Akron Acs Rubber

BASIC COURSE SUMMARIES GUIDE: Print out and use this PDF booklet with your textbook:
“Basic Elastomer Technology” as you work on each assignment in the course.
“Basic Rubber Technology Course

Summaries Study Guide”
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ASSIGNMENT 1
Chapter 1: Historical Perspective
Chapter 2: Elastomer Technology
Pages 1 to 39
Historical Perspective - Pages 1 to 11

This chapter should be of interest as it describes the early
development of the rubber industry and the role of the compounder in
the early years of industrial growth.
Industrial Growth - Pages 3 to 11

Information on the usage of both natural and synthetic elastomers is
described and shown in Tables X through XII and shown in Figure 1.
Note some of the variations that occurred during the past
century.Elastomer Technology - Pages 12 to 23
Introduction - Pages 12 & 13

An individual should recognize the basic chemical terms related to
elastomers as shown in Table I.
Classification - Pages 13 to 16
The three classes of polymeric materials used in the rubber industry
are discussed with emphasis of grouping elastomers into three use
categories: general purpose, solvent resistant and temperature
resistant. The use of the ASTM system to identify elastomers is
introduced.
Polymerization Methods - Pages 16 & 17

The four most common methods used for preparing polymers are
discussed with emphasis on the preferred method most commonly
used in the synthesis of many industrial products.
Structure & Molecular Properties - Pages 18 to 21

The relationships used to describe the various molecular characteristics
of these materials are discussed. Examples of the molecular weight
ranges for common polymers are given in Table V. Note the wide
range of molecular weights that occur with the individual polymers and
how most elastomers have much higher molecular weights than either
plastics or silk or wool.
Information on Rubber Science and Technology - Pages 24 to

39
This section is included to give anyone an excellent source of
references that can be very useful when specific information is desired
for any aspect the rubber industry. Study it carefully as it may be the
source to answer questions that you may have about processes,
physical properties and testing procedures.
ASSIGNMENT 2
Chapter 3: Introduction to Rubber Compounding
Pages 40 to 56
Purpose
To acquaint a new compounder with basics of rubber compounding,
functions of formulation ingredients and common rubber properties.
Major Compounding Ingredients & Their Functions - Page 41

This section briefly describes the functions of major compounding
ingredients in rubber compounds.
Additional Information on Compounding Ingredients - Page 41-

52
Elastomers are grouped into three categories: general purpose,
solvent resistant and heat resistant rubbers. Examples are given on
types of rubber in each category in Table I. Basic properties of
common elastomers are listed in Table II.
Uses of carbon black and non-black fillers are included on pages 45 to

47. Table III gives ASTM classification of carbon blacks. Carbon blacks
and silica reinforce properties of rubber compounds. The smaller the
particle size of carbon blacks, the more the reinforcement.
Definitions and uses of processing aids, vulcanizing agents and

antidegradants are given on pages 47 to 51. Use of antioxidants and
antiozonants is very important in prolonging the service life of rubber
products.
Compound Formulation - Page 52

Table IX gives an example of a radial passenger tire tread recipe. All
compounding ingredients are always based on 100 parts of rubber
(phr). This section also gives methods of calculating batch sizes for
mixing in internal mixers as well as methods of calculating compound
cost.
Selected Compound Properties & Tests - Page 53

Brief descriptions of tests for uncured and cured rubber are included.
Table X lists properties and corresponding ASTM designated tests.
Properties & Compound Costs - Page 54

Usually the better the properties, the higher the compound cost,
primarily because of higher rubber contents. Figure 7 shows a plot of
tensile strength verses compound cost for 21 different compounds.
Procedure for Compound Development - Pages 54 & 56
This section lists various steps one can follow for compound
development for a given rubber product. The easiest way is to first
determine, via chemical analysis the composition of an existing
product and change the ingredients to improve the desired properties.
If it is a brand new product, then rubber compounders have to start
from scratch including proper selection of rubber, fillers,
antidegradants and curing agents.
ASSIGNMENT 3
Chapter 4a: Fillers - Carbon Black
Pages 57 to 81
Carbon Black Manufacturing - Pages 58 to 61

