubricant. A combination
of the gas being evacuated from the system. Oil or another approach in which a penetrating lubricant is used to saturate
suitable substance is evaporated to produce the vapor the core, followed with a coating lubricant to seal and pro-
stream. Ejector pumps use high-pressure steam or another tect the outer surface, is recommended. Wire rope lubricants
gas, which is discharged through a nozzle that directs a high can be petrolatum, asphalt, grease, petroleum oil, or the veg-
velocity jet across a suction chamber into a venturi-shaped etable oil-based 关720兴. It is important to note that when the
diffuser case. Molecules of the gas being removed are picked asphaltic materials are used to enhance adhesion, lubricant
up and entrained in the jet stream and discharged with it. hardening and chipping off can occur at cold temperatures,
Vacuum pumps, especially of the diffusion type, are for example, those encountered in mining operations.
used in a number of research and instrumentation related Wire rope lubricants are formulated with rust inhibitors
applications. Examples include electron microscopes and and EP/antiwear agents. Typical viscosity grades for wire
vacuum evaporators and the associated instrumentation. rope lubricants are between ISO VG 32 and ISO VG 100.
Pump fluids are classified according to the vacuum pump Tests used to assess suitable performance of a wire rope lu-
type, for example, mechanical versus diffusion; or by the bricant include four-ball EP 共ASTM D2783兲, salt spray
fluid type. Fluids used in these pumps are based on hydrocar- 共ASTM B117兲, and humidity cabinet 共ASTM D1748兲 关721兴.
bons, poly共phenyl ether兲s, perfluorinated polyethers, sili- Table 9.19 compares typical properties of three materials
cone, or diesters 关718,719兴. which are often used as wire rope lubricants 关720兴.
Lubricants for Wire Ropes or Wire Cables
Wire ropes are used in many machines and structures to per- Machine Tool Lubricants
form a number of functions, such as pulling, dragging, and Machine tools are a set of basic tools that the industry uses to
hoisting. Applications include drag lines, cranes, elevators, create many of its products. These include milling machines,
shovels, drilling rigs, suspension bridges, and cable-stayed lathes, grinders, planers, broaches, drills, and a wide variety
towers. There are many kinds of wire ropes, each type de- of other multipurpose and specialized tools. The quality of a
signed for a specific application. Most ropes are made of con- machine tool is determined by its precision which is greatly
tinuous wire strands wound around a central core. The core facilitated by a quality lubricant. A lubricant helps achieve
may be made of steel, fiber, and even plastic. However, most this by reducing friction, heat, and wear. Depending on the
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CHAPTER 9 䊏 MISCELLANEOUS INDUSTRIAL LUBRICANTS 439
complexity of the machine, it may require one lubricant or heavily-loaded ball and roller element bearings. Greases
many lubricants. For example, if the machine contains a containing MoS2 are also used in extreme pressure applica-
power transmission, it will require a transmission fluid. If it tions, especially in machine parts that operate at very low
contains bearings, it will require a bearing lubricant or lubri- speeds. Normally greases used in machine tools do not con-
cating grease. In some cases, no lubricant is necessary since tain fillers such as clay, mica, or asbestos. Lubricating
the machine tool component has a wear-resistant surface greases of NLGI Grades 1 and 2 take care of the lubrication
coating of chromium or phosphate. needs of most applications.
When a lubricant is necessary, one must consider a
number of factors before selecting a suitable lubricant. Lubricants Used in Mining Industry
These include ambient and operating temperatures, humid- Lubricating mining equipment poses a challenge, primarily
ity, and particles in the air. This is because these factors can because of the distinctive operating environment. Because
profoundly affect precision and surface finish. Depending on of the space constraint, mining equipment dimensions are
the machine element, the lubrication method may be small, which tends to limit the size of the lubricant sumps or
manual, partial immersion, splash, centralized forced feed, reservoirs, the amount of air space around them, and the size
or oil mist type. These and other lubrication methods were of the bearings and bearing surfaces. These factors increase
described in Chapter 1 on Lubrication Fundamentals. The the lubricant and bearing temperatures, gear pressure, and
viscosity of these oils is defined by ISO viscosity grades. loadings, and makes servicing of these parts difficult be-
Gear oils used in machine tool applications are based on cause of the space limitations. In addition, the presence of
mineral base stocks that contain extreme pressure additives dust in the air further exacerbates the situation.
to provide high-load carrying capability. The additive may be Mining environment determines the extent of the lubri-
animal tallow or preferably of sulfur-phosphorus type. These cation challenges, If the ore is located near the surface of the
lubricants are required to lubricate highly loaded gears or earth, the mining is called “surface” or “strip” mining and
gears, such as worm gears, that have extensive sliding con- “open pit” techniques are used. The lubrication needs of ma-
tact. For lightly loaded high-speed gears, hydraulic fluids or chinery in this case are different from that used in under-
spindle lubricants suffice. Typical viscosity ranges for gear ground mining where the ore is located in the earth’s crust at
lubricants are ISO 68, 150, 320, and 460 共SAE 80W to 140兲. some depth. Primary factors that alter the nature of lubrica-
Spindle oils are highly refined mineral oils with good oxida- tion in the two cases are the amount of dust and the tempera-
tion resistance. These oils typically are of low viscosity 共2 to ture differential. Dust is the particulate matter, airborne or
22 cSt at 40°C兲 since they are used to lubricate parts, such as otherwise, that may contaminate the lubricant and impede
antifriction and hydrostatic bearings, electromagnetic its flow through small orifices. If the dust is acidic, it may
clutches, and lightly loaded gears, that have high operating cause an additional concern since it may hydrolyze the lubri-
velocities. Other common lubricants that are used in ma- cant components, thereby leading to corrosion of the mining
chine tools are slide way lubricant, hydraulic fluids, and equipment. Temperature effects are related to the lubricant’s
greases. As mentioned in the earlier part of the chapter, the viscosity change. Too high a temperature will lower the lu-
primary function of slide way lubricants is to prevent stick- bricant viscosity, which will impair its ability to form a suit-
slip; hence they are formulated with anti-squawk and tacki- able lubricating film to protect surfaces against friction and
ness additives to lubricate plain bearing slide ways. These lu- wear. Too low a temperature will increase lubricant viscosity,
bricants usually are of ISO viscosity grades 32, 68, and 220. causing “drag” or even failure to flow to the critical parts.
Hydraulic oils used in this application are either R&O 共rust High temperatures will also increase the oxidation rate of
and oxidation inhibited兲 oils or antiwear hydraulic fluids. the lubricant which may result in an increase in its viscosity
While the basic function of the hydraulic oils is to transmit and also produce deposit-forming species. An additional fac-
power, they also lubricate pumps, valves, and other system tor that may need to be considered when mining in closed
components. R&O oils have adequate performance in low- environment is potential fire hazard. This implies that the lu-
pressure systems but for high-pressure systems, especially bricants used in this type of environment must have a high
those employing vane and rotor type pumps, fluids with flash point.
good oxidation and antiwear performance may be required. Mining operation uses both automotive and industrial
These oils contain either metal-free sulfur-phosphorus com- equipment and includes engines operated on diesel, gaso-
pounds or stabilized zinc dialkyl dithiophosphates as anti- line, LPG, and natural gas fuels; gear systems; hydraulics;
wear additives. Normal zinc dialkyl dithiophosphates are and various other devices that need to be lubricated. Engines
too unstable to be useful in controlling oxidation and wear are lubricated with good quality four–stroke cycle and two-
since they easily decompose in the presence of moisture, stroke cycle engine oils of suitable viscosity. Please note that
copper and bronze, and elevated operating temperatures the oil and the oil filter change interval is likely to be nar-
and lead to sludge formation due to oxidative degradation of rower for engines used in mining than for those used in on-
the lubricant. Hydraulic fluids typically are of ISO viscosity road and other off-road applications. This is because of the
grades 32, 46, 68, and 150. Lubricating greases used in this dusty and the enclosed environment. A typical way of deter-
industry are multipurpose and are used to lubricate plain mining a lubricant’s in-sevice life is to analyze it for wear
and roller element bearings and miscellaneous other parts. metals; the amount of water, fuel, coolant and silica that is
Lithium soap greases are often preferred, primarily because part of the dust; oil thickening; and base reserve.
of their excellent resistance to softening upon working and Automotive gear lubricants are primarily used in auto-
good resistance to removal by water. Extreme pressure motive equipment utilized in open pit mining and are of
greases containing EP additives are also used in lubricating GL-4 or GL-5 quality. While for enclosed industrial gears the
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440 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
R&O oils usually suffice they may be substituted with an EP lubricant. Such lubricants must have increased oxidation
product if an unusual rise above ambient temperature is ob- stability, lower volatility, and higher viscosity index; all these
served. This is to offset any drop in lubricant viscosity due to properties exist in synthetic lubricants. Hence, they are ideal
the higher temperature which will adversely affect a lubri- for sealed-for-life applications. Examples include sintered
cant’s film-forming ability. Open industrial gear lubrication metal plain bearings that are used in appliances, hand tools,
may involve continuous or intermittent lubrication. Con- and automotives, and high-speed spindle bearings that are
tinuous lubrication methods include splash or idler immer- used in many applications. Lubricants based upon PAGs, es-
sion, gravity feed, drip, and recirculating spray. Intermittent ters, and perfluorinated aliphatic ether 共PFAE兲 provide ex-
lubricating includes manual application and maually- cellent performance in sintered bearings and the lubricants
activated or automatically-timed mechanical sprays. based on esters and PAOs perform well in high-speed spindle
Hydraulic fluids used in mining include mineral hy- bearings.
draulic fluids, R&O oils, antiwear-R&O oils, and fire- Some synthetic lubricants have the ability to survive
resistant hydraulic fluids. For details on these fluids, please specialized environments, such as vacuum, pure oxygen, ac-
refer to Chapter 7 on Hydraulic and Transmission Fluids. ids and alkalis, and solvents. For example, lubricants based
Underground mining operations utilize most types of fire- upon PFAE and PTFE 共polytetrafluoroethylene兲 are most
resistant fluids, which is due to the enclosed nature of the op- suitable for aero-space and vacuum applications. This is be-
eration and sometimes due to government mandate. Lubri- cause of their extremely low vapor pressure
cating greases used in mining equpiment are both specialty 共⬍10−9 mbar at room temperature兲, high thermal stability
and general-purpose types. However, the growing trend is to without deposit formation 共up to a temperature of 350 ° C, or
use only general-purpose greases, which is to manage inven- 650 ° F兲, resistance to electron and ion bombardment, and
tory storage limitiations and costs. In addition to the lubri- ignition resistance. Lubricants based upon polyalphaolefins,
cants discussed so far there are additioanl lubricants that are silicones, and polyglycols offer varying degree of resistance
used in the mining industry 关Okon, L. W., “Mining Industry,” towards the aggressive species listed above and are therefore
CRC Handbook, Vol. I, pp. 405–430兴. These are listed below. suitable for use in environments that contain them. PAGs are
At least three of these were discussed in the earlier part of less prone to hydrocarbon dilution; hence they maintain
this chapter. their viscosity in high hydrocarbon environments. There-
1. Dragline cam lubes. fore, they are lubricants of choice in propane production and
2. Rope oils. refrigeration. PFAE, in view of being inert, can be used in al-
3. Rock drill oils. most all aggressive environments 关447兴.
4. Compressor oils. Concern for chemical accumulation in the environment
has led to an interest in developing environmentally degrad-
able lubricants. One of the tests that are used to determine
Industrial Uses of Synthetic Fluids
the environmental compatibility of a substance is a 21-day
While discussing turbine oils, compressor lubricants, and biodegradability test, CEC-L 33-T 82. A lubricant is consid-
refrigeration lubricants, we commented on the use of the ered highly biodegradable if 90 % or more of the sample de-
synthetics and their unique attributes. There are many other grades during the test. Typically, mineral oils and PAGs de-
applications that can benefit from the use of synthetics. In grade 20 to 40 %, diesters and polyol esters degrade ⬎90 %,
addition, there are many industries which use processes that and poly共ethylene glycol兲s degrade ⬎90 %. For greases, all
involve temperatures between 150 ° C and 1000 ° C to manu- currently used thickeners are suitable.
facture and finish their products. These temperatures are ei- Examples of some of the industrial operations that can
ther at the borderline or outside the effective range of the benefit from the superior properties of the synthetic lubri-
mineral oil-based lubricants; hence synthetic fluids must be cants are described below 关447兴.
used by necessity. In this section, we will discuss the uses of
the synthetics in these applications and industries. Textiles
Synthetic lubricants do not have a direct advantage over Operations in this industry that have specialized lubrication
mineral oils in most applications, but they do possess certain needs include fabric transport through tenter oven to dry
unique properties that give them a performance edge. These and stretch, fabric finishing by the use of a calender machine
include higher viscosity-pressure coefficients and higher that has two or more heavy rolls, and synthetic fiber
surface affinity, for example in synthetic esters, which help production—extrusion of the melted polymer or the poly-
in the formation of thicker lubricant films in ball bearings mer solution through the spinneret to form continuous fiber
and gears, operating under elasto-hydrodynamic and mixed- filaments. Fabric transport uses ball bearings, roller chains,
film lubrication conditions. In addition, synthetics have and sliding chains that operate at temperatures of
higher oxidation resistance, which makes their use suitable 80 to 250 ° C. For ball bearing rollers, PFAE/PFPE-derived
in high-speed environments where significant agitation and grease, thickened with polytetrafluoroethylene 共PTFE兲 par-
aeration occurs. Some synthetics handle heavy loads better ticles, is most suitable since it performs well and requires
than other synthetic and mineral oil-derived lubricants. For only an annual service. For lubricating roller chains and slid-
example, the use of the synthetic hydrocarbon fluids and ing chains, both diester and polyol ester lubricants are em-
PAGs in gear drives operating at high speeds results in lower ployed. Diesters are used if the operating temperature is be-
frictional losses; hence higher efficiency, lower energy con- tween 120 and 200 ° C, and polyol esters are used if the
sumption, and longer life 关447兴. temperature is above 200 ° C. These fluids have the advan-
In some applications, it is impractical or impossible to tages of low evaporation, minimal residue build-up, and
relubricate and the initial lubricant becomes a sealed-for-life lower lubricant consumption 关447兴.
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CHAPTER 9 䊏 MISCELLANEOUS INDUSTRIAL LUBRICANTS 441
Fabric finishing involves passing the fabric through a Automotive Manufacturing Industry
calender machine that has two or more heavy rollers, which Curing of the paints and coatings after the finished compo-
are used to produce special effects, such as luster and em- nent assembly is an important part of the automobile manu-
bossing. The rollers are heated to around 200 ° C by the use facturing process. The trolley wheel bearings of the con-
of a polyglycol circulating fluid, which acts as a lubricant as veyor, which are exposed to temperatures of up to 250 ° C,
well as survives the high temperatures for a reasonable pe- are lubricated with a PFAE-derived grease. The oil-
riod of time. The bearings on the rollers are lubricated with lubricated overhead conveyor systems employ an ester-
ester-based grease, if their temperature is 150 ° C or less; sili- based lubricant.
con oil grease, if it is between 150 and 200 ° C; and PFAE
Brick and Ceramics Industry
grease, if it is above 200 ° C. In synthetic fiber production,
Two major operations in the production of bricks and ceram-
the melted synthetic polymer is converted into fiber by ex- ics are kiln curing and exhaust removal. Premanufactured
truding through a metal disk with small holes, called a spin- bricks are moved into the kiln on a large, heavy-duty cart
nerette. This device, which has a face temperature of 250 ° C, running on steel tracks. Since the wheel bearings in these
is coated with a thin silicone lubricant film, or the separating carts approach a temperature of 1000 ° C, the fluid portion of
agent, to prevent build-up of the polymer residue and clog- the lubricant will either evaporate or burn. Polyglycol 共PAG兲
ging of the holes 关447兴. type fluid, supplemented with solid lubricant to form a
Textiles also involve high-speed operations. For ex- grease-like paste, is used to lubricate these bearings. PAG
ample, separator rollers used in fiber manufacturing can fluids decompose/burn cleanly and leave little or no carbon
reach speeds of up to 30,000 r / min and the false twist tubes residue to hinder the rotation of the wheel bearings. This is
in textile machines operate at speeds as high as because PAG depolymerizes around a temperature of 200 ° C
80,000 r / min. In these operations, the use of the ester- and to form low flash products, leaving behind the dry lubricant
PAO-derived greases eliminates the problems associated on the bearings that help remove the cart from the kiln. Ex-
with the use of the oil mist method of lubrication. haust fans that are used to remove the hot air and fumes
from the process contain sealed-for-life motor bearings,
Wood Products Industry which are lubricated by a PFAE fluid thickened with PTFE
Wood processing has many operations where the use of the particles 关447兴.
synthetic lubricants is beneficial. Board production from
wood particles and fibers mixed with resins is a prime ex- Food Processing Industry
ample. The process involves supporting the particles-resin Baking, painting, decoration of the beverage cans, and heat-
mixture between two steel belts and passing it through a ma- curing, prior to filling, and freezer storage are some of the
chine that uses high temperatures 共⬃240° C兲 and high pres- operations of the food industry that benefit from the use of
sures to convert the mixture into a wooden board. Parts that the synthetic lubricants. Baking involves continually con-
need lubrication are rollers that are between the hot plates veying the food product through the oven. The chains that
and the steel belts, and the chains that drive the rollers and drive the conveyor are equipped with sealed bearings to
the feed guide chains. All these parts are lubricated by an withstand the oven temperatures of 200 ° C and above. These
ester-based fluid, which being thermally stable minimizes bearings are usually packed with a PFAE-derived grease.
the residue build-up due to lubricant oxidation. The chain Painted beverage cans are heat-cured in an oven that typi-
sprocket bearings are lubricated with a PFAE grease to pro- cally operates at a temperature of around 200 ° C. The high
long their service life. speed chains used to bring the cans in the curing oven are
lubricated by an ester type oil to minimize residue forma-
Pulp and Paper Industry tion, resulting from the lubricant oxidation. Bearings used
in blast freezers for food storage help maintain a tempera-
Many of the processes in this industry are similar to those of
ture of −40° C. These bearings are lubricated with silicone or
the textile industry; hence the lubricants employed are simi-
ester greases, using thickener systems that provide low ap-
lar. Calenders and rotating unions, which operate at high
parent dynamic viscosities, to facilitate smooth motion and
temperatures, are lubricated by polyglycol based circulating
low torque operation.
oil and for rotating union bearings, ester grease, silicone
grease, or PFAE/PTFE grease are used, depending on the Metal Industries
temperature. These industries employ a variety of operations where the
use of the synthetic fluids is beneficial. Such operations in-
Plastic Film Industry clude part 共piece兲 forming/die casting, mining/steel produc-
Two of the many plastic film production processes that in- tion, and metalworking. Synthetic hydrocarbon and silicone
volve high temperatures are extrusion and passing the film oils are used as die lubricants and separating agents during
through a die and the film stretching and width control. Ex- the pressure die casting operation. Water-miscible synthetic
trusion produces a sheet or a tube that is forced through a waxes are also used as the separating agents in die casting.
heated die that is at a temperature of 240° C. The sheet film is Synthetic hydrocarbon oils mixed with metallic solids pastes
then subjected to a film stretching and width control ma- are used as ladle dressing. When the ladle is exposed to the
chine that also operates at high temperatures. The die bear- molten metal and the synthetic hydrocarbon oil oxidizes and
ings are lubricated with a PFAE-derived grease, the chains carbonizes to become part of the solid bonding matrix, it
on the film stretching machine are lubricated by an ester acts as a protective insulation. Phosphate esters are used as
type fluid, and the width control spindles are lubricated with fire-resistant hydraulic fluids in steel mills, foundries, and
silicone grease 关447兴. underground mines. Synthetic fluids are often used as water-
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442 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
soluble cutting fluids, grinding coolants, and rolling fluids. and 0.18 % hydroxypropyl t-dodecyl sulfide oxidation inhibi-
The use of the synthetic fluids in place of petroleum-based tors, 0.05 % alkylamine salts of alkyl phosphoric acids and
products results in a drop in the lubricant consumption and 0.002 % tolyltriazole rust and corrosion inhibitors, ethylene-
parts cleaning costs and increases tool life. For detailed dis- propylene oxide copolymer demulsifier, and 0.02 % 共2-
cussion on metalworking fluids, refer to Chapter 11 on the Ethylhexyl/Ethyl兲 acrylate copolymer foam inhibitor. The
Metalworking Fluids. balance is a 90: 10 mixture of 220N and 600N API Group II
base oils. The addition of a pour point depressant and a vis-
Machine Tool Industries
Machine tool manufacturers continuously strive to increase cosity modifier is optional 共formulation extracted from Ref
speed for improving the efficiency of their cutting operation. 关723兴兲.
Bearings used in the cutting devices are typically lubricated Turbine Lubricant „EP…: 2.0 % Synthetic triaryl phos-
with an oil mist that creates the worker hazard. Many manu- phate EP/antiwear agent, 0.3 % 2,6-di-t-butylphenol oxida-
facturers are switching to an ester or polyalphaolefin-based tion inhibitor, 0.075 % caprylic acid vapor phase rust inhibi-
grease as a lubricant, which help them achieve similar tor, 0.017 % benzotriazole corrosion inhibitor, 50 ppm
speeds and eliminates the worker hazard. These greases can poly共alkyl acrylate兲 foam inhibitor, and 0.015 % of alkylma-
also be used to lubricate high speed ball screws on the ma- leic acid and dodecyl di-hydrogen phosphate mixture. The
chine tools. balance is mineral oil 共formulation extracted from Ref
High-speed gears in the gear head of the multi-spindle 关724兴兲.
drives, lubricated with mineral oil, suffer from the sealing Compressor Lubricant: 0.5 % Phenolic and alkylated
difficulties. The result is leakage into the high-speed spindle diphenylamine oxidation inhibitors, 0.1 % alkenylsuccinic
bearings, which reduces their service life. The use of the acid half ester rust inhibitor, 0.1 % triazole derivative corro-
ester—or PAO-based grease eliminates this problem. sion inhibitor. The balance is a base fluid blend comprising
PAO and polyol ester of ISO VG 68 共formulation extracted
Formulation Examples from Ref 关725兴兲.
Turbine Oil/R&O Oil: 0.2 % Ashless dithiocarbamate Refrigeration Lubricant: 0.2 % Ethoxylated phos-
EP/Antiwear agent, 0.05 % tolyltriazole derivative corrosion phate ester and 0.2 % mercaptobenzothiazole EP/
inhibitor, 0.25 % alkylated diphenylamine oxidation inhibi- antiwearagents, 0.3 % propoxylated amine such as
tor. Balance is API Group II oil 共formulation extracted from Jeffamine® rust inhibitor, 0.1 % tolyltriazole corrosion in-
Ref 关722兴兲. hibitor. The balance is PAG fluid of 100 to 1200 SSU
Industrial R&O Oil: 0.375 % Alkylated diphenylamine 共20.5 to 259 cSt兲 at 100° F 共38° C兲. For automotive air condi-
and 0.1 % hydroxyethyl n-dodecyl sulfide oxidation inhibi- tioning a viscosity of 500 SSU 共108 cSt兲 at 100° F is preferred
tors, 0.05 % ethylenediamine salt of dinonylnaphthalene- 共formulation extracted from Ref 关726兴兲.
sulfonic acid and 0.002 % tolyltriazole rust and corrosion in- Pneumatic Tool Lubricant: 0.79 % Sodium petroleum
hibitors. The balance is a 90: 10 mixture of 220N and 600N sulfonate detergent, 0.2 % sulfur, 0.1 % mercaptobenzothia-
API Group II base oils. The addition of foam inhibitor; zole copper corrosion inhibitor, 0.5 % polyisobutylene anti-
demulsifier, pour point depressant, and a viscosity modifier misting agent, and 10 ppm polysiloxane foam inhibitor. The
is optional 共formulation extracted from Ref 关723兴兲. balance is naphthenic base oil 共formulation extracted from
Industrial R&O Oil: 0.75 % Alkylated diphenylamine Ref 关726B兴兲.
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MNL59-EB/Mar. 2009
10
Lubricating Greases
IN THIS CHAPTER WE REVIEW THE TECHNOLOGY 2. Sinitsyn’s definition is based upon rheology rather
of lubricating greases. Because of their distinct physical than the appearance and composition. According to
form relative to liquid lubricants, greases are used in spe- this definition, the lubricating grease is “a lubricant
cialized applications, such as roller bearings and slow which under certain loads and within its range of tem-
speed gear systems, where a liquid lubricant either cannot perature application, exhibits the properties of a solid
be used or has inadequate performance. Composition, body, undergoes plastic strain and starts to flow like a
chemistry, properties, manufacture, and methods to pro- fluid should the load reach the critical point and regains
duce lubricating greases are discussed. The chapter also solid body properties after the removal of the stress.”
includes discussion pertaining to selection criteria, testing 关731兴
requirements, and handling and disposal of greases. We The ASTM definition acknowledges the lubricating
close the chapter with examples of grease formulations. grease to be thickened oil, comprising at least a two-
The use of animal fat in combination with lime, a component system, containing a thickener and a liquid lu-
crude form of the modern lubricating grease dates back to bricant. Sinitsyn’s definition establishes the dual nature of
1400 B.C. 关33兴. In fact, the word “grease” is derived from the grease as being both a solid and a liquid, depending on
the Latin word “crassus” for fat. Lubricating grease is one the physical conditions of temperature, stress, etc. This
of the oldest lubricants used by man. The use of the animal definition also recognizes an additional property of the
fat for lubrication continued until the late 19th/early 20th grease that is not present in a conventional liquid lubri-
century when mineral oil-derived greases were developed. cant, a yield value. Yield value is the minimum shear stress
This occurred after the discovery of petroleum in 1859. In- that produces flow. Shear stress is the force per unit area
cidentally, in this chapter, grease and lubricating grease that causes shearing of a structure. However, shear stress
and oil and fluid are interchangeable terms and imply the differs from stress in that it acts parallel to the surface
same. 共cross section兲, while normal stress acts perpendicular
Mineral oil thickened with calcium carboxylate 共lime 共normal兲 to the cross section. Since each of the two defini-
soap兲 was the first grease that was marketed in volume. tions describes different but important properties of the
This was followed by aluminum stearate grease, sodium lubricating grease, a combined definition is probably more
soap grease, calcium complex soap grease, and lithium appropriate. The combined definition reads “Lubricating
and barium soap greases. A great break through occurred grease is a solid-to-semisolid lubricant that results from
in 1942 when it was discovered that lithium 12- dispersing a thickening agent in a liquid lubricant. It loses
hydroxystearate-derived greases possess superior proper- its structure under load or stress, thereby releasing the liq-
ties. The evolution of the lubricating greases is depicted in uid lubricant, and regains its solid-to-semisolid appearance
Fig. 10.1. One way to look at the timeline is that a particu- after the stress is removed.”
lar lubricating grease had some inherent deficiencies; Obviously, in this definition, we are envisioning the lu-
hence another grease was developed to overcome them. bricating grease to be a two phase system consisting of:
The development of the current generation of lubricat- 1. A liquid phase that may or may not contain
ing greases was first reported in the early 1940s, after the performance-enhancing chemicals, or additives.
invention of lithium12-hydroxystearate-derived grease, 2. A solid phase that either has a network structure, such
which was almost 65 years ago. During this duration, as a metal salt or soap, that has intimate association
many new developments have occurred that have shaped with the oil or fluid, or is simply dispersed in oil, as in
the lubricating grease industry to its present state. The lu- the case of the nonsoap thickeners, such as polyurea,
bricating grease has been defined in many ways 关727–731兴, modified clay, and graphite.
but the two that we find of importance are stated below. Soap thickeners possess interlocked fibrous structures
1. The ASTM definition, provided in ASTM Standard that are responsible for the above-mentioned affiliation be-
D288, defines grease in terms of its physical appear- tween the soap and the lubricant. The mechanism by
ance and composition. This definition characterizes which this occurs will be addressed under the section on
the lubricating grease as “a solid-to-semifluid product soaps. However, the nonsoap thickeners do not usually
of dispersion of a thickening agent in a liquid lubricant. possess fibrous structures and hence do not interact with
Other ingredients imparting special properties may be in- the oil by the same mechanism and to the same degree as
cluded.” Incidentally, because of its inadequacies, this soaps. It is important to note that such a two-phase system
definition of the lubricating grease no longer appears must perform the functions of a lubricant. This primarily
in the book of ASTM standards. occurs when under operating conditions the thickener re-
443
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444 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
leases the lubricant to fulfill the function of lubrication. common to the vertically positioned equipment, and
There are many solid-oil mixtures that look like centrifugal removal usually occurs in equipment that
greases, for example, pastes. However, they differ from lu- operates at high speeds.
bricating greases in two major aspects, their solids content 2. Lubricating greases have the ability to act as a seal
is very high, in the vicinity of 70–95 %, and the affinity against dirt, water, and other contaminants. Examples
between the solid and the oil is not essential. The latter include industrial bearings that are commonly exposed
factor makes such systems unstable and makes them poor to water and exposed gears that encounter a significant
lubricants in applications where greases do an excellent amount of airborne dust.
job. 3. Lubricating greases have thicker film-forming ability
For a lubricating grease to meet the specifications of and better adhesion properties, both of which are useful
the above definitions, the grease must comprise three com- in lubricating equipment/parts that operate at high tem-
ponents: A base fluid, a thickening agent, and an additive peratures and under extreme conditions of shock-
package; and in most cases it must have a network struc- loading, reversible operation, slow speeds, or very high
ture. While a wide variety of agents can disperse in oil to speeds. In this regard, the use of the lubricating grease
yield grease-like dispersions, only those that form disper- assures better friction and wear protection and rust and
sions with lubricating properties are useful. In addition, corrosion protection than the liquid lubricants. Ex-
grease contains additives that impart other desirable prop- amples of parts where lubricating grease is a suitable lu-
erties, such as EP, water resistance, etc. The lubrication bricant include journal bearings that encounter heavy
function is carried out by the small amount of oil that is shock loading and mining equipment that is usually op-
released during the equipment’s operation. Because of erated on slow speeds and heavy loads. Shock loading is
their semisolid nature, greases are used when fluid lubri- an instantaneous and severe increase in stress. It tends
cants are inefficient, the need for lubrication is infrequent, to rupture the thin lubricant film, leading to rapid wear.
and the lubricant is required to maintain its original posi- Greases form durable films. Shock loading is common
tion in a mechanism, or combinations thereof. in the rolling mill operation when a thick steel slab hits
Lubricating grease is a unique product and its cre- the rollers which have been preset to a lesser thickness.
ation, manufacture, and use requires knowledge in chem- 4. Lubricating greases reduce noise and vibration due to
istry, physics, tribology, rheology, formulation, manufactur- worn parts. If their use in equipment designed to lubri-
ing, chemical engineering, and health and environmental cate with a liquid lubricant is possible, they extend the
sciences. For example, the lubricating grease manufacture life of the worn parts by coating them with a thick lubri-
is based on chemistry, but its function as a mechanical bar- cating film.
rier between two moving surfaces comes under the domain 5. Lubricating greases are suitable to lubricate equipment,
of physics; its structural design so that it possesses suitable such as ball bearings, roller bearings, and sealed for life
viscosity to adhere to and stay between the surfaces falls bearings, where the operation is intermittent and the re-
under rheology 共the science of flow兲; and its impact when it lubrication need is infrequent or not necessary.
enters the environment is a concern of health and environ- 6. Lubricating greases are useful in applications where it is
mental sciences. necessary for a lubricant to maintain its properties over
Since lubricant grease is used in a large number of long periods in spite of unfavorable temperature, pres-
machine components, it is important to consider it as an sure, and environmental influences; for example, to lu-
integral part of the equipment design rather than an after bricate aerospace equipment.
thought necessity. 7. Lubricating greases are largely impervious to water and
Lubricating Grease Versus Liquid Lubricant can easily handle small amounts of water.
8. Because lubricating greases are designed to have good
As stated above, lubricating greases are thickened lubricants compatibility with seal materials, in some cases they
with less mobility than their liquid counterparts. Because of can be used as inexpensive seals. This is partly due to
their physical characteristics, the lubricating greases offer a their viscoelastic properties because of which the seals
number of advantages over liquid lubricants, when used in are not constantly subjected to a fresh amount of lubri-
certain specialty applications. Some of the advantages of lu- cant.
bricating greases are listed below. 9. Lubricating greases facilitate the use of the solid addi-
1. Lubricating greases resist leakage through dripping, tives or those that have limited solubility in traditional
splattering, loss due to high pressure, and centrifugal re- mineral base oils or synthetic fluids.
moval. Dripping is a gravity-induced loss, splattering is 10. Lubricating greases, especially those derived from the
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CHAPTER 10 䊏 LUBRICATING GREASES 445
natural acids and fats, can be considered environmen- bility of the sodium soaps. Some of these in the presence of
tally compatible products. Many are biodegradable. water emulsify at room temperature while others need
Of course, lubricating greases also possess the major higher temperatures for emulsification, although in both
disadvantage of lacking little or no ability to provide cooling cases the lubricating grease loses its soap and hence its tex-
and cleaning. In additions, its removal and replenishment ture. Despite this disadvantage, sodium soap greases have a
after it is past its usefulness is not a trivial task. temperature tolerance of about 100° F 共56° C兲 above that of
the calcium soap greases, as long as the use conditions stay
History Of Lubricating Grease Development anhydrous. They have the additional advantages of better
mechanical handling, called working, and better stability
The use of a lubricant to minimize friction dates back in
than both the calcium and the aluminum soap greases. So-
time. As mentioned earlier, the use of fat-based grease dates
dium soap greases have been used to lubricate automotive
back to about 1400 BC. The evidence regarding its use is
wheel bearings, electric motors, and a variety of industrial
based on the analyses of the residues from the wooden axle
machinery. However, they are now being replaced by nonwa-
hubs of chariots and carriages of the ancient Egyptians of
ter washable products with equal or better heat resistance.
that time. The use of animal fat and vegetable oil-derived
In the 1930s and 1940s, search for new thickeners that
greases continued until the mid-1800s at which time the
resulted in better lubricating greases, especially those for
composition of the lubricating greases changed. The pri-
use in multi-purpose greases, ensued. Calcium complex
mary driving force behind this development was the discov-
soaps were developed first which was closely followed by the
ery of mineral oil in 1859 关727兴.
development of lithium soaps and barium soaps. Today,
Lime or calcium soap 共calcium carboxylate兲 greases
date back to the 1880s 关728兴. They were among the first to be lithium soap greases constitute almost 38 % of the total
produced and marketed in volume. These greases were made world production and use. The reasons for the popularity of
by the cold mixing of lime 共calcium hydroxide兲 with rosin oil these products are their superior thermal stability and water
共an acid兲 solution in mineral oil and dispersing the resulting tolerance. Previously, animal fats and fatty acids were used
product in water and oil. Such lubricating grease while ad- as the soap precursors. In some cases, hydrogenated fatty ac-
equate to lubricate the slow-moving machinery of the late ids were subsequently added in an effort to improve the
19th and early 20th centuries has little use in the machines of properties of the resulting grease. A similar approach was
today. extended to lithium soaps. During experimentation, it was
Modern greases owe their invention to the industrial age discovered that the use of hydrogenated castor oil, a triglyc-
when diverse equipment needing superior lubrication was eride of 12-hydroxystearic acid, yielded a soap that led to a
developed. The invention of the modern machines, such as grease with superior overall properties than the greases
automobiles and railroad engines, underscored the need for made from the other fatty acids or esters.
lubricants, including greases, which could survive higher Barium soap greases, although similar to lithium soap
operating speeds and temperatures. Developing the calcium greases in terms of water tolerance and heat resistance, suf-
soap greases made by the reaction of animal fats with cal- fer from poor low-temperature performance. This is partly a
cium bases at high temperatures was the next evolutionary consequence of the high molecular weight of the soap mol-
step. The greases thus formed had a smooth texture and bet- ecule. As a result, these greases are not as popular as the
ter water tolerance than those made by the cold reaction. lithium-based products. In addition, their use is diminishing
However, these greases still required the presence of 1–2 % because of the concern for the toxicity of barium and its im-
water to impart structural stability. As a result, their use was pact on the environment, due to it being a heavy metal. Most
limited to applications that will not experience a tempera- barium soap greases in use are complex soap greases rather
ture of 100° C or more. Otherwise, the fate of these greases than the simple soap greases. Many other grease thickeners
will be no different than that of their counterparts made by were developed during the 1930–1950 period, but most of
cold mixing of the ingredients. The next generation of the derived greases were short-lived, with little or no com-
greases were invented to overcome the use temperature limi- mercial success.
tation. Calcium complex soap grease, the first of the complex
Aluminum stearate soaps led to the formation of lubri- soap greases discovered, has been in use since the 1950s but
cating grease that was clear and smooth, with good water its share is progressively decreasing. The reason for their ini-
tolerance and fair rust resistance. However, its heat resis- tial success was their good thermal stability and the ability to
tance is not that much better than lime soap greases. Limit- carry heavy loads in bearings. Unfortunately their water sen-
ing temperature in this case was around 175° F 共79° C兲, sitivity is one of the reasons for their demise. In the presence
above which it lost its clarity and smooth texture and be- of water, they change their consistency to softer or harder,
came rubbery. The rubbery texture on cooling became brittle depending upon the conditions. Aluminum complex soap
and lost most of the oil. Poor heat resistance of these greases grease was the next complex soap grease to become commer-
is not related to the water loss since these greases are anhy- cial. While these greases have a small share of the overall
drous. They are still produced for use in a limited number of grease market, their use appears to be growing. The primary
applications where their strengths are beneficial. reasons for their increasing demand is their superior water
Anhydrous sodium soap greases were also developed in tolerance, making them the lubricating grease of choice in
an attempt to replace lime soap greases, to overcome the applications that see a substantial amount of water, such as
structural instability due to water loss. These greases, de- in rolling mills. Lithium complex soap greases, which at 30
spite being anhydrous, did not prove very useful since their % enjoy the largest share of today’s complex soap grease
water tolerance is low, owing to the substantial water solu- market, were first commercialized in 1962. The reasons for
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446 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
their overwhelming success are their good water resistance • Application Range—multi-purpose grease, normal
and thermal stability. grease, and specialty grease.
Nonsoap thickeners, like lithium complex soap greases, • Soap Type—soap-free or nonsoap grease and soap-
are also a somewhat recent development. This class of thick- containing grease. While the use amount of the nonsoap
eners comprises organic thickeners and inorganic thicken- greases is smaller than that of the soap-containing
ers. Organic thickeners include polyureas and substituted greases, the nonsoap greases have a larger variety than
ureas; salts of terephthalic acids, phosphoric acids, thio- the soap-containing greases. Soap-containing greases
phosphoric acids, and phosphonic acids; and polyethylenes are classified based on the metal ion of the soap or the
and halogenated polyethylenes, such as Teflon® polycarbo- thickener; for example, lithium, sodium, calcium,
hydrates; and pigments. None of these, except polyureas, barium, aluminum soap greases. The soap in greases
have been used in greases that are commercially available in can be simple soap, complex soap, or mixed soap.
large volume. Originally, arylureas were used to make lubri- Simple soap greases are made from a single carboxylic
cating greases but the new greases use alkyl aryl polyureas
acid. Complex soap greases are made from a mixture of
instead. Polyurea greases have good oxidation stability
carboxylic acids. Usually, one of the acids in such a mix-
which in part may be due their low hydrocarbon content.
ture is a low molecular weight acid. Mixed soap greases
These greases are ideally suited for lubricating ball bearings
contain more than one metal ion. Lubricating grease
that are exposed to high temperatures, such as those used in
classification according to the metal ion is quite useful
electric motors. Polyurea complex greases made from mixed
polyurea-calcium acetate thickeners are also available. since in many cases metal ion imparts certain important
These have extreme pressure properties equal to those of the properties, such as high dropping point, to the lubricat-
calcium complex greases. ing grease. For example, the dropping point of the lime
A variety of inorganic materials have also been used as 共calcium兲 soap greases is around 100° C, but that of
thickeners for lubricating greases. They include modified lithium soap greases is around 180° C.
clays, molybdenum disulfide 共MoS2兲, and graphite. Natural • Base Oil—mineral oil-based grease or synthetic fluid-
clays are hydrophilic and as such are not useful as thickeners based grease. A number of important properties of lubri-
for lubricating grease. However, their structure can be modi- cating greases depend on the oil component 关4兴, which is
fied to make them hydrophobic, or oleophilic, by exchanging discussed later in the discussion.
the alkali metal or alkaline earth cation with a quaternary • Load Level—normal load grease or high load or extreme
ammonium cation. This is achieved by reacting or coating pressure 共EP兲 grease.
the clay with suitable quaternary ammonium salt. The re- • Consistency—consistency is the resistance of the lubri-
sulting modified clays are easy to disperse in oil and the re- cating grease to deform under load, or in other words it
sulting greases are resistant to heat and somewhat resistant measures the degree of hardness of the grease. Consis-
to water. tency is usually measured by the ASTM Cone Penetra-
tion Test, ASTM D217. The higher the penetration, the
Lubricating Grease Classification softer is the grease. Various classes of lubricating
There are a number of ways in which the lubricating greases based on consistency are provided in the Na-
greases are classified. Some of these are listed below. tional Lubricating Grease Institute’s 共NLGI兲 classifica-
• Application—industrial, automotive tion system. Under this system, the lubricating greases
• Application Temperature—low-temperature grease, are classified into nine classes, which are provided in
normal temperature grease, and high-temperature Table 10.1, along with potential applications. This classi-
grease. fication is old but is still widely used.
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CHAPTER 10 䊏 LUBRICATING GREASES 447
Lubricating Grease Market construction are largely responsible for the automotive
grease use. Figure 10.3 shows the break down of the automo-
The actual size of the world market for lubricating tive grease market. The use share of the greases for various
greases is hard to estimate since there is ongoing develop- industries is shown in Fig. 10.4. There are indications that
ment of new products to meet the constantly changing per- compared to the United States the percentage of the indus-
formance specifications and environmental compatibility trial grease consumption in Europe is slightly higher.
requirements. The worldwide production and usage of the It is important to note that various regions of the world
lubricating grease for the year 2007 is estimated at 2.31 bil-
use different quality products because their uses differ. For
lion pounds, or almost 1050 thousand metric tons 关732兴. Fig-
example, North America, Europe, and Japan use higher
ure 10.2 provides use of the lubricating grease by region and
quality products than the rest of the world because of their
Table 10.2 shows its use by thickener type. Lubricating
primary use in more demanding applications. Africa uses
greases represent about 3 % of the total lubricant market; of
products that are specifically suited to lubricate mining
which 7–15 % comprises synthetic greases, depending on
their definition. With respect to the soap greases, lithium equipment and Asia primarily uses polyurea greases.
soap greases amount to 68 % of the worldwide lubricating While in North America and Europe, the use of the low
grease market, followed by the aluminum soap grease at 9 % cost/low performance greases also called commodity
and the calcium soap greases at 6 %. The use of the nonsoap greases predominates; their value in terms of dollars is less
greases is about 15 % and is equally divided between organo- than that of the high performance greases. Commodity
clay greases and polyurea greases. Approximately 51 % of greases are based on lithium, calcium, and sodium soaps
the lubricating greases used in the United States and 78 % of and are normally used as general purpose products. Because
the lubricating greases used in Europe are based on mineral of their high volume use and production, their cost is low.
oils. Regarding the main consumers of the lubricating Besides commodity greases, some multi-purpose greases,
grease, about 50 to 60 % of the greases are used for industrial such as some extreme-pressure 共EP兲 and lithium complex
applications and the rest is needed for automotive applica- greases, are low cost as well and for the same reasons. Con-
tions. Trucks and buses, automobiles, and agriculture and versely, specialty greases which as the name indicates are not
general purpose are designed to meet superior performance. Common thickeners used to make lubricating greases are
Their higher cost is due to the presence of high quality per- listed below.
formance additives that are necessary to meet the higher per- 1. Soap Thickeners
formance requirements of some applications. As will be de- • Simple soaps
scribed later in the formulation section, the additives can be • Mixed soaps
liquid or solid and are used in small amounts to impart the • Complex soaps
desired properties to the lubricating grease. Because of their 2. Nonsoap Thickeners
somewhat higher cost of production and greater use in high • Organic thickeners
performance products, the additives account for the higher a. Polyureas
value of the specialty greases. b. Polytetrafluoroethylene 共PTFE兲
Specialty greases, sometimes referred to as high- c. Fluoroethylenepropylene Polymer
specification greases, because of their ability to meet the • Inorganic Thickeners
higher standards or specifications, are primarily based on
a. Bentonite
complex soaps and highly refined mineral oils or synthetic
b. Silica gel
base fluids. Specialty greases are typically used in applica-
Thickener is the component that is primarily respon-
tions whose performance requirements cannot be met by the
sible for the gel-like structure of the lubricating grease.
commodity greases. As mentioned earlier, North American
Thickeners can be classified into two general classes: Metal
and European use of lubricating greases is largely for highly
demanding applications and therefore it is not surprising soap or metal carboxylate thickeners and the nonsoap thick-
that the use of the commodity greases in these regions is pro- eners. Nonsoap thickeners can be further subdivided into or-
gressively decreasing and that of the specialty greases is in- ganic thickeners and inorganic thickeners. Modern lubricat-
creasing. ing greases predominantly use metallic soaps, of which
lithium soaps top the list in terms of the market share. Ac-
Grease Composition cording to a conservative estimate, soap-thickened lubricat-
Lubricating greases are composed of three components: ing greases account for well over 60% of the greases manu-
These are thickener, base fluid, and additives, which are used factured and used.
to enhance grease properties and performance. While the Soaps are the metal salts of the naturally occurring car-
amount of each differs from grease to grease, as a general boxylic acids. The term soap does not apply to the metal salts
guideline the lubricating grease contains 70–90 % base fluid, of the man-made, or synthetic, carboxylic acids. The metals
which can be mineral, synthetic, or natural in origin; about that have been found suitable to make soaps for use as thick-
5–25 % thickener; and the additives make up the difference. eners in greases are lithium, sodium, calcium, barium, and
It is the base fluid and the additives that perform the lubrica- aluminum. The carboxylic acids or fats and oils that are
tion function and impart various desirable performance commonly used to make these soaps are those that are natu-
properties to the lubricating grease. Soap’s or thickener’s ral in origin. For example, stearic acid is available from the
function is to provide structure to the grease. It contributes animal fat, 12-hydroxystearic acid is available from castor
little, if any, towards the lubrication function of the grease. beans, and oleic acid is available from soybean, cottonseed,
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CHAPTER 10 䊏 LUBRICATING GREASES 449
and many other vegetable oils. These natural fatty acids nor- high and that of soaps of very short chain lengths is very low.
mally contain an even number of carbons in a straight chain The ideal soaps are those that have borderline solubility in
arrangement and preferably contain zero to one double oil so as to maintain its network structure, which is required
bond. in lubricating grease. Optimal chain length for the carboxy-
Fats and oils that are directly used to make these soaps late group in soaps is C18. The presence of the extensive
include animal fats such as beef tallow and bovine fat, and branching in the carboxylate portion increases oil solubility
vegetable oils and fats such as those available from natural and lowers the melting point of the soap. The result is a drop
seeds and fruits, for example coconut oil, palm oil, soybean
in thickening efficiency and the dropping point of the de-
oil, and cottonseed oil. The use of soaps derived from fish oils
rived grease, which is undesired. Unsaturation in the soap
is rare. Frequently, hydrogenation is used to remove the un-
molecule also increases oil solubility and has a similar nega-
saturation present in many natural fats and acids derived
from vegetable oils since it improves the oxidation stability tive effect on thickening and the dropping point of the
of the derived lubricating grease. Hydrogenated castor oil grease. Unsaturation in soap is in addition lowers the oxida-
used to make lithium 12-hydroxystearate is one such ex- tion stability of grease, thereby limiting its use in most high-
ample. The metal to form soaps is in the form of metal oxides temperature applications. Polar groups, such as hydroxyls,
or hydroxides, the hydroxide form being more prevalent. on the other hand, decrease the oil solubility and increase
When the reaction involves a carboxylic acid and a metal the melting point of the soaps. The result is an increase in
base, the reaction is called a neutralization reaction. How- thickening efficiency and the dropping point of the derived
ever, when the reaction involves vegetable oils or animal fats, greases. Of course, the position of these groups on the side
which are also called triglycerides; the reaction is called a sa- chain is also critical to the grease performance. 12-
ponification reaction. Each reaction is presented in Fig. 10.5 Hydroxystearic acid, which possesses all the advantages
by a chemical equation. listed above, is the most widely used carboxylic acid for lu-
Metal ion, or cation, in the soap determines many of the
bricating greases. Lithium and calcium soap greases are
critical properties of the lubricating grease. It determines
among the most desirable of the soap containing greases.
the thickening ability, water resistance, and dropping point.
The use of aluminum, barium, and sodium soap greases is
The carboxylate portion of the grease influences other prop-
erties. For example, the length and branching of the carboxy- progressively decreasing.
late portion affects its oil solubility and hence consistency The thickener structure can range from being linear, as
and the surface properties of the grease. In order to achieve in the case of metal carboxylates 共soaps兲, to more complex
optimum consistency there is an optimal carboxylate chain circular structures, as in the case of the nonsoap thickeners.
length. If the chain length is too long or too short, the thick- Approximate dimensions of the thickener particles along
ening efficiency of the soap will be affected. This is because with the appearance they impart to lubricating greases are
the oil solubility of the soaps of very long chain length is very provided in Table 10.3 关4兴.
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450 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
Soap-thickened Lubricating Greases tion. Some water may remain in the grease. In some cases,
Soaps used in the grease manufacture are classified as for example in the case of calcium grease, its presence is ben-
simple soaps, complex soaps, and mixed soaps. Detailed de- eficial since it help stabilize the grease structure.
scription of each type of soaps and the derived lubricating Simple soap greases make up the largest proportion of
greases is provided in the following sections. the lubricating grease production. These greases contain the
three components in the following ratios: 4–20 % by weight
Simple Soap Greases soap, 75–96 % by weight base oil, and 0–5 % by weight addi-
Simple soaps are prepared by the reaction of a single fatty
tives. The amount of soap used to make the grease also af-
acid and a single metal base. Metal bases of interest belong
fects its consistency: the higher the amount of soap, the
to the groups of alkali metals; such as lithium and sodium,
higher the consistency of the lubricating grease.
alkaline earth metals; such as calcium and barium; and alu-
minum that belongs to Group III in the periodic table of ele- Aluminum Soap Greases
ments. The bases can be in the form of oxides, hydroxides, or Aluminum soaps have a high thickening effect because of
alcoholates. Metal hydroxides are usually preferred. Alcoho- their greater network forming tendency, owing to the pres-
late is only used in making aluminum soaps because of its ence of three carboxylate chains for each aluminum atom
higher reactivity. The soap formation reaction usually re- and their borderline solubility in oil. Carboxylic acids used
quires heat, sometimes pressure, and mixing. Water is in making the aluminum soap greases include ethylhexanoic
present in the reaction either as added water, as in the case of acid, dimerized polyunsaturated fatty acids, stearic acid,
the saponification reaction, or as a by-product of neutraliza- and other fatty acid mixtures. Sometimes the hydrogenated
fish oil is also used to make greases. Unlike alkali and alka- 1. Difficult large-scale manufacture.
line earth metal oxides or hydroxides, which are highly reac- 2. Need to use a higher amount of soap to obtain a given
tive towards weak acids, such as carboxylic acids, aluminum consistency, presumably a consequence of the high
oxide and hydroxide are not. Hence, they are not good bases atomic weight of barium.
for making aluminum soaps. However, aluminum alcohol- 3. Poor low-temperature properties.
ate, with a higher reactivity towards carboxylic acids, is a 4. High raw-material costs.
good starting material. Another way to obtain water-tolerant 5. General concern towards toxicological properties of
aluminum grease is by the reaction of the water-soluble barium and its impact on the environment.
soaps with aluminum salts. See Fig. 10.6 for the reaction Because of these drawbacks, barium soap greases are
scheme 关4兴. Water tolerance in lubricating grease is a highly not suitable for use at low temperatures and in very high
desirable property. Aluminum soap greases are usually speed applications; hence they are being replaced by the
made by dissolving the preformed soap in oil and not by mak- other types of greases 关4兴. The same is true about strontium
ing the soap in the presence of oil, as is the case in other soap greases, which are used in some specialty applications.
greases. Aluminum stearate is the most common conven- Calcium 共Lime兲 Soap Greases
tional aluminum soap that is used to make the aluminum These greases are among those used most often. They are
soap greases. The manufacture of the aluminum soap lubri- relatively inexpensive to produce. They are used as axle
cating grease does not present any problems; the soap is sim- grease, water pump grease, and general-purpose grease for
ply added to the stirring oil and the mixture held at machinery.
240 to 350° F, or 116 to 177° C, until complete homogeneity These greases are usually produced in situ and not by
is achieved. Cooling of the mixture to room temperature making the soap separately and dissolving it in oil. For mak-
yields the grease. The cooling can be carried out without ing calcium soap greases, the usual fatty component is tal-
mixing, which will result in a firm grease. However, if the low. The use of the fatty acids derived from beef tallow or an-
cooling rate is slow and is accompanied by mixing, a softer other similar source leads to the formation of unstable
grease is obtained. Aluminum greases are smooth clear gels, grease. However, this problem can be overcome by using a
slightly stringy in texture, especially if made with high- blend of fat and fatty acid. The alkali needed for making cal-
viscosity oils. Their stringiness is often enhanced with addi- cium soap grease is calcium hydroxide, also called hydrated
tives. lime. This is why, calcium soap greases are often called lime
The use of the paraffinic base oils in making aluminium soap greases. For making the calcium soap, the amount of
soap greases is preferred since they have a stronger thicken- lime is used in excess of the stoichiometric amount needed.
ing effect than naphthenic oils 关4兴. Aluminum soaps possess This assures completion of the soap formation reaction. If
good adhesion and water-resisting properties. However, they fat alone is used as the starting material, the addition of a
suffer from the disadvantages of low shear stability, low certain amount of water is necessary to facilitate saponifica-
dropping point 共120° C兲, pronounced thixotropic character- tion. If a mixture of an acid and fat is used, the water result-
istics, and a gel-forming tendency. Also, the aluminum soap ing from the neutralization reaction fulfills this function.
greases have low maximum worked temperature of To manufacture calcium soap grease, hydrated lime and
60° C to 100° C 关4兴. In addition, when they are exposed to water are added to a stirring mixture of fat, fatty acid, if used,
temperatures above 170° F 共77° C兲, they lose their smooth and oil. The reaction temperature is raised to a temperature
texture and become rubbery. This makes the grease lose its that the reactor permits. A higher temperature is preferred
adhesion and hence its lubricating ability. Aluminum soap since it causes the saponification reaction to proceed faster.
greases also suffer from serious aerating tendency on vigor- A temperature of around 300° F or 149° C is typical, if a pres-
ous mixing. Because of these limitations, these greases are sure reactor is used. In case of an open kettle, the tempera-
being replaced by other greases, for example, lithium soap ture must be kept below the boiling point of water to mini-
greases. mize its loss. The reaction is checked for completion by
Barium Soap Greases checking the alkalinity 共strong base number兲 of the mixture.
For many years, barium soap greases were the most widely If the reaction is complete or close to completion, the alka-
used greases in the United States, primarily because of their linity should be low. Once the reaction is complete, the cool-
very unique properties. They are prepared by the reaction of ing can be started. If initially less oil was used than needed
barium hydroxide with various fatty acids or natural fats in for the finished grease, adding additional oil will facilitate
mineral oil. Sometimes oxidation inhibitors, corrosion in- cooling. At first, the oil may need to be added in smaller por-
hibitors, and EP agents are added to improve their oxidation tions until the grease is fluid enough to accept larger
stability and corrosion protecting and load-carrying proper- amounts. Once the batch cools down to 230° F 共110° C兲, wa-
ties. They have buttery to fibrous texture and are reddish- ter is added to break the sticky gel-like texture of the grease.
yellow or green in color. This is called the hydration step; hence the name hydrated
Barium soap greases have the advantages of good water calcium soap grease. The amount of water that leads to the
resistance, good shear stability, and a high dropping point formation of a stable grease structure is about 10 wt %. If
350° F 共177° C兲. Hence, they were among the first multi- the water level is too low, a grainy product with strong oil
purpose greases used. These greases are often used to lubri- separating tendency will be obtained. On the other hand, if
cate nearly all types of bearings and electrical cables for the water level is too high, an opaque grease of low soap con-
power transmission lines. Barium soap greases suffer from a tent results. The 10 wt % water is just a guideline; the opti-
number of serious disadvantages. These include the follow- mum amount of water depends upon the presence of the so-
ing: called structure modifiers. These include glycerol, free fatty
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452 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
acid, and glycol. While the first two of the three will invari- operated at high speeds. Hence, there is little or no concern
ably be present during the soap formation, glycol will need to for the greater oxidation stability of these greases.
be added. It is believed that water associates with the cal- The overall performance of the calcium soap greases is
cium soap to enhance its thickening ability. Complete re- improved if they are made by the reaction of 共85: 15兲 weight
moval of the hydration water leads to a complete grease mixture of 12-hydroxystearic acid and stearic acid. The
structure break down, resulting in the formation of an oil greases thus made can be used at temperatures of up to
layer and a soap layer. In the manufacture of the calcium 120° C and at higher bearing speeds. The dropping point of
soap greases, naphthenic and aromatic mineral oils are the these greases also increases to almost 150° C, or 300° F. The
oils of choice. Calcium-soap greases are yellow or reddish in higher dropping point of these greases and their enhanced
color, and have a smooth buttery texture. oxidation stability are ascribed to the presence of only trace
As commented earlier, the consistency of the lubricating amounts of water, in the range of 0.1– 1 wt % 关4兴. For the
grease is affected by the type and the quantity of the soap, the same reason, these greases are called anhydrous calcium
base oil, and the type of additives. If one wishes to develop an soap greases and can be used as multi-purpose greases
NLGI Grade 2 consistency grease, 11 to 16 wt % calcium within their temperature limitations.
soap is required. Calcium soap greases possess a smooth Because of their excellent water resistance, calcium
structure; good low-temperature properties, they do not soap greases find use in water pumps, wire ropes, food
phase transform and remain pumpable; good water resis- plants, wet industrial and sewage plant machinery, equip-
tance; and good adhesion properties. In addition, they do not ment exposed to weather, harvesting equipment for damp
form emulsions with water; hence they resist washout from crops, marine hardware, and chassis lubrication. In general,
the bearings. Their smooth texture is due to small, closely the calcium soap greases are suitable to lubricate machine
packed, fibrous network of the soap, see Fig. 10.7, Part D components that operate at temperatures of no more than
关727,733兴. These greases suffer from a number of disadvan- 125 to 150° F, or 52 to 66° C. For water pumps, the use of
tages which include low maximum working temperature of the NLGI Grade 4 grease is preferred. However, to lubricate
175° F 共⬃80° C兲, low dropping point of 195 to 210° F light-duty equipment, such as tractor track rollers, farm
共90 to 100° C兲, and insufficient stability at high speeds when equipment, mine cars, and textile machinery, a softer, more
used in antifriction bearings. The low dropping point is due easily pumpable grease is the lubricant of choice. For use in
to the breakdown of the calcium soap-water thickening sys- food plants, calcium 12-hydroxystearate soap grease con-
tem. Common uses of calcium soap greases include lubrica- taining zinc oxide is commonly used. However, the base oil
tion of the machinery and water pumps that either do not used in these greases must be acceptable for incidental food
contain antifriction or plain bearings or they are not being contact 关713兴. The lower thermal stability and shear stability
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CHAPTER 10 䊏 LUBRICATING GREASES 453
of the calcium soap greases preclude their use in plain and hydroxystearic acid or its triglyceride leads to a product
roller bearings. whose dropping point is even higher, ⬃190° C, or 374° F.
Lithium Soap Greases High dropping point is very desirable since it greatly im-
The use of lithium soap greases has increased manifold since proves the working stability of the grease. This means that
their discovery in the early 1940s. According to a recent the grease does not soften when worked. This advantage is
NLGI estimate, these greases account for almost among many others that are responsible for the widespread
70 % of the total grease use. Lithium soaps are made by the use of the lithium 12-hydroxystearate greases. Lithium
reaction of lithium hydroxide with fatty acids, or natural greases have good overall performance and are extremely
fats, in mineral oils or synthetic fluids. Since lithium hydrox- cost effective.
ide is a weaker base than sodium hydroxide and calcium hy- The grease properties that most interest an end user are
droxide, lithium soap formation requires temperatures in listed below:
the range of 160 to 220° C. These temperatures are substan- • Decomposition temperature
tially higher than the temperatures required to make the so- • Resistance to aggressive elements
dium and calcium soaps. • Radiation stability
The fatty acids commonly used in lithium soap produc- • Corrosion protection properties
tion are either stearic acid, 12-hydroxystearic acid, or their • Oxidation stability
triglycerides. Lithium soap greases are made by dispersing • Oil separating tendency
the soap in oil, either mineral oil or synthetic fluid such as an • Structural stability
ester, ether, and silicone oil. Lithium 12-hydroxystearate • Dropping point
soap can be dispersed at temperatures around 200° F 共93° C兲 • Load-carrying capacity
but other lithium soaps require much higher temperatures, • Antiwear properties
generally in the range of 400° F 共204° C兲, or more. After the • Viscosity-temperature characteristics 共VI兲
soap dispersion, the resulting greases are cooled. This can be • Suitability of use in different bearing types that operate
carried out without stirring, for example in shallow pans, by over a wide speed range
circulating through coolers, or by stirring during cooling. • Adhesion properties
Slow cooling results in long fibers. This improves mechani- • Noise characteristics in bearings
cal stability of the grease, but degrades its ability to retain • Sealing ability
oil. Fast cooling, on the other hand, does the opposite. That • Service life
is, it forms short fibers, because of which the grease has good As mentioned earlier, both the base oil and the thickener
oil retention but poor mechanical stability. Lithium soap determine the properties of the lubricating greases. Of the
grease is buttery in texture with a brownish-red color. One properties listed, the properties that are solely dependent
way to develop lubricating grease with good mechanical sta- upon the thickener include the dropping point, water resis-
bility as well as good oil retention is to mix the soaps of differ- tance, and sealing ability and those that solely depend upon
ent fiber lengths. The variation of the fiber structure in the base oil include the low-temperature behavior and the
greases is also a function of the starting acid or the fat. compatibility with seal materials 关4兴. Lithium soap greases
Lithium stearate greases exhibit a smooth, stringy tex- possess a great number of these very desirable characteris-
ture. Their advantages include the following: tics; hence they are the lubricating greases of choice in most
• Exceptional shear stability, which makes them suitable applications. The properties that are especially worth men-
for use in high-speed plain and rolling-element bearings. tioning are dropping points of above 180° C, good water re-
• High dropping points; almost as high as 350° F, or sistance, and excellent structural and shearing stabilities,
177° C, which are significantly higher than those for the even in applications that involve high-speed bearings. Their
sodium, calcium, and aluminum simple soap greases; other properties, such as oxidation stability, corrosion pro-
and good thermal stability. tection, and EP and antiwear performance are mediocre, but
• Maximum service temperature approaches 300° F, or these can be enhanced by the use of the appropriate addi-
150° C. tives.
• Good low-temperature properties, when made by using If one wished to manufacture an NLGI grease of Consis-
oils of low pour point. Can be used at temperatures as tency 2, one needs to use approximately 6 wt % of the
low as −60° F, or −51° C. lithium soap in a naphthenic oil or approximately 9 wt % in
• Good tolerance towards water; which makes them suit- a paraffinic oil. The base oil to formulate multi-purpose
able for use in mill bearings where water washout is a grease typically has a 40° C viscosity of 60 to 129 cSt
concern. 共mm2 / s兲. It is interesting to note that to obtain equivalent
• Rust and corrosion protection is at least equal to that of thickening the amount of lithium soap necessary is substan-
the sodium greases. tially less for napthemic base oils than for paraffinic base
• Response to the performance additives, such as rust in- oils. Besides the oil viscosity, the thickening effect of the soap
hibitors, oxidation inhibitors, and EP agents is superior also depends upon the composition of the base oil; the
to that of the other metal soap greases. This factor is ben- higher the naphthenic or the aromatic content, the greater
eficial in custom designing products for use in diverse the soap-related thickening. Figure 10.8 adequately demon-
applications. strates the base oil effect 关4兴. In this figure, Oil A is 95VI sol-
• Excellent sealing properties. vent refined paraffinic oil, Oil B is 50 VI solvent raffinate—a
• Readily pumpable. highly aromatic oil, and Oil C is 50 VI acid-treated,
Replacing the common fatty acid or natural fats by 12- aromatics-free, primarily naphthenic oil. In all three cases
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454 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
Fig. 10.8—Soap content versus viscosity for different base oil types in an NLGI Grade No. 3 grease 关worked penetration 220 共tenth of a
millimetre兲兴 关4兴.
the objective is to come up with a grease of NLGI Consis- which lithium soap greases lack sufficient adhesion for use
tency Grade 3 with a worked penetration rating of 220. Ex- in such applications. Overall, lithium soap greases do not
amination of the graph suggests the following. suffer from many serious disadvantages. However, their se-
• In the case of the primarily paraffinic Oil A, as the base lection for use in applications that involve extremely high
oil viscosity 共shown on x-axis兲 increases, the amount of temperatures, speeds, loads, and pressures needs careful
soap necessary to make a Consistency Grade 3 grease de- consideration.
creases. It is at least true until the oil viscosity of 640 cSt Lithium-12-hydroxystearate greases are used in many
is reached. After that the curve turns upwards and the other applications as multi-purpose greases. They contain
amount of soap necessary increases. no unsaturation in the carboxylate portion of the soap;
• In the case of the highly aromatic Oil B and the largely hence they have good oxidation stability. They also possess
naphthenic Oil C, such a transition does not occur; and good shear stability, which is ascribed to the hydrogen bond-
the amount of soap necessary to make Consistency ing ability of the hydroxyl group. NLGI Consistency Grades
Grade 3 grease decreases with an increase in the base oil 1, 2, and 3 are based on mineral oils of 40° C viscosity of
viscosity. 60– 120 cSt 共mm2 / s兲. The EP greases for high load-carrying
In order to meaningfully assess the base oil effect, the oil applications use oils of somewhat higher viscosity, presum-
viscosity of 200 cSt 共mm2 / s兲 at 25° C was chosen. This is in- ably to boost the film-forming ability 共adhesion兲 of the
dicated in Fig. 10.8 by vertical dotted line. This value is fairly grease. Oils of 40° C viscosities of 100– 350 mm2 / s are often
close to the real life viscosity of 60 to 129 cSt at 40° C for oils employed for this purpose. Lithium 12-hydroxystearate
used to formulate lithium soap greases. This is so because as greases for specialty uses are created by the use of the syn-
the temperature increases from 25 to 40° C, the viscosity of thetic base fluids. For use in aviation and space travel, di-
the oil is expected to fall from 200 cSt to the 60 to 129 cSt esters are the base fluids of choice; for use in gears poly共alky-
viscosity range. As indicated by the horizontal dotted lines, lene glycol兲s are used as the base fluids.
the amount of soap necessary to make the Consistency Lithium simple soap greases suffer from a number of
Grade 3 grease from the aromatic Oil B is ⬃14.7 %, which is disadvantages, including high raw material costs, high pro-
the lowest; for the naphthenic Oil C, it is ⬃14.9 %, the next duction costs because of the higher production tempera-
highest; and for the paraffinic Oil A, it is ⬃16.5 % is the high- tures, and the dropping point of around 180° C, which is
est. much lower than 240° C for most modern complex soap
Lithium soap greases were the first multi-purpose greases. This leads to the rapid softening of the grease with
greases invented. They provide both the good water resis- an increase in temperature.
tance, which is similar to that of the calcium soap greases, Sodium Soap Greases
and the high-temperature properties that are superior to The use of the sodium soap greases is miniscule compared to
even the sodium soap greases. Lithium soap greases are suit- that of the lithium and calcium soap greases. However, these
able for use in both automotive and industrial equipment. greases are of interest for specialty applications, such as lu-
They have provided satisfactory performance in journal and brication of gears and high-speed bearings. Sodium soap
antifriction bearings, and lubricated-for-life rolling contact greases are manufactured in situ by the reaction of the fatty
bearings. However, their use in some devices, such as those acids or natural fats with an excess of sodium hydroxide in
involving sliding and reciprocating action, is not recom- oil at a temperature of 300– 500° F, or 150– 260° C. One
mended. This is because of their smooth texture due to problem that typically occurs during the making of the so-
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CHAPTER 10 䊏 LUBRICATING GREASES 455
dium soap is the foam formation; hence heating the ingredi- terial costs are low and the process to manufacture them is
ents slowly is advisable. Sometimes polysiloxane 共silicone兲 fairly straightforward. Despite these advantages, sodium
foam inhibitors are used to contain the foam. Sodium soap soap greases suffer from a number of serious disadvantages
greases are made in a variety of structures. The structure ob- as well. These include water sensitivity, gel-forming ten-
tained depends upon a number of factors. These include the dency, and incompatibility with most other grease. Water
type of fat or the fatty acid, their ratio in the starting materi- sensitivity relates to high solubility or emulsifiability of the
als, the presence of the residual moisture, presence of struc- sodium soaps in water. However, they do tolerate the pres-
ture modifiers, effectiveness of mixing and milling, cooling ence of a small amount of water, without an adverse effect on
rate, and so on. When the reaction temperature is high, for consistency. Because of the soap’s high water solubility,
example above 400° F 共204° C兲, the soap will be completely in these greases are not normally used in industrial applica-
solution and the resulting greases will be completely anhy- tions and steel rolling mill applications, where bearings
drous. The presence of the residual moisture generally leads come in contact with copious amounts of water. Sodium
to a fibrous grease. Most sodium soap greases are of spongy soap greases are also susceptible to phase transformations
texture. When the grease is made from animal or vegetable and hardening. Their compatibility with other soap greases,
fat, which are triglycerides, the glycerol by-product acts as a especially with calcium soap greases, is poor and results in a
stabilizer for the fibrous structure of the grease. However, it mixture with fluid-like consistency. The resulting mixture is
impairs the grease’s oxidation stability. Since the fibrous fluid-like in consistency. Since sodium soap greases possess
structure in a grease is desirable because of its superior inherent EP properties, they are formulated solely by the use
shear stability, the presence of some water and glycerol in of oxidation inhibitors to lubricate ball and roller bearings.
the lubricating greases is beneficial. However, the EP additives, such as sulfurized fatty oils, or-
The base oil selected depends on the end use. As usual, ganic sulfides and polysulfides, and organo-chlorine deriva-
viscosity is an important consideration. With a high- tives can also be used to enhance the load-carrying proper-
viscosity index, medium to light viscosity base oil the sodium ties of these greases. Tackiness additives and rust inhibitors
based greases can equal or surpass the low-temperature per- are usually not needed.
Water resistance of these greases can be improved by
formance of the calcium and lithium soap greases. However,
adding a small amount of the calcium soap. However, when
the high viscosity oils give rise to variations in other grease
used in completely anhydrous environments, sodium soap
characteristics. Naphthenic oils are oils of choice but some-
greases perform well even at a temperature of 156° C, which
times the grease can gel. Both short and long fiber sodium
is substantially higher than the temperature that most
greases are commercially available.
simple soap and some complex soap greases can withstand.
Sodium soap greases have relatively high dropping
Sodium 12-hydroxystearate greases possess greater thermal
points of ⬃165° C or 175° C 共330– 350° F兲, which is the high-
and shear stabilities than the regular sodium soap greases.
est among the simple soap greases. Hence, they can be used
in antifriction bearings that experience temperatures of up Mixed Soap or Mixed Base Greases
to 120° C. Short fiber greases, which have good mechanical Mixed soap greases are those that contain two or more
stability, can be used to lubricate antifriction bearings that metal-derived soaps. In other words, they contain more than
operate at speeds of up to 500 metres/ min. Sodium soap one metal ion. Typical examples of such greases are those
greases do possess a number of desirable properties, which that contain sodium and calcium, lithium and calcium, or
include good rust and corrosion inhibition, high tempera- sodium/lithium/calcium mixed soaps. The final properties of
ture stability, and fair shear stability. Because of these prop- these greases depend upon the actual proportion of the each
erties, sodium soap greases are used to lubricate high-speed type of soap present in the grease. In most cases, the pres-
spindle bearings, sometimes gears, some rolling element ence of an additional metal ion improves specific property or
bearings, and electric motor bearings, which experience properties of a particular soap grease. The examples below
moderately high temperatures. Lighter consistency sodium adequately demonstrate this fact.
soap greases are used in textile plants so that if the grease • The presence of the calcium soap in the sodium soap
leaks on to the cloth, it is easily removed during the normal greases improves their water resistance. In addition, it
washing process. For many years, sodium soap greases were decrease the overall cost of the sodium soap greases.
used in automotive wheel bearings, but they are being re- • The presence of the sodium soap in the calcium soap
placed by better quality multi-purpose greases with superior greases improves their thermal stability, thereby making
water tolerance. Sodium soap greases made with lighter oils their use possible in applications that experience high
are also used for ball and roller bearing lubrication, as are temperatures. In such applications, the calcium soap
the combinations 共mixed base兲 of the calcium and sodium greases do not perform well.
greases. Because of their working stability and intermediate • Calcium-sodium mixed soap greases can be used at
melting point, sodium soap greases are used for lubricating higher temperatures than the calcium soap greases
wheel bearings, other than those used with disk brakes, and alone.
for general-purpose industrial applications. Typical ex- • Lithium-calcium mixed soap greases have better water
amples include rough, heavy bearings operating at slow tolerance than the pure lithium soap greases and have a
speeds, as well as skids, track curves, and heavy-duty convey- lower overall cost. In addition, the dropping point of
ors. ⬃150° C of the mixed soap grease is significantly higher
Sodium soap greases have the additional advantages of than 85– 105° C for the calcium soap greases.
good gear lubricating ability and superior corrosion protec- Many of the cited properties can be optimized by pro-
tion properties. They are cheaper to make since the raw ma- ducing the desired metal soaps in situ and in proper
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456 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
amounts. This is achieved by the reaction of the carboxylic Complex Soap Greases
acid with one metal base first and then reacting the residual The major driving force behind the invention of the complex
acid with the other metal base. Usually the primary metal soap greases was to fulfill the lubrication needs of the mod-
base is charged in larger amount than the secondary metal ern equipment that operates at higher temperatures. In such
base and the two together equal the stoichiometric amount applications, the performance of most conventional greases
necessary to completely neutralize the acid. The mixed soap was inadequate. See the dropping point data and the maxi-
thus obtained can then be mixed with the base oil and the mum use temperatures provided in Table 10.4. The complex
additives to make the mixed soap grease. Alternatively, one soap greases exemplify the best in the soap-based grease
can make a mixed soap grease by mixing the finished simple technology and because of their high dropping points they
soaps in the desired amount at room temperature. The latter are used in applications such as those involving high tem-
approach does not always work well and if it does, the ob- peratures where the simple soap greases do not suffice. Of all
tained grease has less stable properties. the complex soap greases that can be made, those based
As mentioned earlier, the sodium soap greases are in- upon aluminum, barium, calcium, and lithium are commer-
compatible with many other soap greases. However, mixed cially available.
soap greases involving sodium soaps do not suffer from this A complex soap is prepared by the reaction of a mixture
problem. Sodium-calcium soap mixed base greases are of two or more carboxylic acids with a single metal hydrox-
products with good structure and are used to lubricate wheel ide base. The complexing acids usually have a lower molecu-
bearings and ball and roller bearings. In this mixed soap lar weight than the fatty acid components and are short
grease, the calcium soap is claimed to shorten the fibers. chain acids, such as formic acid and acetic acid. The higher
Sodium-aluminum soap greases, which can also be made molecular weight fatty acid is usually stearic acid or 12-
without difficulty, are used in many industrial applications. hydroxyxtearic acid. See Fig. 10.9 for the reaction schemes.
The aluminum soap provides the smooth texture to the It is important to note that the each high molecular weight
grease and the presence of the sodium soap boosts its drop- soap requires a different complexing agent to yield grease
ping point to 375 to 425° F 共191 to 218° C兲. Incidentally, alu- with superior thermal properties. According to the ASTM
minum simple soap grease has a dropping point of around 关4兴, the soap crystals or soap fibers in a “complex soap” are
90– 110° C. Similarly, the presence of the aluminum soap formed by the co-crystallization of two or more compounds.
overcomes the poor water tolerance of the sodium soap If one reacts a monovalent metal base, such as lithium or so-
greases, at least at low temperatures. dium hydroxide, with a mixture of stearic acid and acetic
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CHAPTER 10 䊏 LUBRICATING GREASES 457
acid, the complex soap will have only two components as water-soluble salt of a high molecular weight aliphatic car-
part of the crystal structure. These are lithium or sodium boxylic acid with an aluminum salt, such as the aluminum
stearate and lithium or sodium acetate. However, if the chloride. When the reaction is complete, the aluminum com-
metal is divalent or polyvalent, such as calcium or alumi- plex soap which has low water solubility separates. This is
num, the crystal structure will have more than two compo- collected and dispersed in oil to form the lubricating grease
nents. If only two fatty acids are used, the resulting soap will 关4兴. However, a better method is to dissolve the mixed car-
be a mixture of two simple soaps; each derived from the indi- boxylic acids in oil and to react them with aluminum isopro-
vidual acid, and one complex soap which will be the cross- poxide, or its trimer. When the aluminum isopropoxide is
salt of the two acids. For example, a calcium complex grease used for making the soap, the reaction is completed by the
will have three components: calcium acetate, a simple soap; addition of water. This generates a free hydroxyl 共OH兲 group
calcium stearate, again a simple soap; and calcium acetate-
stearate, a cross-acid soap. Of course, the amount of each
component in this soap composition will depend upon the
ratio of the two acids present in the starting material. The
combination of soap components imparts unique properties
to the derived grease. Incidentally, physical mixing of the
two soaps have little or no effect on the properties of the
grease because it is the co-crystallization of the two soaps
made in situ that produces the desired effect. Figure 10.10
shows the variations of lithium grease structures and a com-
parison of the lithium simple soap structure with that of the
lithium complex grease structure. Some complex soap
greases can also contain inorganic salts, such as metal car-
bonates. Dropping point is the normal measure used to as-
sess the heat resistance of a grease. The presence of another
acid or an inorganic salt during the complex soap formation
increases the dropping point of the grease by about
80– 130°F, or 30– 50° C. As a consequence, the complex soap
greases are more suitable for use in high temperature appli-
cations than the corresponding simple soap greases. Com-
plex soap lubricating greases are made both by the use of the
mineral base oils and the synthetic base fluids.
Aluminum Complex Soap Greases
Aluminum complex soap greases have dropping points of
250° C or higher, excellent mechanical stability, good water
tolerance, and low oil-separation 共bleeding兲 tendency. Unfor-
tunately, they lack the corrosion protecting ability and have a
higher production cost relative to that of the lithium soap Fig. 10.10—SEM micrographs of various lithium 12-
based multi-purpose greases. hydroxystearate soap structures in mineral oil. 共a兲 Lithium soap
There are two ways to obtain the complex aluminum normal, coarse structure, 共b兲 lithium soap fine structure, 共c兲 lithium
soaps. They can be obtained by the reaction of a mixture of a soap very fine structure, and 共d兲 lithium 12-hydroxystearate com-
water-soluble salt of a low molecular aromatic acid and a plex soap structure 关730b兴.
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458 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
in the soap structure. However, when the aluminum isopro- Sodium complex soaps are made by the reaction of a
poxide trimer is used, there is no need to add the water. In mixture of C2-C6 acid, such as acrylic acid, with a fatty acid.
order to make the aluminum complex soap grease, a mixture As a general practice, the fatty acids in a base oil are reacted
of stearic acid, benzoic acid, and part of the oil in the desired with the sodium hydroxide first and then with the acrylic
proportion are heated until the mixture becomes homoge- acid. The reaction temperature can be as high as 260° C 关4兴.
neous. The trimer is then added and the mixture heated to Calcium Complex Soap Greases
380 to 400° F, or 193 to 204° C. When the reaction is com- In terms of use, calcium complex soap greases are the sec-
plete, the reaction is cooled by turning the heat off and add- ond highest after the lithium soap greases. They have the
ing the rest of the oil in portions. The grease is finished by the dropping points of 500– 570°F 共260– 300° C兲, good shear sta-
addition of the additives and milling to make it smooth. bilities, good water tolerance, and a low oil separating ten-
The thickening efficiency of the complex aluminum dency. Properly formulated calcium complex soap greases
soap decreases as the aniline point of the mineral oil in- can be used in antifriction bearings that experience tem-
creases 关4兴. Since high aniline point equates with low aro- peratures of up to 160° C. The performance of these greases
matic character, or the high paraffinic character, of the base starts to drop off beyond this temperature, due to the decom-
oil, this behavior of the aluminum soap is not atypical and position of the soap. These greases possess excellent
resembles that of the lithium soap. See Fig. 10.8 which extreme-pressure properties and provide good friction and
shows paraffinic oils to lead to the least thickening of the wear performance, but they have the tendency to harden
grease. However, this problem can be alleviated by increas- when worked.
ing the fatty acid/benzoic acid ratio. Since the fatty acid is These greases are manufactured by the reaction of a
the high molecular weight acid, it will effectively increase mixture of stearic acid and usually acetic acid in mineral oil
the yield hence the amount of the soap in oil. The conse- with excess calcium hydroxide. A small excess of the base is
quence will be increased thickening. However, the drawback beneficial in increasing the rate of reaction, but the presence
of this strategy is that although the grease is thicker, it is due of a large amount of the excess base has a negative effect on
to the higher soap content and not because of the improved the consistency of the grease; it may lead to the formation of
structural stability. Such a grease is likely to have a low drop- softer grease. Initially, the reaction temperature is kept be-
ping point. Another way to improve the structural stability low 80° C so as to minimize the loss of the highly volatile ace-
and increase the yield is by using fatty acids that contain 20 tic acid. Alternatively, a closed pressure vessel can be used to
or greater carbon atoms 关4兴. minimize its loss and exposure to the manufacturing person-
As stated earlier, the aluminum complex soap greases nel. After the acetic acid has reacted, the temperature is in-
have high dropping points and excellent water tolerance and creased to remove the reaction water. It is important that all
because of these, they are used in steel mills and other wet water be removed from the finished grease. If it is not, grease
environment applications. These greases are not always can change its consistency on storage. The maximum reac-
compatible with other greases. tion temperature is in the 160 to 250° C range. The molar ra-
Barium Complex Soap Greases tio of the two acids can be altered to optimize the desired
In the past, barium complex soap greases were extensively properties. Lowering the amount of the acetic acid in the
used in the United States as general purpose greases. How- mixture increases the structural stability of the grease but in-
ever, because of the concern for the toxicological properties creasing it raises the hardening tendency. The strategy is
of barium, their use has been declining. At present, their use analogous to that used for the aluminum complex soap
is limited to applications that can benefit from their superior greases. As a positive note, the higher amount of acetic acid
EP properties, good water resistance, and high dropping does improve EP properties of the grease, as indicated by
points. These greases are made in a manner similar to that of Timken OK load. In these greases, the calcium acetate is the
the calcium complex soap greases. The short chain acid used primary component that makes the soap a complex soap and
to make the complex soap is the acetic acid. The energy re- hence is responsible for improving the properties of the
quirement for making these greases is higher because the grease. Other components, such as the excess calcium hy-
complex soap attains firm and stringy consistency during droxide and calcium carbonate, present in the product, may
manufacture. also contribute towards the overall properties. Sometimes
Sodium Complex Soap Greases other medium molecular weight acids, such as caprylic acid
Despite the fact that sodium complex soap greases suffer 共octanoic acid兲 or caproic acid 共hexanoic acid兲, are also
from the disadvantage of water solubility, they are still in use added to further impact grease properties. Calcium soap
in a limited number of specialty applications. In this regard, greases are usually made with a thickener content of 20–30
the sodium complex soap greases with soap contents of % because of the ease and the belief that the high soap con-
⬃25 wt % or higher, are of special interest. Their high drop- tent is necessary to obtain reasonable thickening efficiency.
ping points 共⬃240° C兲, low oil separation tendency, and good However, the grease with a lower thickener content but the
adhesion properties make them suitable for use in the lubri- same consistency can be made by controlling the processing
cation of the wheel bearings. In this application, these variables. Calcium complex soap greases with the higher
greases are superior to the conventional lithium soap thickener content have poor low-temperature performance
greases. Sodium complex greases containing 35 wt % soap and have the tendency to harden on long-term storage and in
and a worked penetration of 210 共tenth of a millimeter兲 are high pressure lubrication systems. Also, such greases can
ideal for lubricating the outer ring runners, for example in sometimes lead to the bearing failures.
braiding spindles, which can experience a speed of Since this type of grease has a dropping point of 260° C
25,000 per min, or higher 关4兴. or above, it is used to lubricate the rolling-element bearings
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CHAPTER 10 䊏 LUBRICATING GREASES 459
that operate at temperatures of 160– 200° C. If the operating solution of the 12-hydroxystearic acid in oil at 82– 88° C. The
temperature is higher than this, the grease deteriorates, re- reaction temperature is brought to 194° C with stirring and
leasing ketones. Ketones are the decarbonylation products the remaining oil is added to the grease. The grease is then
of the calcium carboxylates at high temperatures. While the cooled and homogenized to obtain the finished product. Me-
calcium complex grease is still in use in some applications, thyl salicylate is added to the reaction mixture to improve
its demand is declining. These greases are not always com- the dropping point. However the increase is only moderate.
patible with other greases. Lithium complex soap greases possess good lubricating
Lithium Complex Soap Greases properties, high dropping points, stable consistency, and low
Lithium complex soap greases enjoy the largest share of the oil separation tendency. Because of these characteristics,
complex grease market and are second only to lithium these greases have a longer service life than the lithium
simple soap greases with respect to overall use. Previously, simple soap greases in the antifriction bearings that operate
lithium complex soap greases were made from the in situ re- at high temperatures 关4兴. The maximum service temperature
action of the stearic acid, fish oil, and acetic acid with for these greases is around 175° C, which is significantly
lithium hydroxide 关4兴. These greases suffered from the re- higher than 140° C for the lithium simple soap greases. Syn-
versibility of consistency and were not suitable for many ap- thetic ester-based lithium complex soap greases when for-
plications. Today, some lithium complex greases are made mulated with proper additives are effective across all tem-
from mixtures of the hydroxy fatty acids and aliphatic fatty peratures, low, medium, and high.
acids. Others are made by the use of the lithium borate and
the lithium soaps of the hydroxy fatty acids 关4兴, with and Thickening Mechanism
without lithium salicylate. These greases have properties su- For a soap to be an effective thickener it must have the cor-
perior to those made by the use of the previous methodology. rect particle size and the shape and it must have the ability to
The performance of the lithium complex greases is simi- associate with the oil. As stated earlier, the materials that are
lar to that of the lithium simple soap greases, except that good thickeners have only a marginal solubility in oil. Too
their dropping points are about 50° C higher. The higher much or too little solubility will not allow the formation of a
dropping point in this case can not be due to the presence of good grease. Association between the soap particles and the
a cross-bridged soap molecule containing both acids since oil requires week attractive forces, called the van der Waals
lithium is a monovalent metal, and such a salt is not possible. interactions. The van der Waals interactions involve only
Lithium can have only a single carboxylate attached to it. surfaces. In general, the larger the surface area of the soap
This situation is analogous to that of the sodium complex molecule, more extensive is the association with the oil,
grease. The possibility of co-crystallization of the long chain which results in greater thickening. Similarly, the larger the
soap and the short chain soap to boost the dropping point of number of the soap molecules, that is, higher the soap con-
the grease is a reasonable possibility. Other strategy that is centration, the greater is the thickening. Again in this case
effective in enhancing the dropping point of a grease is to the overall surface area is large. Linear soap molecules, be-
add a dibasic acid, such as azelaic or sebacic acid, or their cause of their geometry, associate with the oil to a greater de-
esters to the starting acid mixture. Azelaic acid is gree than the branched chain soaps; hence they cause
nonanedioic acid and sebacic acid is decanedioic acid. Their greater thickening. Many other factors affect this associa-
structures are given below: tion between a thickener and the oil. Twisted fibers or inter-
locked three-dimensional molecular structures 共networks兲,
HOOC共CH2兲7COOH HOOC共CH2兲8COOH in addition, trap oil much more effectively. Further details
Azelaic Acid Sebacic Acid
on this are provided in the section on lubricating grease
In this case again we are depending upon the co- structure.
crystallization mechanism and not the cross-bridged salt The formation of the lubricating grease with optimal
formation to improve the dropping point. Lithium complex performance requires the formation of the thickener in situ.
soap greases have good all temperature performance when Making soap separately and then suspending it in oil does
used to lubricate the tapered roller bearings. not always result in a grease with stable structure and its
The manufacture of the lithium complex soap greases properties usually deteriorate over time, or during use. The
from 12-hydroxystearic acid involves its reaction with con- presence of the oil during grease formation is beneficial be-
centrated lithium hydroxide solution by heating the mixture cause it facilitates the formation of fibers, or particles, of
in oil. The reaction temperature is held at 149° C until all the proper length and geometry for maximum association with
water is removed. The reaction mixture is then cooled to the base fluid. Besides the presence of the oil, many other
100– 110° C and azelaic acid is added. This is followed by the factors play a role in defining the quality of lubricating
addition of an additional amount of the saturated aqueous grease. These include the processing temperature, cooling
lithium hydroxide solution. The reaction temperature is rate, intensity of mixing, and milling.
raised first to 149° C and then to 199° C to completely remove
the water. At this stage, the product is cooled and the remain- Nonsoap Greases
ing oil and additives are added to complete the formation of Soap thickened greases make up the largest share of the lu-
the grease. It is the presence of the azelaic acid, or its mono- bricating grease market. According to a more recent esti-
lithium salt that is responsible for the complex structure of mate, the worldwide share of the soap-based greases is 83 %.
this grease 关4兴. The balance is made up by the nonsoap greases. The use of a
Lithium complex soap grease that involves the use of number of nonsoap thickeners in greases has been at-
lithium borate is manufactured as follows. Aqueous solu- tempted, but only a few have gained significant use. Organo-
tions of boric acid and lithium hydroxide are added to a 50% clay and polyurea derived greases, with a combined market
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460 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
share of about 17 %, top the list. Compared to the ordinary low-temperature properties and have dropping points of
metal soap greases some of these thickeners result in greases over 500° F, or 260° C. They are primarily used in high-
that may be superior with respect to the following proper- temperature ball bearing and aerospace applications.
ties: Polyurea Greases
• Higher dropping points Urea itself is not oil soluble, but is water soluble. However,
• Better cold flow behavior substituted ureas, where the hydrogens on the nitrogen have
• Broader temperature service range been replaced with oleophilic groups, such as a long-chain
• Better consistency stability or cyclic hydrocarbon groups, are oil compatible/oil soluble.
• Better water stability Nevertheless, these materials are not good thickeners be-
• Better corrosion protection behavior cause of their low molecular weight. However, when two or
Non-soap thickener derived greases suffer from a num- more of these moieties are linked together, there is signifi-
ber of disadvantages as well and include the following: cant improvement in thickening ability. The term polyurea
• Lack of resistance to steam refers to diureas and tetraureas. Polyureas are prepared by
• No compatibility with other thickeners the reaction of proper amounts of amine or diamine with an
• Poorer thickening efficiency organic diisocyanate in oil.
• Poorer consistency recovery
• Higher noise generating behavior H2N – CO – NH2 RHN – CO – NHR
Urea Substituted Urea
• More problematic production processes
Two classes of thickeners that are used to make the non- R = Hydrocarbon Substituent
soap greases are organic thickeners and inorganic thicken-
ers. Organic thickeners can be subdivided into 共1兲 pre-made, Polyureas are the most predominantly used organic,
largely oil-insoluble materials, and 共2兲 those that are pro- non-soap greases thickeners. Polyurea is a low molecular
duced in situ by the reaction of the two or more ingredients. weight organic polymer that is generated in situ in oil from
As a matter of fact, there is only one thickener worth men- the raw materials, an organic isocyanate and an amine. Re-
tioning that falls under the latter group and it is polyurea. action schemes for polyurea synthesis are provided in Fig.
10.11, along with the possible polyurea structures. Polyurea
Organic Thickeners possesses borderline solubility in oil and a gel-forming ten-
1. Carboxylate soap-like salts dency, both of which are necessary attributes for a good lu-
2. Noncarboxylate-based organic thickeners bricating grease thickener. During the production of a poly-
3. Pigments urea greases due care must be practiced because the
4. Medium to high molecular weight polymers isocyanates and the amines are hazardous and toxic. It is im-
5. Polyureas portant to point out that while the reactants are hazardous,
Carboxylate soap-like salts include alkali metal and the product polyurea is not. The reaction does not require
alkaline-earth metal salts of terephthalic acid, sebacic acid any heat and proceeds at a good rate at room temperature.
N-laurylamide, n-octadecyl terephthalate, and N-lauroyl-6- There are no by-products of the reaction to be concerned
aminocaproate. Noncarboxylate-based organic thickeners about. The use of polyfunctional isocyanates provides prod-
include calcium salt of N-stearoyl-sulfanilic acid, lithium ucts of higher molecular weights. If a diisocyanate is used,
propyl phosphate, lithium stearamidomethane phospho- two moles of a monofunctional amine, or a monoamine, are
nate, and some anilides. Some metal alkyl thiophosphates required to form a product called diurea, which is a urea
serve as thickeners as well as EP additives 关4兴. dimer. This is a popular thickener for greases destined for
Pigments, such as alizarin, anthraquinone, indigo, azo the Japanese market. However, in the United States, tetrau-
compounds, indanthrene and phthalocyanine dyes, and Ul- rea is the polyurea that is used to make the polyurea greases.
tramarine Blue 关4兴 are primarily used for silicone greases. Tetraurea is made from the reaction of a bifunctional isocy-
Copper phthalocyanine, which has an intense blue color, is anate with a bifunctional amine, charged in the stoichio-
available as very fine particles and is used to thicken spe- metric amounts. The term polyurea is normally applied to
cialty silicone fluids. Some of these products are used by the tetraurea.
U.S. military in aircraft applications 关734兴. The properties of diurea and polyurea greases depend
A number of medium to high molecular weight poly- upon the structure of the isocyanate and the amine starting
mers has also been tried as thickeners for greases. These in- materials. They also depend upon the average molecular
clude linear, branched, and partially branched polyethyl- weight and the molecular weight distribution, or polydisper-
enes; halogenated polyethylene, for example polytetra- sity. This is because both these factors affect thickening and
fluoroethylene 共PTFE兲; isotactic polypropylenes; poly- hence determines the amount of thickener needed to de-
isobutenes; poly共4-methyl-1-pentene兲s; alkyl acrylate- velop the lubricating grease of a certain consistency. If the
acrylamide copolymers; condensation products of alkylphe- polyurea has a greater weight-average molecular weight
nol, fatty acid, and formaldehyde; polycarbohydrates; alkyl 共Mw兲 and has low polydispersity 共closer to 1兲, it will not only
hydroxyethylcellulose; and polyureas 关4兴. A few of these are have good thickening ability but will also have good me-
used in commercial products; others are just an academic chanical properties. Polyurea greases normally have a
curiosity. Most of these materials are chemically and ther- smooth “buttery” texture, but can be made to possess a fi-
mally stable; hence they form greases that have use across a brous texture for heavy duty applications. The amount of the
broad temperature range. Also, since these thickeners are polyurea needed to make lubricating greases of NLGI Con-
metal free, they do not deteriorate oxidation properties of sistency Grade 2 is about 7–12 %. If the diurea is used as a
the base oil. The greases based on these thickeners have good thickener, its amount will be higher because of its lower mo-
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CHAPTER 10 䊏 LUBRICATING GREASES 461
lecular weight 关735,736兴. Polyurea greases possess many de- ity with other greases. However, some of these deficiencies
sirable properties, which include the following: can be overcome by means of proper formulation.
• High dropping point, ⬃250° C 共480° F兲 Polyurea greases are more expensive than the soap-
• Good thermal stability based greases because of the higher cost of the raw materials
• Excellent water resistance and complex processing. These greases are not suitable for
• Excellent compatibility use in centralized lubrication systems because of their poor
• Excellent pumpability pumpability characteristics.
• Low oil separation Polyurea Complex Greases
• Long bearing life Polyurea complex greases are made by incorporating cal-
• Excellent oxidation stability cium acetate or calcium phosphate complexing agents into
Excellent oxidation stability of the polyurea greases can the polyurea greases. Such greases possess all the attributes
be ascribed to their somewhat lower hydrocarbon content of the polyurea greases and in addition have excellent water
and being devoid of metals which are known to promote oxi- resistance, good low temperature characteristics, and su-
dation. Because of their superior oxidation resistance and perb EP/antiwear and load-carrying properties. Polyurea
the high dropping points, polyurea greases are extensively complex greases are used in a number of industrial and auto-
used in sealed-for-life ball bearings and as factory-fill in elec- motive applications, especially those that can benefit from
tric motor bearings, alternators, water pump bearings, and their unique advantages.
constant velocity universal joints. Sealed-for-life bearings
are filled during assembly, permanently sealed, and operated Inorganic Thickeners
without relubrication for the life of the equipment. Polyurea Clays, such as bentonite and hectorite, silica-gel, and graph-
greases are also used in automotive, industrial, and aviation ite are examples of this type of grease thickeners. Most inor-
applications as multi-purpose greases. These greases can ganic thickeners appear as fine, almost amorphous powders,
also be used to lubricate food machinery since they can eas- but on a microscopic scale they consist of either tiny spheres
ily be formulated for USDA Class H1 approval. Polyurea or platelets. Nevertheless, it is their small particle size that
greases also have a number of deficiencies. These include provides them large surface area to associate with a large
poor shear stability, poor storage stability, and incompatibil- amount of oil, which is the reason for the thickening effect.
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462 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
Since these materials do not have a fibrous structure, like them swell and increase their affinity towards oil. Com-
soaps, the mechanism by which they thicken is different monly used dispersing aids include acetone, ethanol, metha-
from that of the soaps. These thickeners consist of electro- nol, and propylene carbonate. The presence of a small
chemically charged colloidal particles 共platelets兲, which in amount of water facilitates swelling of the clay particles,
oil form a matrix that holds the oil. They essentially form hence the formation of the dispersion. Some of the water
gels in oil with grease-like appearance and properties. Out of comes from the organo-clay itself, some from the dispersing
the above listed inorganic thickeners, silica and modified- aid, and the rest must be added. Since the presence of too
clays have found extensive use in greases. Unfortunately, much water is not beneficial, it is advisable that the proper
both in their natural state have affinity towards water, mak- amount of water to be added is determined by experimenta-
ing them unsuitable for use in oil. This hindrance is over- tion. Dispersing aids are all volatile, combustible liquids and
come through modifying them by coating with an appropri- pose a fire hazard; hence proper precautions must be taken.
ate organic reagent, hence the name organo-clay or modified After the dispersing step, the batch is milled at around 250° F
clay. The coatings resist removal until the temperature
共121° C兲. This causes the dispersing aids and water to evapo-
reaches 300 ° F 共149° C兲, or above.
rate. In the final step, the batch is cooled to around 180° F
In its natural form, silica is a hard, abrasive material
共82° C兲, 0.1 % water, additives, and balance of the oil are
that has no affinity for oil, but by the use of the specialized
added. Organo-clay greases are smooth textured greases
processes, such as precipitation or deposition as fine par-
with excellent overall properties.
ticles from the gas phase, it is converted into a light, fluffy,
The clays used to make these greases either do not melt
noncrystalline powder called fumed silica. In this form, it
has extremely large surface area which is suitable for its use or have extremely high melting points. Hence, greases thick-
as a lubricating grease thickener. However, the problem is ened by clays have essentially no melting point, and their ser-
that it still lacks affinity towards oil, which is absolutely nec- vice temperatures solely depend upon the oxidation stability
essary for it to form a lubricating grease. This problem is of the base oil and the additives. Since the oxidation resis-
solved by its reaction with surface altering chemicals, such tance of the base oil is the sole limitation, the dropping
as diisocyanates or epoxides 关4兴. Fumed silica thickeners are points for these greases are estimated to be greater than
used in various base fluids to create high-melting greases. 500° F 共260° C兲 but the maximum use temperature is esti-
These greases are inherently water sensitive, but when they mated as 350° F 共177° C兲. These are similar to those reported
are made in silicone fluids, their water-resistance greatly im- for other high-temperature greases of the complex soap and
proves. They are costly to produce and hence are used only in nonsoap types. In the absence of the inhibitors, the mineral
certain specialty applications. oil-based clay greases start to decompose around 250° F
Bentonite clays 共montmorillonite, hectorite兲, are made 共121° C兲. However, with the use of the proper oxidation in-
water resistant by exchanging sodium or potassium ions of hibitors these greases can be effectively used in most high-
the natural clays with quaternary ammonium ions. This is temperature applications, such as the aerospace lubrication.
achieved by the reaction of the clay with quaternary ammo- Organo-clay greases are versatile lubricants and are
nium chloride or bromide 关4兴. used both in industrial and automotive applications. Indus-
trial uses include lubrication of the rolling contact bearings
Specialty Thickeners operating at moderate speeds and temperatures, and auto-
Besides the thickeners discussed so far, there are many other motive uses include both as a general purpose grease as well
important thickeners that are used commercially, though in as to lubricate the wheel bearings. These greases can even be
relatively small amounts. Some fine grades of carbon black used in some high temperature applications, if the equip-
have good thickening power. Greases made from this thick- ment relubrication is an option. While the low-temperature
ener are good for high temperature applications. However, properties of these greases are acceptable, many organo-clay
they suffer from low water resistance. Again, their water- greases are formulated for high-temperature applica-
resistance problems can be alleviated by making them in sili- tions. High viscosity oils are normally used to make such
cone and other synthetic fluids. In some applications, car-
products. Of course, such formulations will have poor low-
bon black is combined with soaps to form mixed greases.
temperature properties. Work stability of these greases is
Carbon black greases are black in color, which the users do
rated as fair to good. Since these greases do not have a fi-
not always appreciate. These greases find use in specialty ap-
brous structure, they have better pumpability than the soap
plications, such as those requiring good oxidation stability,
based lubricating greases but lack the ability to retain oil, es-
heat resistance, and lubricity. These can also conduct elec-
pecially under high pressures. To make NLGI Consistency
tricity and can be used in bearings used in xerography ma-
Grade 2 grease, one needs to use 5–8 % of the organo-clay
chines.
thickener.
Making Organo-clay Lubricating Grease Consistency of these greases depends on the type of the
Unlike soap greases that require heating the reactants, usu- shearing forces applied. If the shear force is two-
ally in the presence of oil, the organo-clay greases are made dimensional and laminar, the clay platelets slide, interrupt-
by cold dispersing the clay in oil, but under vigorous 共high- ing the attractive forces between the clay particles and the
shear兲 mechanical stirring to ensure a uniform dispersion. oil, leading to a loss in penetration. However, if the grease is
In most cases, the chemicals called dispersing aids are in a turbulent three-dimensional environment, such as that
needed. Dispersing aids, also called propelling agents and of a rotary mill, the loss of interaction due to movement is
dispersants, are polar compounds that aid clay dispersion by re-established when the shearing stops. In other words, the
absorbing on to the surface of the clay particles to make loss of penetration, that is, the apparent viscosity loss, is
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CHAPTER 10 䊏 LUBRICATING GREASES 463
temporary. This is because unlike soaps, clay platelets do not • Viscosity and viscosity index
shear. • Oxidation and thermal stability
Organo-clay greases suffer from a number of deficien- • Chemical stability
cies. These are as follows: • Additive solubility
• They have poor work stability relative to the soap • Volatility and flash point
greases. • Behavior towards elastomers
• They can not be formulated with some performance ad- • Environmental compatibility
ditives, such as metal sulfonates, lead naphthenates, and Most of these properties were discussed in detail in
some organophosphorus compounds. This is because Chapters 2 and 3 while discussing base fluids. Hence, here
these additives disrupt the gel structure of the grease. we will only comment on properties that impact the proper-
• Although these greases are water resistant, they are sus- ties of the grease.
ceptible to degradation from other contaminants, such
as brine. Mineral Oils
• While their low-temperature performance in low to me- Base fluid viscosity has the most profound effect on the vis-
dium viscosity oils is acceptable, their performance in cosity of the finished grease. Mineral oils used to manufac-
high-viscosity base oils is far from satisfactory. These ture lubricating greases range from being 90N 共neutral兲 to
oils are usually used to formulate greases for high- 600N; which covers almost the whole range of the
temperature applications. petroleum-derived base stocks. Some of the greases even use
• They lack compatibility with some of the other types of bright stocks, which are extremely viscous oils with high
greases. aromatics content and excellent solvency. There are many
As mentioned earlier, silica is made oil compatible by re- applications where the conventional oil-based greases do
acting it with diisocyanates or epoxides. Silica-thickened not work well. For such applications, high performance
greases produced in aromatic oils are used in roller element greases made from base oils of higher oxidative and thermal
bearings employed in the nuclear power plants. This is be- stability are employed. Such oils include highly refined,
cause of their tolerance to radiation. chemically modified mineral oils, that is, API Group II and
Greases containing organo-clay thickeners in both the Group III oils and synthetic base fluids.
mineral oils and the synthetic fluids are useful in high tem- Mineral oil’s overall chemical composition, that is its
perature applications where the soap-based greases may de- paraffinic, naphthenic, and aromatic content affects seal
compose. Greases prepared by the use of the carbon black or compatibility, thermal and oxidation stability, and tendency
the colloidal silica serve for the lubrication of hot, dust- of the grease to separate oil. The effect of greases on seal ma-
exposed open gears. Some organic thickeners are used in terials 共swelling, tensile strength兲 is largely a function of the
silicone oils for the manufacture of the high-temperature oil’s aromatic content. In general, the higher the aromatic
greases. However, they can cause fouling of the machine content of the oil, the greater is the grease-related damage to
parts. seals. This is because some aromatic compounds migrate
into the seal material and cause swelling and the loss of its
Grease Chemistry tensile strength. Other compounds tend to remove the plasti-
cizer from the seal and cause seal shrinkage and cracking.
As stated earlier, lubricating grease is a lubricant that is Oxidation stability and the decomposition temperature of
immobilized by the use of a thickener and like any other lu- the base oil impact the maximum working temperature and
bricant, it is made by blending an assortment of additives in the service life of the grease, especially with respect to its use
a base fluid. The thickener, the immobilizing component in in antifriction bearings. Oil separation increases as the aro-
lubricating grease, is usually a metal salt of a fatty carboxylic matic character of the oil decreases. This is because the soap
acid or metal salts of a mixture of carboxylic acids. These has better solubility in the aromatic component of the oil
salts are obtained from the animal and vegetable fats either and hence maintains its structural integrity.
by a direct reaction with a metal base or via hydrolysis of the Paraffinic mineral oils have excellent oxidative stability,
fat to yield the fatty acid which is then reacted with the metal high VI, and good behavior towards elastomers, so do the
base. Acids in uncombined form are not plentiful in nature greases made from these oils. Because of these characteris-
but fats are; hence sometimes mixtures of fats and acids are tics, the greases have the ability to perform over a broad
used to make lubricating greases. Commonly used acids in 共wide兲 temperature range. However, the highly paraffinic
the manufacture of grease include acetic acid 共CH3COOH兲, oils suffer from lower ability to dissolve polar additives 共poor
stearic acid, 共C17H35COOH兲, and 12-hydroxystearic acid. solvency兲, meager low-temperature properties, and low
Base fluid is an integral part of the lubricating grease, thickening response to most soap type thickeners, as is
both with respect to structure as well as performance. It is shown in Fig. 10.8. Low thickening due to soap is related to it
either petroleum-derived 共mineral oil兲, synthetic in origin, or being polar and these oils being nonpolar and therefore lack-
is obtained from plants and animals. Since the base fluid in ing good association with each other. These factors make for-
the lubricating grease makes up about 70–90 % by weight of mulation of the high performance greases from these oils
its composition, proper selection of the base oil is important somewhat of a challenge. The low-temperature properties in
to the grease’s overall properties. greases derived from these oils are not of great concern be-
cause many thickeners function as pour point depressants as
Base Fluids well. Colorless base stocks, called the white oils, are used in
The base fluid properties that influence the properties of the food grade, USDA H1 greases that are formulated for inci-
finished lubricating grease include the following: dental food contact.
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464 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
As stated previously, for mineral oil-based greases naph- tions and applications where there is a need for a longer lu-
thenic oils are the oils of choice, although aromatic base oils bricant life or a cleaner operation, i.e., the formation of the
are also quite suitable and are often used. While naphthenic less carbon, sludge, and varnish. Synthetic fluid-based
oils have lower viscosity indices than paraffinic oils, their greases are useful in high temperatures applications
use is still preferred in greases because of their low- 共95 to 315° C, or 200 to 600° F兲 and low temperature appli-
temperature fluidity and better thickening by soaps. Aro- cations 共−40 to − 75° C, or −40 to − 100° F兲. Unfortunately,
matic oils, or bright stocks, although have good solvency and the cost of the synthetics is significantly higher than that of
boost the thickening power of the soaps well, are oxidatively the mineral oils, which may act a deterrent towards their use
less stable; hence they cannot be effectively used to formu- in greases other than high-performance products. Relative
late high-temperature greases. When using naphthenic or cost comparison of the various synthetics with mineral oils
aromatic base stocks, the use of the oxidation inhibitors is is provided in Table 10.6 关4兴. See Table 10.7 to examine the
essential. Elastomer-seal compatibility of the lubricating strength and weaknesses of the each type of base stock 关737兴.
grease is also important and is negatively impacted by naph- Of the base oils listed in Table 10.6, diesters, poly共alky-
thenic and aromatic oils; more by the aromatic oils than the lene glycol兲s or poly共glycol ether兲s, silicones, phosphoric
naphthenic oils. acid esters, perfluoroalkyl and chlorofluoroalkyl ethers, and
Oil blends of a viscosity between ISO VG 100 and VG hydrocarbons are of the greatest importance with respect to
220 are among those that are used most often, but for use in grease. The greases developed from these synthetic
greases designed for specialty uses, the oils of lower or oils have certain advantages over mineral oil-based greases,
higher viscosity grades may also be employed. Greases for which will be pointed out during different parts of the subse-
low-temperature and or high-speed use utilize lower viscos- quent discussion. Most synthetics are available in different
ity base oils and greases for slow speed, high loads, and viscosity grades and have excellent viscosity-temperature
shock loading benefit from the use of the oils of higher vis- and low-temperature properties. However, some fluids, such
cosity. Lubricating greases made from low-viscosity oils pos- as poly共phenyl ether兲s and silicones, either have high pour
sess good low-temperature properties and good transport- points or have a strong creeping tendency on the metal sur-
ability. They also have low working and equilibrium faces and are therefore not useful in typical grease applica-
temperatures and hence find use in plain bearings and joints tions. Greases made from some synthetic base stocks are
and high speed antifriction bearings. Lubricating greases negligible in use volume, which is partly due to their higher
from base oils of high viscosities are employed in slow-
running bearings and gears that operate under high loads
and experience high ambient temperatures. An increase in TABLE 10.6—Relative cost of synthetic fluids
the oil viscosity minimizes its evaporative loss, enhances ad- †4‡.
hesion and the corrosion preventing properties, controls Oil/Fluid Relative Cost
noise, and improves water tolerance. Solvent Raffinates 1
Mineral base oil properties and their influence on the Hydrocracked oils 2…3
behavior of the lubricating greases are summarized in Table Polyolefins 3…10
Dicarboxylic acid esters 4…10
10.5 关729兴.
Phosphoric acid esters 5…10
Synthetic Fluids Poly共glycol ether兲s 关Poly共alkylene glycol兲s兴 6…10
Synthetic fluid-derived greases are used when the Silicic acid esters 20…30
Silicone oils 30…100
petroleum-derived products do not perform the intended
Poly共phenyl ether兲s 200…500
functions. Some situations where mineral oil-derived
PolychlorofIluorohydrocarbons 400…600
greases are deficient include extreme-temperature applica-
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CHAPTER 10 䊏 LUBRICATING GREASES 465
TABLE 10.7—Typical properties of lubricant base fluids †737‡.
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466 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
cost and limited use only in highly specialized products. other synthetic fluids used in greases have viscosities in the
Such fluids include fluorinated hydrocarbons and perfluo- range of the lighter HVI neutral mineral oils. However, vis-
ropolyethers, which are extremely resistant to oxidation, cosity indices and flash points of the synthetics are higher
and poly共phenyl ether兲s, which have high thermal stability and the pour points are considerably lower than those of the
and radiation resistance. comparable mineral base oils. In addition to the higher cost,
Synthetic fluids have well defined structures and hence esters have the additional disadvantage of having greater
have precise physical and chemical properties. The lubricant seal-swelling tendencies. It is therefore important to pay at-
greases made from synthetic fluids have the following at- tention to the type of the seal material used in the equip-
tributes: ment, prior to formulating an ester-based grease. Ester-
1. Good broad temperature behavior based greases are used in applications that experience broad
2. Good to excellent chemical resistance temperature ranges, such as for aircraft lubrication. The
3. Superior corrosion protection greases made from poly共alkylene glycol兲s have reasonable
4. Low volatility at high temperatures thermal stability, are nonaggressive to most elastomer seals,
5. Excellent oxidation stability and on decomposition leave only the thickener-derived resi-
6. Excellent extreme-pressure/antiwear properties due.
7. Good compatibility with other greases Silicones, or polysiloxanes, possess excellent fluidity at
8. Good electrical properties low temperatures, low volatility, good oxidation resistance,
9. Ability to lubricate nonmetallic surfaces good water resistance, good elastomer seal compatibility,
10. Environmental compatibility; no or low toxicity, re- and excellent thermal stability. These properties make these
duced fire hazard fluids useful base stocks for making greases that can be used
11. Biodegradability for high-temperature and broad-temperature applications.
Synthetic fluid-based greases find extensive use in high- However, silicone-derived greases are not suitable for appli-
performance aircraft, missiles, and space vehicles. When the cations involving high loads since they do not provide pro-
thickener and the fluid are both synthetic, the grease is used tection against wear. To make things worse, their response to
almost exclusively in high-performance equipment. For the load-carrying additives is also weak. Another disadvan-
some missile applications, a service life of minutes, or less, tage of these fluids is that if they get on metal surfaces they
may be adequate. Military specifications for a variety of syn- prevent the surface coatings, such as paint, to adhere. How-
thetic greases and their temperature ranges are shown in ever, they do not harm an already painted surface. In terms
Table 10.8 关738兴. of cost, silicone fluids are quite expensive.
With the exception of the poly共alkylene glycol兲s, all Synthetic hydrocarbons that have utility in greases in-
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CHAPTER 10 䊏 LUBRICATING GREASES 467
TABLE 10.9—Typical additives used in lubricating greases „adapted from Ref †742‡….
clude polyalphaolefins 共PAOs兲 and alkylated aromatics. Table 10.9 lists the properties of the various additives
These materials do not contain any hydrolyzable functional that are used in lubricating greases along with their typical
groups, hence they are hydrolytically stable. In addition, treat level and their chemistry 关742兴. The additives in a lubri-
they are not harmful to the surface coatings, again because cating grease may interact with one another or with the
of the absence of the highly polar functional groups. Relative thickener and the interaction may be synergistic or antago-
to the mineral oils, these fluids have low volatility, better heat nistic. The knowledge of the possible interactions will help
resistance, greater oxidation resistance, and good low and design better lubricating grease. The assessment of the addi-
high temperature viscometrics. Because of these properties, tives needed in a grease requires a number of considerations,
these fluids are ideally suited to make greases for use in some of which are listed below:
broad-temperature applications, such as airplanes and • Performance requirements consistent with the intended
ships, and at a reasonable cost. The PAO-derived greases are application/s.
also used in some industrial applications. Greases made • Compatibility, synergistic or antagonistic reactions with
from alkylated aromatics possess good hydrolytic stability, the soaps, the additives, and the other greases.
thermal stability, harmlessness to surface coatings, and low • Environmental considerations; such as the product use,
volatility. However, they suffer from poor oxidation stability, odor, disposal, and biodegradability.
primarily due to their aromatic structure. • Color.
Incidentally, there is a move towards the greater use of • The overall cost.
the vegetable oil-based greases, especially in Europe, due to While the lubricating greases are formulated to deliver
their high environmental compatibility. specific performance, the overall cost of their components,
that is the base oil, thickener, and additives, cannot be ig-
Additives nored. For a detailed discussion on the role of additives in
A variety of additives are used in lubricating greases to en- lubricants, please refer to Chapter 4.
hance their properties. The properties of interest that need Solid additives, also called fillers or physical additives
to be improved are structural, rheological, and chemical. Ad- are occasionally used in lubricating greases. They are more
ditives that are used to achieve this include oxidation inhibi- suitable for use in greases than in liquid lubricants since they
tors, metal deactivators, extreme pressure 共EP兲/antiwear do not need be soluble but be dispersible. The purpose of us-
agents, film-strength improvers 共friction modifiers兲, rust in- ing these solids is to impart friction reduction and extreme
hibitors, copper deactivators, viscosity modifiers, adhesion pressure properties to grease. Materials that are commonly
promoters, sludge control agents, tackifiers, water repel- used include the following 关738兴:
lants, odor masks, and specialty solids. 1. Graphite
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468 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
2. Molybdenum disulfide 共MoS2兲 pended in the grease, on the metal surface, which acts as a
3. Zinc oxide, magnesium oxide, and cerium fluoride low-shear film that provides the boundary lubrication. Par-
4. Copper and nickel powders ticle size of the fillers is important since in some bearings,
5. Carbon black, talc, and mica such as rolling element bearings, the clearance may be as
6. Inorganic boron compounds, such as boric acid, borax, small as 0.0001 inch. If the particle size is too large, it can
boron nitride, and metal borates lead to abrasive wear. Solid additives are also well suited in
7. Bismuth, zinc, and lead naphthenates; and zinc stearate space applications where vacuum can cause the loss of liq-
8. Inorganic sulfur-phosphorus compounds, phosphate- uid additives. This is because these have low volatility and
thiosulfate blends 关739兴 excellent lubricity. In these applications, the greases con-
9. Calcium acetate, carbonate, and phosphate taining fluorinated polymers and perfluoropolyalkylethers
10. Phosphate glasses have been used successfully.
11. Fluorinated polymers. Graphite-based greases are effective in minimizing
Lubricating greases derived from these materials help metal-to-metal contact and wear in sliding surface bearings
protect heavily loaded bearings from galling and seizing. but are not too useful in rolling element bearings. For rolling
These materials do no provide the EP protection by reacting element bearings, molybdenum disulfide is the filler of
with the metal at high temperatures like the conventional choice. Grease containing 3 % or more of this filler provides
oregano-sulfur and organo-phosphorus compounds. In- an effective protective film. Molybdenum disulfide and
stead they do so by physically depositing the fine solids, sus- graphite are sometimes used for back-up lubrication in high-
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CHAPTER 10 䊏 LUBRICATING GREASES 469
temperature applications over 315° C 共600° F兲. Zinc and quality and type of fats and carboxylic acids starting materi-
magnesium oxides are usually used in greases for food pro- als, the metal cation/s, the base oil, the soap concentration,
cessing industries, primarily because they are lighter in and the pH during the reaction 共excess alkali or acid兲; and
color and have the ability to neutralize acids. Metal flakes most importantly the manufacturing process. So much so
and powdered soft metals, such as lead, tin, zinc, and alumi- that many of the grease manufacturers consider the grease
num, are used in pipe threading and anti-seize compounds. production an art and the details of the grease manufacture
Talc has use in greases for die and drawing and roll neck are kept confidential. Lubricating greases can be manufac-
bearing applications. The best way to incorporate many of tured either by a two-step process or by a one-step process.
the fillers in a grease is during the milling step. Carbon black, The two-step process involves producing the soap first, by
although commonly used as a filler, also acts as a thickener the reaction of the acid and or the fat with a metal base and
for greases. It is important to note that the fillers can accu- isolating it. The soap is then dissolved in the hot oil, and the
mulate in bearings and cause abrasive wear damage. Accu- mixture cooled under prescribed conditions to obtain the
mulation of the filler can result due to evaporative loss of the grease. In the one-step process, the soap is created directly in
oil because of heat or bleeding. Therefore, it is imperative the oil. The fatty acid or the triglyceride is mixed with a por-
that when using solids-based grease proper regreasing tion of the base oil and the mixture reacted with the aqueous
schedule is followed to prevent this from happening. base. After the salt formation or the saponification reaction
EP properties of the phosphate glasses, inexpensive is complete, the reaction mixture is held at an elevated tem-
white powders, in lubricating greases were compared with perature until either a crystalline fluid is formed, as in the
those of the molybdenum disulfide, graphite, molybdenum case of lithium soap greases, or the mixture becomes homo-
dithiocarbamate, polytetrafluoroethylene 共PTFE兲, and bo- geneous, as in some sodium complex soap greases. It is im-
ron nitride. Under severe conditions, the phosphate glass portant to note that in some greases the maximum produc-
greases demonstrated superior load-carrying capacity com- tion temperature is well below the temperature where the
pared to others 关740,741兴. crystalline fluids are formed. This is the case in the sodium
Grease types, along with the thickener used and their soap greases and choosing different maximum production
performance capabilities, are provided in Table 10.10 关744兴. temperatures can lead to the greases with different proper-
Table 10.11 summarizes the critical grease properties and ties, even though the soap is the same.
the ASTM test procedures which are used to determine Most modern greases are made by batch production.
them. The simplest way to make the lubricating grease is to employ
Grease Manufacture a heated open reactor, commonly called a kettle. Alterna-
tively, a contactor, a pressurized reactor, can be used. A kettle
Production of the modern lubricating greases on a large reactor is well suited for greases that are produced in small
scale is quite complex. The complexity increases when the volume and is often used by small grease manufacturers.
production process involves saponification, which is the re- Such reactors typically have a capacity of 1500 to 2000 gal-
action of a natural fat with a base. Most thickener systems lons 共5.7 to 7.6 m3兲. However, to manufacture the low vol-
are produced by this process. The properties of the final ume products, smaller kettles can be used. The contactor, on
grease depend upon a number of factors. These include the the other hand, is necessary in the manufacture of the com-
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470 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
plex soap greases, since the contactor help keep volatile low years. The steps involved are the same as listed under the
molecular weight acids in the reaction. The contactor is use- batch production but in continuous production everything
ful for producing greases in medium quantities. Batch pro- is automatic. Again citing the example of making a lithium
cess is preferred because the product quality is easier to simple soap grease, measured quantities of the prefabri-
monitor. However, there are a limited number of continuous cated soap or of the fatty raw materials, alkali, and mineral
grease manufacturing plants in operation. Continuous pro- oil are introduced into the reactor by means of adjustable re-
duction is at least four times cheaper than the batch process. ciprocating pumps. The desired temperature and pressure
are dialed in to initiate the soap formation. Good heat trans-
Batch Production fer and short residence times can be achieved by preheating
A number of factors determine the number of steps involved the raw materials. The reactor residence time is in the order
in the batch production of the lubricating grease, the thick- of five minutes, or less. The grease at this time is pumped
ener being the most important. In order to demonstrate into the next reactor, where dehydration under vacuum is
steps in a batch production, we use the example of a lithium carried out to remove the volatiles and water. Next, the dehy-
simple soap grease. The steps involved are as follows: drated soap is moved to the finishing section, where the addi-
• The carboxylic acid or the natural fat raw materials are tional base fluid and the additives are combined and dis-
dispersed in oil. persed.
• The lithium hydroxide base dissolved or suspended in
water is added. Finishing
• The mixture is heated to facilitate salt or soap formation,
Deaeration, milling, and filtration are the final steps neces-
either through neutralization or through saponification.
sary to obtain the finished grease. Deaeration is used only on
• Removal of water by further increasing the temperature
some products. Greases made in the kettle often contain en-
and further addition of the oil.
trained air because of the vigorous mixing. Air must be re-
• Cooling of the reaction mixture to help crystallize the
moved to improve clarity and the brightness of the lubricat-
completely or partially dissolved soap.
ing grease.
• Mixing in of the additives.
Milling is important since its influence on the size and
• Homogenizing the resulting grease.
shape, hence the surface area, of the fibers is the largest. The
• Adjusting the grease to specific worked penetration.
primary purpose of the milling step is to break down the
• Checking the quality parameters.
solid particles, or the fibers, and to uniformly disperse the re-
If a fatty acid is used in the manufacture of the lubricat-
sultant small particles in the liquid 共homogenization兲. Dur-
ing grease, the salt or soap formation is fairly fast. However,
ing manufacture after the soap formation, the grease is al-
if a natural fat is used as the starting material, one must con-
most always obtained as a heterogeneous mixture,
sider factors that influence the saponification reaction. Sa-
irrespective of the rate of cooling. To obtain grease of good
ponification is a process by which triglycerides 共natural fats兲
quality, it needs to be homogenized, which is accomplished
are reacted with an alkali metal 共lithium or sodium兲 hydrox-
by the use of the pressure valves, tooth-colloid mills, and
ide to produce glycerol and a fatty acid salt, or the soap. The
high pressure homogenizers. In all cases, the process in-
rate of the saponification reaction depends upon the reac-
volves high shear mixing, which converts the fibers of differ-
tion temperature, the concentration of the base, the intensity
ent sizes into fibers of similar sizes, thereby resulting in
of mixing, the kind of fat used, and the catalyst, if used.
grease with a uniform creamy texture. However, too much
While the higher temperatures increase the rate of the sa-
milling can be harmful in that it will sever the soap fibers, or
ponification reaction, a temperature of over 100° C requires
decrease the particle size to an extent that will have less asso-
the use of a pressurized reactor. This is to keep the water in
ciation with the oil and hence weakening the lubricating
the aqueous base in the reactor until the reaction is com-
grease structure. Greases that are milled are more durable,
plete. Since the intimate contact between the reactants fa-
that is, they maintain their consistency longer during use.
cilitates reaction, good mixing by the use of an efficient stir-
Filtration removes the unwanted particulate matter
rer is extremely effective. The batch process usually involves
from the grease. Most of the greases are filtered prior to
the use of at least one reactor and a number of tanks. The
packaging and use; however, the firm greases cannot easily
reactor is used to mix the ingredients and convert them into
be filtered. NLGI recommends installation of the 40 mesh fil-
soap or the soap concentrate. This reactor must have high
ters on the centralized grease dispensing systems, suggest-
temperature capability and should be able to handle pres-
ing that the filtration through 40-mesh or finer screen is ap-
sures of greater than one atmosphere. The soap concentrate
propriate.
from the reactor is passed through different tanks where the
soap is diluted, treated with additives, and the final grease
adjusted for consistency. Since all these steps require mix- Incorporation of Additives
ing, these tanks are equipped with stirrers and some tanks Most chemically active additives used in lubricating greases
also have heating capabilities. Multiple-reactor and are sensitive to heat and will decompose at high tempera-
multiple-tank capability adds flexibility and minimizes the tures and hence become ineffective. They may also lose their
possibility of cross contamination from other types of structure or the activity in the presence of the strong bases,
greases that were manufactured in the system previously. calcium, sodium, or lithium hydroxide, which are used to
make soaps. Therefore, the normal practice is to incorporate
Continuous Production the additives after the soap formation and when the partly
Technical challenges to produce lubricating greases on an finished grease is being cooled. At this time, the batch tem-
industrial scale have been overcome during the past few perature is around 185° F 共85° C兲, or below. There are some
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CHAPTER 10 䊏 LUBRICATING GREASES 471
exceptions to this guideline. This is the case for additives reasonable association with the oil; too much or too little
that are not heat sensitive and need to be heated to facilitate will lead to a thinner grease, either because of the high solu-
blending in the grease. Therefore, it is important to know bility of the soap in the oil or the limited association of the
which additives can be added at different stages of the grease soap with the oil. The presence of a polar group, such as hy-
manufacture, so that the finished grease has all the additives droxyl that is present in 12-hydroxystearic acid soaps, leads
in tact. to improved thickening, which is a consequence of the hy-
drogen bonding in the soap molecules. This effectively in-
Desirable Grease Properties creases the soap’s molecular weight; hence its hydrodynamic
For grease to be effective in the intended application, it volume. Certain polar chemical agents, referred to as struc-
must possess certain specific properties, which include the ture modifiers, facilitate dispersibility of the soap in the oil,
following: thereby improving the grease consistency. A decrease in the
• Consistency and Consistency Stability particle size of the soap also improves consistency because
• Penetration the smaller particles, if the soap content of the grease is the
• Rheological Properties same, have a greater surface area; hence a greater associa-
• Thermal Stability 共Heat Resistance兲 tion with the oil resulting in increased thickening. Many
• Oxidation Stability grease manufacturers take advantage of this property of the
• Storage Stability soap by creating small particles by controlling the tempera-
• Sensitivity to Water ture and the stirring rates during the production of grease.
• Corrosion Protection Consistency of lubricating greases ranges from almost
• Load-carrying Capacity fluid, or semi-fluid, to very firm, or hard. Too soft a grease
• Wear Control will leak out of the equipment and too hard a grease will
cause trouble while using. Consistency also influences pum-
Consistency pability; the softer greases generally being easier to pump.
Consistency is the degree of hardness of the lubricating When the equipment is to be greased by the use of a dispens-
grease and is a measure of the resistance of the lubricating ing system, the consistency used may be a compromise be-
grease against deformation under load. Consistency of the tween that required for lubrication and that required for dis-
lubricating grease is a surrogate measure of its rheological pensing.
properties. It is an important measure since the greases are Consistency is commonly measured by the ASTM Cone
classified and adjusted according to consistency. Greases are Penetration Test 共D217兲. Penetration is the depth, in tenths
available in a variety of consistencies, which are defined by of millimetres, to which a standard cone, weighing 150 g,
the National Lubricating Grease Institute’s Consistency sinks into the grease under prescribed conditions. Thus, the
Grades. The grades consist of numbers 000, 00, 0, and 1 to 6 higher penetration numbers indicate softer greases, since
which are based on worked penetration of the grease at 25° C the cone sinks in the sample deeper. Penetration can be un-
共77° F兲. Worked penetration is measured according to the worked or worked. Unworked penetration is carried out on
procedures described in the ASTM Standard D217 and DIN the grease sample at 77° F 共25° C兲 without subjecting the
Standard 51 804, Part 1. It is important to note that if the grease to any mechanical treatment. Worked penetration is
temperature falls, say to 32° F 共0 ° C兲, the grease will be firmer measuring the effect of manipulation on the lubricating
by one or two NLGI consistency numbers. Conversely, if the grease since working can have a significant effect on its con-
temperature rises to 110° F 共43° C兲, the grease will be at least sistency; hence the service behavior. A significant difference
one consistency number softer. NLGI classifies greases into between unworked and worked penetration numbers indi-
eight classes, but DIN standard classifies them into seven. cates poor shear stability of the lubricating grease. The de-
These classes along with their recommended uses are pro- tails of both of these tests are provided in the ASTM Stan-
vided in Table 10.1. dard D217. Incidentally, the penetration value is commonly
Consistency of the lubricating grease depends upon a expressed without units, which are in tenths of a millimetre.
number of factors. These include the amount and the nature Firm greases have low-penetration values and soft greases
of the thickener; its particle size; the structure of the fatty have high-penetration values. Generally, the unworked con-
acid salt; i.e., the number of carbon atoms, degree of unsat- sistency measurement is less reliable than the worked con-
uration, branching, or the presence of another polar group, sistency measurement. This is because the first parameter is
if soap is the thickener; and the presence of the additional measured by simply transferring the lubricating grease from
rheology modifiers. A greater amount of thickener will lead a container to the measurement device, with minimum dis-
to a higher consistency grade. However, the acid structure turbance. Unfortunately, the disturbance cannot be totally
has a varying effect. The soaps of higher than C18 chain eliminated and some invariably occurs. The reason for in-
length, the C18 chain length appears to be ideal, will lead to a consistency in the unworked consistency numbers is the in-
thinner grease; so will the soaps with a higher degree of un- ability to reproduce the same amount of disturbance in each
saturation or the branching. Lower molecular weight acid measurement because it cannot be controlled or repeated to
derived soaps, on the other hand, are less effective thicken- the same extent. On the other hand, worked consistency data
ers since they associate with the lubricant to a lesser degree. are easier to reproduce since each sample is worked 60
Incidentally, thickening results from the van der Waals type double strokes, in the standard grease worker, prior to mea-
of interaction/association of the hydrocarbon portion of the surement. This helps in standardizing the disturbance in
soap with the hydrocarbon lubricant. One way to express the each sample.
situation is that to be an effective thickener, a soap must have A full-scale penetration test requires a large sample,
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472 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
about 500 lb. For smaller samples, an alternative ASTM cal roller weighing 11 pounds 共5 kg兲 is inserted in a chamber
Method, D1403 共IP 310兲 is used. However, the data obtained along with 50 g sample of the test grease. The chamber re-
are less precise than those obtained from the ASTM D217 volves at 165 r / min for two hours at room temperature. The
procedure. Because of this problem, these data are math- roller mashes, kneads, and works the grease. Worked pen-
ematically converted to reflect as if the data were obtained by etration after rolling is compared with that before rolling.
a full-scale measurement. The difference is indicative of the mechanical stability of the
There are three other modifications that are used to grease. There is a recent trend to run this test at higher tem-
measure consistency that are worth mentioning. These are peratures, sometimes above 100° C, instead of at room tem-
prolonged worked penetration, undisturbed penetration, perature.
and block penetration. In prolonged worked penetration, the
grease sample is first worked for a long period in the grease
Penetration
worker, for example, by subjecting it to 10,000, 50,000, or
100,000 double strokes, cooling it to the penetration test As stated under consistency, penetration is the depth in
temperature of 25° C 共77° F兲, and then working it 60 double tenths of a millimetre that a standard cone penetrates under
strokes, prior to the penetration measurement. Many con- the prescribed conditions defined in the ASTM Cone Pen-
sider this test to truly assess the shear stability of a lubricat- etration Test 共ASTM D217 and D1403兲. Examination of the
ing grease. Block penetration is used to estimate the consis- NLGI Consistency Numbers, provided in Table 10.1, suggest
tency of the grease that is too firm to transfer to a worker cup. each NLGI Consistency Grade to differ from the other by 30
The penetration is determined on three faces of a freshly-cut, units. The grease of Consistency Grade 2 is the most com-
50-mm 共2-in.兲 cube of grease. Undisturbed penetration is monly used grease. Other grades are chosen if an application
measured on the grease sample in a container as received, requires softer or harder grease. Softer greases are good with
without any disturbance. This measurement used to be a re- respect to pumpability and if the equipment operates at
quirement in ASTM D217, but because of the difficulty in ob- lower temperatures. Conversely, harder greases are better in
taining analogous results on another sample of the same lubricating high-speed bearings and applications where
grease, this measurement is no longer a requirement. This leakage is likely to occur.
measurement was used to control consistency during the
grease manufacture and to evaluate the grease’s tendency to Rheological Properties
change on prolonged storage. Rheology is the study of the deformation and the flow of mat-
As stated above, based upon worked penetration NLGI ter. In the case of the lubricating grease, we are interested in
has classified lubricating greases in nine grades, from 000, observing its behavior under stress. Factors influencing the
00, and 0 to 6. In general, the greases of Consistency Grades
rheology of grease include the shear stress, shear rate, tem-
1–3 are used in automotive and industrial applications, and
perature, and time. Shear stress is the per unit load tending
in the largest amount. Others are used in small volume and
to cause relative movement between the adjacent layers of
only in specialty applications.
grease, and shear rate is the rate at which this movement oc-
curs. Fluid viscosity is defined as the ratio of the shear rate to
Consistency Stability the shear stress. Fluids are of two general types: Those that
Greases can change consistency during service or storage. exhibit viscosity that is directly proportional to shear stress
Service-related change is primarily due to the mechanical 共兲 over shear rate 共␥兲, or / ␥, and those that do not exhibit a
shear, which can alter the size and the shape of the thickener direct relationship to shear stress over shear rate. The
particles. This will affect their association with the oil, former types of fluids are called Newtonian and the latter
thereby changing the grease’s apparent viscosity, or consis- types of fluids are called non-Newtonian. The non-
tency. A change in consistency during service will lead to in- Newtonian fluids are further divided into dilatant, pseudo-
adequate lubrication and may lead to equipment damage. It
plastic, and Bingham plastic, depending upon their response
is therefore imperative that a grease that maintains its con-
to the shear stress and the shear rate. Figures 10.12 and
sistency during use be chosen and the shear forces have a
10.13 shows the behavior of different types of fluids under
minimum effect on its thickener consistency. Alternative
the influence of shear rate and shear stress. Greases,
terms used for consistency stability are shear stability, work
like many plastic solids, are non-Newtonian. The non-
stability, and mechanical stability. Consistency change in the
Newtonian behavior of greases is due to the presence of
lubricating grease depends upon the thickener used and the
application. The grease may harden or soften during use, but thickeners that are used to develop the grease’s gel structure.
the change should not be too drastic to impair the lubricat- Because the greases are not true fluids, they do not exhibit
ing ability of the grease. Aging and wide temperature fluc- true viscosity, but apparent viscosity. If a fluid’s apparent vis-
tuations can also change the consistency of a lubricating cosity increases with the increasing shear rate, it is a dilatant
grease. This tendency can be determined by carrying out fluid; and if its apparent viscosity decreases with the increas-
controlled experiments. ing shear rate, it is a pseudoplastic fluid. Plastic fluids are
Consistency stability is assessed by the prolonged similar to pseudoplastic fluids, except that they have a yield
worked penetration test 共ASTM D217兲 or by the roll stability point, beyond which flow takes place. Lubricating grease is a
test 共ASTM D1831兲. These tests are low shear tests and the plastic solid, and like other non-Newtonian fluids, its appar-
results are only meaningful for low shear applications. If ent viscosity changes with varying shear rate. Thus its viscos-
shear rate in a particular application is higher, more special- ity must be specified at a specific shear rate, as indicated in
ized tests may be required. In the roll stability test, a cylindri- Fig. 10.13.
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CHAPTER 10 䊏 LUBRICATING GREASES 473
Fig. 10.14—SEM micrographs of various complex soap and non-soap greases 关727兴.
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CHAPTER 10 䊏 LUBRICATING GREASES 475
separation tendency, and its useful temperature range. lower, the thickener is responsible for the slow release of the
In the case of the specialty greases there are additional oil; which actually performs the lubrication function. The oil
performance-related properties that are of interest. The release occurs when the thickener network collapses, which
lower NLGI grade greases, such as 000 and 00, contain only a primarily occurs due to shear.
small amount of soap and their performance is primarily
governed by the quality of the oil. The greases with the NLGI Flow Properties
grades of 1–3, contain a substantially higher amount of soap, Viscosity and Apparent Viscosity
which contributes towards the friction-reduction and Although some grades of lubricating grease are firm they
extreme-pressure/antiwear performance of these greases. must flow so that they can lubricate. As mentioned earlier,
The amount of soap in hard greases, such as NLGI Consis- the greases flow when the applied stress is beyond their yield
tency Grades 5 and 6, is close to 50 %, or more, and in this point. And since the greases are non-Newtonian fluids, their
case, it is primarily the soap that performs the lubrication flow is not directly proportional to the applied stress. This is
function. In the case of the greases of NLGI Grades of 3 and in contrast to the Newtonian fluids where flow is directly
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476 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
proportional to the applied stress, which is the true defini- from other components of the grease to determine the melt-
tion of viscosity. To distinguish the grease’s behavior from ing point, which is virtually impossible. However, most oth-
that of the Newtonian fluids, the term apparent viscosity is ers feel that the grease properties depend upon it being a sys-
used. Apparent viscosity of the grease varies with the shear tem and the soap properties alone will provide little, if any,
rate but that of a Newtonian fluid, such as an additive-free clue to the usefulness of the grease. Hence, they give cre-
oil, does not. Of course, both types of viscosities vary with dence to the properties of the greases as a whole.
temperature. Apparent viscosity is measured by the ASTM As stated earlier, grease structure is a result of associa-
D1092 test, as mentioned in the test methods section. The in- tion of oil and the soap. In some cases, the association be-
formation on apparent viscosity is useful in determining tween the two is strong, but in other cases it is weak. All
pumpability and dispensability and other related param- greases release oil; some to a lesser degree and others to a
eters of the lubricating grease. NLGI provides charts that greater degree. The release of the loosely held oil is the basis
help in converting the apparent viscosity data to pipe flow of the grease’s performance as a lubricant. If no oil is re-
data. Another test by U.S. Steel, called the mobility test, is leased, the grease fails to perform most of its functions. The
used to predict pumpability of the grease at low tempera- loss of the oil can even occur at room temperature and under
tures. The method employs the same equipment as ASTM storage conditions, which is often called bleeding. This is of
D1092, but the piston is activated by nitrogen instead of by concern because it will alter the consistency of the grease,
hydraulic actuation. minimizing its usefulness. The ASTM D1742 test is used to
determine the grease’s bleeding tendency. As the tempera-
Low-Temperature Torque
For the bearing lubrication, grease flows during the opera- ture increases, the oil separation increases as well. Federal
tion of the bearing. Because of the grease structure when the Test Method Document 791, Method 321, is also used to
bearing moves through grease it encounters increased resis- measure oil separation tendency of a grease, but at higher
tance, or torque, relative to what it will experience if a free temperatures.
flowing fluid was being used as a lubricant. This needs addi- Evaporation of the oil component of the grease is a fre-
tional energy, which is not a problem in most applications quent occurrence in most applications. This is because most
since they have ample power to spare. However, in some de- of them either have high operating temperatures or have
vices this can pose a problem since they lack the extra energy. high frictional heat. However, the rate of evaporation in
In some applications, such as aircraft control devices, the most cases is fairly slow. If there is a major reason for con-
low-temperature torque can restrict the use of the equip- cern, synthetic base stocks with high boiling points are an
ment. ASTM D1478 is used to measure the low-temperature alternative. Typically the greases used in low-temperature or
torque of grease using a ball bearing at −55° F 共−54° C兲. broad-temperature applications, such as those used by the
Other test temperatures may also be used. The method suf- military, are based on synthetics. This is because these oils
fers from poor precision, presumably because of the low have excellent low and high temperature properties.
temperature. Just the same, the test is useful in designing de- Two tests that are commonly used to measure evapora-
vices for aerospace applications. tion are ASTM D972 and ASTM D2595. ASTM D972 uses a
temperature between 210° F 共99° C兲 to 300° F 共149° C兲 and
D2595 uses a temperature range between 200° F
Thermal Stability „Heat Resistance… 共93° C兲 to 600° F 共316° C兲.
High heat affects a number of important properties of lubri-
cating grease, namely, consistency, bleeding 共oil separation兲,
oil evaporation, and grease oxidation. High temperatures
Storage Stability
make greases softer, as well as increase their tendency to A number of undesirable things happen to the lubricating
separate oil, which can evaporate. Also, at high tempera- greases on storage. These include deterioration of perfor-
tures, the rate of oxidation increases, which adversely affects mance, oil separation 共bleeding兲, and age hardening—a con-
all three components of the grease: the soap thickener, the sequence of the thixotropic nature of the grease. A rare
base fluid, and the additives. Neither of the changes is de- storage-related change that can occur in arid climates is the
sired since it can seriously diminish grease’s ability to per- loss of water, for example, from hydrated calcium soap
form satisfactorily. greases. These greases need water to maintain the stable
Too drastic a consistency loss in grease implies that it structure and its loss due to low humidity causes a loss in
has lost its structural integrity, hence ability to act as a thick- their consistency. In some cases, the addition of water helps
ened lubricant. The temperature at which grease loses its gel in reverting consistency. The most serious consequence of
structure more or less completely is called the dropping the long-term storage is oxidative breakdown of the grease.
point. Two ASTM methods are used to measure the dropping
point of grease: ASTM D566 and ASTM D2265. The details of Oxidation Stability
these tests are described in the pertinent ASTM Standards. It Lubricating greases are largely comprised of oil; hence they
is important to note that the dropping point is beyond a have the same tendency towards oxidation as the liquid lu-
grease’s use temperature. bricants. In lubricant greases, the oxidation results in a
Some users of the lubricating grease consider the melt- change in one or more of the grease properties. These in-
ing point of the thickener to be the threshold limit for the clude drying and cracking of the grease, increase in penetra-
usefulness of a grease. Beyond this temperature, the thick- tion, lowering of the dropping point, increased acidity, and
ener loses its ability to impart network structure to the the deposits formation on various parts of the equipment, es-
grease, thereby making it ineffective in the grease-related ap- pecially those that experience high temperatures. Hence, it
plications. Of course, the thickener must be first removed is important that its oxidation be controlled. Oxidation of
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CHAPTER 10 䊏 LUBRICATING GREASES 477
grease occurs both on storage and during service and a vari- 3. Another bearing test is ASTM D3337, which deals with
ety of oxidation inhibitors are used to alleviate it. These addi- the greases suitable for very small bearings
tives include peroxide decomposers, radical scavengers, and 4. For automotive service or for use in tapered roller bear-
metal deactivators. These were discussed in some detail in ings, two service-related tests are available. The older
Chapter 4 on Lubricant Additives. The structures of some of test, ASTM D1263, is run at 220° F 共104° C兲 and a newer
the inhibitors used in lubricating greases are provided in Fig. test, ASTM D3527, is run at 150° C 共302° F兲.
10.15. The figure also shows the possible mechanism by
which metal deactivators remove oxidation-promoting Sensitivity to Water
metal ions from the oxidation mechanism. Water contamination of the grease can alter many of its
Inhibiting the grease oxidation is a challenge. Soap- properties. These include a change in consistency, becoming
thickened greases are difficult to inhibit because of the pres- softer or firmer, change in texture, loss of adhesion, emul-
ence of the oxidation-catalyzing soaps. Clay-thickened sion formation, which will not only diminish the grease’s lu-
greases are hard to inhibit because the bentonite thickeners brication capability, but may also lead to washout or loss of
have an affinity towards the aromatic amines, which get ab- rust and corrosion protection, or both. There are two tests
sorbed on clay’s platelet surfaces. This prevents the additive that are used to determine the effects of water on lubricating
to be present in the oil phase where it is meant to perform its grease: The water washout test and the water spray-off test.
function as an oxidation inhibitor. Inhibitor response of the A number of nonstandard tests are also used to analyze the
grease also depends upon the type of the oil used to make the effect of water on lubricating grease.
grease. Low viscosity index naphthenic oils and bright ASTM D1264, Test for Water Washout Characteristics of
stocks, because of the types of structures they contain, are Lubricating Greases, evaluates the resistance of a lubricat-
more prone to oxidation than the largely paraffinic oils. ing grease in a bearing to be washed out by water. The test
Therefore, greases made from the latter group of oils are oxi- temperature is either 38° C 共100° F兲 or 79° C 共175° F兲. The
datively more stable and respond better to the presence of test suffers from a number of deficiencies, which include
the oxidation inhibitors. poor test precision and the results depend upon the grease
Greases differ in their composition, i.e., with respect to texture and consistency.
thickener and the base oil, application, and the level of per- ASTM D4049, Test Method for Resistance of Lubricat-
formance. Hence it is important to choose the oxidation ing Grease to Water Spray, is used to assess the ability of
inhibitor/s that meet use and performance objectives. The grease to adhere to a metal panel, when subjected to direct,
other considerations that should dictate the inhibitor selec- intense water spray. The test measures the amount of grease
tion are protection during storage and whether it is normal removed. Grease removal occurs by two mechanisms: Solu-
purpose, multi-purpose, or specialty grease. Multi-purpose bility and impingement. Water soluble greases are not gener-
and specialty greases are designed for high-temperature use; ally evaluated in this test. Greases that do not have good ad-
hence it is important that the additives survive the desig- hesion, such as those that are soft or are made by the use of
nated service life. Incidentally, one should also consider the low viscosity oils, are easily removed. This test has good
whether the grease was made from natural fat 共triglycerides兲 correlation with the operations involving direct water im-
via saponification. Such greases contain a significant pingement, such as steel mill roll neck bearing service and
amount of glycerol which oxidizes faster that the oil; hence certain automotive body hardware applications. The test
the inhibitor/s will be depleted much faster. uses water at a temperature of 38° C 共100° F兲.
In order to measure damage due to oxidation during
storage, ASTM D942 共Pressure Vessel Oxidation Test兲 is Corrosion Protection
used. Although used extensively, the test appears to have its Corrosion involves deterioration of the metal surfaces by
limitations; the major one being that it is not applicable to all chemical or electrochemical attack. Yellow metal corrosion
products. The following tests can also provide some infor- is chemical in nature and ferrous corrosion 共rusting兲 is elec-
mation on this grease parameter: trochemical in nature. Yellow metal corrosion occurs in cop-
1. ASTM D1741, functional life of the ball bearing greases, per and its alloys, such as brass and bronze, due to sulfur
which is run at 125° C 共257° F兲. containing additives and is normally measured by using
2. ASTM D3336 is run at a temperature of up to 700° F ASTM D130 test method. The problem with this method is
共371° C兲. that it was devised for liquids and hence is not easy to extend
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478 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
to greases because of their semi-solid consistency. A new minimize metal-to-metal contact, hence wear. Wear occurs
ASTM Method, D4048, has been introduced to measure cop- when 共1兲 high spots, called asperities, of one surface rub
per corrosion in grease. Yellow metal inhibitors are useful in against those of another surface, 共2兲 metal breaks, due to fa-
controlling this type of surface damage. Ferrous 共iron兲 cor- tigue, or 共3兲 cross-surface weld spots resulting from the ex-
rosion, commonly called rusting, occurs when iron or steel treme temperatures in the contact zone shear. The resulting
comes in contact with water, oxygen, and trace amounts salt, wear debris may cause additional wear through abrasion.
acids, or alkalis. These compounds catalyze rusting. Rusting This is because unlike liquid lubricants where there is a
tendency of the greases is evaluated by the ASTM D1743 chance for wear debris to be removed through filtration or
Test. Rusting can be controlled, and even prevented, by add- an oil change, in greases that have minimal fluidity there is
ing rust inhibitors to the lubricant. little chance for this to occur. Therefore, it is critical that the
formation of the wear debris in grease-related applications
Load-carrying Capacity is minimized, so as to prevent abrasion of the metal surfaces.
The foremost function of a lubricant is to form a low/no fric-
Lubricating greases differ in their load-carrying capa-
tion barrier between surfaces to keep them apart. This will
bility. In this regard, greases formulated from high viscosity
oils are better than those formulated from low-viscosity oils.
TABLE 10.14—Guide to requirements for Of course, this is only valid when the loads are low to moder-
grease categories „ASTM D4950…. ate. When the loads are high, the lubricant viscosity becomes
Test Description LA LB GA GB GC irrelevant since there is little lubricant in the contact zone to
D217 Penetration 冑 冑 冑 冑 冑 form a lubricating film. As a consequence, extensive surface
D566a Dropping Point 冑 冑 冑 冑 冑 contact, welding, and wear will occur. In these situations, the
D1264 Water Washout 冑 冑 use of sulfur and phosphorus-based antiwear/EP agents is
D1742 Oil Separation 冑 冑 冑 warranted.
D1743 Rust Protection 冑 冑 冑
A number of tests are used to evaluate the load-carrying
D2266 4 Ball Wear 冑 冑 冑 冑
D2596 4 Ball EP 冑 冑 ability of a grease. Three that are most widely used are: Four-
D3527 High Temperature Life 冑 冑 Ball Wear 共ASTM D2266兲, Four-Ball EP 共ASTM D2596兲, and
D4170 Fretting Wear 冑 Timken Lubricant and Wear Test 共ASTM D2509兲. The first
D4289 Elastomer Compatibility 冑 冑 冑 冑 test measures wear at relatively light loads and the test re-
D4290 Leakage 冑 冑 sults are reported as average scar diameter; low wear is indi-
D4693 Low Temperature Torque 冑 冑 冑 冑 cated by a smaller scar. The results only pertain to steel-on-
a
D2665 may be substituted. steel and not to other metal combinations. Since the test
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CHAPTER 10 䊏 LUBRICATING GREASES 479
conditions involve only light loads, seizure or welding does at which scoring is not observed and Score Value is a load at
not occur. Correlation with the real service needs to be estab- which scoring occurs. The Timken test, like the other two,
lished. The other two tests measure severe wear and the has poor precision. The results from this test do not coincide
welding tendency. Four-Ball EP results are reported as sei- with those obtained in the Four-Ball tests since the speeds,
zure load, weld load, and load wear index 共LWI兲. It is impor- loads, test duration, and geometry of contact are different.
tant to be prudent in interpreting the results from this test This is shown in Table 10.12.
since again they apply only to steel-on-steel and at one speed Many bearings are used in applications that create oscil-
and one load. The extent of correlation of this test with the latory motion, which is small amplitude vibration, in rolling
field performance is also uncertain. The Timken test can be elements while contacting a bearing race. This leads to fret-
used to measure wear at low loads as well as at high loads, to ting wear, which is characterized by the removal of the fine
assess a grease’s load-carrying capacity. The test measures particles from the surfaces in contact. A number of tests are
two parameters, OK Load and Score Value, although usually designed to evaluate the grease’s performance in this type of
OK Load is the only parameter reported. OK Load is the load environment. The tests include the following:
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480 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
1. ASTM D3704—Wear Preventive Properties of Lubricat- greases and GA, GB, and GC are classes for wheel bearing
ing Greases Using the 共Falex兲 Block on Ring Test Ma- greases. LA is for mild duty, frequent relubrication service
chine in Oscillation Motion. and LB is for infrequent relubrication, high loads, and water
2. ASTM D4170—Fretting Wear Protection by Lubricating exposure type service. GA is for mild duty, GB is for moder-
Greases. ate duty, and GC is for severe duty service. Prior to this classi-
Fretting failures commonly occur in wheel bearings of fication, the SAE recommended practice, published in SAE
automobiles shipped across long distances before operation information report J310, was used for this purpose. The re-
and in equipment stored for emergency service. port, first introduced in 1951, had several revisions 关745兴.
Table 10.15 summarizes the performance requirements of
Grease Classifications the various classes of the chassis and bearing greases.
Greases are described by the National Lubricating Characteristics Of Modern Greases
Grease Institute 共NLGI兲 Consistency Grades and NLGI Ser-
vice Classification System, first implemented in 1991 Modern greases are based upon flexibility in formulat-
关318,727兴. As stated earlier, NLGI classifies the lubricating ing, preferably for use in many applications. In order to
greases based upon consistency, which is described in the achieve this goal, the lubricating grease must be developed
ASTM Standard D217. NLGI grades range from 000 to 6 and from thickeners, oils, and additives that have the ability to
are based upon the Cone Penetration Test. The lower num- deliver optimal performance. Table 10.16 lists many of the
bers are for softer greases and the higher numbers are for requirements of the lubricating greases in relation to service
firmer greases; the Consistency Grade 2 greases, with the 关727兴. We already mentioned that many of the grease proper-
medium hardness, provide the line of demarcation. Each ties are determined by the combination of the thickener, the
consistency number has a range of 30 points, and between base oil, and the additives; and the others are determined by
numbers is a space of 15 points. The spacing was established the additives alone. Hence, the optimal grease formulation is
with the consideration that the penetration repeatability is possible only if each component possesses the appropriate
within five units. NLGI Grade 2 grease is the most commonly characteristics to contribute towards the overall properties
used grease and for use in central lubricating systems and at of the grease. Thickener influences the dropping point, low-
lower temperatures, greases of the lower consistency are temperature limit, maximum use temperature, water resis-
more suitable. Heavier grade greases have limited use, ex- tance, load-carrying capacity, and corrosion protection.
cept to feed grease to journal bearings in some paper mills Table 10.17 provides the effect of the common thickener
and to lubricate high-speed bearings that operate at speeds types on these properties. Also see Grease Application Guide
of above 5000 r / min. Softer grades greases are used for good provided in NLGI Lubricating Grease Guide 关727兴. Base oil
pumpability or low-temperature service. Firmer grades are properties that influence the properties of grease include its
used for certain high-speed bearings and to preclude leakage viscosity, viscosity index 共VI兲, pour point, and pumpability.
concerns. Table 10.11 shows ASTM laboratory testing proce- For formulating the low-temperature greases, we need to use
dures used for lubricating greases. low viscosity oils because they possess better low-
Table 10.1 summarizes greases based on NLGI consis- temperature performance than the high viscosity oils. On
tency grades and the matching specifications for industrial the other hand, too low an oil viscosity will not form lubricat-
use and Table 10.10 lists the lubricating greases based on the ing film of proper thickness, resulting in extensive equip-
thickener type and suitable characteristics for various appli- ment wear.
cations 关744兴. Table 10.13 provides the NLGI service classifi- For high-temperature greases, the viscosity index of the
cation for automotive use and Table 10.14 describes the oil becomes important. A high VI oil is more suitable in such
chassis and wheel bearings greases according to ASTM applications than a low VI oil since at high temperatures the
D4950, published in 1989. LA and LB are classes for chassis former maintains its viscosity better; which translates into
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CHAPTER 10 䊏 LUBRICATING GREASES 481
better durability of the lubricating film. Similarly, for a viscosity oils, it will have poor pumpability, or slumpability.
heavily loaded bearing, where because of the high pressures This property depends upon the grease structure as well. If
the lubricating film is too thin to be effective, we must use the grease is fibrous or stringy, it will be easier to feed into the
oils of as high a viscosity as possible, as long as they do not application device. On the other hand, if the grease is but-
interfere in pumping or dispensing of the grease. Paraffinic tery, the converse is true.
oils have better viscosity indices than naphthenic and aro- The rheological properties of the lubricating greases can
matic oils. The VI of paraffinics is around 100 and of naph- be considered to relate to their viscosity, the same as in the
thenics is from 0 to 50; however a VI of between 25 and 50 is case of the lubricating oils. However, it is the apparent vis-
more reasonable for use in greases. Highly refined mineral cosity and not the viscosity which is used as a surrogate mea-
oils, or synthetics, have viscosity indices of well over 100. sure of the rheological properties. The apparent viscosity de-
Hence, with respect to the high temperature or the broad pends upon the temperature, shear rate, shearing time, and
temperature applications, paraffinic and highly refined oils the history of the sample 关4兴. The apparent viscosity de-
are better. Synthetics can also be used, if their high price creases rapidly with increasing temperature, shear rate, and
does not pose a constraint. Most mineral oil-based greases, if shearing time. This is because these parameters destroy the
they have a suitable dropping point, can be used in equip- grease’s network structure. The result is the reversal of the
ment that operates up to a temperature of 250° F 共121° C兲. A grease’s viscosity loss to that of the base oil 关4兴. The mecha-
few can also be used in applications with an ambient tem- nism by which the grease loses its structure is simply that
perature of up to 350° F 共177° C兲. Around or beyond this tem- these parameters overcome the weak van der Waals forces
perature, the synthetic fluids may be necessary. This is espe- that are responsible for the formation of the soap-oil com-
cially the case if relubrication of the machine part is plex. Some lubricating greases, such as sodium soap greases,
sporadic. are more susceptible to shear-related viscosity loss than
While considering the use in low-temperature applica- other greases, for example, the lithium soap greases. Some-
tions, pour point of an oil is an important criterion to con- times the greases undergo unexpected consistency changes,
sider. Paraffinic base oils are poorer in this property than such as hardening, softening, and the like, with temperature.
naphthenics and aromatics; hence they are least suitable of These are related to alteration of the grease structure due to
the three for use in low-temperature applications. However, phase transformation or chemical reaction between the
this deficiency may be corrected by the use of the pour point soap and the chemically reactive additives, or both.
depressants. Inter-Grease Compatibility
For applications that require good load-carrying capac-
ity, such as universal joints and needle bearings, naphthenics All greases are not compatible with each other. The in-
are better since they have a superior viscosity-pressure rela- compatibility of the two greases is indicated by a deteriora-
tionship. This helps in forming a more durable film at higher tion of certain desired properties, such as structural integ-
contact pressures. rity, consistency 共worked penetration兲, oil separation, and
Many times the greases need to be pumped into a reser- the dropping point 关4兴. The incompatibility may occur either
voir, distribution system, an applicator, or directly into a ma- because of the soap or the additives used to formulate a
chine part. If the lubricating grease is made from the high grease. Compatibility or incompatibility is hard to predict
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482 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
without carrying out the actual experimentation. However, • Pipe threads as sealants
based upon the previous experience, the following is true: • Tool joints as thread compounds
1. Greases containing the same type of soap are usually
compatible. Grease Selection
2. Lithium soap greases are incompatible with sodium For lubricating grease to be effective, its properties must be
soap greases and the calcium soap greases are incom- matched with the lubrication needs of the equipment. See
patible with calcium complex soap and sodium complex Table 10.19 for the grease selection guide 关727兴. Grease is the
soap greases. lubricant of choice when the equipment runs intermittently,
3. The addition of small quantities of calcium 共lime兲 soap is stored for long periods of time, experiences extreme oper-
grease to the complex soap grease does not cause any ating conditions such as high temperatures, pressures,
changes in properties, but the addition of a small quan- shock loads, slow speeds, or is severely worn. Lubricating
tity of a calcium complex soap grease to a lime soap greases are used in these types of equipment to perform the
grease causes a change in the pH of the mixture which following functions:
leads to significant structural change. 1. Prevent wear
4. When soap greases are added to bentonite 共nonsoap兲 2. Reduce relubrication frequency
greases, the exchange reaction takes place between the 3. Act as a sealant
soap cations, the cations of the additives, and the quater- 4. Provide rust and corrosion protection
nary ammonium ions of the clay. This results in the dete- 5. Inhibit oxidation
rioration of the structure of the bentonite grease, result- 6. Suspend or act as a reservoir for the solid additives
ing in its softening. 7. Protect elastomer seals
Table 10.18 provides intercompatibility of the mineral 8. Reduce noise and vibration
oil-based greases containing different thickeners 关733,746兴. 9. Minimize leakage, dripping, and spattering
Applications Involving Lubricating Each application has specialized lubrication needs
which one must determine before selecting an appropriate
Greases
lubricating grease. One must also assess the grease proper-
Greases are used to lubricate a number of machine parts ties that will be necessary for a good match. These include
in many industries. Common use applications include the consistency, penetration, dropping point, bleeding tendency,
following: mechanical stability, and various other characteristics, such
• Bearings 共rolling element and plain兲 as oxidation resistance, volatility, and viscometrics of the oil
• Gears 共open and enclosed兲 component. The other needed properties can be imparted to
• Universal joints grease by the use of the additives.
• Chassis
• Electric motors Bearing Lubrication
• Couplings Industrial machinery has a number of components that are
• Centralized lubricators amenable to grease lubrication. These are bearings, cou-
• Wipe ropes plings, open gears, and a variety of other moving parts. Bear-
• Chains ings are extensively used in many industries to reduce fric-
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CHAPTER 10 䊏 LUBRICATING GREASES 483
tion, for converting the linear motion into the rotary motion. lead, copper, and antimony. The advantage is that in this ar-
Such industries include steel mills, mining, construction, rangement the bearing assumes most of the wear. This is an
and transportation. Because of their design and use configu- important economic advantage because the bearings are
rations, the use a liquid lubricant in these machine elements more conveniently replaced or adjusted than the relatively
is not suitable, but the use of the lubricating grease is. inaccessible moving components. Plain bearings can be de-
Bearings are of two basic types: plain bearings and scribed by their configuration, by their motion, or by the
rolling-element bearings. Plain bearings are based on sliding type of loading they accommodate. Three major categories
motion between a stationary and a moving element; rolling- of plain bearings are: Journal, guide, and thrust bearings.
element bearings have either balls or rollers which separate Details to their design and functions are available elsewhere
motion between the stationary part and the moving part. In and will not be discussed here 关744兴.
either case, a film of lubricant separating the moving sur- Plain bearings can be divided into three main designs:
faces is essential for a long service life. As a general guide- hydrodynamic plain bearings, hydrostatic plain bearings,
line, the grease dropping point should be about 27° C 共80° F兲
and maintenance-free plain bearings. The lubrication needs
above the bearing temperature, so that the grease does not
of each type are different. For example, for the hydrody-
liquefy. Also, the base oil used to make such a grease must be
namic type, if the conditions are not suitable to create a fluid
selected by taking into consideration the bearing’s operating
film that will separate the journal and the bearing surface,
temperatures. If the temperatures are too high, the base oil
the bearing is in the boundary or mixed-film lubrication re-
evaporation rate may be too high for the grease to be suitable
gime. In these regimes, the surfaces are not fully separated
for long term use.
and have some metal-to-metal contact. This situation com-
Plain Bearings monly occurs when the shaft is at rest or moving at slow
A plain bearing is the most basic type of bearing and con- speeds, which typically occurs at start-up and at high loads.
tains no moving parts. The bearing is held in a stationary ma- This means that the lubricating grease needs to provide the
chine element and consists of a sleeve or a bushing and a wear protection. This can be achieved by improving the lu-
moving part. The bushing is made of a material, or an alloy, bricant’s film-forming ability, either by adjusting the grease
that is softer than that of the part that slides or moves against viscosity or by using surface-active or EP additives. Obvi-
it. Examples of metals that are suitable as bearing material ously, as the speed increases, the boundary lubrication pro-
include bronze and Babbitt metal, which is an alloy of tin, gressively changes first to mixed-film and then to hydrody-
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484 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
namic lubrication, and the need for the film-forming Needle bearings that contain fewer rollers handle lower load
additives is not as critical. In the case of the hydrostatic plain capacity, but have the advantage of operating at higher
bearings, the need for the lubricating grease does not exist speeds. These bearings encounter high rolling and sliding
since these are lubricated with oil, which is continuously friction, hence the grease used to lubricate them must offer
supplied under pressure to the bearing. In the case of the protection against the wear damage. Additional require-
maintenance-free plain bearings, again the need for lubrica- ments that must be met by the lubricating grease are preser-
tion does not exist since the surface of the bushing has a vation of the surface finish against corrosion and pitting and
coated layer of a polymer, such as polytetrafluoroethylene to act as a sealant.
共PTFE兲; a low friction material. Ball Bearings
Ball bearings are machine components which comprise an
Antifriction Bearings
Most antifriction bearings are lubricated with greases of outer ring, an inner ring, balls, retainers, shields, and snap
NLGI Consistency Grades 1, 2, and 3. See Table 10.1 for the rings. The balls are made of hardened steel, ground to a true
recommended applications for the lubricating greases of sphere, and polished to a fine finish. These bearings are nor-
various consistencies. Table 10.20 lists various greases that mally used in light precision machinery where high speeds
are used for lubricating antifriction bearings, along with are maintained. Friction encountered is minimal because of
their properties 关4兴. The type of grease is chosen by consider- the rolling action of the hard steel balls as well as the small
ing a number service and operation-related factors. These contact area. Radial ball bearings are functionally similar to
include the service life, speed, working temperature, posi- plain journal bearings and the thrust ball bearings are func-
tion of the bearings, starting torque, and bearing sealing. In tionally similar to plain thrust bearings. Bearing housings
antifriction bearings, the greases are exposed to mechanical, differ in design, depending on the application, and serve to
thermal, and chemical stresses which can alter the grease’s support the bearing and contain the lubricant. Suitable seals
structure over time. One thing that commonly occurs is the are usually installed to exclude water, dust, dirt, or other ex-
loss of oil through the process of bleeding. Bleeding occurs ternal contaminants from the bearing components and to
when the liquid lubricant separates from the thickener due prevent leakage of the lubricant from the housing.
to the grease’s exposure to high temperatures, a consequence
of the inability of the grease to effectively dissipate heat. Gear Lubrication
When the loss of oil from the grease due to bleeding is 50 %, Greases used to lubricate gears are fluid greases that have
the grease is beyond its useful life 关4兴. This class of bearings NLGI Consistency Grades of 1 or lower. These greases are
includes rolling-element bearings and ball bearings, both of usually made from the sodium soaps with long fibers, a high
which operate on the concept of the rolling friction. viscosity oil, and the EP additives. All three components con-
Rolling-Element Bearings tribute towards the load-carrying properties of the grease,
These bearings consist of rollers, a retainer, races, a shaft, a which are necessary to avert wear damage and welding that
bearing housing, and seals. The contact surface of these commonly occurs in gears as a result of the extensive metal-
bearings has a fine surface finish, which increases their effi- to-metal contact. EP greases, if they can be used, offer a
ciency. Also, these bearings are made of hard steel alloys be- number of advantages over gear oils. These include good
cause their small rolling elements must carry a wide range of sealing, low losses due to leakage, and good adhesion, which
loads, which makes the stresses on the contact surfaces very is clearly beneficial during the start-up where the boundary
high. These bearings may contain one or more rows of roll- conditions prevail and the presence of an effective lubricant
ers, which are either cylindrical, spherical, or tapered 共coni- film between surfaces is critical. It is important to note that
cal兲. When the rollers are long and of small diameter, bear- soft greases are only suitable for lubricating slow running,
ings are called needle bearings. Such bearings have a higher poorly sealed gears, such as those used in cranes, geared en-
load-carrying capacity than the ball bearings of the similar gines, and nonstationary drives in the mining industry. For
size. They overcome frictional resistance by a rolling contact equipment that uses toothed gears, such as drills and small
and are suited to large, heavy assemblies. Roller bearings are tools, soft greases are not adequate and the greases of NLGI
more efficient in reducing friction than sliding bearings, Consistency Grade of at least 2 are needed. Again, because of
have the ability to operate at high speeds, and are easier to the superior load-carrying capacity, the sodium soap greases
lubricate. containing long fibers are the lubricants of choice. They are
Cylindrical roller bearings, the most basic type of rolling sometimes applied to the gear teeth via a spray. Because of
element bearings, are designed to carry heavy radial loads, their less fluid nature they have better adhesion to the tooth
and can operate at high speeds. Tapered roller bearings, be- surfaces. Incidentally, the selection of an appropriate gear
cause of the shape of their rollers and the race geometry, grease requires the same considerations as the selection of a
have the ability to carry both heavy radial and thrust loads, good gear oil.
making them especially useful for use in the automotive ap-
plications. Spherical roller bearings use convex or barrel- Automotive Aftermarket
shaped rollers, which accommodate high radial and shock For automotive applications, lubricating greases of NLGI
loads but they are limited on speed. Needle bearings, be- Consistency Grade 2 are used most often. This is because
cause of containing the cylindrical rollers with a high length- these greases stay soft in cold weather. Common automobile
to-diameter ratio, have the highest load-carrying capacity parts that are lubricated by grease include chassis, power
among the rolling-element bearings. These bearings are de- train, and wheel bearings. These greases have the following
signed to accommodate the oscillating motion and have high attributes:
load-carrying capacity, but again they are speed limited. • High temperature stability.