Carbon Blacks are made by three methods: furnace, channel and
thermal process. The furnace process is the most important one. Next
is the thermal process. In the furnace process, the hydrocarbon
feedstock is preheated to 250°C, injected into the flame zone, causing
incomplete combustion and carbon black formation. The carbon black
formed at temperatures around 1,400°C is passed through a furnace
section at very high speed. The hot carbon stream is quenched with
water to about 650°C. Upon further cooling, the black is palletized.
Thermal black process is carried out at comparatively lower

temperatures (~1,300°C) with longer residence time than in the
furnace process. This causes the particles to grow more slowly and
become larger. Thermal blacks are produced by thermal decomposition
of natural gas in the absence of oxygen.
Mechanism of Carbon Black Formation - Pages 61 & 62

Production of carbon black is viewed as a dehydrogenation of aromatic
feedstock molecules resulting in graphitic planes. These are crystalline
in nature. When some molecules are not dehydrogenated, amorphous
carbon is formed. Carbon thus obtained is in aggregate form.
Carbon Black Classification - Pages 53-64

The rubber industry uses ASTM designation for carbon blacks. Major
common types are listed in Table 2. "N" means normal cure carbon
blacks. The second designation indicates grouping based on nitrogen
surface area. For example, N-330 means normal cure, 3 means
nitrogen surface are range of 70 to 79 m2/gm (see Table I). This is a
HAF (high abrasion furnace) black.
Carbon Black Characterization - Pages 65-69

Specific surface area and structure are the most important properties
of carbon black. Specific area is the total exposed surface per unit
mass available for interaction with a polymer or filler. There are
several methods to measure surface area of carbon black. The most
widely used is the BET method.
Structure is another important characteristic. The parameter defines

the empty space between randomly packed aggregates.
Other characteristics of carbon blacks are non-carbon contents, sulfur
content, hydrogen and oxygen in surface groups and tint strength.
Carbon Black in Rubber - Page 69

This section includes formulations for evaluating carbon blacks in SBR
and NR compounds, and gives the effects of carbon clack loading on
processing and cured physical properties of compounded rubber. It
also compares properties of rubber compounds containing reinforcing
black (N-339) and semi-reinforcing (N-660).
Rubber Processing Properties - Pages 69 & 70

Carbon Black increases the viscosity of rubber compounds due to
shear strain amplification. Die swell of elastomers is improved by the
addition of carbon black. This is due to the reduction of the elastic
component of the compound and the decrease in polymer relaxation
time.
Dispersion of Carbon Black in Rubber - Pages 70 & 71

Dispersion of carbon black in rubber takes place in four steps:
• Incorporation
• Deagglomeration
• Distribution
• Dispersion
Agglomeration occurs on the scale of 1 µm to 1 mm. Filler

microdispersion occurs at the aggregate scale of 10 nm to 1 µm. In a
polymer blend, each phase may end up with different loading
depending on affinity of each polymer for the carbon black.
ASSIGNMENT 4
Chapter 4b: Non-Black Fillers
Pages 82 to 111
Overview of Non-Black Fillers - Pages 83-86

The general term "non-black fillers" covers a range of rubber pigments
from non-reinforcing to high reinforcing fillers. Clay, calcium carbonate
and silica are some of the common non-black fillers. In general, the
higher the filler content (loading), the higher the hardness. Silica,
which is a reinforcing filler, increases hardness more than clays and
calcium carbonate at a given loading.
Primary Factors in Polymer Reinforcement - Pages 86 to 89

Figure 3 compares particle sizes of various fillers. Fillers with higher
surface area provide greater reinforcement.
Naturally Occurring Mineral Fillers - Pages 89 to 94

More than 80% of the non-black fillers used in rubber compounds are
naturally occurring mineral fillers. These are primarily used to reduce
the cost of the compound rather than to reinforce rubber. Kaolin clay,
calcined clays, calcium carbonate (e.g. limestone), alumina trihydrate
(ATH) and natural silicas are examples of such fillers.
Synthetic Fillers - Pages 94 to 97

Precipitated calcium carbonate, silicates and synthetic silicas fall into
this category. Precipitated calcium carbonates have similar particle
sizes and higher surface areas. Precipitated silicates cover the semi-
reinforcing to reinforcing filler range.
Synthetic silicas have three categories: 1) precipitated silicas, 2)

fumed silicas and surface-treated silicas. Precipitated silicas provide a
high degree of reinforcement. Fumed silicas have a surface area range
of 50 to 400 m2/g. They have reduced moisture sensitivity.
Surface Chemistry Effects and Silane Modification - Pages 92 to