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CHAPTER 10 䊏 LUBRICATING GREASES 485
• Shear stability—resist breakdown due to mechanical ac- tain no poisonous ingredients. For approval as Category H1
tion. lubricants, they must be developed from the ingredients that
• Water resistance—do not easily wash out. are deemed safe. These are identified in another USDA publi-
• Oxidation resistance. cation, AH562, under “Lubricants.” This publication identi-
• Rust and wear protection, especially against fretting fies a number of thickeners that are safe to use in food grade
wear. greases. The thickeners include aluminum stearate, alumi-
• Easy to handle. num complex 共aluminum stearoyl, benzoyl hydroxide兲,
• Universal use—ability to lubricate all mechanical parts organo-clay 共dialkyldimethylammonium aluminum sili-
in a vehicle. For lubricating wheel bearings in cars with cate兲, and polyurea. Additives that can be used to formulate
disk brakes, greases with thermal stability of 350° F lubricating greases are also identified. These must be used in
共177° C兲 or higher, are required. the least amount needed to fulfill the performance objective
Other properties shown in Table 10.15 must be matched sought. The base fluid must be pure as is defined in the Code
with the needs of the application, to select the appropriate of Federal Regulation 共CFR兲 under Title 21, Part 178, Section
grease. For use in the heavily loaded trucks, high load- 178.3620共a兲 or 共b兲. The oil is specified by color and ultraviolet
carrying capability is also needed. Original Equipment absorbance. Commercial products meeting H1 require-
Manufacturers’ 共OEMs兲 recommendations can also be help- ments are often marketed as “food industry” greases or “food
ful in selecting proper grease. For example, for wheel bear- machinery” greases. Please note that while the USDA regu-
ings, one builder uses lithium grease containing polyethyl- lates food grade lubricants, the National Science Founda-
ene and molybdenum disulfide, while another prefers tion 共NSF兲 oversees the approval process and maintains
lithium complex soap grease instead. records. Liquid food grade lubricants were discussed in
Chapter 9 on Miscellaneous Industrial Lubricants.
Primary Metals—Steel Mills
Major steel producers use at least 15 or more different Textiles
greases. They specify their own compositions and perfor- The textile industry primarily uses multi-purpose greases.
mance for lubricating greases that suit their needs. In steel However, because of the unique needs of this industry, the
mills, the EP multi-purpose greases based upon lithium and same as others, the customized products are preferred. Due
aluminum complex soaps are used in the highest volume. to a concern for staining by the grease, the light-colored
These are used to lubricate machinery with typical operating greases that are easier to clean and leave no stains are fa-
temperatures of less than 135° C 共275° F兲. Depending upon vored. Since humidity in the textile plants is kept high to
the plant size, the greases are pumped over a long distance minimize the formation of the static charges, the greases
and applied by the use of complex dispensing systems. Obvi- with rust-preventive properties are highly desired.
ously, this requires good pumpability. Since copious amount Additional properties for greases used in the textile in-
of water is employed around the bearings for cooling or the dustry include load-carrying capacity, oxidation resistance,
scale removal, the lubricating greases must be water resis- and good adhesion. The last requirement is specifically for
tant. In addition, the greases used in steel mills must possess the semi-fluid, NLGI Consistency Grade 000 grease, which is
high load-carrying capacity and be inexpensive. used as a loom lubricant. This lubricant has the additional
The steel industry also uses a variety of bearings that are requirements of having low resistance to flow and develop
lubricated with grease. These include plain journal bearings, low torque; the latter requirement is to save on energy cost.
especially in rolling mill operations, rolling-element bear- Greases used for dryers require products of high dropping
ings, and table and roll neck bearings. Rolling-element bear- point because of the high temperatures in their immediate
ings are more effective than the plain journal bearings in vicinity.
transmitting power and withstanding loads, hence they are
used in the newer mills. They are also used in cranes, unload- Grease Storage
ers, conveyor belts, and furnaces. Some steel mills have Greases during storage can suffer from the problems of
separate lubrication systems for bearings operating at lower oxidation, bleeding, contamination, change in appearance
temperatures. In these systems calcium soap greases, which and texture, and the loss of consistency. The degree of
are cheaper, are sometimes used to minimize cost. change of the grease properties depends upon the duration
of storage, temperature, and the nature of the grease. Lubri-
Food Processing cating grease is a thixotropic fluid and like all other fluids of
Lubricating greases are also used in machinery employed in this type shows a time dependent change in viscosity, or the
food-related industries, such as bakeries, breweries, dairies, consistency. They lose their consistency 共soften兲 under the
fruit and vegetable packaging, soft drink canning, and metal influence of shear and when the shear forces are removed
can manufacturing. The United States Department of Agri- they see a reversal towards the original consistency. If the du-
culture 共USDA兲 regulates “nonfood compounds,” such as lu- ration of the grease being subjected to the shear forces is
bricants, that come in contact with the food. One needs to short, the reversal to the original consistency is easy. How-
obtain permission from the Food Ingredient Assessment Di- ever, the longer the grease is under the influence of shear, the
vision 共FIAD兲 for use in such plants. Lubricants authorized harder the reversal becomes when the shear forces are re-
for the incidental food contact are identified in Publication moved. This is commonly referred to as age-hardening.
1419 as Category Code H1. Category Code H2 is for lubri- However, all greases do not harden to the same degree once
cants used to lubricate parts that have no food contact. Food the shear forces are removed. The degree of age-hardening
grade lubricants are regular commercial products that con- after work softening varies from grease to grease. Some
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486 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
greases show a higher degree of thixotropy than others, grease technology is used in the following industries:
meaning that they become firmer under long-term storage. 1. Waste water purification plants
Another long-term storage effect is a greater tendency of the 2. Food processing machinery
grease to lose oil, or bleeding, which gets further aggravated 3. Automobiles 共chassis and wheel bearing lubricants兲
by high temperatures. Contaminants, such as moisture, can 4. Railroads 共curve and flange greases兲
deteriorate the lubricating grease. Sodium soap greases that 5. Mining 共open-gear greases兲
have low water tolerance will become soft in the presence of 6. Steel 共rolling mill lubricants兲
moisture. Conversely, clay and calcium complex soap 7. Agriculture 共cotton picker-spindle lubricants兲
greases become firmer. Water contamination can also make 8. Construction 共dipper-stick lubricants兲
some lubricating greases to look hazy. While the oxidation of 9. Marine and nature preserves 共construction and excavat-
greases under storage is not a common problem, but when it ing equipment lubricants兲
occurs, darkening of the grease surface may result. 10. Forestry 共cam lubricants兲
At present, the biodegradability of the lubricant greases
Handling and Disposal of Used/ is tested by the use of the OECD 301B Modified Sturum,
Waste-Greases ASTM D5864, and CEC L-33-T-82 tests, which are designed
Proper handling and disposal of the used or waste to test lubricants in general. The CEC L-33-T-82 test is now
greases and other lubricants are covered by the United listed as CEC L-33-A-94 test. In the United States, the ASTM
States Federal laws, through the guidelines issued by the En- committee has adopted the OECD 301 Modified Sturum pro-
vironmental Protection Agency, and by the state laws. Cur- cedure within the ASTM D5864 test. The highest level of bio-
rently, the final composition of the used or waste greases de- degradability is attained when the amount of carbon dioxide
termines whether it is a hazardous material or not. The four 共CO2兲 evolved is 60 %, or greater, of the theoretical amount
characteristics of ignitability, corrosivity, reactivity, and tox- 关747兴. The pass criterion in the OECD 301 Modified Sturum
icity are used by the EPA as criteria for determining the haz- Test is 70 % removal of dissolved organic carbon 共DOC兲 and
ard status of a waste material. The definition of these terms 60 % of theoretical oxygen demand 共THOD兲. Also consult
is available elsewhere. Chapter 13 on Lubricants and the Environment.
While biodegradability of is the primary consideration
Environmentally Compatible Greases in environmental compatibility, by far it is not the only one.
There are other actions which can be taken to minimize the
These are greases that combine the high-performance environmental impact. These include the following:
properties with the environmental safety and compliance. • Lowering toxicity of the finished products by the use of
These greases are used both for civilian industrial and auto- the environmentally innocuous chemicals.
motive applications as well in military applications. The • Curb the use of the heavy metals, such as lead, bismuth,
main objective of these greases is to minimize their negative and antimony.
impact on the environment. This implies no harm or damage • Minimize or eliminate the use of chlorine to improve the
to water, soil, or life. One raw material that helps in this re- EP performance. Chlorine leads to the formation of the
gard is vegetable oil. It can be used both to make soap as well carcinogenic dioxins.
as the base oil component in grease. Vegetable oils, because • Sealed-for-life applications to reduce the amount of
of being natural products, are inherently biodegradable. grease used.
Two of the problems with these oils and the derived thicken- • Greater use of synthetic greases, such as those based
ers are that they have polyunsaturation and have high pour upon polymers. They will have a lower tendency to wash
points. These make the greases made from them to have off or leak.
poor oxidation stability and poor low temperature proper- • Use leakage-resistant greases for surface mining
ties. One can improve the properties of the greases by replac- applications.
ing the vegetable base oil with largely paraffinic mineral base
stocks and some synthetic fluids; many of which have good Grease Testing Requirements
to acceptable biodegradability. A vegetable oil of high oleic
content, that is, 75–85 % mono-unsaturation, is commer- As mentioned earlier, the properties of the lubricating
cially available. Greases derived from the use of this base oil grease must be matched with the needs of the equipment to
have better properties than those made by the use of the be lubricated. The producer or the marketer of the lubricat-
regular vegetable oils. Biodegradable greases from clay, ing grease must find a way to let the user know the suitability
polyurea, and aluminum complex soaps have also been de- of the lubricating grease for a particular application. This is
veloped, but they all suffer from performance and cost limi- done by meeting the performance or use specifications.
tations. There are many national and international standards that
If one wants to design a lubricating grease which is envi- define the grease quality. The standardized test specifica-
ronmentally compatible, one must also be concerned with tions provide a means to determine and verify the lubricat-
the toxicity and biodegradability of the third component of ing grease performance. Typical automotive, industrial, and
the grease, the additive package. In some instances, toxicity military grease specifications are available elsewhere
of the additives is related to the presence of metals and the 关4,744兴. These references also includes common interna-
sulfur and phosphorus. Replacement of such additives with tional 共European and Japanese兲 grease specifications and
metal-free 共ash-less兲 additives will reduce pollution. Never- standards, such as DIN 51 502 and DIN 51 825. Besides
theless, identifying the biodegradable additives for use in these, there are additional specifications for use in automo-
these products is a challenge. Environmentally compatible tive application as well as in military equipment.
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CHAPTER 10 䊏 LUBRICATING GREASES 487
Major organizations that are responsible for developing out under laboratory conditions, others must be carried out
specifications or standards for the lubricating greases in- in the real use environment, that is, in the field. Test methods
clude NLGI, ASTM, IP 共The Institute of Petroleum兲, AFNOR are designed to properly assess the appropriate property or
共Association Française de Normalisation兲, and TGL 共state properties. The two major organizations that are instrumen-
standards of the GDR兲. Each specification is accompanied tal in designing and standardizing tests for the lubricating
by a number of tests that must be qualified to assure grease’s greases are ASTM and IP. These tests measure a number of
performance in that application. The tests that accompany performance parameters of grease, including flow proper-
these standards are numerous, some of which are standard- ties, heat resistance, oxidation stability, antiwear/EP perfor-
ized but the others are not and are based on consumer feed- mance, and corrosion control. Most of the tests for greases
back. Nonstandardized tests are carried out to evaluate the are the standardized ASTM tests, the details of which are de-
grease performance in a specific application or in specific scribed in the books of ASTM Standards 关27兴. Lists of the
operating environments. While some of the tests are carried common grease tests used in the United States are provided
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488 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
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CHAPTER 10 䊏 LUBRICATING GREASES 489
in Tables 10.21 and 10.22 and the list for the tests used in Eu- perature range of 93– 316° C 共200– 600° F兲.
rope is given in Table 10.23 关748兴. Please note that the lists 3. Oil Separation—Oil separation, or bleeding, in storage
are representative and not exhaustive. The properties tested is a common occurrence in greases, but they differ from
are briefly described below 关748兴. grease to grease. Too much oil separation will harden
the grease, which will impair its ability to lubricate ef-
Flow Properties fectively. On the other hand, greases that do not separate
As mentioned earlier, the consistency of grease is one of the some oil during operation can be noisy in service. Bleed-
most important properties of the lubricating grease that de- ing in grease is a function of the gel structure, the nature
termines its performance in various applications. The limi- and the viscosity of the lubricating fluid, and the applied
tations of the NLGI consistency scale is that it reflects perfor- pressure and temperature.
mance only at 25° C 共77° F兲 but most applications involve Oil Separation 共Static Test兲—ASTM D1742, Test Method
temperatures other than 25° C. The effect of temperature on for Oil Separation from Lubricating Greases is used to
consistency can occur due to phase changes in the thickener determine the bleeding tendency of the grease to simu-
or the degree of its association with the oil. Similarly, me- late oil loss during storage.
chanical stresses in most real use applications differ from Oil Separation 共Centrifuge Test兲—ASTM D4425 de-
those simulated by the worked penetration. These differ- scribes a procedure for determining the tendency of the
ences must be recognized, so that one can predict the perfor- lubricating grease to separate oil when subjected to high
mance of the grease at different temperatures and at differ- centrifugal forces. This test is used to assess grease per-
ent operating conditions. There are methods that determine formance in shaft couplings, universal joints, and roll-
the flow measurements under different conditions than ing element thrust bearings, which are subjected to
those used in the ASTM D217 test. These methods are listed large or prolonged centrifugal forces.
below. The details of these test methods are available in the 4. Leakage from Wheel Bearings—Two tests are used to
appropriate ASTM Standards: determine leakage of grease from wheel bearings at high
1. ASTM D3232, Test Method for Measurement of Flow temperatures.
Properties of Lubricating Greases at High Tempera- ASTM D1263, Test Method for Leakage Tendencies of
tures. Automotive Wheel Bearing Greases, an old test, utilizes
2. ASTM D1092, Test Method for Apparent Viscosity of Lu- a modified automotive front hub assembly 共1940s vin-
bricating Greases. Since apparent viscosity varies with tage design and bearings兲. ASTM Test D1263, the new
the temperature and the shear rate, the specific tem- test, differentiates grease products with differing leak-
perature and shear rate must be reported along with the age characteristics.
measured viscosity. 5. Accelerated Leakage from Wheel Bearings—ASTM
3. ASTM D1478, Test Method for Low-Temperature D4290, Test Method for Determining Leakage Tenden-
Torque for Ball Bearing Greases, measures the starting cies of Automotive Wheel Bearing Grease under Accel-
and running torque of lubricating greases packed in erated Conditions, is a modern test that uses a model
small ball bearings at temperatures as low as −54° C front wheel-hub-spindle assembly employing current
共−65° F兲. production, tapered roller bearings.
4. ASTM D4693, Test Method for Low-temperature Torque
of Grease Lubricated Wheel Bearings. This method is Oxidation Stability
better suited to test low-temperature flow properties Oil, additives, and the thickener, if it is organic, all are sus-
than the ASTM D1478 Method. ceptible to oxidation. The rate of oxidation depends upon a
number of factors; those worth mentioning include the oil
Heat Resistance characteristics, whether it is paraffinic, naphthenic, or aro-
Heat affects the lubricating grease in a number of ways. It matic; the soap, whether it contains unsaturation; high tem-
increases its rate of oxidation, causes it to lose oil due to perature; and the presence of metals. A number of tests are
volatilization, causes melting of the thickener, and lowers used to assess the oxidation stability of greases. Some of
the thickener’s association with oil. The tests that are used to these are listed below:
evaluate these events are provided below: 1. Bomb Oxidation Test—The Standard Test Method for
1. Dropping Point—Two procedures are used to determine Oxidation Stability of Lubricating Greases by the Oxy-
the dropping point. gen Pressure Vessel Method, ASTM D942 共IP142兲, deter-
ASTM D566 共IP 132兲, Test Method for Dropping Point of mines the resistance of the lubricating greases to oxida-
Lubricating Grease and ASTM D2265, Test Method for tion when stored statically in an oxygen atmosphere in a
Dropping Point of Lubricating Grease Over Broad Tem- sealed system at an elevated temperature. This test suf-
perature Range. The results from the two methods con- fers from many deficiencies; the lack of correlation with
cur up to about 260° C 共500° F兲. field performance is at the top of the list. At present,
2. Evaporation Loss—Two ASTM test methods are used to there are no standard, dynamic oxidation tests.
measure this grease parameter. ASTM D972, Evapora- 2. PDSC Oxidation Test—A recently developed grease test
tion Loss of Greases and Oils, determines mass evapora- uses Pressure Differential Scanning Calorimetry
tive losses at a temperature in the range of l00– 150° C 共PDSC兲 to evaluate oxidation stability of grease.
共210– 300° F兲. ASTM D2595, Test Method for Evapora- 3. Greases in Ball Bearings at Elevated Temperatures—
tion Loss of Lubricating Greases over Broad Tempera- ASTM D3336, Test Method for Performance Character-
ture Range, determines the evaporative loss over a tem- istics of Lubricating Greases in Ball Bearings at El-
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490 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
requires testing using reference elastomers CR 共poly- are mixed, sometimes the mixture may reflect a deteriora-
chloroprene兲 and NBR-L 共acrylonitrile-butadiene兲. tion of the physical properties, or a drop in service perfor-
mance. The term incompatibility is commonly used to de-
Stability scribe this phenomenon. Common consequences of the
1. Dropping Point—A standard measure of the resistance incompatibility include a drop in heat resistance, a change
of grease to flow as temperature is increased is the Drop- in consistency, usually softening, and a loss in shear stability.
ping Point 共ASTM D2265兲 关16兴. Incompatibility is not always due to thickeners, but can also
2. High Temperature Stability—High Temperature Bleed arise from all three components of the grease, the thickener,
共ASTM D1742兲, Trident Probe 共ASTM D3232兲, Cone fluid, or additives. Incompatibility is not predictable and
Bleed 共FTM 791B兲, Evaporation 共ASTM D972 and must be determined either through experimentation or by
D2595兲, Rolling Stability 共ASTM D1831兲, Oxidative Sta- monitoring performance during service.
bility 共ASTM D942兲, and a High Speed Bearing Test 1. ASTM Standard D6185, Practice for Evaluating Com-
共ASTM D3336兲. patibility of Binary Mixtures of Lubricating Greases,
can be used to judge grease incompatibility.
Water Tolerance Tests 2. There are several nonstandard ways to determine grease
1. Water washout is measured using ASTM D1264, Water incompatibility. One involves mixing two or more
Washout Characteristics of Lubricating Greases. greases in different ratios and subjecting the mixture/s
2. Water spray-off is measured using ASTM D4049, Resis- to various grease tests to determine deterioration in per-
tance of Lubricating Greases to Water Spray. formance. The tests that can be used for this purpose in-
3. The Wet Roll Stability of Grease is evaluated using a clude measuring the dropping point 共ASTM D566 or
modified ASTM D1831 test. D2265兲, shear stability 共either by prolonged working or
by the roll test, ASTM D1831兲, oil separation 共ASTM
Bench Performance Tests D1742兲, and storage stability 共change in consistency af-
A number of bench performance tests are used to evaluate ter prolonged storage, such as one to six months兲. Other
greases prior to field evaluation. These include the following: tests, such as ASTM D3527 共life performance兲, ASTM
1. High-Temperature Wheel Bearing Test 共ASTM D3527兲, D4290 共leakage兲, ASTM D4049 共water spray-off兲, or
an SKF R2F Test that simulates paper mill applications,
the FE-8 Test, CEM Electric Motor Test, and a GE Elec-
tric Motor Test. TABLE 10.26—High operating temperature
2. Low temperature torque is evaluated using ASTM and behavior towards water ratings used in
D1478 and ASTM D4693 at a temperature of −54° C. DIN 51 502 coding of synthetic greases †733‡.
Grease Compatibility
As mentioned earlier, all greases are not compatible with
each other. When the greases made from different thickeners
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492 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
−54 to 315° C, or −65 to 600° F; which is beyond the capa- with those of the mineral oil-derived greases reveals the syn-
bilities of the petroleum-based greases. Besides extreme thetic greases to be superior, see Table 10.24 关733兴. The supe-
temperatures, there are a number of other factors that deter- rior properties include dropping point, range of operating
mine the need for synthetic grease. These include the follow- temperatures, water resistance, corrosion protection, EP/
ing: antiwear performance, and suitability for use in roller and
1. Extreme operating temperatures, both low and high. journal bearings. In these tables, the mineral oil grease rat-
2. Low-pressure applications, for example those involving ing is 0. Of course, the synthetic greases suffer from a num-
vacuum. ber of deficiencies as well, which were already listed.
3. Stability against the surrounding mediums, such as Synthetic greases are coded according to DIN 51 502, es-
those containing reactive compounds and or corrosive pecially for the European use. Coding uses both letters and
vapors. numbers, see Fig. 10.17 关733兴. The letters are used to indicate
4. Special requirements regarding low friction and low the recommended application, fluid type, high-temperature
noise. limit, and water resistance. The numbers are used to repre-
5. Physiologically harmless 共food, beverages, pharmaceu- sent the NLGI Consistency Grade and the low temperature
ticals, cosmetics兲. limit. Tables 10.25–10.27 provide the designations along
6. Rapidly biodegradable. with their significance 关733兴. Table 10.25 provides the num-
7. For life lubrication. bers for the NLGI Consistency Grade. Table 10.26 provides
Applications include fan motor bearings, clutch release the high temperature limit and the water resistance behavior
bearings, paper machines, drying installations, water and Table 10.27 provides the low temperature limit. To cite
pumps, power generators, power tools, conveyors for dry- an example, a synthetic lubricating grease that is recom-
ing, painting and burning-in machines, conveyors in textile mended for use in journal bearings and contains EP/
machines, high-speed spindle bearings in machine tools, antiwear additives, is made from a synthetic ester base fluid,
aerospace, and automobile applications. Also, please refer to is of the NLGI Consistency Grade 2, has a high temperature
section on industrial uses of synthetic fluids in Chapter 9 on limit of 100° C 共212° F兲, the water tolerance behavior of 0–90
Miscellaneous Industrial Lubricants. or 1–90 共DIN 51 807兲, and the lowest operating temperature
Comparison of the properties of the synthetic greases of −20° C will be coded as KE2G-20. In addition, the grease
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494 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
must meet minimum requirements with respect to the mills, a product with superior water resistance and higher
chemical, physical, and technological properties, as pre- thermal stability is needed.
scribed in DIN 51 528 and DIN 51 502. The strengths and
weaknesses of the soap greases are shown in Table 10.28 and Automotive Requirements
As stated earlier, SAE specifies greases for the automotive
the nonsoap greases are provided in Table 10.29 关733兴.
use and according to the importance of properties needed
for specific applications. See Table 10.31, which lists the de-
Multiple Use Greases sired properties. As stated earlier, NLGI classifies greases
Multiple use greases are those that are formulated for use
共Table 10.13兲 according to NLGI Service Classification Sys-
both in industrial and automotive applications. Table 10.30
tem, which primarily relates to automotive applications,
lists the desired properties of the multiple use greases. In-
that is, for chassis and wheel bearing lubrication.
dustrial use of these greases is much larger than automotive
use; the ratio is about 60: 40. Generally, the automotive Wheel Bearings Greases
wheel bearing greases, due to their superior performance Wheel bearings are the most critical grease-lubricated com-
characteristics, can easily fulfill the needs of the most indus- ponents of a motor vehicle. Rolling-element bearings, such
trial applications. However, in certain special circumstances as tapered roller bearings, are commonly used in the wheel
the automotive products do not suffice and there is a need for assemblies. The bearings generally operate under severe
a customized product. For example, for use in steel rolling conditions of speed and load, and in hostile environments
face condition, and design. Load-carrying capacity in a or zinc dialkyldithiocarbamate antiwear agent, 1.0–4.0 %
grease is determined by tests such as Timken or Four-Ball sulfur-phosphorus EP agent, 0.5–1.0 % arylamine oxidation
EP. These are commented on in the tests section. inhibitor, 0.5–0.8 % metal sulfonate corrosion inhibitor, 1.0–
5.0 % molybdenum disulfide or graphite antiseize agent
Roll Neck Greases
Roll neck greases are specialized products that are used al- 共friction modifier兲. The balance is naphthenic oil.
most exclusively for lubricating plain bearings in rolling EP Grease: 3–15 % Lithium 12-hydroxystearate soap
equipment. This grease is very hard, is of NLGI Consistency thickener 共depending upon grease consistency grade de-
Grade 6, which is carved to a shape suited for application to sired兲, 4 % alkali metal borate EP/AW agent, 1 % antimony
the bearing of heavily loaded equipment. dipentyldithiocarbamate load-carrying additive, 1–2 %
Application and Industry Trends amine salts of dibutyl phosphate and dibutyl thiophosphate
EP agent, and 1–2 % sulfurized isobutylene EP agent/
As mentioned earlier, the lubricating grease market is oxidation inhibitor. The balance is mineral oil, formulation
ever changing. The user-related factors that are influencing extracted from Ref 关750兴.
the worldwide development of the future greases include the Grease for Constant Velocity Joints: 6.5 % Lithium
following: simple soap thickener, 2 % sulfur-free molybdenum-amine
• Improved performance complex friction modifier, 1 % molybdenum dialkyl dithio-
• Longer life phosphate EP agent, 2 % primary/secondary mixed alcohol
• Extreme pressure performance
derived zinc dialkyl dithiophosphate antiwear agent/
• Water resistance
oxidation inhibitor, 1.3 % calcium sulfonate rust inhibitor,
• Oxidation stability
0.5 % sulfur-phosphorus EP additive system, 0.3 % ary-
• Thermal stability
• Improved compatibility with seals, bearing hous- lamine oxidation inhibitors. The balance is semi-synthetic
ings, and soft metals base fluid comprising naphthenic oil, paraffinic oil, PAO,
• New component design and dioctyl sebacate in a 25: 50: 20: 5 weight ratio 共formula-
• Smaller and lighter in weight tion extracted from Ref 关751兴兲.
• Higher operating speeds and heavier loads Grease with improved rust prevention and abrasion
• New fabrication materials, such as ceramics and resistance: 10 % Diurea thickener, 3 % sodium thiosulfate
plastics and hydrated sodium thiosulfate, 2 % calcium salicylate and
• Greater safety and environmental acceptability magnesium salicylate mixture, and 2 % benzotriazole yellow
• “Cradle to Grave” responsibility metal corrosion inhibitor. The balance is purified mineral oil
• Removal of heavy metals, such as barium, zinc, and 共formulation extracted from Ref 关752兴兲. Reference also pro-
lead vides analogous formulations using lithium soap, lithium
• No chlorine complex soap, and aluminum complex soap.
• Biodegradability General Purpose Grease: 8 % Lithium 12-
• Low eco-toxicity hydroxystearate soap thickener, 1 % hindered phenol 共BHT兲
• Global product acceptance oxidation inhibitor, and 2 % calcium sulfonate rust inhibitor.
• Cost-effectiveness
The balance is 59 % paraffinic-naphthenic oil blend and 30 %
It is important that we consider the lubricating grease a
dioctyl sebacate 共formulation extracted from Ref 关753兴兲.
value-added product and not a commodity, paying little at-
Biodegradable Grease: 1.5 % Sodium alginate thick-
tention to its cost but more to its performance. This is be-
cause the greases are the only lubricants that are effective in ener, 30 % glycerol emulsion stabilizer/compatibilizer, 2 %
specialty applications, such as bearing lubrication, where emulsifier, 36.5 % water, and 30 % beef tallow film-forming
the liquid lubricants will not be adequate. The complex na- agent after emulsification 共formulation extracted from Ref.
ture of the lubricating greases and the intricate manufactur- 关754兴兲.
ing process further justifies this consideration. Biodegradable Grease: 5 % Ammonium alginate thick-
ener, 50 % greater than C18 alcohols emulsion stabilizers/
Formulation Examples
compatibilizers, 10 % graphite friction modifier, 10 % water,
EP Grease: 5.0–10.0 % Olefin copolymer viscosity 25 % rapeseed oil film-forming agent after emulsification
modifier/thickener, 0.5–2.0 % zinc dialkyl dithiophosphate 共formulation extracted from Ref 关754兴兲.
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11
Metalworking and Machining Fluids
DISCUSSION IN THIS CHAPTER PERTAINS TO cation, and protection against corrosion. They, therefore,
fluids that facilitate metalworking and machining opera- improve the efficiency of the operation, and hence increase
tions. The nature of the various working operations is ex- productivity.
amined, along with the properties of the lubricants needed Irrespective of the type of the metal cutting operation,
for each. Discussion includes metalworking fluid classifica- whether it is turning, milling, drilling, planing, shaping,
tions, composition, formulating, and testing. Representa- broaching, or sawing, the mechanism of action of all cut-
tive examples of the various metalworking fluid formula- ting tools is the same. That is, the cutting is performed by
tions are also provided at the end of the chapter. the tool either as it moves across the metal surface being
Metalworking is the process of converting the bulk machined, or the tool is stationary and the metal surface
metal into a component, or a part, and primarily involves moves against it. In either case, the process is accompanied
two types of operations: Those that produce metal debris by plastic deformation of the metal surface at the front of
and those that produce no debris. The former type is clas- the cutting edge of the tool and the rubbing of the formed
sified as the metal removal operations and the latter type is chip with the tool surface, as shown in Fig. 11.1. The tem-
classified as the metal forming operations. Cutting and perature estimates in the cutting zone are 900° C on the
grinding are examples of the first type and drawing, stamp- tool’s cutting edge, 500° C on the chip, and 200° C on the
ing, and bending are examples of the second type. All met- work-piece. As we move away from this zone, the tempera-
alworking operations involve bringing two solids, a tool ture of the tool drops to 400° C on the tool’s outer edge and
and a work-piece, together to create a new part or a shape. to 200° C on the chip. About 75% of the heat generated is
The process involves high friction, high pressures, high due to the deformation of the metal and the other 25%
temperatures, and tool wear, and it is the job of the lubri- results from the friction due to sliding of the chip on the
cant, or the metalworking fluid, to control them. Metal- tool face. Metal deformation occurs due to shear or plastic
working fluids accomplish this by providing cooling, lubri- flow along the shear plane that extends from the edge of
497
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498 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
the tool to the surface of the work-piece metal, see Fig. consumption. However, controlling friction by the use of a
11.1. Below the shear plane the metal is undisturbed; above lubricant with cooling ability or the ability to form a low-
it the metal is deformed and ultimately results in the for- friction, low shear lubricating film at the chip-tool inter-
mation of a chip. It is critical that the high temperatures in face is a more effective strategy. This is because a lubricant
the cutting zone are decreased, otherwise extensive tool will reduce extensive metal-to-metal contact and facilitate
wear and rough finish of the work-piece will occur. In the sliding of the chip on the tool face; thereby reducing tool
case of the brittle materials, high temperatures in addition wear, increasing tool life, reducing the built-up edge, pro-
may cause the fracture of the metal along the shear plane, viding smooth finish, and permitting fast-machining
which will form a discontinuous or segmental-type chip. speeds.
This is undesired since it will interrupt the continuous cut- Grinding is a special type of cutting where extremely
ting action. In the case of the ductile metals, high tempera- small chips are removed by a large number of irregularly
tures will also cause a built-up-edge on the nose of the tool, shaped abrasive particles bonded in a wheel. Excessive
which will result in a severe plowing action and again poor heat is a problem in grinding operations as well. The func-
finish of the work-piece surface will occur. The built-up tion of a grinding fluid is to improve the grinding action as
edge is the stagnant mass of the metal that sheared away well as act as a coolant. The problem is that a liquid cannot
from the body of the chip by the high tool-face friction. be present at the point of grinding contact and hence can-
The efficiency of the cutting operation may be im- not cool the surface. However, the fluids that contain
proved by reducing tool-face friction in two ways. One way extreme-pressure additives mediate the heat generation by
is to increase the shear angle shown in Fig. 11.1 and the forming a low-friction EP film.
second is to use a lubricant. An increase in the shear angle Unlike the metal removal operations that are mecha-
produces a thinner chip and deforms less metal. The result nistically quite similar to one another, metal forming op-
is lower friction and heat generation and reduced energy erations are quite diverse. However, they do have common-
alities among them. They all involve high pressures and types: Wedge and squeeze. Wedge type films occur when two
temperatures, wear, and friction. Two of the latter factors nonparallel surfaces in motion converge and squeeze type
definitely need to be controlled. films occur when the parallel surfaces in motion come to-
gether 关757兴. In metal forming operations, the wedge type
Lubrication films are more common than the squeeze type. As the lubri-
Mechanical equipment primarily experiences four types of cant enters the converging zone, there is an increase in pres-
lubrication environments, which are hydrodynamic or full- sure that causes an increase in lubricant viscosity. This is a
film lubrication, elasto-hydrodynamic lubrication, mixed- consequence of the lubricant molecules coming closer. The
film lubrication, and boundary lubrication 关11,13–15兴. These increase in viscosity changes the nature of the lubrication in
are depicted in Figs. 11.2 关11兴 and 11.3. The cross-hatched the contact zone from being hydrodynamic to elasto-
area in Fig. 11.3 indicates a solid lubricant film that causes hydrodynamic. Based upon the pressure and speed consid-
elastic deformation of the metal surfaces. erations, we believe that we have moved from the right end
Metalworking operations are designed to have at least of the curves, shown in Fig. 1.3, closer to the border of the
some metal-to-metal contact. This is because total separa- mixed-film lubrication regime. As the lubricant exits, the gap
tion of the surfaces will make the process inefficient. For ex- widens and there is a decrease in viscosity and an increase in
ample, in the metal removal operations, separation will lead velocity. This causes a reversal to hydrodynamic lubrication,
to poor tool work-piece contact, which will interfere in the that is, a movement away from the mixed-film regime. The
chip formation. In metal forming operations, this will lead to result is the separation of the surfaces and hence minimal
low friction and hence loss of control. This implies that in metal-to-metal contact. A drop in viscosity is a consequence
metalworking processes, the lubricant must be designed to of the widening gap that permits the lubricant molecules to
perform in elasto-hydrodynamic, mixed-film, and boundary move away from one another.
lubrication regimes. In general, metal removal operations The quality of the lubricant film determines the metal
require boundary lubrication and metal forming operations forming efficiency: The higher the operation speed, the
require elasto-hydrodynamic and mixed-film lubrication. higher the film thickness. Similarly, the higher the viscosity,
The metal removal operations therefore involve little or no the higher is the film thickness. Therefore, both these condi-
lubricant film and the metal forming operations involve a tions force the converging surfaces to move away from each
fairly thin lubricant film. As mentioned earlier, the metal other 共the gap widens兲, which improves the operation effi-
forming operations primarily involve high pressures and ciency. For example, in the rolling operations, the speed of
high temperatures. Figure 11.4 depicts the effect of the load the strip determines the film thickness. Since the tempera-
and movement during metal forming operations. The as- ture and pressure also impact viscosity, hence the lubricant
perities start to flatten as the load on the work-piece in- film thickness; these factors also affect the efficiency of the
creases. This increases contact and the heat generated due to metal forming operations. Different base fluids have differ-
loading causes high spots to weld 关756兴. The use of an ex- ing response to temperature and pressure, and therefore
treme pressure lubricant helps avoid this. However, in cer- their properties can influence the properties of the metal
tain situations, some lubricants cause metal movement forming lubricants. Naphthenic base stocks are usually pre-
when the metal is being pressed against the die, especially if ferred over paraffinic base stocks. This is because they not
they are not shear stable. The result is tearing of the welds, as only experience a faster viscosity decrease with an increase
shown in the figure. Metal movement can only be controlled in temperature 共have a lower viscosity index兲; they also un-
by altering the lubricant properties. dergo a greater viscosity increase with an increase in pres-
Lubricant film in the metal forming operations is of two sure. These factors make lubricants derived from these base
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500 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
or additives or both in water. These fluids are of three types: sulfur, chlorine, and phosphorus-derived extreme pressure
Soluble oils, semi-synthetic fluids, and synthetic fluids. additives. However, there is a growing trend towards the use
The worldwide use of the oil-based fluids is estimated at of the paraffinic base stocks because the derived fluids have a
45 % and that of water-based fluids is estimated at 53 %; with lower tendency to produce mist. The cooling ability of these
synthetics, semi-synthetics, and soluble oils, having a share of fluids is not as good as that of the water-based systems, but it
4, 16, and 33 %, respectively. Solid suspensions make up the is respectable.
rest. The ASTM Standard D2881 关758兴 and the European Straight oils are used in severe cutting operations in-
Standard DIN 51 385 关759兴 classify metalworking lubricants volving screw machines, cold headers, and other machines
according to their nature and functions. Classes of metal- having a common sump for both hydraulic and machining
working fluids are described below and are also described in lubricants. Because of this and their excellent lubricating
Table 11.1 关4兴. The essential difference between the various ability, these lubricants are often used in high-temperature
classes is that as one moves from straight oil to synthetic operations that involve high unit pressures and high spot
fluid, the amount of water increases and the amount of oil temperatures. That is, those involving slow machine speeds.
decreases. They are also the fluids of choice in most heavy-duty opera-
1. Straight Oil 共not dilutable兲—not supportive of the micro- tions and for the machining of extremely hard metals.
bial growth. Straight oils can be classified as either “active” or “inactive.”
2. “Soluble” Oil 共oil-based emulsifiable concentrate, di- These oils are labeled active if they contain additives capable
luted with water at the point of use兲—more likely to sup- of releasing active sulfur 共see discussion under the extreme
port bacterial growth. It primarily contains oil, emulsifi- pressure agents in Chapter 4兲. Otherwise, they are classified
ers, and other additives. When diluted, the typical as inactive. Sulfur-releasing ability is high when the sulfur-
dilution ratio is between 5 to 20 parts of water to 1 part ized olefins and the sulfurized fats used as additives are of
of concentrate. This produces an emulsion. Oil provides high sulfur content, that is, their sulfur to olefin ratio is
the lubrication and the corrosion protection and the wa- greater than 1. Active fluids are commonly used in machin-
ter provides cooling. In some grinding applications, the ing steel. However, some metal removal operations, such as
dilution ratio can be as high as 200 to 1. blanking, do employ inactive fluids. Inactive fluids contain
3. Semi-synthetic Fluid 共oil-in-water emulsion concen- fatty oils, and fatty oil-mineral oil mixtures or inactive sulfur
trate; diluted prior to use兲—more likely to support bac- additives, or a combination thereof. The in-house use of
terial growth. These contain oil and additives emulsified these fluids is higher than the water-based chemistry and the
in water. These preformed emulsions when diluted fur- residues cause some housekeeping problems.
ther are used to provide lubrication, cooling, and corro-
sion protection. Water-based Fluids
4. Synthetic Fluid 共water-based solution concentrate; di- These fluids are emulsions consisting of an organic phase
luted prior to use兲—more likely to support fungal and an aqueous phase. In emulsions, one phase is consid-
growth. It contains no oil but is a solution of the corro- ered a dispersed phase and the other a continuous phase,
sion inhibitors and the friction reducing additives in wa- usually the larger of the two. When the organic material, that
ter. These fluids provide cooling and corrosion protec- is the oil and or the additives, is the dispersed phase and wa-
tion but their lubrication properties arise from the ter is the continuous phase, the emulsions are called normal
synthetic lubricity components. or oil-in-water emulsions. If, however, water is the dispersed
phase and the organic material is the continuous phase, the
Oil-based Fluids emulsions are called invert, or water-in-oil emulsions. The
These lubricants, commonly referred to as straight oils, are two types of emulsions are depicted in Fig. 11.5 关459兴.
mineral oil-based, vegetable oil-based, or synthetic fluid- Metalworking and machining fluids are usually of oil-
based. Vegetable oil-based fluids are more expensive than in-water type emulsions. The emulsions are of transient sta-
the mineral oil-based fluids but have the advantage of a bility 共ASTM D3342, D3707, and D3709兲. Their stability de-
higher degree of biodegradability. This facilitates the de- pends upon a variety of factors. These include the nature of
posal of the spent fluid. With respect to the thermo-oxidative the oil phase, the amount and the type of the emulsifier/s, the
stability, which is a concern in all vegetable oils, rapeseed, pH, the operating temperatures 共ASTM D3707兲, the nature
castor, or coconut oils are the best. This is because either and the amount of additives, and the impurities, either in-
their saturate content or the mono-unsaturate content is herently present or externally introduced into the system. All
high. The oil-based fluids do not contain any water; hence these factors can lead to coalescence of the fine droplets into
they do not support microbial growth. Therefore, they do not larger ones and lead to oil-water separation. In general, the
need any biocides. In addition, these oils have good ability to emulsions that are used as metalworking fluids are kineti-
wet surfaces, provide good rust protection, and are most cally stable but thermodynamically unstable 关757兴. This
trouble-free of all the metal removal fluids. In addition to the means that such emulsions maintain their integrity during
higher cost than the water-based fluids, these have the disad- use, but have the tendency to phase separate when not in use.
vantages of the mist formation and hence pose a potential While the phase separation in the bulk fluid is undesired, the
fire hazard. They may or may not contain any surface reac- emulsions must phase separate on surfaces to release the oil/
tive additives. Additive-free oils are used only in light-duty additives that improve lubrication. Oil availability in these
applications involving metals with high machinability, such emulsions depends upon its amount being present in the for-
as aluminum, magnesium, and brass. Additive-treated oils mulation and the emulsion stability. As a rule, the higher the
primarily utilize hydrotreated naphthenic base stocks and oil content and the lower the emulsion stability, the greater is
contain polyol esters and fatty oils as lubricity agents and the oil availability. The problem is that the two essential
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502 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
Fig. 11.5—A representation of 共a兲 water-in-oil emulsion and 共b兲 oil-in-water emulsion.
properties of the emulsions, namely the lubricating ability 11.2. The quality of the emulsions in metalworking fluids is
and the cooling capacity, are inversely related. Emulsions of maintained by taking the following steps.
high oil content 共lower water content兲 not only have inad- 1. The use of the biocides.
equate cooling ability, but they are also of lower stability, 2. Maintaining the pH 共bacteria are dormant at pH of
which decreases their useful life. To further complicate mat- greater than 8.8; 8.8–9.2 is a good range兲.
ters, some metalworking operations, such as rolling, tend to 3. Controlling the dissolved oxygen levels.
destabilize these high oil-based emulsions. In other words, 4. Periodic removal of the contaminants, such as the
there is lubrication-cooling tradeoff when the emulsion type tramp oil.
metalworking fluids are used. 5. The use of the filtration equipment.
Emulsions are usually supplied as concentrates, which It is important to periodically check the organic 共oil兲
need to be diluted with water prior to use. In addition to content of the emulsion by breaking it. An acid or salt, such
cooling and lubricity 共ASTM D2782, D2783, D4172, and as sodium chloride, is used for this purpose. Alternatively,
D5619兲, these fluids possess inherent rust prevention proper- one can use a refractometer to determine the oil content. If
ties 共ASTM D4627兲, and detergency. Another attribute of the oil content is too low, it may be appropriate to top up the
these fluids is the ability to incorporate additional perfor- fluid with the fresh concentrate. Since the contaminants,
mance additives. The main disadvantages are their sensitiv- such as the tramp oils, metal debris, and microbes, can de-
ity towards hard water, susceptibility to microbial attack, stroy the integrity of emulsions, they should either be re-
and skin sensitivity. moved or controlled. Tramp oils are removed via skimming
Water-based fluids are susceptible to microbial attack, and the metal debris is removed via filtration. As mentioned
primarily because of their low organic 共high water兲 content. above, the microbes are controlled by the periodic addition
Bacterial infestation of the fluid can lead to an objectionable of the antimicrobial agents.
odor due to the formation of the hydrogen sulfide, a change Foaming is another problem 共ASTM D892兲 with emul-
of color to gray, the formation of black stains on the work- sions that relates to the presence of the emulsifiers. Foaming
piece, and foaming. Fungal growth can produce slime and is not only leads to poor 共spotty兲 lubrication, but it also impairs
more difficult to control than the bacterial growth. The ma- the fluid’s heat transfer properties. While the new emulsions
jor side effect of the microbial attack is the emulsion’s ten- are more stable than the old emulsions, the lubricating abil-
dency to phase separate. Monitoring and control of the ity 共ASTM D2782, D2783, D4172, and D5619兲 of the emul-
emulsion quality are therefore important. The common sions improves with use. This is because the debris resulting
techniques used for this purpose are summarized in Table from the metalworking operations and the decomposition
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CHAPTER 11 䊏 METALWORKING AND MACHINING FLUIDS 503
inhibition 共ASTM D665兲 and TEFLON® 共PTFE, polytet- fluids are appropriately called synthetic lubricants, or the
rafluoroethylene兲, glycols and poly共alkylene glycol兲 for lu- chemical coolants. Synthetics, like emulsions and micro-
bricity. Since these fluids are solutions and not emulsions, emulsions, are obtained by diluting the additive concentrate
they do not suffer from destabilization problems and are with water, typically in 1 : 10 to 1 : 50 ratio.
useful for high-speed machining applications. Their higher Semi-synthetic Fluids 共Micro-emulsions兲
stability is due to their small micelle size, which also makes These fluids are in between the soluble oils and the synthetic
them appear clear, and the low organic content. The micelle fluids in terms of their oil content. In every other aspect they
size in these fluids typically ranges between 0.005 and resemble the soluble oils. Because of the low oil content,
0.015 m. The fluids that do not contain any metal or amine these fluids also appear clear. However, some semi-synthetic
carboxylates are quite stable in hard water. They sometimes fluids of the high oil content contain greater than 3.0 % oil
contain borates and phosphates for water softening/friction and are translucent. As mentioned earlier, the emulsion ap-
modification; soaps and wetting agents for lubrication and pearance is a function of the droplet size: The larger the
the reduction of the surface tension; phosphorus, chlorine, droplet size, the milkier the appearance. These fluids consist
and sulfur compounds for the extreme pressure properties; of fine colloidal dispersions of organic and inorganic materi-
and germicides and biocides to reduce biological degrada- als in water. The water content in these fluids can vary be-
tion. Despite their cleanliness, excellent hard water stability, tween 10 and 60 %. Organic materials commonly used in
long service life, and effectiveness under high machining these fluids include fat, sulfur, and chlorine-containing
speeds, they have the disadvantages of being expensive, have chemicals, which impart extreme-pressure properties. Bio-
the tendency to wash away greases and paints from the ma- cides and corrosion inhibitors can also be added to obtain
chinery, and leave behind hard crystalline residues. the biological stability and rust inhibition. The advantages
Synthetics can be formulated to shed tramp oil, that is, of these fluids include the ability to incorporate both the oil-
the undesirable contaminant oil, for easy skim-off. These soluble and the water-soluble chemicals, good lubricity, im-
fluids are resistant to bacterial degradation 共ASTM D3946兲 proved wettability, and easy waste treatment and disposal.
because of the low organic content and have good work- However, the high levels of the tramp oil can destabilize
piece visibility because of the clarity. The disadvantages in- these fluids.
clude reduced lubricity due to the absence of the petroleum Table 11.4 summarizes some of the characteristics of
oils; tendency to leave hard crystalline residues; and high al- the liquid metalworking fluids that were discussed in the
kalinity, higher cost, and a greater tendency to foam. The preceding sections.
higher cost and the greater tendency to foam relate to the
higher amount of the emulsifiers and the coupling agents Solid Dispersions
that are necessary to formulate them. Foam is usually con- These lubricants contain solids suspended in water or in oil.
trolled by the use of the foam inhibitors. Synthetics, in addi- Most solids are inorganic in origin, although at times or-
tion, are difficult to dispose of because it is not easy to sepa- ganic polymers are also used. Dispersions are made by me-
rate the organics from water without sophisticated chanically agitating the finely divided solids in the presence
separation techniques. Sodium nitrite 共NaNO2兲 corrosion of a high molecular weight dispersant. Common solids used
inhibitor in water is a true solution. It was previously used to formulate these lubricants include graphite, molybdenum
for applications where effective cooling was the only consid- disulfide 共MoS2兲, metal powders, metal oxides, metal ha-
eration. The use of the sodium nitrite is being discontinued lides, mica, and polytetrafluoroethylene or TEFLON®. Dis-
because of the carcinogenic nitrosamine formation, result- persions are hard to maintain because the solid particles are
ing from its interaction with proteins. Because the additives quite large and hence have an increased tendency to settle.
used to formulate these fluids are synthetic in origin, these During use, these lubricants form low-shear solid films, films
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506 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
that are easily removed when the two contacting surfaces cause local welding during cutting. Shearing of the welded
slide, at the tool work-piece interface, which protect surfaces spots will not only increase the roughness of the surfaces,
against metal-to-metal contact. The use of these fluids is lim- but it will also expose fresh surfaces that are more prone to
ited to certain metal forming operations, such as extrusion welding. Consequently, additional frictional heat will be gen-
and forging. They are rarely used in the metal removal lubri- erated. The function of the fluid is to dissipate this heat and
cants because of their propensity to settle in the presence of reduce the number and the size of the welded spots. Lubrica-
debris. Commercial passive EP 共PEP兲 agents, which are col- tion effectiveness depends upon the properties of the oil and
loidal dispersions, are used in these lubricants. the presence or the absence of the friction reducing addi-
tives. Cooling ability, on the other hand, is a function of the
Classification Based on End-use amount of water and the thermal conductivity and specific
heat of all of the components present in the formulation. See
Metalworking operations generate a significant amount of
Table 7.18 for values of these thermodynamic parameters for
heat, which if not controlled or quickly dissipated, will lead
oil and water.
to tool damage and inefficiencies in the metalworking opera-
tions. Metalworking fluids generally cool as well as lubri- Metal Removal Fluids
cate; hence, they are sometimes called metalworking cool- As stated earlier, the metal removing operations are of two
ants, or lubricant coolants. These fluids are formulated to types: those where the work-piece is moved against the sta-
fulfill the cooling and wear control needs of the specific op- tionary tool and those where the tool is moved against the
erations because each one differs in these requirements. stationary work-piece. In both cases, the tool cuts into the
This makes formulation or selection of a modern metal- work-piece, resulting in the chip formation. These fluids,
working lubricant that meets all the process and product re- also called the metal cutting fluids, are utilized in operations
quirements a complicated task. In addition to cooling and that are used to remove the excess metal in the process of
lubrication, other properties sought in a metalworking fluid manufacturing a new part. Both oil and water-based fluids
include appropriate viscosity 共ASTM D445兲, ability to wet are used for these operations. Oil-based fluids can be of pe-
and adhere to surfaces 共ASTM D2782, ASTM D5183, D2783, troleum, synthetic, or biological 共vegetable and animal兲 ori-
and D4172兲, and noncorrosivity to ferrous and nonferrous gin. These fluids are designed to perform the following key
metals 共ASTM D665 and D130兲. Metalworking fluids are functions:
sprayed or poured at the metal-tool interface to dissipate 1. Cooling to prolong the tool life.
heat, lubricate, protect the freshly exposed metal surfaces 2. Lubrication to minimize friction, and hence improve
against corrosion, and remove debris away from the critical the surface finish.
areas. 3. Facilitate removal of the chips and the metal debris.
Metalworking lubricants, based on the mode of their op- 4. Protect the freshly exposed surfaces against rust and
eration, can be classified as metal forming fluids, metal re- corrosion.
moval fluids, and miscellaneous others. Others include 5. Increase productivity and reduce cost through faster
metal protecting fluids, metal treating fluids, and slide way material removal rates and lower power consumption.
lubricants. Because these fluids are not directly involved in Heat produced during metal removal is primarily fric-
metalworking, the present discussion will largely deal with tional and the most is generated during the chip formation.
the metal forming and metal removal fluids, which are of the Additional heat results from deformation of the metal and
most predominant type. Metal removal fluids are lubricants during the travel of the chip across the tool surface 关4,757兴.
that are used in applications where the metal is removed The primary function of the lubricant in metal removal op-
from the work-piece in order to obtain the desired shape. erations is to reduce friction as well as remove heat quickly.
Such applications include cutting, drilling, broaching, turn- It must also remove the metal debris, resulting from the cut-
ing, grinding, milling, threading, reaming, boring, and saw- ting and grinding operations, away from the work-piece.
ing. The primary functions of the lubricant are cooling, fa- Otherwise, extensive tool wear will occur. While water is an
cilitate debris removal, and minimize tool wear. Metal excellent coolant, it lacks the ability to reduce friction and
forming fluids are lubricants that are used in operations wear. Therefore, these fluids contain the friction reducing
where the metal in the work-piece is plastically deformed to and wear control additives. Friction reducing additives pri-
obtain the desired shape. Such operations involve molding marily generate protective surface films via physical interac-
of the metal by the processes of bending, stretching, e.g., tion. Wear control additives, on the other hand, generate
wire drawing, and pounding. The primary function of a lu- such films via a chemical reaction. The former type includes
bricant in these operations is to reduce friction. Lower fric- fatty materials, such as vegetable oils and animal fats, and
tion helps in increasing the tool life and in lowering the en- the latter type includes sulfur, chlorine, and phosphorus de-
ergy usage. Metal forming operations include hot rolling, rivatives. The presence of these additives also minimizes
cold rolling, foil rolling, forging, wire drawing, tube draw- welding of the generated metal debris onto the tool edge to
ing, deep drawing, ironing, extrusion, and spinning. form the “built-up” edge. The friction and wear control not
Heat removal has an effect on the surface finish and cold only reduces blemishing, but it also improves the surface fin-
welding of the tool and the work-piece, which affects the tool ish of the work-piece.
life. The frictional heat generated during some metalwork- The material used for the cutting tools is selected to fa-
ing operations, depending upon the metal hardness, can cilitate metal 共chip兲 removal. Vibration, the metal feed rate,
reach temperatures of 1000 ° C or higher. In addition, exten- cutting speeds, and the lubricant availability in the cutting
sive cutting pressures at points of contact can lead to specific zone also play a roll in this process. These factors must there-
surface loads of up to 5000 N / mm2. Both these factors can fore be taken into consideration when selecting proper tool
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CHAPTER 11 䊏 METALWORKING AND MACHINING FLUIDS 507
better coolant than the oil. More specifically, straight oils ing wear and equipment damage. Common types of wear
and emulsifiable oils that contain combinations of sulfur, that can occur in cutting tools due to the lubricant failure are
fat, phosphorus, overbased sulfonates, or chlorine are the lu- as follows:
bricants of choice for severe operations, such as broaching, 1. Adhesive wear—Welding between the tool surface and
tapping, deep hole drilling, heavy forming 共e.g., drawing, the work-piece surface can occur due to the high local
cold heading兲, form grinding and honing. Semi-synthetics temperatures. On shear, these spots can either produce
are useful for the moderate severity operations, such as mill- the metal debris or result in the metal transfer from the
ing, turning, grinding, and stamping; and synthetics are tool to the work-piece. This kind of damage is more
ideal for most high-speed operations such as drilling. Please likely to occur at slow cutting speeds.
note that these uses are not absolute and an operator has the 2. Abrasive wear occurs when the fragments of cutting or
option of using a fluid other than that suggested if the opera- the wear debris embedded in the chip abrade the rake
tion has severity different than that suggested here. face of the tool.
Tool Wear 3. Diffusive wear occurs when the metal atoms from one
Besides the severity of the machining operation, tool wear is crystal lattice diffuse into the crystal lattice with the
also a function of the quality of the cutting fluid and the ma- lower atomic density 共concentration兲. This type of wear
chinability of the metal. Cutting fluid is essential to minimiz- is likely when the tools made of hard materials are used
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CHAPTER 11 䊏 METALWORKING AND MACHINING FLUIDS 509
to machine softer metals, for example, during the use of ramics, cermets, and diamonds. The attributes of the various
the tungsten carbide tools. tool materials are provided in Table 11.5 and the characteris-
4. Corrosive wear results from the attack of the atmo- tics of the metals machined are provided in Table 11.6.
spheric oxygen, moisture, or the decomposition prod- Of the metals listed, ferrous metals such as carbon steel,
ucts from the antiwear and extreme-pressure additives low alloy steel, stainless steel, and aluminum are the largest
on the tool surface. Such additives include chlorine, sul- volume metals machined. Copper, brass, and titanium are
fur, and phosphorus-containing chemicals. the next group, followed by the nickel-based alloys, cobalt-
5. Premature wear is the progressive loss of tool material at based alloys, magnesium, zinc, tin, beryllium, zirconium,
the tool work-piece interface and occurs due to the plas- tungsten, molybdenum, tantalum, uranium, and vanadium.
tic flow of the metal at high temperatures. The order with respect to the ease of machinability, from the
Machinability primarily relates to metal hardness, al- easiest to the most difficult, is as follows:
though other factors, such as cutting speed, tool strength, 1. Magnesium 共Mg兲 and its alloys
and power consumption, also play a role. In general, the 2. Zinc 共Zn兲 and its alloys
harder the metal, the greater is the tool wear. It is therefore 3. Brass
important to select proper tool material for the job at hand. 4. Aluminum 共Al兲 and its alloys
Commonly machined materials include steels, both alloy 5. Cast iron 共Fe兲
and stainless, cast iron, aluminum and its alloys, magne- 6. Bronze
sium and its alloys, copper and its alloys, nickel and its al- 7. Copper 共Cu兲
loys, heat resistant alloys that contain nickel, chromium, 8. Carbon steel
molybdenum, tungsten, and titanium, and plastics. Tool ma- 9. Alloy steels
terials include carbon steel, high-speed steel, cast alloys, ce- 10. Stainless steel
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510 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
11. Nickel 共Ni兲 alloys The majority of operations require both cooling and lu-
12. Titanium 共Ti兲 and its alloys brication. Hence, the macro-emulsions 共soluble oils兲 that
Because the metalworking operations involve both the contain substantial amounts of both organic and aqueous
pure metals and the alloys, the selection and use of an appro- components are often employed. The operating range of
priate lubricant is a complex process. Table 11.7 lists cutting these fluids is enhanced by the supplemental use of the fatty
fluid recommendations based upon machinability groups additives. For a cutting fluid to perform effectively, a careful
关762兴 and Table 11.8 recommends the cutting and grinding consideration of its cooling and lubricating requirements is
fluids for specific metals. essential. High-speed cutting operations, such as turning,
Operation severity is a function of the cutting speed. In milling, and drilling, result in high temperatures; hence the
general, the operations involving slow cutting speeds, such cooling ability of the fluid is critical. Water is an excellent
as broaching and tapping, are more severe than those that
coolant but has little or no lubricating ability. However, this
have high cutting speeds, such as turning and milling. Drill-
deficiency is overcome by the use of the friction reducers and
ing and reaming fall in between the two extremes in terms of
the EP agents, which are entrained into water by the use of
severity. High severity at slow speeds is because at these
speeds the metal-to-metal contact is more extensive 共bound- the wetting agents and the emulsifiers. Slow-speed opera-
ary situation兲 and of longer duration than at high speeds tions, such as broaching and tapping, on the other hand, ex-
which promote the hydrodynamic lubrication. Conse- perience high friction and consequently lead to heavy tool
quently, there is a greater need for extreme pressure agents wear. The lubricants for these operations therefore require
and anti-weld additives in the former case than in the latter the use of the extreme pressure additives 关691兴. A new tech-
case, where either the lubricant viscosity or the friction- nique, called dry machining, is being explored. The purpose
reducing additives suffice. Since good cooling and good lu- is to eliminate the purchase, handling, use, and disposal
brication are not easy to obtain in the same fluid, water or costs. Since this technique does not use any lubricant, it in-
micro-emulsions 共semi-synthetic fluids兲 are used for opera- volves high temperatures. Thus far, the technique has been
tions that require more cooling. And, the use of the straight applied only to the boring operations. Efforts are underway
oils is preferred for operations that require better lubrica- to extend it to drilling operations 关692,693兴.
tion. The depth of cut and the surface finish are additional
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CHAPTER 11 䊏 METALWORKING AND MACHINING FLUIDS 511
considerations during metalworking fluid selection. Slow- during certain parts of the operation and lubrication during
speed operations where the cuts are deep and the good work- the other parts of the operation.
piece finish is important, the lubricity of the fluid is critical. Metal forming fluids are designed to perform a number
The use of the straight oils is therefore appropriate. For high- of functions, which include the following:
speed operations that involve shallow cuts, quick heat dissi- 1. Friction control between the work-piece and the die sur-
pation is desired. This makes micro-emulsions or micellar faces.
solutions the lubricants of choice. In most cases, the fluid is 2. Minimizing the tool and die wear.
applied under pressure into the cutting zone, which is to re- 3. Efficient dissipation of heat.
duce friction, minimize metal transfer, and maximize cool- 4. Work-piece and the die surface protection, for example,
ing. against the metal pick-up and corrosion.
The nature of the metal forming operations is much dif-
Metal Forming Fluids ferent than the metal cutting or the metal removal opera-
These fluids are used for operations that depend on the plas- tions. The challenge in the metal forming operations is not
tic flow of the metal. Such operations include rolling, extru- only to deliver the lubricant where needed but also to stay
sion, drawing 共drawing tubes, tube bending, deep drawing, during the period of the operation. This is because a liquid
and wire forming兲, forging, and sheet metal forming. Some lubricant will have the tendency to squeeze out, when pres-
of these operations involve both ambient 共cold working兲 and sure is applied to conform the sheet metal to the die to make
high temperatures 共hot working兲. Metal forming processes the part. However, it is important to note that the use of the
can be distinguished as being steady-state or nonsteady- high viscosity oils is not a universal solution since if the op-
state 关757兴, each type with different lubrication require- eration temperature is too high; the viscosity advantage of
ments. In the steady-state processes, such as rolling, it is pos- using the thicker oils will be lost. The outflow in such opera-
sible to lubricate the surface of the work-piece during its tions is further facilitated under heavy loads when the sur-
approach to the deformation zone. However, in the faces in contact smooth out due to flattening of the asperi-
nonsteady-state processes, such as sheet metal forming, the ties, as shown in Fig. 11.4. Under these circumstances, the
lubrication is not usually possible because of the nature of solid lubricants and the chemically bonded boundary coat-
the operation, and one must depend upon the preapplied lu- ings, such as the phosphated surfaces, may be more suitable.
bricant film. Some processes, such as long billet extrusion, If the liquid lubricant must be used because of the inherent
have characteristics of both; that is no lubricant application advantages, it is customary to apply the lubricant manually
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512 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
on the selected areas of the work-piece. Such application ods of time. That is where the metal treating fluids, such as
methods are expensive, but because of the equipment design the rust preventives, to be discussed later, play a role. These
this may be the only practical way to lubricate effectively. fluids usually contain soaps 共metal carboxylates兲, gelled
Liquid lubricants used in metal forming operations consid- metal sulfonates, and waxes which provide a physical bar-
ered here must contain chlorinated or sulfochlorinated addi- rier between the metal and the environment.
tives that under heat will form effective low friction EP films As mentioned in the above discussion, the primary func-
between surfaces. tions of a lubricant during metal forming operations are to
While such films are an advantage with respect to pre- reduce friction, which lowers the energy consumption, and
venting tool wear because they minimize direct metal-to- to minimize wear, which increases the tool life. It was also
metal contact between the tool and the work metal 共blank兲 or mentioned that the friction reduction is both advantageous
the strip and the die. However, this can be a disadvantage in and disadvantageous, depending upon the nature of the op-
many metal-forming operations, such as forming sheet eration. Advantageous because it will facilitate the release of
metal and deep drawing, because the controlled metal-to- the forged part from the die and improve the surface finish of
metal contact 共i.e., controlled friction兲 is used to manage the the work-piece, and disadvantageous because it can lead to
flow of the work-piece over the die, roll, or the tool surface. slippage and hence make the operation inefficient. Common
Obviously, in such operations some tool wear will occur. The metal forming lubricants include the following types. Addi-
wear rate depends upon the die material as well as the effec- tives for these lubricants include fatty acids and fatty com-
tiveness of the lubricant. For example, the use of the solid lu- pounds, extreme pressure agents 共sulfurized and sulfochlo-
bricants or the chemically bonded work metal is likely to re- rinated fats and oils兲, emulsifiers, coupling agents, inorganic
sult in greater die wear and in the former case in part due to solids, and dispersants.
abrasion. With extreme conditions of pressure and tempera- 1. Mineral oils
ture, welding will occur between the metal asperities, result- 2. Compounded oils, blends of mineral oils and fatty oils
ing in pick-up on either the work metal or the die surface. 3. Synthetic oils and esters
This pick-up will cause damage to both the die and the work- 4. Fatty acids and their derivatives
piece. Hence, it is important to select the lubricant by con- 5. EP oils
sidering these potential problems. The use of the uncoated 6. Aqueous solutions and emulsions
low-carbon steel is the best in such metal forming operations 7. Dry film coatings
as press forming, bending, spinning, roll-forming, and 8. Polymer solutions
punching. 9. Dispersions containing graphite, molybdenum disulfide
Temperature in these operations is primarily controlled 共MoS2兲, salts, glass, bentonite, lime, mica, and talc
by reducing the friction. It can also be controlled by applying Mineral oils are not very effective lubricants in these ap-
a greater amount of lubricant or water, if possible. Water has plications. They are acceptable only if their viscosity is not
a greater specific heat and acts as a better heat sink than min- too high. However, they are easy to apply and to remove from
eral oil. Obviously, in most cases oil-in-water emulsions have the work-piece by the use of a solvent or the detergent clean-
a real advantage since they contain oil that will reduce fric- ers. Compounded oils, which are mixtures of the mineral oils
tion through lubrication and have higher viscosity and are and the animal fat or vegetable oil, such as palm oil, are
therefore more likely to stay in place. much superior. These are extremely efficient lubricants but
The newly formed work-piece has freshly exposed metal are relatively expensive. EP oils are analogous to the com-
which needs to be protected against atmospheric corrosion, pounded oils, except that they are blends of the mineral oils
especially if the part is going to be stored for extended peri- and chlorine, sulfur, nitrogen and phosphorus-containing
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CHAPTER 11 䊏 METALWORKING AND MACHINING FLUIDS 513
TABLE 11.10—Lubricants commonly used in press forming uncoated low carbon steel sheet
†756‡.
EP additives. These additives thermally react with metals to type of emulsion that is used in forming operations is the
form low friction, low shear, sacrificial metal halide, sulfide, soap-fat emulsions. These emulsions are thick paste-like sys-
and or phosphide protective film on the work-piece and the tems that contain 35–40 % fat and can be used as such for
tool surface. operations such as drawing and stamping or diluted with
Soap solutions are generally potassium or sodium stear- water prior to use; the concentration depending upon the op-
ate or oleate diluted with water. For high severity drawing eration severity. Application is easy but removal is difficult
operations, the soap concentration needs to be increased. since the use of the water-based or solvent cleaners leaves a
These solutions are excellent lubricants in high speed opera- residue.
tions since they provide cooling in addition to the friction re- Dry film coatings include any material that will form a
duction. In addition, like the mineral and compounded oils, solid film. Commonly employed materials include solid
these fluids are also easy to apply and to remove by the use of soap, fats, such as lanolin and tallow, paraffin waxes, and or-
the water-based cleaners. Emulsions used in metal forming ganic polymers. Soap-based films can be continuously ap-
are of the oil-in-water type and are useful in moderate speed plied to the strip while removing the water by the use of the
forming operations. They may contain EP additives for use warm air. Film thickness can be controlled within the de-
in operations that involve boundary conditions. Another sired limits. Fats and waxes can be employed as solutions
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514 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
over the blanks, prior to their entry into the press. These
TABLE 11.12—Drawing compound properties
†4‡. coatings provide excellent dry film lubrication.
Graphite and molybdenum disulfide are two common
Powdered Drawing Straight Soap
solid lubricants that are used in the metal forming opera-
Property Compounds Grease Oil Emulsion Solution
Lubricity ⫹ ⫹ ⫹ 共⫹兲 共⫹兲 tions. They can be used as such, as dispersions, or as addi-
Cooling Effect ⫺ 共⫹兲 ⫹ ⫹ ⫹ tives in other lubricant systems. Their ability to lubricate
Filterability ⫺ ⫺ ⫹ 共⫹兲 ⫹ and the way they perform this function were discussed in
Annealing 共⫹兲 共⫹兲 ⫹ 共⫹兲 共⫹兲 Chapter 4 on Additives. Other solids that are used include
Corrosion clay, talc, and chalk. They are usually used in combination
⫺ 共⫹兲 ⫹ ⫹ ⫺
Protection with pastes made from soap and fat. While these materials
Adhesion 共⫹兲 ⫹ ⫹ 共⫹兲 ⫺
protect sliding surfaces from damage under extreme pres-
Note: + = Pronounced; 共+兲 = Limited; ⫺ None. sure by physical separation, they may or may not decrease
friction, which is a function of their crystal structure.
containing the low volatility solvents or as emulsions. Metal forming operations vary widely with respect to se-
Acrylic polymer films are produced by the use of the warm verity. Therefore, it is important that the selected lubricant
trichloroethylene solutions and polyethylene films are pro- meets the lubrication requirements of the intended opera-
duced by placing the low-melting, low density polyethylene tion. While low severity operations are not highly dependent
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CHAPTER 11 䊏 METALWORKING AND MACHINING FLUIDS 515
upon lubricant properties, with increased operation severity methods. These methods have the issues of toxicity, flamma-
proper lubricant properties become more critical. In these bility, and the disposal of the spent solvent and cleaners. Ob-
cases, a lubricant with greater friction control or EP perfor- viously, the materials of low toxicity, low flammability, and
mance may be required. Such lubricants contain friction- easy disposal are highly desirable. Some of these can be used
reducing additives and or the extreme-pressure agents. many times over before disposal. Another option is recy-
Since the friction modifiers are quite effective in the mixed- cling, which will be discussed in Chapter 13 on Lubricant
film lubrication regime, they lose their effectiveness with a Recycling.
significant rise in pressure, temperature, and the shear rate,
three of the boundary lubrication conditions. That is when Miscellaneous Fluids
there is a need for the extreme-pressure additives. Opera- Metal Protecting Fluids
tions where the operation severity changes during the pro- These fluids, also called preservative oils, help protect the
cess need a balanced combination of both types of additives. freshly exposed metal surfaces against air, water, and corro-
In addition, the EP agents are more effective than friction re- sive materials. While most of these are oil-based, the use of
ducers for maintaining a boundary film between the tool and the water-based fluids is gaining popularity because of the
the work-piece under conditions of severe deformation, lower cost, ease of disposal, environmental compatibility,
which extends the tool life. Table 11.9 provides some of the and the reduced volatile carbon content.
criteria used to identify operation severity in metal forming Metal Treating Fluids
operations, as exemplified by metal drawing, and Table These fluids are used for heat-treating operations, such as
11.10 provides a list of lubricants suitable for each severity quenching and tempering. Machining a work-piece from
class 关756兴. Lubricant selection for metal drawing operation hard metals is difficult. Hence, it is often desirable to use soft
is not easy but the information in Tables 11.11–11.13 at- materials, where possible, and then impart to them the re-
tempts to facilitate the process. Table 11.11 suggests the lu- quired hardness by an after-treatment. Work-pieces from the
bricant preference by metal class 关4兴, Table 11.12 lists the lu- ferrous alloys are heated to 750– 1100 ° C, depending on
bricant properties necessary 关4兴, and Table 11.13 provides their composition, and are quenched by immersing them in
the actual lubricant recommendations. a quenching fluid. Quenching is the process of controlled
For metal rolling operation, the type of lubricant se- cooling of the steel components by the use of a fluid to obtain
lected depends upon the surface characteristics of the steel certain metallurgical properties, such as increased hard-
strip, roll speed, roll material, roll condition, and the severity ness, strength, and wear resistance. The process involves
of forming. Table 11.14 lists severity of various metal rolling heating and holding the metal, such as steel, at temperatures
operations and the desirable characteristics of a suitable lu- above 1200° C to disperse carbon and alloying elements
bricant 关756兴. Table 11.15 lists specific lubricant properties throughout the metal mass and then cooling it rapidly. In
that affect various operation parameters 关4兴. For actual lu- iron, this produces the crystal structure, called martensite,
bricant recommendations see Ref 关639兴. which imparts hardness. Slow cooling, called annealing, al-
For bending and spinning operations, the use of the mill ters the iron’s crystal structure to pearlite, a soft ductile me-
oil or light mineral oil is usually sufficient. But for pre- chanical mixture of ferrite and cementite, which is softer.
painted steel, light oil or evaporating oil formulations are Maximum hardness can be imparted to all common tool and
necessary. For spinning operations, such as manual spin- machinery steels by cooling them rapidly. The hardness
ning or when the prepainted steel is used, little or no lubri- achieved varies directly with the carbon content and the
cant is necessary since heat and friction can be controlled by quenching speed. While steel’s alloy content has little effect
the use of the special tools, such as roller heads. Only if nec- on maximum attainable hardness, higher alloy steels attain
essary, one needs to use the mill oil or the light mineral oil. maximum hardness at the slower cooling rates. The cooling
For punching coated steel, usually no lubricant is required; rate depends on the mass, geometry, and the surface condi-
however, in some situations, the use of the punching oil is tion of the work-piece, as well as the quenching medium or
beneficial. the fluid.
In many cases, the residual lubricant from the formed Common quenching fluids include water, brine, and
part must be removed to facilitate further processing opera- other aqueous salt solutions, salt melts, quenching oils, fatty
tions, such as spot welding, coating, and enameling. Solvent oils, and emulsions. Most industrial quenching is carried out
degreasing or the use of the alkali cleaners are the common by the use of the refined petroleum base stocks because they
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516 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
are easy to handle, require little or no specialized equipment, the work-piece is equal to the temperature of the oil. This is
are noncorrosive and nontoxic, and the quenched parts are followed by a prolonged period of slow cooling, which allows
easy to clean. These fluids must be nonirritating to the skin, maximum hardness while minimizing work-piece distor-
provide corrosion protection, be chlorine and sulfur-free, tion. Work-piece distortion commonly occurs in conven-
and have proper viscosity, low volatility, high flash and fire tional quenching because of the nonuniform cooling rates of
points, and extended service life. These fluids act as heat the different zones. Sometimes additives, such as oxidation
transfer agents and can be oil-based or water-based. inhibitors, are added to minimize acid and sludge-forming
Tempering is the heat treatment used to strengthen the tendency of the fluid which extends its service life. Sludge, if
metals and alloys. Usually the process involves two steps. In formed, will mar the work-piece surface through deposition.
the first step, the metal and carbon, as in the production of Oil-based formulations are being replaced by synthetic
steel, or the alloy metals, as in the case of hardened alloys, fluids due to their superior fire resistance and fewer disposal
are heated to create a solid solution by heating them to the concerns. Common synthetic fluids are the nonflammable
melting temperature and quenching. In the second step,
blends of water and water-soluble or water miscible poly-
tempering is carried out by holding it at temperatures lower
mers, such as poly共alkylene glycol兲s 共PAGs兲, poly共vinylpyro-
than those necessary to produce solutions. The composition
lidinone兲s, and sodium acrylate polymers. While PAGs are
of the tempering fluids is analogous to that of the quenching
completely soluble in water at room temperature, they have
fluids.
inverse solubility at higher temperatures. That is, the PAG
The base oils to formulate the oil-based quenching flu-
comes out of solution and coats the metal surface or that of
ids can be synthetic or petroleum in origin. The performance
the part, thereby controlling the rate of cooling, which re-
specifications of these fluids are established by the OEMs
and the end-users. Quench oil temperatures between 50° C duces quench cracking and distortion that occur in many
and 90° C are the best for most applications. However, the other fluids. When the temperature drops below the thresh-
higher temperatures increase the quenching speed. Because old level, the PAG goes back into solution. This is shown in
of the temperatures involved, the water content in the oil Fig. 11.10 关763兴. Please note that in the figure, all transitions
must be low, otherwise serious foaming will occur. The up- are reversible which is indicated by half arrows. With con-
per temperature limit for these fluids is determined by their stant use, the PAG-based coolants will ultimately lose their
potential flammability and, as a general rule, it should be at viscosity due to shear. Since PAGs degrade slowly, it is easy to
least 50° C below the flash point of the oil. Paraffinic oils, monitor and replenish the polymer in the coolant when nec-
with good oxidation stability, are generally preferred. Mar- essary. PAGs are nontoxic and pose minimal environmental
quenching is the process where the steel is quenched in the and health risks compared to the oil-based quenching fluids.
hot oil at 150– 175° C and holding it until the temperature of They are also easy to remove from the work-piece during
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CHAPTER 11 䊏 METALWORKING AND MACHINING FLUIDS 517
cleanup and are moderately biodegradable in the environ- advantage is that it is extremely corrosive, both to the metal
ment. components and to the quenching equipment. Caustic solu-
Because of the presence of water, these fluids can cause tions containing 5–10 % sodium hydroxide are also used, al-
corrosion. Hence, they contain corrosion inhibitors. They though, they need careful handling, storage, and use.
are useful in quenching both ferrous and nonferrous metals. Slide Way Lubricants
They have faster cooling ability than the oil-based quen- These lubricants are used to lubricate slide ways and the ac-
chants because of the presence of water and unlike aqueous companying pneumatic equipment. Slide ways are sliding
salt containing quenchants they do not leave crystalline resi- surfaces on the bed of a machine along which a table or a
dues on the work-piece surface. In addition, the quench se- carriage moves. Since the surfaces that slide over each other
verity can be controlled by altering the water to poly共alky- are flat, the area of contact is large. This leads to increased
lene glycol兲 ratio. The presence of water in these fluids makes adhesive wear. In addition, these devices experience motion
them susceptible to microbial attack, which can be averted involving varying speeds, which causes sticking and slipping
by the use of the biocides. of the sliding surfaces. After the wear-in, the opposing sur-
Figure 11.11 compares the effectiveness of the various faces form an even closer fit, which squeezes out and wipes
cooling media 关4兴. As one can see that with respect to the away any lubricant that is in the path of motion. Essentially,
cooling rate, water and water-based quenchants are ex- a boundary lubrication condition exists. This type of lubrica-
tremely effective. However, they have a number of limita- tion to a degree is by design; otherwise, the excess lubricant
tions, because of which their use is less desirable in some ap- would form a hydrodynamic wedge that will interfere with
plications, such as steel hardening. The limitations include the smooth motion of the plane.
water loss due to boiling and the formation of the air pock- Boundary lubricated surfaces will adhere to each other,
ets. The latter inhibits uniform cooling, which can cause dis- especially during slow speed operations. Adhesion occurs
tortion of the work-piece. These problems are overcome by when the static friction either equals or exceeds the force of
constant stirring of the coolant. However, this decreases the motion. If the adhesion is followed by movement due to the
water’s cooling efficiency. Water as a coolant is applied for applied force, the phenomenon is called stick-slip. Regular
low alloy steel objects that are thin and are therefore easier occurrence of stick-slip causes not only vibration and noise
to harden. When choosing water, it is important that it is de- but also damage to the work piece, tool, and the rider and
void of salts, which can also cause inconsistent quenching. way.
Brine 共5–7 % sodium chloride solution兲 cools faster than the Slide way lubricants perform at extreme temperatures,
pure water 共compare Items H and G in Fig. 11.11兲, but again high loads, moisture, and poor ambient air quality. They
it suffers from the same disadvantages. In addition, brine must therefore possess both the EP activity and the rust and
separates a layer of salt on the metal surface, which inter- corrosion-inhibiting properties. These lubricants are formu-
feres with uniform cooling; hence it results in metal distor- lated with the friction reducers, primarily fatty carboxylic
tion. Brine is commonly used in quenching high carbon acid derivatives, which minimize stick-slip and the extreme
steels or parts requiring high hardness. Its most serious dis- pressure agents, which control the wear damage resulting
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518 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
cause of the ease of emulsibility and superior viscosity— usually less than 2000 g / mol, its HLB 共hydrophile-lipophile
pressure relationship. Poly共alkylene glycol兲s are extensively balance兲 value, water pH and hardness, the nature of the oil,
used in metal removal fluid formulations, where their in- and the operating conditions, such as temperature. HLB
verse solubility is an advantage. Inverse solubility is a unique scale spans zero 共0兲 to greater than 30. The higher numbers
property of PAGs which makes them water-soluble at low indicate oil compatibility decreasing and water compatibil-
temperatures but water-insoluble at high temperatures. At ity increasing. Emulsifiers of HLB of greater than 13 gener-
high temperatures, they form a persistent lubricating film ally lead to clear water solutions. Emulsifiers with an HLB of
that contains additives at the hot tool-work piece interface, 3 to 6 are suitable for water-in-oil emulsions and those with
which can be easily cleaned off with water at low tempera- an HLB of 8 to 18 are suitable for oil-in-water emulsions. The
tures. PAG solution’s solubility reversal was discussed earlier manner in which these additives form emulsions is shown in
and is depicted in Fig. 11.10. Fig. 4.156.
As a general rule, the nonionic emulsifiers are used in
Additives metalworking fluids based on naphthenic stocks, and the
Additives used in metalworking fluids include emulsifiers, fatty acid carboxylates are used in those based on paraffinic
coupling agents, friction reducers, extreme pressure/ stocks. Poly共alkylene glycol兲s, also called hydroxyalkyl
antiwear agents, oxidation inhibitors, rust and corrosion in- ethers, are sometimes avoided because their enhanced solu-
hibitors, foam inhibitors, and antimicrobial agents. Com- bility in water does not allow clean separation for disposal.
mon types of additives that are typically used in the As mentioned earlier, the alkali metal salts 共soaps兲 of car-
metalworking fluids are provided in Table 11.16, along with boxylic and sulfonic acids are among the most commonly
their chemistry and the mode of action. Discussion below used emulsifiers. However, the metal ion exchange with cal-
pertains to the specific functions that these additives per- cium and magnesium, whose salts are present in hard water,
form in metalworking fluids. degrade emulsions by removing these soaps as insoluble cal-
cium and magnesium salts. Nonionic emulsifiers lead to
Emulsion Promoters emulsions that are less sensitive to hard water.
These additives facilitate the formation of emulsions and im- Some emulsifiers show mild anti-rust performance
part to their stability. These include emulsifiers and coupling 共ASTM D665兲. Since emulsification is a liquid phase phe-
agents. Emulsifiers are chemicals that are used to emulsify nomenon and the rust inhibition occurs at the liquid-solid
共solubilize兲 organic additives and or mineral and synthetic interface, optimizing both these properties is not easy. One
oils in water. These are used to create the soluble oils, syn- can obtain both the emulsification and the anti-rust perfor-
thetics, and semi-synthetics, all of which are water-based lu- mance by altering the hydrocarbon chain length in the emul-
bricants. Emulsifiers contain the functional groups that sifier molecule. However, in many cases, this strategy is not
have the capability to associate with water as well as oil. very effective and it is necessary to improve the anti-rust per-
These additives tend to be situated at the boundary between formance of the fluid by the use of supplemental additives.
the oil and water 共the oil-water interface兲, where they help The common ones include sodium nitrite, borax, boric acid
reduce the interfacial tension and make the two phases mis- amides and esters, alkanolamines, and alkanolamides.
cible, to form a stable emulsion. Emulsion formation re-
quires high-speed mixing or stirring. Coupling Agents 共Couplers兲
Emulsifiers are classified as nonionic or ionic, depend- Some additives that need to be emulsified have a greater
ing upon whether the polar part is uncharged or charged. solubility in water than in oil. Consequently, they are not
Ionic compounds can be subdivided further into cationic, if easy to formulate into the emulsifiable oil concentrate 共pack-
the charge is positive and anionic, if the charge is negative age兲 without the presence of a large amount of water 共as
关458兴. Nonionic emulsifiers that are often used in metal- much as 50 %兲. Coupling agents facilitate the emulsification
working fluids include carboxylic acid amides and esters, of water into the base oil, emulsifier system, and other addi-
polymeric ethers 关poly共glycol ether兲s兴, esters of polyhydric tives. In the long term, these additives maintain the emul-
alcohols, and alkoxylated alkylphenols. Anionic emulsifiers sion stability. Common coupling agents are low molecular
include inorganic salts, primarily sodium, of the carboxylic weight alcohols, glycols 共diols兲, and glycerols 共triols兲, which
acids, alkyl phosphoric acids, and aromatic sulfonic acids— become part of the non-oil portion of the package. This de-
both natural and synthetic. Because of the lower cost, these creases the need for large amount of water necessary to solu-
emulsifiers are used as the general-purpose additives. Cat- bilize additives thereby improving emulsification. It is im-
ionic emulsifiers include mineral acid salts of amines and portant to note that although these components are organic
imidazolines. Compounds that find extensive use as emulsi- in nature, they impart little or no lubricity to the final fluid,
fiers include the following: because of their relatively short hydrocarbon chains. Struc-
1. Alkali metal 共primarily sodium兲 arylsulfonates, both pe- tures of some of these additives are given in Fig. 11.12. Com-
troleum and synthetic mon examples of these additives include the following:
2. Alkali metal carboxylates 1. Fatty alcohols, such as tridecyl alcohol
3. Alkoxylated alcohols, phenols, fatty amines, fatty acids, 2. Glycols, such as ethylene glycol, diethylene glycol, and
and fatty amides propylene glycol
4. Sulfated fatty oils 3. Glycol ethers, such as propylene glycol monomethyl
The structures of some of the emulsifiers are shown in Fig. ether and hexylene glycol monomethyl ether
4.157. 4. Fatty acids, such as caprylic acid, iso-nonanoic acid,
As mentioned in Chapter 4 on Additives, the efficiency of and neo-decanoic acid
an emulsifier depends upon its molecular weight which is 5. Nonionic surfactants, ethoxylated alcohol, nonylphenol
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520 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
ethoxylates, and poly共ethylene glycol兲 esters chemical mechanism to form protective surface films. See
Chapter 4 on Additives.
Film-forming Agents One common structural feature of the friction modifiers
This additive class includes friction modifiers, also called the is the presence of a fatty hydrocarbon group, a longer than
lubricity agents, film-strength additives and oiliness addi- C12 linear chain. In addition to fatty alcohols and acids, this
tives; anti-wear and extreme pressure agents, also called class of additives includes fatty esters, natural and synthetic,
boundary additives and load-bearing additives; and corro- fatty amides, fatty amines, and fatty alcohol-derived phos-
sion inhibitors. phites and alkyl acid phosphates. Those used most often in
These additives are surface active because of their high metalworking fluids include animal and vegetable oils, com-
polar to nonpolar ratio, and hence they have the tendency to monly called the triglycerides, alkyl and polyol esters of fatty
separate on surfaces where they interact by a physical or a acids, ethylene oxide/propylene oxide polymers, TEFLON®,
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CHAPTER 11 䊏 METALWORKING AND MACHINING FLUIDS 521
alkanolamides, and mono, di, and tri-ethanolamine salts of rine, sulfur, and phosphorus react with the metal to form the
carboxylic acids. The structures of some of these additives metal halide, sulfide, and phosphite, phosphate, and phos-
are shown in Fig. 11.13. phide protective films. These films are effective only below
A greater degree of protection is needed in some appli- their eutectic point, or the decomposition temperature, of
cations, such as metal removal operations, than that pro- these salts. Chlorine compounds can lead to the metal corro-
vided by the friction modifiers. This is because these applica- sion by hydrogen chloride, which results from their hydroly-
tions generate high temperatures which make physically sis. Hence, this must be taken into account prior to their use
and chemically adsorbed additive films easy to remove. That in cutting oils. In view of their effective range, sulfur com-
is where extreme pressure/antiwear agents become impor- pounds are used in heavy-duty and extra heavy-duty cutting
tant. These additives chemically react with metal surfaces to operations. Metal sulfide films appear to have a higher load-
form more tenacious protective films. The degree of EP pro- carrying capacity and shear strength than the carboxylic
tection in the equipment depends upon the conjunction tem- acid soaps and metal phosphates.
perature of the two metal surfaces in contact 关6兴; the higher As stated earlier, the film formation by these additives
the temperature, the greater the need for EP/antiwear pro- occurs by a two-step mechanism: Adsorption on the metal
tection. To be effective, it is important for the activation tem- surface and thermal decomposition and reaction with the
perature of the EP additive to match the conjunction tem- metal surface, due to frictional heat. The resulting metal salt
perature. The effective temperature ranges of different types films have low coefficients of friction and also demonstrate
of additives when used in metalworking applications are anti-weld properties, both of which minimize the tool wear.
provided in Table 11.17 关4兴. Tests that are commonly used to Metal chloride films have an approximate transition tem-
determine the effectiveness of the various classes of the EP/ perature of 600° C and metal sulfide films have a transition
antiwear agents are listed in Table 11.18. temperature of 1000° C. This makes the organic sulfides bet-
Extreme pressure agents are primarily organic com- ter extreme pressure additives than the organic chlorides,
pounds of chlorine, sulfur, and phosphorus; although some- because the sulfide films can endure higher temperatures be-
times boron and sulfur-nitrogen compounds are also used. fore becoming soft and getting removed. Figure 11.14 shows
Please refer to Chapter 4 for their structure and the mecha- the temperature ranges over which the EP films from the
nism of performance. In all cases, the active elements chlo- metal cutting fluids will be effective 关4兴. Chlorinated fats,
Fig. 11.14—Durability temperatures of boundary films resulting from cutting oil additives 关4兴.
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522 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
Fig. 11.15—EP performance versus surface activity and active sulfur 关425兴.
chlorinated esters, and the chlorinated paraffins are the sulfur, on the other hand, is the bound form of sulfur, for ex-
common organic chlorides used in formulating metalwork- ample as a sulfide or disulfide, and is released or reacts with
ing fluids. the metal only at high temperatures. Inactive sulfur addi-
Sulfurized fats, sulfurized oils, sulfurized paraffins, dis- tives are commonly used to machine brass and copper al-
solved sulfur, and sulfochlorinated products are the com- loys. Incidentally, active sulfurized mineral oils are excellent
mon organic sulfides used. Typical sulfur level in these addi- lubricants for machining the hard high carbon and alloy
tives is between 10 and 40 %. The sulfur in these additives is steels and are the most widely used fluids in the industry.
of the two types: Active and reactive. Active sulfur is the dis- These oils minimize tearing and rough finish, often encoun-
solved or the easily releasable form of sulfur, which has the tered in machining such metals. The “active” sulfur con-
tendency to corrode yellow metals—a low temperature reac- tained in the oil tends to form an iron sulfide film on the steel
tion. Because of this, the presence of the active sulfur in the surface, which because of lower shear strength facilitates the
metalworking fluid formulations is of concern. Experimen- cutting action. Such oils may be dark or light-colored and
tally, active sulfur is determined by the use of the ASTM odorous straight sulfurized or sulfochlorinated mineral or
D1662 test. Reactive sulfur, sometimes referred to as inactive fatty oils. Excellent EP properties of these oils are depicted
in Fig. 11.15 关425兴. As indicated by the four-ball weld load durability of the metal films resulting from the thermal reac-
共DIN 51350 Part 2兲, both the sulfur activity and the sub- tion of the film-forming additives; we surmise that if one is
strate’s affinity for the surface are important. The weld load interested in maintaining the EP protection over a broader
of the more surface-active sulfurized esters and the fatty oils temperature range, one must combine various classes of
B, C, and D is higher than that of the less polar sulfurized ole- film-forming additives. Figure 11.16 shows the effect of such
fin A, which is despite its very high sulfur activity. The effect a venture 关440,764兴. The figure shows that with respect to the
of the sulfur activity is demonstrated by the weld load of the friction control, the fatty additives although better than the
additive D relative to that of the additive C, which is negative straight mineral oil lose their effectiveness first. They are fol-
or minor until the oil sulfur level becomes high. All in all, the lowed by the chlorine-containing materials, phosphorus-
surface activity of the additive is more important than the ac- containing materials, and sulfur-containing materials. How-
tive sulfur level. It is important to note that the active sulfur- ever, a combination of all four classes of additives is effective
reactive sulfur ratio is a function of many factors, the sulfur- in keeping the friction at a very low level, i.e., at less than
ization temperature being one. Typically, the fast high- 0.1 , over the 0 to 1000° C range.
temperature sulfurization by the use of the elemental sulfur Because of the reactivity of the sulfurized hydrocarbons
yields products with high active sulfur 关425兴. Since all sulfur- towards copper, bronze, and the other nonferrous metals,
ized products contain both types of sulfur and each type af- and the tendency of the chloro-paraffins to corrode metals
fects the lubricant properties differently, it is important to via hydrolysis or thermolysis, the need for new extreme pres-
develop products with a proper balance of the two types of sure agents exists. New extreme pressure additive technol-
sulfur to meet the lubrication needs of a particular operation ogy based on overbased alkylbenzenesulfonates and car-
or the application. Table 11.19 shows the effects of the two boxylates, which does not suffer from these disadvantages,
types of sulfur on the various lubricant parameters. As one has recently become available. Such additives, called the
can see, a higher amount of active sulfur has a positive effect passive EP agents, are believed to function by forming a
on reactivity and hence provides superior EP performance. metal carbonate film at the tool work-piece interface. The
However, with respect to all other parameters, it has either high effectiveness of these additives in cutting, tapping, and
no effect or an undesirable effect. For all other lubricant pa- threading operations suggests an alternative mechanism.
rameters, a higher amount of inactive sulfur is more desir- That is, the high pressures at the tool-metal interface convert
able. Copper activity of the active sulfur compounds can be the amorphous calcium carbonate, present in the basic sul-
reduced without diminishing their EP/antiwear perfor- fonates and carboxylates, into crystalline salts that facilitate
mance. This may be achieved by the use of the zinc dialkyl the metal removal. The films formed are of low shear
dithiophosphates. Table 11.20 demonstrates the improving strengths and high melting points. These additives do not
effect of the zinc dialkyl dithiophosphate on copper activity contain phosphorus, sulfur, or chlorine in an active form but
of the sulfurized products 关425兴. are synergistic with the sulfur-containing EP additives. In
We commented earlier that the various types of film- addition, they are less corrosive, easier to dispose of after
forming additives have a specific temperature range, outside use, cause little or no foaming, and are easily removed from
which they are either ineffective or lose their effectiveness. the work piece surface. They can be used both for ferrous
Based upon the data presented in Fig. 11.14 on the thermal and nonferrous metals, which is an added benefit.
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CHAPTER 11 䊏 METALWORKING AND MACHINING FLUIDS 525
metals to be protected. For straight oils, the neutral and over- as an antibacterial agent and the other as an antifungal and
based metal sulfonates are used to protect against iron cor- yeast control agent. Microbial attack on the fluid is undes-
rosion 共ASTM D665 and D4627兲. For the other types of met- ired because it causes a buildup of the acidic materials, cor-
alworking fluids, these include fatty amines, neutral and rosion of machinery and tools, destruction of the additives,
basic barium and calcium alkylaromatic sulfonates, and objectionable odors, and produces materials that destabilize
metal and amine salts of carboxylic acids, boric acid, and the emulsions. Fungal attack can lead to a slimy material that
organic acid phosphates. Metal sulfonates are either alkyl- can coat the machinery and tools, as well as clog the pumps
benzene derived or alkylnaphthalene derived. Both fatty ac- and filters. This makes monitoring the microbe level in a
ids and high molecular weight oxidates 共oxidized hydrocar- fluid a necessity. Monitoring is carried out through commer-
bons兲 are used to manufacture soaps 共metal carboxylates兲. cial culture techniques. Standard practice to correct a prob-
Alkanolamides, imidazolines, and sarcosines, often used as lem is to use biocides. Often two different biocides are used
rust inhibitors, are also the alkaline derivatives of the car- in an alternating fashion to guard against microbes develop-
boxylic acids. Of these, amines and overbased sulfonates, ing immunity 关757兴.
which are basic, perform by neutralizing acids and others Commonly used biocides include formaldehyde-release
perform by forming films that act a barrier against the envi- agents and others. Others can be further divided into the het-
ronment. For yellow metal protection 共ASTM D130兲, benzot-
erocyclics and the organo-halogen compounds. The struc-
riazole and dimercaptothiadiazole 共DMTD兲 derivatives are
tures of some of the biocides are shown in Fig. 11.17. 1,3-
used. Structures of these inhibitors are provided in Figs.
Di共hydroxymethyl兲-5,5-dimethyl-2,4-dioxoimidazole,
4.151 and 4.152.
2-hydroxymethyl-aminoethanol, hexahydro-1,3,5-tris共2-
Antimicrobial Agents hydroxyethyl兲-s-triazine, and oxazolidine are examples of
These additives, also known as biocides, are control specific. the formaldehyde-release agents. These additives control
A fluid can therefore have a combination of these: One acts bacterial growth by releasing formaldehyde, an antibacte-
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CHAPTER 11 䊏 METALWORKING AND MACHINING FLUIDS 527
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528 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
rial agent. Formaldehyde results from the hydrolysis of these Foam Inhibitors 共Antifoam Agents, Defoamers兲
additives in water-based fluids. Heterocyclics include These additives are used to control foam 共ASTM D892 and
isothiazolone, benzisothiazolinones, morpholine, sodium D3601, IP312兲 in metalworking fluids. Foam in lubricants
pyrithione 共sodium omadine兲, benzotriazole, and dimercap- occurs because of air or gas entrainment and impairs their
tothiadiazole 共DMTD兲. Organo-halogen compounds include flow and lubricating ability. Air entrainment is common dur-
2,4,5-trichlorophenol, bis-共2-chloroethyl兲 ethertetra- ing spraying and pumping of the fluids. Foam is particularly
methylenediamine copolymer, and 2,2-dibromo-3-nitrilo- common in water-based fluids because they usually contain
propionamide. A variety of other compounds that are out- surfactant type water-soluble additives. Foam is undesired
side these general classes are also used to control the micro- because it interferes with proper lubrication, inhibits cool-
bial infestation and include o-phenylphenol, carbamates, ing, and creates a problem if it overflows sumps and tanks.
dithiocarbamates, glutaraldehyde, and nitro alcohols. Foam inhibitors are readily dispersible additives, which are
Most of these compounds destroy bacteria directly. So- added to the fluid in a low concentration, i.e., in parts per
dium omadine is an effective antifungal agent. Materials, million or parts per billion. They perform by reducing the
such as 2,2-dibromo-3-nitrilopropionamide, are useful in surface tension of the bubbles 共ASTM D1590兲, thereby re-
controlling bacteria and fungi, including yeast. These addi- sulting in their coalescence. Common types include amide
tives, by virtue of protecting against infestation from the all and ester waxes, silicones and modified silicones, long-chain
three types of microbes, minimize worker exposure and pro- saturated alcohols, certain triglycerides, water-insoluble
long emulsion batch life. Boron containing formulations polyglycols, ethylene glycol-propylene glycol copolymers,
usually do not experience bacterial growth. While choosing and polyacrylates.
an antimicrobial agent, one must consider its toxicity, its ef- Silicone type inhibitors can adsorb on the metal surface
fect on the emulsion stability, and regulations considering its and prevent paint or coating to adhere to the metal part.
discharge into the waste streams. Their use is also undesired because of the environmental and
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CHAPTER 11 䊏 METALWORKING AND MACHINING FLUIDS 529
waste treatment concerns, plating out effect or the clude cooling, lubrication, wear control, and protection
“fisheyes,” and the effects on cleaning and finishing. They are against corrosion. These fluids must meet performance
hard to remove by washing, which may be necessary for fin- specifications, which for these fluids are primarily estab-
ishing the part via painting, varnishing, and enameling. The lished by the OEMs and the end-users. Table 11.21 provides
structures of some of the foam inhibitors are shown in Fig. the additive composition of the metal removal fluids and
4.190. Table 11.22 provides the additive composition of the metal
forming fluids and the miscellaneous others.
Oxidation Inhibitors Test methods to evaluate performance of these fluids are
These additives are used in lubricants to minimize deteriora- not well standardized. Some are standardized tests, such as
tion of their organic component due to the oxidative attack. the ASTM, IP, and DIN tests, while the others are additive
Metalworking fluids of high organic content such as straight supplier or the end-user required tests. The standardized
oils are more susceptible to oxidation than fluids of low or- tests that are either presently used or can be used to judge the
ganic content, such as synthetic fluids. Other types fall in be- suitability of the metalworking fluids are listed in Table
tween the two with respect to oxidation susceptibility. Metal- 11.23, and the parameters they evaluate are briefly described
working fluids employ all three types of oxidation inhibitors, in Table 11.24. Many standards contain these tests, as sum-
viz., hydroperoxide decomposers such as zinc dialkyl dithio- marized in Table 11.25. Details of these tests are available in
phosphates, dialkyldithiocarbamates, and dialkyl polysul- the books on the ASTM, IP, and DIN Standards 关27,759,765兴.
fides; radical scavengers, such as hindered phenols and ary- It is important to note that the tests across standards do not
lamines; and metal passivators, or chelators, such as always match. They may differ because of the disparity in the
thiadiazole derivatives, organic diamines, ethylenediamine- hardware, the test method, or the way they are performed.
tetraacetic acid 共EDTA兲, and nitrilotriacetic acid. The use of
the first two types predominates in fluids of high organic Formulation Examples
content and of the third type predominates in fluids of low
organic content. Metal chelators, which control oxidation by Fluid-based Formulations
complexing with the metal ions and making them innocu- Straight Oil: Mineral Oil 共60 %兲, usually solvent-refined
ous, are of great importance in metalworking fluids because blends to achieve ISO 10, 15, 22, 32, 46, 68 grades; Lubricity
of the high probability of contamination of these fluids by Agent 共15.3 %兲—natural fats, synthetic esters; EP Additives
metals and metal ions. Structures of the commonly used oxi- 共20 %兲 chlorinated paraffins, overbased sulfonates, phos-
dation inhibitors are provided in Fig. 4.21. phorus, sulfur, sulfurized fats, and sulfurized olefins; Corro-
sion Inhibitor 共4.7 %兲.
Dyes Soluble Oil: Mineral Oil of 40° C viscosity of 15– 20 cSt 共53.9
These additives are used to color code some lubricants and %兲; Emulsifier/Corrosion Inhibitor 共30.3 %兲—anionic—
include anthraquinones, azo compounds, and triphenyl- sulfonates, alkanolamine salts—amphoteric—amino acid
methane. soaps—nonionic—ethoxylates, alcohols, amines; Other ad-
Odor Control Agents ditives 共10.3 %兲—foam inhibitor, bactericide/fungicide, ex-
These agents are used to mask undesirable odors that are ei- treme pressure agent/s; Water 共5.5 %兲.
ther present in metalworking fluids because of the additives This additive package is diluted with water in 1 : 10 to 1 : 50
or are produced during use because of the microbial attack. ratio to yield the finished fluid, which appears opaque.
Odor control agents include synthetic sassafras, pine oil, ter- Semi-synthetic Fluid: Mineral Oil 共14.7 %兲; Emulsifier/
penes, such as terpinol and d-limonene, and methyl salicy- Corrosion Inhibitor 共50 %兲—anionic—sulfonates, alkanola-
late. mine soaps, boron amides; nonionic—ethoxylates, alcohols,
and amines; Other Additives 共10.3 %兲—foam inhibitor, oili-
Inorganic/Organic Solids ness agent, extreme pressure agent/s; water 共25 %兲.
These additives include graphite, MoS2, metal powders, This additive package is diluted with water in 1 : 20 to
metal oxides, metal halides, mica, and tetrafluoroethylene 1 : 60 ratio to give the finished fluid that appears almost clear.
polymer. Tetrafluoroethylene polymer, or TEFLON®, is one Synthetic Fluid: Corrosion Inhibitor 共39.7 %兲—
of the few organic materials that are used to formulate met- alkanolamines, water soluble soaps, boron soaps/salts, fatty
alworking fluids. These additives are generally not used in acids/esters; Wetting/lubricity Agents 共7.2 %兲—polyglycols
metal removal lubricants, although some passive EP agents and esters; Other Additives 共3.1 %兲—bactericide/fungicide,
that are colloidal dispersions are used. However, the use of foam inhibitor, extreme pressure agent; water 共50 %兲.
the inorganic solids is more common in formulating fluids This additive package is diluted with water in 1 : 10 to
for certain metal forming operations, such as extrusion and 1 : 100 ratio to give the finished fluid that appears completely
forging. The suspension process generally involves mechani- clear.
cally agitating the finely divided powders in oil or water, in
the presence of an emulsifier or a dispersant. Application-based Formulations
Metalworking Fluid Formulations and Mineral Forming Fluid: Extreme Pressure Agent 共20.0–
Testing 35 %兲—Chlorinated wax and sulfurized fat mixture; Corro-
sion Inhibitor 共1.0–2.0 %兲—alkanolamine; Lubricity Agent/
Each metalworking operation places a different de- Friction Modifier 共10.0–20.0 %兲—soap or lard oil. The bal-
mand on the lubricant. A lubricant must therefore possess ance is mineral oil.
the specific properties to perform effectively. The properties Soluble-oil Forming Fluid: Extreme Pressure Agent 共25.0–
that fulfill the common needs of most working operations in- 30.0 %兲—Chlorinated wax and sulfurized fat mixture; Corro-
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530 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
sion Inhibitor 共4.0–6.0 %兲—alkanolamine; Lubricity Agent/ rosion Inhibitor/Buffer 共5.0–10.0 %兲—alkanolamine; Lubric-
Friction Modifier 共10.0–20.0 %兲—soap or lard oil; Foam ity Agent/Friction Modifier 共4.0–6.0 %兲—carboxylic acid de-
Inhibitor 共0.5–1.0 %兲—polyacrylate; Buffer 共4.0– rivative; Foam Inhibitor 共1.0–2.0 %兲—polymethacrylate;
6.0 %兲—diethanolamine or triethanolamine; Biocide 共1.0– Biocide 共2.0–3.0 %兲—triazine; Emulsifier 共5.0–10.0 %兲—soap
2.0 %兲—triazine; Emulsifier 共4.0–6.0 %兲—soap. The balance or petroleum sulfonate. The balance is water.
is water. Mineral Protecting Fluid: Corrosion Inhibitor 共2.0–
Straight Oil Removal Fluid: Extreme Pressure Agent 共10.0– 3.0 %兲—Neutral metal sulfonate mixture. The balance is
20.0 %兲—Chlorinated wax or sulfurized olefins; Corrosion mineral oil.
Inhibitor 共0.5–1.0 %兲—alkanolamine or triazole; Friction Synthetic Protecting Fluid: Corrosion Inhibitor 共0.5–1.0
Modifier 共5.0–10.0 %兲—carboxylic acid derivative. The bal-
%兲—Amine carboxylate and amine borate mixture; Lubricity
ance is mineral oil.
Agent/Friction Modifier 共0.5–1.0 %兲—phosphate ester; Buffer
Soluble-oil Removal Fluid: Extreme Pressure Agent 共10.0–
共5.0–10.0 %兲—alkanolamine; Biocide 共1.0–5.0 %兲—triazine.
15.0 %兲—Chlorinated wax or sulfurized olefins; Corrosion
The balance is water.
Inhibitor/Buffer 共4.0–6.0 %兲—alkanolamine; Lubricity Agent/
Mineral Treating Fluid: Oxidation Inhibitor 共0.1–
Friction Modifier 共5.0–10.0 %兲—carboxylic acid derivative;
Foam Inhibitor 共1.0–2.0 %兲—polymethacrylate; Biocide 共2.0– 0.5 %兲—Phenol and arylamine mixture; Speed Improver 共1.0–
3.0 %兲—triazine; Emulsifier 共5.0–10.0 %兲—soap. The balance 10.0 %兲—calcium sulfonate.The balance is mineral oils.
in mineral oil. Synthetic Treating Fluid: Corrosion Inhibitor 共1.0–
Semi-synthetic Removal Fluid: Extreme Pressure Agent 2.5 %兲—Alkanolamine; Foam Inhibitor 共0.5–1.0 %兲—
共4.0–6.0 %兲—Chlorinated wax or sulfurized olefins; Corro- polyacrylate; Buffer 共5.0–10.0 %兲—alkanolamine; Biocide
sion Inhibitor/Buffer 共5.0–10.0 %兲—alkanolamine; Lubricity 共2.0–3.0 %兲—triazine. The balance is water.
Agent/Friction Modifier 共5.0–8.0 %兲—carboxylic acid deriva- Aqueous Quenching Fluid: Thickener 共10%兲—Water-
tive; Foam Inhibitor 共1.0–2.0 %兲—polymethacrylate; Biocide soluble ethylene oxide/propylene oxide coploymer; Corri-
共2.0–3.0 %兲—triazine; Emulsifier 共5.0–10.0 %兲—soap or pe- sion Inhibitor 共0.03%兲—nitrobenzoic acid or its alkali metal
troleum sulfonate. The balance is water. salts; Corrosion Inhibitor Synergist 共0.03%兲—salicylic acid or
Synthetic Removal Fluid: Extreme Pressure Agent 共2.0–3.0 its alkali metal salts; Buffer 共0.1%兲—diethanolamone. The
%兲—Sulfurized olefins or zinc dialkyl dithiophosphate; Cor- balance is water. Formulation extracted from Ref 关763b兴.
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MNL59-EB/Mar. 2009
12
Lubricant Testing
IN THIS CHAPTER WE DESCRIBE ANALYTICAL AND the end-users and relates either to the inadequate perfor-
spectroscopic techniques and physical and chemical tests mance of the existing products in the current equipment or
that are used to establish structural/compositional identity the perceived needs of the equipment under development. To
and physical and chemical properties of the additives, base fulfill this need, various organizations, such as SAE, API,
stocks, and finished lubricants. Tribological 共mechanical兲 ASTM, AGMA, ACEA, JASO, and OEMs, initiate the develop-
tests are also included and so are the performance require- ment of new performance specifications and the test meth-
ments of the finished lubricants and their in-service condi- ods.
tion monitoring. The chapter also contains discussion per- Additive companies, either alone or in collaboration
taining to the new lubricant approval process and a list of with a lubricant supplier, attempt to satisfy the performance
ASTM and other standardized tests that are commonly requirements established for the new product. If the additive
used to assess lubricant quality. company is unable to develop the additive system using their
Lubricant additives are either supplied individually or existing technology base, they initiate a project to develop
as a performance package for the user to blend in the base and test a new additive or additives. The newly developed ad-
fluid of his or her choice to make a finished lubricant. The ditive or additives are blended with other additives in a cus-
former is the case for nonautomotive lubricants and the tomer’s base oil and the lubricants thus obtained are
latter is the case for automotive lubricants. In either case, screened in a number of physical, analytical, and mechani-
the finished lubricant must meet the performance require- cal tests, called the preliminary tests 关4兴. Physical tests deal
ments established by a variety of technical organizations, with colligative molecular properties of the lubricant, such
OEMs, and the end-users. At high concentrations, the ad- as density, viscosity, shear stability, emulsion-forming ten-
ditive molecules exist as association structures, called mi- dency, foaming characteristics, refractive index, flash point,
celles, due to intermolecular association via their polar cloud point, pour point, and evaporation loss. Chemical
ends. Upon dilution, deaggregation occurs and the additive tests, in conjunction with spectroscopic methods, are used to
molecules attain a more active form. Because the additives characterize the lubricant. Important analytical tests per-
are reactive chemicals, they can interact with one another, tain to structural analysis, hydrolytic stability, carbon resi-
when in a package, either synergistically or antagonisti- due, water, sulfur, ash content, acidity, alkalinity, alkaline
cally 关765兴. The formulator’s challenge is to deliver the in- residue, corrosion, corrosion protection, seal compatibility,
tended performance by minimizing the antagonistic effects and aging characteristics to predict a lubricant’s service life.
and maximizing the synergistic effects through careful bal- Some of these tests are standardized ASTM tests while oth-
ancing. ers are proprietary bench tests. Bench tests, also called the
For automotive use, the viscosity modifier and the per- screen tests, are accelerated tests that are devised to closely
formance package are usually sold separately 关308兴 and for simulate conditions the lubricant is likely to experience in
the applications needing a viscosity modifier, it is blended actual service. This kind of testing is quite common because
in the base fluid along with the performance package to it allows the evaluation of a large number of additives and
obtain the finished lubricant. Typically, the lubricant addi- formulations quickly and inexpensively. Candidates that
tive suppliers develop general-purpose performance pack- demonstrate good performance in these tests are taken to
ages, which when blended in widely available base stocks the next stage to test performance, which is to test in full-
in a predetermined amount meet industry specifications. scale tests.
Additive suppliers may fine tune their packages for an in-
dividual company’s use in its base stocks. Table 4.33 shows
The Approval Process
the classes of additives that are used to formulate engine
lubricants and Table 4.34 contains the classes of additives The purpose of the approval process is to ensure that the new
that are used to formulate nonengine lubricants. Formula- lubricant meets the established performance criteria. Since
tion examples were provided in previous chapters dealing the quality of the lubricant depends upon the quality of its
with the various fluid types. components, preliminary tests are also performed on the
base fluid, additives, and of course the lubricant itself to en-
Introduction of a New Additive sure quality and performance, prior to subjecting the lubri-
or a Product cant to more expensive full-scale testing. Typically, additive
quality is determined by establishing their identity and pu-
The development of a new additive/formulation is initiated rity and the lubricant quality is assessed by its performance
after a new product 共lubricant兲 need is identified. The need in the established tests. Full-scale testing is carried out using
for the new product is usually expressed by the OEMs and actual equipment either in a laboratory or in collaboration
531
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532 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
the presence of the additives used to formulate them. The viscosity, as shown in Table 12.1 关154兴. It is important to note
properties that are critical to lubricant performance are that the modern hydrocracking technology significantly im-
listed below. These are the properties that are evaluated by proves these properties of the mineral base stocks 共API
the various physical and analytical tests: Group II, Group III, and VHVI stocks兲 as well, and of course
1. Viscosity the use of the polymeric viscosity modifiers and pour point
• Viscosity-temperature Relationship depressants further boosts them.
• Viscosity-pressure Relationship Consideration of the lubricant’s viscosity-temperature
• Viscosity-shear rate Correlation and viscosity-pressure relationship is critical to applications
• Viscosity-volatility Relationship
that involve high temperatures and high pressures, such as
2. Vapor Pressure
the hydraulic systems. Bulk pressures in these systems range
3. Density
from atmospheric to 10,000 psi 共0.1 and 69 MPa兲 and tem-
4. Bulk Modulus
peratures from −65 to 300 ° F 共−54 to 149 ° C兲. Hydrody-
5. Thermal Properties
6. Surface Tension namic bearings experience temperature of around 100 ° F
7. Gas Solubility 共55 ° C兲 above these temperatures and the pressures of
8. Foaming Tendency 10,000 psi 共69 MPa兲 over the bulk system values. For elasto-
9. Electrical Properties hydrodynamic 共EHD兲 contacts in gears, cams, and roller and
10. Thermal Stability ball bearings, the temperature may be 100 to 300 ° F
11. Oxidation Stability 共55 to 167 ° C兲 over the bulk value and the pressures may be
Viscosity in the 50,000 to 500,000 psi 共345 to 3450 MPa兲 range.
The viscosity values most frequently reported for a lubricant Boundary lubrication implies temperatures in the order of
are at 40 ° C and 100 ° C 共previously 100 ° F and 210 ° C兲 at at- 650 ° F 共343 ° C兲, or higher, and pressures in the same range
mospheric pressure and low-shear rates. Viscosity is a mea- as in the EHD contacts 关154兴. Viscosity-temperature and
sure of a fluid’s resistance to flow. The basic unit for absolute viscosity-pressure properties of the synthetics provide a
or dynamic viscosity is the Pascal-second 共10 Poise兲. The much broader range, as shown in Table 12.1. The viscosity-
common unit of absolute viscosity is centiPoise, cP pressure coefficient determines the quality of the elasto-
共1 mPa· s兲. The most common method of viscosity measure- hydrodynamic film in bearings and gears.
ment is described in the ASTM D445 standard. Viscometers Many premium hydraulic fluids and lubricants are
are devices that are used to measure viscosity. Most depend based on mineral oils, to which the polymeric viscosity
on the force of gravity to drive the fluid through a capillary. modifiers are added to improve their high temperature per-
The viscosity value thus obtained is referred to as kinematic formance. Some synthetic base stocks are also polymeric,
viscosity. The unit of kinematic viscosity is Stoke 共St兲 or for example, polysiloxanes 共silicones兲, poly共glycol ether兲s,
centi-Stokes 共cSt= 0.01 St兲. One centiStoke equals 1 mm2 / s. polyesters, and poly共perfluoro ether兲s. Polymers are suscep-
Absolute viscosity in centiPoise 共cP兲 is equal to kinematic
tible to shear, which can cause a reduction in viscosity, re-
viscosity in centiStokes multiplied by the density of the fluid
versibly or irreversibly, depending upon the magnitude and
in kg/ m3. Two types of rotational viscometers are also used
the duration of the shear forces. Such shear forces result
to measure viscosity. These are Brookfield 共ASTM D2669 and
ASTM D2983兲 and the cone and plate type. Brookfield vis- from turbulent flow and in high contact applications, such
cometer is often used to measure low temperature viscosity as gears and bearings. These forces either deform the poly-
since at low temperatures some fluids do not flow under the mer, causing a temporary viscosity loss, or mechanically de-
force of gravity. Viscosity index 共VI兲, which is a measure of a grade it, causing a permanent viscosity loss. Shear rates in
lubricant’s viscosity-temperature relationship, is based on most lubricant applications range from very low values to
40 ° C and 100 ° C viscosity values 共ASTM D2270兲. 106 s−1. Shear also occurs during cold starting of an automo-
Mineral oils have good viscosity indices 共VIs兲 but syn- tive engine. During cold starts, the oils of 3000 to 50,000 cP
thetics have generally higher VIs and lower low-temperature 共3 to 50 Pa· s兲 are subjected to shear rates of 103 to 104 s−1.
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534 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
Volatility and Flash Point or gas chromatography 共ASTM D2887兲. The latter procedure
In automotive crankcase oils, vapor pressure, or volatility, is only works for oils that have a boiling point of less than
important in determining the rate of the oil consumption 1000 ° F 共538 ° C兲. Distillation 共boiling兲 temperatures at re-
and the quality of the exhaust emissions. In other applica- duced pressures 共vacuum兲 can be converted into those at at-
tions, such as steam turbines, high volatility can create a fire mospheric pressures and vice versa by the use of a vapor
hazard. The volatility of an oil is tested according to the pressure chart 关154兴 or on line conversion 关771兴. Since the
ASTM Test Method D92 共Cleveland Open Cup flash and fire mineral oil contains components of different volatilities, va-
points兲. High vapor pressure of the mineral oil at elevated por pressure of the mineral oil based lubricant is influenced
temperatures is due to the presence of the highly volatile, by its more volatile components. In addition to oil consump-
low boiling components; hence the flash point of a well- tion, evaporation, and safety 共flammability兲, the volatility
distilled mineral oil can be higher by about 10 ° F 共5 ° C兲 and also affects the boundary lubrication. High volatility lubri-
fire point by about 100 ° F 共55.5 ° C兲 than the normally ob- cants are known to cause more wear than the lubricants of
tained mineral oil. The flash point of 400 ° F 共204 ° C兲 and a low volatility 关772,773兴.
fire point of 440 ° F 共227 ° C兲 are expected of a typical lubri- Density and Specific Gravity
cating oil fraction. Gas chromatographic analysis of a typi- Density of a substance is defined by mass per unit volume
cal mineral oil indicates that 5 to 95 % of the oil has a boiling and in liquids, such as lubricants, is expressed as gram/
range of 150 to 170 ° C 共302 to 338 ° F兲. In general, the high millilitre 共g/mL兲. Relative density, also known as specific
VI oils have higher boiling points. Figure 12.2 shows gravity, is a measure of the density of a material relative to
viscosity-boiling point plots of the synthetic fluids and the another material. Specific gravity of the liquids is equal to
narrow boiling range 共30 ° C兲 mineral oil of the different VIs the density of the liquid divided by the density of water, and
关154兴. For the oils of the same viscosity, the boiling point of in gases, it is the density of the gas divided by the density of
the high VI oils is higher than that of the low VI oils. This is air. Specific gravity has no units. For liquids, density, hence
shown in the figure for oils that have a 40 ° C viscosity of specific gravity, is typically measured at 60° F or 15.6° C. In
20 cSt. Since the boiling points of the oil or its components petroleum products, the API gravity is used more often. As
are quite high, simple distillation cannot be used to deter- stated earlier, it is related to specific gravity at 60 ° F. API
mine them. However, one can either use vacuum distillation gravity and specific gravity are inversely related. Table 12.2
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CHAPTER 12 䊏 LUBRICANT TESTING 535
tive suppliers market air-release agents, which are modified TABLE 12.4—Surface tension of base fluids
siloxanes, fatty acid esters, fatty alcohols, alkoxylates, and
†154‡.
polyalcohols based on ethylene-propylene block copolymer.
Surface Tension
Thermal Properties Fluid dyne/cm „N/m…
Thermal properties of lubricants that are of interest are ther- Water 72共⫻10−3兲
mal conductivity, specific heat, and heat of vaporization. The Mineral Oils 30– 35共⫻10−3兲
first two are concerned primarily with the heat transfer and Esters 30– 35共⫻10−3兲
the last with the ease of evaporation. Thermal conductivity is Methylsilicone 20– 22共⫻10−3兲
the ability of a material to conduct heat. In liquid hydrocar- Fluorochloro Compounds 15– 18共⫻10−3兲
bons it ranges from 0.14 W / m · K at 0 ° C 共273 K兲 to
0.11 W / m · K at 400 ° C 共673 K兲 关154兴. These values should
essentially hold for all mineral oil and synthetic D1331. Surface tension data for several base fluids are
hydrocarbon-based lubricants. Polarity and hydrogen bond- shown in Table 12.4 关154兴. Interestingly, additives have a pro-
ing affect thermal conductivity; for example, ethylene glycol found effect on the surface tension of the finished lubricant.
has a much higher thermal conductivity, of 0.31 W / m · K at For example, the addition of only 0.1 wt % silicone, com-
100 ° C. Specific heat is the heat required to raise the tem- monly used to suppress foam in a mineral oil lubricant,
perature of a specific quantity of a substance, in our case a causes a reduction in its surface tension to almost that of the
fluid, by one degree kelvin. The same as thermal conductiv- silicone fluid itself and hence improve surface wetting of the
ity, specific heat also varies linearly with temperature and in- bearings. Wetting is due to the preferential interaction of the
creases with increased polarity or the hydrogen bonding of fluid molecules with the molecules of the solid surface than
the molecules. Specific heat of water at 100 ° C is about twice with each other, that is, the adhesive forces are stronger than
that of the oil 关154兴 and for mineral oil and synthetic hydro- the cohesive forces. In general, the fluids of low surface ten-
carbon lubricants, the values range from 0.45 Btu/ lb-F sion have better wetting characteristics. The surface tension
共1882 J / kg· K兲 at 0 ° C 共273 K兲 to 0.78 Btu/ lb-F 共3263 J / values of the fluids, listed in Table 12.4, suggest that the wet-
kg· K兲 at 400 ° C 共673 K兲. The higher values for these param- ting tendency increases as we go down the table. However, as
eters for a lubricant indicate a better heat dissipation ability. mentioned above, the presence of additives in the lubricant
Heat of vaporization is the energy required to transform a can easily change that.
given quantity of a substance into its vapor. Heat of vaporiza- Interfacial tension between two immiscible liquids is
tion depends on the pressure and the molecular weight or approximately the difference between the surface tensions
the boiling point of the oil. Most conventional mineral oil- of the two liquids. Additives that create stable emulsions and
based lubricants have latent heats of vaporization between micro-emulsions are capable of reducing the interfacial ten-
60 and 90 Btu/ lb 共140 to 209 kJ/ kg兲 at atmospheric pres- sion between the two phases to very low values, almost ap-
sure. By comparison, the heat of vaporization of water is proaching zero, which results in thorough mixing of the two
969.7 Btu/ lb 共2255 kJ/ kg兲 at atmospheric pressure. This im- phases. While the emulsions in metalworking and hydraulic
plies that much less heat is required for evaporating oil than fluids are useful, in other applications such as automotive
water, if the conditions are such that the two liquids have the engine oils they are not. Detergents and dispersants, which
same vapor pressure. are added to the automotive lubricants to neutralize and sus-
Electrical Conductivity pend combustion and oxidation products, reduce interfacial
Electrical conductivity is a measure of a material’s ability to tension of the oil contaminated with 10 to 15 % water to such
conduct an electric current. If the electrical conductivity of a an extant that the stable emulsions that form cannot be eas-
lubricant is high, it indicates the presence of ions and ion- ily separated. As mentioned earlier, the use of the additives,
forming materials, such as metals and metal-containing ad- called demulsifiers, sometimes help. Both surface tension
ditives, water, and thermo-oxidative degradation products. and interfacial tension are altered by additives and by the lu-
In water-based lubricants, low electrical conductivity is de- bricant degradation products.
sired since it is associated with metallic corrosion and the Thermal Stability
corrosion products promote oxidative degradation of the lu- Thermal stability is the resistance of a lubricant to break
bricant. Electrical conductivity of a well-refined and dry down or to structurally change under the influence of heat
mineral oil and most synthetic lubricant base stocks is ex- and in the absence of oxygen. One of the methods used to
tremely low, in the order of 10−14 mho/ cm2. Electrical con- measure this lubricant parameter is described in the ASTM
ductivity of the unused lubricant is of primary concern if the Standard D2879. The method uses isoteniscope, a closed
lubricant is to be used in an electrical environment, such as vessel with a manometer for measuring the rate of pressure
for transformers and some aircraft and industrial control increase at a specified heating rate. Thermo-gravimetric
systems. analysis 共ASTM E1131, ISO 11358兲 and differential thermal
Surface Tension analysis 共ASTM E1782, ASTM E537兲 can also be used to
Surface tension is the force that makes the surface layer of a evaluate thermal stability. Several thermal stability tests are
liquid behave like an elastic sheet and is the result of the in- described in the Federal Standards 共FED-STD-791/ 2503.2
termolecular forces in a liquid that keep its molecules to- and FED-STD-791/ 2508.1兲 关775兴. Thermal stability tests
gether. Surface tension involves a liquid and a gas or a vapor, must allow for the decomposition of a significant portion of
and the related force interfacial tension involves two immis- the test sample and provide an analysis of the liquid and
cible liquids. Two methods that can be used to measure sur- solid decomposition products, as well as the gases formed.
face tension/interfacial tension are ASTM D971 Rev A and Mineral oils show a thermal stability of 650 to 700 ° F
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CHAPTER 12 䊏 LUBRICANT TESTING 537
共343 to 371 ° C兲. Synthetic hydrocarbons that are primarily TABLE 12.5—Oxidation life of mineral oils un-
aliphatic in nature, such as PAOs that are prepared by the po- der ideal conditions †777‡.
lymerization of olefins followed by hydrogenation, show a
Maximum Temperature
thermal stability of 600 to 650 ° F 共316 to 343 ° C兲. This is
Fluid Type for 1000-h Life
50 ° F 共28 ° C兲 or more below that of the mineral oil. Decom-
Uninhibited 共used in once-through systems兲 75 ° C
position of the mineral oil results primarily in methane but Extreme-pressure Gear Lubricant 84 ° C
also ethane and ethylene. A synthetic hydrocarbon on de- Hydraulic Fluid 99 ° C
composition will produce a major amount of the monomer Turbine Lubricants 106 ° C
from which it was made 关154兴. Materials that contain aro- Heavily Refines, Hydrocracked 121 ° C
matic rings in their structure are somewhat more stable and
have a decomposition temperature of 850 to 900 ° F
共454 to 482 ° C兲. This class includes poly共phenyl ether兲s, synthetic lubricants as a function of temperature, see Fig.
chlorinated biphenyls, and condensed ring aromatic hydro- 12.4 关777兴. Polyol esters are proposed to be thermally and
carbons, such as alkylated naphthalenes. Organic esters oxidatively most stable and mineral oils to be the least stable.
have thermal stability in 500 to 600 ° F 共260 to 316 ° C兲 The others fall in between the two extremes with respect to
range, the ester functional group being the primary site for the oxidative stability.
decomposition. Methyl esters have thermal stability similar
to that of the mineral oil. Polymeric viscosity modifiers have Elemental and Structural Analysis
Petroleum, or crude oil, contains a wide variety of elements,
lower thermal stability than their nonpolymeric analogues.
some of which are present at percent levels and others at
Polymethacrylate have a decomposition temperature of
parts per million levels. However, refining processes used to
450 ° F 共232 ° C兲 and polybutenes have a decomposition tem-
manufacture fuels and mineral base oils remove most ele-
perature of 550 ° F 共288 ° C兲. Most additives used to formu-
ments other than carbon, hydrogen, oxygen, nitrogen, and
late lubricants have thermal stability lower than that of the
perhaps sulfur. Additives used to formulate lubricants con-
base fluids. For example, zinc dialkyl dithiophosphates that
tain elements that are used either to facilitate their solubility
are used as oxidation inhibitors and EP/antiwear agents, de-
in base fluids or impart special properties. Common ele-
grade at 400 to 500 ° F 共204 to 260 ° C兲. More active EP addi-
ments include nitrogen, sulfur, phosphorus, alkaline earth
tives have even lower thermal stability 关154兴.
metals, zinc, copper, and molybdenum. A list of elements
Oxidation Stability that are generally used in lubricants is provided in Table
Most lubricant applications are in the presence of air or oxy- 12.6, along with their role 关778兴.
gen; hence a lubricant to have good oxidation stability is A variety of analytical techniques are used for elemental
highly desirable. All hydrocarbon materials undergo oxida- analysis of the petroleum products and includes atomic
tive degradation, which was described in the Additives chap- spectroscopy 共atomic absorption spectroscopy, AAS兲, and in-
ter, Chapter 4. Unlike thermal stability which is inherent to ductively coupled plasma atomic emission spectroscopy,
the base stock, oxidation stability can be greatly improved by ICP-AES兲, X-ray fluorescence 共XRF兲, and micro-elemental
the use of the oxidation inhibitors. The consequences of oxi- techniques 关779兴. These analytical techniques are not only
dation are a lubricant’s viscosity increase and the formation used for new oils but also for used oils, at the end of their
of acids and deposits, such as varnish and sludge. A wide va- service life. The objective in the latter case is to analyze wear
riety of tests are available to assess a lubricant’s oxidation metals, find their source, and devise ways to minimize wear
stability. These include tests that are described in the ASTM in those machine parts. Wear metals originate primarily
Standards D2272 and D1313, and in the Federal Test Stan- from the mechanical wear of the various parts of the equip-
dard 791 共FED-STD-791兲, methods 2504, 3405.2, and 3407.2. ment. Wear metals in the lubricant usually exist in a sus-
These tests are suitable for measuring a lubricant’s stable life pended form, which can settle on their own or after dilution
and the effectiveness of the oxidation inhibitors. To monitor of the lubricant by a low viscosity hydrocarbon solvent, such
the oxidation process, a micro-oxidation test, such as the as pentane or hexane. Sometimes centrifugation is em-
Penn State micro-oxidation test, has been developed along ployed to separate them from the lubricant. Some wear met-
with the analytical procedures based on gel permeation als are specific enough to be able to identify the machine part
chromatography 共GPC兲 and atomic absorption spectroscopy or parts from which the metal originated. A list of wear met-
共AAS兲 关776兴. als found in used combustion engine lubricant is provided in
Oxidation life of a lubricant depends upon the service Table 12.7, along with their source 关778兴. Normal wear rate is
conditions. Khonsari and Booser estimated a mineral lubri- slow; hence a sudden increase suggests a serious problem.
cant’s life solely based on application’s temperature, assum- Elemental analysis of the used oils is generally per-
ing no contamination 关777兴. The estimates are shown in formed by the use of the atomic spectroscopy techniques,
Table 12.5. Obviously, in real life there is contamination, ad- particularly ICP-AES, because of its ability to analyze sev-
verse catalytic effects from metals, such as copper and iron, eral elements at the same time. Rotating disk electrode emis-
and oxidation-inhibitor loss due to evaporation; all of which sion spectrometry and ICP-mass spectrometry are also ca-
will affect an oil’s expected life. By taking into account these pable of analyzing multiple elements at the same time 关779兴.
factors, the researchers estimated oil life to be much shorter In addition, the ICP-mass spectrometry has the ability to de-
than that predicted. A real life temperature effect on the sta- tect elements even if their concentration is in parts per bil-
bility of a lubricant is provided in Fig. 12.3 关154兴. In both lion. However, this technique lacks the precision and the ac-
cases, the lubricant life is longer at lower temperatures. curacy of the other atomic spectroscopy techniques 关780兴.
Khonsari and Booser also estimated the service life of the ASTM methods for wear metal analysis include D5185,
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538 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
which is an ICP-AES method, and D6595 and D6728, both of such as dispersants, viscosity modifiers, and pour point de-
which are based on the rotating disk electrode technology. pressants require similar knowledge to understand their be-
Wet chemistry methods, not very popular today, are havior. The diversity of the chemical structures present in
combination methods involving gravimetry to convert the the mineral oil requires sophisticated separation and ana-
metal into its derivative, which is then analyzed by tech- lytical techniques to identify them. The methods used in-
niques such as photometry, titrimetry, or other wet analysis clude gas chromatography, liquid chromatography, size ex-
techniques. Bomb combustion methods also involve con- clusion chromatography or gel-permeation chromato-
verting the metal into a water-soluble derivative and analyz- graphy 共GPC兲, ultraviolet 共UV兲 spectroscopy, infrared 共IR兲
ing it using gravimetry or titrimetry. Most of these methods spectroscopy, mass spectrometry 共MS兲, and nuclear mag-
are being replaced by less tedious and more facile modern netic resonance 共NMR兲 spectrometry. There are numerous
instrumental methods. For analyzing nonmetallic elements ASTM standards that describe the use of these techniques.
that are present in petroleum products in very small quanti- Of the spectroscopic techniques, the first three are the sepa-
ties, micro-elemental methods were devised. These methods ration techniques and the last four are the identification
involve burning the material to convert the element to be techniques.
analyzed into a gaseous product, which is then analyzed by Gas Chromatography 共GC兲
the use of a variety of techniques 关779兴. These ASTM meth- This is one of the most common techniques used for separat-
ods are listed in Table 12.8. ing hydrocarbons for identification by other techniques. In
Hydrocarbon Analysis some cases, GC can also be used for identification, if the
The next step after the elemental analysis is to identify the model compounds exist or are known. GC uses volatility as
discrete chemical structures that make up the base oils and the primary property for separation. The first step is to con-
the additives; hence the lubricants. With respect to the base vert the oil components into vapor, which is passed through
oils, the structural determination of the mineral base stocks a packed column along with an inert carrier gas, such as ni-
is the most challenging since they are complex mixtures of trogen or helium, to elute them. The carrier gas helps these
the hydrocarbons of various types and various sizes. And, components to travel through the column to a detector,
each component influences the base oil properties differ- which generates signals to be recorded on a chromatogram
ently. Structure determination of the synthetic base stocks, 关781兴. Two most common types of detectors used are flame
on the other hand, is relatively straight forward since their ionization and thermal conductivity 关782兴. In flame ioniza-
manufacture employs reagents of well-defined structures tion type detectors, the column effluent is mixed with hydro-
and purity and in known proportions. Polymeric 共or oligo- gen and air and ignited. The organic material such as hydro-
meric兲 synthetics, such as polyalphaolefins, poly共alkylene carbons produces, among other species, ions and electrons,
glycol兲s, and others, although structurally homogeneous, which create a signal. Thermal conductivity detectors con-
have a molecular weight distribution 共polydispersity兲, which tain a tungsten filament that is heated using a constant cur-
is sometimes beneficial to know to understand their behav- rent 关781兴. The eluting hydrocarbon compounds increase the
ior in certain operating environments. Polymeric additives, filament temperature, since they do not equal the cooling ef-
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540 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
TABLE 12.7—Wear metals in used engine oil and their source †778‡.
fect of the pure carrier gas and generate a signal. Other de- 6. ASTM D5480—Standard Test Method for Engine Oil
tection systems, such as atomic emission spectroscopy Volatility by GC.
共AES兲 and chemiluminescence are used in specialized cases, 7. ASTM D3525—Standard Test Method for Gasoline Dilu-
for example for the detection of the sulfur compounds in ent in Used Engine Oils by Gas Chromatography.
light petroleum liquids 共ASTM D5623兲. In GC, high volatility 8. ASTM D5623—Standard Test Method for Sulfur Com-
samples usually come out 共elute兲 first. This method works pounds in Light Petroleum Liquids by Gas Chromatog-
well for high to medium volatility samples. Low volatility raphy and Sulfur Selective Detection.
samples either take a long time to elute or stay on the col- Liquid Chromatography 共LC兲
umn. Incidentally, volatility is a function of a chemical’s mo- As mentioned while discussing GC, LC is a closely related
lecular weight and the polar functional group, if present. For technique that also separates materials based on their physi-
low volatility samples, a related method, called liquid chro- cal and chemical properties. However, this technique em-
matography, is employed. If the presence of a particular ploys a liquid instead of a gas to separate and analyze
component is suspected in the sample and that component is samples. Liquid chromatography techniques that are used
otherwise available, it can be used to confirm its presence in for the analysis of the hydrocarbon petroleum products in-
the original sample. If not, GC can be used in combination clude absorption chromatography, high performance liquid
with identification techniques, such as MS, IR, and UV. The chromatography 共HPLC兲, size exclusion chromatography
use of the GC-MS and GC-FTIR is quite common and is ex- 共SEC or GPC兲, fluorescent indicator absorption 共FIA兲 and su-
tremely beneficial. GC is used for many other purposes be- per critical fluid chromatography 共SFC兲. In conventional LC,
sides hydrocarbon separation with the intention of identifi- a liquid sample is introduced either neat or diluted with an
cation 关54兴. Other lubricant-related uses include identifying appropriate solvent into a glass column prepacked with an
contaminants, such as ethylene glycol which is used as a appropriate solid material, such as silica, alumina, or some
coolant in combustion engines, and the fuel dilution in die- other solid medium. The sample is then washed down the
sel engine lubricant samples. ASTM standards that relate to column using a flowing stream of a solvent, starting with a
the use of the GC for hydrocarbon analysis of mineral oils low polarity solvent and progressing to higher polarity sol-
and the derived lubricants include the following: vents until the sample is completely eluted from the column.
1. ASTM D6352—Standard Test Method for Boiling Range The sequence of elution depends upon the strength of the af-
Distribution of Petroleum Distillates in Boiling Range finity between the components of the sample towards the
174 to 700 ° C by Gas Chromatography. stationary phase 共column packing兲. Those with least affinity
2. ASTM D2887 REV A—Standard Test Method for Boiling 共low polarity兲 will come out first, followed by the compo-
Range Distribution of Petroleum Fractions by Gas nents with greater affinity 共higher polarity兲. Absorption liq-
Chromatography. uid chromatography is the method used most often for hy-
3. ASTM D3524—Standard Test Method for Diesel Fuel drocarbon analysis. In this method, the advantage is taken
Diluent in Used Diesel Engine Oils by Gas Chromatogra- from the greater affinity 共absorption兲 of certain components
phy. towards the stationary phase, which slows down their elu-
4. ASTM D6417—Standard Test Method for Estimation of tion, thereby leading to their separation. In some cases, ab-
Engine Oil Volatility by Capillary Gas Chromatography. sorption by the stationary phase is so effective that the ab-
5. ASTM D4291—Standard Test Method for Ethylene Gly- sorbed components can only be removed by washing with a
col in Used Engine Oil. very highly polar solvent 关783兴. Of the various LC methods,
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CHAPTER 12 䊏 LUBRICANT TESTING 541
two that are used most often are high-performance liquid well with compounds that contain multiple bonds or aro-
chromatography 共HPLC兲 and gel-permeation chromatogra- matic rings and the RI detector works well with compounds
phy 共GPC兲. that are not UV active.
In HPLC, the material to be analyzed is forced through a Size exclusion chromatography 共SEC兲, also known as
column with the stationary phase by a liquid at high pres- gel permeation chromatography 共GPC兲 or gel filtration chro-
sure. The use of pressure provides the components less time matography, separates materials based on their molecular
to diffuse within the column, leading to improved resolution size, or their hydrodynamic volume. SEC/GPC is the pri-
in the resulting chromatogram. Solvents that are commonly mary technique for determining the average molecular
used include any miscible combination of water and an or- weights of natural and synthetic polymers. GPC was dis-
ganic liquid, such as methanol and acetonitrile. Water may cussed in Chapter 4 under the viscosity modifiers section.
contain buffers or salts to assist in the separation of the Ion-exchange chromatography allows the separation of ions
sample components. HPLC chromatography is of four types and polar molecules based on the charge properties of the
关784兴. These are normal phase chromatography, reverse molecules. It is not often used in the analysis of the petro-
phase chromatography, size exclusion chromatography, and leum products. ASTM test methods relating to the use of the
ion-exchange chromatography. Normal phase HPLC 共NP- liquid chromatography in the analysis of the petroleum
HPLC兲 retains the analysis sample based on polarity. It uses products are listed below:
a polar stationary phase and a nonpolar mobile phase, an 1. ASTM D2007—Test Method for Characteristic Groups
eluent or solvent, and is used for analyzing polar materials. in Rubber Extender and Processing Oils and Other
Conversely, reversed phase HPLC 共RP-HPLC兲 consists of a Petroleum-Derived Oils by the Clay-Gel Absorption
nonpolar stationary phase and a polar mobile phase. This Chromatographic Method
method is especially suitable for analyzing large nonpolar 2. ASTM D2549—Test Method for Separation of Represen-
hydrocarbons and biomolecules. In this method, the polar tative Aromatics and Nonaromatics Fractions of High-
molecules elute first and nonpolar molecules elute later. The Boiling Oils by Elution Chromatography
eluted materials are detected by the use of either a UV or an Other Chromatographic Techniques
RI 共refractive index兲 detector, which generates signals to be Fluorescent Indicator Adsorption 共FIA兲 is based on conven-
recorded on a chromatogram 关781兴. The UV detector works tional open column liquid chromatography, with the differ-
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542 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
ence that the column in addition to containing the normal terpretation is to separate the mixture into components and
silica gel is topped with a small portion of silica gel treated then subjecting the components to the MS analysis. This is
with a mixture of dyes. The dye mixture passes through the precisely what is done in GC-MS and LC-MS combination
column with the sample and marks the boundaries 共inter- techniques. The most common use of mass spectrometry in
faces兲 of the adsorbent 共silica gel兲 sections containing satu- hydrocarbon analysis is to determine the composition of the
rates and olefins, olefins and aromatics, and aromatics and different process streams and the boiling fractions during
isopropanol: the alcohol is used as an eluent. By measuring the refining process. The ASTM standards pertaining to this
the separation of each dye, the relative proportions of the analytical technique are listed below:
saturates, olefins, and aromatics can be determined fairly ac- 1. ASTM D2786—Standard Test Method for Hydrocarbon
curately. Super Critical Fluid Chromatography 共SFC兲 uses a Type Analysis of Gas-Oil Saturates in Gas Oil Fractions
neither a liquid nor a gas, but uses a supercritical fluid, most by High Ionizing Voltage Mass Spectrometery.
commonly CO2 关781兴. A supercritical fluid is a fluid that has 2. ASTM D2789—Standard Test Method for Hydrocarbon
been heated above its critical temperature and pressure and Types in Low Olefinic Gasoline by Mass Spectrometery.
has the properties between that of a gas and a liquid. For hy- 3. ASTM D3239—Standard Test Method for Aromatic
drocarbon analysis, SFC has an advantage over GC, because Types Analysis of Gas-Oil Fractions by High Ionizing
it uses lower temperatures, and over HPLC, because it offers Voltage Mass Spectrometery.
a higher resolution. ASTM Standard D1319 共Universal Oil Infrared Spectroscopy 共IR兲
Products UOP Standard 311-02兲 describe the use of FIA to Infrared spectroscopy is a widely applied nondestructive test
determine hydrocarbon types in liquid petroleum products. method that is used to obtain an insight into a material’s
Ultraviolet Spectroscopy 共UV兲 structure and or composition. Each material has a number
Ultraviolet 共UV兲 spectroscopy, also known as UV spectrom- of IR absorptions, which occur at specific frequencies 共wave
etry, is used to identify characteristic molecular fingerprints, numbers兲. Most lubricants and mineral oils are mixtures
enabling quantitative detection of specific molecules or mo- and so are additives. Despite this, their IR spectra are suffi-
lecular species in complex mixtures. UV spectrophotometer ciently unique to help identify structural features of many of
in association with high performance liquid chromatogra- the individual components. However, in certain cases, a
phy 共HPLC兲 is the most commonly used detection tool in hy- physical or chemical separation of the target components,
drocarbon analysis. UV spectroscopy works only with spe- for example by the use of gas or liquid chromatography, may
cific organic structural types, those that have a high degree facilitate structural identification of the components. The
of conjugation, such as aromatics. UV absorption maxima most important feature of the IR analysis is the ease to iden-
occur at 190, 230, and 260 nm and correspond to mono-, di-, tify functional groups in organic compounds, most of which
and poly-aromatics. The amounts of these components in contain hetero atoms, such as nitrogen, oxygen, sulfur, and
the analysis sample can be quantified by the use of a simple phosphorus. While the identification of these groups is non-
formula based on molecular mass, and the average molar ab- equivocal, that of the purely hydrocarbon groups, such as
sorptive of each species at the these wavelengths 关785兴. One multiple bonds and aromatic rings, is not always easy. This
of the most common uses of the UV spectrometry is to deter- makes IR an invaluable tool in structure elucidation of the
mine the amount of the toxic impurities, particularly pol- additives but less useful in identifying the structural features
yaromatic hydrocarbons, in lubricants and fuels. EPA has in purely hydrocarbon materials, such as mineral base oils.
established limits on these compounds because of their car- IR frequencies of the various organic groups are provided in
cinogenicity. Since UV spectroscopy is incapable of distin- Table 12.9 and an actual IR spectrum of ethanol is depicted
guishing between two structures with absorptions on the in Fig. 12.5 关786兴. Figure 12.6 identifies various regions in an
same wavelength, its real value in hydrocarbon analysis lies infrared spectrum 关787兴. Table 12.10 provides infrared ab-
in its use in combination with separation techniques, such as sorptions of some of the lubricant components 关647兴.
liquid chromatography 共LC兲 or gas chromatography 共GC兲. Nuclear Magnetic Resonance 共NMR兲
Another closely relates technique, spectrofluorometry, is Spectroscopy
also used for hydrocarbon analysis 关785兴. Nuclear magnetic resonance spectroscopy is a technique
Mass Spectrometry 共MS兲 that exploits the magnetic properties of the atomic nuclei.
This is a structure identifying technique which involves gas Two important techniques are proton 共 1H兲 NMR and
phase analysis of the samples. Those that are not gases are carbon-13 共 13C兲 NMR spectroscopy, although some other
converted into gases through vaporization. The gas sample magnetic nuclei can be measured as well 关788兴. NMR spec-
is then ionized either through electron ionization or chemi- troscopy allows the identification of the individual atoms in
cal ionization to form primary and fragmented ions, which a pure molecule. This technique is one of the most powerful
are separated according to masses by the use of a magnetic techniques for determining structure of the organic com-
field and their mass-to-charge ratio and the relative abun- pounds. Like infrared 共IR兲 and ultraviolet 共UV兲 spectroscopy,
dance is recorded. Each molecule has a unique fragmenta- NMR is a form of absorption spectrometry where the
tion pattern and the relative abundance and its structure can amount of the absorbed electromagnetic radiation at a spe-
be reverse-synthesized from its fragments. The major limita- cific frequency can be related to certain chemical species
tions of the MS is that the complexity of the mass spectrum which absorb at that frequency. The portion of the molecule
increases with increasing molecular size 共molecular mass兲 that absorbs the energy transitions from the lower energy
and the number of components in the analysis sample, as is level to a higher energy level and the absorbed energy ap-
the case in mineral oil. These make analysis of the MS data a pears on the appropriate spectrum as a signal. Unlike IR
challenge. One way to overcome complexity and facilitate in- spectroscopy, which examines the functional groups within
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CHAPTER 12 䊏 LUBRICANT TESTING 543
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544 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
a molecule, or UV spectroscopy, which examines the mol- Signal Frequency − Reference Frequency
ecules as a whole, the NMR examines specific atoms and ␦共ppm兲 =
Operating Frequency of the Magnet
their environment in the sample. Proton and carbon-13
NMR are ideal for obtaining structural information of or- The value obtained is called chemical shift, which is repre-
ganic compounds since they are largely composed of carbon sented by the Greek letter ␦ and is expressed in ppm. The rea-
and hydrogen atoms. Additional attribute of the NMR spec- son for using the ppm unit for the chemical shift is because
troscopy is that it can quantify the number of atoms in each the signal frequency is in hertz 共Hz兲 and magnetic frequency
structural environment, which helps define the molecular is in megahertz 共MHz兲. By understanding the different
structure of the compound accurately. chemical environments, the chemical shift can be used to
When the NMR active nuclei, such as 1H or 13C are obtain some structural information about the molecule in
placed in a magnetic field, they resonate at a specific fre- question, to assign signals 共peaks兲 to an atom or a group of
quency, hence the name magnetic resonance for the tech- atoms. Modern analysis software allows the analysis of the
nique, depending upon the strength of the magnetic field. area under each peak, to deduce the number of protons or
Local chemical environment affects the resonance fre- carbons that are responsible for that peak by a mathematical
quency of these atoms, altering their resonance frequency process, called integration. The chemical shifts for peaks
slightly. Since there are many chemical environments within due to atoms or groups of atoms are known in the scientific
each molecule, each atom or group of atoms in the molecule literature. By comparing these values with the observed val-
resonates at slightly different frequencies. These frequen- ues for the sample, one can accurately identify various struc-
cies, which are magnetic field dependent, are converted into tural entities that exist in the molecule.
field-independent variable by dividing the difference be- The chemical shifts ranges for protons in various elec-
tween the frequency of the signal and the frequency of the tronic environments are shown in Fig. 12.7 关789兴 and their
reference 共tetramethylsilane兲 by the frequency of the mag- typical values are provided in Table 12.11 关789兴. These values
netic field, as shown below: are not precise, and deviations of ±0.2 ppm, or more, are ex-
pected. The exact value of the chemical shift depends on the the mineral base oil with respect to the amount of the paraf-
molecular structure and the solvent in which the spectrum is finic, naphthenic, and aromatic components. By combining
being recorded. Chemical shifts ranges for carbons in vari- this knowledge with the abundant data that are available on
ous electronic environments are shown in Fig. 12.8 and typi- physical and chemical properties of the three types of hydro-
cal values are provided in Table 12.12 关54,790兴. Figures 12.9 carbons, a competent formulator will know which additives
and 12.10 depict 1H and 13C NMR spectra for vanillin as an are necessary to design a lubricant that meets the perfor-
example 关789,790兴. Despite the versatility of the NMR spec- mance needs of a specific application.
troscopy to determine the chemical structures easily and ac-
curately, its value in mineral oil analysis can only be realized Lubricants
by using it in conjunction with a separation technique, for
Tests that are used to assess the properties and the suitability
example, chromatography. The use of the NMR for analyz-
of the lubricants for use in the intended application are listed
ing mineral oils and or its components is described in the
ASTM Standard ASTM D5292, Test Method for Aromatic in Tables 12.13–12.15. It is important to note that while the
Hydrogen and Aromatic Carbon Contents of Hydrocarbon list is exhaustive, it is by no means complete. The detailed
Oils by High Resolution Nuclear Magnetic Resonance Spec- descriptions of these tests are available in publications by
troscopy and the references 关54,791–794兴. various standards-establishing organizations, such as
By coordinating all the information gathered from the ASTM, ISO, DIN, and U.S. Military. Here, we provide a short
above-described separation and spectroscopic techniques, a description of the most widely used physical and analytical
formulator will have a good idea about the composition of tests.
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546 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
Fig. 12.7—Chemical shift ranges for protons in different electronic environments 关789兴.
Fig. 12.8—Chemical shift ranges for carbons in different electronic environments 关790兴.
Specific Gravity 共ASTM D941, D1217, and Viscosity 共ASTM D445, D2161, D2983兲
D1298兲 Viscosity is considered the most significant and fundamental
Specific gravity is the ratio of the weight of a given volume of property of the lubricants. The importance of viscosity is
oil and an equal volume of water at a specified temperature. demonstrated by the fact that it is one of the major factors in
While specific gravity has some use, for example in estimat- selecting a lubricant. Viscosity is equally important in new
ing volume if the weight is known and the force required to and is in-service oils. In new oils, it assures proper lubrica-
pump a fluid, the API gravity is of greater value in lubricants. tion across a broad temperature range and in-service oils, it
To determine API gravity, specific gravity measured at the de- indicates the lubricant condition, degradation due to oxida-
sired temperature is converted into API gravity at 60 ° F by tion, and useful life. For a detailed discussion on viscosity,
the use of the Petroleum Measurement Tables, issued jointly refer to Chapter 1 on Lubrication Fundamentals.
by ASTM and IP 共ASTM D1298兲. The API gravity scale mea-
sures the relative density of the various petroleum liquids. Chlorine Content 共ASTM D808 and D1317兲
Refer to Chapter 2 for details. In general, the oils of higher Two methods for determining the chlorine content are the
API gravity, such as paraffinics and light crude oils, are com- bomb method, which involves a gravimetric determination,
mercially more important than those with lower API gravity, and the volumetric or the titration method, which deter-
such as naphthenic and heavy crude oils. mines the amount of chlorine by converting it into sodium
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CHAPTER 12 䊏 LUBRICANT TESTING 551
chloride and titrating it with silver nitrate. Both methods are Oxidation Stability 共ASTM D943, D2272, D2893,
suitable for either new or the used oils, as well as greases. D1313, D2446, D2893, and ASTM D942兲
While the compounds containing chlorine and chlorine plus Oxidation resistance of a lubricant is a critical property, par-
sulfur are often used in extreme pressure lubricants, such as ticularly in applications that involve high temperatures and
cutting fluids, their use is on the decline, especially in Eu- exposure to air, such as internal combustion engines, steam
rope, because of its role in producing carcinogenic polychlo- turbines, and transformers. The most widely used method to
robiphenyls 共PCBs兲 and dioxins. When used in a lubricant, it assess oxidation resistance is ASTM D943, which is appli-
is important to determine the optimal amount to deliver the cable to most lubricating oils, especially to those containing
desired performance. Too small an amount will not provide the oxidation inhibitors. Consequences of the poor oxida-
appropriate friction and wear control and too large an tion stability are sludge, acids, foaming, emulsification, cor-
amount will lead to increased corrosion. rosion, and restricted oil flow in the operating units. Oxida-
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552
TABLE 12.15—Typical bench test results for some lubricating oils †795‡.
Sulfur/Chlorine
Content Oxidation Wear/EP Properties
Font
Color
Aniline Rust Copper Metal Foaming Emulsion Stability
Point Prevention Strip Content Volume Volume h to 2 mg Timken OK Four-Ball Falex,
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Type of Oil °C D 665 D 130 %S % Cl % mL mL KOG/g Load, kg Wear Scar kg
Air Compressor
Times-Bold
Reciprocating 104 Pass A 1 … … … 0/0/0 40-4-0 1200 … … …
Downloaded/printed
共10 min兲
by
Vane 106 Pass B 1 … … … 0/0/0 40-40-0 1500+ … … …
共4 min兲
Aircraft Engine
Reciprocating 120 … 1 0.6 … … … … … … 0.63 …
Gas Turbine 114 … 1 0.05 … … 5/5/5 … 19 共204 ° C兲 2600 0.51 680
Automatic Transmission 102 Pass B 1b 0.17 … 0.04 共Zn兲 10/ 20/ 10 … … … … …
Automotive Engine 110 … 1 0.32 0.05 0.14 共Zn兲 0/0/0 … … … … …
Ball and Roller Bearing 111 Pass B 1 0.02 … … 0/0/0 40-40-0 1500+ 25 … …
共10 min兲
Diesel Cylinder 103 … 1 0.47 … 0.11 共Zn兲 5/5/5 … … … … …
Electric Motor Bearings 106 Pass B 1 … … … 0/0/0 40-40-0 1500+ … … …
共4 min兲
Gas Engine 112 … 1 0.32 0.05 0.135 共Zn兲 0/0/0 … … … … …
Gas Compressor 112 … 1 0.32 0.05 0.135 共Zn兲 0/0/0 … … … … …
Gear Oils
General Purpose … Pass B 1 0.78 … … 5 / 15/ 5 … 3.3 25 0.3 共42/250兲 2040
Hypoid 102 Pass A 1 1.26 1.1 0.04 共P兲 15/ 45/ 15 … 5.0 25 0.3 共42/250兲 1700
Aircraft
Light … … … … … … … … … 16 … 1360
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Medium … … … … … … … … … 18 … 1475
Heat transfer 110 Pass A 1 … … … … … 115 … … …
Hydraulic 106 Pass B 1 … … … 0/0/0 40-40-0 1500+ ⬎2.3 0.28 380
共4 min兲
… …
共10 min兲
Steel Mill Bearing 122 5 / 15/ 5 40-40-0
䊏
… … … … … … … … …
共10 min兲
Textile Spindle 87 Pass B 1 0.23 … … 5/20/20 … 1000 … … …
CHAPTER 12 䊏 LUBRICANT TESTING 553
tion resistance of the steam turbine oils is especially critical volve mixed film and boundary lubrication. One of the test
because of the danger of the turbine bearing failure. Other machines that are used extensively to measure the EP prop-
applications, such as gear, transformer, hydraulic, heat erties of the lubricants is the Timken machine, which em-
transfer, and gas turbine systems also require lubricants ploys a hardened steel ring rotating against a flat steel block.
with excellent oxidation stability. The test can be used either for oils 共ASTM D2782兲 or greases
ASTM D2893 is used for evaluating the oxidation prop- 共ASTM D2509兲. Two other ASTM methods, Falex 共D3233兲
erties of the EP lubricants. However, the observed viscosity and Four-ball 共D2783兲 testers are also used. Please note that
change and change in precipitation number may be partly these tests are only screening tools and cannot be used to de-
due to the thermal effects. While the ASTM procedure re- termine the true extreme pressure properties of the lubri-
quires a temperature of 95 ° C 共203 ° F兲, some laboratories cants. Hence, it is recommended that the oils to be used in
conduct the test at 121 ° C 共255 ° F兲 to increase severity. gear systems must be tested employing actual gears and op-
ASTM D942 is used to determine the oxidation resistance of erating parameters, such as load, speed, and temperatures,
greases during storage in mechanical parts. In this test, a that are representative of the intended application 关795兴.
pressure vessel containing the grease at 99 ° C is pressurized Wear Properties 共ASTM D2670兲
with oxygen and the vessel is held for a specified time. Little The Falex tester is one of many that are used to test the wear
or no drop in pressure indicates oxidation stability. Grease properties of the lubricants. In the ASTM D2670 test proce-
must show good resistance to oxidation to yield a long ex- dure, the wear performance of the lubricants is compared on
pected service life. the basis of the final load before seizure of the pin and block
Interfacial Tension 共ASTM D971, D2285兲 assembly. Results from this test machine do not provide ab-
Lubricants differ in their wetting, spreading, and boundary solute values of the film strength or the extreme-pressure
lubrication ability due to the presence of additives or the oxi- properties of the lubricant, but this test method is quite ef-
dation degradation products. These differences are indi- fective for comparing the wear properties of different lubri-
cated by their interfacial tension 共IFT兲 values. This lubricant cants.
parameter is measured by the use of a tensiometer. A drop in Hydrolytic Stability 共ASTM D2619兲
IFT indicates oil deterioration; hence it can be used to detect This test method evaluates a lubricant’s ability to resist hy-
an increase in the rate of oxidation of the oil 关796兴. This infor- drolysis. However, this test has limited use for screening and
mation can be used to determine the need for oil mainte- evaluating ester-based hydraulic fluids. This test is useful in
nance or, if permissible, to replenish the consumed oxida- monitoring the lubricant condition and assessing the effec-
tion inhibitors in transformer oils, hydraulic fluids, and tiveness of hydrolysis inhibitors that are often used to pro-
steam and marine turbine oils. IFT measurement on the new tect phosphate and silicate ester fluids against hydrolysis.
oils is significant only in transformer oils 关795兴. Thermal Stability 共ASTM D2160兲
Demulsibility 共ASTM D1401 and D2711兲 This test is used primarily for hydraulic oils to evaluate their
These methods measure a lubricant’s tendency to quickly resistance to property changes due to thermal stresses. This
separate from water. Good demulsibility is a requirement for information is useful in selecting a lubricant for sealed hy-
most nonaqueous lubricants; a lubricant of poor demulsibil- draulic applications and heat transfer systems 关795兴. This
ity will form persistent emulsion, which can plug oil lines, test is not suitable for water-based fluids.
insulate coolers, and accelerate failure of the bearings and Low-Temperature Viscosity 共ASTM D2602兲
other equipment parts due to inadequate lubricant film for- This test is used solely for automotive engine oil to measure
mation. Steam cylinder oils, used in closed systems, also re- the apparent viscosity and the response of the oil to a rotor in
quire good separation from water to prevent the entrance of a device called Cold-Cranking Simulator. The device repli-
oil into the steam generating system 关795兴. The time for oil cates cranking of an engine and its effect on the lubricant
separation from an emulsion depends upon the presence of during cold climatic conditions.
the foreign matter and the build-up of the oxidation prod- Grease Penetration 共ASTM D217 and D1403兲
ucts; both of which will decrease the emulsion’s ability to These tests assess consistency or hardness of grease via cone
break. For water-based hydraulic and metalworking fluids, penetration. ASTM D217 uses a standard cone and ASTM
emulsion stability is important, which in certain oil-in-water D1403 employs fractional scale cones, which permit mea-
emulsions may be determined by the use of the ASTM Meth- surements on small volumes of grease. While the measure-
ods D1479 and D3342. ment can be carried out on an unworked grease, worked pen-
Load-carrying Capacity 共ASTM D1947, obsolete兲 etration simulates real-life use conditions and hence is more
A number of devices are used to evaluate the load-carrying beneficial. A worked penetration value of about 265 to 295 is
capacity of the gear lubricants, Ryder gear test machine be- considered desirable for general purpose greases and a pen-
ing one. Gear tests are useful in assessing the load-carrying etration of about 200 to 250 is considered appropriate for
capacity of the lubricants that contain antiwear, anti-scuff, grease use in small double-sealed bearings since good “chan-
and extreme pressure additives. These tests are intended for neling” is more important than “feedability” of the grease
low-viscosity oils for circulating systems; hence they are not 关795兴.
generally suitable for lubricants formulated with fatty mate- Grease Dropping Point 共ASTM D566 and D2265兲
rials for use in open or hypoid gears 关795兴. Dropping point is the temperature at which a grease exhibits
Extreme Pressure Properties 共ASTM D3233, a change from being a semisolid to a liquid. Of these tests,
D2782, and D2783兲 ASTM D2265 is used for high temperature greases. Please
The ability to sustain load without seizure or scoring is an note that the dropping point only approximates the melting
important property for applications such as gears that in- point of lubricating grease since greases lack a well-defined
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554 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
melting point. The measurement has little significance with and other elements. For this test, aluminum test panels
respect to a grease’s in-service performance. are normally used. However, other metals may also be
Apparent Viscosity of a Grease 共ASTM D1092 used, if so desired.
and D3232兲
Rheological properties of a grease are determined by the use Mechanical or Tribological Tests
of pressure to make it flow through a cylinder into an at- These tests help assess a lubricant’s performance in labora-
tached capillary flow tube. The results are indicative of any tory tests that are designed to simulate the actual service
flow problems that may occur during distribution and dis- conditions. Machine tests, such as SAE #1, Four-ball, Falex,
pensing of grease from a central distribution system. FZG, and Ryder gear tests, evaluate a lubricant’s effective-
Evaporation Loss in Lubricating Greases 共ASTM ness under mixed-film and boundary lubrication conditions.
D972 and D2595兲 The outcome of the tests depends upon the tribological sys-
These test methods can be used both for oils and greases. tem as a whole—that is, the equipment, the operating condi-
The tests may be carried out at any temperature between 99 tions, the base oil quality, and the nature of the additives 关4兴.
and 150 ° C. A significant loss of oil will result an increase in The type and the condition of materials that form the contact
viscosity and in the worst case in a loss of the grease struc- surfaces, surface load, equipment speed, nature of the con-
ture. tact 共whether rolling or sliding兲, temperature, contaminants,
Wear Prevention and Extreme Pressure in and moisture are all important in this regard.
Greases 共ASTM D2266 and D2596兲 The base oil quality affects the lubricant’s film-forming
Both these methods are Four-ball methods and are used to ability and the durability of such films under a variety of tem-
assess the wear prevention characteristic of a grease. peratures and pressures. Paraffinic base oils, for example,
Leakage of Wheel Bearing Greases 共ASTM form stronger and more durable films than naphthenic or
D1263兲 aromatic base oils. Additives, such as viscosity modifiers,
Greases used in automotive wheel bearings may leak due to friction modifiers, and extreme-pressure agents all enhance
thermal softening resulting from high speeds, loads, and ex- lubricant performance. Viscosity modifiers improve the lu-
cessive braking. The ASTM D1263 test determines the leak- bricant’s film-forming ability under elasto-hydrodynamic
age tendency of a grease. conditions by influencing its viscosity. Friction modifiers im-
Water Washout 共ASTM D1264兲 prove the nature of the lubricant film through physisorption
This test measures washout of the greases at either 38 or or chemisorption on the surfaces and at the same time asso-
79 ° C when sprayed with a water jet. Grease loss in one hour ciating with the bulk lubricant. See the discussion in Chap-
is a measure of its resistance to washout by water. Some ter 4 on Friction Modifiers. Such films are less durable than
greases reject water or incorporate it as droplets, others may those formed by the extreme-pressure agents. Extreme-
absorb water forming emulsions or may even liquefy. pressure agents form irreversible films by chemically react-
Grease Performance in Ball Bearings 共ASTM ing with the surfaces.
DI741, D3336, and D3337兲 Machines used for these tests measure the effect of load
ASTM D1741, now obsolete, measured performance life and and temperature on the film-forming ability, as reflected by
leakage tendency of a grease. ASTM D3336 is a similar test the friction coefficients and wear. Results for newly formu-
that is conducted at a high temperature of up to 371 ° C. The lated oils are compared with those of the reference oils to
ASTM D3337 method, analogous to D3336, employs small measure their relative effectiveness. Commonly used test
ball bearings. All three test methods are good for screening machines include the Almen-Wieland rig, the Falex tester,
greases to identify those that are the most effective. the Timken Wear and Lubricant testing machine, the Four-
Lubricating Properties of Solids 共ASTM D1367, ball Test rig, and the SAE #1 tester, although there are many
D2510, D2511, D2625, D2649兲 others. The test elements of the three commonly used ma-
These tests are designed to evaluate lubricating properties of chines are shown in Fig. 11.8.
solids alone and in combination with oils and greases. The These film strength tests are the only way to assess the
lubricating parameters they measure are listed below: suitability of the lubricants for driveline applications, such
1. ASTM D1367 evaluates the lubricating qualities of as gears, where mixed and boundary lubrication conditions
graphite and other similar solids. The test can be used predominate. However, the data obtained from these tests
for comparative evaluation of the various solid lubri- are subjective. To draw meaningful conclusions, the data
cants in combination with other lubricating fluids. must be substantiated by testing in real gear rig tests, such as
2. ASTM D2510 determines the adhesion properties of sol- FZG, Gleason, and Ryder tests, that simulate the operating
ids by assessing the effectiveness and continuity of the conditions somewhat more closely. The configuration of Ry-
solid-film formed by the lubricant. der, Gleason, and FZG machines is shown in Fig. 12.11.
3. ASTM D2511 evaluates thermal shock sensitivity of the The objective of mechanical and tribology testing is not
solid lubricant film. Applications that involve extreme only to ascertain that the lubricant provides adequate lubri-
temperature variations may cause damage to the coated cation and wear control in the intended application, but also
lubricant film. The evaluation is more qualitative than that it does it quickly and inexpensively. This is because the
quantitative. full-scale laboratory and field tests are long and expensive, as
4. ASTM D2625 measures wear and load-carrying charac- was stated earlier. Another objective of the tribology testing
teristics of the solid lubricants. is to screen a large number of candidates to identify those
5. ASTM D2649 is used to evaluate corrosiveness of the that are the best with respect to both cost and performance.
solid lubricants, many of which contain chlorine, sulfur, The major challenge is to develop a test that is meaning-
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CHAPTER 12 䊏 LUBRICANT TESTING 555
ful; that is, it predicts a lubricant’s performance in service. face films play a major role in applications involving exten-
For a tribology test to be able to meet this goal, one must un- sive metal-to-metal contact, such as gears and bearings, and
derstand the lubrication needs of the intended application the highly stressed long-life mechanical systems.
and simulate them in the laboratory. It is also important to As mentioned earlier, for a tribology test to be of practi-
recognize that while the tribology mechanism or mecha- cal value, it must have a clear link to the real life perfor-
nisms simulated in the laboratory may work effectively on a mance. For it to do so, the test must duplicate the perfor-
micro-scale, they may or may not indicate adequate perfor- mance mechanisms operating in the tribological system of
mance on a macro-scale. The key to developing a meaningful the intended application. The major objective of the lubrica-
test is to incorporate all of the important variables into the tion is to avoid or reduce the effects of friction and wear
test so that a close conformity to the lubrication needs of the upon a mechanical system. A lubricant may also act as a
final application is achieved. cooling agent and remove heat from the location of the fric-
The performance of a tribo-system contact primarily de- tion process, which will also help control wear. A schematic
pends upon how well its lubrication needs are met, either by of a tribological system is provided in Fig. 12.12. 关798兴. A
the base oil itself or in combination with the additives that typical lubricated mechanical system has inputs that it
are added to enhance its lubrication ability. This translates transforms into outputs. The inputs are external to the sys-
into a lubricant’s ability to form a suitable lubrication film tem and comprise the operating variables. Those of impor-
under hydrodynamic, elasto-hydrodynamic, and boundary tance are the type of motion, load, velocity, temperature, and
conditions. Hydrodynamic films generated within the con- duration. The outputs are the friction-related parameters,
formal contacts may be tens of microns 共m兲 thick and hy- such as the frictional force and friction coefficient; vibration
drodynamic or elasto-hydrodynamic 共EHD兲 films generated or noise, or both; and an increase in temperature, wear, and
in nonconforming contacts may be around 1 m thick, see the contact conditions. These provide information as to how
Table 4.20. Hydrodynamic films are largely a consequence of efficiently the tribological system is working. The manner in
the lubricant’s bulk viscosity and in the case of the mineral which the inputs are transformed into outputs is the techni-
oil lubricants depend primarily upon its paraffinic content. cal function of the system and in turn depends upon the
Elasto-hydrodynamic films, on the other hand, depend upon characteristics of the system, which include tribo-elements
the lubricant viscosity in the contact zone and are mainly in- or metal pairs, lubricant, and the lubricating environment.
fluenced by a mineral oil’s naphthenic and aromatic content. Other factors that impact performance of the tribological
Boundary films, which are present on the thin outer layers of system include surface metallurgy, topography, and the sur-
the surface, may consist of surface oxides, adsorbed films, face composition 关798兴.
and chemical reaction films derived from the EP/antiwear The first input for the tribological system is the type of
additives present in the lubricant. These films are almost al- motion. It is important to know if the motion involves roll-
ways less than 1 m thick 关797兴. Chemically-generated sur- ing, sliding, spinning, or is of the impact type. Bearings in-
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556 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
volve spinning motion or rolling motion, depending on their tening and increased adhesion tendency than the harder
type; straight bevel gears have rolling motion, and hypoid metals, hence increased wear. Harder metals may be more
gears have a combination of both rolling and sliding motion. prone to abrasive wear by the wear debris and the
Sliding motion is more strenuous with respect to contact environment-related particulate matter. Chemical elements
and wear than rolling motion. In addition to characterizing are usually added to improve mechanical properties of the
the type of motion, its dependence on time is also important, bulk metal, such as hardness and ductility. Chemical treat-
such as being continuous, oscillating, reciprocating, or inter- ment, such as phosphating, galvanizing, and case harden-
mittent. Duration of the operation affects the lubricant vis- ing, is carried out to improve appearance, corrosion protec-
cosity due to the increased temperature, which will have an tion, wear resistance, and friction control. Thermal
influence on lubrication quality in the tribological system. conductivity is the ability of the metal to conduct heat. Met-
The load is the next significant input. Light 共low兲 load im- als differ in their ability to conduct heat, which is a function
plies less metal-to-metal contact than heavy 共high兲 load and of their structure and the temperature. Thermal conductiv-
will affect frictional parameters of the system and the degree ity of some of the metals that are used in tribological ele-
of wear. Velocity or speed will affect the amount of the lubri- ments is listed in a decreasing order below. Metals with high
cant in the contact zone, hence affect the nature of the lubri- thermal conductivity will effectively take the heat away from
cation. High speeds promote hydrodynamic lubrication and the contact zone.
slow speeds promote mixed film lubrication. Temperature 1. Silver 共Ag兲, pure
affects the lubricant viscosity, as well as promotes adhesion 2. Copper 共Cu兲, pure
in the absence of the lubricant in the contact zone. For some 3. Gold 共Au兲, pure
tribological systems, other inputs, such as flow rate of the lu- 4. Aluminum 共Al兲, pure
bricant, vibration, and radiation must also be taken into con- 5. Brass 共Cu plus 35–15 % Zn兲
sideration 关798兴. 6. Iron 共Fe兲, pure
The first parameter for the tribological system is the 7. Cast iron 共Fe plus 2–3.5 % C plus 1–3 % Si兲
properties of the tribological elements. These include geom- 8. Bronze 共Cu plus 11 % Sn兲
etry, metallurgy, chemical composition, thermal conductiv- 9. Carbon Steel 共Fe plus 1.5–0.5 % C兲
ity, elastic modulus, hardness, density, and other properties. Elastic modulus, or modulus of elasticity, is the math-
Metallurgy defines the degree of hardness, adhesion ten- ematical description of an object’s or a substance’s tendency
dency, propensity to wear, and the lubricant’s effectiveness to to deform under the influence of force. Metal stiffness, as
form a lubricating film. Softer metals, for example, are more measured by Young’s modulus, for some of the metals fol-
likely to have extensive content under load due to easy flat- lows the order given below:
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CHAPTER 12 䊏 LUBRICANT TESTING 557
Wrought iron and steel⬎ Titanium the actual tribo-engineering system in which the lubricant is
⬎ Brass and bronze⬎ Aluminum Alloy⬎ Magnesium metal to be used. Environmental factors include chemical compo-
Density of some of the metals used in the tribological el- sition of the environment and the effect of its components,
ements follow the order: especially of the water vapor. If the inputs, or the operational
Platinum⬎ Gold⬎ Tungsten⬎ Lead⬎ Silver⬎ Copper parameters, are taken into account, along with the elements
⬎ Iron⬎ Steel⬎ Tin⬎ Titanium⬎ Aluminum⬎ Magnesium of the tribological system, it is possible to devise a quality tri-
Again, as with thermal conductivity, the effect of the bological test. While it is impractical or possible to include
elastic modulus and density on lubrication and wear cannot all the system characteristics into a test, it is important to en-
be predicted without considering the other properties of the sure that none of the essential operational aspects or the in-
metals. fluencing parameters is overlooked.
Surface topography is also important. Finely finished A well designed test will provide the desired outputs
surfaces or those with too rough a finish may experience listed in Fig. 12.12 under the tribometric characteristics.
more wear than those that have intermediate finish. This is Table 12.13 shows examples of a number of tribological sys-
because the former type of surface finish will not be able to tems and their elements 关799兴. In ultra-high vacuum applica-
hold the lubricant film effectively, thereby resulting in exten- tions, the tribological system diminishes to only the interact-
sive surface contact; and the latter type will have extensive ing tribological elements since there is no lubricant and
metal contact because of the large surface asperities. Sur- there exists almost no environment. The main interactions
face composition effect is related to metal’s ductility, which involve contact deformation, surface fatigue, abrasion, and
will affect its wear characteristics. In systems, such as worm adhesion. In air, these processes are supplemented by inter-
gears, and other systems where the contacting parts are actions with the atmosphere 关800兴. Finally, in a lubricated
made of different 共dissimilar兲 metals or of different materi- system, direct 共contact兲 interactions between moving and
als, the degree of wear may be more or less than if both tribo- stationary elements are prevented or influenced by the dif-
logical elements were made of the same material, depending ferent mechanisms of lubrication.
upon the material. The tribological tests predominantly assess the overall
The lubricant and the environment are the remaining ability of a lubricant to permit the rubbing surfaces to oper-
two factors of the tribological system. Properties of the lubri- ate without scuffing, seizing, or other signs of material de-
cant may be classified into system-dependent properties and struction. The tests can be broadly classified into three
system-independent characteristics. System-dependent groups. These are simple bench tests, tribo-technical tests,
properties essentially depend upon the specifications of the and full-scale tests, and in terms of usefulness they go from
whole tribological system and include viscosity, viscosity- being the least effective to being the most effective 关801兴.
pressure, viscosity-temperature, and EP/antiwear proper- Simple bench tests use simplified geometries that in-
ties. System-independent properties include other physical volve point, line, or flat contact, and are designed to differen-
and chemical properties of the lubricants 关799兴. It is impor- tiate between EP and nonEP oils; hence their accuracy is just
tant to note that it is critical to match the system-dependent adequate. Predicting the performance of the lubricants in
characteristics of the lubricant with the technical function of real life applications purely on the basis of these tests is al-
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558 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
TABLE 12.17—Typical bench test results for some lubricating greases †795‡.
most impossible. However, these are useful for screening DIN, ISO, and IP standards. Table 12.19 lists DIN and DIN-
candidates to identify the best ones for further testing. Be- ISO combined standards and Table 12.20 provides AFNOR
cause of the limitations of the simple tests, more advanced standards and specifications 关802兴. Tables 12.21 and 12.22
tribo-technical tests must be performed. Such tests use as comprise non-ASTM Standards other than DIN and
many variables as possible when simulating the actual per- AFNOR, and Table 12.23 lists standards and specifications
formance. These tests use a complete tribo-engineering unit that pertain to the military lubricants 关803兴. As one can see
and are best performed in the laboratory, where it is possible there is significant overlap across tables and some tests are
to control the operating conditions better 关799兴. These tests included in more than one list. This is despite the fact that we
use a number of test element geometries to simulate various attempted not to include the same tests in more than one
contact situations that occur in real-life applications. These table. Absolute classification in some cases was not possible
test geometries are shown in Figure 4.147. As stated earlier, because of the slightly different description for the test meth-
the lubricant candidates that meet the preliminary tests ods that may have been the same. We decided to exercise
must be subjected to full-scale tests to ascertain satisfactory prudence and included both in our lists.
performance in actual tribo-engineering systems. Since the
cost of running such tests is quite high, they are only used to In-service Lubricant Analysis
provide the final proof of a lubricant’s performance. A sys- The analysis of a lubricant in service is at least as important
tematic lubricant selection procedure is described by Horst as that of a new lubricant or the used lubricant. This is be-
Czichos 关799兴. cause it can help identify problems in their infancy. Lubri-
Table 12.14 lists the typical physical properties and cant monitoring is routine in many industries and involves
Table 12.15 lists the bench test results of some of the lubri- assessing physical appearance, viscosity, metals content,
cants 关795兴. Tables 12.16 and 12.17 list the same for greases and the rate of the lubricant degradation. Once the problems
关795兴. Please note that Table 12.17 is a continuation of Table are identified, they can be corrected either by replenishing
12.16, but it lists other grease properties. Tables 12.18–12.23 the consumed additives or by the used lubricant replace-
list the tests used to analyze and assess lubricant quality. ment.
Table 12.18 lists ASTM standards and the corresponding Oil and wear particle analyses are also valuable failure
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CHAPTER 12 䊏 LUBRICANT TESTING 559
TABLE 12.18—ASTM and related standards used in lubricant analysis and testing.
ASTM ISO
Standard Standard Other Standards Test Description
A1415 … … Test Method for Rubber Property-International Hardness
D56 … … Test Method for Flash Point by Tag Closed Cup Tester
D86 3405 IP 123 Test Method for Distillation of Petroleum Products at Atmospheric Pressure
D91 … … Test Method for Precipitation Number of Lubricating Oils
D92 2592 IP 36 Test Method for Flash and Fire Points by Cleveland Open Cup
DIN 51 376
FED-STD-791-1103
D93 2719 IP 34 Test Method for Flash Point by Pensky-Martens Closed Cup Tester
NF EN 22719
DIN 51 758
D94 6293 IP 136 Test Method for Saponification Number of Petroleum Products
DIN 51 559
D95 3733 IP 74 Test Method for Water in Petroleum Products and Bituminous Materials by Distillation
DIN 51 582
D96 … … Test Method for Water and Sediment Determination in Crude Oil by Centrifuge Method
D97 219/ 3016 IP 15 Test Method for Pour Point of Petroleum Products
DIN 51 568
DIN 51 597
NFT 60105
FED-STD-791-201
D117 … … Guide to Sampling Test Methods, Standard Practices, and Guides for Electrical
Insulating Oils of Petroleum Origin
D128 … … Test Methods for Analysis of Lubricating Grease
D129 IP 1/IP 336 Test Method for Sulfur in Petroleum Products 共General Bomb Method兲
DIN 51 400
NF EN 24260
D130 2160 IP 154 Test Method for Detection of Copper Corrosion from Petroleum Products by the Copper
DIN 51 759 Strip Tarnish Test
FED-STD-791-5325
D156 … … Test Method for Saybolt Color of Petroleum Products 共Saybolt Chromometer Method兲
D189 6615 IP 13 Test Method for Conradson Carbon Residue of Petroleum Products
DIN 51 551
D217 2137 IP 50 Test Method for Cone Penetration of Lubricating Grease
D287 … … Test Method for API Gravity of Crude Petroleum and Petroleum Products 共Hydrometer
Method兲
D341 … DIN 51 563 Standard Test Method for Viscosity-Temperature Charts for Liquid Petroleum Products
D445 3104 IP 71 Test Method for Kinematic Viscosity of Transparent and Opaque Liquids 共the Calculation of
DIN 51 550 Dynamic Viscosity兲
DIN 51 372
DIN 53 015
FED-STD-791-305
D446 3105 IP 71 Specifications and Operating Instructions for Glass Capillary Kinematic Viscometers
DIN 51 366
DIN 51562 Part 1
D471 … … Test Method for Rubber Property Effect of Liquids
D482/ 3987/ 6245 IP 4/IP 223 Test Method for Ash from Petroleum Products
D874 DIN 52 005
D524 4262 IP 14 Test Method for Ramsbottom Carbon Residue of Petroleum Products
D566 2176 IP 132 Test Method for Dropping Point of Lubricating Grease
DIN 51 806
D611 2977 IP 2 Test Methods for Aniline Point and Mixed Aniline Point of Petroleum Products and
Hydrocarbon Solvents
D664 6619 IP 177 Test Method for Acid Number of Petroleum Products by Potentiometric Titration Method
DIN EN 12634
FED-STD-791-5106
SAE ARP 5088
D665/ 7120 IP 135/I 287 Test Method for Rust-Preventing Characteristics of Inhibited Mineral Oil in the Presence of
D3603 Water
D1748
D808 … DIN 51 408 Test Method for Chlorine in New and Used Petroleum Products 共Bomb Method兲
D848 … … Test Method for Acid Wash Color of Industrial Aromatic Hydrocarbons
D874 3987 IP 163 Test Method for Sulfated Ash from Lubricating Oils and Additives
DIN 51 575
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CHAPTER 12 䊏 LUBRICANT TESTING 569
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CHAPTER 12 䊏 LUBRICANT TESTING 571
TABLE 12.20—AFNOR standards and specifications used in lubricant analysis and testing †802‡.
AFNOR Standard Test Description
NF E 48-614 Air Release Properties
NF E 48-690 Filterability of Hydraulic Fluids
NF E 48-691 Filterability of Hydraulic Fluids
NF EN 23015 共T60181兲 Cloud Point Determination
NF EN ISO 3104 共T60100兲 Kinematic Viscosity and Calculation of Dynamic Viscosity
NF EN ISO 3675 共T60101兲 Density by the Use of Hydrometer
NF EN ISO 12185 共T60172兲 Density by Oscillating U Tube Method
NF ISO 3733 共T60113兲 Water Content by Distillation Method
NF ISO 6615 共T60116兲 Carbon Residue by Conradson Method
NF ISO 6618 共T60112兲 Acid and Base Number by Color Indicator
NF ISO 6296 共T60154兲 Water Content by Karl Fischer Potentiometric Titration
NF ISO 8681/NF T60-500 共T60500兲 Classification of Petroleum Products and Lubricants–Definition of Classes
NF ISO 14935 共T60177兲 Determination of Wick Flame Persistence of Fire-resistant Fluids
NF EN 24260 共T60142兲 Sulfur Content by Wickbold Combustion Method
NF M 07-003 Saybolt Color
NF M 07-015 Copper Corrosion
NF M 07-020 Centrifuge for Water and Sediment in Oils
NF M 07-024 Hydrocarbon Types by FIA
NF M 07-047 Oxidation Stability
NF T60-100 Kinematic Viscosity Determination and The Calculation of Dynamic Viscosity
NF T60-101 Laboratory Determination of Density
NF T60-102 Drop Point of Grease
NF T60-103 Closed Cup Flash Point of Lubricants and Fuel Oils
NF T60-104 Determination of Color 共ASTM Scale兲
NF T60-105 Pour Point Determination
NF T60-106 Determination of Additive Elements, Wear Metals and Contaminants in Unused and Used Lubricating
Oils-Method by Inductively Coupled Plasma Atomic Emission Spectrometry 共ICP/AES兲
NF T60-107 Glass Capillary Kinematic Viscometers. Specifications and Operating Instructions
NF T60-110-1 Determination of Saponification Number–Part 1: Color-Indicator Titration Method
NF T60-110-2 Determination of Saponification Number-Part 2: Potentiometric Titration Method
NF T60-111 Aging Characteristics-Determination of Change in Conradson Carbon Residue after Oxidation
NF T60-112 Determination of Acid or Base Number
NF T60-114 Melting Point of Paraffins
NF T60-115 Determination of Asphaltene Content 共Heptane Insoluble兲
NF T60-116 Determination of Carbon Residue-Conradson Method
NF T60-117 Determination of The Ramsbottom Residue
NF T60-118 Determination of Flash and Fire Points-Cleveland Open Cup Method
NF T60-119 Determination of Cone Penetrability of Paraffinic Products
NF T60-123 Automated Penetrometer
NF T60-125 Determination of Water Separability of Petroleum Oils and Synthetic Fluids
NF T60-126 Mineral Oils-Determination of Interfacial Tension of Oil Against Water
NF T60-129 Determination of Foaming Characteristics of Lubricating Oils
NF T60-131 Electrical Insulating Oils. Detection of Corrosive Sulfur
NF T60-132 Cone Penetration and Water Resistance Properties of Lubricating Greases
NF T60-133 Lubricating Greases-Determination of Free Acidity and Alkalinity
NF T60-135 Determination Of Rust-Prevention Characteristics of Lubricating Greases
NF T60-136 Calculation of Viscosity Index From Kinematic Viscosity
NF T60-138 Determination of Flammability Characteristics of Fluids in Contact With Hot Surfaces-Manifold IgnitionTest
NF T60-140 Cone Penetration of Lubrication Grease Using One-Quarter or One-Half Scale Cone Equipment
NF T60-141 Industrial Liquid Lubricants. ISO Viscosity Classification
NF T60-142 Determination of Sulfur Content. Wickbold Combustion Method
NF T60-143 Lubricating Oils and Additives. Determination of Sulfated Ash
NF T60-144 Lubricating Greases-Determination of the Sulfated Ash
NF T60-148 Determination of the Kinematic Viscosity According to the Temperature
NF T60-149 Determination of Air-Release Properties of Steam Turbine and Other Oils-Impinger Method
9NF T60-150 Determination of the Aging Behavior of Inhibited Oils and Fluids-TOST Test-Part 1: Procedure forMineral
Oils
NF T60-150-2 Determination of the Aging Behavior of Inhibited Oils and Fluids-TOST Test-Part 2: Method for HFCType
Hydraulic Fluids
NF T60-151 Assessment of Rust-Preventing Characteristics of Turbine Oil in the Presence of Water
NF T60-152 Measurement of the Viscosity at Low Temperatures Using a Brookfield Viscosity Meter
NF T60-154 Determination of Water-Potentiometric Karl Fischer Titration Method
NF T60-156 De-Emulsification Number of New Non Inhibited Turbine Oils. Water Vapor Test
NF T60-159 Temporary Anticorrosion Products. Degreasing Ability by Dipping
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CHAPTER 12 䊏 LUBRICANT TESTING 573
Full-scale Testing
analysis tools. The objective of these analyses is to determine As stated earlier, the quality of the finished lubricant is deter-
the lubricant condition by physical inspection and the mined by its ability to meet the requirements of the estab-
chemical analysis of the wear debris, contaminants, and re- lished performance standards. Examples of such standards
action products from lubricants. Wear in mechanical equip- include the following:
ment is inevitable and results from the surface contact be- • The SAE Viscosity Classification System
tween various machine parts, so is the lubricant breakdown • API, ILSAC, and ACEA Engine Oil Standards for gaso-
due to oxidation and thermal degradation. Besides wear, the line and diesel engine lubricants
other types of metal damage also need to be assessed. This • GM’s DEXRON® Standard and Ford’s MERCON® Stan-
includes deposits and corrosion. Unfortunately, this type of dard for automatic transmission fluids
damage is not as simple to assess as the lubricant sampling • API Standard for Gear Lubricants.
and analysis since it will require dismantling the equipment. • U.S. Military Standards
The extent of the lubricant contamination or break down is • OEM Specifications
determined by analyzing such lubricant parameters as color, • End-user Requirements
viscosity, insolubles, etc. Each of these standards accompanies a battery of per-
Oil and wear particle analyses are noninterruptive diag- formance tests in which proper lubricant performance must
nostic techniques that attempt to estimate the extent of wear be demonstrated prior to use.
in machine part/s and the lubricant condition by its reaction
or decomposition products. Based upon these determina- Performance Tests
tions, the equipment condition or the impending failure can The testing of the finished lubricant involves evaluating
be predicted 关647兴. Methods used for metal analysis include many of its properties and establishing the identity, the com-
spectrometric methods, such as atomic absorption spectros- position, and the properties of all of its components, i.e., ad-
copy 共AA兲, atomic emission spectroscopy 共AES兲, inductively ditives and the base fluid. Testing involves both the prelimi-
coupled plasma emission spectroscopy 共ICPE兲 关804,805兴, nary testing and the full-scale testing. Full-scale testing
and X-ray fluorescence 共XRF兲 spectrometry 关806兴. Of these entails testing a lubricant in a laboratory via accelerated
methods, AES and ICPE that rely on the detection of the light tests in the real world equipment and by simulating the ac-
emitted by various elements are most popular. This is be- tual service conditions. That is, the tests are carried out us-
cause of cost, speed, and other factors 关647兴. It is important ing actual engines, transmissions, axles, hydraulic pumps,
to note that the metals in the oil come from both wear and and so on. These tests usually evaluate more than one lubri-
those that are present in various additives. The latter group cant property at a time. At the end of each test, the equip-
is represented by calcium, magnesium, barium, zinc, and ment is disassembled and its parts rated based on different
molybdenum. Ferrography is another technique that is used criteria. Standardization of the laboratory test conditions
for analyzing the particles resulting from mechanical wear ascertains that the lubricants meet the performance require-
that are present in the fluid. This technique uses microscopic ments established by the various organizations. Standard-
examination and was developed in the 1970’s for predictive ized methods to test lubricants are published in the United
maintenance, by analyzing ferrous particles in lubricating States by ASTM and in Europe by CEC, DIN, IP, and NF.
oils 关807,808兴. Ferrography allows potential determination These organizations also ensure close adherence of the in-
of the amount and the type of wear, as well as the source of dustry to these methods. Almost all lubricants are perfor-
wear 关647兴. mance tested prior to their introduction into the market-
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CHAPTER 12 䊏 LUBRICANT TESTING 575
place. The preliminary step to assess performance is the ued efforts to devise tests to evaluate a lubricant’s perfor-
selection of the oils with demonstrated field performance for mance quickly and inexpensively 关50兴, no good substitute for
use as reference oils. These oils are run in the laboratory us- full-scale laboratory tests has yet been found, and the use of
ing production equipment from various manufacturers, such tests is expected to continue in the foreseeable future.
simulating the actual service conditions. A good correlation
between the field performance and the laboratory perfor- Elements of a Quality Test
mance standardizes the test to evaluate the new lubricants. A quality test contains a number of key elements, which in-
The development of the laboratory tests is costly and clude the quality of the parts, the way in which the equip-
time consuming. Hence, future performance requirements ment is assembled, for example engine build, operating pro-
must be anticipated and defined as accurately as possible. cedures, and the end of the test ratings. Low part-to-part
This can only be achieved by the cooperation of the equip- variability is extremely critical to the proper evaluation of
ment manufacturers, lubricant and additive marketers, and the lubricant. If parts vary in quality, it is difficult to assess
the end-users. Laboratory tests, especially engine tests, are whether the test results reflect the effectiveness of the lubri-
expensive to house, operate, and maintain. Despite contin- cant, the part-to-part variance, or both. The way the equip-
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CHAPTER 12 䊏 LUBRICANT TESTING 577
ment is assembled may also have an impact on the labora- are consistent among industry laboratories. For engine oils
tory test results. It is therefore important that the test and gear oils, in the United States, these bodies include the
equipment be built according to the established procedures Test Monitoring Center 共TMC兲, ASTM surveillance panels,
and with parts of good and consistent quality. and SAE Lubricants Review Institute 共LRI兲.
As stated earlier, in the United States ASTM has the pri- TMC, the key part of the ASTM monitoring system, is a
mary responsibility to ensure that the defined operating pro- neutral body that deals with the calibration and the monitor-
cedures for a particular test are followed. Most modern test- ing of the test facilities to ensure that laboratory tests are
ing facilities use computer data acquisition and control conducted according to the procedures prescribed by ASTM
systems to monitor the operation of a test. Ratings are con- 关27,809兴. TMC also supplies reference oils, validates stands
ducted by qualified raters who are trained by a self-policing for reference purposes, and approves laboratories for test-
industry-supported group. Previously, much emphasis was ing. If in TMC’s opinion a laboratory is not operating accord-
placed on the operations and the ratings of a test. That em- ing to established guidelines, TMC has the authority to in-
phasis is being replaced by the realization that the quality of validate such a laboratory. Since TMC oversees most test
parts, the manner in which the equipment is built, operating laboratories, it also provides statistics and identifies trends.
procedures, and the end of the test ratings all contribute to- The surveillance panels are made up of experts, usually
ward a quality test. from the test laboratories, which monitor a specific test and
Several controlling bodies ensure that the established ensure that the test is run as prescribed and is providing con-
test procedures are properly carried out and that the ratings sistent and on-target data.
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578 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
LRI ensures that the candidate products meet the U.S. bricant and additive marketers therefore select procedures
Military performance requirements. To obtain approval, the that best describe the performance characteristics of their
additive or lubricant supplier submits the selected parts products.
from the prescribed tests along with the test parameters and Once the lubricants have met all the requirements estab-
the test results to the LRI. If these are acceptable, a recom- lished by SAE, API, ASTM, AGMA, ISO, OEMs, the U.S. Mili-
mendation for approval is granted for the pertinent U.S. tary, and the end-users, some lubricant and additive market-
Military specification. Final approval is granted by the mili- ers choose to field test their products. This is the final test of a
tary upon review of the LRI’s recommendations and sup- lubricant’s performance and involves testing in equipment
porting documentation. Since many of these candidate
that is in actual service. Again, equipment parts are exam-
products also meet the performance requirements described
ined periodically to assess the lubricant’s performance 关811兴.
in the SAE standards for lubricants marketed in the private
For automotive lubricants, fleets of commercial vehicles or
sector, the LRI recommendations also impact commercial
oils 关810兴. vehicles which involve extensive use are employed. Such
For automatic transmission fluids and tractor hydraulic tests can take up to one year or longer. Because of the time
fluids, the appropriate OEMs are responsible for developing and cost associated with such testing, ILSAC, a result of col-
the test procedures and monitoring the compliance of the laboration between AAMA and JAMA, has at present elimi-
various testing facilities to these procedures. For the indus- nated the fleet testing requirement in its passenger car en-
trial gear oils and the industrial hydraulic fluids, OEMs and gine oil standards. A lubricant with demonstrated good
AGMA are mainly responsible for these activities. For metal- performance in the laboratory tests and field tests is ready
working fluids, there are no established test procedures. Lu- for the marketplace.
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MNL59-EB/Mar. 2009
13
Lubricants and the Environment
THIS CHAPTER DEALS WITH THE IMPACT OF tion. Particulate contaminants, such as dirt and wear debris,
lubricants on the environment. Primary emphasis is placed cause abrasive wear; and water and acidic species from the
on the used lubricants since they may contain materials lubricant oxidation and decomposition act as catalysts in
that are harmful to life or the environment, or both. Topics further degradation of the lubricant. Estimates of the per-
of lubricant conservation and the used oil reclamation, re- cent drop in additive concentration in an engine oil at the
processing, and disposal are also addressed and so are the end of a drain period are provided below 关812兴:
concepts of the environmental compatibility, biodegrad- 1. Detergent 共46 %兲
ability, and toxicity of the lubricants. 2. Ashless dispersant 共16 %兲
Concern for the entry of used lubricant into the envi- 3. Zinc dialkyl dithiophosphate 共45 %兲
ronment is on the rise, especially in industrialized coun- 4. Oxidation inhibitor package 共45 %兲
tries. There are three main avenues to restrain the ever- 5. Viscosity modifier 共9 %兲
increasing use of lubricants. These are to develop Oxidation is the major reason for the degradation of the
equipment, wherever and whenever possible, that does not most lubricants. Those based on carboxylate and phosphate
require a lubricant, extend service intervals, and when pos- esters in addition decompose thermally and hydrolytically.
sible recycle the used lubricant. In order to attain the ex- Oxidation products from the lubricants are either soluble
tended service interval, one must use lubricants with ex- and stay dissolved in the lubricant causing a viscosity in-
tended useful life. Recycling is the option to minimize the crease, or are oil insoluble solids such as resins that form de-
used lubricant’s entry into the environment. This translates posits when they separate on hot surfaces. Oxidation rate of
into cost savings, with respect to buying a batch of a new the properly inhibited mineral oil is quite low at tempera-
lubricant as well as in disposal costs, and the potential tures below 60 ° C. However, as the temperature increases,
damage to the environment, if the disposal method is inap- so does the oxidation rate. As a rough approximation, the
propriate. Ways to minimize inadvertent entry of the lubri- rate doubles for every 10 ° C rise in temperature. In addition,
cant into the environment is to use a closed system, where certain contaminants, such as water and metals, can act as
appropriate. A prime example is the modern automobile, catalysts and accelerate the oxidation rate. The effect of the
where the automobile manufacturers have successfully various contaminants on oxidation rate is shown in Fig. 13.1
minimized the loss of the lubricant or its volatile compo- 关813兴. In the figure, the total acid number 共TAN兲 is correlated
nents into the environment through leakage and evapora- with the lubricant’s useful life. Turbine oil is considered to
tion. They have achieved this by building closely fitting have useful life until TAN reaches 2.0 mg KOH/ g. As the fig-
parts and recycling the volatiles into the engine by install- ure shows, the wet lubricant, in the presence of either the
ing closed ventilation systems. Many industrial users of lu- iron or the copper, has a short life of less than 1000 hours,
bricants employ such self-contained systems to prevent the
while in all other cases, the lubricant meets the test require-
unintended lubricant loss into the environment.
ments even after 3500 hours. With respect to the acid num-
Lubricant Deterioration In Service ber, dry and metal-free lubricant has the lowest acid number,
which is followed by the lubricants that contain iron, copper,
Lubricants lose their effectiveness during use, due to degra- and water as contaminants. The presence of a significant
dation. The degradation rate depends upon operation sever- amount of water in the lubricant has other repercussions as
ity, time in service, system temperatures, make-up rate, and well, such as rusting. Besides temperature and the metal and
the environmental conditions. Lubricant degradation may water contaminants, other factors that increase the rate of
result from both physical and chemical factors, some of oxidation include the amount of air in the lubricant and tur-
which are a result of extraneous contamination. A lubricant bulence. Depending upon the lubricant, the amount of air
that has passed its effectiveness is either too contaminated dissolved in a lubricant can be as high as 10 % 关814兴. Besides
or too viscous to use. Besides viscosity, other indications that the ASTM D943 test, another test that is often used to assess
suggest that the lubricant is ready to be supplemented with the oxidation stability of the turbine oils and a variety of
additives or replaced include increased corrosion of the sys- other industrial fluids is ASTM D2272. Even the use of the
tem components and the formation of resin, varnish, sludge, simple physical parameters, such as color, odor, and the
and carbonaceous deposits. Degradation of the lubricant amount of insolubles, can be used to judge the health of a
properties is a consequence of the additives being depleted. lubricant. Oxidation-related breakdown in most organic lu-
The function of the additives is to increase a lubricant’s sta- bricants is similar, whether they are hydraulic fluids, gear
bility, hence improve its useful life, and to impart specific oils, or turbine oils. Tables 13.1–13.5 compare new and used
properties that are useful for its use in the intended applica- oils from various applications and Table 13.6 compares new
579
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580 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
Fig. 13.1—Catalytic effects of contaminants on oil oxidation 共modified ASTM D943兲 关813兴.
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CHAPTER 13 䊏 LUBRICANTS AND THE ENVIRONMENT 581
and used press roll bearing grease 关813兴. In each case, the understand bearing failures, malfunction of equipment, or
rightmost column shows a change in the lubricant param- in setting relubrication schedules. Flame Photometric
eter. In almost all cases, a significant negative change occurs analysis data in Table 13.6 show the grease to be lithium soap
in viscosity 共ASTM D445兲, color 共ASTM D1500兲, appearance, grease that contains a lead-based extreme-pressure additive
water content 共ASTM D95 and D1744兲, acid number 共ASTM system. NLGI consistency grade change and reduced drop-
D664兲, and the amount of insolubles 共ASTM D893兲. This is ping point show the used grease to be considerably softer.
indicated in the tables by a plus 共⫹兲 sign. This suggests that The high amount of the insoluble matter and the iron con-
the analyses of these lubricant parameters will provide use- tent shows high wear.
ful information on a lubricant’s condition. Of course, there The methods described so far are useful in assessing a
are other application-specific tests that must also be run. The lubricant’s reclamation and recyclability potential. They
data in the table also indicate that an analysis of the trace have limited use in assessing the condition of a lubricant in
metals is also beneficial in identifying contamination, con- service. One method that is useful in evaluating a lubricant’s
firming additive content 共additive depletion兲, and indicating life quickly is to determine the amount of the oxidation in-
system wear. This is indicated in the tables by a minus 共–兲 hibitor left in the lubricant since oxidation is the primary
sign. Two procedures that are suitable for determining the reason for lubricant degradation 关815兴. Oxidation inhibitors,
trace metals are emission spectroscopy and atomic absorp- natural or added, increase the thermo-oxidative stability of
tion. It is important to note that many of these liquid lubri- the lubricants. Their depletion over time will result in the de-
cant parameters do not apply to the lubricating greases. terioration of the physical and chemical properties of the lu-
Analysis of grease on a routine basis is seldom required, be- bricant. The problem with the commonly used measures of a
cause greases are not reused. Most analyses are performed to lubricant’s useful life, such as viscosity and acidity, is that
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582 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
they are not very responsive to changes in the lubricant’s re- matography 关816兴, weight loss 关817兴, gas evolution rate 关818兴,
sidual life. In addition, they are affected by the extraneous and differential scanning calorimetry 共DSC兲. Standard Test
factors, such as fuel dilution, shear-related viscosity change, Method E2009-02 for Oxidation Onset Temperature of Hy-
and removal of the oxidation products, through evaporation drocarbons by Differential Scanning Calorimetry is used to
or corrosion 关816兴. Hence, the condition monitoring tech- determine the oxidation induction times of the lubricants.
niques based on viscosity and acidity are inappropriate in The rotating pressure vessel oxidation test 共RPVOT兲 is an ac-
predicting a lubricant’s remaining life. Techniques that have celerated technique used extensively in monitoring the re-
been deemed capable of achieving this goal include thermo- maining oxidation inhibitor capacity of steam and gas tur-
oxidative stressing, chemical-oxidative stressing, and elec- bine oils that are supplemented with phenolic and amine
trochemical and instrumental methods. type inhibitors.
Thermo-oxidative stressing involves long-term stability Chemical-oxidative stressing involves the use of a free
tests, which employ specific operating parameters, such as radical generating material, such as cumene hydroperoxide.
air flow, metal catalysts, sample size, temperature, etc., to In this method, a sample of the lubricant diluted with hexa-
simulate the operating conditions of the specific equipment. decane and cyclohexene at 60 ° C is titrated with the free
Methods used to determine the oxidation onset time or onset radical generating reagent. When the oxidation inhibitor is
temperature include chemiluminescence, inverse gas chro- depleted, cyclohexene oxidizes causing a rapid decrease in
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CHAPTER 13 䊏 LUBRICANTS AND THE ENVIRONMENT 583
the oxygen pressure. The indicator used is a nickel complex mines the ability of the materials to harm life. While harm to
laser dye, which changes color by reacting with cumene hy- humans is a major concern, the effect of chemicals on the en-
droperoxide at the end point. The color change is monitored vironment as a whole cannot be ignored. Unused lubricants
using a visible spectrophotometer. The electrochemical are generally considered less toxic than the used lubricants.
technique that is commonly used for this purpose is cyclic Despite extensive efforts to reclaim and recycle the used oil,
voltammetric analysis 关819,820兴. This technique determines sooner or later some ends up in the environment. The expo-
the individual oxidation inhibitor concentrations through sure to used oils primarily occurs through skin absorption.
current-voltage relationships at the electrodes. The lubri- Over the short-term, they can lead to skin irritation; over the
cant is dissolved 共ester oils兲 or suspended 共hydrocarbon oils long-term, they can act as carcinogens. The Occupational
and greases兲 into a solvent containing an electrolyte prior to Safety and Health Administration 共OSHA兲 requires all lubri-
analysis. The voltage and the magnitude at which the current cant manufacturers to provide material safety data sheets
flow increases are used to identify and quantify the inhibitor 共MSDSs兲 on their products. While each MSDS contains a va-
or inhibitors present in the lubricant. Instrumental tech- riety of information, its primary purpose is to provide physi-
niques, such as gas chromatography and liquid chromatog- cal and health hazard data on the products so as to facilitate
raphy have also been used for inhibitor analysis, but with safe handling. Human exposure can be minimized by avoid-
varying degrees of success. ing contact with the lubricant, by using protective equip-
Used Oil—Environmental Considerations ment, such as gloves, oil-impervious clothing and boots, and
by adopting explosion and fire prevention measures. Envi-
Toxicity, safety, and environmental compatibility of the ronmental protection requires that neither new nor used lu-
chemicals are becoming a growing concern. Toxicity deter- bricant is released into the air, water, or soil. This can be
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584 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
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CHAPTER 13 䊏 LUBRICANTS AND THE ENVIRONMENT 585
achieved only if proper procedures pertaining to collection, ⬃30 % of the United States lubricant demand will be met
storage, and handling of the lubricants, lubrication, equip- 关52兴.
ment maintenance, and the disposal of the used lubricants Lubricant Conservation
are in place. Because the lubricant disposal is costly and is
subject to a number of federal, state, and local regulations, Conserving oil should be the primary goal of every user/
minimizing the volume of the used or the leaked lubricant is business because it minimizes the amount of the used oil to
highly desired. be recycled or disposed of, thereby conserving valuable re-
The interest in lubricant conservation, used oil recy- sources. Today, controlling the generation of the used oil and
cling, and nonpolluting disposal is because of many reasons. its recycling is even more important due to the steadily in-
These include progressively increasing crude oil prices, creasing oil prices, supply shortages, environmentally dam-
which affect the price of all petrochemicals including those aging illegal disposal, and the cost of the legal disposal.
of the lubricant base stocks, both mineral and synthetic, and Conservation of oils can be achieved by taking the fol-
a concern for the environment. It is estimated that the lowing steps:
United States generates around 2.4 to 2.5 billion gallons of 1. In-use condition monitoring
used oil each year 关821兴. Worldwide, this number soars to 2. Regular vehicle maintenance
about 5.3 billion gallons. The U.S. Environmental Protec- 3. Reduction in use
tion Agency 共EPA兲 considers that out of 2.4 billion gallons of 4. In-plant recycling and re-use
used oil 1.5 billion gallons is recoverable. Approximately 12 5. Efficient and economical retrieval from the waste
% of this volume is re-refined for re-use as lubricating oils, 12 streams
% is reprocessed for use as metalworking fluids and other in- 6. Utilizing out-plant commercial recycling processing
dustrial oils, and 15 % is used for spraying on the roads and 7. Re-use of the nonrecoverable oily waste as fuel
for other uses. And almost half is used as fuel, after mixing it In the previous chapters, we discussed extended drain
with fresh residual and distillate fuels. In 1976, the U.S. Con- 共service兲 intervals for automotive lubricants and pointed out
gress through Resource Conservation and Recovery Act of the lubricant attributes and the equipment operating param-
1976 encouraged recycling of the used oil to produce re- eters that affect an oil’s service duration. Factors and condi-
cycled oils that are “substantially equivalent” to the new oils. tions that affect the oil service interval in an automobile in-
It is estimated that if all the recoverable oil is recycled, clude the following:
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586 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
1. High-mileage engines degradation in the first three categories was largely a func-
2. Diesel engines tion of the oil temperature. During extreme short-trip driv-
3. Vehicles that use alcohol-gasoline blends ing, the fourth category, the principle cause of oil degrada-
4. Short trip intermittent 共stop and go兲 driving tion is water condensation and contaminants in the oil; the
5. Hot running conditions lower the oil temperature, the greater the contamination.
6. Turbo-charged engines Daimler Chrysler’s version of the oil monitor is called
7. Towing/heavy loads ASSYST in Europe and the Flexible Service System 共FSS兲 in
8. Synthetic lubricants the United States. Like GM’s sensor, the FSS uses a comput-
9. High-capture efficiency oil filter erized system to track multiple engine operating conditions.
10. Predominant highway driving In addition to the consumer driving habits, driving speeds,
11. Low-mileage engines 共less than 50,000 miles兲 and temperatures, the system also monitors oil levels. It uses
12. On-board diagnostics this information to determine the remaining time and the
The first seven shorten the service interval and the last mileage before the next oil change and displays it. Daimler-
five extend it 关822兴. The primary reasons that negatively im- Benz uses a digital oil quality sensor in its Mercedes-Benz ve-
pact the drain interval are the increased entry of the blow-by hicles, which measures changes in capacitance. Capacitance
gases from the combustion chamber into the crankcase, wa- is a surrogate for the amount and the type of contaminants
ter accumulation in the oil, and the elevated operating tem- and oil degradation products present in the oil. An increase
peratures; all of which lead to accelerated lubricant degrada- in dielectric constant 共less resistance to electrical current
tion due to oxidation. For the factors that have a positive flow兲 indicates oil contamination and degradation.
impact on the service interval, the converse is true. Although Delphi Corporation’s INTELLEK® oil condition sensor
prolonging the life of the oil in this manner will help the con- uses both a computer algorithm and a sensor. The algorithm
servation effort, yet judging the optimal drain interval is takes into account factors such as temperature, driving se-
what will have a direct impact on conservation. While the verity, oil level and oil type, all of which affect oil degrada-
original equipment manufacturers publish guidelines that tion. The sensing element measures various oil properties
define realistic service interval for their equipment, consum- such as oil conductivity, water-glycol contamination, oil
ers in the United States tend to go for a shorter drain interval. temperature, and determines the oil level.
This is because of the marketing efforts of the service provid- Bosch is in the process of developing a multifunctional
ers and the consumers’ perceptions that changing the oil oil sensor that will determine oil level and oil condition in
more often is good for the longevity of their automobile. both spark-ignition and compression-ignition engines. The
While there is some merit to this philosophy, in most cases oil level sensor will allow the oil dipstick to be omitted from
the oil is changed before its useful life is over. While more the automobile.
and more oil analysis laboratories are targeting passenger Eaton’s fluid condition monitor 共FCM兲 technology
car owners to grow their market, it is not convenient for the monitors multiple fluid properties by the use of impedance
consumers to take the in-use oil sample for analysis. In addi- spectroscopy—a technology that measures multiple electri-
tion, the cost of such a service to a normal consumer is high. cal properties of the fluid. It measures the surface properties
To remove the uncertainty out of judging the proper of the fluid as well as the bulk properties and it can indepen-
drain interval, new on-board sensors and related technology dently track multiple lubricant parameters. Measuring bulk
is gaining popularity 关822兴. GM’s Oil Life System 共GMOLS兲 properties provides information about changes in conduc-
uses the engine’s operating variables to suggest the best time tivity and dielectric constant, which indicate changes in the
for an oil change. The suggested drain interval is not only ve- base fluid and the additives due to oxidation, water, acids,
hicle specific but also changes based on the driving condi- mixed fluids, and wear debris. Measuring surface properties
tions and the consumer’s driving habits. For example, gentle provides a quantitative measure of the physical and chemi-
highway driving in a warm climate will maximize the inter- cal properties of the fluid at the fluid-metal interface.
val and short-trip driving in a cold climate or log duration While the primary function of in-use oil monitoring
fast speed highway driving in an extremely hot climate will technologies is to optimize oil drain intervals, these can also
shorten the interval between the oil changes. Depending on provide information on viscosity, permittivity, conductivity,
the vehicle, the former could be between 7000 and and temperature. These lubricant parameters provide an in-
12,000 miles and the latter could be 3000 miles, or less. sight into the functioning of the engine or a change in lubri-
Since most people’s travel involves city and highway combi- cant quality. Viscosity and permittivity, or the dielectric con-
nation driving, the GMOLS is likely to suggest an oil change stant, are the primary values that relate to the oil condition;
every 5000 to 6000 miles. GM data show that the OLS ex- viscosity increase is an indication of the oil oxidation and a
tends oil change intervals without risk to the engine. It does viscosity decrease indicates mechanical wear 共shear兲 and
not use an oil sensor and maximizes engine oil performance fuel dilution.
by sensing engine speed 共r/min兲, temperature, and other op- Conservation of the other lubricants, such as hydraulic
erating factors. Interestingly, the technology does not actu- oils, metalworking fluids, and greases require other strate-
ally monitor even a single chemical or physical property of gies. These include preventing oil loss due to leakage; con-
the oil. The sensor used in this technology is based on GM’s trolling oil degradation, filtering off wear-causing solids, and
determination that nearly all driving conditions can be removing water and other contaminants to prolong a lubri-
grouped into one of four categories: easy freeway driving; cant’s useful life, thus avoiding its premature disposal. Leak-
high-temperature, high-load service; city driving; or extreme age is prevented by ascertaining proper installation of the
short-term, cold-start driving. GM discovered that the oil damage-resistant seals and protecting their integrity during
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CHAPTER 13 䊏 LUBRICANTS AND THE ENVIRONMENT 587
use. Oil degradation either relates to thermal factors, oxida- must be replaced with new or re-refined oil to do the job at
tion, hydrolysis, and in the case of the water-based hydraulic hand. EPA uses three criteria to determine if the oil meets the
and metalworking fluids to biodegradation. Temperature definition of the used oil. These are summarized below:
control to lower levels, where possible, minimizing water 1. Origin—Used oil must have been refined from the crude
contamination, and controlling air entrainment can help oil or made from synthetic materials. Animal and veg-
slow down the oil degradation. Centrifugation, gravity set- etable oils are not included in the EPA’ s definition.
tling, and distillation with or without vacuum can be used to 2. Use—Oils used as lubricants, hydraulic fluids, heat
remove solids and water; and the microbial degradation of transfer fluids, buoyants, and for other similar pur-
the aqueous fluids can be minimized by the use of the bio- poses. Other fluids, for example, cleaning agents, anti-
cides and sterilization. Other methods that can be used to re- freeze, and kerosine are excluded.
move solids and water include screening, paper, cloth, and 3. Contaminants—EPA’ s definition requires the used oil to
diatomaceous earth 共clay兲 and the membrane filtration. become contaminated as a result of being used. Physical
contaminants include metal shavings, sawdust, or dirt,
Used Oil Recycling and chemical contaminants may include solvents, halo-
EPA considers used oil to be a danger to the environ- gens, or salt water.
ment and has mandated its re-use and disposal. The EPA’ s Used oils that meet EPA’ s definition include the follow-
regulatory definition of the used oil is: Any oil that has been ing:
refined from crude oil or any synthetic oil that has been used 1. Engine oils—typically includes gasoline and diesel en-
and as a result of such use is contaminated by physical or gine crankcase oils and piston-engine oils for automo-
chemical impurities. During normal use, contaminants such biles, trucks, boats, airplanes, locomotives and heavy
as oxidation and degradation products, dirt, metal scrap- equipment
ings, water, and chemicals enter the oil and over time the oil 2. Transmission fluids
loses its ability to perform the intended functions. Such oil 3. Refrigeration oils
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588 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
4. Compressor oils 2.4 to 2.5 billion gallons, only 1.5 billion gallons of oil is
5. Metalworking fluids and oils considered recoverable by the EPA. This leaves behind
6. Laminating oils ⬃1 billion gallons unaccounted for, which is somewhere in
7. Industrial hydraulic fluids the environment. EPA notes that improperly disposed used
8. Copper and aluminum wire drawing solutions oil is the largest single source of oil pollution in our nation’s
9. Electrical insulating oils waters. The automotive gasoline engine oil, estimated at
10. Industrial process oils 757 million gallons, makes up almost one-third of the total
11. Oils used as buoyants lubricating oil sold in the United States. The engine oil ser-
12. Synthetic oils—usually derived from coal, shale, or vice market comprises service providers and do-it-
polymer-based starting materials yourselfers. About 55 % of the oil change market is con-
trolled by the first group and the remaining 45 % is
Oil Reconditioning
controlled by the second group. The first group collects and
According to the EPA estimate, 380 million gallons of recycles used oil efficiently and correctly. However, this is
used oil are recycled each year. The volume equates to about not the case for the do-it-yourselfers. While some take the
half the annual engine oil use in the United States. Recycled used oil to collecting stations for recycle, others do not and
used oil can either be used in the same application or in a the used oil ends up in storm drains, dumped on the ground,
different application. For use in the same application, the oil burned, or in some cases, used for other purposes, such as
must be segregated, so as not to mix with the other types of dust control. Industrial oils, even those used in automotive
oils. A prime example is used engine oil, which is obtained applications such as railroads and other transportation do
from automobile dealerships and quick oil change service not suffer from this dilemma. Industrial oil users have a
organizations, such as Jiffy Lube, and is re-refined and sold greater degree of control on selection and use, which allows
in stores as engine oil. As mentioned earlier, out of more effective conservation and recycling. Because of the
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CHAPTER 13 䊏 LUBRICANTS AND THE ENVIRONMENT 589
sheer volume, the used oils from the industrial applications • Clay treatment to remove polar oxygenated materials or
are either reconditioned on-site and reused, or sent out for to improve color
reclamation. • Aeration or biocide treatment to get rid of the bacterial
The recycling processes include mechanical purifica- contamination
tion, reconditioning or reprocessing, reclamation or re- • Additive blending to make up the depleted additives
refining, and incineration. In mechanical purification, there Some feed streams need fewer steps than others. A com-
is no change in the chemical content of the oil. It involves mercial lubricant reclaiming company uses a host of analyti-
just removing the particulate impurities. cal techniques to determine the degree of treatment required
In terms of simplicity, reconditioning 共reprocessing兲 is to operate cost effectively. The analyses that are generally
the next. The process involves removing impurities from the performed prior to reclamation are listed in Table 13.7,
used oil and using it again in the same application or in a dif- along with the test methods. The steps listed for reprocessing
ferent but related application. Typically, segregation of used and reclamation are shown diagrammatically in Fig. 13.2. It
oils at their source offers more of an opportunity for re-use is important to point out that the quality of the reclaimed lu-
in the original application. While this form of recycling bricant is either the same or lower than that of the lubricant
might not restore the oil to its original condition, it does pro- prior to use. It is also important to make certain that none of
long its life. In some cases, it may be appropriate to replenish the recoverable used oils, including those that are emulsifi-
some of the spent additives, such as oxidation inhibitors, to able, are added to the waste water stream. This is because
improve oil’s useful life and performance. The major advan- they can decrease the effectiveness and efficiency of water
tage of this process over others, except mechanical purifica- treatment/oil removal.
tion, is that in most cases, it can be implemented on-site, Re-refining is the most complex of the recycling pro-
which eliminates the cost of shipping. In-plant recycling, in cesses and uses petroleum refining techniques, such as
addition, allows a secondary use for the used oil or the fluid. vacuum distillation and hydrotreating, both of which re-
For example, a used hydraulic fluid with suitable additives quire specialized equipment. Because of this, only a limited
can be used as a metalworking fluid. number of companies are involved in this process. Re-
Reclamation involves a higher degree of processing and refining, primarily used to recycle engine oils, results in
is primarily used for industrial lubricants, such as hydraulic clean high quality base stocks. The process involves pretreat-
oils, gear oils, and metalworking fluids. It is more effective if ment to reduce contaminant levels, multi-stage vacuum dis-
the feed streams are unmixed, otherwise used oil may have tillation, and catalytic hydrotreating. Pretreatment com-
to be processed for use as the furnace fuel oil. Reclamation prises application of heat, filtration, and treatment with
involves the following steps: acids, caustic, and other chemicals. The by-products of this
• Settling, centrifuging, and filtering to remove solids process are asphalt, reclaimed fuel that finds entry into the
• Clay and alkali treatment to remove acidic contami- crankcase during the low temperature operation, and kero-
nants, followed by washing to remove the resulting sine resulting from hydro-treatment. For every gallon of the
soaps used oil that is re-refined, approximately 50 % is converted
• Mild heating or distillation to remove volatile compo- into re-refined base oil, 25 % distills as light ends 共fuels兲, 15 %
nents remains as bottoms 共asphalt flux兲, and 10 % is water. The re-
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590 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
refined base oil produced is sold to the lubricant manufac- the other used oil streams, compare this figure with Fig. 13.3.
turers that compound it with additives and then package the The differences between the two processes pertains to qual-
product for the industrial and automotive markets. The as- ity control of the waste stream and the lack of pretreatment,
phalt flux may be sold to roofing manufacturers, road as- presumably both because of the relatively clean nature of the
phalt suppliers for road building, or steel mills as a fuel. The used engine oil and its intended re-use as engine oil base
water is treated and discharged. stock after purification. Table 13.8 compares the properties
A simplistic flow diagram of the re-refining operation is of the re-refined oils produced by the IFP 共Institut Francais
given in Fig. 13.3. Re-refining is usually used for large vol- Du Patrole兲 process with those of the fresh solvent neutral
ume lubricant streams, such as engine oils. Currently, about oils 关4,824兴. One can see that the properties of the re-refined
14 % of the used engine oil is re-refined. However, re-refining base oils from the used oil compare well with those of the
is not economically efficient for the new oil manufacturers fresh solvent neutral oils of comparable viscosity. Hence,
and as a result the re-refined motor oil is more expensive these oils are well suited to make finished engine oils, gear
than the new engine oil. Figure 13.4 depicts the process used lubricants, hydraulic fluids, metalworking fluids, and
by Safety Kleen to re-refine used engine oil 关823兴. Please note greases. Properly re-refined oils not only meet the API Group
that this process is very similar to that used for re-refining of I and Group II requirements but also have a comparable
TABLE 13.8—Quality comparison—Solvent refined fresh oils versus re-refined base oil †4‡.
150 Neutral 350 Neutral 600 Neutral Bright Stock
Base Oil Parameter Fresh Re-refined Fresh Re-refined Fresh Re-refined Fresh Re-refined
Density, g/mL 共ASTM D4052 and
0.875 0.874 0.835 0.882 0.895 0.888 0.910 0.903
D1298兲
Color 共ASTM D1500兲 ⬍2 ⬍1.5 ⬍3 ⬍2 ⬍3.5 ⬍2.5 ⬍6.5 ⬍5.5
Viscosity at 50 ° C, mm2 / s
19–21 18–20 40–46 37–41 60–74 60–64 242–272 226–242
共ASTM D445/IP 71兲
Viscosity Index 共ASTM D2270兲 97 95 95 95 95 95 95 95
Pour Point, °C 共ASTM D97兲 −15 −9 −9 −12 −9 −12 −9 −9
Flash Point, Open Cup, °C
200 215 215 245 240 255 290 275
共ASTM D92兲
Neutralization Number, mg KOH/g
0.05 0.03 0.03 0.05 0.05 0.05 0.05 0.03
共ASTM D664 and D974兲
Conradson Carbon, wt % 0.03 0.01 0.1 0.02 0.15 0.09 0.8 0.85
Ash, wt % 0 0 0 0 0 0 0 0
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CHAPTER 13 䊏 LUBRICANTS AND THE ENVIRONMENT 591
quality. This is demonstrated by the use of these base oils in These include environmentally friendly, environmentally
formulating lubricants that meet the newest standards for compatible, environmentally acceptable, environmentally
automotive lubricants listed below 关823兴: responsible, environmentally aware, environmentally be-
1. API SM/ILSAC GF-4 nign, environmentally harmless, environmentally safe, envi-
2. API CI-4 Plus ronmentally sensitive, and environmentally suitable. Two
3. DEXRON®-IIIG Automatic Transmission Fluid others that are used in the same context are green fluids,
4. U.S. Military Specification 共e.g., MIL-PRF-2104G兲 which are mostly manufactured from vegetable oils, and the
The cost of the re-refined base oils is comparable, al- food grade lubricants that are approved by the U.S. Depart-
though a little higher, to those obtained from the crude oil. ment of Agriculture 共USDA兲 through NSF. Food grade lubri-
Hopefully, there will be a cost advantage as the availability of cants were described in Chapter 9 while discussing miscella-
the quality used oil increases 关823兴. Figure 13.4 shows vari- neous industrial lubricants. These lubricants are primarily
ous uses of the used oil. As one can see, almost 40 % is used in used in the food industry where incidental food contact may
combustion-related applications and only 14 % is re-refined occur. Although the food grade lubricants are made by the
关825兴. use of the U.S.P. grade white mineral oil, or its equivalent
Lubricants and the Environment synthetic hydrocarbon oil, which is considered nontoxic,
they do not have to meet the biodegradability criteria, com-
Since there are limitations to the used lubricant recy- monly required of the environmentally compatible lubri-
cling, both with respect to collection and indefinite recondi- cants. Environmentally acceptable is the most widely used
tioning and reclamation, sooner or later some of the used lu- term which is also used by some ASTM committees to ad-
bricant is going to enter the environment. That is why the dress the environmentally friendly lubricants. While pres-
Federal and State governments have passed several laws and ently there are no established standards for such lubricants,
countless regulations covering the effect of the used oil on
there is a consensus that such lubricants must be biodegrad-
the environment and occupational health and safety. EPA
able and nontoxic. The problem is that the levels of these two
has also established standards on emissions resulting from
parameters are subject to interpretation. Nonetheless, there
the burning of the waste oil as fuel. The emissions pertain to
is a general increase in the desirability of such lubricants, as
carbon monoxide 共CO兲, sulfur oxides 共SOX兲, nitrogen oxides
indicated by their 5 – 10 % per year growth rate. Lubricants
共NOX兲, particulate matter 共PM兲, particles less than
of high biodegradability are primarily based on vegetable
10 micrometres in size 共PM10兲, toxic metals, organic com-
oil, animal fat, or the derived ester base stocks. These base
pounds, hydrogen chloride, and the global warming gases—
stocks are used in lubricants for applications, such as chain
carbon dioxide 共CO2兲 and methane 共CH4兲. Limits are also es-
tablished on certain metals and organic pollutants. Metals saws and hydraulic equipment, which are used in agricul-
include lead, antimony, arsenic, beryllium, cadmium, chro- ture and forestry settings. This is to alleviate concerns for the
mium, cobalt, manganese, nickel, selenium, and phos- lubricant’s unintended release into the environment and
phorus. Organic materials that are regulated include phenol; causing harm.
chlorinated organics, such as PCBs, dichlorobenzene, and One of the major challenges is to meaningfully evaluate
trichloroethylene; fused ring hydrocarbons, such as naph- a lubricant biodegradability. This requires the existence of
thalene, phenanthrene, anthracene, pyrene, benz共a兲an- suitable tests. An additional problem is defining the level of
thracene, chrysene, and benzo共a兲pyrene; and aromatic es- biodegradability that is considered acceptable. To exacer-
ters, such as dibutyl phthalate, butyl benzyl phthalate, bis共2- bate the problem further, of a dozen or so tests that are used
ethylhexyl兲 phthalate. worldwide to assess biodegradability, each uses different test
criteria and conditions. These cause variances, making it dif-
Environmental Compatibility ficult to develop a universal standard. Another complex issue
As described in Chapter 7, a number of terms are used to de- that needs to be resolved is to distinguish between environ-
scribe a lubricant’s compatibility with the environment. mental friendliness and biodegradability. Unlike biodegrad-
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592 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
ability, which is based upon specific test data, the term envi- • RALUZ-64 Lubricating oils and greases 共also appli-
ronmental friendliness is purely subjective. According to one cable to concrete mold release agents兲
interpretation, environmentally friendly implies that the lu- 2. Sweden 共Swedish Standard兲
bricant is not toxic and is biodegradable within a short time. • SS 155434 Hydraulics
There is no suggestion on how to test toxicity and which test • SS 155470 Greases
organisms to use. According to another interpretation, the 3. Nordic Countries 共Nordic Swan兲—Lubricating oils 共in-
term environmentally friendly suggests the existence of cluding chain oil, mold oil, hydraulic oil, two-stroke
some adverse environmental effects, but with minimal nega- cycle-oil, lubricating grease, metal cutting fluid, and
tive impact. transmission/gear oil兲
In Europe, there is consensus on which test methods 4. The Netherlands 共VAMIL regulation兲
and organisms to use and the duration of the tests. However, • Hydraulics
there is a need to agree on an acceptable test result for an en- • Greases
vironmentally acceptable lubricant. In addition to testing for 5. Austria
short-term compatibility, it is also important to consider the UZ 14 Chain Saw oils
long-term effects of the lubricants on the environment, 6. France 共NF-Environment Mark兲
which are a function of the nature of the base fluid, additive • Chain saw oils
chemistry, and the ability to recycle. As mentioned earlier, • ISO 15380
environmental compatibility of the lubricant in off-road • Hydraulics
natural settings is absolutely critical. In these applications, The ecological requirements for these standards include
up to 75 % of the lubricants used must be environmentally biodegradability, aquatic toxicity, and renewability 共recycla-
friendly. This is especially true in Europe, where strict na- bility兲. This suggests that to assess overall environmental ef-
tional standards have led to wide adoption of the environ- fects of a lubricant beyond biodegradability may require
mentally friendly fluids. European national standards that more testing and understanding of how the lubricant com-
are presently in effect include the following. Further review ponents perform, functionally and ecologically, at all stages
of these standards is presented in Ref 关829兴. of their lifetime 关826兴.
1. Germany 共Blue Angel兲 As stated in Chapter 3, Europe is considering Eco-
• RAL UZ-79 Hydraulics labeling the lubricants. Eco-labeling is a voluntary scheme
• RAL UZ-48 Rapidly Biodegradable Chain Lubri- designed to encourage businesses to market products and
cants for Motor Saws services that are kinder to the environment and for Euro-
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CHAPTER 13 䊏 LUBRICANTS AND THE ENVIRONMENT 593
pean consumers, both public and private purchasers, to eas- the organisms in the areas where the material has been re-
ily identify them. Flower is the symbol used for this purpose leased or spilled. Although field studies are the most realistic
关827兴. Eco-labeling is mainly driven by the wish of the Euro- way of evaluating all possible chemical effects, they are un-
pean industry and the users to harmonize many of the exist- able to quantify the level of harm caused by the release. This
ing national eco-labels, which are listed above. At this time, is because of the continuously changing exposure concen-
five classes of lubricants have been proposed to be included trations due to diffusion away from the point of release,
in the labeling scheme. These are hydraulic fluids, chain saw movement to other media 共i.e., transport between soil, water,
lubricants, gear oils, greases, and concrete mold release sediment, and air兲, and degradation 共biological and abiotic兲
agents. The proposed criteria and the scientific evidence of the material. A more reliable approach is to evaluate the
supporting the inclusion are based on the criteria described inherent hazards of a material by testing its chemical proper-
in the German Blue Angel and the Nordic Swan standards. ties in the environmental components under carefully con-
Life cycle assessments 共LCAs兲 are included while evaluating trolled laboratory settings 关831兴. Toxicity to organisms may
fluids. In the case of the lubricants, the biodegradability is be determined in a single species test using suitable organ-
not the main criterion, but all cradle-to-grave processes are. isms under carefully controlled, constant environmental
Figure 13.6 shows examples of the life cycle analyses of lu- conditions. The advantages of using controlled conditions
bricants based on vegetable oil and mineral oil 关828兴. For de- are that direct comparison among test samples is possible
tails of the steps in these schemes and the typical findings and the test results can be extrapolated to the environment.
and limitations of the past LCAs, see Ref 关829兴. Incidentally, This is due to the development of the predictive models.
the Council of European Union have recent adopted a new Physical properties that are especially relevant to the envi-
law, called the REACH legislation, which went into effect on ronmental behavior of the substances include water solubil-
June 1, 2007. The acronym stands for Registration, Evalua- ity, vapor pressure, etc. While these properties are easy to
tion, and Authorization of CHemicals. The objective of the measure in pure substances, they are not easy to measure in
new legislation is to avoid chemical contamination of air, mixtures. Hence, for substances with multiple components,
water, soil, and the human environment 关830兴.
specific test methods must be applied that measure range
The environmental compatibility requirements for off-
rather than the average value of the property. It is also impor-
road lubricants are changing, not only for base stocks but
tant to know the chemical structure and composition of the
also for additives. For example, one of the most effective
test sample. Table 13.9 lists substance properties that are of
types of additives used in heavy-duty hydraulic fluids is zinc
importance in determining a chemical’s entry into the envi-
dialkyl dithiophosphates, potent antiwear and extreme-
ronment 关831,832兴.
pressure additives. Zinc, being a heavy metal, is undesired
The knowledge of the chemical structure and the com-
and the new antiwear technology developed for use in biode-
position of the substance, in this case the lubricant, are im-
gradable lubricants is metal-free, or ash-less. However, for
portant because they impact many other properties. For ex-
the traditional hydraulic fluids, zinc dialkyl dithiophos-
ample, hydrocarbon lubricants will have greater lipophilic
phates are here to stay, primarily for economic reasons. As
character than the water-based lubricants or the extremely
eco-friendliness moves beyond biodegradability, lubricant
polar triaryl phosphate lubricants which have a consider-
marketers may have to demonstrate an understanding of the
able affinity towards water. Similarly, more polar additives,
lifecycle issues, sooner or later.
such as oleic acid and low molecular weight alkenylsuccinic
Need for Standardized Testing acids, which are used in certain lubricants to reduce friction
The potential for materials to cause harm to the environ- and control rust, will have significantly higher water solubil-
ment must be evaluated. The most obvious way is to examine ity than their higher molecular weight analogues, such as
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594 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
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596 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
Guidelines, is OECD 301B CO2 Evaluation Test 共Modified degradation to CO2 or O2 or 70 % removal of the dissolved
Sturm兲: Biodegradability Assessment for Water Soluble and organic carbon 共DOC兲 within 28 days. Further, the pass cri-
Insoluble Chemical Compounds and Formulations. teria must be met within ten days after biodegradation ex-
Eurospec distinguishes between ready and inherent bio- ceeds 10 % of the mass loaded 关839,840兴. Ready biodegrada-
degradability 关747兴. Inherent biodegradability is used to de- tion tests are so stringent that the substance that passes the
scribe organic compounds, which are not readily biodegrad- test will rapidly degrade under most environmental condi-
able within 28 days. However, they must exhibit levels of tions. ASTM Test Method D 5864, which includes the OECD
degradation similar to those that are readily biodegradable 301B Modified Sturm procedures, evaluates biodegradation
over prolonged exposure periods. A chemical, which shows of the fully formulated lubricants or their components. It de-
ultimate biodegradation in this situation, is likely to be con- termines both the rate and the degree of the aerobic aquatic
sidered as nonpersistent in the environment. A failure to biodegradation, when exposed to an inoculum under labora-
show biodegradation after prolonged exposure renders the tory conditions. The inoculum may be the activated sewage-
chemical as nonbiodegradable, or persistent. If a product sludge from a domestic sewage treatment plant, may be de-
does not pass the 28-day readily biodegradable part of the rived from soil or natural surface waters, or any
test, the chemical producer must consider if it wants to sub- combination of the three sources. The bacterial microorgan-
ject the material to inherently biodegradable portion of the isms used in the biodegradation tests are some of the sim-
test, which can take 84 days to complete. For a detailed dis- plest forms of life, and like all living organisms, are adversely
cussion on biodegradability testing, see Ref 关837兴. affected by the presence of the chemical toxins. In this test,
Like abiotic degradation, biodegradation tests are many the low toxicity of the test sample is demonstrated by the mi-
关838兴. Certain standardized tests evaluate both the rate and croorganisms’ ability to multiply and biodegrade the
the extent of biodegradation 关831兴. The rate is described by sample. The degree of biodegradability is measured by cal-
the terms inherent and ready. Inherently biodegradable culating the rate of conversion of the lubricant to CO2. This
means that the biodegradability is proven by any established test method is intended to specifically address the difficulties
test method. Degradation in the test must be at least 20 % but associated with testing the water insoluble materials and
the duration is not specified, which may imply as long as complex mixtures such as those that are found in many lu-
needed. Tests used to determine inherent biodegradability bricants. This test method is designed to be applicable to all
include OECD 302A SCAS 共ISO 9887兲, OECD 302B ZAHN- lubricants that are not volatile and are not inhibitory at the
WELLENS 共ISO 9888兲, and OECD 302C MITI 共II兲. Readily test concentration to the organisms present in the inoculum.
biodegradable means that the substance 共lubricant兲 de- For the water soluble test substances, the suggested refer-
grades at least 80 % in salt water within 21 days. Most ence substances are sodium benzoate or aniline. For the wa-
readily biodegradable fluids are based upon naturally occur- ter insoluble test substances, the suggested reference sub-
ring triglycerides 共vegetable oils兲. Most common tests used stance is a low erucic acid rapeseed oil, also called LEAR,
to determine ready biodegradability are OECD 301A-F 共ISO such as canola oil. Other organizations that have accepted
7827, ISO 9439, MITI 共I兲, ISO 10707, ISO 9408, and ISO the % theoretical CO2 test method for determining the aero-
14593兲, OECD 310, and CEC L-33-A-93. bic aquatic biodegradation of lubricants include ISO,
In these tests, the substance must demonstrate 60 % OECD, U.S. EPA, and the EUC. A lubricant, hydraulic fluid,
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CHAPTER 13 䊏 LUBRICANTS AND THE ENVIRONMENT 597
or lubricating grease is classified as readily biodegradable soluble metabolites, which are difficult to extract and there-
when 60 % or more of the carbon of the test material is con- fore cannot measure extensive degradation or mineraliza-
verted into CO2 in 28 days, as determined by the use of this tion. The CEC method has identified the following trends in
test method. The test is considered complete when the CO2 lubricants 关747兴.
evolution reaches a plateau. The most established test meth- 1. Mineral oils, alkylated benzenes, PIB, PAOs, and poly-
ods used by the lubricant industry for evaluating biodegrad- 共alkylene glycol兲s have poor biodegradability, i.e., 0–40
ability of their products are Method CEC-L-33-A-94 devel- %.
oped by the Coordinating European Council 共CEC兲; Method 2. Vegetable oils 共triglycerides兲, diesters, polyol esters
OECD 301B, the Modified Sturm Test, developed by the Or- show good biodegradability, 共60–100 %兲. n-Alkyl mono-
ganization for Economic Cooperation and Development carboxylic acids are common in nature and often ap-
共OECD兲; and Method EPA 560/6-82-003, number CG-2000, pear as products from ˜ decarboxylation of the alkane
the Shake Flask Test, adapted by the U.S. Environmental moieties. Hence, they easily degrade as esters. The deg-
Protection Agency 共EPA兲. These tests also determine the rate radation products are also more soluble, although the
and the extent of aerobic aquatic biodegradation under labo- effects on the ecosystem and groundwater contamina-
ratory conditions. The Modified Sturm Test and Shake Flask tion are not known.
Test also calculate the rate of conversion of the lubricant into 3. Biodegradability of the aromatic polycarboxylate esters
CO2. The CEC test measures the consumption of the lubri- ranges from 5–80 %. Polyethers show poor biodegrad-
cant by analyzing the test material at various incubation ability but have the advantage of being water-miscible.
times by the use of the infrared spectroscopy. Laboratory Because of which they do better in tests that are based
tests have shown that the degradation rates may vary widely on oxygen consumption, carbon dioxide evolution, or
among the various test methods indicated above and com- organic carbon removal. According to these tests, biode-
paring the results from the different test methods for the gradability is between 0 to 80 %. Polyethers of higher
same or similar materials is not easy. This is because % deg- ethylene oxide content are more biodegradable than
radation is very dependent upon the type of biodegradability. those with higher propylene oxide.
A result of 100 % primary degradation in an inherent test 4. Biodegradability decreases if carbon number is less
cannot be compared with that of a ready test, where 100 % than C4 or greater than C25 and as the chain branching
degradation is not possible and the conditions are more increases.
stringent. Also, there are many other variables to be con- 5. Biodegradability depends on the available nitrogen and
cerned about 关831兴. phosphorus in the environment and the inoculum size,
OECD 301B modified Sturm test is adequate for soluble if the lab test assessment is made after 21 to 28 days.
and insoluble organic, nonvolatile materials. This test mea- Certain cultures of bacteria utilize tricresyl phosphate
sures the carbon dioxide evolved and therefore measures and zinc dialkyl dithiophosphate as carbon and phos-
only the “complete” oxidation. Organic impurities will com- phorus sources. Nitrogen heterocyclic may act as nitro-
plicate the interpretation of the carbon dioxide production gen sources and, if so, it may be possible to deliberately
data. While the test is designed to last 28 days, it may end formulate blends in which the additives supply the nec-
before if the degradation curve reaches a plateau for at least essary nitrogen, sulfur, and phosphorus for total base oil
three determinations. The test may also extend beyond degradation.
28 days if the biodegradation has started but the plateau has 6. Additives usually retard degradation in proportion to
not reached by Day 28. However, the test material will not be their concentration and are themselves poorly de-
classed as readily biodegradable. The pass levels for ready graded, especially those with heterocyclic structures,
biodegradability are 70 % removal of DOC 共dissolved or- such as triazine, and triazole.
ganic carbon兲 and 60 % of ThOD 共theory oxygen depletion兲 7. Typical values in the CEC L-33-T-82 biodegradability
or ThCO2 共theory carbon dioxide兲 production for the test for common hydrocarbons are 15–35 % for mineral
respirometric methods. The lower limits are to take into ac- oil, 25–45 % for white oil, 70–100 % for natural and veg-
count some of the carbon of the test chemical being retained etable oil, 5–30 % for PAO, 0–25 % for polyether, 0–25 %
in the new cells. These values must be attained within a for polyisobutylene, 5–80 % for phthalate and trimelli-
10-day window of the 28-day period of the test. The window tate esters, and 55–100 % for polyols and diesters.
starts when the degree of biodegradation reaches 10 % DOC Hydrocarbons are biodegradable to varying degrees.
and ThOD. Figure 13.7 compares biodegradability of the Part of the problem is their low water solubility, which de-
same material by various methods 关831兴. creases their availability to microorganisms. Aromatics,
The CEC L-33-T-82, now listed as CEC L-33-A-934 test which are somewhat more soluble, give better results in bio-
applies to most organic compounds, whether water soluble degradability tests than paraffinics, and among paraffins the
or insoluble and determines the overall biodegradability of linear structures are considered more biodegradable than
the hydrocarbons, or similar compounds containing the me- the branched structures. The outcome of the microbial oxi-
thylene 共CH2兲 groups, measuring all transformations of the dation is the formation of a carboxylic acid; hence the pres-
starting material including oxidation and hydrolysis. This ence of the steric hindrance due to branching slows down
CEC test is accepted in a number of Blue Angel Environmen- the process somewhat.
tal Labels and requires 80 % or greater biodegradability. De- Bioaccumulation is an increase in the concentration of
spite being convenient and easy, the CEC test only measures a chemical in a biological organism over time. Materials that
the IR absorbance of the lipophilic molecules extractable have the tendency to bioaccumulate are those that have high
into the chloroalkane solvent. It does not measure the water- affinity towards lipids and are therefore resistant to meta-
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598 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
bolic breakdown by plants and animals. A number of stan- the material. In order to relate the effects to exposure, one
dards, such as ASTM E1022, E1688, and E1676 are used to must define the duration of the exposure so that it is long
evaluate the tendency of a material to bioaccumulate enough to ensure maximum uptake of the material by the
关27,747兴. test organism. For testing low water solubility materials in
acute toxicity tests, such periods range from two days for
Toxicity Daphnia tests to four days for most fish tests. Test guidelines
Acute ecotoxicity of a substance is generally evaluated by usually require analytical conformation of the actual con-
conducting the acute toxicity tests. Such tests employ plants centration over the course of the exposure period so that the
共algae兲, vertebrates 共fish兲, and invertebrates 共daphnia兲. Acute collected data can be analyzed by the use of statistical tech-
toxicity towards soil is determined by testing on inverte- niques and to find the midpoint, or LC50 关841兴. See the ASTM
brates 共earthworms兲 and plants 共lettuce兲. Aquatic toxicity Standards E1847, E1023, and E729 关27兴. The same approach
data on additives is rarely available. Interestingly, some ad- is used to establish other effect endpoints, such as impact on
ditives, such as those used in food grade lubricants, are con- growth or reproduction, for chronic testing. Typically, lubri-
sidered to be too toxic towards other life but are considered cants are considered “difficult materials” for aquatic toxicity
safe to humans. The most common test methods used for testing, which is due to their low water solubility and being
evaluating the acute toxicity of the lubricants are ASTM complex mixtures. Hence, designing, conducting, and inter-
D6081 关27兴; EPA 560/6-82-002, Sections EG-9 and ES-6; and preting aquatic toxicity studies on such materials involve
OECD 203. These tests determine the concentration of a sub- special considerations 关842兴.
stance that produces a toxic effect on a specified percentage There are a number of issues that need to be addressed
of test organisms in 96 hours. The acute toxicity test is nor- because of the lubricants being of low water solubility. The
mally conducted using rainbow trout and the results are ex- acute LC50 values for a homologous series of chemicals are
pressed as concentration in parts per million 共ppm兲 of the hard to distinguish because of the little differences in solu-
test material that results in a 50 % mortality rate after bility across members. Also, as the hydrocarbon number in-
96 hours 共LC50兲. A substance, such as a lubricant, is gener- creases there is a point where the material solubility in water
ally considered acceptable if aquatic toxicity 共LC50兲 exceeds is too low to show an effect on mortality. The presence of the
1000 ppm 关841兴. water-soluble minor components can have a profound effect
Standardization of toxicity testing is important because on the test results and the toxicity observed in such samples
it takes variability out of the test, making test results more is not indicative of the toxicity of the bulk material. In some
reproducible. In the standardized tests, biological variability cases emulsifiers or solvents are used to improve the water
is reduced by using the organisms of selected species that are solubility of the poorly soluble substances. If there is no tox-
of the same age range, similar in size, and in good health, icity associated with these dissolution aids themselves, there
with no observable abnormalities 关838兴. With quality data, it is no problem using this approach 关841兴.
is possible to establish quantitative structure-activity rela- As mentioned earlier, the lubricants on account of being
tionships 共QSARs兲, which can be used to predict toxicity to complex mixtures are difficult to test. Most lubricants com-
aquatic organisms based on structural or physical proper- prise a base fluid as the major component, which either con-
ties of the substance 共ASTM E1242兲 关27兴. QSAR is the pro- tains the same size molecules or is a mixture of homologues
cess by which chemical structure is quantitatively correlated or isomers. These structural differences do not have much
with a well defined process, such as biological activity or effect on aquatic toxicity. This complicates evaluating their
chemical reactivity 关841兴. As with the biodegradation test toxicity. However, since most hydrocarbons are believed to
methods, each specific test provides data that are represen- show toxicity by the same mechanism and the effect to be ad-
tative of a specific aspect of the natural environment. The ditive, a toxic unit approach can be used to predict their
dominating factor relating the toxicity test to the environ- acute toxicity 关843兴. The approach involves determining the
ment is the mode of exposure. As with the variability associ- threshold value 共TV兲 of a component, which is the aqueous
ated with the test organisms, each test material has unique concentration of the component divided by the component’s
characteristics that must be considered when conducting a corresponding LC50. Then the threshold values of all compo-
standardized toxicity test. These include volatility, water nents in the mixture are added. If the result is greater than
solubility, and complexity/variability of the composition of one, the composition is considered toxic, and if it is less than
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CHAPTER 13 䊏 LUBRICANTS AND THE ENVIRONMENT 599
used oil fails this testing, it must be specially treated and tures are not suitable for use in space heaters. In some coun-
managed. The uncontaminated used oil is slowly heated to tries, the used oil is sprayed on coal to improve its coking
separate the water from the oil. The water is sent to a waste- qualities.
water treatment plant and the oil is filtered and blended with Air emissions associated with burning the used oil result
the crude oil or other potential fuels described below, and from the chemical constituents in the oil itself. Used oil con-
burned. tains residual additives or additive decomposition products.
Used oil has a high caloric value of 10,000 Kcal/ kg Additives that are of special concern are those that contain
共39,700 BTU/ lb兲; hence it is a good source of energy. There sulfur, phosphorus, halogens 共chlorine and bromine兲, and
are three burning options for the used oil. These are inciner- transition and heavy metals, such as zinc, barium, lead, and
ating at high temperatures, for example, in cement and lime molybdenum; as well as the aromatic organics, such as
kilns, burning untreated used oil, and blending it with the naphthalenes and phenols. In addition, many of the used oils
fuel oil, prior to burning. Incineration is the most effective contain wear metals, such as arsenic, chromium, cobalt,
way of destroying the used oil since it does not require any
manganese, and nickel. While recycling can remove many of
pretreatment. This is because the very high combustion tem-
these products through filtration and re-refining, when
peratures and long retention times in the burning zone en-
burned in space heaters and in industrial furnaces, the con-
sures the destruction of the toxic compounds. This mini-
taminants in the used oil are discharged into the atmosphere
mizes the environmental disposal costs. However, it is a low
or stay in the ash. Industrial facilities scrub emissions prior
value option. Burning the untreated used oil, especially in
space heaters, is also inadvisable since it merely releases the to their release into the air and dispose of ash by sending it to
harmful components into the environment. Used oil space the landfills. Industrial users sometimes remove metal de-
heaters are essentially regular oil heaters that are slightly bris from the lubricant through filtration, prior to burning. It
modified to burn less volatile and more viscous engine oils lowers the amount of ash that needs to be disposed of. In Fig.
and other hydrocarbon lubricants. Though modified, these 13.5, we show various applications where the used oil is
heaters operate without pollution controls. Burning used oil used. Each application has its own requirements and specifi-
in space heaters is a small volume use and hence it is very cations, or both. Specifications for burning for energy recov-
difficult to get rid of the used oil in large volume by this ery are summarized in Table 13.14. State-specific rules can
method. Mixing the used oil with another fuel, such as gaso- vary, but the federal rules that must be adopted by each state
line, diesel, kerosene, Jet-A fuel, or fuel oil produces rich as the minimum requirements are found under Title 40 of
combustible mixtures and is a better option. Such mixtures the Federal Regulations at Part 279. The EPA also maintains
can be used in industrial facilities if they are registered with a Website for the used oil which can be accessed at
the EPA to power various operations. Incidentally, such mix- www.epa.gov/epaoswer/haswaste/usedoil/.
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MNL59-EB/Mar. 2009
Copyright Permissions
1. Title Cover Background — 2008 GMC Sierra Heavy-duty 共GMT900兲 Allison 1000 Six-speed Automatic Transmission
and 2005 GMC Canyon Double Overhead Cam In-Line 4-Cylinder Engine — Courtesy of General Motors.
2. Figure 4.140 and 11.16 — Mandakovic, R., “Assessment of EP Additives for Water Miscible Metalworking Fluids,” J.
Syn. Lubr, Vol. 16, No. 1, 1999, pp 13–26. © John Wiley & Sons Limited. Reproduced by permission.
3. Figures 3.14, 3.28, and 3.46 — van der Waal, G., “The relationship Between the Chemical Structure of Ester Base
Fluids and Their Influence on Elastomer Seals and Wear Characteristics,” J. Syn. Lubr. Vol. 1, No. 4, 1985, pp. 281–
301. John Wiley & Sons Limited. Reproduced by permission.
4. Figures 4.30, 4.147, and 4.148 — Hamblin, P. C., Kristen, U., and Chasan, D., “A Review: Ashless Antioxidants, Cop-
per Deactivators, and Corrosion Inhibitors, Their Use in Lubricating Oils,” Lubrication Science, Vol. 2, 1990, pp.
287–318. John Wiley & Sons Limited. Reproduced by permission.
5. Tables 2.4, 3.17, 4.13, 5.25, 5.26, 5.28, 5.29, 5.37, 7.4, 7.5, 7.6, 7.7, 7.8, 7.9, 7.10, 7.40, 7.41, 7.42, 7.43, 8.10, 8.15, 9.3,
9.4, 10.10, and 10.30. © The Lubrizol Corporation. Reproduced by permission.
6. Figures 1.18, 1.20, 1.21, 1.22, 1.23, 1.24, 1.25, 1.26, 1.27, 4.64, 4.189, and 5.35. © The Lubrizol Corporation. Repro-
duced by permission.
7. Figures 4.160 — Rempp. P. and Herz, J. E. “Model Polymers,” Concise Encyclopedia of Polymer Science and Engi-
neering, J. I. Kroschwitz Editor, 1990, pp. 633–634, Wiley InterScience. John Wiley & Sons Limited. Reprinted with
permission.
8. Tables 6.3 to 6.15 and 6.18 to 6.24. © DieselNet.com Reproduced by permission.
9. Figures 5.19 to 5.33. © Southwest Research Institute — SwRI® 共http://www.swri.org兲. Reproduced by permission.
10. Figures 10.7, 10.14, 10.16, 10.17 and Tables 10.17, 10.19, 10.24 to 10.29. © National Lubricating Grease Institute,
Missouri, USA. Reproduced by permission.
11. Figure 11.4 and Tables 11.9, 11.10, and 11.14. © BlueScope Steel Corporation. Reproduced by permission.
12. Figures 1.3, 4.8, 4.112, 4.115, 4.157, 4.158, 4.181, 4.182, 6.18, 6.25, 6.41, and 11.2; Table 2.1. Society of Automotive
Engineers 共SAE兲. Reproduced by permission.
13. Figure 8.9. Author Y. Kamura, “Some Problems in the Adhesion Theory of Friction,” Fundamentals of Tribology, N.
P. Suh and N. Saka Editors, Published by MIT Press, Cambridge, 1980, pp. 385-391. © MIT Press. Reproduced by
permission.
14. Figures 4.145, 5.11, 5.13, 8.2, 8.10, 11.6, 12.12; Tables 10.5, 10.7, 10.31, and 12.12; and some items from Glossary of
Terms. © ASM International. Reproduced by permission.
15. Figures 2.12, 4.120, 4.129, 4.130, 4.133, 4.134, 4.135, 4.139, 4.141; Tables 2.13 and 3.9. © Society of Tribologists and
Lubrication Engineers 共STLE兲. Reproduced by permission.
16. Figures 5.14 and 8.11. © Energy Institute UK. Reproduced with kind permission of the Energy Institute UK.
17. Tables 2.8, 4.24, 7.3, 7.24, 7.32, 7.35, 12.14, 12.15, 12.16, 12.17, 13.1, 13.2, 13.3, 13.4, 13.5, 13.6; Figures 3.49, 3.52,
4.154, 8.4, 13.1. Copyright 1983 — From CRC Handbook of Lubrication: Theory and Practice of Tribology, Vol. I —
Application and Maintenance, E. Richard Booser Editor. Reproduced by permission of Taylor & Francis Group,
LLC, a division of informa plc.
18. Tables 3.20, 3.21, 4.16, 4.17, 4.20, 7.18, 10.9, 12.1, 12.2, 12.3, 12.4, 12.13; Figures 4.102, 4.103, 4.126, 4.127, 4.136,
4.137, 4.145, 8.8, 12.2, and 12.3 Copyright 1988/1989 — From CRC Handbook of Lubrication: Theory and Practice
of Tribology, Vol. II — Theory and Design, E. Richard Booser Editor. Reproduced by permission of Taylor & Francis
Group, LLC, a division of informa plc.
19. Tables 3.1, 4.23, 7.44, 7.45, and 9.1; Figures 3.9, 3.10. 7.10, and 9.1 Copyright 1993/1994 — From CRC Handbook of
Lubrication and Tribology, Vol. III — Monitoring, Materials, Synthetic Lubricants, and Applications, E. Richard
Booser Editor. Reproduced by permission of Taylor & Francis Group, LLC, a division of informa plc.
20. Figures 4.35, 4.36, 4.37. 4.170, and 11.15; Tables 4.14, 4.15, 4.19, 4.21, 4.22, 4.29, 4.32, 10.8, 11.19, and 11.21 Copy-
right 2003 — From Lubricant Additives: Chemistry and Applications, Leslie R. Rudnick Ed., Marcel Dekker, Inc. Re-
produced by permission of Taylor & Francis Group, LLC, a division of informa plc.
21. Figures 2.2, 3.15, 4.16, 4.19, 4.20, , 4.140, 4.142, 4.179, 4.183, 5.15, 4.40, 7.64; Tables 3.4 and 7.28. Springer. Repro-
duced by permission.
22. Figures 6.28, 6.29, 6.30, 6.36, 6.37, 6.38, 6.40, 6.46, and 6.47. Chevron Corporation. Reproduced by permission.
23. Fig. 3.54 共Source: Cargill兲; Fig. 4.97–4.99 共Source: Ken Crosthwaite et al., ExxonMobil, NPRA Lubricants and Waxes
Paper, November 1999兲; Fig. 4.100 共Source: G. Bleimschein, J. Fotherigham, and A.Plaomar, BP Chemicals兲; Fig.
4.192 共Source: ILSAC兲; Figs. 5.43, 5.44 共Source: Cummins兲; Figs 6.33 共Source: Argonne兲. © Lubes’N’Greases, Repro-
duced by permission.
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Appendix
Acronyms for Organizations and the Terms Air Entrainment—Incorporation of air in the form of
Related to Lubricants, Lubrication, and Tribology bubbles as a dispersed phase in the bulk liquid. Air entrain-
†667‡ ment may be because of the mechanics of the system or by
AAM—Alliance of Automobile Manufacturers. the release of the dissolved air due to a sudden change in en-
AAMA—American Automobile Manufacturer Associa- vironment, or both. Appearance of a liquid, such as being
tion. bubbly, opaque, etc., is an indication of air entrainment. It is
ACC—American Chemistry Council. important to note that the dissolved air can only be deter-
Abrasion „Abrasive Wear…—A process in which hard mined by analysis.
particles or surface roughness 共protuberances兲 are forced Alkali—While chemically any substance with basic
against and moving along a solid surface causing displace- properties 共alkaline兲 is considered an alkali, the term usually
ment of material. Also, see Abrasive Erosion. implies hydroxides of ammonium, lithium, potassium, and
Abrasive Erosion—Erosive wear caused by the relative sodium. The last three are members of the class of alkali met-
motion of solid particles which are entrained in a fluid, mov- als. These substances are water soluble and have the ability
ing nearly parallel to a solid surface. to neutralize acids. The term is also extended to the hydrox-
ACEA—Association des Constructeurs Européens de ides of the alkaline earth metals, such as magnesium, cal-
l’Automobile 共Association of European Automotive Manu- cium, barium, and strontium.
facturers. Alkylaromatics „Alkylbenzene and
Acidity—The amount of free acid in any substance. Alkylnaphthalene…—These additives, made by the alkyla-
Acid Number—A measure of the amount of potassium tion of benzene and naphthalene, are used as base fluids as
hydroxide 共KOH兲 needed to neutralize all or part of the acid- well as sulfonated to sulfonic acids to make detergent addi-
ity in a petroleum product. tives.
ACS—American Chemical Society. Alkylbenzenesulfonic and Alkylnaphthalene-
Additive—In lubrication, a material added to a base sulfonic Acids—These are used to make detergent additives
stock for the purpose of imparting new properties or of en- by their reaction with an alkali metal or an alkaline earth
hancing its existing properties. Major classes of additives in- metal base, with or without carbon dioxide.
clude dispersants, detergents, oxidation inhibitors, viscosity Alkylphenol—Product of alkylation of phenol. Some
modifiers, and antiwear/extreme pressure agents. alkylphenols, such as 2,6-di-t-butylphenol and its derivatives
Additive Treat Level—The total percentage of all addi- are used as oxidation inhibitors in lubricants. Others, such
tives in a lubricating oil or grease. as dodecylphenol, are converted into metal salts, called
Adherence—Physical attachment, either by adhesion phenates, for use as detergent additives.
or by other means, of a material to a surface. Alkylsalicylic Acid—Made from alkylphenol by base
Adhesion—Attraction or joining of two materials. The catalyzed carbonation. Used as a starting material for mak-
strength of adhesion is reflected by the force or forces neces- ing alkaline earth metal salicylate detergents for use in en-
sary to separate them. In frictional contacts, adhesion is the gine oils.
attractive force between adjacent surfaces. In physical Almen EP Lubricant Tester—A journal bearing ma-
chemistry, it is the attraction between a solid surface, such as chine used for determining load-carrying capacity or ex-
metal and a second liquid or solid phase, such as lubricating treme pressure properties of the gear lubricants, or both.
grease. In some instances, adhesion is reversible but in oth- ALTENER—Alternative Energy Programme of the Eu-
ers, it is irreversible. When adhesion is solely due to inter- ropean Commission.
locking of the asperities, it is called mechanical adhesion. AMT—Automated Manual Transmission.
Adhesive Wear—Wear caused by the transfer of mate- ANFAVEA—Auto Manufacturers Association 共Brazil兲.
rial from one surface to another during movement 共tearing兲 Anhydrous—Free of water. Term is often used to de-
of the solid-phase welded surfaces. Welding occurs due to scribe lubricating grease.
frictional heat resulting from metal-to-metal contact. The Aniline Point—The lowest temperature at which equal
particles removed from one surface are either permanently volumes of aniline and a hydrocarbon liquid 共fuel or lubri-
or temporarily attached to the other surface. cant base stock兲 are completely miscible. A lower aniline
AF,AFR—Air/Fuel Ratio. point is a measure of high aromatic content of the liquid.
AFNOR—Association Française de Normalisation. Aniline point is used to assess solvency of a base stock or the
AFV—Alternative Fuel Vehicle. cetane number of distillate diesel fuel. A product of high
Age Hardening—An increase in consistency 共harden- aniline point will be low in aromatics and naphthenes and,
ing兲 of greases over time. Also see Thixotropy. therefore, high in paraffins. In conjunction with API gravity,
AGELFI—Co-operative Research Organisation of the the aniline point may also be used to calculate the net heat of
oil companies AGIP, ELF and FINA. combustion of aviation fuels.
AGMA—American Gear Manufacturers’ Association. ANSI—American National Standards Institute.
AGO—Automotive Gas Oil. Anticorrosion Additive—See Corrosion Inhibitor.
AHEM—Association of Hydraulic Equipment Manu- Antifoam Agent/Additive—See Foam Inhibitor.
facturers. Antifriction Bearing—A type of bearing that employs
603
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rollers or balls. They are also called rolling element bearings. Aromatic—Derived from, or characterized by, the pres-
These may or may not contain a solid lubricant. ence of a benzene ring.
Antifriction Material—Material that exhibits low- Arylsulfonic Acid—Also see Alkylbenzenesulfonic Acid
friction or self-lubricating properties. and Alkylnaphthalenesulfonic Acid. Alkylbenzene sulfonic
Antiknock—Resistance to detonation or pinging in acids can be natural or synthetic in origin. Natural sulfonic
spark-ignition engines. acids are obtained as by-products during base oil manufac-
Antioxidant—See Oxidation Inhibitor. ture. Synthetic sulfonic acids are obtained from alkylation of
Antiscuffing Lubricant—Lubricant that is formulated benzene.
to avoid scuffing, a type of wear damage. A more descriptive ASEAN—Association of South-East Asian Nations.
name is extreme-pressure lubricant. Ash—Metal-derived deposits formed in the combustion
Antiseizure Property—Ability of a bearing material to chamber and other engine parts during high-temperature
resist seizure during momentary lubrication failure. operation.
Antistatic Additive—Additive that increases the con- Ash Content—Residue in weight percent left after com-
ductivity of a hydrocarbon fuel to quickly dissipate electro- bustion of a sample of a petroleum product.
static charge during fast dispensing, thereby reducing the ASLE—American Society of Lubrication Engineers,
fire/explosion hazard. Now called Society of Tribologist and Lubrication Engineers
Antiwear Additive—Lubricant additive used to reduce 共STLE兲.
wear. Additives or their reaction products form thin, tena- ASM—American Society of Metals.
cious chemical films on highly loaded parts to separate the ASME—American Society of Mechanical Engineers.
potentially contacting surfaces. Asperities—Small irregularities on a solid surface.
Antiwear Agents—See Antiwear Additive. Shape, size, and mechanical properties of asperities are the
Antiwear Number „AWN…—A variant of the wear coef- basis for developing many theoretical models for friction, lu-
ficient 共k兲. AWN= −log10 k brication, and wear.
Anti-weld Characteristic—See Antiseizure Property. Asphalt—Black to dark-brown solid or semi-solid ma-
APE—Association of Petroleum Engineers 共USA兲. terial left during petroleum refining after removal of fuels
API—American Petroleum Institute. and lubricant base stocks. Bitumens are the primary con-
API Engine Service Classification System— stituents of asphalt.
Classifications and designations for automotive engine oils Asphaltic—Materials that are largely composed of or
developed by API in conjunction with SAE and ASTM. are similar to asphalt. Term is often used to describe lubri-
API Gravity „API Degree…—Measure of density used in cating oils derived from crude oils which contain asphalt.
the U.S. petroleum industry where: API° ASTM—International 共formerly American Society for
= 关共141.5/ Specific Gravity at 60 ° F兲兴 − 131.5. Testing and Materials兲, whose D2 Committee deals with Pe-
API Oil Group—Classification of base fluids, both troleum Products and Lubricants.
petroleum-derived and synthetic, based on VI and sulfur ASTM Colorimeter—Apparatus widely used for deter-
content, for use in formulating lubricants. mining the color of lubricating oil 共ASTM Method D1500兲.
Apparent Area of Contact—Area of contact between The color so determined is known as ASTM Color.
two solid surfaces defined by the boundaries of their macro- ASTM Viscosity-Temperature Equation—Relates ki-
scopic interface. nematic viscosity 共v兲 with temperature.
Apparent Viscosity—Ratio of shear stress to shear rate ATC—Technical Committee of Petroleum Additives
of a non-Newtonian fluid, for example, thickened lubricants, Manufacturers 共Europe兲.
such as viscosity modified oils and greases. In greases, the ATEIL—Association Technique de l’Industrie Eu-
apparent viscosity depends on shear rate and temperature. ropéennes des Lubrifiants.
Hence, both these parameters must be specified while re- ATF—Automatic Transmission Fluid.
porting apparent viscosity. Auto-ignition—Spontaneous ignition and the resulting
Appearance/Bulk Appearance—General term relat- rapid reaction of a portion or all of the fuel-air mixture in an
ing to characteristics that are observable by visual inspec- engine. The flame speed is many times greater than that of
tion. It is usually reported for greases as bloom, color, luster, normal spark ignition. The noise associated with it is called
and texture. Bulk appearance determination involves an ex- knock.
amination of the grease surface in an undisturbed state and Automatic Transmission Fluid „ATF…—Lubricant/
is expressed as bleeding, cracked, grainy, rough, smooth, hydraulic fluid used in automotive transmissions.
bright, dull, etc. Bactericide—See Biocide.
1. Bleeding, if there is free oil on the surface. Base—Compound that reacts with acids to form salts
2. Cracked, if there are surface cracks. and water. Alkalis are water-soluble bases that are used in pe-
3. Grainy, if the surface contains granules or lumps. troleum refining to remove acidic impurities. Oil soluble
4. Rough, if the surface shows irregularities. bases are used as lubricant additives to neutralize acids
5. Smooth, if surface is free of irregularities. formed during the combustion and oxidation of the lubri-
6. Bright, if it reflects light with a relatively strong inten- cant.
sity. Base Number—Amount of acid 共perchloric or hydro-
7. Dull, if it reflects light with a relatively weak intensity. A chloric兲 needed to neutralize part or all of a lubricant’s basic-
high water content or certain thickeners and fillers may ity. When the acid in a sample is completely neutralized, the
impart lubricating grease dull luster. base number is called the total base number 共TBN兲. Base
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䊏 APPENDIX 605
number is usually expressed as mg KOH/g of sample, the BOCLE—Ball on Cylinder Lubricity Evaluator.
same as the acid number. Body—Nonscientific term used to designate viscosity or
Base Stock—Base fluid, usually a refined petroleum consistency.
fraction or a selected synthetic material, into which addi- BOI—Base Oil Interchanger.
tives are blended to produce finished lubricants. Base stock Boiling Point—Temperature at which a substance ex-
comprises major portion of the lubricant. periences a phase change from being liquid to vapor. Boiling
Basic Sulfonate—See Overbased Sulfonate. point is directly affected by pressure: It increases with an in-
Batch—Quantity of material handled or considered as a crease in pressure and decreases with a decrease in pressure.
unit in processing. Bonded Film Lubricant—See Bonded Solid Lubri-
Bath Lubrication—See flood lubrication. cant.
Bentonite—Mineral montmorillonite, a magnesium- Bonded Solid Lubricant—Solid lubricant dispersed in
aluminum silicate, which is used as a component of drilling a continuous matrix of a binder, or attached to a surface by
mud and a thickener in greases. the use of an adhesive material.
BHRA—British Hydromechanics Research Associa- Boundary Lubricant—Lubricant that protects metal
tion. surfaces against wear under boundary conditions. This type
Bingham Solid—An idealized solid that begins to flow of lubricating environment occurs when the loads are high
appreciably only when the amount of applied stress exceeds and speeds are low. Boundary lubricants contain sulfur and
its yield stress. After which the flow rate is proportional to phosphorus containing antiwear or extreme pressure 共EP兲
the difference between the applied stress and the yield stress. additives that prevent surface wear damage by making resil-
Many lubricating greases can be considered as Bingham sol- ient chemical surface films. Boundary conditions exist in
ids. bearings, gears, and some metalworking operations. Also
Biocide—Additive used to inhibit bacterial growth in see Elasto-hydrodynamic Lubrication, Extreme-pressure
the water-based hydraulic and metalworking fluids. Lubrication, and Thin-film Lubrication.
Biodegradation—Process of biochemical breakdown Boundary Lubrication—Lubrication environment in
or transformation of a substance caused by micro- which the lubricant film is too thin to effectively separate
organisms and their enzymes. mutually rubbing surfaces and as a result, contact of surface
BIS—Bureau of Indian Standards. asperities occurs. Consequently, friction and wear protec-
Bitumen—Also called asphalt or tar, bitumen is the tion are determined by the chemical nature of the lubricant
brown or black viscous residue left after the vacuum distilla- rather than its bulk properties.
tion of crude petroleum. It consists of high molecular weight Break-in—See running-in.
hydrocarbons and minor amounts of sulfur and nitrogen Break In—Operate a newly installed bearing, seal, or
compounds. other tribo-component to condition its surface共s兲 for im-
Black Oils—Lubricants that contain asphaltic materi- proved functional operation. The term run in is also used to
als, which improve adhesion and hence they are used to lu- describe this process.
bricate open gear systems and steel cables. Bright Stock—Refined, high viscosity lubricating base
Bleeding—Oil released on the surface of a lubricating stock obtained from residual stocks by the use of processes
grease when it is not in service. such as acid treatment, solvent extraction, dewaxing, and or
Blending—Process of mixing various lubricant base clay finishing. These stocks have low pour points, excellent
stocks to obtain base oils/fluids of desired physical proper- solvency, and superb viscosity-pressure relationship.
ties. Brookfield Viscosity—Apparent viscosity of a non-
BLF—British Lubricants Federation. Newtonian fluid at controlled temperature and shear rate as
Block Grease—Lubricating grease that is sufficiently measured by Brookfield viscometer.
hard to maintain its shape in block or stick form. BRT—Ball Rust Test.
Bloom—Typical blue or green surface color of a grease BSI—British Standards Institution.
when viewed by reflected daylight. The color is associated BSN—Bacharah Smoke Number.
with the absorption of the ultraviolet light in the oil and is BTC—British Technical Council of the Motor & Petro-
not always visible when the sample is viewed by artificial leum Industries 共UK National Body in CEC兲.
light. BTU—British Thermal Units.
Bloom Fluorescence—Different color of an oil in re- Built-up Edge—Material collected from the machining
flected light than in transmitted light. For some applications, of a work piece that is collected at the edge of the cutting tool.
oils with yellowish-green bloom are preferred over those Also see wedge formation.
with bluish-green bloom. This demand is met either by spe- Burning—Oxidation of a surface due to local heating in
cial processing or by the use of fluorescent additives. an oxidizing environment that commonly occurs in sliding
Blow-by—Unburned and partially burned fuel and contacts.
combustion gases that travel past the piston rings into the Burnish—Alteration of an originally machined surface
internal combustion engines. This not only results in fuel di- to a more polished condition as a consequence of sliding or
lution of the lubricant and its contamination, but also results rolling action.
in extensive oxidation of the oil by the chemically reactive CAFE—Corporate Average Fuel Economy.
species and free radicals that are present in the blow-by. Cam—Eccentric shaft that is used in most internal com-
Blown Oil—Fatty oil artificially thickened by blown air. bustion engines to coordinate opening and closing of the
BNP—Bureau de Normalisation des Petroles. valves.
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CL „Cleanliness level…—A measure of relative freedom ping point of the resulting greases is effectively increased.
from contaminates. Complexing agent used in such soaps is a low molecular
CLR—Cooperative Lubrication Research. weight carboxylic acid, such as acetic acid or lactic acid, or
CMA—Chemical Manufacturers Association. inorganic salts, such as metal carbonate or metal chloride.
CNG—Compressed Natural Gas. Compounding—Process of mixing various additives in
CO—Carbon Monoxide. base oils/fluids to develop a finished lubricant of desired per-
CO2—Carbon Dioxide. formance. Certain industrial oils, called compounded oils,
Cocoa—Powdery debris resulting from fretting wear, contain fatty oils and similar materials which impart these
primarily consisting of iron oxides, that is expelled from a lubricants special properties. While compounding is differ-
ferrous metal joint near the location where fretting wear is ent from blending, it is important to note that most formula-
occurring. tors do not recognize the subtle distinction and use the terms
Coefficient of Adhesion—Ratio of the normal force re- compounding and blending interchangeably.
quired to separate two bodies to the normal load with which Compression Ratio—In an internal combustion en-
they were previously placed together. gine, the ratio of the volume of combustion space at bottom
Coefficient of Friction—Coefficient of static friction is dead center to that at top dead center.
the ratio of the tangential force initiating sliding motion to CONCAWE—Conservation of Clean Air and Water 共Eu-
the load perpendicular to that motion. Coefficient of kinetic rope兲.
friction 共usually called coefficient of friction兲 is the ratio of Cone Resistance Value „CRY…—A measure of the yield
the tangential force sustaining sliding motion at constant ve- stress of a grease, obtained by static indentation with a cone.
locity to the load perpendicular to that motion. In tribology, Also see Penetration.
the dimensionless ratio of the friction force 共F兲 between two Conformability—Quality of plain bearing material to
bodies to the normal force 共N兲 pressing these bodies together adjust itself to shaft deflections and minor misalignments by
共Ref. 2兲: or f = 共F / N兲. deformation or by wearing away, without creating operating
Cohesion—Molecular attraction causing particles of a difficulties.
substance to attract each other and stick together. Cohesion Consistency—Imprecise measure of the degree of a
contributes to the resistance of a lubricating grease to flow. plastic material, such as a lubricating grease, to resist defor-
Cold Cranking Simulator „CCS…—Intermediate shear mation under applied force 共load兲.
rate viscometer that predicts the ability of an oil to assure
Contact Lubrication „Obsolete Term…—Lubrication
satisfactory cranking speed in a cold engine.
obtained when solid lubricant powders get rubbed into a sur-
Colloid—Substances of particle size larger than mol-
face.
ecules, but small enough to possess reasonable dispersion
Conversion Coating—See Chemical Conversion Coat-
stability in two phase systems. For example, lubricating
ing.
grease is a colloidal system. See also Thickener.
Copper Strip Corrosion—Measure of the tendency of a
Color—Predominant hue of lubricating grease, could
petroleum product to corrode pure copper 共ASTM D130兲.
be natural or due to an added dye. Some lubricants are color
Corrosion—Chemical-related surface damage of the
coded to facilitate identification or recommended use. Ex-
metal. Corrosion involves the attack of the metals by oxygen,
amples include transmission fluids, brake fluids, and two-
sulfur, and acidic and basic chemicals. Chemically, corro-
stroke cycle engine oils. Color rating of dye-free oils is car-
sion is the oxidation of the metal to its oxides or salts. Rust-
ried out by the use of many methods, including the ASTM
D1500 procedure, under specified conditions and using spe- ing is the air-mediated formation of iron oxide and yellow
cialized equipment. Some oils that are too dark for direct metal corrosion is sulfur-mediated formation of copper sul-
rating are diluted to report color. fides.
Compatibility „Frictional…—Materials that exhibit Corrosion Inhibitor—An additive used to reduce cor-
good sliding behavior, including resistance to adhesive wear. rosion. Metals whose corrosion is of primary concern in
Some materials that are considered metallurgically incom- lubricant-related applications are iron, a copper, and lead.
patible, for example, silver and iron, may be frictionally very Corrosive Wear—Wear caused by a chemical or an elec-
compatible. trochemical reaction. See also Oxidative Wear.
Compatibility „Lubricant…—Measure of the degree to cP—centiPoise, the unit of dynamic viscosity.
which lubricants or lubricant components can be mixed CR—Common Rail 共Diesel Injection兲.
without phase separation or deterioration in performance. Cracking—Process of converting unwanted long-chain
Compatibility „Metallurgical…—Measure of the extent hydrocarbons into short-chain molecules by thermal or
to which materials are mutually soluble in the solid state. catalytic action. The latter is called catalytic cracking.
Complex Grease or Complex Soap Grease— Crater Wear—Wear that occurs on the rake face of a
Lubricating grease thickened by a complex soap consisting cutting tool due to the contact with the material in the chip
of a normal soap and a complexing agent. The use of soap that is sliding along that face.
complexes yields products which have higher softening CRC—Coordinating Research Council. Organization
points than greases made from normal soaps. supported by American Petroleum Institute and Society of
Complex Soap—Soap formed by co-crystallization of Automotive Engineers, which administers the work of vari-
two or more compounds. Complex soaps are mixtures of two ous committees pertaining to test work on fuels, lubricants,
or more components with structure or structures that im- engines, etc.
prove their oil-retaining ability. More specifically, the drop- Crown—Top of the piston in an internal combustion en-
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608 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
gine above the fire ring, which is exposed to direct flame im- Dilatant—Reversible increase in viscosity with an in-
pingement. crease in shear stress.
CRTV—Commercial Road Transport Vehicle. Dilution of Engine Oil „Oil Dilution…—Contamination
cSt—CentiStoke, the unit of kinematic viscosity. of the crankcase oil by the unburned fuel, leading to reduced
CSTCC—Continuously Slipping Torque Converter viscosity and flash point. Reduced oil viscosity may lead to
Clutch. poor lubrication; hence increased wear.
CUNA—Commissione Tecnica de Unificazione dell’ Au- DIN—Deutsches Institut für Normung.
toveicolo. Dirt Content—Measure of the size and concentration
Cut—Product or fraction obtained by distillation within of foreign particles present in a lubricant. Lubricant decom-
a specified temperature range. position products are also sometimes referred to as dirt.
Cutting Wear—See Abrasive Wear. Dispensability—Property of a grease which reflects the
CVT—Continuosly Variable Transmission. ease of a grease being dispensed from a container. Dispens-
Cyclohexane Derivatives—These fluids were devel- ability is related to pumpability and feedability.
oped for use in automotive transmission applications requir- Dispersant—Additive that is capable of dispersing oil-
ing high traction. insoluble lubricant decomposition products, such as var-
DAP—Detroit Advisory Panel. nish, lacquer and sludge precursors.
DASMIN—Deutsche Akkreditierungsstelle Mineralöl Dispersant Oil—Heavy-duty oil that contains dispers-
共Germany兲. ant additive.
Debris—See Wear Debris. Distillate—Any of a wide range of products produced
Deformability—See Conformability. by distillation of crude petroleum.
Deformation Wear—Sliding wear involving plastic de- Distillation—Process involving converting a volatile
formation of the wearing surface. liquid into its vapor and then collecting it as a liquid. Distilla-
Delamination Wear—Wear process in which thin lay- tion is also used to characterize volatility of a gasoline or dis-
ers of material are removed from the wear surface. tillate fuel.
Demulsibility—Measure of an organic water- DN Value—Product of bearing bore diameter in milli-
immiscible fluid’s ability to separate from water. metres and speed in revolutions per minute. DN value is used
Density—Mass per unit volume. Useful in formulating to select proper grease for bearings used in high speed appli-
lubricants with additives by volume and to calculate the cations.
amount of energy required to pump a fluid. DOHC—Double Overhead Cam 共Twin Cam兲.
DEO—Diesel Engine Oil. DOT—Department of Transportation.
DEOP—Diesel Engine Oil Advisory Panel 共API/EMA兲. Drawing Compound—Extreme-pressure lubricant
Detergent—Substance added to fuel or lubricant to used for such metalworking operations as wire drawing.
keep engine parts clean. In engine oil formulations, the most Drip Feed „Drop Feed… Lubrication—Lubrication sys-
commonly used detergents are basic metal sulfonates that tem in which the lubricant is supplied to a device in the form
have reserve basicity to neutralize acids formed from com- of drops at regular intervals.
bustion and lubricant oxidation. They also possess the abil- Drop „Dropping… Point—Temperature at which a drop
ity to suspend ordinarily oil-insoluble materials in the bulk falls from a grease through a specified orifice. It indicates
lubricant. grease transition from being a semisolid to a liquid state. In
Detergent/Dispersant—Additive package that com- view of the test being a static test, dropping point does not
bines a detergent with a dispersant. Both in combination are necessarily coincide with maximum operating temperature
extremely effective in keeping harmful lubricant decomposi- of a grease.
tion products away from surfaces. Dry Film Lubricant—Solid material placed between
Detergent Oil—Lubricating oil possessing sludge- two moving surfaces to prevent metal-to-metal contact, thus
dispersing properties for use in internal-combustion en- reducing friction and wear. Lubricating properties arise
gines. Such oils hold sludge particles in suspension and thus from sliding of the crystal lattice layers under low shear. Ma-
promote engine cleanliness. terials that are often used as lubricants include graphite and
Detonation—Uncontrolled burning of the last portion molybdenum disulfide. They are especially useful in mixed
共end gas兲 of the air-fuel mixture in the cylinder of a spark- film lubrication regimes. They may be applied in the form of
ignition engine. Also known as “knock” or “ping.” a paste, dispersion, or by spraying, dipping, and brushing in
DGMK—Deutsche Gesellschaft für Mineralölwissen- an air-drying carrier, which evaporates leaving a dry film.
schaft und Kohlechemie 共Germany兲. Dry Sliding Wear—Sliding wear in which there is no in-
DI—Detergent Inhibitor. tentional lubricant or moisture introduced into the contact
DI—Direct Injection. area. Adsorbed species or oxides and other metal films that
Dicarboxylic Acid Ester—Made from a dicarboxylic are either present or form during sliding may act as a lubri-
acid and an alcohol. Such esters are used as synthetic base cant. The proper term is unlubricated since solid lubricants,
fluids. when used, will also form dry films.
Dielectric Strength—Measure of the adequacy of elec- Durometer Reading—Durometer is a device that is
trical insulating oils of petroleum origin to be used in electri- used to test the hardness of elastomers. Durometer reading
cal devices, such as cables, transformers, oil circuit break- is an index used to rank relative hardness of these materials.
ers, and similar apparatus. Dynamic Viscosity—See Viscosity.
Diester—See Dicarboxylic Acid Ester Elasto-hydrodynamic Lubrication „EHD…—
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䊏 APPENDIX 609
Lubrication regime which is characterized by high loads and EP—Abbreviation for extreme pressure.
high speeds in rolling elements where the mating parts de- EPA—Environmental Protection Agency.
form elastically due to the incompressibility of the lubricant EPA Complex Model Gasoline—Gasoline designed to
film under very high pressure. improve emissions quality. Limits were implemented on
ECCC—Electronically Controlled Converter Clutch. Reid Vapor Pressure 共RVP兲, T-50 and T-90 共50 % and 90 %
EEB—European Environmental Bureau. evaporated gasoline temperatures兲, oxygen content, aromat-
EELQMS—European Engine Lubricants Quality Man- ics content, and amounts of olefins, benzene, and sulfur. Ef-
agement System. fective date January 1, 1997.
EEV—Enhanced Environmental Friendly Vehicles and EPA Simple Model Gasoline—Gasoline that was for-
Engines. mulated to minimize volatile organic compound 共VOC兲
EFI—Electronic Fuel Injection. emissions. Parameters manipulated included RVP and oxy-
EFTC—Engine Fuels Technical Committee 共of CEC兲. gen content and limits were placed on oxygen, benzene, sul-
EGR—Exhaust Gas Recycling. fur, olefins, and T-90 content at levels equal to or lower than
EHD—Elastohdrodynamic Lubrication. those of a refiner’s 1990 baseline. Effective date January 1,
EKS—Electronic Knock Sensor. 1995.
ELTC—Engine Lubricants Technical Committee 共of EP „Extreme Pressure… Agent—Additive used in a lu-
CEC兲. bricant to impart or improve load-carrying capacity or anti-
EMA—Engine Manufacturer’s Association. weld quality. It prevents sliding metal surfaces from adher-
EMD—General Motors Electromotive Division. ing to each other under extreme pressure conditions.
Emissions „Mobile Sources…—While emissions from EPEFE—European Programme on Emissions, Fuels &
an internal combustion engine include water, CO2, CO, NOx Engine Technologies.
and hydrocarbons 共HC兲, only the last three are subject to EP Lubricant—See Extreme-pressure Lubricant.
stringent legislative control. Diesel engines in addition emit Erosion—Surface wear of a solid due to the motion of a
particulates 共PM兲 which are also controlled. Efforts are be- fluid in contact that contains solid particles.
ing made to decrease the amount of the greenhouse gases, ESCS—Engine Service Classification System 共API兲.
such as CO2, in the environment due to a concern for global ESI—Extended Service Interval.
warming. ETC—European Transient Test Cycle.
Emissions „Stationary Sources…—Emissions from sta-
ETLP—Engine Test of Lubricants Panel 共IP兲.
tionary sources are hydrocarbons from evaporation of fuel
EU—European Union.
and sulfur-derived emissions. These are in addition to CO
EUC—European Union Commission.
and PM. Since fuel composition can influence emission of
EUI—Electronic Unit Injector.
some of these pollutants, efforts are on the way to control
Evaporation Loss—Lubricant loss due to volatilization
sulfur content of heavy fuel oils used in such facilities.
during use or storage.
Emulsifier—Additive that promotes the formation of a
Exhaust Gas Recirculation „EGR…—Process involving
stable oil-water systems, called emulsions. Emulsifiers are
recycling of the exhaust gases into the carburetor or intake
bipolar additives with solubility in both phases. They are
manifold to dilute the combustion mixture and reduce peak
nonionic, if none of the atoms in their structure contain any
combustion temperatures. The result is the lowering of the
electrical charges; anionic, if the charge on the organic por-
tion is negative; and cationic, if the charge on the organic amount of NOx formation.
portion is positive. Extreme Pressure Lubricant—Lubricating oil or
Emulsion—Dispersion of fine droplets of one liquid grease which is supplemented with an EP agent to prevent
共dispersed phase兲 in another liquid 共continuous phase兲. metal-to-metal contact in operations involving high loads.
Emulsions used as lubricants are oil-water systems that Such lubricants are typically used in gear and bearing appli-
maintain their integrity with the help of a chemical com- cations. These lubricants usually contain sulfur, halogens, or
pound called the emulsifier. Oil-in-water emulsions are phosphorus. Another name for extreme pressure lubricant is
called normal emulsions and water-in-oil emulsions are anti-scuffing lubricant.
called invert emulsions. FA,FAR—Fuel Air Ratio.
ENGVA—European Natural Gas Association. Fat—Naturally-occurring ester which is a reaction
Engine Deposits—These include sludge, varnish, lac- product of fatty acid and glycerol. It is also called a triglycer-
quer, and carbonaceous residues. They are derived both ide.
from the fuel combustion and the lubricant oxidation. Fuel Fatigue—Cracking, flaking or spalling of a surface due
combustion products contain unburned and partially to stresses beyond the endurance limit of the material.
burned fuel fragments which enter the crankcase as blow-by Fatigue Wear—Removal of particles as a consequence
and cause break down of the lubricant. Water from the con- of fatigue resulting from repeated localized stress. Fatigue
densation of the combustion products, carbon, residues wear in a part is usually indicated in the form of fracture or
from fuel and lubricating oil additives, dust, and metal par- spall.
ticles also contribute towards deposits. Fatty Acid—Organic acid derived from fats and natural
Engine Oil—Oil used to lubricate internal combustion oils.
engine. Fatty „Natural… Oil—Fat 共glycerol ester兲 that is liquid at
EOLCS—Engine Oil Lubricant Classification System room temperature.
共of API兲. FEO—Fuel Economy Oil.
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610 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
Grease—See Lubricating Grease. equipment speed, and low load promote this type of lubrica-
Grease Texture—Texture of a grease is determined by tion. It is also called fluid film lubrication.
pressing a small portion of a grease together and then by Hydrofinishing „Hydrogen Finishing…—Process for
slowly drawn apart. Texture is described as: treating extracted base stocks with hydrogen to remove un-
1. Brittle, if it ruptures or crumbles when com- saturation; hence improve stability.
pressed. Hydrogenation—Chemical reaction between hydro-
2. Buttery, if it separates in short peaks with no vis- gen and a material that has unsaturation or aromatic rings.
ible fibers. Hydrolytic Stability—Resistance of additives and cer-
3. Long Fibers, if it stretches or strings out into a tain synthetic lubricants against decomposition in the pres-
single bundle of fibers. ence of water.
GTL „Gas-to-Liquid… Base Stocks—Made by the con- Hydrophilic—Affinity of a substance towards water.
version of the natural gas, primarily methane, into a syn- Hydrophobic—Lack of affinity towards water. Related
thetic hydrocarbon base fluid. term is lipophilic—an affinity for organic materials. Usually
Gum—Rubber-like, sticky deposit, black or dark brown hydrophobic materials are lipophilic.
in color, which results from the oxidation and polymeriza- Hydroprocessing „Hydrogen Processing…—Treating
tion of the fuels and lubricating oils, or both. Harder depos- petroleum fractions with hydrogen, typically in the presence
its are described as lacquers or varnishes. of a noble metal catalyst. Simple addition of hydrogen sim-
Hardness—Property of a solid material that indicates ply removes unsaturation. Hydrogenation under more se-
its resistance to penetration or abrasion by other bodies. vere conditions leads to bond breaking and bond forming,
Hardness of a solid depends on the method of its measure- thereby altering chemical structures of the original hydro-
ment. carbons. When bond breaking is the primary outcome, the
HC—Hydrocarbons. process is called hydrocracking, and when hydrocracking is
HD—Heavy Duty 共vehicle or lubricant兲. followed by bond formation, it is called hydroisomerization.
HDDO,HDDEO—Heavy-duty Diesel Engine Oil. Hydrostatic Lubrication—Lubrication in which the
Heat Transfer Oil—Medium used to transfer heat away lubricant is supplied to a plain bearing under sufficient ex-
from a part or the equipment. Such oils are usually based on ternal pressure to separate the opposing surfaces by a con-
high-boiling petroleum fractions. tinuous lubricant film.
Heavy-duty Oils—Lubricants used in gasoline and die- Hypoid Gear Lubricant „Hypoid Oil…—Lubricant with
sel engines. These oils are stable against oxidation, protect extreme-pressure characteristics suitable for use in hypoid
bearings from corrosion, and have detergency and dispers- gears, which are often used in automobiles.
ancy. IChemE—Institute of Chemical Engineers 共UK兲.
Hershey Number—Dimensionless number used to ICOMIA—International Council of Marine Industries
evaluate performance of bearings. It is normally written as Associations.
ZN/P, where Z denotes viscosity, N the frequency of rotation, IDI—Indirect Injection.
and P the pressure. Often used in Stribeck curve to indicate IEA—International Energy Agency.
various lubrication regimes. IFP—Institut Français de Pétrole.
HFO—Heavy Fuel Oil. ILSAC—International Lubricant Standardization
HFRR—High Frequency Reciprocating Rig. Committee.
Homogenization—Intimate mixing of a grease to pro- Impingement Corrosion—Form of erosion/corrosion
duce a uniform dispersion of components. generally associated with the impingement of a high-velocity
HSDI—High Speed Direct Injection 共diesel engine兲. flowing liquid containing air bubbles against a solid surface.
HT/HS—High Temperature/High Shear 共viscosity兲. ILMA—Independent Lubricant Manufacturers Asso-
Humidity Cabinet Test—Test used to evaluate the rust- ciation.
preventing properties of metal protecting oils 共metal preser- Incompatibility—Fluids that do not mix well. Incom-
vatives兲 under conditions of high humidity. patibility may be reflected by phase separation, or loss of ac-
Hydrated Soap—Soap with water associated with its tivity and or performance. This commonly occurs in lubri-
structure, for example, that present in water-stabilized cal- cating greases and synthetic fluids.
cium soap grease. Induction Period—Time during which oxidation of a
Hydraulic Fluid—Fluids used as a medium to transfer material proceeds at a constant but a relatively slow rate.
hydraulic pressure to operate devices. They may or may not This period ends at the point where the oxidation rate in-
possess lubricant properties and may be water-based, min- creases sharply.
eral oil-based, or synthetic fluid-based. Inhibitor—Chemical whose presence in a petroleum
Hydrocarbon—Compound that is made of carbon and product prevents or retards undesirable chemical changes
hydrogen atoms only. The simplest hydrocarbons are gases from taking place, or in the condition of the equipment in
at ordinary temperatures, but as their molecular weight in- which the product is being used. Common inhibitors include
creases, they become liquid, and ultimately solids 共waxes兲. oxidation inhibitors and rust and corrosion inhbitors. These
Hydrocarbons are the major constituents of petroleum. retard the rate of oxidation or corrosion.
Hydrodynamic Lubrication—Formation of a continu- Inorganic Thickener—See Nonsoap Thickener.
ous lubricating fluid film of appropriate thickness between Insolubles—Contaminants in used oils that include
surfaces to prevent them from touching each other, thereby dust, dirt, wear particles, and or oxidation products. In oils,
minimizing friction and wear. High lubricant viscosity, high their amount is often measured as pentane or benzene in-
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612 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
solubles. In greases, they are measured by the use of pre- force is more precise and therefore preferred; however, the
scribed reagents according to special analytical procedures, term normal load is also used. If applied vertically, the load
such as ASTM D128. Additional identifying analytical tests can be expressed in mass units, but it is preferable to express
are required to determine the nature and composition of the force in as Newton units 共N兲.
isolated materials that comprise fillers, additives, and cer- Load-carrying Capacity—Maximum load that a slid-
tain types of thickeners. ing or rolling system can support without failure; or maxi-
Insulating Oil—Oil used in circuit breakers, switches, mum load or pressure that can be sustained by a lubricant,
transformers, and other electrical apparatus for insulating, when used in a system under specific conditions, without
cooling, or both. In general, such oils are highly-refined pe- failure.
troleum distillates of low volatility, with high resistance to Load Wear Index „LWI…—Measure of the relative abil-
oxidation and sludging. ity of a lubricant to prevent wear under applied loads. See
IP—Institute of Petroleum, now called Energy Institute Four-Ball Test. It is calculated from the loads applied and
ISO—International Standards Organization. corrected for elastic deformation of the balls under static
Iso-dewaxing—Hydroisomerization of the linear hy- loading and for the size of the wear scar. Formerly, it was
drocarbons 共waxes兲 into branched hydrocarbons to improve called Mean Hertz Load.
low-temperature properties, such as pour point of the min- LRI—Lubricants Review Institute 共USA兲.
eral base stocks. Also see Hydroprocessing. LSADO—Low Sulfer Automotive Diesel Oil.
IVD—Inlet Valve Deposit. Lubricant—Any substance interposed between two sur-
JALOS—Japanese Lubricating Oil Society. faces in relative motion for the purpose of reducing friction
JAMA—Japan Automobile Manufacturers Association. or wear that may occur. The term implies externally added
JARI—Japan Automobile Research Institute. substance. However, species such as oxide layers and tar-
JAST—Japan Society of Tribologists. nishes on certain metals can also prevent friction and wear.
JASO—Japan Automobile Standards Organization. Lubricant Compatibility—See Compatibility 共Lubri-
JIS—Japan Industrial Standards. cant兲.
JSAE—Society of Automotive Engineers, Japan. Lubricating Grease—A lubricant in which a lubricat-
Kinematic Viscosity—Measure of a fluid’s resistance to ing fluid is thickened with soap or another material to a solid
flow under gravity at a specific temperature, usually 40 ° C or semisolid consistency. Common soaps include calcium
and 100 ° C. Kinematic viscosity is easier to measure than soap, sodium soap, barium soap, lithium soap, and alumi-
dynamic viscosity. Kinematic viscosity can be converted into num soaps, both simple and complex. The liquid phase may
dynamic viscosity by dividing its value by fluid density, and be mineral oil or a synthetic base fluid.
vice versa. The units of kinematic viscosity are Stoke 共St兲 and Lubrication—Control of friction and wear by introduc-
centiStoke 共cSt兲, which correspond to cm2 / s and mm2 / s in ing a friction-reducing film between moving surfaces in con-
Metric System. The units for dynamic or absolute viscosity tact. Such a film may be due to the presence of a fluid, solid,
are Poise 共P兲 and centipoise 共cP兲, which correspond to 0.1 or a plastic substance. See Lubrication Regimes.
and 0.001 Pa· s, respectively. Lubrication Regimes—Lubrication environments de-
Kinetic Coefficient of Friction—Coefficient of friction fined on the basis of operating conditions, such as speed,
under conditions of macroscopic relative motion between load, etc., in lubricated tribo-systems. Different regimes
two bodies. have different amount of separation of surfaces and surface
Knock—Audible hammering noise resulting from vio- interaction; hence different frictional characteristics. Also
lent, explosive combustion of air-fuel mixture in a spark igni- see Boundary Lubrication, Elasto-hydrodynamic Lubrica-
tion engine. tion, Full-film Lubrication, Hydrodynamic Lubrication, and
KV—Kinematic Viscosity. Quasi-hydrodynamic Lubrication.
Lands—Circumferential areas between the grooves of a Lubricious—Relating to a substance or surface condi-
piston. tion that tends to produce relatively low friction.
Lard Oil—Animal oil prepared from the fat of pig. Such Lubricity—Ability of a lubricant to reduce friction and
oils are compounded with mineral oils to yield lubricants wear other than by its viscosity.
with special properties, especially cutting oils. Luster—Reflected light intensity from a grease, its
LCV—Light Commercial Vehicle. sheen or brilliance. See Appearance/Bulk Appearance.
LEV—Low Emissions Vehicles. Main Bearing—Bearing supporting the main power-
Liquefied Natural Gas „LNG…—Similar to LPG but transmitting shaft.
consisting of lighter hydrocarbons, such as methane and MDCL—Medium Diesel Cylinder Lubricant.
ethane. MDO—Marine Diesel Oil.
Liquefied Petroleum Gas „LPG…—Light hydrocarbon MGO—Marine Gas Oil.
material, gaseous at atmospheric temperature and pressure, Mechanical Activation—Acceleration or initiation of a
held in the liquid state by pressure to facilitate storage, trans- chemical reaction by mechanical exposure of a nascent solid
port and handling. Commercial liquefied gas consists essen- surface, for example obtained by a metal cutting operation.
tially of propane, butane, or their mixture. Mechanical Stability „Grease…—Shear stability as
LMAO—Locomotive Maintenance Officer’s Associa- tested in a standard rolling tester.
tion. Mechanical Wear—Removal of material due to me-
Load—Force applied normal to the surface of one body chanical processes involving sliding, rolling, or repeated im-
by another contacting body or bodies. The term normal pact. Mechanical wear includes adhesive wear, abrasive
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䊏 APPENDIX 613
wear, and fatigue wear, but not corrosive wear and thermal Naphthenic—Petroleum-derived fluid, usually ob-
wear. tained from naphthenic crude oil, containing a high propor-
Melt Lubrication—Lubrication provided by steady tion of saturated cyclic structures.
melting of a lubricating species. Natural Sulfonate—Metal salt of the petroleum-
Metal Deactivator—Fuel or lubricant additive, usually derived 共natural兲 sulfonic acid.
a chelating agent, which through complexation deactivates NEMA—National Electrical Manufacturers Associa-
metal surfaces and metal ions that will ordinarily catalyze tion.
fuel and lubricant breakdown; thereby inhibiting the forma- Neutral Oil—Petroleum-derived lubricant base stock
tion of resin and other oxidation products. Copper in fuel that is devoid of acidity or alkalinity. Neutral oils are the ba-
lines and iron are of concern both in metallic form and in sis of most commonly used automotive and diesel lubri-
oxidized form 共ions兲. cants. They are light overhead cuts from vacuum distillation.
Metallic Wear—Wear due to rubbing or sliding contact Neutralization Number—Measure of acidity or alka-
between metallic materials. Its cause is cold welding of as- linity of an oil. Neutralization number is the amount of milli-
perities, followed by separation and inter-surface metal grams of acid 共HCI兲 or base 共KOH兲 required to neutralize one
transfer. Also see Adhesive Wear and Severe Wear. gram of oil. It is expressed as mg of KOH/g of oil. Also see
Metallurgical Burn—Modification of the microstruc- Acid Number and Base Number.
ture near the contact zone due to frictional temperature in- Newtonian Behavior—Lubricant exhibits Newtonian
crease. behavior if its shear rate is directly proportional to the shear
Metallurgical Compatibility—See Compatibility stress. This constant proportion is the viscosity of the liquid.
共Metallurgical兲. Newtonian Flow—Fluid exhibits Newtonian flow if its
Methylene-bridged Alkylphenol—Obtained by the re- viscosity is independent of the shear stress.
action of alkylphenol with formaldehyde. Used as starting Newtonian Fluid—Fluid that exhibits Newtonian vis-
materials to make detergent additives for heavy-duty diesel cosity, that is, shear stress is proportional to the rate of shear.
engine oils. Nitration—Process where nitrogen oxides react with
Mineral Oil—Refined hydrocarbon oil obtained di- hydrocarbon 共petroleum兲 fluids at high temperatures, result-
rectly from petroleum refining. ing in oxidation products that cause viscosity increase and
MIRA—Motor Industry Research Association.
deposit formation.
Mist Lubrication—Lubrication by an oil mist pro-
NLGI—National Lubricating Grease Institute.
duced by injecting oil into a gas stream.
NLGI Consistency Number—Scale comparing consis-
MITI—Ministry of International Trade and Industry
tency 共hardness兲 of greases. Scale range is from 000 to 6;
共Japan兲.
higher consistency numbers indicate firmer 共harder兲
MON—Motor Octane Number.
greases. Greases both softer and harder than indicated by
Morphology—Pertaining to structure and form.
these consistency numbers are well known in the industry.
MRV—Mini Rotary Viscometer.
However, such greases do not have an NLGI Number.
MTAC—Multiple Test Acceptance Criteria.
NMMA—National Marine Manufacturers Association.
MTBE—Methyl Tertiary Butyl Ether.
NMOG—Non-Methane Organic Gases.
MTF—Manual Transmission Fluid.
NOx—Nitrogen Oxides, primarily Nitrous Oxides.
Multi-grade Oil—Engine or gear oil that meets the re-
quirements of more than one SAE viscosity grade, for ex- Non-Newtonian Behavior—Fluids exhibit this type of
ample 10W-30, which meets the requirements of both SAE behavior if they have variable relationship between shear
10W and SAE 30. Such multi-viscosity oils provide broad- stress and shear rate. This implies that they do not possess
temperature performance and are usually made by adding a real viscosity but apparent viscosity. Such fluids, exemplified
viscosity modifier to a low viscosity oil. In some case, such as by greases and polymeric additive-containing lubricants, are
narrow viscosity range gear oils 共80W-90兲, multi-grades are called Non-Newtonian fluids.
made by blending base oils of two different viscosities. Nonsoap Thickener—Lubricating grease thickener
Multiply-alkylated cyclopentanes, or MACs—These that is not derived from metal carboxylates 共soaps兲. Such
are made by the reaction of cyclopentadiene with an alcohol thickeners can be organic or inorganic. Former type in-
or an alkyl halide. They are used as base fluids in formulating cludes polyurea and cellulosic materials and the latter type
high-temperature lubricants. includes silica and modified clays.
Multi-purpose Grease—Lubricating grease that meets NPRA—National Petroleum Refiners Association.
the requirements of various applications. For example, it is NVMA—National Vehicle Manufacturers Association.
suitable for use as a chassis lubricant, bearing lubricant, OBD—On-board diagnostics.
joint lubricant, water-pump lubricant, and cup grease. OCP—Olefin Co-polymer.
MVEG—Motor Vehicle Emmisions Group 共of the Euro- Octane Number—Measure of a fuel’s ability to prevent
pean Commision兲. detonation in a spark ignition engine. Measured in a stan-
MVMA—Motor Vehicle Manufactures Association. dard single cylinder, variable-compression-ratio engine by
Naphthene—A group of cyclic hydrocarbons, which is comparison with primary reference fuels which are blends
also termed cycloparaffins or cycloalkanes. Polycyclic mem- of iso-octane 共Octane Number 100兲 and n-heptane 共Octane
bers are also found in the higher boiling fractions. The gen- Number 0兲. Under mild conditions, the engine measures Re-
eral formula for naphthenes is CnH2n, where n is a whole search Octane Number 共RON兲; under severe conditions it
number. measure Motor Octane Number 共MON兲. Posted Octane
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Number of commercial gasolines, called Antiknock Index Oxidative Wear—Corrosive wear in which a chemical
共AK兲, is the average of the two values. reaction with oxygen or oxidizing environment predomi-
Octane Requirement „OR… or Octane Number Re- nates. This type of wear is usually a mild form of wear, but it
quirement „ONR…—Lowest octane number reference fuel can be severe in highly oxidative environment, such as those
that will allow an engine to run knock-free under standard involving liquid oxygen or liquid fluorine.
conditions of service. Oxygenate—Oxygen-containing, metal-free organic
Octane Requirement Increase „ORI…—As deposits in compound, such as alcohol or ether, that can be used as a
automobiles combustion system increase, the ORI of the en- fuel or fuel supplement.
gine increases. That is, higher octane number fuel is re- Oxygenated Fuels—Fuels for internal combustion en-
quired for trouble-free operation. Addition of deposit gines that contain oxygenates, such as alcohol and
control/cleanliness additives to gasoline help prevent this methyl-t-butyl ether 共MTBE兲, which increase gasoline’s oc-
from happening. tane value.
ODI—Oil Drain Interval. Oxygenated Gasoline—Required annually from Sep-
OECD—Organization Economic Cooperation and De- tember 15 to March 15 for use in carbon monoxide 共CO兲 non-
velopment. attainment areas. Oxygenated gasoline contains a minimum
OEM—Original Equipment Manufacturer. of 2.0 % mass oxygen and a maximum of 1.0 % volume ben-
OICA—Organisation Internationale des Constructeurs zene.
d’Automobiles. Ozone and CO Nonattainment Areas—Any area in the
Oil—A liquid of vegetable, animal, mineral, or synthetic continental United States that does not meet the 1990 Clean
origin that feels slippery to the touch. Air Act requirements for carbon monoxide or ground-level
Oil Fog Lubrication—See Mist Lubrication. ozone pollutants.
Oil Groove—A channel or interconnected channels cut PAG—See Poly共alkylene glycol兲.
in a part to improve oil flow. When applied to a bearing, this PAH—Polyaromatic Hydrocarbon.
strategy facilitates distribution of oil over the shaft as well. PAJ—Petroleum Association of Japan.
Oiliness—Capability of a fluid to orient itself on metal Pale Oil—Petroleum lubricating oil or process oil re-
surfaces and lower friction. Also see lubricity. fined until its color by transmitted light is straw to pale yel-
Oiliness Agent—Chemical with the ability to form an low. Typically, it is a naphthenic oil.
adsorbed film on metal that reduces friction. Paraffinic—Type of petroleum fluid derived from paraf-
Oil Pocket—A depression designed to retain oil on a finic crude oil and containing a high proportion of straight
sliding surface. chain saturated hydrocarbons, because of which it suffers
Oil Ring—A mobile ring whose inner surface rides a from cold flow problems.
shaft or journal, causing the ring to rotate and pick up lubri- PCB,PCBs—Polychlorinated Biphenyls.
cant by dipping into the lubricant reservoir and delivering it PCD—Passenger Car Diesel.
to the top of the shaft for distribution to a bearing. An PCMO—Passenger Car Motor Oil.
internal-combustion engine piston also contains an oil ring PCV—Passenger Car Vehicle.
which controls the lubrication of the piston and cylinder Penetration—Measure of consistency 共hardness兲 based
walls. on an inverse penetration measurement 共the softer the con-
Oil Ring Lubrication—See Oil Ring. sistency, the higher the penetration number兲. Penetration is
Oil Starvation—Situation in which a bearing, or an- measured as the distance in millimetres that a standard
other tribo-component, receives an inadequate supply of lu- needle or cone penetrates vertically into a sample of the ma-
bricant. terial, under known conditions of loading, time, and tem-
OPEST—Oil Protection and Emission System Test. perature. Penetration may be measured without disturbing
Organic Thickener—See Nonsoap Thickener. the grease 共Undisturbed penetration兲, with minimum distur-
ORI—Octane Requirement Increase. bance 共Unworked penetration兲, and with substantial distur-
Overbasing—Technique to impart base reserve in addi- bance 共Worked Penetration兲.
tives, called detergents. Such base exists in the additive in a Pentane Insolubles—See Insolubles.
colloidal form. Addition of overbased additives to a lubricant Percent Permanent Viscosity Loss „PPVL…—Measure
imparts ability to neutralize acidic oxidation products. of the PVL related to the viscosities of the fresh oil—equals
Oxidation—Reaction of oxygen with organic and inor- PVL divided by fresh oil viscosity, multiplied by 100.
ganic materials. Hydrocarbon 共petroleum兲 fluids oxidize to Percent Temporary Viscosity Loss „PTVL…—
yield highly polar oxygenated materials of polymeric struc- Difference between the viscosity of an oil measured at low
ture and carboxylic acids. These species lead to lubricant vis- and high shear stresses, divided by viscosity measured at low
cosity increase, deposit formation, and metal corrosion. Oxi- shear stress, multiplied by 100.
dation rate is accelerated by heat, light, metal catalysts and Perfluoropolyethers „PFPEs…—These are poly共alky-
the presence of water, acids, or solid contaminants. lene glycol兲 analogues, where all hydrogen atoms in their
Oxidation Inhibitor—Additive used for the purpose of structure are replaced by fluorine atoms. They are used in
reducing the rate of oxidation and subsequent deterioration specialty applications due to unique properties.
of oil or grease. Permanent Viscosity Loss „PVL…—Difference between
Oxidation Stability—Resistance of a petroleum prod- the viscosity of fresh oil and that of the same oil after engine
uct to oxidation and, therefore, it is a measure of a product’s operation or special test conditions to determine polymer
potential service or storage life. degradation.
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䊏 APPENDIX 615
Petroleum Oil—See Mineral Oil. with 90 mL of petroleum naphtha of defined quality and cen-
PFI—Port Fuel Injection. trifuged under prescribed conditions. Precipitation number
Phosphate Esters—Made from phosphorus oxychlo- indicates the amount of asphaltic components in the lubri-
ride and a hydroxy compound, such as an alcohol or a phe- cating oil, although a certain amount of paraffinic compo-
nol. Phenol and alkylphenol esters are used as base fluids for nents may also separate.
fire-resistant lubricants and hydraulic fluids. Preignition—Ignition of the fuel-air mixture in a gaso-
PIB—See Polyisobutylene. line engine before the spark plug fires. Often caused by in-
Pitting—Surface damage in the form of cavities, which candescent fuel- or lubricant-derived deposits in the com-
may be related to fatigue, overload, or corrosion. bustion chamber, it wastes power and may damage the
Plastic Flow—Surface deformation of metal as a result engine.
of yielding under heavy load. Pressure Lubrication—System of lubrication in which
Plowing „ploughing…—Formation of grooves by plastic the lubricant is supplied under pressure to various parts of
deformation of the softer of the two surfaces in relative mo- the equipment or the device.
tion. Pressure-Viscosity Coefficient—Slope of a graph that
PM—Particulate Matter. shows variation of viscosity with pressure on a logarithmic
PM2.5—Particulate matter of the diameter 2.5 or less. scale. The term pressure-viscosity coefficient assumes a lin-
PM10—Particulate matter with particle size below 10 ear relationship between these two parameters.
microns. Process Oil—Oil used as a component in another mate-
Poise „P…—Metric unit of dynamic viscosity. Also see Ki- rial or as a carrier for other products.
nematic Viscosity. Protuberances—See Asperities.
Polishing—A surface-finishing process utilizing suc- PTF—Power Transmission Fluid.
cessive grades of abrasive. Pumpability—Flow properties of a grease that permits
Polishing „Bore…—Excessive smoothening of the sur- proper delivery through lines, nozzles, and fittings of the
face finish of the cylinder bore or cylinder liner in an engine grease dispensing systems and subsequent lubrication of the
to a mirror-like appearance, resulting in depreciation of ring moving components. Also see Dispensability and Feedabil-
sealing and oil consumption performance. ity.
Polishing Wear—Mild form of wear that may involve Quasi-hydrodynamic Lubrication—A loosely defined
fine-scale abrasion, plastic smearing of micro-asperities, tri- regime of lubrication, especially in metalworking, where
bochemical material removal, or a combination thereof. thin-film lubrication predominates.
Poly„alkylene glycol…—Made by acid or base-catalyzed Quenching Oil—Oil used for quenching metals during
polymerization of alkylene oxides, such as ethylene oxide a heat-treating operation.
and propylene oxide. Used as synthetic base fluids. R&O Oil—Rust and oxidation inhibited oil. Such oils
Polyisobutylene—Made by the polymerization of are highly-refined lubricating oils, which are formulated for
isobutene 共isobutylene兲. Used as a starting material for mak- long service in circulating systems, compressors, hydraulic
ing additives, such as dispersants, and after hydrogenation systems, bearing housings, gear cases, etc.
used as a viscosity modifier in lubricants. REACH—Acronym for European environmental legis-
Polyol Esters—These are the reaction products of poly- lation pertaining to chemical contamination of the
hydric alcohols 共polyols兲 and carboxylic acids. These are environment—Registration, Evaluation, and Authorization
used as base fluids to design high temperature lubricants. of CHemicals.
Poly„phenyl Ether…s, Polyphenyl Ethers, or PPEs— Reclaimed Oil—Lubricating oil which, after undergo-
These materials are obtained by the reaction of an alkali ing a period of service, is collected, reprocessed, and sold for
metal phenate with a halogenated benzene. These are used reuse.
in lubricants for high-temperature and radiation environ- Refining—Series of processes to convert crude oil and
ments. its fractions into finished petroleum products. Processes in-
Positive Crankcase Ventilation „PCV…—System in- clude thermal cracking, catalytic cracking, polymerization,
volves recycling the blow-by gases, which contain unburned alkylation, reforming, hydrocracking, hydroforming, hydro-
hydrocarbons, from the crankcase through the carburetor genation, hydrogen treating, Hydrofining®, solvent extrac-
intake manifold into the combustion chamber to burn them. tion, dewaxing, de-oiling, acid treating, clay filtration, and
The objective is to reduce hydrocarbon emissions. de-asphalting.
Pour Point—The lowest temperature at which the fluid Re-refining—Process of reclaiming used lubricant oils
will flow when cooled under prescribed conditions. Pour and restoring them to a condition similar to that of virgin
point is an indicator of the ability of an oil or the distillate stocks by filtration, clay adsorption, or more elaborate refin-
fuel to flow at cold operating temperatures. ing methods.
Pour Point Depressant, PPD—Additive which lowers Reversibility—Ability of a grease to return to its normal
the pour point of a paraffinic oil which contains wax. grease-like consistency after temporary exposure to tem-
Pour Stability—Ability of a pour point depressant- peratures near or above its dropping point. Only a few types
treated oil to maintain its original ASTM pour point when of greases possess this property.
subjected to storage at low temperature approximating win- Reynold’s Equation—A basic equation of hydrody-
ter conditions. namic lubrication.
Precipitation Number—Number of millimetres 共mL兲 Rheology—Deformation or flow characteristics, or
of precipitate formed when 10 mL of lubricating oil is mixed both, of grease in terms of stress, strain, temperature, and
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616 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
time—commonly measured by Penetration and Apparent Saponification—Making of a metal salt 共soap兲 from a
Viscosity. carboxylic acid ester, such as natural oils and fats, by the re-
Rheopectic Material—A material that shows an in- action of an alkali metal base, such as sodium hydroxide and
crease in viscosity with time under constant shear stress. Af- potassium hydroxide.
ter the removal of the shear stress, the viscosity slowly re- Saponification Number—Measure of the amount of
turns to the original level. material in petroleum products that will saponify under test
Rheopectic Grease—Lubricating grease which in- conditions. Saponification number, like the acid and base
creases its consistency number 共hardens兲 upon being sub- numbers, are expressed as number of milligrams of base, in
jected to shear. this case sodium hydroxide, consumed by 1 g of oil. Saponi-
Ridging—Form of plastic flow on the surface of the gear fiable 共fatty兲 material is not naturally present in petroleum
teeth that is characterized by a rippled appearance. Damage products but is added to improve their lubricity.
appears in the form of deep scratches that run as parallel Saybolt Color—Color standard for petroleum products
ridges and is a consequence of plastic flow of the subsurface 共ASTM Method D156兲.
layer. Saybolt Universal Viscosity „SUS or SSU…—It is based
Rings—Circular metallic elements that ride in the on time, in seconds, taken for 60 mL of fluid to flow through
grooves of a piston and provide compression sealing during a capillary tube in a Saybolt Universal Viscometer at a given
combustion and to spread oil for lubrication. temperature 共ASTM Method D88兲.
Ring Sticking—Freezing of a piston ring in its groove in Scoring—Formation of significant scratches in the di-
a piston engine or reciprocating compressor due to heavy de- rection of sliding. Scoring may be due to local solid-phase
posits in the piston ring zone. welding or to abrasion. In the United States, the term scuff-
Ripple Formation „rippling…—Formation of periodic ing is sometimes used as a synonym for scoring. It can be
ridges and valleys transverse to the direction of motion. prevented by the use of antiwear, extreme pressure, and fric-
Roller Bearing—See Anti-friction Bearing. tion reducing additives.
Rolling—Motion of two moving bodies of opposite cur- SCR—Selective Catalyst Reduction.
vature whose surface velocities in the common contact area Scratching—Fine abrasive furrows in the direction of
are identical in magnitude and direction. sliding, which are produced by the cutting or plowing action,
Rolling and Peening—Forms of plastic flow on the sur- or both, of a sharp particle or protuberance moving along
face of the gear teeth that gives the appearance of being ham- that surface.
mered. Metal may even be rolled over the teeth tips. Scuffing—See Scoring.
Rolling-contact Fatigue—Repeated stressing of a solid Seal—Device used to prevent leakage between moving
surface due to rolling contact between it and another solid parts, movement of the fluid from one chamber to another,
surface or surfaces. or to exclude contaminants.
Rolling-contact Wear—Wear to a solid surface that re- Seizure—Stopping of relative motion due to interfacial
sults from rolling contact between that surface and another friction. Seizure may be accompanied by gross surface weld-
solid surface or surfaces. ing.
Rolling-element Bearing—Bearing in which the mov- Selective Transfer—Process involving transfer and at-
ing parts are separated by balls, rollers, or needles. tachment of a specific species from one contacting surface to
RON—Research Octane Number. the other contacting surface during sliding.
RPM—Revolutions Per Minute. Self-lubricating Bearing—See Anti-friction Bearing.
Run In—Applying specified initial operating conditions Self-lubricating Material—Solid material that shows
to a tribological system to improve its long-term frictional or low friction without the application of a lubricant. Examples
wear behavior, or both. It may involve conditions either include graphite, molybdenum disulfide, and polytetrafluo-
more severe or less severe than the normal operating condi- roethylene, and even composite materials with inherently
tions and may also involve the use of special lubricants or low friction. Also see Solid Lubricant.
surface chemical treatments, or both. Also see Break-in. SEM—Scanning electron microscope/microscopy.
Running-in—Process by which machine parts improve Separation Test—Test to determine the tendency of the
in conformity, surface topography, and frictional compat- oil to separate from a lubricating grease under conditions
ibility during the initial stage of use. Chemical processes in- prescribed in ASTM Method D1742.
clude formation of surface an oxide film and metallurgical SHC—See Synthetic Hydrocarbons.
processes include strain hardening. Shearing—Relative slipping or sliding between one
Rust Preventative—Compound used to coat metal sur- part of a substance and an adjacent part. In solids, shearing
faces with a film that protects against rust, primarily in involves breaking or altering of the crystal structure; in a
stored equipment. fluid or plastic, shearing may or may not destroy the con-
RVP—Reid Vapor Pressure. tinuous nature of the substance.
SAE—Society of Automotive Engineers. Shear Rate—Rate of sliding within a flowing sub-
SAE Viscosity Grade—An arbitrary number used for stance. See ASTM D1092.
classifying engine oils, automotive transmission fluids, and Shear Stability—Resistance of a grease to changes in
gear oils, according to their viscosities, established by the consistency 共hardness兲 during mechanical working. In a lu-
Society of Automotive Engineers. SAE Grades are selected bricant, it is the ability of a lubricant to withstand the shear-
on the basis of the operating temperature and tribological ing action without degradation.
requirements of the equipment. Shear Stability Index „SSI…—Measure of a viscosity
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䊏 APPENDIX 617
modifier’s contribution towards percent loss in viscosity of Soluble Oil—Mineral oil containing additives that en-
an oil when subjected to engine operation or in specialized able it to form a stable emulsion with water.
tests. Solvent Extraction—Refining process used to separate
Shear Stress—Stress 共force per unit area兲 that can reactive components 共unsaturated hydrocarbons兲 from the
cause shearing. Ratio of shear stress to shear rate in a fluid is lubricant distillates in order to improve their oxidation sta-
its viscosity. bility, viscosity index, and additive response.
Shear-thickening—Increase in viscosity with an in- Solvent Refining—Process of extracting lubricant base
crease in shear rate or time. stocks from heavy gas oil or another heavy, stripped crude
Shear-thinning—Decrease in viscosity with an increase stream by the use of selective solvents such as furfural or
in shear stress or time. Decrease in viscosity may be tempo- phenol.
rary or permanent. The latter happens when the shear stress Spalling—Separation of particles from a surface in the
is sufficiently high to cause structural breakdown of the form of flakes, leaving behind a surface that consists of large
polymeric additives. Permanently sheared fluid has a lower pits, cavities, and related cracks. The term spalling is com-
viscosity than it had prior to shearing. monly associated with rolling-element bearings and with
SHPD—Super High Performance Diesel 共oil兲. gear teeth. Spalling is usually a result of subsurface fatigue
Silicate Esters—These are organic esters of orthosilicic due to overloading and is more extensive than pitting.
acid, H4SiO4, which are made by the hydrolysis of alkoxysili- Specific Gravity—Ratio of the weight 共in air兲 of a given
con chlorides with an alcohol. Used in lubricants for spe- volume of a material to the weight 共in air兲 of an equal volume
cialty application. of water at the stated temperature.
Silicones/Polysiloxanes—Made by water-catalyzed Spindle Oil—Oil of low viscosity used to lubricate light
polymerization of dialkyl/diaryl silicon halides. Used as base spindles operating at high speeds.
fluids for specialty lubricants and as foam-inhibiting addi- Splash Lubrication—System of lubrication in which
tives. the lubricant is splashed onto the moving parts.
SIP—Styrene Isoprene Copolymers. Squeeze Film Lubrication—Development of fluid
Slide-roll Ratio—Ratio of sliding velocity to rolling ve- pressure sufficient to support a load between surfaces
thickly coated or flooded with lubricant and rapidly moving
locity, for example, in gear sets.
toward each other. Because of viscosity 共or apparent viscos-
Sliding—Motion of two relatively moving bodies, in
ity兲, the lubricant cannot immediately flow away from the
which their surface velocities in the common contact area
area of contact. Squeeze-film lubrication occurs between
are different with regard to magnitude or direction, or both.
gear teeth.
Sliding Velocity—Difference between the velocities of
SSI—Shear Stability Index.
each of the two surfaces relative to the point of contact.
SSU „or SUS…—Saybolt Seconds Universal 共or Saybolt
Sludge—Semisolid to solid thick, dark residue contain-
Universal Seconds兲 a unit of vicosity. Also see Saybolt Uni-
ing oil, oxidation products, carbon, and water, which results
versal Viscosity.
from the low temperature operation of a combustion engine.
Starting Torque—Torque required for initiating rotary
Sludge is normally of mayonnaise consistency that accumu-
motion.
lates on nonmoving interior surfaces of the engine and is
Static Coefficient of Friction—Coefficient of friction
usually removable by wiping, unless baked to a carbon-
corresponding to the maximum frictional force that must be
aceous consistency. overcome to initiate motion of the two bodies in contact.
Slumpability—Flow of a grease in a container under Stick-Slip—Transition from high coefficient of friction
gravity, thereby allowing it to be fed into a pump or can. Also 共stick兲 to low coefficient of friction 共slip兲, as the relative ve-
see Feedability. locity increases. This phenomenon can be explained in
Slurry—Mixture of solid particles in a liquid, of a con- terms of the formation of the interfacial junctions on a mi-
sistency that is capable of being pumped as a liquid. croscopic scale first and then their destruction. Time dura-
Slushing Oil—Mineral oil containing additives that en- tion between stick and slip will depend upon the velocity and
able it to protect the parts of a machine against rusting. the elastic characteristics of the system. Stick-slip in a sys-
Soap—Alkali or alkaline metal salt of a carboxylic acid, tem is indicated by a jerky motion.
especially a fatty acid. Also see Thickener, Complex Soap, Stoke „St…—Nonmetric unit of Kinematic viscosity.
and Saponification. While soaps are of importance as thick- STLE „Formerly ASLE…—Society of Tribologists and
eners in greases, metal soaps formed in boundary lubrica- Lubrication Engineers.
tion regime by the in situ reaction of fatty additives and Storage Stability—Measure of the ability of a lubricant
metal play an important role in reducing friction and wear. to undergo prolonged periods of storage without showing
Solid-film Lubrication—Lubrication by the applica- any adverse conditions due to oxidation, oil separation, con-
tion of solid lubricants. tamination, or any type of deterioration. Storage stability
Solid Lubricant—Solid used as a powder or a thin film tests are often run on lubricants to determine their shelf life.
on a surface to provide reduced friction and wear protection STOU—Super Tractor oil Universal.
during the relative movement of the surfaces in contact. Stribeck Curve—Graph showing the relationship be-
These lubricants have a layered 共lamellar兲 structure, for ex- tween coefficient of friction and the dimensionless number
ample, graphite and molybdenum disulfide. Certain solids, 共ZN/P兲, where Z is the dynamic viscosity, N is the equipment
such as glass, lubricate only in the melted state at the inter- speed 共revolutions per minute兲, and P is the load per unit of
face. These are not considered solid lubricants. projected area.
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618 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
tion and wear behavior of materials or components. lose viscosity with temperature at a slower rate than the low
Tribosystem—Functional combination of tribo- VI oils.
elements, including thermal and chemical surroundings. Viscosity Modifier—High molecular weight polymer
Tribotechnology—Aspect of tribology that involves en- that is used to maintain the viscosity of an oil in the desired
gineering applications of tribo-science and the design, devel- viscosity range. Also see VI Improver.
opment, analysis, and repair of the components for tribo- VOC—Volatile Organic Compound.
logical applications. Water Resistance—Resistance of an oil or the lubricat-
U.S. Military Specification—Guide in determining the ing grease to be adversely effected by water. Water can cause
quality requirements of products used by the military ser- hydrolysis of the additives or the base fluids such as carboxy-
vices, published by the U.S. Department of Defense. late esters, phosphate esters, and poly共alkylene glycol兲s,
UEIL—European Union of Independent Lubricant thereby diminishing lubricant performance. Some greases
Manufacturers. can experience soap washout, depending on the amount of
UFIP—Union Française des Industries Pétrolières. water.
UHC—Unburned Hydrocarbon. Water Spray Resistance—Ability of a grease to resist
UK-PIA—United Kingdom Petroleum Industry Asso- displacement from a surface by the impact of water spray.
Wear Debris—Particles that become detached in the
ciation.
wear process.
ULEV—Ultra-low Emissions Vehicle.
Wear Resistance—Resistance of a body against wear-
UTAC—Union Technique de l’Automobile, du Moto-
related material removal.
cycle et du Cycle.
Wear Scar—Portion of a solid surface that indicates re-
UTTO—Universal Tractor Transmission Oil.
moval of material due to wear.
Vacuum Residue—Residue from vacuum distillation
Wear Scar Diameter—Dimensions of the wear scar.
of crude oil.
White Oil—Highly refined lubricant stock used for spe-
Vapor-phase Lubrication—Type of lubrication in
cialty applications such as cosmetics and medicines.
which one or more gaseous reactants are supplied to the vi- Wick Lubrication—System in which the lubricant is
cinity of the surface to be lubricated and which subsequently delivered to the metal surface by means of a wick.
react with the surface to form a chemical lubricating film. Wiping—Spreading or removal of material from one
Vapor Pressure Reid „RVP…—Pressure of the vapor ac- point and deposition at another point on the surface of the
cumulated above a sample of gasoline or other volatile fuel two bodies in sliding contact. Smeared metal is usually in a
in a standard closed vessel 共bomb兲 at 100 ° F 共37.8 ° C兲. RVP softened or a melted form.
is used to predict the vapor locking tendencies of the fuel in a Working—Subjecting the lubricating grease to inten-
vehicle’s fuel system. tional agitating or shearing action.
Varnish—Thin, insoluble, nonwipeable film occurring Worked Penetration—Penetration of a sample of lu-
on some interior engine parts. It can cause sticking and mal- bricating grease immediately after it has been worked 60
function of the moving parts with close clearances. Such film strokes at 77 ° F in a standard grease worker.
in a diesel engine is called lacquer. Varnish and lacquer de- Yield Point „Yield Value or Yield Stress…—Minimum
posits result from the oxidation or polymerization, or both, shear stress that produces flow in a plastic material.
of fuels and lubricants, or both. ZDDP—Zinc Dialkyl Dithiophosphates.
VI „Viscosity Index… Improver—Also called viscosity ZEV—Zero Emissions Vehicle.
improver. It is usually a polymeric additive which is added to
The Systeme International „SI… Units and
an oil to increase its viscosity index, that is, to reduce varia-
Conversion Factors
tion in oil viscosity with temperature. VI improvers are the This section of the Appendix provides a summary of the
additives that are used to make multi-grades. units of measurement that apply to the material included in
Viscoelasticity—Combined property where the fluid is this book, together with the appropriate conversion factors
both viscous and elastic. Viscoelastic fluid deformation is de- needed to change them into a “standard” unit of the SI. 共See
pendent both upon temperature and strain rate. Tables A.1 and A.2.兲
Viscosity—Measure of a fluid’s resistance to flow, which The SI is founded on seven SI base units for seven base
is due to friction that exists between fluid layers, called inter- quantities assumed to be mutually independent, as given in
nal friction. Also see Kinematic Viscosity. Table A.3. In addition, there are quantities, called derived
Viscosity Conversion Table—Table or chart which is quantities, which are defined in terms of the seven base
used to convert kinematic viscosity, in centistokes, into Say- quantities via a system of quantity equations 关844兴. Ex-
bolt viscosity in seconds at the same temperature. Conver- amples of the SI derived units are given in Tables A.4–A.6. SI
sion into Saybolt Universal viscosities may be carried out by also employs 20 prefixes to form decimal multiples and sub-
the procedures and tables described in ASTM Method D446, multiples of SI unit, which are provided in Table A.7. Certain
and into Saybolt Furol viscosities by those described in units are not part of the International System of Units per se,
ASTM Method D666. Augmented tables are published in but are important and widely used. These units are accepted
ASTM Special Technical Publication 43B. for use with the SI and are given in Table A.8. Table A.9 lists
Viscosity Index „VI…—Relationship of viscosity of a some of the commonly used Metric System units and sym-
fluid to temperature in 40° and 100 ° C range. High VI fluids bols and Table A.10 provides the conversion factors.
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䊏 APPENDIX 621
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䊏 APPENDIX 623
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TABLE A.5—SI derived units with special names and symbols †844‡.
Expression in Terms Expression in Terms of
Derived Quantity Name Symbol of Other SI Units SI Base Units
plane angle radian rad ¯ m · m−1 = 1 共b兲
frequency hertz Hz ¯ s−1
force Newton N ¯ m · kg· s−2
pressure, stress Pascal Pa N / m2 m−1 · kg· s−2
energy, work, quantity of heat Joule J N·m m2 · kg· s−2
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䊏 APPENDIX 625
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䊏 APPENDIX 627
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628 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
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MNL59-EB/Mar. 2009
Index
A lubricating greases, 446, 480
metalworking and machining fluids, 500–517
additives cleanliness agents, 325–327
gear oil formulation, 404–406 combustion chamber
lubricating greases, 467–469 deposit buildup, 301
metalworking and machining fluids, 519–528 design, 302
air-fuel ratio, 300 combustion engine lubricants, 212–272
air intake temperature control, 302 classifications, 216
aldehydes, 278 emissions control, 256–259
ambient air quality standards, 280 engine oil classification based on end-use, 229–245
analytical tests, gear lubricants, 407–408 engine types, 213–215
anti-icing agents, 327 European standards, 222–228
anti-wear agents, lubricants, 21 extended service, 260–267
antistatic agents, 332 formulating engine oils, 249–255
application-based formulations, metalworking formulation examples, 268–269
and machining fluids, 529–530 fuel economy, 256
approval process Indian standards, 229
lubricant additives, 211 Japanese standards, 229
lubricant testing, 531–532 lubricant-related causes of engine malfunction, 246
automatic transmission fluids, 365–368 operation mode, 213–215
automotive aftermarket, lubricating greases, 484–485 railroad diesel engine oil concentrates, 270–272
automotive gear oils, 393–396 rating of engine parts, 247–248
specifications, 216
trends on new standards, 217
B U.S. standards, 218–221
combustion modifiers, 330
base fluids composition
gear oil formulation, 402–404 lubricating greases, 448–463
lubricating greases, 463–467 metalworking and machining fluids, 518–519
metalworking and machining fluids, 500–505, 518 natural oils and structural modifications, 97–99
base oil properties, mineral base oils, 42–46 transmission fluid, 370–373
bearing lubrication, 482–484 compression ratio, 302
bevel gears, 382 compressor and refrigeration oils, 424–432
biocides, 331–332 condition-monitoring, hydraulic fluids, 364
biodegradability, lubricants, 595–598 conservation, lubricants, 585–587
biodegradable grease, 496 continuously variable transmissions, 373–376
biodiesel, 311 lubricants, 376–378
biological 共natural兲 base stocks, 92–99 controlled auto-ignition combustion, 302
composition of natural oils and structural coolant temperature effect, 302
modifications, 97–99 corrosion
manufacture and processing, 95 inhibitors, 331
melting point/pour point, 94 protection, 477–478
oxidative stability, 94 criteria for suitable base stocks, lubricant additives, 103
Blue Sky emissions standards, 292
brake fluids, 378–380
D
C demulsifiers, 331
lubricant additives, 181–184
California emissions standards, 286–288 deposit control additives, 325–327
carbon monoxide, 277 deposit formation, 322–325
carboxylate esters, synthetic base stocks, 54–61 desirable properties, lubricating greases, 471–480
cetance improvers, 329 detergents
chassis grease, 495 lubricant additives, 137–148
chemical tests, 531 in lubricants, 21
chemistry, lubricating greases, 463–469 diagnostics, gear failure, 385
classification diesel combustion, 307–308
combustion engine lubricants, 216 diesel emissions standards, 288–292
629
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630 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
selection T
gear lubricants, 406–407
gear lubrication, 393–401 testing
lubricating greases, 482 gear lubricants, 407–408
shock absorber fluids, 380–381 lubricating greases, 486–492
smoke suppressants, 330 transmission fluid, 370–373
soap lubricating greases, 448–459 textiles, lubricating greases, 485
soot, 278 toxicity, 583
spalling, 389 lubricants and environment, 598–599
specialty lubricating greases, 492–496 track roller lubricants, 495
specifications, combustion engine lubricants, 216 tractor hydraulic fluids, 335
spur gears, 382 transmission fluids, 364–378
stabilizers/deposit control agents, lubricant automatic, 365–368
additives, 105–109 composition and testing, 370–373
standardized testing, lubricants and environment, 593–595 formulation examples, 378–381
standards power, 368–370
ambient air quality, 280 trends on new standards, combustion engine lubricants, 217
Blue Sky emissions, 292 turbine, industrial lubricants, 411–424
California emissions, 286–288 turbo-charging, 303
combustion engine lubricants, 218–221
diesel emissions, 288–292 U
emissions, 281–295
European, 222–228 unburned hydrocarbons, 276–277
European Union, 293–296 U.S. standards
evaporative emissions, 292 combustion engine lubricants, 218–221
gasoline engines, 283–288 emissions, 281–293
Indian, 229 used oil recycling, 587–588
Japanese, 229
light-duty vehicle cold temperature emissions, 292
trends, 217
V
U.S., 281–293
steel mills, lubricating greases, 485 valve overlap, 301
storage viscosity
lubricating greases, 485–486 metalworking and machining fluids, 500
stability, lubricating greases, 476 modifiers in lubricants, 22
stroke-to-bore ratio, 302 and wear, 8–18
sulfur and nitrogen compounds effects, mineral base oils, 42
sulfur dioxide, 278 W
surface temperature, 301–302
surface-to-volume ratio, 302 water sensitivity, lubricating greases, 477
synthetic base fluids versus petroleum base stocks, 76–91 wax modifiers, 330
synthetic base stocks, 47–91 wear, viscosity and, 8–18
carboxylate esters, 54–61 worm gears, 382–383
versus petroleum base stocks, 76–91
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636 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
Lubricants Technology: An Overview, SP.603, Society tional, West Conshohocken, PA, Chapter 24, 2003, pp. 649–
of Automotive Engineers, Oct. 1984, pp. 1–10. 673.
关36兴 “Water-based Drilling Fluids Using Latex Additives,” U.S. 关55兴 Cochrac, G. J. and Rizvi, S. Q. A., “Oxidation of Lubricants and
Patent 6,703,351 共March 9, 2004兲. Inventors: D. K. Clap- Fuels,” Fuels and Lubricants Handbook: Technology,
per, C. Joseph Stowe II, R. G. Bland, T. Xiang, T., and S. Properties, Performance, and Testing, MNL37WCD, Ed.,
Benaissa. ASTM International, West Conshohocken, PA, Chapter 30,
关37兴 Clark, R. K., “Petroleum 共Drilling Fluids兲,” Kirk-Othmer En- 2003, pp. 787–824.
cyclopedia of Chemical Technology, Fourth Edition, M. 关56兴 Fresco, G. B., Klaus, E. E., and Tewksbury, E. J., “Measure-
Grayson, Ed., John Wiley and Son, NY, Vol. 18, 1996, pp. 370– ment and Prediction of Viscosity-Pressure Characteristics of
405. Liquids,” ASME J. Lubr. Technol., Paper No. 68-Lub-8,
关38兴 “Drilling Mud Viscosifier,” U.S. Patent 4,240,915 共Decem- 1968, pp. 1–7.
ber 23, 1980兲. Inventor: J. Block. 关57兴 Roelands, C. J. A., Vlugter, J. C., and Waterman, H. I., “The
关39兴 Speight, J., “Petroleum 共Refinery Processes兲,” Kirk-Othmer Viscosity-Temperature-Pressure Relationship of Lubricating
Encyclopedia of Chemical Technology, Fourth Edition, Oils and Its Correlation with Chemical Constitution,” J. Basic
M. Grayson, Ed., John Wiley and Son, NY, Vol. 18, 1996, pp. Eng., Dec. 1963, pp. 601–610.
433–469. 关58兴 Errichello, R., “Selecting Oils with High Pressure-Viscosity
关40兴 Rakow, M. S., “Petroleum Oil Refining.” Fuels and Lubri- Coefficient-Increase Bearing Life by More Than Four Times,”
cants Handbook: Technology, Properties, Performance, Machinery Lubrication Magazine, March 2004. “http://
and Testing, MNL37WCD, Ed., ASTM International, West www.machinerylubrication.com/article_detail.asp?articleid
Conshohocken, PA, Chapter 1, 2003, pp. 3–30. ⫽586&relatedbookgroup⫽Lubrication
关41兴 Prince, R. J., “Base Oils from Petroleum,” Chemistry and 关59兴 Blair, S., Klaus, E., and Bala, V., “An Experimental Verifica-
Technology of Lubricants, R. M. Mortier and S. T. Orszulik, tion of the Significance of the Reciprocal Asymptotic Isovis-
Eds., Blackie Academic and Professional-Chapman & Hall, cous Pressure for EHD Lubricants,” ASLE Tribology Trans-
London, UK, 1996, Chapter 1, pp. 1–33. actions, Vol. 36, No. 2, 1993, pp. 153–162.
关42兴 Stipanovic, A. J., “Hydrocarbon Base Oil Chemistry,” Fuels 关60兴 Murray, D. W., MacDonald, J. M., White, A. M., and Wright, P.
and Lubricants Handbook: Technology, Properties, Per- W., “The Effect of Basestock Composition on Lubricant Oxi-
formance, and Testing, MNL37WCD, Ed., ASTM Interna- dation Performance,” Petroleum Review, 1982, pp. 36–40.
tional, West Conshohocken, PA, Chapter 7, 2003, pp. 169– 关61兴 “Base Oils for Automotive Lubricants,” Special Publication
184. SP 526, Society of Automotive Engineers, Warrendale,
关43兴 Congram, G. E., “Chemical Additives Aid Processing Effi- PA, 1982, and references therein.
ciency,” The Oil and Gas Journal, Feb. 9, 1976, pp. 102– 关62兴 Stipanovic, A. J., Smith, M. P., Firmstone, G. P., and Patel, J.
105. A., “Compositional Analysis of Re-refined and Non-
关44兴 Lubrication Theory and Practice, www.lubrizol.com conventional Lubricant Base Oils: Correlations to Sequence
关45兴 Gedeon, B. J. and Yenni, N. L., “Use of “Clean” Paraffinic Pro- VE and IIIE Engine Tests,” SAE Publication 941978, Society
cessing Oils to Improve TPE Properties,” Presented at TPEs of Automotive Engineers, Warrendale, PA, 1994.
2000, Philadelphia, PA, Sept. 27–28, 1999. 关63兴 Firmstone, G. P., Smith, M. P., and Stipanovic, A. J., “A Com-
关46兴 Sequeira, A., “Lubricant Base Oil Processing,” Lubrication, parison of Neural Network and Partial Least Squares Ap-
Vol. 75, No. 1, 1989, pp. 1–12. proaches in Correlating Base Oil Composition to Lubricant
关47兴 Sequeira, A., Lubricant Base Oil and Wax Processing, Marcel Performance in Gasoline and Industrial Oil Applications,” Spe-
Dekker Inc., NY, 1994. cial Publication SP 952534, Society of Automotive Engineers,
关48兴 “1999 Lubricating Oil and Wax Capacities of Refiners and Re- Warrendale, PA, 1995.
finers in the Western Hemisphere,” National Petroleum and 关64兴 Roby, S. H., Supp, J. A., Barrer, D. E., and Hogue, C. H., “Base
Refiners Association 共NPRA兲, 1999. Oil Effects in the Sequence IIID and Sequence VD Engine
关49兴 “Viscosity Index Tables for Celsius Temperatures,” ASTM Tests,” SAE Publication 892108, Society of Automotive Engi-
Data Series Publication-DS-39B, ASTM International, neers, Warrendale, PA, 1989.
West Conshohocken, PA, Sept. 1965. 关65兴 “The Increasing Significance of Base Oils in the Evolution of
关50兴 Schilling, A., Motor Oils and Engine Lubrication, Scientific Heavy-Duty Diesel Engine Oils,” 1999 National Petro-
Publications, Great Britain, 1968. leum Refiners Association 共NPRA兲, LW-99–130, Hous-
关51兴 http://www.prod.exxonmobil.com/refiningtechnologies/pdf/ ton, TX, 1999.
refin_EMICT_santiesteban_japan050701.pdf. The link is no 关66兴 Yoshida, T., Igarashi, J., and Watanabe, H., “Pro-Oxidation
longer active. Properties of Basic Nitrogen Components in Base Oil,” Pro-
关52兴 Johnson, R. L., “Conservation of Lubricants, Materials and ceedings of the 11th International Colloquium Technol-
Energy,” CRC Handbook of Lubrication, Vol. I, Theory ogy, Esslingen, Germany, Jan. 1998.
and Practice of Tribology: Applications and Mainte- 关67兴 Kramer, D. C., Ziemer, J. N., Cheng, M. T., Fry, C. E., Rey-
nance, R. E. Booser, Ed., CRC Press, Boca Raton, 1983, pp. nolds, R. N., and Lok, B. K., et al., “Influence of Group II and
551–565. Group III Base Oil Composition on VI and Oxidation Stabil-
关53兴 Cornitius, T., “Base Stock Market Outlook,” Lubricants ity,” National Lubricating Grease Institute 共NLGI兲 Pa-
World, 1998, pp. 16–23. per 9907, Tucson AZ, 1999.
关54兴 Fitch, J. C. and Barnes, M., “Hydrocarbon Analysis,” Fuels 关68兴 Mangone, C., “Gas to Liquids—Conversions Produce Ex-
and Lubricants Handbook: Technology, Properties, Per- tremely Pure Base Oils,” inMachinery Lubrication Magazine,
formance, and Testing, MNL37WCD, Ed., ASTM Interna- Nov. 2002.
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䊏 REFERENCES 637
关69兴 “Physical and Chemical Properties of Engine Oils” SAE J357, tion Polyalphaolefins—The Next Step in the Evolution of Syn-
SAE Information Report, Completely Revised May 1984, Soci- thetic Hydrocarbon Fluids,” Innovene USA LLC 11/22/05
ety of Automotive Engineers. revision; posted 11/22/05. http://www.innovene.com/
关70兴 Asseff, P. A., “Lubrication Theory and Practice,” Publication liveassets/bp_internet/innovene/STAGING/
183-320-59, The Lubrizol Corporation, Wickliffe, OH. home_assets/assets/products/polyalphaolefins/pdfs/
关71兴 Ripple, D. E., and Fuhrmann, J. F., “Performance Compari- Next_Generation_PAOs.
sons of Synthetic and Mineral Oil Crankcase Lubricant Base 关89兴 “Biodegradable Polyalphaolefin Fluids and Formulations Con-
Stocks,” Presented at the 4th International Colloquium, taining the Fluids,” U.S. Patent 6,071,863 共2000兲. Inven-
Esslingen, Germany, Jan. 1984. tors: R. Benda, J. V. Bullen, and A. J. Plomar.
关72兴 Smith, T. G., “Neopentyl Polyol Esters,” Synthetic Lubri- 关90兴 http://www.atiel.org/downloads/code_practice/
cants, R. C. Gunderson and A. W. Hart, Eds., Reinhold Pub- AppendixBissue13.pdf#search⫽/22polyinternalolefins/
lishing Corporation, NY, Chapter 10, 1962. 20pios/22
关73兴 Goddard, D. R., “Synthetic Fluids,” Lubrication and Lubri- 关91兴 “Europeans Adopt 6th Base Oil Group,” by Tim Sullivan,
cants, E. R. Braithwaite, Ed., Elsevier Publishing, Chapter 4, Lube Report, Sept. 23, 2003.
1967, pp. 166–196. 关92兴 “Alkylation of Aromatic Hydrocarbons,” U.S. Patent
关74兴 Synthetic Lubricants and High-performance Functional Flu- 2,939,890 共June 7, 1960兲. Inventor: G. L. Hervert.
ids, 2nd Ed., L. R. Rudnick and R. L. Shubkin, Eds., Marcel 关93兴 “Aromatic Lubricants and Their Method of Preparation,” U.S.
Dekker, Inc., NY, 1999. Also see the 1993 Edition, R. L. Patent 3,173,965 共March 16, 1965兲. Inventors: J. J. Pappas
Shubkin, Ed. and F. H. Kant.
关75兴 Toxics Release Inventory: List of Toxic Chemicals Within the 关94兴 “Preparation of Synthetic Hydrocarbon Lubricants,” U.S.
Polychlorinated Alkanes Category and Guidance for Report- Patent 4,148,834 共April 10, 1979兲. Inventors: C. D.
ing United States Office of Pollution, June 1999, Environmen- Kennedy and G. E. Nicks.
tal Protection Prevention and Toxics Agency Washington, 关95兴 “Alkylation of Aromatic Compounds,” U.S. Patent
DC 20460, http://www.epa. gov/tri/guide_docs/1999/ 4,551,573 共Nov. 5, 1985兲. Inventor: R. L. Cobb.
polychloroalkanes1999. pdf 关96兴 Aromatics Alkylation—Towards Cleaner, More Selective
关76兴 Adrianus, H., and van Dijk, J., “The Fischer-Tropsch Synthe- Processes. 关http://www.prod.exxonmobil.com/
sis: A Mechanistic Study Using Transient Isotopic Tracing,” refiningtechnologies/pdf/
2001, 关http://alexandria. tue. nl/extra2/200111083.pdf兴. aromatics_alkylation_catalyst_gen_shape_sel_france.pdf兴.
关77兴 共a兲 http://en. wikipedia.org/wiki/Linear_alpha_olefins 共b兲 关97兴 “Synthetic oil With a High Viscosity Number and a Low Pour
http://nexant.ecnext.com/com2/gi_0255-148/Alpha- Point 共Zeolite/alumina兲,” U.S. Patent 6,491,809 共Dec. 10,
Olefins.html. 2002兲. Inventors: A. Forestiere, E. Benazzi, P. Briot, L. Lew,
关78兴 Mazzone, L. C. A., and Fernandes, F. A. N., “Modeling of and S. Gautier.
Fischer-Tropsch Synthesis in a Tubular Reactor,” Lat. Am. 关98兴 “Hydrocarbon Hydraulic Oils,” U.S. Patent 3,478,113
Appl. Res. Vol. 36, 2006, pp. 141–148. 共Nov. 11, 1965兲. Inventors: U. B. Bray and M. Fainman.
关79兴 Buenemann, T. F., Boyde, S., Randles, S., and Thompson, I., 关99兴 “Preparation of Synthetic Hydrocarbon Lubricants,” U.S.
“Synthetic Lubricants-Non Aqueous,” Fuels and Lubricants Patent 3,909,432 共Sept. 30, 1975兲. Inventors: S. McGuire,
Handbook: Technology, Properties, Performance, and J. L. Riddle, G. E. Nicks, O. C. Kerfoot, and C. D. Kennedy.
Testing, MNL37WCD, Ed., ASTM International, West Con- 关100兴 “Emulsifier/Detergent Compounds for Metalworking Lubri-
shohocken, PA, Chapter 10, 2003, pp. 249–266. cants,” Thomas, S. C., Jr., Application 20050075252 April 7,
关80兴 “Verfahren zur Herstellung von Polyethylen, Polypropylen 2005.
und Copolymeren,” Patent DE3007725, 1980. 关101兴 Suva® Refrigerants—Suva® 134-a in Chillers, http://
关81兴 “Metallocene Catalysis Polymerization,” http://www.pslc. refrigerants.dupont.com/Suva/en_US/pdf/h42444.pdf
ws/mactest/mcene.htm. 关102兴 http://www.exxonmobilchemical.com/Public_Files/
关82兴 Patent WO 96/23010, 01 August 1996 - Alpha-olefins and ole- Synthetics/Synthetic_ Lubricants_and_Fluids/Worldwide/
fin polymers and processes therefore. Data_Sheet_Synesstic_v5.pdf
关83兴 “Post-metallocene Catalyst,” http://en. wikipedia.org/ 关103兴 “Condensation Product from Olefins and Hydrocarbons of
wiki/post-metallocene_catalyst Naphthalene Series and Process of Making the Same,” U.S.
关84兴 “Synthetic Lubricants by Oligomerization and Hydrogena- Patent 1,667,214 共April 24, 1928兲. Inventor: R. Michel.
tion,” U.S. Patent 3,780,128 共1973兲. Inventor: R. L. 关104兴 “Hydrocarbon Oil and Process for Manufacture of the Same,”
Shubkin. U.S. Patent 1,815,022 共July 14, 1931兲. Inventor: G. H. B.
关85兴 “Polymerization of Olefins with BF3,” U.S. Patent Davis.
3,382,291 共1968兲. Inventor: J. A. Brennan. 关105兴 “Methylene Linked Aromatic Pour Point Depressant,” U.S.
关86兴 “Process of Producing a C6 – C16 Normal Alpha-olefin Oligo- Patent 4,753,745 共June 28, 1988兲. Inventors: J. L. Kos-
mer Having a Pour Point Below about −50 °F,” U.S. Patent tusyk and S. Q. A. Rizvi.
3,763,244 共1973兲. Inventor: R. L. Shubkin. 关106兴 Randles, S. J., Stroud, P. M., Mortier, R. M., Orszulik, S. T.,
关87兴 Shubkin, R. L., “Polyalphaolefins,” CRC Handbook of Lu- Hoyes, T. J., and Brown, M., “Synthetic Base Fluids,” Chem-
brication, Theory and Practice in Tribology, Vol. III, istry and Technology of Lubricants, R. M. Mortier and S. T.
Monitoring, Materials, Synthetic Lubricants, and Appli- Orszulik, Eds., Blackie Academic and Professional-Chapman
cations, R. E. Booser, Ed., CRC Press, Boca Raton, 1993, pp. & Hall, London, UK, 1996, Chapter 2, pp. 34–74.
219–235. 关107兴 van der Waal, G., “The Relationship Between the Chemical
关88兴 Moore, L., Bagheri, V., Barrett, C., and Palm, J., “Next Genera- Structure of Ester Base Fluids and Their Influence on Elas-
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638 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
tomer Seals and Wear Characteristics,” J. Syn. Lub., Vol. 1, 关124兴 Ohsaka, Y., “Recent Advances in Synthetic Lubricating Oils.,
No. 4, 1985, pp. 281–301. 共8兲. Perfluorinated Polyethers,” Petrotech 共Tokyo兲, Vol. 8,
关108兴 Alber, F., Kloppenburg, D., Kloppenburg, H., Schär, D., and No. 9, 1985, pp. 840–843.
Utz, R., “Citric Acid Esters Based on Mixtures of Alcohols— 关125兴 Kinzig, B. J., and Ravner, H., “Factors Contributing to the
New Kind of Polymer Additives and Plasticizers for a Variety Properties of Fluoropolymer Barrier Films,” ASLE Trans.,
of Polymers,” 共http://www.priorartdatabase.com/ Vol. 21, 1978, pp. 291–298.
IPCOM/000029795/兲. 关126兴 Hilton, M. R., and Fleischaur, P. D., “Lubricants for High-
关109兴 Kirk-Othmer Encyclopedia of Chemical Technology, 4th ed., vacuum Application,” Aerospace Report No. TR-0091
John Wiley & Sons, Inc., NY, Vol. 18, 1991, p. 1991. 共6945-03兲-6, March 1993.
关110兴 “Process for the Production of Trimellitic Anhydride,” U.S. 关127兴 Bell, G. A., Howell, J., and DelPasco, T. W., “Perfluoroalkyl
Patent 4,587,350 共May 6, 1986兲. Inventors: P. H. Kilner, J. Polyethers,” Synthetic Lubricants and High Performance
P. Egan, Jr., S. G. Ceisel, and W. P. Schammel. Functional Fluids, R. L. Rudnick, and R. L. Shubkin, Eds.,
关111兴 “Preparation of Aliphatic Alpha, Omega-dicarboxylic Acids,” Marcel Dekker, Inc., NY, 1999, p. 215.
U.S. Patent 6,437,180 共August 20, 2002兲. Inventors: M. 关128兴 Gulino, D. A., and Coles, C. E., “Oxygen Plasma Effects on
Schelhaas, H. Greiving, and M. Jautelat. Several Liquid Droplet Radiator Fluids,” J. Spacecr. Rock-
关112兴 “Manufacturing Method of Neopentyl Glycol,” U.S. Patent ets, Vol. 25, No. 2, 1988, pp. 99–101.
6,268,539 共July 31, 2001兲. Inventors: H. Sen-Huang, T. 关129兴 Jones, W. R., Jr., Johnson, R. L., Winer, W. O., and Sanborn, D.
Chia-Ruey, and C. Jung-Jen. M., “Pressure-Viscosity Measurements for Several Lubricants
关113兴 “Process for the Preparation of Pentaerythritol,” U.S. Patent to 5.5⫻ 108 per Square Metre 共8 ⫻ 104 psi兲 and 149 ° C
5,741,956 共April 21, 1998兲. Inventor: L. Eek. 共300 °F兲,” ASLE Trans., Vol. 18, No. 8, 1975, pp. 249–262.
关114兴 “Method for Purifying Trimethylolpropane, Which is Pro- 关130兴 Quinn, C., Traver, F., and Murthy, K., “Silicones,” Lubrica-
duced by Hydrogenation, by Means of Continuous Distilla- tion at the Frontier, D. Dowson et al., Eds., Proceedings of the
tion,” U.S. Patent 6,692,616 共February 17, 2004兲. Inven- 25th Leeds-Lyons Symposium on Tribology, 1998, Elsevier, NY,
tors: D. Dernbach, D. Kratz, A. Stammer, H. Rust, and G. 1999, p. 267.
Schulz. 关131兴 Aderin, M., Johnston, G. J., Spikes, H. A., and Caporiccio, G.,
关115兴 Murrenhoff, H. and Remmelmann, A., “Environmentally “The Elasto-hydrodynamic Properties of Some Advanced Non
Friendly Oils,” Fuels and Lubricants Handbook: Technol- Hydrocarbon-Based Lubricants,” Lubr. Eng., Vol. 48, No. 8,
ogy, Properties, Performance, and Testing, G. E. Totten 1992, pp. 633–638.
Ed., ASTM International, West Conshohocken, PA, Chapter 关132兴 Lagow, R. J., and Margrave, J. L., “Direct Fluorination: A New
11, 2003, pp. 267–295. Approach to Fluorine Chemistry,” In Progress in Inorganic
关116兴 Cerny, J., “Using Calorimetry to Measure Motor Oil Remain- Chemistry, Vol. 26, 1979, pp. 162–210. S. J. Llppard, Ed.,
ing Useful Life,” Practical Oil Analysis Magazine, Sept. Wiley, NY.
2004. http://www.practicingoilanalysis.com/article_detail. 关133兴 Jones, W. R., Bierschenk, T. R., Juhlke, T. J., Kawa, H., and
asp?articleid⫽649 Lagow, R. J., “Improved Perfluoroalkyl Ether Fluid Develop-
关117兴 Sanvordenker, K. S., “Material Compatibility of R134a in Re- ment,” Ind. Eng. Chem. Res., Vol. 26, 1987 pp. 1930–1935.
frigerant Systems,” Presented at The American Society of 关134兴 Blerschenk, T. R., Kawa, H., Juhlke, T. J., and Lagow, R. J.,
Heating, Refrigeration and Air-Conditioning Engineers, “The Development of New, Low-Cost Perfluoroalkylether Flu-
Winter Meeting, Jan. 1989. ids with Excellent Low and High-Temperature Properties,”
关118兴 Quinn, C., Traver, F., and Murthy, K., “Silicones,” Synthetic NASA CR 182155, May 1988.
Lubricants and High Performance Functional Fluids, R. 关135兴 Conley, P. L., and Bohnerj, J. J., “Experience with Synthetic
L. Rudnick and R. L. Shubkin, Eds., Marcel Dekker, Inc., NY, Fluorinated Fluid Lubricants,” 24th Aerospace Mecha-
1999, pp. 267–286. nisms Symposium, NASA CP 3062, April 18–20, 1990, pp.
关119兴 Coolanol® Silicate Ester Dielectric Heat Transfer Fluids, http:// 213–230.
www.exxonmobil.com/lubes/exxonmobil/emal/ 关136兴 “Method of Quenching Metal,” U.S. Patent 5,490,886
Coolanol_Silicate_Ester_Dielectric_Heat_Transfer_Fluids. 共February 13, 1996兲. Inventor: D. G. Placek.
html 关137兴 “Military Fluids—MIL-H-19457 D 共SH兲,” http://
关120兴 Jones, Jr., W. R., “The Properties of Perfluoroethers Used for www.radcoind.com/MIL-H-19457D. htm.
Space Applications,” NASA Technical Memorandum 关138兴 Ullmann’s Encyclopedia of Industrial Chemistry, 5th ed., W.
106275, July 1998. http://gltrs.grc.nasa.gov/reports/1993/ Gerhartz, Exec. Ed., Deerfield Beach, FL: VCH Publishers,
TM-106275.pdf Vol A1, 1985 to Present, VA11 364.
关121兴 Gumprecht, W. H., “PR-143—A New Class of High- 关139兴 Purdy, E. M., “Use of CTFE as an Additive to Enhance Fire
temperature Fluids,” ASLE Transactions, Vol. 9, 1966 pp. Resistance of Single Hydraulic Fluid,” TARDEC Report
24–30. 13610, Nov. 1994.
关122兴 Sianesi, D., Zamboni, V., Fontanelli, R., and Binaghi, M., 关140兴 Chemical and Process Technology Encyclopedia, D. Considine,
“Perfluoropolyethers. Their Physical Properties and Behavior McGraw-Hill Education, 1974, p. 286.
at High and Low Temperatures,” Wear, Vol. 18, 1971, pp. 85– 关141兴 “Halovac Inert Pump Fluids,” http://www.
100. inlandvacuum.com/halovac.html.
关123兴 Sianesi, D., Pasetti, A., Zamboni, V., Fontanelli, R., and Ber- 关142兴 Hawley’s Condensed Chemical Dictionary, 12th ed., R. J.
nardi, G. C., “Perfluoropolyethers by Photo-oxidation of Lewis, Sr., Ed., Van Nostrand Rheinhold Co., NY, 1993.
Fluoro-olfins,” Chim. Ind., 共Milan兲, Vol. 55, 1978, pp. 208– 关143兴 共a兲 Santolubes Product Brochure. 共b兲 Joaquim, M., “Polyphe-
221. nyl Ether Lubricants,” Synthetic Lubricants and High-
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Downloaded/printed
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䊏 REFERENCES 639
performance Functional Fluids, R. L. Rudnick, and R. L. 关162兴 Fuhr, J., Oetinger, J., Totten, G. E., and Webster, G. M., “Min-
Shubkin, Eds., Marcel Dekker, Inc., NY, 1999, p. 239. Swed- eral Oil Heat Transfer Fluids,” Fuels and Lubricants Hand-
bers, S., “What is up next?” Lubes ‘n’ greases. Vol. 13, July book: Technology, Properties, Performance, and Testing,
18, 2008, pp. 674. MNL37WCD, Ed., ASTM International, West Conshohocken,
关144兴 Herber, Sr., J. F. and Joaquim, M., “Polyphenyl Ethers: Lubri- PA, Chapter 21, 2003, pp. 573–586.
cation in Extreme Environments,” http://www. 关163兴 Reddy, R. G., Wu, B., and Roger, R. D., “Ionic Liquids as Ther-
chemassociates.com/products/findett/PPEs_LubEng. mal Energy Storage Media for Solar Thermal Electric Power
pdf. Systems,” http://www.eere.doe.gov/troughnet/pdfs/
关145兴 OS 124, Polyphenyl Ether Fluid by Santovac®, Commercial rreddy_ionicfluids.pdf.
Literature, Santovac® Fluids, Saint Charles, MO, 1999. 关164兴 Joaquim, M. E., and Herber, J. F., “Lubrication of Electronic
关146兴 Venier, C. G. and Casserly, E. W., “Cycloaliphatics,” in Syn- Connectors and Equipment in Radiation Environments,”
thetic Lubricants and High Performance Functional http://www.chemassociates.com/products/findett/
Fluids, R. Shubkin, Ed., 1993. pp. 241–269. PPEs_Radiation2.pdf.
关147兴 Venier, C. G. and Casserly, E. W., “Cycloaliphatics,” Syn- 关165兴 Bolt, R. O., “Radiation Effects on Lubricants,” CRC Hand-
thetic Lubricants and High-performance Functional book of Lubrication, Vol. I, Theory and Practice of Tri-
Fluids, R. L. Rudnick and R. L. Shubkin, Eds., Marcel Dek- bology: Applications and Maintenance, R. E. Booser, Ed.,
ker, Inc., NY, 1999, p. 325. CRC Press, Boca Raton, 1983, pp. 209–233.
关148兴 “Lubricants Comprising Novel Cyclopentanes, Cyclopenta- 关166兴 Carroll, J. G., and Bolt, R. O., Radiation Effects on Organic
dienes, Cyclopentenes, and Mixtures Thereof and Methods of Materials, R. O. Bolt and J. G. Carroll, Eds., Academic Press,
Manufacture,” U.S. Patent 4,721,823 共January 6, 1988兲. NY, 1963.
Inventors: C. G. Venier and E. W. Casserly. 关167兴 Harrington, R., “Elastomers for Use in Radiation Fields IV. Ef-
关149兴 “Control of the Reaction Parameters Changes the Alkylate fects of Gamma Radiation on Miscellaneous Elastomers and
Composition 关Substituted Cyclopentadienes, Methods of Rubber-like Materials,” Rubber Age, Vol. 83, No. 1, 1958, p.
Manufacture and Uses,” U.S. Patent 5,144,095 共Septem- 472.
ber 1, 1992兲. Inventors: C. G. Venier and E. W. Casserly, 关168兴 “Eco-Label,” http://europa.eu.int/scadplus/leg/en/lvb/
关150兴 “MACS vs. PFPEs: Choosing between Multiply Alkylated Cy- l28020.htm
colpentanes and Perfluoropolyethers for Vacuum Applica- 关169兴 “Concept Background Document: Development of Criteria for
tions,” http://www.nyelubricants.com/pdf/literature/ the Award of the European Eco-label to Lubricants,” by D.
Lube-Insights-Pennzane. pdf. Theodori, R. J. Saft, H. Krop, P. van Broekhuizen
关151兴 Venier, C. G. and Casserly, E. W., “Multiply-Alkylated Cyclo- http://europa.eu.int/comm/environment/ecolabel/pdf/
pentanes 共MACs兲: A New Class of Synthesized Hydrocarbon lubricants/backgrounddoc_111203.pdf
Fluids,” Lubr. Eng. Vol. 47, No. 7, 1991, pp. 586–591. 关170兴 “Lubricating Oil Basestocks,” Summary prepared by
关152兴 Brown, P. L., Miller, J. B., Jones, Jr., W. R., Rasmussen, K., American Petroleum Institute, July 24, 2001 http://
Wheeler, D. W., Rana, M., and Peri, F., “The Clouds and the www.petroleumhpv.org/Product_Categories/Lube_Oils/
Earth’s Radiant Energy System Elevation Bearing Assembly 2004_03_03_Lubes_Revised_Robust_Summary.pdf
Life Test,” 33rd Aerospace Mechanisms Symposium, 关171兴 “Biodegradability and Alternatives,” http://mbm.net.au/
Pasadena, CA, NASACP-1999-209259, 1999, pp. 197–212. b100/biodegrade.html
关153兴 Jones, Jr., W. R. and Jansen, M. J., “Space Tribology,” NASA/ 关172兴 “A Comparison of the Environmental Performance of Olefin
TM—2000-209924, March 2000. http://gltrs.grc.nasa.gov/ and Paraffin Synthetic Base Fluids 共SBF兲,” Nov. 2006. http://
reports/2000/TM-2000-209924. pdf www.americanchemistry.com/s_acc/bin.asp?CID
关154兴 Klaus, E. E. and Tewksbury, E. J., “Liquid Lubricants,” ⫽1075&DID⫽4210&DOC⫽FILE.PDF
Handbook of Lubrication: Theory and Practice of Tribol- 关173兴 Randles, S. J., and Wright, M., “Environmentally Friendly Es-
ogy, Volume II, Theory and Design, R. Booser, Ed., CRC ter Lubricants for the Automotive and Engineering
Press, Inc., Boca Raton, 1983, pp. 229–253. Industries—Esters, Base Oils for Synthetic Lubricants,” Inter-
关155兴 “Metric Conversion Chart—Pressure,” http://www. national Congress about Lubricants, Lubricants for Fu-
engnetglobal.com/tips/convert.asp?catid⫽17 ture and the Environment, Brussels, Sept. 1991, p. 197.
关156兴 Errichello, R., “Selecting Oils with High Pressure-Viscosity 关174兴 “Gearing Up Performance—An Introduction to Synthetic Lu-
Coefficient—Increase Bearing Life by More Than Four bricants by Jeffrey Lay,” 关http://www.nyelubricants.com/
Times,” Machinery Lubrication Magazine, March 2004. pdf/nye_gear_tech_v2.pdf兴
关157兴 Lehmus, M. and Holmqvist, H. G., “Top Tier Base Oil Trends 关175兴 Applewhite, T. H., “Fats and Fatty Oils,” Kirk-Othmer Ency-
Reflect European Engine Oil Demands,” Lubricants World, clopedia of Chemical Technology, Third Edition, M. Gray-
Nov. 2000. pp. 25–26. son, Ed., John Wiley and Son, NY, Vol. 9, 1981, pp. 795–831.
关158兴 DePuy, C. H. and King, R. W., “Pyrolytic Cis Elimination,” 关176兴 Krizek, F. Ch., and Coffin, P. S., “Vegetable Oil Based Lubri-
Chemical Reviews, Vol. 60, 1960, pp. 431–445. cants and Their Applications,” Presented at the 13th World
关159兴 High Temperature Lubrication, A. R. Lansdown, Mechanical Petroleum Congress, Buenos Aires, 1991.
Engineering Publications Ltd., London, 1988. 关177兴 共a兲 Honary, L. A. T., University of Northern Iowa,
关160兴 Szeri, A. Z., Tribology—Friction, Lubrication, and Wear, Hemi- “Biodegradable/Bio-based Lubricants and Greases,” Machin-
sphere Publications, Washington, DC, 1980. ery Lubrication Magazine, Sept. 2001. 共b兲 Erhan, S. Z. and
关161兴 Mock, III G. B., “Checking Plastic and Lubricant Compatibil- Sharma, B. K., “Environmentally Friendly Biobased Lubri-
ity Helps Avoid Warranty Problems,” www.nyelubricants. cants,” http://www.apfct.com/download/report/
com/pdf/1nyeplasticcomp.pdf. PM%20Session/877.pdf.
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640 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
关178兴 Begstra, R., “Green means Go,” Lubes-N-Greases, Novem- 1996, Chapter 4, pp. 98–143.
ber 2004, pp. 40–41. 关199兴 Abou El Naga, H. H. and Salem, A. E. M., “Effect of Worn Met-
关179兴 “Fats, Oils, Fatty Acids, Triglycerides,” http:// als on the Oxidation of Lubricating Oils,” Wear, Vol. 96, 1984,
www.scientificpsychic. com/fitness/fattyacids.html. pp. 267–283.
关180兴 共a兲 Erhan, S. Z. and Perez, J. M., Biobased Industrial Fluids 关200兴 Al-Malaika, S., Marogi, A. and Scott, G., “Mechanisms ofAnti-
and Lubricants, L. R. Rudnick, Ed., AOCS Press, Champaign, oxidant Action: Transformations Involved in the Antioxidant
IL, 2002. 共b兲 Swedberg, S., “What is Bio—and What is Next?” Function of Metal Dialkyl Dithiocarbamates, III,” J. Appl.
Lube & Greases, Vol. 14, No. 7, July 18, 2008, pp. 6–14. Polym. Sci., Vol. 33, 1987, pp. 1455–71.
关181兴 Barwell, F. T., “Lubricant Additives—The History of Their In- 关201兴 “Molybdenum Sulfur Antioxidant Lube Additive,” U.S.
troduction and Assessment,” Erdol-Erdgas-Kohle, Vol. 102, Patent 4,995,996 共February 26, 1991兲. Inventors: C. L.
No. 6, 1986, pp. 308–314. Coyle, M. A. Greaney, E. L. Stiefel, and J. N. Francis.
关182兴 Barwell, F. T., “Lubricant Additives—The History of Their In- 关202兴 Johnson, M. D., Korcek, S. and Zinbo, M., “Inhibition of Oxi-
troduction and Assessment,” Erdol-Erdgas-Kohle, Vol. 102, dation by ZDTP and Ashless Antioxidants in the Presence of
No. 12, 1986, pp. 561–567. Hydroperoxides at 160 ° C,” Lubricant and Additive Ef-
关183兴 Rizvi, S. Q. A., “Additives for Automotive Fuels and Lubri- fects on Engine Wear, SP-558, Fuels and Lubricants
cants,” Journal of the Society of Tribologists and Lubrica- Meeting, San Francisco, CA, October 31–November 3,
tion Engineers, Vol. 34, 1999, p. 55–. 1983, pp. 71–81.
关184兴 “Lubricant Additive Chemistry,” W. C. Gergel, Presented at the 关203兴 “2,6-Di-tertiarybutyl-4-methylphenol,” U.S. Patent 2,265,
International Symposium on Technical Organic Additives and 582 共December 9, 1941兲. Inventors: D. R. Stevens and W. A.
Environment, Interlaken, Switzerland, May 24–25, 1984. Gruse.
关185兴 “Lubricating Oil Additives-A Chemist’s Eye View,” J. F. Ford, 关204兴 “Process for the Production of Hydroxyalkylphenyl Deriva-
J. Inst. Pet., Vol. 54, 1968, pp. 188–210. tives,” U.S. Patent 4,228,297 共October 14, 1980兲. Inven-
关186兴 “Additive Expansion Unlikely, Says Afton,” by Nancy De- tors: J. Haeberli, K. P. Park, A. F. Vellturo, and G. F. Nurn-
Marco, Lube Report, March 7, 2006. berger.
关187兴 Rizvi, S. Q. A., “Dispersants,” Lubricant Additives: Chemis- 关205兴 “Procedure for Producing Stearyl-beta.-共3,5-dibutyl-4-
try and Applications, Chapter Leslie R. Rudnick, Ed., Mar- hydroxyphenyl兲 propionate and Bis-共beta., 共3,5-dibutyl-4-
cel Dekker, Inc., NY, Chapter 5, 2003, pp. 137–170. hydroxybenzyl兲-methylcarboxyethyl兲sulphide,” U.S. Patent
关188兴 Rizvi, S. Q. A., “Detergents,” Lubricant Additives: Chemis- 4,694,099 共September 15, 1987兲. Inventors: M. Ahlfors, S.
try and Applications, Chapter Leslie R. Rudnick, Ed., Mar- Koskimies, L. Lahtinen, and P. Idelman.
cel Dekker, Inc., NY, Chapter 4, 2003, pp. 113–136. 关206兴 “Liquid Phenolic Sulphur-containing Antioxidants,” U.S.
关189兴 “Lubrication Seminar,”—Lubrizol Report No. C-10337, Patent 7,026,438 共April 11, 2006兲. Inventors: H. Camen-
published July 1991. zind, P. Dubs, R. Martin, D. E. Chasan, G. Demme, and J. Rob-
关190兴 Bouman, C. A., Properties of Lubricating Oils and Engine De- bins.
posits, McMillan and Co., London, 1950, pp. 69–92. 关207兴 Hamblin, P. C., Kristen, U. and Chasan, D., “A Review: Ash-
关191兴 Kreuz, K. L., “Diesel Engine Chemistry as Applied to Lubri- less Antioxidants, Copper Deactivators, and Corrosion Inhibi-
cant Problems,” Lubrication, Vol. 56, 1970, pp. 77–88. tors, Their Use in Lubricating Oils,” Lubr. Sci., 2, 1990, pp.
关192兴 Kreuz, K. L., “Gasoline Engine Chemistry as Applied to Lubri- 287–318.
cant Problems,” Lubrication, Vol. 55, 1969, pp. 53–64. 关208兴 Developments in Polymer Stabilization, G. Scott, Ed., Elsevier
关193兴 Nahumck, W. M., Hyndman, C. W., and Cryvoff, S. A., “Devel- Applied Science Publishers, 1984, pp. 65–104.
opment of the PV-2 Engine Deposit and Wear Test,” An ASTM 关209兴 Vijh, A. K., “Electrochemical Mechanisms of the Dissolution of
Task Force Progress Report, SAE Publication 872123, Metals and the Contaminants Oxidation of Lubricating Oils
Presented at International Fuels and Lubricants Meet- under High-temperature Friction Conditions,” Wear, Vol. 104,
ing and Exposition, Toronto, Canada, November 2–5, 1987. 1985. pp. 151–158.
关194兴 Covitch, M. J., Humphrey, B. K., and Ripple, D. E., “Oil 关210兴 Bartz, W. J., “Lubrication of Industrial and Automotive Gears:
Thickening in the Mack T-7 Engine Test—Fuel Effects and the A Review,” Performance and Testing of Gear Oils and
Influence of Lubricant Additives on Soot Aggregation,” Pre- Transmission Fluids, R. Tourret and E. P. Wright, Eds.,
sented at SAE Fuels and Lubricants Meeting, Tulsa, Okla- Heyden and Son, Chapter 16, 1981, pp. 247–287.
homa, October 23, 1985. 关211兴 Scott, G., “New Developments in the Mechanistic Understand-
关195兴 Lewinsky, P. M., Cooke, V. B., and Andrews, C. A., “Lubrica- ing of Antioxidant Behavior,” J. Appl. Polym. Sci., Applied
tion Oil Requirements for Low Emission Diesel Engines,” Polymer Symposium, 35, 1979, pp. 123–149.
Presented at AVL Conference, Engine and Environment, 关212兴 Migdal, C., “Antioxidants,” Lubricant Additives: Chemis-
Graz, Austria, August 1–12, 1989. try and Applications, Leslie R. Rudnick, Ed., Marcel Dek-
关196兴 Ingold, K. U., “Inhibition of Autoxidation of Organic Sub- ker, Inc., NY, Chapter 7, 2003, pp. 1–27.
stances in Liquid Phase,” Chemical Reviews, Vol. 61, 1961, 关213兴 Gatto, V. J., Moehle, W. E., Cobb, T. W., and Schneller, E. R.,
pp. 563–589. “Oxidation Fundamentals and Its Application to Turbine Oil
关197兴 “Electromagnetic Spectrum,” http://en.wikipedia.org/ Testing,” J. ASTM Int., Vol. 3, No. 4, 2006.
wiki/Electromagnetic_spectrum. 关214兴 Phillips, W. D., “Turbine Lubricating Oils and Hydraulic Flu-
关198兴 Rasberger, M., “Oxidative Degradation and Stabilization of ids,” Fuels and Lubricants Handbook: Technology, Prop-
Mineral Oil based Lubricants,” Chemistry and Technology erties, Performance, and Testing, MNL37WCD, Ed., ASTM
of Lubricants, R. M. Mortier and S. T. Orszulik, Eds., Blackie International, West Conshohocken, PA, Chapter 12, 2003, pp.
Academic and Professional-Chapman & Hall, London, UK, 297–351.
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Downloaded/printed
Font Times-Bold by
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Color red of Virginia pursuant to License Agreement. No further reproductions authorized.
䊏 REFERENCES 641
关215兴 Lachowicz, D. R. and Kreuz, K. L., “Peroxynitrates: the Un- 4,985,156 共January 15, 1991兲. Inventors: H. Ashijan and H.
stable Products of Olefin Nitration with Dinitrogen Tetroxide A Gawel.
in the Presence of Oxygen. A New Route to ␣-Nitroketones,” J. 关233兴 “Acylating Agents and Dispersants for Lubricating Oil and Fu-
Org. Chem., Vol. 32, 1967, pp. 3885–3888. els,” U.S. Patent 6,846,783 共January 25, 2005兲. Inven-
关216兴 Covitch, M. J., Graf, R. T., and Gundic, D. T., “Microstructure tors: S. Bartley, J. D. Burrington, and R. Yodice.
of Carbonaceous Diesel Engine Piston Deposits,” Lubricant 关234兴 “Dispersant and Dispersant Viscosity Index Improvers from
Engineering, Vol. 44, 1988, p. 128. Selectively Hydrogenated Aryl-substituted Olefin Containing
关217兴 Covitch, M. J., Richardson, J. P., and Graf, R. T., “Structural Diene Copolymers,” U.S. Patent 6,248,702 共June 19,
Aspects of European and American Diesel Engine Piston De- 2001兲. Inventors: T. S. Coolbaugh, F. C. Loveless, J. E. Marlin,
posits,” Lubr. Sci., Vol. 2, 1990, pp. 231–251. II, and D. N. Matthews.
关218兴 Personal Communication, R. E. Kornbrekke, Lubrizol Re- 关235兴 Stambaugh, R. L., “Viscosity Index Improvers and Thicken-
search and Development. ers,” Chemistry and Technology of Lubricants, R. M.
关219兴 Kornbrekke, R. E., Patrzyk-Semanik, P., Kirchner-Jean, T., Mortier and S. T. Orszulik, Eds., Blackie Academic and
Raguz, M. G., and Bardasz, E., “Understanding Soot-mediated Professional-Chapman & Hall, London, UK, 1996, pp. 144–
Oil Thickening—Part 6: Base Oil Effects,” SAE Technical 180.
Paper 982665, Society of Automotive Engineers, Octo- 关236兴 “Nitrogen-containing Esters and Lubricants Containing
ber 1, 1998. Also see Parts 1–5 by E. Bardasz et al., SAE Pa- Them,” U.S. Patent 4,604,221 共August 5, 1986兲. Inven-
pers 952527, October 1995; 961915, October 1, 1996; 971692, tors: C. P. Bryant and H. M. Gerdes.
May 1, 1997; 976193, May 1, 1997; and 972952, October 1, 关237兴 “Nitrogen-free Ester of Carboxy Containing Interpolymers,”
1997. U.S. Patent 5,256,752 共October 26, 1993兲. Inventors: D.
关220兴 “Lubricating Oil Compositions Containing Alkenyl Succinim- M. Dishong and R. M. Lange.
ides of Tetraethylene Pentamine,” U.S. Patent 3,361,673 关238兴 “Lubricating Oil Additives,” U.S. Patent 6,071,862 共June
共January 2, 1968兲. Inventors: F. A. Stuart, R. G., anderson, 6, 2000兲. Inventors: J. R. Shanklin, Jr. and N. C. Mathur.
and A. Y. Drummond. 关239兴 Colyer, C. C. and Gergel, W. C., “Detergents/Dispersants,”
关221兴 Cooper, A. R., “Molecular Weight Determination,” Concise Chemistry and Technology of Lubricants, R. M. Mortier
and S. T. Orszulik, Eds., CH Publishers, Inc., NY, Chapter 3,
Encyclopedia of Polymer Science and Engineering, J. I.
1992, pp. 62–82.
Kroschwitz, Ed., Wiley InterScience, 1990, pp. 638–639.
关240兴 “Lubricating Oils Containing Metal Derivatives,” U.S.
关222兴 Ravve, A., “Molecular Weights of Polymers,” Organic Chem-
Patent 2,628,942 共February 17, 1953兲. Inventors: J. R.
istry of Macromolecules, Marcel Dekker, NY, Chapter 3,
Morris and J. R. Roach.
1967, pp. 39–54.
关241兴 “Modified Olefin-diolefin Resin,” U.S. Patent 2,634,256
关223兴 Meunier, D. M., “Molecular Weight Determination,” Chapter
共April 7, 1953兲. Inventors: W. J. Sparks, D. W. Young,
46, 关http://prenhall.com/settle/chapters/ch46.pdf兴.
Roselle, and J. D. Garber.
关224兴 Deanin, R. D., Polymer Structure, Properties, and Applications,
关242兴 “Reaction Product of High Molecular Weight Succinic Acids
Cahner Books, NY, Chapter 3, 1972, p. 53.
and Succinic Anhydrides with an Ethylene Polyamine,” U.S.
关225兴 Randall, J. C., “Microstructure,” Concise Encyclopedia of
Patent 3,172,892 共March 9, 1965兲. Inventors: W. M. Le
Polymer Science and Engineering, J. I. Kroschwitz, Ed.,
Suer and G. R. Norman.
Wiley InterScience, 1990, p. 625.
关243兴 “Novel Carboxylic Acid Acylating Agents, Derivatives
关226兴 Rizvi, S. Q. A., “Lubricant Additives and Their Functions,”
Thereof, Concentrate and Lubricant Compositions Containing
American Society of Metals Handbook, 10th ed., S. D.
the Same, and Processes for Their Preparation,” U.S. Patent
Henry, Ed., ASM International, Vol. 18, 1992, pp. 98–112.
4,234,435 共November 18, 1980兲. Inventors: N. A. Mein-
关227兴 Rizvi, S. Q. A., “Additives and Additive Chemistry,” Fuels
hardt and K. E. Davis.
and Lubricants Handbook: Technology, Properties, Per- 关244兴 “Lubricant,” U.S. Patent 3,215,707 共November 2, 1965兲.
formance, and Testing, MNL37WCD, Ed., ASTM Interna- Inventor: R. J. Rense.
tional, West Conshohocken, PA, Chapter 9, 2003, pp. 199– 关245兴 Weill, J. and Sillion, B., “Reaction of Chlorinated Poly-
248. isobutene with Maleic Anhydride: Mechanism of Catalysis by
关228兴 Fotheringham, J. D., “Polybutenes,” Synthetic Lubricants Dichloromaleic Anhydride,” Revue de l’Institut Francais
and High-performance Functional Fluids, R. L. Shubkin, du Petrole, Vol. 40, No. 1, 1985, pp. 77–89, Also see J. Weill’s
Ed., Marcel Dekker, Inc., NY, 1993. Ph.D. Dissertation, 1982.
关229兴 “Ethylene Alpha-olefin Polymer Substituted Mono- and Dicar- 关246兴 “Process for Manufacturing Anhydrides of Alkenyl Dicar-
boxylic Acid Dispersant Additives,” U.S. Patent 5,435,926 boxylic Acids,” U.S. Patent 4,433,157 共February 21,
共July 25, 1995兲. Inventors: A. Gutierrez, R. A. Kleist, W. R. 1984兲. Inventors: J. Weill, J. Garapon, and B. Sillion.
Song, A. Rossi, H. W. Turner, H. C. Welborn, and R. D. Lund- 关247兴 “Treatment of Organic Compounds to Reduce Chlorine
berg. Level,” U.S. Patent 5,708,097 共January 13, 1998兲. Inven-
关230兴 “Novel Ethylene Alpha-olefin Copolymer Substituted Man- tors: C. K. Baumanis, M. M. Maynard, A. C. Clark, M. R. Sivic,
nich Base Lubricant Dispersant Additives,” U.S. Patent C. P. Kovall, and D. L. Westfall.
5,017,299 共May 21, 1991兲. Inventors: A. Gutierrez, W. R. 关248兴 “Low Chlorine Polyalkylene Substituted Carboxylic Acylating
Song, R. D. Lundberg, and R. A. Kleist. Agent Compositions and Compounds Derived Therefrom,”
关231兴 “Lubricant Additives,” U.S. Patent 5,384,055 共January 24, U.S. Patent 5,885,944 共March 23, 1999兲. Inventors: J. K.
1995兲. Inventor: H. Ashijan. Pudelski, M. R. Sivik, K. F. Wollenberg, R. Yodice, J. Rutter,
关232兴 “Production of Borated Ashless Dispersants,” U.S. Patent and J. G. Dietz.
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642 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
关249兴 “Low Chlorine Content Composition for Use in Lubricants and Vol. 7, 1965, pp. 22–37.
Fuels,” U.S. Patent 6,077,909 共June 20, 2000兲. Inventors: 关266兴 “Amines II. Reactions,” Organic Chemistry, R. T. Morrison,
J. K. Pudelski, C. J. Kolp, J. G. Dietz, C. K. Baumanis, S. L. and R. N. Boyd, Eds., 3rd ed., Allyn and Bacon, Inc., Boston,
Bartley, and J. D. Burrington. Section 23.1, 1976 pp. 745–748.
关250兴 Wollenberg, K. F. and Pudelski, J. K., “Preparation, NMR 关267兴 “High Molecular Weight Nitrogen-containing Condensates
Characterization and Lubricant Additive Application of Novel and Fuels and Lubricants Containing Same,” U.S. Patent
Polyisobutenyl Phthalic Anhydrides,” Symposium on Re- 5,053,152 共October 1, 1991兲. Inventor: T. F. Steckel.
cent Advances in the Chemistry of Lubricant Additives, 关268兴 “Preparation of Tris共hydroxymethyl兲aminomethane,” U.S.
Paper Presented before the Division of Petroleum Chemistry, Patent 4,233,245 共November 11, 1980兲, Inventors: J.
Inc., 218th National Meeting of the American Chemical Soci- Bourguignon, M-X Sion, and M. Moreau.
ety, New Orleans, LA, August 22–26, 1999. 关269兴 “Dispersants and Process for Their Preparation,” U.S. Patent
关251兴 “One-step Process for the Preparation of Alkenyl Succinic An- 3,980,569 共September 14, 1976兲. Inventors: J. F. Pindar, J.
hydride,” U.S. Patent 5,319,030 共June 7, 1994兲. Inventors: M. Cohen, and C. P. Bryant.
J. J. Harrison, R. Ruhe, Jr., and R. William. 关270兴 “Artificial Resins and Method of Making,” U.S. Patent
关252兴 “Two-step Thermal Process for the Preparation of Alkenylsuc- 2,098,869 共November 9, 1937兲. Inventors: J. Harmon, and
cinic Anhydride,” U.S. Patent 5,625,004 共April 29, 1997兲. F. M. Meigs.
Inventors: J. J. Harrison, R. Ruhe, Jr., and R. William. 关271兴 “Aminoalkylation and Amidoalkylation,” Advanced Organic
关253兴 Morrison, R. T. and Boyd, R. N., “The Diels-Alder Reaction,” Chemistry, Reactions, Mechanisms, and Structure by J.
Organic Chemistry, 3rd ed., Section 27.8, Allyn and Bacon, March, 4th ed., Chapter 11 on Aromatic Electrophilic Substi-
Inc., Boston, 1976, pp. 876–878. tution, Section 1–25, Wiley-Interscience Publication, 1992,
关254兴 “Hydroxy-group Containing Acylated Nitrogen Compounds pp. 550–551.
Useful as Additives for Lubricating Oil and Fuel Composi- 关272兴 “Ethylenediamine Salts of Thiophosphonic Acids,” U.S.
tions,” U.S. Patent 5,696,067 共December 9, 1997兲. Inven- Patent 3,185,728 共May 25, 1965兲. Inventors: E. E. Schal-
tors: P. E. Adams, M. R. Baker, and J. G. Dietz. lenberg and R. G. Lacoste.
关255兴 “Mixed Carboxylic Compositions and Derivatives and Use as 关273兴 “Friction Reducing Agents for Lubricants,” U.S. Patent
Lubricating Oil and Fuel,” U.S. Patent 6,030,929 共Febru- 3,702,824 共November 14, 1972兲. Inventor: R. C. Sclicht.
ary 29, 2000兲. Inventor: J. K. Pudelski. 关274兴 “Olefin-thionophosphine Sulfide Reaction Products, Their De-
关256兴 “Substituted Carboxylic Acylating Agent Compositions and rivatives, and Use Thereof as Oil and Fuel Additives,” U.S.
Derivatives Thereof for Use in Lubricants and Fuels,” U.S. Patent 4,042,523 共August 16, 1977兲. Inventor: S. J. Brois.
Patent 5,912,213 共June 15, 1999兲. Inventors: M. R. Baker, 关275兴 “Olefin-thionophosphine Sulfide Reaction Products, Their De-
J. G. Dietz, and R. Yodice. rivatives, and Use Thereof as Oil and Fuel Additives,” U.S.
关257兴 “Acylated Nitrogen Compounds Useful as Additives for Lubri- Patent 4,100,187 共July 11, 1978兲. Inventor: S. J. Brois.
cating Oil and Fuel Compositions,” U.S. Patent 5,856,279 关276兴 “Oil Containing Dispersant VII Olefin Copolymer,” U.S.
共January 5, 1999兲. Inventor: M. R. Baker. Patent 4,715,975 共December 29, 1987兲. Inventors: M. M.
关258兴 “Process for Preparing Condensation Product of Hydroxy- Kapusciniski, B. J. Kaufman, and C. S. Liu.
substituted Aromatic Compounds and Glyoxylic Reactants,” 关277兴 “Dispersant-antioxidant Multifunction Viscosity Index Im-
U.S. Patent 6,001,781 共December 14, 1999兲. Inventors: prover,” U.S. Patent 4,699,723 共October 13, 1987兲. Inven-
M. R. Baker, K. M. Hull, and D. L. Westfall. tors: M. M. Kapuscinski and R. E. Jones.
关259兴 “Intermediates Useful for Preparing Dispersant-viscosity Im- 关278兴 “Dispersant Anti-oxidant VI Improver and Lubricating Oil
provers for Lubricating Oils,” U.S. Patent 6,117,941 共Sep- Composition Containing Same,” U.S. Patent 4,948,524
tember 12, 2000兲. Inventors: P. E. Adams, R. M. Lange, R. 共August 14, 1990兲. Inventors: M. M. Kapuscinski, T. E.
Yodice, M. Baker, and J. Dietz. Nalesnik, R. T. Biggs, H. Chafetz, and C. S. Liu.
关260兴 “Nitrogen Containing Dispersant-viscosity Improvers,” U.S. 关279兴 “Lubricant for Use in Diesel Engines,” U.S. Patent
Patent 6,492,306 共December 10, 2002兲. Inventors: M. R. 6,187,721 共February 13, 2001兲. Inventors: I. Goldblatt, M.
Sivik, R. M. Lange, D. M. Vargo, and P. E. Adams. McHenry, K. Henderson, D. Carlisle, N. Ainscough, M.
关261兴 “Alkylation of Phenols,” Kirk-Othmer Encyclopedia of Brown, and R. Tittel.
Chemical Technology, Vol. 1, 1963, pp. 894–895 and “Ion 关280兴 “Graft Copolymers and Lubricants Containing Such as
Exchange,” Kirk-Othmer Encyclopedia of Chemical Tech- Dispersant-viscosity Improvers,” U.S. Patent 5,298,565
nology, Vol. 2, 1967 pp. 871–899, Interscience Publishers, 共March 29, 1994兲. Inventors: R. M. Lange and C. V. Luciani.
NY. 关281兴 “Dispersant Viscosity Index Improvers,” U.S. Patent
关262兴 “Aromatic Mannich Compound-containing Composition and 6,083,888 共July 4, 2000兲. Inventor: R. J. Sutherland.
Process for Making Same,” U.S. Patent 6,179,885 共Janu- 关282兴 “Lubricating Oils and Fuels Containing Graft Copolymers,”
ary 30, 2001兲. Inventor: J. R. McAtee. U.S. Patent 3,506,574 共April 14, 1970兲. Inventors: R. L.
关263兴 “Manufacture of Alkylphenol Compounds,” U.S. Patent Stambaugh and R. D. Bakule.
4,202,199 共May 13, 1980兲. Inventors: F. Merger, and G. Nes- 关283兴 “Viscosity Index Improvers with Dispersant Properties Pre-
tler. pared by Reaction of Lithiated Hydrogenated Copolymers
关264兴 “Methods for Preparing Alkylated Hydroxyaromatics,” U.S. with 4-Substituted Aminopyridines,” U.S. Patent 4,402,843
Patent 5,663,457 共September 2, 1997兲. Inventor: C. J. 共September 6, 1983兲. Inventor: W. J. Trepka.
Kolp. 关284兴 “Viscosity Index Improvers with Dispersant Properties Pre-
关265兴 “Ethylene Amines,” Kirk Othmer’s Encyclopedia of pared by Reaction of Lithiated Hydrogenated Copolymers
Chemical Technology, 2nd ed., Interscience Publishers, NY, with Substituted Aminolactams,” U.S. Patent 4,402,844
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䊏 REFERENCES 643
共September 6, 1983兲. Inventor: W. J. Trepka. 关303兴 “Middle Distillate Containing Storage Stability Additive,”
关285兴 “Viscosity Improvers for Lubricating Oil Compositions,” U.S. U.S. Patent 4,948,386 共August 14, 1990兲. Inventors: R. L.
Patent 6,124,249 共September 26, 2000兲. Inventors: J. G. Sung, B. J. Kaufman, and K. J. Thomas.
Seebauer and C. P. Bryant. 关304兴 “Non-ash Containing Lubricant Oil Composition,” U.S.
关286兴 “Dispersant-viscosity Improvers for Lubricating Oil Composi- Patent 3,189,544 共June 15, 1965兲. Inventors: H. Ratner
tions,” U.S. Patent 5,969,068 共October 19, 1999兲. Inven- and R. F. Bergstrom.
tors: C. P. Bryant, B. A. Grisso, and R. Cantiani. 关305兴 “Reaction Products of Hydrocarbon-substituted Succinic
关287兴 “Dispersant-viscosity Improvers for Lubricating Oil Composi- Acid-producing Compound, an Amine, and an Alkenyl Cya-
tions,” U.S. Patent 5,821,313 共October 13, 1998兲. Inven- nide,” U.S. Patents 3,278,550 共October 11, 1966兲 and
tors: M. R. Sivic and C. P. Bryant. 3,366,569 共June 30, 1968兲. Inventors: G. R. Norman and W. M.
关288兴 “Dispersant-viscosity Improvers for Lubricating Oil Composi- Le Suer.
tions,” U.S. Patent 5,512,192 共April 30, 1996兲. Inventors: 关306兴 “Cleavage of Amine Oxides,” Advanced Organic Chemis-
R. M. Lange and C. V. Luciani. try, J. March, Ed., 4th ed., Chapter 17 on Eliminations, Sec-
关289兴 “Dispersant-viscosity Improvers for Lubricating Oil Composi- tion 7–8, Wiley-Interscience Publication, 1992, pp. 1018–
tions,” U.S. Patent 5,540,851 共July 30, 1996兲. Inventor: R. 1019.
M. Lange. 关307兴 “Hydrolysis of Amides,” Section 20–13, pp. 671–672 and
关290兴 “Graft Copolymers from Solvent-free Reactions and Dispers- “Alkaline and Acidic Hydrolysis of Esters,” Sections, 20.17
ant Derivatives Thereof,” U.S. Patent 5,429,758 共July 4, and 20.18, pp. 677–681, Organic Chemistry, R. T. Morrison
1995兲. Inventors: K. Hayashi, T. R. Hopkins, and C. R. Scharf. and R. N. Boyd, 3rd ed., Allyn and Bacon, Inc., Boston, 1976.
关291兴 “Novel VI Improver, Dispersant, and Anti-oxidant Additive 关308兴 Baczek, S. K., and Chamberlin, W. B., “Petroleum Additives,”
and Lubricating Oil Composition Containing Same,” U.S. Encyclopedia of Polymer Science and Engineering, Sec-
Patent 4,863,623 共September 5, 1989兲. Inventor: T. E. ond Edition John Wiley and Sons, Vol. 11, 1988, p. 22.
Nalesnik. 关309兴 “Engine Oil Viscosity Classification,” SAE J300—Revised May
关292兴 “Functionalized Graft Co-polymer as a Viscosity Index Im- 2004, SAE Standard, Society of Automotive Engineers.
prover, Dispersant, and Anti-oxidant Additive and Lubricating 关310兴 “Multigrade Lubricating Compositions Containing No Viscos-
Oil Composition Containing Same,” U.S. Patent 5,409,623 ity Modifier,” U.S. Patent 5,965,497 共October 12, 1999兲.
共April 25, 1995兲. Inventors: M. K. Mishra and I. D. Rubin. Inventors: D. R. Adams and P. Brice.
关293兴 “Lubricating Oil Containing Dispersant Viscosity Index Im- 关311兴 “High Functionality Low Molecular Weight Oil Soluble Dis-
prover,” U.S. Patent 5,520,829 共May 28, 1996兲. Inventors: persant Additives Useful in Oleaginous Compositions,” U.S.
M. K. Kapuscinski, C. S. Liu, L. D. Grina, and R. E. Jones. Patent 5,788,722 共August 4, 1998兲. Inventors: J. Emert
关294兴 “Process for Making Dispersant Viscosity Index Improvers,” and R. D. Lundberg.
U.S. Patent 5,486,563 共January 23, 1996兲. Inventor: R. J. 关312兴 “Polymers Derived From Ethylene and 1—Butene for the Use
Sutherland. in the Preparation of Lubricant Dispersant Additives,” U.S.
关295兴 “Star-shaped Dispersant Viscosity Index Improver,” U.S. Patent 6,030,930 共February 29, 2000兲. Inventors: J.
Patent 4,077,893 共March 7, 1978兲. Inventor: T. E. Kiovsky. Emert, A. Rossi, S. Rea, J. W. Frederick, and M. W. Kim.
关296兴 “Multifunctional Viscosity Index Improver-dispersant Anti- 关313兴 “Lubricating Oil Containing Dispersant VII and Pour Depres-
oxidant,” U.S. Patent 5,439,607 共August 8, 1995兲. Inven- sant,” U.S. Patent 4,668,412 共May 26, 1987兲. Inventors:
tor: A. O. Patil. W. P. Hart and C. S. Liu.
关297兴 “Lubricants Containing Ashless Antiwear-dispersant Additive 关314兴 “Ethylene Alpha-olefin/diene Interpolymer-substituted Car-
Having Viscosity Index Improver Credit,” U.S. Patent boxylic Acid Dispersant Additives,” U.S. Patents 5,759,967
5,698,500 共December 16, 1997兲. Inventors: J. R. Baranski 共June 2, 1998兲 and 5,681,799 共October 28, 1997兲. Inventors:
and C. A. Migdal. W. R. Song, A. Rossi, H. W. Turner, H. W. Welborn, R. D. Lun-
关298兴 “Dispersant Viscosity Index Improvers,” U.S. Patent dberg, A. Gutierrez, and R. A. Kleist.
5,360,564 共November 1, 1994兲. Inventors: R. J. Sutherland 关315兴 “Ethylene Alpha-olefin Polymer Substituted Mono- and Dicar-
and R. B. Rhodes. boxylic Acid Dispersant Additives,” U.S. Patent 5,433,757
关299兴 Brady, J. E. and Humiston, G. E., “Chemical Bonding: Gen- 共July 18, 1995兲. Inventors: W. R. Song, A. Rossi, H. W.
eral Concepts—Polar Molecules and Electronegativity,” Gen- Turner, H. C. Welborn, and R. D. Lundberg.
eral Chemistry: Principles and Structure, 2nd ed., Section 关316兴 “Borated Ethylene Alpha-olefin Copolymer Substituted Man-
4.8, John Wiley and Son, NY, 1978, pp. 114–117. nich Base Lubricant Dispersant Additives,” U.S. Patent
关300兴 “Dispersant Additives and Process,” U.S. Patent 5,804,667 5,382,698 共January 17, 1995兲. Inventors: W. R. Song, R. D.
共September 8, 1998兲, and U.S. Patent 5,936,041 共August 10, Lundberg, A. Gutierrez, and R. A. Kleist.
1999兲. Inventors: W. B. Diana, J. V. Cusumano, K. R. Gorda, J. 关317兴 “Polyalkylene Polysuccinimides and Post-treated Derivatives
Emert, W. B. Eckstrom, D. C. Dankworth, J. E. Stanat, and J. Thereof,” U.S. Patent 6,146,431 共November 14, 2000兲.
P. Stokes. Inventors: J. J. Harrison and W. A. Ruhe, Jr.
关301兴 “Ashless Dispersants Formed from Substituted Acylating 关318兴 “Ready Reference for Lubricant and Fuel Performance,” Lu-
Agents and Their Production and Use,” U.S. Patent brizol Publication; 2004.
5,241,003 共August 31, 1993兲. Inventors: D. J. Degonia and 关319兴 “Engine Oil Having Dithiocarbamate and Aldehyde/epoxide
P. G. Griffin. for Improved Seal Performance, Sludge and Deposit Perfor-
关302兴 “Oil Soluble Dispersant Additives Useful in Oleaginous Com- mance,” U.S. Patent 6,121,211 共September 9, 2000兲. In-
positions,” U.S. Patent 5,026,495 共June 25, 1991兲. Inven- ventors: C. F. Stachew, W. D. Abraham, J. A. Supp, J. R. Shan-
tors: J. Emert, R. D. Lundberg, and A. Gutierrez. klin, and G. D. Lamb.
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Downloaded/printed
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644 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
关320兴 “Viton Seal Compatible Dispersant and Lubricating Oil Com- Amount of Water,” U.S. Patent 6,015,778 共January 18,
position Containing Same,” U.S. Patent 5,188,745 共Febru- 2000兲. Inventors: A. J. Rolfes and S. E. Jaynes.
ary 23, 1993兲. Inventors: C. A. Migdal and T. E. Nalesnick. 关341兴 “Magnesium Low Rate Number Sulphonates,” U.S. Patent
关321兴 “Dibasic Acid Lubricating Oil Dispersant and Viton Seal Addi- 5,922,655 共July 13, 1999兲. Inventors: D. Moulin, J. A. Clev-
tives,” U.S. Patent 4,663,064 共May 5, 1987兲. Inventors: T. erley, and C. H. Bovington.
E. Nalesnik and C. M. Cusano. 关342兴 “Method of Preparing Overbased Barium Sulfonates,” U.S.
关322兴 “Lubricating Oil Dispersant and Viton Seal Additives,” U.S. Patent 3,959,164 共May 25, 1976兲. Inventor: A. R. Sabol.
Patent 4,636,322 共January 13, 1987兲. Inventor: T. E. 关343兴 “Overbased Alkali Metal Sulfonates,” U.S. Patent
Nalesnik. 4,867,891 共September 19, 1989兲. Inventor: M. W. Hunt.
关323兴 “Dispersant Additives,” U.S. Patent 6,127,322 共October 3, 关344兴 “Metal Phenates,” U.S. Patent 4,221,673 共September 9,
2000兲. Inventors: R. M. Scott and R. W. Shaw. 1980兲. Inventors: R. Robson, B. Swinney, and R. D. Tack.
关324兴 “Method for Preparing Engine Seal Compatible Dispersant for 关345兴 “Preparation of Overbased Magnesium Phenates,” U.S.
Lubricating Oils Comprising Reacting Hydrocarbyl Substi- Patent 4,435,301 共March 6, 1984兲. Inventors: C. G. Bran-
tuted Dicarboxylic Compound with Aminoguanidine or Basic nen and M. W. Hunt.
Salt Thereof,” U.S. Patent 5,080,815 共January 14, 1992兲. 关346兴 “Process for the Preparation of Sulfurized Overbased Phenate
Inventors: D. J. Fenoglio, P. R. Vettel, and D. W. Eggerding. Detergents,” U.S. Patent 4,973,411 共November 27,
关325兴 “Compositions for Control of Induction System Deposits,” 1990兲. Inventors: T. C. Jao, C. K. Esche, E. D. Black, and R. H.
U.S. Patent 5,679,116 共October 21, 1997兲. Inventors: L. J. Jenkins Jr.
Cunningham, D. P. Hollrah, and A. M. Kulinowski. 关347兴 “Methods for Preparing Group II Metal Overbased Sulfurized
关326兴 “Deposit Control Additives and Fuel Compositions Containing Alkylphenols,” U. S. 4,971,710 共November 20, 1990兲. In-
the Same,” U.S. Patent 5,334,228 共August 2, 1994兲. Inven- ventor: T. V. Liston.
tors: H. Ashjian, M. P. Miller, D.-M. Shen, and M. M. Wu. 关348兴 “Production of Overbased Metal Phenates,” U.S. Patent
关327兴 “Additive Formulation for Fuels Incorporating Ester Function 4,104,180 共August 1, 1978兲. Inventors: V. C. E. Burnop.
Products and a Detergent-Dispersant,” U.S. Patent 关349兴 “Method of Preparing Overbased Lubricating Oil Additives,”
5,433,755 共July 18, 1995兲. Inventors: P. Mulard, Y. Labruy- U.S. Patent 4,057,504 共November 8, 1977兲. Inventors: M.
ere, A. Forestiere, and R. Bregent. Shiga, K. Hirano, and M. Matsushita.
关328兴 “Gear and Transmission Lubricant Compositions of Improved 关350兴 “Recovery of Overbased Alkaline Earth Metal Additives from
Sludge-Dispersibility, Fluids Comprising the Same,” U.S. Centrifugates,” U.S. Patent 4,910,334 共March 20, 1990兲.
Patent 5,665,685 共September 9, 1997兲. Inventor: S. Taki- Inventors: F. A. Stuart and W. A. Tyson, Jr.
gawa. 关351兴 “Process for Preparing Overbased Naphthenic Micronutrient
关329兴 “Automatic Transmission Fluids and Additives Thereof,” U.S. Compositions,” U.S. Patent 4,243,676 共January 6, 1981兲.
Patent 5,441,656 共August 15, 1995兲. Inventors: H. Otani Inventor: W. R. Ali.
and R. J. Hartley. 关352兴 “Process for Overbased Petroleum Oxidate,” U.S. Patent
关330兴 “Hydraulic Automatic Transmission Fluid with Superior Fric- 5,013,463 共May 7, 1991兲. Inventor: F. J. Slama.
tion Performance,” U.S. Patent 4,253,977 共March 3, 关353兴 “Preparation of Basic Salt,” U.S. Patent 4,810,398 共March
1981兲. Inventor: R. O’Halloran. 7, 1989兲. Inventors E. M. G. A. Van Kruchten and R. R. Van
关331兴 “Lubricating Oil Composition for Automatic Transmission,” Well.
U.S. Patent 5,972,854 共October 26, 1999兲. Inventors: T. 关354兴 Weamer, G. L., “Additives—A Way to Quality in Motor Oils,”
Ichihashi, H. Igarashi, J. Deshimaru, and T. Ikeda. Petroleum Refiner, 38, 1959, pp. 215–219.
关332兴 “Automatic Transmission Fluid Composition,” U.S. Patent 关355兴 “Metal Salts of Organic Acids of Phosphorus,” U.S. Patent
5,958,286 共September 28, 1999兲. Inventor: M. Kitanaka. 2,785,128 共March 12, 1957兲. Inventor: A. H. Popkin.
关333兴 “Automatic Transmission Fluids Having Enhanced Perfor- 关356兴 “Preparation of Overbased Magnesium Sulfonates,” U.S.
mance Capabilities,” U.S. Patent 5,972,851 共October 26, Patent 4,148,740 共April 10, 1979兲. Inventors: V. J. Cease
1999兲. Inventors: S. Srinivasan, D. W. Smith, and J. P. Sunne. and G. R. Kirk.
关334兴 “Gear Oil Additive Concentrates and Lubricants Containing 关357兴 Price, C. C., “The Alkylation of Aromatic Compounds by the
them,” U.S. Patent 6,096,691 共August 1, 2000兲. Inventors: Friedel-Crafts Method,” Organic Reactions, John Wiley and
G. S. Conary and R. J. Hartley. Sons, Inc., Vol. III, Chapter 1, 1946, pp. 1–82.
关335兴 “Lubricating Oil Composition for High-speed Gears,” U.S. 关358兴 “Alkylation of Aromatics with Olefins in the Presence of an
Patent 5,756,429 共May 26, 1998兲. Inventor: T. Ichihashi. Alumina Catalyst,” U.S. Patent 4,219,690 共August 26,
关336兴 “Hydraulic Fluids,” U.S. Patent 5,767,045 共June 16, 1980兲. Inventor: S. M. Kovach.
1988兲. Inventor: H. T. Ryan. 关359兴 “Process and System for Alkylation of Aromatic Compounds,”
关337兴 “Use of Dispersant Additives as Process Antifoulants,” U.S. U.S. Patent 5,770,782 共June 23, 1998兲. Inventors: J. F.
Patent 5,368,777 共November 29, 1994兲. Inventor: D. R. Knifton, P. R. Anantaneni, and M. Stockton.
Forester. 关360兴 Olah, G. A., Friedel-Crafts and Related Reactions, Interscience-
关338兴 “Multifunctional Antifoulant Compositions,” U.S. Patent Wiley Publishers, Vol. 2, 1964.
4,927,561 共May 22, 1990兲. Inventor: D. R. Forester. 关361兴 “Aromatic Alkylation,” U.S. Patent 2,754,341 共July 10,
关339兴 “Multifunctional Antifoulant Compositions and Methods of 1956兲. Inventor: E. V. Kirkland.
Use Thereof,” U.S. Patent 4,775,458 共October 4, 1988兲. 关362兴 “Process for the Production of Light Alpha Olefins by Oligo-
Inventor: D. R. Forester. merization of Ethylene,” U.S. Patent 5,345,023 共Septem-
关340兴 “Process For Making Overbased Calcium Sulfonate Deter- ber 6, 1994兲. Inventors: Y. Chauvin, D. Commereuc, F. Hu-
gents Using Calcium Oxide and a Less Than Stoichiometric gues, H. Olivier, and L. Saussine.
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䊏 REFERENCES 645
关363兴 “Process for the Conversion of Ethylene into Light Alpha Ole- 5,556,569 共September 17, 1996兲. Inventor: N. Z. Huang.
fins with the Use of Additives Based on Quaternary Ammo- 关383兴 “Metal Complexes and Methods of Making Same,” U.S.
nium Salts,” U.S. Patent 5,817,905 共October 6, 1998兲. In- Patent 2,777,874 共January 15, 1957兲. Inventors: P. A. Ass-
ventors: D. Commereuc, Y. Glaize, F. Hugues, P. Panzarella, eff, T. W. Mastin, and A. Rhodes.
and L. Saussine. 关384兴 “Metal-containing Lubricant Compositions,” U.S. Patent
关364兴 “Oligomerization Reaction System,” U.S. Patent 4,020,121 4,767,551 共August 30, 1988兲. Inventors: M. W. Hunt and S.
共April 26, 1977兲. Inventors: A. T. Kister, and E. Lutz. Kennedy.
关365兴 “Continuous Manufacturing Process for Alpha-olefins,” U.S. 关385兴 “Process for Overbasing via Metal Borate Formation,” U.S.
Patent 6,555,723, April 29, 2003. Inventor: R. S. Schiffino. Patent 6,090,757 共July 18, 2000兲. Inventor: T. F. Steckel.
关366兴 “Manufacture of Alpha-olefins,” U.S. Patent 6,103,946 关386兴 “Method of Preparation of Superbased Salts,” U.S. Patent
共August 15, 2000兲. Inventors: M. S. Brookhart III and B. L. 2,695,910 共November 30, 1954兲. Inventors: P. A. Asseff, T.
Small. W. Mastin, and A. Rhodes.
关367兴 “Process for Producing High Vinylidene Polyisobutylene,” 关387兴 “Sulfurized Overbased Compositions,” U.S. Patent
U.S. Patent 6,683,138 共January 27, 2004兲. Inventors: E. 5,484,542 共January 16, 1996兲. Inventors: J. M. Cahoon, J.
C. Baxter III, G. Valdez, C. Lobue, and T. Lowry. L. Karn, N. Z. Haung, and J. P. Roski.
关368兴 “Cationic Polymerization of 1-olefins,” U.S. Patent 关388兴 “Process for Overbasing via Metal Borate Formation,” U.S.
4,605,808 共August 12, 1986兲. Inventor: J. R. Samson. Patent 5,064,545 共November 12, 1991兲. Inventor: T. F.
关369兴 “Aromatics Alkylation Process,” U.S. Patent 5,191,135 Steckel.
共March 2, 1993兲. Inventors: F. G. Dwyer and Q. N. Lee. 关389兴 “Borated Basic Metal Salt and Lubricating Oil Composition,”
关370兴 Suter, C. M., and Weston, A. W., “Direct Sulfonation of Aro- U.S. Patent 4,539,126 共September 3, 1985兲. Inventors: J.
matic Hydrocarbons and Their Halogen Derivatives,” Or- J. Bleeker, M. Booth, M. G. F. M. van Grieken, W. J. Krijnen,
ganic Reactions, John Wiley and Sons, Inc., Vol. 3, Chapter and G. D. van Wijngaarden.
4, 1946, pp. 141–197. 关390兴 “Overbased Carboxylate Gels,” U.S. Patent 5,919,741
关371兴 “Conversion of Sulfonic Acids into a Hydrocarbon Oil of Su- 共July 6, 1999兲. Inventors: S. E. Jaynes and W. R. Sweet.
perior Oxidation Stability,” U.S. Patent 4,188,500 共Febru- 关391兴 “Mixed Carboxylate Overbased Gels,” U.S. Patent
ary 12, 1980兲. Inventors: D. S. Bosniack and P. F. Korbach. 5,401,424 共March 28, 1995兲. Inventors: J. N. Vinci and W.
See the “Background of Invention” portion of the patent. R. Sweet.
关372兴 “Verfahren zur Herstellung von Sulfonsauren,” DRP 735096, 关392兴 “Calcium Containing Micellar Complexes,” U.S. Patent
1940. Inventors: C. Platz and K. Schimmelsschmidt. 3,766,067 共October 16, 1973兲. Inventor: R. L. McMillen.
关373兴 “Reaction of Petroleum Oils with Sulfur Dioxide and Chlo- 关393兴 “Magnesium Overbasing Process,” U.S. Patent 5,173,203
rine,” U.S. Patent 2.263.312 共November 18, 1941兲. In- 共December 22, 1992兲. Inventors: W. P. Nichols and J. L.
ventor: C. F. Reed. Karn.
关374兴 “Fatty Acids,” http://www.cyberlipid.org/fa/acid0001. 关394兴 “Basic Alkali Metal Sulfonate Dispersions, Process for Their
htm#3. Preparation, and Lubricants Containing Same,” U.S. Patent
关375兴 “Lubricating Oil Compositions Containing Saligenin Deriva- 5,037,565 共August 6, 1991兲. Inventor: L. E. King.
tives,” U.S. Patent 6,310,011 共October 30, 2001兲. Inven- 关395兴 “Compounds Useful as Detergent Additives for Lubricants and
tors: J. L. Karn, J. A. Kocsis, L. E. King, P. E. Adams, and V. A. Lubricating Compositions,” U.S. Patent 5,021,174 共June 4,
Notaro. 1991兲. Inventors: P. Koch and A. Di Serio.
关376兴 “Oil Formulations Containing Overbased Multi-functional Ad- 关396兴 Hunter, M. E., and Baker, R. F., “Corrosion,” Fuels and Lu-
ditive,” U.S. Patent 4,954,273 共September 4, 1990兲. In- bricants Handbook: Technology, Properties, Perfor-
ventors: R. A. Denis and F. W. Koch. mance, and Testing, G. E. Totten, Ed., ASTM International,
关377兴 “Lubricating Oil Compositions Containing a Polyoxyalkylene West Conshohocken, PA., Chapter 31, 2003, pp. 825–832.
Carboxylic Acid Salt Additive,” U.S. Patent 5,250,203 共Oc- 关397兴 Boner, C. J., “Theory of Action and Performance,” Gear and
tober 5, 1993兲. Inventors: R. A. Denis and F. W. Koch. Transmission Lubricants, Reinhold Publishing Company,
关378兴 “Carboxylation with Carbon Dioxide. Kolbe-Schmitt Reac- NY, Chapter 8, 1964.
tion,” Advanced Organic Chemistry, Reactions, Mecha- 关398兴 Bhushan, B., and Gupta, B. K., “Physics of Tribological Mate-
nisms, and Structure by J. March, 4th ed., Chapter 11 on rials,” Handbook of Tribology; Materials, Coatings, and
Aromatic Electrophilic Substitution, Section 1-20, Wiley- Surface Treatments, McGraw-Hill Inc., NY, Chapter 3, 1991.
Interscience Publication, 1992, pp. 546–547. 关399兴 Buckley, D. H., “Properties of Surfaces,” CRC Handbook of
关379兴 “Additives for Lubricating Oils and Processes for Producing Lubrication, Theory and Practice of Tribology, Vol. II:
Them,” U.S. Patent 5,089,158 共February 18, 1992兲. In- Theory and Design, R. E. Booser Ed., CRC Press, Boca Ra-
ventors: E. M. G. A. Van Kruchten and G. W. J. Heimerikx. ton, 1988, pp. 17–30.
关380兴 “Phosphorus Pentasulfide,” http://en.wikipedia.org/wiki/ 关400兴 “Improved Fuel Economy,” http://www.fueleconomy.gov/
Phosphorus_pentasulfide feg/why.shtml
关381兴 Huang, N. Z., “Overbased Products Using Non-ionic 关401兴 http://www.dieselnet.com
Substrates—Chemistry and Properties,” Presented at the 关402兴 Oliver, C. R., Reuter, R. M., and Sendra, J. C., “Fuel Efficient
Symposium on Recent Advances in the Chemistry of Lu- Gasoline-Engine Oils,” Lubrication, Vol. 67, 1981, pp. 1–12.
bricant Additives, Division of Petroleum Chemistry, 218 关403兴 McFall, D., “Road Map for Engine Oils: ‘Six D’ Fuel Economy
National Meeting of the American Chemical Society, Test Points the Way,” Lubes‘N’Greases, April 2006, p. 1.
New Orleans, LA, August 22–26, 1999. 关404兴 Kick, G. K., “Automotive Engine Lubrication,” Standard
关382兴 “Non-conventional Overbased Materials,” U.S. Patent Handbook of Lubrication Engineering, J. J. O’Connor,
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646 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
Ed., McGraw-Hill Book Company, NY, Chapter 32, 1968, p. tors: S. A. Di Biase and J. W. Pialet.
32–37. 关423兴 “Sulfur-containing Compositions, and Additive Concentrates,
关405兴 McFall, D., “Sequence VI Fuel Economy Test,” Lubricating Oils, Metal Working Lubricants and Asphalt Com-
Lubes‘n’Greases, March 8, 2000, pp. 6–12. positions Containing Same,” U.S. Patent 4,740,322 共April
关406兴 McFall, D., “Light-Duty Diesel: What Are We Missing?” 26, 1988兲. Inventors: S. A. Di Biase and R. L. Sowerby.
Lubes‘N’Greases, November 2002, pp. 23–31. 关424兴 “Composition of and Method for Polysulfides Having a Re-
关407兴 O’Brien, J. A., “Lubricant Additives,” CRC Handbook of Lu- duced odor level,” U.S. Patent 6,362,374 共March 26,
brication, Theory and Practice of Tribology, Vol. II, 2002兲. Inventors: D. R. Forester, R. L. Sowerby, B. B. Malik,
Theory and Design, R. E. Booser, Ed., CRC Press, Boca Ra- and V. A. Gober.
ton, 1988, pp. 301–315. 关425兴 Rossrucker, T., and Fessenbecker, A., “Sulfur Carriers,” Lu-
关408兴 Lansdown, A. R., “Extreme Pressure and Anti-wear Addi- bricant Additives: Chemistry and Applications, Leslie R.
tives,” Chemistry and Technology of Lubricants, R. M. Rudnick, Ed., Marcel Dekker, Inc., NY, Chapter 9, 2003, pp.
Mortier and S. T. Orszulik, Eds., VCH Publishers, Inc., NY, 259–291.
Chapter 12, 1992, pp. 269–281. 关426兴 Thorn, G. D., and Ludwig, R. A., The Dithiocarbamates and
关409兴 Crawford, J., and Psaila, A., “Miscellaneous Additives and Related Compounds, Elsevier Publishing Company, 1962.
Vegetable Oils,” Chemistry and Technology of Lubricants, 关427兴 Gerrard, W., and Hudson, H. R., “Organic Derivatives of
R. M. Mortier and S. T. Orszulik, Eds., Blackie Academic and Phosphorous and Thiophosphorous Acids,” Organic Phos-
Professional-Chapman & Hall, London, UK, 1996, Chapter 6, phorus Compounds, G. M. Kosolapoff and L. Maier, Eds.,
pp. 181–202. Wiley InterScience, Vol. 5, Chapter 13, 1973, p. 21.
关410兴 共a兲 McFall, D., “On the Road to New Diesel Regs,” Lube & 关428兴 Cherbuliez, E., “Organic Derivatives of Phosphoric Acid,” Or-
Greases, November 2002, pp. 23–27. 共b兲 Hoocendoohn, R., ganic Phosphorus Compounds, G. M. Kosolapoff and L.
and Kenbeek, D., “Friction Modifiers to the Rescue,” Lube & Maier, Eds., Wiley InterScience, Vol. 6, Chapter 15, 1973, p.
Greases, November 2003, pp. 14–20. 共c兲 ibid., Lubricant’s 211.
World, November 2003, pp. 16–18. 关429兴 “Introduction to Wear,” http://ocw.mit.edu/NR/rdonlyres/
关411兴 Kenbeek, D., and Benemann, T. F., “Organic Friction Modifi- Mechanical-Engineering/2-800Fall-2004/3EB7EE5A-
ers,” Lubricant Additives: Chemistry and Applications, 43BF-4B4B-860B-1FD57DD8207F/0/
Leslie R. Rudnick, Ed., Marcel Dekker, Inc., NY, Chapter 7, ch4a_wear_intro.pdf
2003, pp. 203–221.Lubricant’s World, November 2003, pp. 16– 关430兴 Nieman, G., Rettig, H., and Lechner, G., “Scuffing Tests on
18. Gear Oils in FZG Apparatus,” ASLE Transactions, Vol. 4,
关412兴 “Friction,” http://www.synlube.com/howsyn.htm 1961, p. 71.
关413兴 Taylor, R. I., “Car Lubricants: Fact & Fiction,” Tribology and 关431兴 Forbes, E. S., and Battersby, J., “The Effect of Chemical
Lubrication Technology, October 2004. Structure on the Load-carrying and Adsorption Properties of
关414兴 Stewart, R. M., Spohn, C. R., and Meyer, W. A. P., “Influence of Dialkyl Phosphites,” ASLE Trans., Vol. 17, No. 4, 1974, pp.
Lubricating Oil Formulation on Winter Hot-starting Engine 263–270.
Torque Requirements,” SAE Paper No. 690157, Paper pre- 关432兴 Sakurai, T., and Sato, K., “Chemical Reactivity and Load-
sented at SAE Automotive Engineering Congress, De- carrying Capacity of Lubricating Oils Containing Organic
troit, Jan. 1969. Phosphorus Compounds,” ASLE Trans., Vol. 13, 1970, pp.
关415兴 Jayne, G. J., Matthews, B. M., and Thomas, A. S., “Hypoid 252–261.
Gear Oils for the 1980s,” Performance and Testing of Gear 关433兴 McFadden, C., Soto, C., and Spencer, N. D., “Adsorption and
Oils and Transmission Fluids, R. Tourret and E. P. Wright, Surface Chemistry in Tribology,” Tribology International,
Ed., Heyden and Son, Chapter 19, 1981, pp. 307–319. Vol. 30, No. 12, 1997, pp. 881–888.
关416兴 Feng, I. M., Perilstein, W. L., and Adams, M. R., “Solid Film 关434兴 Rowe, C. N., “Lubricated Wear,” CRC Handbook of Lubri-
Deposition and Non-sacrificial Boundary Lubrication,” ASLE cation, Theory and Practice in Tribology, Vol. II, Theory
Transactions, Vol. 6, 1963, pp. 60–66. and Design, R. E. Booser, Ed., CRC Press, Boca Raton, 1988,
关417兴 “DMTD Derivatives as Antiwear/antioxidant Additives,” U.S. pp. 209–225.
Patent 5,318,712 共June 17, 1994兲. Inventors: S. Q. A. Rizvi, 关435兴 Barcroft, F. T., and Daniel, S. G., “The Action of Neutral Or-
R. M. Lange, and R. E. Gapinski. ganic Phosphates as EP Additive,” ASME J. Basic Eng., 64-
关418兴 “Dynamic Light Scattering Studies of Neutral Di-isobutyl Zinc Lub-22, 1964.
Dithiophosphate,” E. S. Yamaguchi et al., Tribol. Trans., Vol. 关436兴 Dorinson, A., “The Additive Action of Some Organic Chlo-
40, No. 2, 1997, pp. 330–337. rides and Sulfides in the Four-Ball Lubricant Test,” ASLE
关419兴 Jones, R. B., and Coy, R. C., “The Thermal Degradation and EP Transactions, Vol. 16, No. 1, 1973, pp. 22–31.
Performance of Zinc Dialkyl Dithiophosphate Additives in 关437兴 Forbes, E. S., and Reid, A. J. D., “Liquid Phase Adsorption/
White Oil,” ASLE Transactions, Vol. 24, 1981, pp. 77–90. Reaction Studies of Organo-sulfur Compounds and Their
关420兴 Brazier, A. D., and Elliot, J. S, “The Thermal Stability of Zinc Load-carrying Mechanism,” ASLE Transactions, Vol. 16,
Dithiophosphates,” J. Institute of Petroleum, Vol. 53, 1967, No. 1, 1973, pp. 50–60.
pp. 63–76. 关438兴 Plaza, S., “Some Chemical Reactions of Organic Disulfides in
关421兴 Bateman, L., and Moore, C. G., “Reaction of Sulfur with Ole- Boundary Lubrication,” ASLE Transactions, Vol. 30, No. 4,
fins,” Organic Sulfur Compounds, N. Kharasch, Ed., Per- 1987, pp. 493–500.
gamon Press, Vol. 1, Chapter 20, 1961, pp. 210–228. 关439兴 Kawamura, M., Moritani, H., Esaki, Y., and Fujita, K., “The
关422兴 “Sulfur-containing Lubricant and Functional Fluid Composi- Mechanism of Synergism Between Sulfur- and Phosphorus-
tions,” U.S. Patent 4,800,031 共January 24, 1989兲. Inven- type EP Additives,” ASLE Transactions, Vol. 29, No. 4,
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Downloaded/printed
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䊏 REFERENCES 647
1986, pp. 451–456. Int. Con. Solid Lubr., SP-3, American Society of Lubrica-
关440兴 Phillips, W. D., “Ashless Phosphorus-containing Lubricating tion Engineers, Park Ridge, IL, 1976.
Oil Additives,” Lubricant Additives: Chemistry and Appli- 关454兴 Braithewaite, E. R., and Greene, A. B., “A Critical Analysis of
cations, Leslie R. Rudnick, Ed., Marcel Dekker, Inc., NY, the Performance of Molybdenum Compounds in Motor Ve-
Chapter 3, 2003, pp. 45–108. hicles,” Wear, Vol. 46, 1978, p. 405.
关441兴 Anonymous Author, “Fundamentals of Wear,” Lubrication, 关455兴 Messina, J., “Rust-inhibited, Non-reactive, Pefluorinated Poly-
Vol. 12, No. 6, 1957, pp. 61–78. mer Greases,” Proc. ASLE Conf. Solid Lubr. SP-3, Ameri-
关442兴 Anonymous Author, “Lubricant Additives,” Ind. Lubr., and can Society of Lubrication Engineers, Park Ridge, IL, 1976.
Trib., Vol. 49, No. 1, 1997, pp. 15–30. 关456兴 Corrosion—Causes and Prevention, F. N. Speller, McGraw-
关443兴 Mandakovic, R., “Assessment of EP Additives for Water Mis- Hill Publishing, 1935.
cible Metalworking Fluids,” J. Syn. Lubr, Vol. 16, No. 1, 关457兴 “Standard Electrode Reduction and Oxidation Potential,”
1999, pp. 13–26. http://www.siliconfareast.com/ox_potential.htm.
关444兴 Rounds, F. G., “Additive Interactions and Their Effect on the 关458兴 Becher, P., Emulsions: Theory and Practice, American Chemi-
Performance of a Zinc Dialkyl Dithiophosphate,” ASLE cal Society Monograph Series, Reinhold Publishing Corpora-
Transactions, Vol. 21, No. 2, 1978, pp. 91–101. tion, Chapter 6, 1957, pp. 209–231.
关445兴 共a兲 Rounds, F. G., “Some Effects of Amines on Zinc Dialkyl 关459兴 Karsa, D. R., “Industrial Applications of Surfactants,” Indus-
dithiophosphate Antiwear Performance as Measured in 4-Ball trial Applications of Surfactants—An Overview, D. R.
Wear Tests,” ASLE Transactions, Vol. 24, No. 4, 1981, pp. Karsa, Ed., Published by Royal Society of Chemistry, Cam-
431–440. 共b兲 Bovington, C. H., “Friction, Wear, and Role of bridge, England, 1987.
Additives,” Chemistry and Technology of Lubricants, R. 关460兴 Hancock, R. I., “Macromolecular Surfactants,” Surfactants,
M. Mortier and S. T. Orszulik, Eds., Blackie Academic and Th. F. Tadros, Ed., Academic Press, Chapter 12, 1984, pp.
Professional-Chamber & Hall, London, UK, 1996, Chapter 287–321.
12, pp. 320-370. 关461兴 Salomon, M. F., Galic, M., and Jaynes, S. E., “Application of a
关446兴 Liang, H., Totten, G. E., and Webster, G. M., “Lubrication and New Fleet Test Procedure to Investigate Emulsion Formation
Tribology Fundamentals,” Fuels and Lubricants Hand- Tendencies of Motor Oils,” SAE Technical Paper 912398,
book: Technology, Properties, Performance, and Testing, 1991.
MNL37WCD, Ed., ASTM International, West Conshohocken, 关462兴 Rempp., P., and Herz, J. E., “Model Polymers,” Concise En-
PA, Chapter 35, 2003, p. 961. cyclopedia of Polymer Science and Engineering, J. I.
关447兴 Lauer, D., “Industrial Applications,” CRC Handbook of Lu- Kroschwitz, Ed., Wiley InterScience, 1990, pp. 633–634.
brication, Theory and Practice in Tribology, Vol. III, 关463兴 Van Krevelen, D. W., and Hoftyzer, P. J., “Typology of Poly-
Monitoring, Materials, Synthetic Lubricants, and Appli- mers,” Properties of Polymers: Correlations with Chemi-
cations, R. E. Booser, Ed., CRC Press, Boca Raton, 1993, pp. cal Structure, Elsevier Publishing Company, Amsterdam,
195–205. Chapter 2, 1972.
关448兴 共a兲 Lancaster, J. K., “Solid Lubricants,” CRC Handbook of 关464兴 Freeman, W. J., “Characterization of Polymers,” Concise En-
Lubrication, Theory and Practice in Tribology, Vol. II, cyclopedia of Polymer Science and Engineering, J. I.
Theory and Design, R. E. Booser, Ed., CRC Press, Boca Ra- Kroschwitz, Ed., Wiley InterScience, 1990, pp. 139–142.
ton, 1988, pp. 269–290. 共b兲 Mariani, G., “Selection and Appli- 关465兴 Tung, L. H., “Fractionation,” Concise Encyclopedia of Poly-
cations of Solid Lubricants as Friction Modifiers,” Lubricant mer Science and Engineering, J. I. Kroschwitz, Ed., Wiley
Additives: Chemistry and Applications, L. R. Rudnick, InterScience, 1990, p. 417.
Ed., Marcel Dekker, Inc., New York, 2003, Chapter 6, pp. 171– 关466兴 Muller, H. G., “Mechanism of Action of Viscosity Index Im-
201. provers,” Tribol. Int., June 1978, pp. 189–192.
关449兴 共a兲 Peterson, M. B., and Johnson, R. L., “Friction Studies of 关467兴 Covitch, M., “Olefin Copolymer Viscosity Modifiers,” Lubri-
Graphite and Mixtures of Graphite with Several Metallic Ox- cant Additives: Chemistry and Applications, L. R. Rud-
ides and Salts at temperatures to 1000 ° F,” TN-3657, Na- nick, Ed., Marcel Dekker, Inc., NY, Chapter 10, 2003, pp. 293–
tional Aeronautics and Space Administration, Wash- 327.
ington, DC, 1956. 共b兲 Sliney, H. E., “Solid Lubricants,” 关468兴 Kleiser, W. M., Walker, H. M., and Rutherford, J. A., “Determi-
American Society of Metals Handbook, Friction, Lubri- nation of Lubricating Oil Additive Effects in Taxicab Service,”
cation, and Wear Technology, S. D. Henry, ed., ASM Inter- Soc. Automotive Engr. Tech. Paper Ser. No. 912386,
national, Vol. 18, 1992, pp. 113–122. 共c兲 http://www.a-m.de/ 1991.
englisch/lexikon/molybdaendisulfid-bild1.htm. 关469兴 Kinker, B. G., “Polymethacrylate Viscosity Modifiers,” Lubri-
关450兴 Haltner, A., and Flom, D. G., “Lubrication in Space,” CRC cant Additives: Chemistry and Applications, L. R. Rud-
Handbook of Lubrication, Vol. I, Theory and Practice of nick, Ed., Marcel Dekker, Inc., NY, Chapter 11, 2003, pp. 329–
Tribology: Applications and Maintenance, R. E. Booser, 353.
Ed., CRC Press, Boca Raton, 1983, pp. 389–404. 关470兴 Arlie, J. P., Dennis, J., and Parc, G., 2003, “Viscosity Index Im-
关451兴 Fusaro, R. L., “Friction and Wear Life Properties of Polyimide provers I, Mechanical and Thermal Stabilities of Poly-
Thin Films,” TN-D-6914, National Aeronautics and methacrylates and Polyolefins,” IP Paper 75–005, Inst.
Space Administration, Washington, DC, 1972. Petr., London, 1975.
关452兴 Brydson, J. A., Platics Materials, 3rd ed., Butterworth, Lon- 关471兴 Polymer Handbook, J. Branderup, and E. H. Immergut Eds.,
don, 1975. Interscience, NY, V-5 to V-11, 1966.
关453兴 Theberge, J. E., “Properties of the Internally Lubricated, Glass- 关472兴 Kinker, B. G., “Automatic Transmission Fluid Shear Stability
fortifies Thermoplastics for Gears and Bearings,” Proc. ASLE Trends and Viscosity Improver Trend,” Proc. 98 Intl. Symp.
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648 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
Tribology of Vehicle Trans., Yokohama, 1998, pp. 5–10. 关492兴 “Global Performance Specifications for Light Duty Diesel En-
关473兴 Watson, R. W., and McDonnell, Jr., T. F., “Additives—The gine Oil 共Global DLD-1, DLD-2 and DLD-3兲,” http://
Right Stuff for Automotive Engine Oils,” Fuels and Lubri- www.enginemanufacturers.org/admin/library/
cants Technology: An Overview SP.603, Oct. 1984, Society upload/287.pdf
of Automotive Engineers, pp. 17–28. 关493兴 “Recommended Guideline: Global Performance Specification
关474兴 “Lubricant Additives and the Environment,” CEFIC, Brus- for Diesel Engine Oil 共Global DHD-1兲,” http://www.jama-
sels, Belgium 共1993兲. english.jp/release/release/2001/dhd-1.pdf
关475兴 “Fuel Additives and the Environment,” CEFIC, Brussels, Bel- 关494兴 McFall, D., “Diesel Oil Specs: Converging or Diverging?,”
gium 共1994兲. Lubes-N-Greases, Aug. 2002, pp. 6–13.
关476兴 McFall, D., “Is Scrutiny of Engine Oils Slipping?,” 关495兴 Sullivan, T., “Heavy-duty Oil Specs: Convergence on Hori-
Lubes‘N’Greases, Jan. 8, 2001 p. 6. zon?” Lube Report, Vol. 6, No. 45, Nov. 8, 2006.
关477兴 Internal Combustion Engines, V. Ganesan, Mcgraw-Hill Inc., 关496兴 Carter, B. H., “Marine Lubricants,” Chemistry and Technol-
NY, 1995. ogy of Lubricants, R. M. Mortier and S. T. Orszulik, Eds.,
关478兴 Norbye, J. P., The Wankel Engine: Design, Development, Appli- Blackie Academic and Professional-Chapman & Hall, Lon-
cations, Chilton Book Company, Philadelphia, 1971. don, UK, 1996, Chapter 10, pp. 287–305.
关479兴 “Gas and Expansion Turbines,” Van Nostrand’s Scientific 关497兴 “Shipboard Investigations with Selected Fuels of Tomorrow,”
Encyclopedia, Fifth Edition, D. M. Considine, Ed., Van Nos- G. J. Hellingman and S. Barrow, Presented at 14th In-
trand Reinhold Company, NY, 1976, pp. 1138–1148. ternational Congress on Combustion Engines, Helsinki,
关480兴 “Engine Service Classification System and Guide to Crankcase 1981.
Oil Selection,” API Publication 1509, American Petroleum 关498兴 Scott, R., “Stationary Natural Gas Engine Lubrication,” Ma-
Institute, Sept. 2002, www.api.org/certifications/engineoil/ chinery Lubrication, Noria Corporation, Sept. 2004, http://
pubs/index. cfm www.machinerylubrication.com/article_detail.asp?articleid
关481兴 “The ILSAC GF-4 Standard for Passenger Car Engine Oils,” ⫽663&pagetitle⫽Stationary%20
International Lubricant Standardization and Approval Natural%20Gas%20Engine%20Lubrication
Committee, January 14, 2004, www.ilma.org/resources/ 关499兴 Scott, R., “Reciprocating Natural Gas Compressors,” Ma-
ilsac_finalstd011404.pdf chinery Lubrication, Noria Corporation, Nov. 2003.
关482兴 McFall, D., “Automakers Push ‘Start’ Button on GF-5 Oils,” 关500兴 Lansdown, A. R., “Aviation Lubricants,” Chemistry and
Lube Report, Vol. 4, No. 52, Dec. 29, 2004. Technology of Lubricants, R. M. Mortier and S. T. Orszulik,
关483兴 Taylor, R. I., Mainwaring, R. and Mortier, R. M., “Engine Lu- Eds., Blackie Academic and Professional-Chapman & Hall,
bricant Trends Since 1990,” 关http://www.iantaylor. London, UK, 1996, Chapter 9, pp. 264–305.
org.uk/papers/IMechEReview.pdf#search⫽%22%E2 关501兴 “TURBO OIL 274—Turbine Engine & Accessory,” BP
%80%9CEngine%20Lubricant%20Trends%20Since% Lubricant Brochure, http://www.bp.com/liveassets/bp_
201990%22%22兴. internet/aviation/air_bp/STAGING/local_assets/
关484兴 “Performance Specification MIL-PRF-2104H: Lubricating downloads_pdfs/b/brochure_bp_turbo_oil_274_sept_02.pdf
Oil, Internal Combustion Engine, Combat Tactical Service,” 关502兴 “TURBO OIL 25—Turbine Engine & Accessory,” BP Lubri-
Published 12 July 2004 关http://www.wbdg.org/ccb/ cant Brochure, http://www.bp.com/liveassets/bp_internet/
FEDMIL/prf2104h.pdf兴. aviation/air_bp/STAGING/local_assets/downloads_pdfs/b/
关485兴 “Two-stroke Cycle Gasoline Engine Lubricant, Recertified,” brochure_bp_turbo_oil_25_sept_02.pdf
SAE J1536—Revised November 2005, SAE Standard, 关503兴 “TURBO OIL 2389—Turbine Engine & Accessory,” BP
Society of Automotive Engineers. Lubricant Brochure, http://www.bp.com/liveassets/bp_
关486兴 “Engine Oil Performance and Engine Service Classification internet/aviation/air_bp/STAGING/local_assets/downloads_
共Other Than ‘Energy Conserving’兲,” SAE J183—Revised pdfs/b/brochure_bp_turbo_oil_2389_march_03.pdf
March 1, 2006, SAE Standard, Society of Automotive 关504兴 “TURBO OIL 2380—Turbine & Accessory,” BP Lubricant
Engineers. Brochure, http://www.bp.com/liveassets/bp_internet/
关487兴 “ACEA and API Tables,” http://www.infineum.com/ aviation/air_bp/STAGING/local_assets/downloads_pdfs/b/
information/tables.html brochure_bp_turbo_oil_2380_sept_02.pdf
关488兴 Chitty, D. B., “A Rig Test Approach to the Investigation of 关505兴 Kudolis, C., “Choosing an Oil for Two-Cycle Engines,” E.A.A.
Valve Train Failures in Automotive Engines,” Performance Experimenter™ Magazine, April, 1994, http://
Testing of Lubricants for Automotive Engines and www.theultralightplace.com/choosing_oil.htm
Transmissions, C. F. McCue, J. C. Cree, and R. Tourret, Eds., 关506兴 “Two-stroke Cycle Gasoline Engine Lubricants: Performance
Applied Science Publishers, Barking, England, 1973. and Service Classification,” SAE J2116—July 2003, SAE
关489兴 McFall, D., and Tocci, L., “Diesel Oils Trend Toward OEM Standard, Society of Automotive Engineers.
Specs,” Lube Report, January 3, 2006, http:// 关507兴 “FC-W™: Four-Stroke Cycle, Water-Cooled Gasoline Engine
www.imakenews.com/lng/e_article000508398.cfm?x Lubricant Certification Procedure Manual,” http://www.
⫽b11,0,w. nmma.org/certification/local/downloads/documents/
关490兴 “ACEA 2007 Sequences,” http://www.acea.be/images/ FCW_Certification_Procedure_Manual.pdf
uploads/pub/ 关508兴 Courtesy of the Suzuki Motor Corporation.
070308_ACEA_sequences_2007_LD_and_HD.pdf 关509兴 CRC Diesel Engine Rating Manual 共CRC Manual No. 15兲, 1986.
关491兴 “International Tests and Specifications for Automotive Oils,” 关510兴 Sludge Rating Manual 共CRC Manual 12兲, 1976.
SAE J2227, Surface Vehicles Information Report, Issued 关511兴 CRC Varnish Rating Manual 共CRC Manual No. 9兲, 1971.
April 2002. 关512兴 CRC Rust Rating Manual 共CRC Manual No. 7兲, 1962; Pub-
char 12 by ASTM Int'l (all rights reserved); Tue Apr 22 03:57:28 EDT 2014
Copyright
Downloaded/printed
Font Times-Bold by
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Color red of Virginia pursuant to License Agreement. No further reproductions authorized.
䊏 REFERENCES 649
lished by Automotive Vehicle Fuel, Lubricant, and Equip- U.S. Patent 6,391,833 共May 21, 2002兲. Inventors: F. Il-
ment Research Committee of the Coordinating Research main, S. Addagarla, and J. Cazin.
Council, Inc., 1986. 关535兴 “Air Pollution Emissions Overview,” http://www.epa.gov/
关513兴 SWRI. http://www.swri.org. oar/oaqps/emissns.html
关514兴 Figure Courtesy of Petro-Canada. 关536兴 “Pollutants,” http://www.epa.gov/oms/invntory/
关515兴 API Base Oil Interchangeability Guidelines for Passenger Car overview/pollutants/index.htm
Motor Oils and Diesel Engine Oils, Paragraph E.1.3. 关537兴 “Integrated Risk Information System,” http://www.epa.gov/
关516兴 “Synthetic Lubricating Oils,” U.S. Patent 4,737,297 共April iris/
12, 1988兲. Inventors: T. Yoshida and H. Watanabe. 关538兴 “Control of Hazardous Air Pollutants from Mobile Sources, 40
关517兴 Shugarman, A. L., “Selecting Synthetics for Off-Highway CFR Parts 59, 80, 85 and 86,” http://www.epa.gov/oms/
Crankcase Applications,” Machinery Lubrication Maga- regs/toxics/proposedrule.pdf
zine, March 2002. 关539兴 “Technology Transfer Network—1999 National Scale Air Tox-
关518兴 Culley, S. A., McDonnell, T. F., Ball, D. J., Kirby, C. W., and ics Assessment,” www.epa.gov/ttn/atw/nata1999
Hawes, S. W., “Emission Control Systems and Phosphorus in 关540兴 “Ambient Air Quality Standards,” http://www.arb.ca.gov/
Oils,” Automot. Eng., Nov. 1996, pp. 35–44. research/aaqs/aaqs2.pdf
关519兴 Kayama, F., Horiguchi, H., and Hamamatsu, A., “Potential 关541兴 “Ambient Air Quality Standards 共NAAQS兲,” www.epa.gov/
Health Effects of Alkylphenols in Japan,” Japanese Medical air/criteria.html
Association Journal 兵JMAJ其, Vol. 3, No. 3, 2003, pp. 108– 关542兴 Eyzat, P. and Guibet, J. C., “A New Look at Nitrogen Oxides
114. Formation in Internal Combustion Engines,” SAE Paper
关520兴 Schettler, T., “Prenatal Exposure to Endocrine Disrupting 680124, 1968.
Chemicals: Effects on Children’s Development and Health,” 关543兴 Zeldovich, Y. B., Sadovnikov, P. Y., and Frank-Kamenetskii,
http://www.epa.gov/Region8/humanhealth/children/ D. A., Oxidation of Nitrogen in Combustion, Academy of Sci-
SchettlerPrenatalExposures- ences, U.S.S.R., Moscow-Leningrad, 1947.
toEndocrineDisruptors.pdf 关544兴 Lavoie, G. A., Heywood, J. B., and Keck, J. C., “Experimental
关521兴 Miller, D., Wheals, B. B., Beresford, N., and Sumpter, J. P., and Theoretical Study of Nitric Oxide Formation in Internal
“Estrogenic Activity of Phenolic Additives Determined by an Combustion engines,” Combust. Sci. Technol. Vol. 1, 1970,
In Vitro Yeast Bioassay,” Environ. Health Perspect., Vol. 313.
109, No. 2, 2001, pp. 133–138. 关545兴 Newhall, H. K., and Shahed, S. M., “Kinetics of Nitric Oxide
关522兴 共a兲 McGeehan, J. of Chevron, “Uncovering the Problems with Formation in High Pressure Flames,” 13th Symposium 共In-
Extended Oil Drains,” Machinery Lubrication Magazine, ternational兲 on Combustion, Salt Lake City, Aug. 1970.
September 2001. 共b兲 DeMarco, N., “GM, California to Bust 关546兴 “Knock and Antiknock Action,” M. M. Sturgis, SAE Trans.
3,000 Mile Myth,” Lube Report, Vol. 8, No. 24, June 11, 2008. Vol. 63, 1955, 253.
关523兴 McFall, D., “Extended of Extreme,” Lubes & Greases, 关547兴 Patterson, D. J., and Henein, N. A., Emissions from Combus-
March 2000, pp. 16–20. tion Engines and Their Control, Ann Arbor Science Publishers,
关524兴 “Cummins Centinel Available for Aftermarket Purchase,” 1972.
www.cummins.com 共Search for Cummins Centinel兲. 关548兴 Data Source—Chevron’s website. “Fuels/Motor Oil,” http://
关525兴 Gatliff, B., “Cummins Centinel,” www.embeded.com/ www.chevron.com/products/prodserv/fuels/
story/OEG2001061850078. 关549兴 “Heavy Duty On-Highway Diesel Engine Certification Test
关526兴 “Fuel economy additive and lubricant composition containing Procedure Issues at the 2007—2010 Emissions Levels,” by
same,” U.S. Patent 5,863,873 共January 26, 1999兲. Inven- Shirish A. Shimpi of Cummins Inc., Chairman EMA
tor: C. H. Bovington. Calibration Standards Task Force, http://www.epa.
关527兴 “Engine lubricant using molybdenum dithiocarbamate as an gov/oms/regs/hd2007/wrkshop2/shimpi.ppt
antioxidant top treatment in high sulfur base stocks,” U.S. 关550兴 “Advanced Petroleum Based Fuels—Diesel Emission Control
Patent 6,706,672 共March 16, 2004兲. Inventor: J. Kelley. Project,” http://www.nrel.gov/vehiclesandfuels/apbf/
关528兴 “Low ash lubricant composition,” U.S. Patent 5,259,967 apbf_dec.html
共November 9, 1993兲. Inventor: D. E. Ripple. 关551兴 Automotive Fuels Handbook, K. Owen and T. Coley, Society of
关529兴 “Diesel crankcase lubricant composition,” U.S. Patent Automotive Engineers, Warrendale, PA, 1990.
4,282,107 共August 4, 1981兲. Inventors: B. H. Zoleski, R. L. 关552兴 Brinkman, N. D., et al., “Effect of Fuel Volatility on Drivability
Sung, G. R. Schierberg, and G. P. Hebert. at Low and Intermediate Ambient Temperatures,” SAE Tech-
关530兴 “Oxidation and corrosion resistant diesel engine lubricant,” nical Paper 830593, 1983.
U.S. Patent 4,758,363 共July 19, 1988兲. Inventors: R. L. 关553兴 Barker, D. A., and Dunn, M. R., “Drivability Number—A
Sung, B. H. Zoleski, and R. L. O’Rourke. Gasoline Volatility Parameter Related to Cold Start Passenger
关531兴 “Lubricating oil compositions,” U.S. Patent 7,053,027 Car Performance,” SAE Technical Paper 831756, 1983.
共May 30, 2006兲. Inventors: L. Chambard and T. Garner. 关554兴 Bitting, B., et al., “Intake Valve Deposits—Fuel Detergency
关532兴 Rose, M., “Gas Engine Oils—A Question of Balance,” In- Requirements Revisited,” SAE Technical Paper 872117,
fineum International Limited, Machinery Lubrication 1987.
Magazine March 2004. 关555兴 Taniguchi, B. Y., et al., “Injector Deposits—The Tip of Intake
关533兴 E. A. A. Experimenter™ Magazine, April, 1994. Article sub- System Deposit Problem,” SAE Technical Paper 861534,
mitted by C. Kudolis 共EAA 299878兲 http:// 1986.
www.ultralighthomepage.com/OIL/oil.html 关556兴 Courtesy of Chevron-http://www.chevron.com/products/
关534兴 “Low sulfur lubricant composition for two-stroke engines,” prodserv/fuels/bulletin/motorgas/
char 12 by ASTM Int'l (all rights reserved); Tue Apr 22 03:57:28 EDT 2014
Copyright
Downloaded/printed
Font Times-Bold by
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Color red of Virginia pursuant to License Agreement. No further reproductions authorized.
650 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
关557兴 Hagen, D. F. and Holiday, G. W., “The Effects of Engine Oper- of Deposits,” SAE Technical Paper 900151, 1990.
ating and Design Variables on Exhaust Emissions,” SAE Pub- 关580兴 Price, R. J., Wilkinson, P. T., Jones, D. A., and Morley, C., “A
lication TP-6, 1964, p. 206. Laboratory Simulation and Mechanism for the Fuel Depen-
关558兴 Heisler, H., Advanced Engine Technology, Society of Automo- dence of SI Combustion Chamber Deposit Formation,” SAE
tive Engineers, 1997. Technical Paper 952445, Presented at Fuels and Lubri-
关559兴 “Proton Exchange Membrane Fuel Cell,” http:// cant Meeting, Toronto, Ontario, Oct. 16–19, 1995.
en.wikipedia.org/wiki/ 关581兴 Daly, D. T., Bannon, S. A., Fog, D. A., and Harold, S. M.,
Proton_exchange_membrane_fuel_cell “Mechanism of Combustion Chamber Formation,” SAE Tech-
关560兴 “Diesel Retrofit Technology Verification,” http://www.epa. nical Paper 941889, Presented at Fuels and Lubricant
gov/otaq/retrofit/index.htm Meeting, Baltimore, MD, Oct. 17–20, 1994.
关561兴 “Recent Developments in Integrated Exhaust Control Tech- 关582兴 Kalghatagi, G. T., “Combustion Chamber Deposits in Spark-
nologies for Diesel Engines,” ftp://ftp.arb.ca.gov/carbis/ ignition Engines: A Literature Review,” SAE Technical Pa-
ds/archpres/meca/diesel.ppt per 952443, 1995.
®
关562兴 “How BlueTec Works,” http://merceds-benz.com/ 关583兴 “Drinking Water,” http://www.epa.gov/mtbe/water.htm
specials/scr/en/index_nocom_en. htm 关584兴 Guidance on Quantifying NOx Benefits for Cetane Improve-
关563兴 The Effect of Cetane Number Increases Due to Additives on ment Programs for Use in SIPs and Transportation Confor-
NOx Emissions from Heavy-Duty Highway Engines, EPA420- mity, EPA420-B-04-005, June 2004, http://www.epa.gov/
S-02–012, June 2002. http://www.epa.gov/otaq/models/ OMS/guidance/420b04005.pdf
analysis/s02012.pdf 关585兴 NFPA Standard T 2.13.7R1-1997: Hydraulic Fluid Power-
关564兴 “Biodiesel,” National Biodiesel Board, www.biodie- Petroleum Fluids-Prediction of Bulk Moduli, National Fluid
sel.org Power Association, Milwaukee, WI 1997.
关565兴 Henein, N. A., and Bolt, J. A., “The Effect of Some Fuel and 关586兴 Totten, G. E., Webster, G. M., and Yeapple, F. D., “Physical
Engine Factors on Diesel Smoke,” SAE Technical Paper Properties and Their Determination,” Handbook of Hydrau-
690557, 1969. lic Fluid Technology, G. E. Totten, Ed., Marcel Dekker, NY,
关566兴 Stone, R., Introduction to Internal Combustion Engines, Soci- 2000 p. 253.
ety of Automotive Engineers, 1993. 关587兴 Esposito, A., Fluid Power with Applications, Prentice Hall,
关567兴 “Exhaust Emissions, Spark-ignition 共SI兲 Engines,” Grö- Englewood Cliffs, NJ, 1988.
zlinger, W., Automotive Handbook, R. Bosch, GmbH, 1993, 关588兴 SAE J754A Lubricant Types—Construction and Industrial
pp. 478–482. Machinery, SAE Handbook, Part 3, Society of Automotive
关568兴 Courtesy of Toyota Motor Corporation. Engineers, Warrendale, PA, 2004, 40.88.
关569兴 Stone, R., and Kwan, E., “Variable Valve Actuation Mecha- 关589兴 Kushwaha, R. L. and Liu, J., “Farm and Construction Equip-
nisms and the Potential for Their Application,” SAE Techni- ment,” Handbook of Lubrication and Tribology, Vol. I,
cal Paper 890673, SAE Transactions, Vol. 98, 1989. Applications and Maintenance, 2nd ed., G. E. Totten, Ed.,
关570兴 “Diesel Fuel Technical Review,” www.chevron.com/ CRC Press, Chapter 21, 2006, pp. 21-1–21-18.
products/prodserv/fuels/diesel/documents/ 关590兴 Cleveland, W. S., “Tractor Wet Brake and Wet Clutch Friction
Diesel_Fuel_TechnicalReview.pdf Properties,” NLGI Spokesman, July 1987 pp. 135–138.
关571兴 Courtesy of R. Bosch GMBH. 关591兴 Hanley, W. J., “Farm and Construction Equipment,” CRC
关572兴 Newton, K., Steeds, W., and Garret, T. K., “Potential for Future Handbook of Lubrication, Vol. I, Theory and Practice of
Development,” The Motor Vehicle, Chapter 17, 1996, pp. Tribology: Applications and Maintenance, R. E. Booser,
389–395. Ed., CRC Press, Boca Raton, 1983, pp. 249–267.
关573兴 Courtesy of Cummins Inc., Moore, W., “Living with Cool- 关592兴 “Ready Reference for Hydraulic and Industrial Fluids,” Lubri-
EGR,” www.contructionequipment.com/prevention/ zol Publication, May 2005.
cd031a004.asp 关593兴 Michael, P. W., Herzog, S. N., and Marougy, T. E., “Fluid Vis-
关574兴 Sullivan, T., “Charting a Safe Course on EGR,” The Effect of cosity Selection Criteria for Hydraulic Pumps and Motors,”
EGR on Various Lubricant Parameters 关Argonne Proceedings of the 48th National Conference on Fluid
Data兴, Lubes‘N’Greases, Sept. 2001. Power, Chicago, National Fluid Power Association, Milwau-
关575兴 Wagner, R. M., Green Jr., J. B., Storey, J. M., and Daw, C. S., kee, WI, 2000, pp. 313–325.
“Extending Exhaust Gas Recirculation Limits in Diesel En- 关594兴 Givens, W. A., and Michael, P. W., “Hydraulic Fluids,” Fuels
gines,” Oakridge National Laboratory Research Ar- and Lubricants Handbook: Technology, Properties, Per-
ticle. formance, and Testing, G. E. Totten Ed., ASTM Interna-
关576兴 “SAE Fuels and Lubricant Standards,” 2007 SAE Hand- tional, West Conshohocken, PA, Chapter 13, 2003, pp. 353–
book, Society of Automotive Engineers, Inc., Warrendale, 381.
PA. 关595兴 Lloyd, B. J., “Water Water Everywhere,” Lubes-N-Greases,
关577兴 Hauser, K. R., and Crossby, T. A., “The Impact of Intake Valve Vol. 11, No. 3, 1997, pp. 44–53.
Deposits on Exhaust Emissions,” SAE Technical Paper 关596兴 Brew, D., Khonsari, M., and Ball, J. H., “Current Research in
922259, 1992. Cavitating Fluid Films,” STLE Special Publication SP-28,
关578兴 Tupa, R. C., “Port Fuel Injector Deposits—Causes/ Society of Tribologists and Lubrication Engineers,
Consequences/Cures,” SAE Technical Paper 872113, Park Ridge, IL, 1990, pp. 63–65.
1987. 关597兴 Barnes, M., “Particle Counting—Oil Analysis 101,” Practic-
关579兴 Esaki, Y., Ishiguro, T., Suzuki, N., and Nakada, M., “Mecha- ing Oil Analysis Magazine, July 2002.
nism of Intake Deposit Formation—Part I—Characterization 关598兴 “Ultra-clean Super Hydraulic Oil,” http://
char 12 by ASTM Int'l (all rights reserved); Tue Apr 22 03:57:28 EDT 2014
Copyright
Downloaded/printed
Font Times-Bold by
University
Color red of Virginia pursuant to License Agreement. No further reproductions authorized.
䊏 REFERENCES 651
关633兴 “Tractions Fluids,” U.S. Patent 6,623,399 共September 23, cation, and Wear Technology, S. D. Henry, Ed., ASM Inter-
2003兲. Inventors: K. C. Fey, G. F. Viaplana Gordon, T. K. national, Vol. 18, 1992, pp. 535–545.
Hilty, R. K. King, T. M. Leaym, L. A. Stark-Kasley, G. M. Wie- 关652兴 Dekock, J., “Laser Heat Treating Advances for the Gear Indus-
ber, and E. D. Groenhof. try,” GEARSolutionsonline, www.gearsolutionsonli-
关634兴 “Method for Lubricating A Continuously Variable Transmis- ne.com
sion,” U.S. Patent 6,730,640 共May 4, 2004兲. Inventors: R. 关653兴 Herring, D. H., and Balme, S. D., “Oil Quenching Technolo-
L. Sowerby, C. D. Tipton, and J. L. Sumiejski. gies for Gears,” GEARSolutionsonline, www.gearsolu-
关635兴 “Traction Fluids Formulation,” U.S. Patent 6,372,696 tionsonline.com.
共April 16, 2002兲. Inventor: C. D. Tipton. 关654兴 “New Standards Released: ANSI/AGMA 1003-H07 and
关636兴 “Cyclic Oligomer Traction Fluid,” U.S. Patent 7,045,488 ANSI/AGMA 1103-H07; ANSI/AGMA 9005-E-02,”
共May 16, 2006兲. Inventors: S. J. Bartley, D. M. Barr, R. M. www.agma.org//AM/Template.cfm?Section⫽Home
Lange, and C. D. Tipton. 关655兴 Benedict, G. H., “Gears,” Standard Handbook of Lubrica-
关637兴 “High Boron Fluids for Continuously Variable Transmis- tion Engineering, J. J. O’Connor, Ed., McGraw-Hill Book
sions,” U.S. Patent 6,451,745 共September 17, 2002兲. In- Company, NY, Chapter 20, 1968, pp. 20-1 to 20-30.
ventor: W. C. Ward. 关656兴 Stucker, J. B., “Rear Axle and Gear Box Lubricants,” CRC
关638兴 “Lubricant composition,” U.S. Patent 6,465,399 共October Handbook of Lubrication, Vol. I, Theory and Practice of
15, 2002兲. Inventors: N. Koishikawa and Y. Tatsumi. Tribology: Applications and Maintenance, R. E. Booser,
关639兴 Bastian, E. L. H., “Metalworking,” Standard Handbook of Ed., CRC Press, Boca Raton, 1983 pp. 55–69.
Lubrication Engineering, J. J. O’Connor, Ed., McGraw-Hill 关657兴 Pilon, E. L., “Gear Lubrication-II,” Lubrication, Vol. 66,
Book Company, NY, Chapter 23, 1968, pp. 23-1 to 23-25. 1980, pp. 13–24.
关640兴 Piermaria, D., and Michaelis, K., “Recognizing Gear Fail- 关658兴 Johnson, W. A., “Laboratory and Field Findings Pertaining to
ures,” published 6/21/2007, 共http:// Axle Lubricants,” Presented at SAE Fuels and Lubricants
machinedesign.com/ContentItem/67968/ Meeting, Chicago, June 5–10, 1960.
Recognizinggearfailures.aspx兲兴
关659兴 Kamura, Y., “Some Problems in the Adhesion Theory of Fric-
关641兴 Volin, R. H., “Literature Review: Techniques and Applications
tion,” Fundamentals of Tribology, N. P. Suh and N. Saka,
of Mechanical Signature,” Eds., Published by MIT Press, Cambridge, 1980 pp. 385–391.
关642兴 Martin, H. R., “Vibration Analysis,” American Society of
关660兴 Roux, F., “Some New Oil Testing Devices, in the Development
Metals Handbook, Friction, Lubrication, and Wear
Stage, for European Engines,” Automotive Engines and
Technology, S. D. Henry, Ed., ASM International, Vol. 18,
Transmissions, C. F. McCue, J. C. Cree, and R. Tourrets Eds.,
1992 pp. 293–298.
Applied Science Publishers, Barking, England, 1973.
关643兴 “Gear Diagnostic Parameters 共Vibration Based兲,” http://
关661兴 Radovich, J. L., “Gears,” CRC Handbook of Lubrication,
mfpt.org/Archive%20OLD%20Pages/
Vol. II, Theory and Practice of Tribology: Theory and De-
mfpt_geardiagnosticparam.html.
sign, R. E. Booser, Ed., CRC Press, Boca Raton, 1988, pp.
关644兴 “A Model-Based Gear Diagnostic Technique,” W. Wang and A.
539–564.
K. Wong, 关http://dspace.dsto.defence.gov.au/dspace/
关662兴 “Lubrication of Gears,” http://www.qtcgears.com/Q410/
bitstream/1947/4127/1/DSTO-TR-1079%20PR.pdf兴
QTC/Q410P440.htm
关645兴 “Diagnostics of Gearing and Gear Couplings Using Envelop
关663兴 “Gears Lubrication,” http://www.agroengineers.com/
Spectrum Methods,” A. Barkov and N. A. Barkova; http://
gears/gears-lubrication.shtml
www.geartools.co.uk/mambo/index.php?option
关664兴 “Axle and Manual Transmission Lubricant Viscosity Classifi-
⫽com_content&task⫽view&id⫽54&Itemid⫽1
关646兴 Kennedy, Jr., F. E., “Surface Temperature Measurement,” cation,” SAE J306-SAE Standard, Society of Automo-
American Society of Metals Handbook, Friction, Lubri- tive Engineers.
cation, and Wear Technology, S. D. Henry Ed., ASM Inter- 关665兴 “Lubricant Service Designations for Automotive Manual
national, Vol. 18, 1992, pp. 438–44. Transmissions and Axles,” API Publication No. 1560,
关647兴 Lockwood, F. E. and Dalley, R., “Lubricant Analysis,” Ameri- American Petroleum Institute.
can Society of Metals Handbook, Friction, Lubrication, 关666兴 Sutherland, J. M., “Proposed Automotive Gear Lubricant Cat-
and Wear Technology, S. D. Henry, Ed., ASM International, egories: Their Impact on the Industry,” Presented at NPRA
Vol. 18, 1992, pp. 299–312. National Fuels and Lubricants Meeting, Houston, TX,
关648兴 Ives, L. K., “Electron Microscopy,” American Society of Nov. 2–3, 1989.
Metals Handbook, Friction, Lubrication, and Wear 关667兴 Blau, P. J., “Glossary of Terms,” American Society of Metals
Technology, S. D. Henry, Ed., ASM International, Vol. 18, Handbook, Friction, Lubrication, and Wear Technology,
1992 pp. 376–392. S. D. Henry, Ed., ASM International, Vol. 18, 1992, pp. 1–21.
关649兴 Bala, V., “Gear Lubricants,” Fuels and Lubricants Hand- 关668兴 “Lubricating Automotive Gears,” Report No. C-7626, The
book: Technology, Properties, Performance, and Testing, Lubrizol Corporation, May 1983.
G. E. Totten, Ed., ASTM International, West Conshohocken, 关669兴 Olszewski, W. F., Nieswender, D. D., Stanek, J. M., and Taylor,
PA, Chapter 16, 2003, pp. 431–463. D. J., “Performance Characteristics of Hypoid Gear Lubri-
关650兴 Herring, D. H., and G. D. Lindell, “Heat Treating Heavy Duty cants,” Performance and Testing of Gear Oils and Trans-
Gears,” GEARSolutionsonline, www.gearsolutionson- mission Fluids, R. Tourret and E. P Wright, Eds., Heyden
line.com and Son, Chapter 17, 1981, pp. 293–305.
关651兴 Errichello, R. “Friction, Lubrication, and Wear of Gears,” 关670兴 “Lubricant Service Designations for Automotive Manual
American Society of Metals Handbook, Friction, Lubri- Transmissions, Manual Transaxles, and Axles,” API Publica-
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䊏 REFERENCES 653
tion 1560, 7th ed., July 1995, http://www.upmpg.com/pdf/ 关692兴 Sutherland, J. W., Olson, W. W., and Bergstrom, A., “Dry Ma-
gearគlubeគdesignations.pdf chining,” Summary of Manufacturing Research 1996–
关671兴 “Limited Slip Differentials,” Lubrication, 564, 1970, pp. 49– 97, Department of Mechanical Engineering and Engi-
60. neering Mechanics, Michigan Technological
关672兴 Chocholek, S. E., “The Development of Differential for the Im- University, Houghton, MI.
provement of Traction Control,” www.torsen.com/files/ 关693兴 Cantor, N. M., “Dry or Near-dry Machining Won’t Replace
traction_control_article.pdf. Traditional Metalworking Fluid Technology Anytime Soon,
关673兴 Nice, K., “How Differentials Work,” http://auto. But They Do Offer Advantages for Some Niche Markets,” Tri-
howstuffworks.com/differential.htm bology and Lubrication Technology, Nov. 2003, p. 31.
关674兴 “Progress is Slow on PG-1 and PG-2,” Lubrizol NewsLine, 关694兴 Tolfa, J. C., “Synthetic Lubricants Suitable for Use in Process
Vol. 111, Jan. 1993. and Hydrocarbon Gas Compressors,” Lubr. Eng., Vol. 47, No.
关675兴 Root, D. C., “Selecting the Right Gear Oil,” , Vol. 32, 1976, p. 4, 1990, pp. 289–295.
8. 关695兴 Miller, J. W., “Synthetic and HVI Compressor Lubricants,”
关676兴 “Sulfurized Polyisobutylene Based Wear and Oxidation Inhibi- Journal of Synthetic Lubricants, Vol. 6, No. 2, 1989, pp.
tors,” U.S. Patent 6,884,855 共April 16, 2005兲. Inventors: 107–122.
K. D. Nelson and F. Plavac. 关696兴 Miller, J. W., “Synthetic Lubricants and Their Industrial Appli-
关677兴 “Sulfide- and Polysulfide-containing Lubricating Oil Additive cations,” Journal of Synthetic Lubricants, Vol. 1, No. 2,
Compositions and Lubricating Compositions Containing the 1984, pp. 136–152.
Same,” U.S. Patent 6,689,723 共February 10, 2004兲. In- 关697兴 Garg, D. R., “Polyalkylene Glycol-Based Compressor Lubri-
ventors: W. T. Sullivan, P. R. Kanga, T. S. Coolbaugh. cants,” Presented at the 6th Annual Reciprocating Com-
关678兴 “Manual Transmission Lubricants with Improved Synchro- pressor Conference, Salt Lake City, UT, 23–26 Sept. 1993.
mesh Performance,” U.S. Patent 6,617,287 共September 9, 关698兴 Patzau, S. and Szchawnicka, E., “Oils for Air and Technical
2003兲. Inventors: M. P. Gahagan and B. M. O’Connor. Gas Compressors,” Trybologia, Vol. 20, No. 4, 1989, pp. 18–
关679兴 “Oil Additive Concentrates and Lubricants of Enhanced Per- 21.
formance Capabilities,” U.S. Patent 5,328,619 共July 12 关699兴 Randles, S. J., “Esters,” Synthetic Lubricants and High
1994兲. Inventor: G. S. Conary. Performance Functional Fluids, R. L. Rudnick and R. L.
关680兴 “Turbine,” http://en.wikipedia.org/wiki/Turbines Shubkin, Eds., Marcel Dekker, Inc., NY, 1999, pp. 63–102.
关681兴 “Gas Compressor,” http://en.wikipedia.org/wiki/ 关700兴 Miller, J. W., “New Synthetic Food Grade Rotary Screw Com-
Gas_compressor pressor Lubricants,” Lubr. Eng., Vol. 40, No. 7, 1983, pp. 433–
关682兴 Garg, D., Totten, G. E., and Webster, G. M., “Compressor Lu- 436.
bricants,” Fuels and Lubricants Handbook: Technology, 关701兴 Oberle, J. and Rajewski, T., “The Development of Lubricants
Properties, Performance, and Testing, G. E. Totten, Ed., for Ammonia Refrigeration Systems,” Presented at the HAR
ASTM International, West Conshohocken, PA, Chapter 14, 19th Annual Meeting, 23–26 March 1997, New Orleans, LA.
2003, pp. 383–412. 关702兴 Mills, A. J., Tempest, M. A., and Thomas, A. S., “Performance
关683兴 Kist, K. R. and Doperalski, E. J., “Brief Introduction to the Testing of Rotary Screw Compressor Fluids in Europe,” Lubr.
Screw Compressor,” Paper 68E, AIChE 86th National Eng., Vol., No. 5, 1986, pp. 278–286.
Meeting, 1979. 关703兴 Henderson, D. R., Rajewski, T. E., Speich, C. F., and Grieg, B.,
关684兴 Cohen, S. C., “Development of a ‘Synthetic’ Compressor Oil “Lubricants in Refrigerant Systems,” ASHRAE Handbook-
Based on Two-stage Hydrotreated Petroleum Basestocks,” Fundamentals, ASHRAE Publications, Atlanta, Chapter 7,
Lubr. Eng., Vol. 44, No. 3, 1987, pp. 230–238. 1997.
关685兴 Matthews, P. H. D., “Lubrication of Reciprocating Compres- 关704兴 共a兲 Devos, R., Davis, TH. 1997, “HFC-134a Qualification, In-
sors,” Journal of Synthetic Lubricants, Vol. 6, No. 4, 1990, dustry Refrigerator Capillary Data,” Proceedings of Interna-
pp. 292–317. tional Conference on Ozone Protection Technologies;
关686兴 Short, G. D., “Development of Synthetic Lubricants for Ex- 1997, November 12–13. Baltimore, MD, Arlington, VA: Alli-
tended Life in Rotary Screw Compressors,” Lubr. Eng., Vol. ance for Responsible Atmospheric Policy, p. 10. 共b兲 DeVos, R.,
40, No. 8, 1983, pp. 463–470. “R-134a Qualification-Industry Refrigerator Capillary Data,”
关687兴 Van Ormer, H. P., “Trim Compressed Air Cost with Synthetic ASHRAE Transactions, BN-97-7-4, 1997, p. 1.
Lubricants,” Power, 1987, pp. 43–45. 关705兴 Michels, H. H. and Sienel, T. H., “Refrigeration Lubricants,”
关688兴 Matthews, P. H. D., Walkden, R. H., and Williams, G. C., “Cur- Fuels and Lubricants Handbook: Technology, Proper-
rent and Future Developments of Lubricants for Industrial Air ties, and Testing, G. E. Totten, Ed., ASTM International,
Compressors,” Paper Number C477/023/94, IMechE West Conshohocken, PA, Chapter 15, 2003, pp. 413–430.
Conference, Proceedings of the Institute of Mechanical 关706兴 Sunami, M., Takidawa, K., Suda, S., and Sasoki, U., “New Im-
Engineers, 1994, pp. 175–183. miscible Refrigeration Lubricants for HFCs,” ASHRAE
关689兴 Takashima, H., “Gas Compressor Oils,” Toraiborojisuto, Transactions, SD-95-83, 1995, p. 940.
Vol. 38, 1993, pp. 135–139. 关707兴 Sunami, M., Takidawa, K., and Suda, S., “New Immiscible
关690兴 Kajdas, C., “Industrial Lubricants,” Chemistry and Technol- Refrigeration Lubricants for HFCs,” Proceedings of
ogy of Lubricants, R. M. Mortier and S. T. Orszulik, Eds., ASHRAE Purdue CFC Conference, Purdue University,
Blackie Academic and Professional-Chapman & Hall, Lon- West Lafayette, IN, 1994, p. 129.
don, UK, 1996, Chapter 8, pp. 228–265. 关708兴 Gunderson, R. C., and Hart, A. W., Synthetic Lubricants, Rein-
关691兴 Kajdas, C., “Additives for Metalworking Lubricants. A Re- hold, NY, 1962.
view,” Sci. Lubr., Vol. 1, pp. 385–409. 关709兴 Glova, D. J., “High Temperature Stability of Refrigerants in
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654 A COMPREHENSIVE REVIEW OF LUBRICANT CHEMISTRY, TECHNOLOGY, SELECTION, AND DESIGN 䊏
Lubricating Oils,” ASHRAE Transactions, Vol. 90, No. 4, 关730兴 共a兲 Gow, G., “Lubricating Grease,” Chemistry and Technol-
1984, p. 806. ogy of Lubricants, R. M. Mortier and S. T. Orszulik, Eds.,
关710兴 Takagi, M., “New Type Refrigeration Lubricants for Alterna- Blackie Academic and Professional-Chapman & Hall, Lon-
tive Refrigerants,” Energy Resources, Vol. 16, 1995, p. 497. don, UK, Chapter 11, 1992, pp. 306–319. 共b兲 Figure courtesy
关711兴 “Food Grade Lubricants Reduce Contamination Threats for of SKF.
Food and Beverage Manufacturers,” by D. Hodson, Shell 关731兴 Sinistyn, V. V., The Choice and Application of Plastic Greases,
Cassida, Machinery Lubrication Magazine, Jan. 2004, Khimiya, Moscow.
http://www.machinerylubrication. com/ 关732兴 Khan, K., “Global Grease Production Rises Sharply,” Lube
article_detail.asp?articleid⫽572&relatedbookgroup Report, Vol. 8, No. 25, June 18, 2008.
⫽Lubrication2 关733兴 Bartz, W. J., “Lubricating Greases Properties and Their Classi-
关712兴 “Understanding Food-Grade Lubricants,” by M. William- fication Especially Synthetic Greases,” NLGI Spokesman,
son, Machinery Lubrication Magazine, Jan. 2003. July 2004, Vol. 68, No. 4, pp. 15–24.
关713兴 “Title 21: Food and Drugs,” www.accessdata. fda.gov/ 关734兴 “Synthetic Lubricating Greases Containing Metal Chelates of
scripts/cdrh/cfdocs/cfCFR/CFRSearch.cfm. Schiff Bases,” U.S. Patent 5,147,567 共September 15,
关714兴 “Inventory of Effective Food Contact Substance Notifica- 1992兲. Inventors: V. S. Agarwala, A. A. Conte, Jr., K. S. Rajan,
tions,” http://www.cfsan.fda.gov/~dms/opa-fcn.html and P. K. Sen.
关715兴 “Transformer,” http://en.wikipedia.org/wiki/ 关735兴 “Polyurea Grease with Reduced Oil Separation,” U.S. Patent
Transformer 4,759,859 共July 26, 1988兲. Inventor: J. A. Waynick.
关716兴 “Transformer Oil Purchase Specification—Test Limits,” 关736兴 “Polyurea-based Extreme Pressure Greases,” U.S. Patent
http://www.doble.com/services/ 4,100,081 共July 11, 1978兲. Inventor: J. L. Dreher.
lab_services_transformer_oil_specs.html 关737兴 Rumierz, J., “Lubricants for Rolling Element Bearings,”
关717兴 “Concrete Form Release Compositions,” U.S. Patent American Society of Metals Handbook, Friction, Lubri-
6,811,810 共November 2, 2004兲. Inventors: V. S. LaFay and cation, and Wear Technology, S. D. Henry, Ed., ASM Inter-
S. L. Neltner. national, Vol. 18, 1992, pp. 132–138.
关718兴 Vacuum Pump Fluids, http://www.2spi.com/catalog/vac/vac- 关738兴 Silverstein, R. and Rudnick, L., “Additives for Grease Appli-
fluids.html cations,” Lubricant Additives: Chemistry and Applica-
关719兴 Burke, L. J., “Compressors and Vacuum Pumps,” CRC Hand- tions, L. R. Rudnick, Ed., Marcel Dekker, Inc., NY, Chapter
book of Lubrication, Vol. I, Theory and Practice of Tri- 19, 2003, pp. 513–539.
bology: Applications and Maintenance, R. E. Booser, Ed., 关739兴 King, J. P., Presented at 1998 NLGI Annual Grease Meeting,
CRC Press, Boca Raton, 1983, pp. 135–147. Dublin, Ireland.
关720兴 Cichelli, E., Unangst, W. C., and Stanzione, L. A., “Wire Rope 关740兴 Tocci, L., “Transparent Grease Bears a Heavy Load,” Lubes-
and Chain,” CRC Handbook of Lubrication, Vol. I, Theory N-Greases, April 1997, Vol. 3, pp. 52–54.
and Practice of Tribology: Applications and Mainte- 关741兴 Ogawa, T., Kimura, H., and Hayama, M., NLGI Spokesman,
nance, R. E. Booser, Ed., CRC Press, Boca Raton, 1983, pp. Vol. 62, No. 6, 1998, pp. 28–36.
193–208. 关742兴 Ruge, I. W., “Lubricating Greases—Characteristics and Selec-
关721兴 Turner, J. E. and Barnes, C., “Lubrication Basics for Wire tion,” CRC Handbook of Lubrication, Theory and Prac-
Ropes,” Machinery Lubrication Magazine, July 2002. tice in Tribology, Vol. II, Theory and Design, R. E. Booser,
关722兴 “Turbine Oils with Excellent High Temperature Oxidative Sta- Ed., CRC Press, Boca Raton, 1988, pp. 255–267.
bility,” U.S. Patent 6,326,336 共December 4, 2001兲. Inven- 关743兴 “Dielectric Constants,” http://www.orioninstruments.
tors: V. J. Gatto, H. Ryan, and R. N. Iyer. com/html/dielectric_constants.asp
关723兴 “Additive Composition for Industrial Fluid,” U.S. Patent 关744兴 “Ready Reference for Grease,” a Lubrizol Publication.
6,645,920 共November 11, 2003兲. Inventor: B. J. Butke. 关745兴 “Automotive Lubrication Greases,” SAE J310-Revised
关724兴 “Turbine Lubricant,” U.S. Patent 4,101,431 共July 18, June 9, SAE Standard, SAE Handbook, Society of Au-
1978兲. Inventor: L. F. Kuntschik. tomotive Engineers.
关725兴 “High Temperature Compressor Oil,” U.S. Patent 5,156,759 关746兴 Bartz, W. J., “Lubricating Greases Properties and their Classifi-
共October 20, 1992兲. Inventor: D. H. Culpon, Jr. cation Especially Synthetic Greases,” Presentation in 2003
关726兴 共a兲 “Refrigerant Lubricant Compositions,” U.S. Patent NLGI Back to Basics Course.
5,152,926 共October 6, 1992兲. Inventor: W. L. Brown. 共b兲 关747兴 “Understanding Biobased/Biodegradable and the Industry’s
“Pneumatic Tool Lubricants,” U.S. Patent 2,918,429 共De- Standardized Tests and Definitions,” http://www.
cember 22, 1959兲. Inventors: Melvin E. Gililland and Rich- renewablelube.com/products/pdf/standardized. pdf
ard C. Givens. 关748兴 Verdura, T. M., Brunette, G., and Shah, R., “Lubricating
关727兴 NLGI Lubricating Grease Guide, National Grease Institute, Greases,” Fuels and Lubricants Handbook: Technology,
Missouri, 1987. Revised 1996, 2006 Properties, Performance, and Testing, MNL37WCD, Ed.,
关728兴 Wilson, T. C., “Modern Automotive Greases,” SAE Paper ASTM International, West Conshohocken, PA, Chapter 20,
841212, Fuels and Lubricants Technology: An Over- 2003, pp. 557–572.
view, SP.603, Society of Automotive Engineers, Oct. 关749兴 Hunter, M. E., and Baker, R. F., “Corrosion,” Fuels and Lu-
1984, pp. 101–106. bricants Handbook: Technology, Properties, Perfor-
关729兴 Boehringer, R. H., “Grease,” American Society of Metals mance, and Testing, MNL37WCD, Ed., ASTM Interna-
Handbook, Friction, Lubrication, and Wear Technology, tional, West Conshohocken, PA, Chapter 31, 2003, pp. 825–
Scott D. Henry, Ed., ASM International, Vol. 18, 1992, pp. 832.
123–131. 关750兴 “Grease Composition with Improved Extreme Pressure and
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䊏 REFERENCES 655
Antiwear Properties,” U.S. Patent 5,246,604 共September trometry: Principles and Applications, John Wiley & Sons, Dec.
21, 1993兲. Inventor: P. F. Vartanian. 1996.
关751兴 “Grease Composition for Constant Velocity Joints,” U.S. 关768兴 Colthup, N. B., Daly, L. H., and Wiberley, S. E., Introduction
Patent 6,656,890 共December 2, 2003兲. Inventors: G. Fish, to Infrared and Raman Spectroscopy, 3rd ed., Academic Press,
J. S. Cooper, J. E., T. D. Davies, and G. R. Isaac. Sept. 1990.
关752兴 “Grease Composition with Improved Rust Prevention and 关769兴 Macomber, R. S., A Complete Introduction to Modern NMR
Abrasion Resistance Properties,” U.S. Patent 6,800,595 Spectroscopy, John Wiley & Sons, Dec. 1997.
共October 5, 2004兲. Inventors: T. Ozaki, N. Shinoda, and K. 关770兴 Derome, A. E., “Modern NMR Techniques for Chemistry Re-
Nakazawa. search,” Tetrahedron Organic Chemistry Series, J. E. Bald-
关753兴 “General-purpose Grease Composition,” U.S. Patent win and P. D. Magnus, Senior Eds., Pergamon Press, Oxford,
4,582,616 共April 15, 1986兲. Inventors: T. Kita, M. Ikeda, 1993.
and A. Aseya. 关771兴 “Reduced Pressure Boiling Point Calculation by JAVA Ap-
关754兴 “Biodegradable Grease Composition,” U.S. Patent plet,” http://www.pirika.com/chem/TCPEE/BP/
4,115,282 共September 19, 1978兲. Inventor: H. D. Grass- RPBP.htm
hoff. 关772兴 Klaus, E. E., and Bieber, H. E., “Effects of Some Physical and
关755兴 “Merchant, M. E., “Deformation,” Standard Handbook of Chemical Properties of Lubricants on Boundary Lubrication,”
Lubrication Engineering, J. J. O’Connor, Ed., McGraw-Hill ASLE Trans., Vol. 7, No. 1, 1964.
Book Company, NY, Chapter 8, 1968, pp. 8-1 to 8-3. 关773兴 Fein, R. S., “Chemistry in Concentrated Conjunction Lubrica-
关756兴 Forming: Lubrication of Steel Sheet and Strip for Forming, tion,” Interdisciplinary Approach to the Lubrication of
Technical Bulletin Tb-F1 Rev 2, November 2003 Concentrated Contacts, National Aeronautics and
关www.bluescopesteel.com.au/go/tools-and-resources/ Space Administration, Washington, D.C., Chapter 12,
technical-library/forming-bulletins兴 1970.
关757兴 Laemmle, J. T., “Metalworking Fluids,” American Society of 关774兴 Balasubramaniam, K., Sankaran, S., and Rajwade, A. V., “Ul-
Metals Handbook, Friction, Lubrication, and Wear trasonic NDE Rheological Measurement Tools For Industrial
Technology, S. D. Henry, Ed., ASM International, Vol. 18, Process Control,” 共http://www.ndt.net/article/
1992, pp. 139–149. wcndt2004/pdf/in-process_ndt-nde/
关758兴 “Standard Classification of Metalworking Fluids and Related 738_balasubramaniam. pdf兲.
Materials,” ASTM Standard D 2881, Annual Book of 关775兴 “Alphabetical List of Federal Standards,” http://
ASTM Standards, ASTM International, West Consho- apps.fss.gsa.gov/pub/fedspecs/fedspecs.cfm?sort
hocken, PA. ⫽8&firstTime⫽Y&RequestTimeout⫽500
关759兴 DIN Handbuch—Mineralöle und Brennstoffe, Beuth Verlag 关776兴 Lockwood, F. E., and Klaus, E. E., “Ester Oxidation Under
GmbH, Berlin, May 2001. Simulated Boundary Lubrication Conditions,” ASLE Trans.,
关760兴 http://www.aral-lubricants.com/lubricants/com/technical/ Vol. 24, 1981, p. 276.
lubricants_abc/metalfluid.content.html 关777兴 Khonsari, M., and Booser, E. R., “Predicting Lube Life—Heat
关761兴 Sargent, L. B., Jr., “Lubricant Performance,” Standard and Contaminants Are the Biggest Enemies of Bearing Grease
Handbook of Lubrication Engineering, J. J. O’Connor, and Oil,” Machinery Lubrication Magazine, Sep. 2003.
Ed., McGraw-Hill Book Company, NY, Chapter 27, 1968, pp. 关778兴 Nadkarni, R. A., “Overview,” Modern Instrumental Meth-
27-1 to 27-21. ods of Elemental Analysis of Petroleum Products and
关762兴 Kelley, R., and Foltz, G., “Cutting Fluids,” CRC Handbook Lubricants, ASTM STP 1109, R. A. Nadkarni, Ed., ASTM
of Lubrication, Theory and Practice in Tribology, Vol. II, International, West Conshohocken, PA, 1991, p. 1.
Theory and Design, R. E. Booser, Ed., CRC Press, Boca Ra- 关779兴 Nadkarni, R. K., “Elemental Analysis,” Fuels and Lubri-
ton, 1988, pp. 357–369. cants Handbook: Technology, Properties, Performance,
关763兴 共a兲 Liscic, B., Tensi, H. M., Totten, G. E., and Webster, G. M., and Testing, MNL37WCD, Ed., ASTM International, West
“Non-lubricating Process Fluids: Steel Quenching Technol- Conshohocken, PA, Chapter 26, 2003, pp. 707–716.
ogy,” Fuels and Lubricants Handbook: Technology, 关780兴 Williams, M. C., Modern Instrumental Methods of Elemental
Properties, Performance, and Testing, George E. Totten, Analysis of Petroleum Products and Lubricants, ASTM STP
Ed., Chapter 22, pp. 587–634, ASTM International, West Con- 1109, R. A. Nadkarni, Ed., ASTM International, West Consho-
shohocken, Pennsylvania 共2003兲. 共b兲 “Corrosion Inhibiting hocken, PA, 1991, p. 96.
Quenchant Compositions,” U.S. Patent 4,595,425 共June 关781兴 Shugar, G., and Ballinger, J., Chemical Technicians’ Ready
17, 1986兲. Inventor Ronald H. Harding. Reference Handbook, 4th Ed., McGraw-Hill, Inc., NY, 1996,
关764兴 Mandakovic, R., “Assessment of EP Additives for Water Mis- pp. 831–896.
cible Metalworking Fluids,” J. Syn. Lubr., Vol. 16, No. 1, 关782兴 Altgelt, K., and Gouw, T., Chromatography in Petroleum
1999, pp. 13–26. Analysis, MarcellDekker, Inc., NY, 1979.
关765兴 Standard Methods for Analysis and Testing of Petroleum and 关783兴 Norris, T. A., “Chromatography II,” Lubrication, Vol. 65, No.
Related Products and British Standard 2000 Parts 1997, John 2, 1979.
Wiley and Sons, N.Y., 1997. 关784兴 “High Performance Liquid Chromatography,” http://
关766兴 “Interactions of Additives and Lubricating Base Stocks,” S. M. en.wikipedia.org/wiki/
Hsu and A. L. Cummings, Lubricant and Additive Effects on High_performance_liquid_chromatography
Engine Wear, SP-558, Fuels and Lubricants Meeting, San 关785兴 Denis, J., Briant, J., and Hipeaux, J., “Lubricant Properties—
Francisco, CA, Oct. 31–Nov. 3, 1983, pp. 61–70. Analysis and Testing,” Editions Technip, Paris 2000.
关767兴 De Hoffmann, E., Charette, J., and Stroobant, V., Mass Spec- 关786兴 “Infrared Spectroscopy Correlation Table,” http://en.
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wikipedia.org/wiki/Infrared_spectroscopy_ chim. Acta, Vol. 40B 共No. 1/2兲, 1985, pp. 49–55.
correlation_table 关806兴 Liu, Y., Harding, A. R., and Leyden, D. E., “Determination of
关787兴 “Infrared Spectroscopy,” http://en.wikipedia.org/wiki/ Wear Metals in Oil by X-Ray Spectrometry,” Anal. Chim.
Infrared_spectroscopy Acta, Vol. 180, 1986, pp. 349–355.
关788兴 “Nuclear Magnetic Resonance Spectroscopy,” http:// 关807兴 Bowen, E. R., and Seifert, W. “Ferrography—A New Tool for
en.wikipedia.org/wiki/ Analyzing Wear Conditions,” Presented at Fluid Power
Nuclear_magnetic_resonance_spectroscopy Testing Symposium, Milwaukee, WI, 16–18 August 1976.
关789兴 “Proton NMR,” http://en.wikipedia.org/wiki/Proton_ 关808兴 Anderson, D. P., and Driver, R. D., “Equilibrium Particle Con-
NMR. centration in Engine Oil,” Wear, Vol. 56, 1979, pp. 415–419.
关790兴 “Carbon-13 NMR,” http://en.wikipedia.org/wiki/ 关809兴 Colyer, C. C., “The ASTM Test Monitoring System—Purpose
Carbon-13_NMR and Operation,” ASTM Stand. News, Oct. 1981, pp. 8–12.
关791兴 Sahoo, S. K., Sharma, B. K., and Singh, I. D., “NMR Studies of 关810兴 Colyer, C. C., “The SAE Lubricants Review Institute—Purpose
Lube Distillates for Making Quality Base Oils,” Preprints and Operation,” Presented at the International Congress
共ACS Division of Petroleum Chemistry兲, Vol. 45, 1999. and Exposition, Detroit, MI, Feb. 28—March 4, 1983.
关792兴 Sarpal, A. S., Kapur, G. S., Mukherjee, S., and Jain, S. K., 关811兴 Colyer, C. C., Davis, K. E., Desing, M. E., Jaynes, S. E., and
“Characterization by 13C-NMR Spectroscopy of Base Oils Copan, W. G., “Field Testing: The Final Proof of Performance,”
Produced by Different Processes,” Fuel, Vol. 76, No. 10, 1997, C. C. Colyer, Presented at the XXII FISITA Congress, Dearborn,
pp. 931–937. MI, Sept. 25–29, 1988.
关793兴 Nessel, C. S., Coker, D. T., King, A. G., and Mumford, D. L., 关812兴 Environmental Health and Safety Publications Series on
“Carcinogenic Assessment of Lubricant Base Oils by Proton Emission Scenario Documents No. 10 EMISSION SCE-
NMR,” Preprints 共ACS Division of Petroleum Chemis- NARIO DOCUMENT ON LUBRICANTS AND LUBRICANT
try兲, Vol. 42, No. 1, 1997, pp. 251–254. ADDITIVES Environment Directorate Organisation for Eco-
关794兴 Adhvaryu, A., Pandey, D. C., and Singh, I. D., “Effect of Com- nomic Co-operation and Development Dec. 2004.
position on the Degradation Behavior of Base Oil,” Preprints 关813兴 Abner, E., Jr., “Lubricant Deterioration in Service,” CRC
共ACS Division of Petroleum Chemistry, Inc.兲, Vol. 42, Handbook of Lubrication, Vol. I, Theory and Practice of
No. 1, 1997, pp. 225–228. Tribology: Applications and Maintenance, R. E Booser
关795兴 Baker, A. E., “Lubricant Properties and Test Methods,” CRC Ed., CRC Press, Boca Raton, 1983, pp. 517–532.
Handbook of Lubrication, Vol. I, Theory and Practice of 关814兴 Keller, G. R., Hydraulic System Analysis, Hydraulic & Pneu-
Tribology: Applications and Maintenance, R. E. Booser matics, Cleveland, 1969.
Ed., CRC Press, Boca Raton, 1983, pp. 481–515. 关815兴 Kaufman, R. E., “Rapid Determination of Remaining Useful
关796兴 Moules, C., “The Role of Interfacial Tension Measurement in Lubricant Life,” CRC Handbook of Lubrication, Theory
the Oil Industry,” http://nttworld.com/docs/camtel.pdf and Practice in Tribology, Vol. III, Monitoring, Materi-
关797兴 Wedeven, L. D., “Bench Test Modeling,” Fuels and Lubri- als, Synthetic Lubricants, and Applications, R. E. Booser,
cants Handbook: Technology, Properties, Performance, Ed., CRC Press, Boca Raton, 1993, pp. 89–100.
and Testing, G. E. Totten Ed., ASTM International, West 关816兴 Sen, A. K., and Kumar, R., “Oxidation Stability of Lubricants
Conshohocken, PA, Chapter 36, 2003, pp. 963–1015. by Inverse Phase Chromatography,” Lubr. Eng., Vol. 47, No.
关798兴 Czichos, H., “Design of Friction and Wear Experiments,” 3, 1991, p. 211.
American Society of Metals Handbook, 10th Ed., S. D. 关817兴 Naga, H. H., and Samen, A. E., “The Effect of Base Stock Vola-
Henry Ed., ASM International, Vol. 18, 1992, pp. 480–488. tility on Lubricating Oil Oxidation Stability,” Lubr. Eng., Vol.
关799兴 Czichos, H., “Systems Analysis,” CRC Handbook of Lubri- 44, No. 11, 1988, p. 931.
cation, Theory and Practice in Tribology, Vol. II, Theory 关818兴 Ravner, H., and Wohltjen, H., “The Determination of the Oxi-
and Design, R. E. Booser, Ed., CRC Press, Boca Raton, 1988, dative Stability of Several Deuterated Lubricants by an Elec-
pp. 645–661. tronic Gas Sensor,” Lubr. Eng., Vol. 39, No. 11, 1983, p. 701.
关800兴 John, P. W. M., Statistical Design and Analysis of Experiments, 关819兴 Herguth, W. R., and Phillips, S., “Comparison of Common
Macmillan, London, 1971. Analytical Techniques to Voltammetric Analysis of Antioxi-
关801兴 Junemann, H., “Mechanical Tests for Lubricants,” Erdol dants in Industrial Lubricating oils,” STLE 1994-Annual
Köhle, Vol. 29, 1976, p. 259. Meeting, Kansas City. 关http://www.herguth.com/technical/
关802兴 List of Standards, http://64.233.179.104/translate_c?hl cyclic_voltametry.pdf#search⫽%22astm%20
⫽en&u⫽http://www.bz01.com/stdfile/NF1.html&prev⫽/ cyclic%20voltammetric%20%22兴.
search%3Fq%3Dafnor%2Bt60-133%26hl%3Den兴 关820兴 Kaufman, R. E., “Remaining Useful Life Measurements of
关803兴 Rudnick, L., “Summary of Lubricant Standard Test Methods Gas Turbine Engine Oils, Diesel Engine Oils, Automotive
and Some Product Specifications,” Lubricant Additives: Oils, Hydraulic Fluids, and Greases Using Cyclic Voltammet-
Chemistry and Applications, L. R. Rudnick, Ed., Marcel ric Methods,” in Condition Monitoring; International
Dekker, Inc., New York, Chapter 23, 2003, pp. 599–616. Conference Proceedings, Joint Oil Analysis Program, Tech-
关804兴 Granchi, M. P., Biggerstaff, J. A., Hilliard, L. J., and Grey, P., nical Support Center, Naval Air Station, Pensacola, FL, Nov.
“Use of a Robot and Flow Injection for Automated Sample 1992.
Preparation and Analysis of Used Oils by ICP Emission Spec- 关821兴 Becker, D. A., and Brinkman, D. W., “Recycling 共Oil兲,” Kirk-
trometry,” Spectrochim. Acta, Vol. 42B 共No. 1/2兲, 1987, pp. Othmer Encyclopedia of Chemical Technology, Fourth
169–180. Edition, M. Grayson Ed., John Wiley and Son, NY, Vol. 21,
关805兴 Evans, S. J., and Klueppel, R. J., “Analysis of Oil With Induc- 1996, pp. 1–10.
tively Coupled Plasma: Total Process Automation,” Spectro- 关822兴 Gebarin, S. K., and Fitch, J., “Determining Proper Oil and Fil-
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䊏 REFERENCES 657
ter Change Intervals: Can Onboard Automotive Sensors Help,” cis, Washington, DC, 1995, pp. 609–656.
Practicing Oil Analysis Magazine, Jan. 2004, 关http:// 关835兴 A Critical Review of Toxicity Values and an Evaluation of the
www.practicingoilanalysis.com/article_detail.asp?artic1eid Persistence of Petroleum Products for Use in Natural Resources
⫽562&relatedbookgroup⫽OilAnalysis兴. Damage Assessments, American Petroleum Institute, Wash-
关823兴 Bachelder, D. L., “Recycling Used Engine Oil by Re-refining,” ington, DC, 1995, p. 196.
Presented at 2005 Used Oil/HHW Conference “Building 关836兴 Lyman, W. J., “Transport and Transformation Processes, in
Hope for Healthy Communities, One Action at a Time,” Fundamentals of Aquatic Toxicology: Effects,” Environ-
San Diego, CA, April 28, 2005, http://www.ciwmb.ca.gov/ mental Fate and Risk Assessment, G. M. Rand, Ed., Taylor
HHW/Events/AnnualConf/2005/April28/Session4/DIYers/ and Francis, Washington DC, 1995, pp. 449–492.
ReRefine.pdf. 关837兴 “OECD Series On the Test Guidelines Programme, Number
关824兴 Quang, D. V. et al., “Hydrocarbon Process,” Vol. 53 No. 4, 2—Detailed Review Paper on Biodegradability Testing Envi-
1974, p. 129. ronment Monograph No. 98,” Published by Organisation
关825兴 Blankenship, F., “Do You Know Where Your Used Oil Goes?,” for Economic Co-Operation and Development, Paris
Machinery Lubrication Magazine, Jan. 2005. 1995, OCDE/GD 共95兲 43, www.olis.oecd.org/
关826兴 Tocci, L., “What Does Biodegradable Really Mean?,” ...dd3491a17c199db2c12569fa005d35af/
Lubes’n’Greases, Vol. 10, No. 5, 2004, pp. 40–43. e846f5796657ed89c12561d40042a27b/$FILE/
关827兴 “European Eco-Label Home Page,” http://ec.europa.eu/ ENE51276.ENG
environment/ecolabel/index_en.htm 关838兴 ISO 10708: “Water Quality—Evaluation in an Aqueous Me-
关828兴 Carnes, K., “Off-road Hydraulic Fluids: Beyond Biodegrad- dium of the Ultimate Aerobic Biodegradability of Organic
ability,” Tribology & Lubrication Technology, Sept. 2004, Compounds—Determination of Biochemical Oxygen De-
pp. 33–40. mand in a Two-phase Bottle Test,” ISO, Geneva, 1997, p. 17.
关829兴 Theodori, D., Saft, R. I., Krop, H., and Van Broekhuizen, P. V., 关839兴 OECD Guideline for Testing of Chemicals: 301-Ready Biode-
“Concept Background Document: Development of Criteria for gradability, Organization for Economic Cooperation and De-
the Award of the European Eco-label to Lubricants,” Pre- velopment, Paris, 1992, p. 62.
sented Nov. 27, 2003, by the IVAM Research and Con- 关840兴 Harmonized Test Guidelines: 835-Fate, Transport and Trans-
sultancy on Sustainability, Amsterdam, Netherlands. formation Test Guidelines—OPPTS 835.3110 Ready Biode-
关http://ec.europa.eu/environment/ecolabel/pdf/ gradability, U.S. Environmental Protection Agency, Office of
lubricants/backgrounddoc_111203.pdf兴. Prevention, Pesticides, and Toxic Substances, Washington,
关830兴 Gill, G., “Blenders Brace as EU Adopts REACH,” Lube Re- DC, 1998, p. 45.
port, Vol. 6, No. 51, Dec. 20, 2006. 关841兴 “Lubricating Oil Base Stocks,” API 2004 Publication,
关831兴 Hinman, M. L., “Environmental Characteristics of Fuels and http://www.petroleumhpv.org/Product_Categories/
Lubricants,” Fuels and Lubricants Handbook: Technol- Lube_Oils/2004-03-03_Lubes_Revised_Robust_
ogy, Properties, Performance, and Testing, MNL37WCD, Summary.pdf
Ed., ASTM International, West Conshohocken, PA, Chapter 关842兴 Guidance Document on Aquatic Toxicity Testing of Difficult
34, 2003, pp. 885–908. Substances and Mixtures, OECD, Paris, 2000, p. 53.
关832兴 “A Practical Guide to Protecting Man and the Environment, 关843兴 Guidance Document on Application and Interpretation of
Machelen,” Exxon Chemical Europe, Inc., Machelen, Single Species Tests in Environmental Toxicology, Environ-
Belgium, 1999. ment Canada, Environment Technology Centre, Ottawa, On-
关833兴 Lyman, W. J., “Octanol/Water Partition Coefficient,” Hand- tario, Canada, 1999, p. 203.
book of Chemical Property Estimation Methods: Envi- 关844兴 “The NIST Reference on Constants, Units, and Uncertainty:
ronmental Behavior of Organic Compounds, W. J. Ly- International System of Units,”
man, W. F. Reehl, and D. H. Rosenblatt, Eds., McGraw-Hill, http://www.physics.nist.gov/cuu/Units/index.html
NY, 1982, pp. 1–54. 关845兴 “Commonly Used Metric System Units, Symbols, and
关834兴 Lipnick, R. L., “Structure-Activity Relationships, in Funda- Prefixes,” http://lamar.colostate.edu/~hillger/
mentals of Aquatic Toxicology: Effects,” Environmental common.html
Fate and Risk Assessment, G. M. Rand, Ed., Taylor & Fran- 关846兴 http://www.simetric.co.uk/si_tz.htm
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Dr. Syed Q. A. Rizvi holds a Ph.D. in
chemistry, an M.B.A. in marketing, and
an M.A. in economics. He has 29 years
of research and development experience
pertaining to the development of lubricant
additives, their formulations, and testing.
During his career as a lubricant technologist
Dr. Rizvi has authored many technical papers
and made numerous presentations at both
national and international technical and
commercial organizations. Dr. Rizvi is the
recipient of 14 U.S. Patents, over 26 foreign
patents, and has published 43 scientific and
technical articles. Dr. Rizvi is listed in Who’s
Who in Science and Engineering, Who’s Who
in the Midwest, and Who’s Who in America
and is an active member of the American
Chemical Society.
www.astm.org
ISBN: 978-0-8031-7000-1
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