102
The surface of non-black fillers is chemically different from that of
carbon black. The high surface-area fillers show the most interaction
with polymers. The surfaces of silica are virtually covered by silanol
groups (=SiOH), which are more polar. Compared to carbon black,
silica is less compatible with general-purpose elastomers.
At equal loading and similar surface area, silicas yield lower tensile
strength and moduli than carbon black in SBR. This may be because
silica is less compatible with SBR and has reduced cohesive forces at
the polymer-filler interface.
Silane chemicals are effective in modifying the surface of silicas and

other non-black fillers via a chemical attachment. Difunctional
organosilanes can "couple" polymer and silica. This leads to additional
polymer-filler bonding that increases tensile strength, modulus and
abrasion resistance. Triethoxysilylpropyltetrasulfane (TESPT) is one of
the most commonly used silanes in rubber containing silica.
Typical Compounds and Applications - Pages 102 to 110

Formulations using non-black fillers and properties are listed in this
section. Product formulations using different fillers are included for
equal hardness SBR compounds in shoe soles, peroxide cured EPDM,
automotive floor mats, hot water bottles, NR compounds for improved
tear and cut growth resistance. Examples are also included for cable
insulation and equal hardness in Hypalon® compound.
ASSIGNMENT 5
Chapter 5: Processing Methods in the Rubber Industry
Pages 112 to 141
Overview of Mixing - Page 113

Mixing of rubber is carried out in an internal mixer, (Banbury®).
Details of internal mixers are given on page 113. Sometimes 2-roll
mills are used for mixing rubber compounds, but not that often. This
section lists important elements of material storage, handling and
weighing of compounding ingredients.
Mixing Operation - (Pages 116 to 119)

There are four main steps involved in the mixing operation:
• Incorporation - The first stage of mixing during which all

ingredients form a coherent mass.
• Dispersion - The second stage of mixing during which filler is
dispersed in the rubber.
• Distribution - The third stage where other ingredients are
homogenized.
• Plasticization - The fourth stage when the mix reaches final
viscosity.
This section describes the three general mixing methods for rubber
compounds and their advantages. Roles of mill mixing, dump criteria,
effects of rotor speed, ram pressure and batch size are discussed.
Discharge, Shaping, Cooling & Packaging - Pages 119 and 120

The dump mill is used to cool rubber dumped from the internal mixer
onto the mill. The mixed compound is stripped from the mill, coated
with antitack material and cooled by blowing air on a wig-wag system.
It is important to note that rubber strips be sufficiently cooled before
stacking or packaging.
Rubber Extrusion - Pages 121 & 122

Extrusion of tubing, hose and other profiles is an important rubber
fabrication process. Here, the compound is fed in the form of a strip at
a controlled rate into the extruder and passes through a die to produce
extrudates of desired shapes. After leaving the die, the product must
be cured, possibly cut to length and packaged.
Cold Feed vs. Hot Feed Extruders - Page 122

Hot rubber strips are fed into hot extruders. Here the function of the
screw is simply to compact and pump the compound. In cold-feed
extruders, L/D is much larger so that sufficient heat is generated to
soften the compound for proper extrusion. It is possible to vary the
temperature profile along the barrel by having separate controlled
temperature zones.
Extruder Operation & Control - Pages 124 to 129

The main parts of an extruder are: 1) Heads, 2) dies and 3) take-off
and curing. The purpose of the head is to equalize pressure across the
profile and to guide the compound into the die. The die shapes the
profile. After a compound is forced through a die orifice, it expands in
cross-section (die swell) and shrinks in length. As a profile leaves the
die, it is still fluid and needs to be cured. During cure, the profile has
to be supported to prevent distortion either by internal reinforcement
or in a fluid medium. Profile curing can be done by using any of these
techniques: a) hot air, b) liquid cure medium such as molten eutectic
salt mixture, c) microwave heating or d) radiation curing.
Calendaring of Rubber - Pages 129 to 132

The calendaring process is used to produce continuous sheets of rubber
compounds. To ensure steady operation of the calendar and to control
shrinkage, the rubber compound needs to be heated to around
200°F. Sheeting is normally carried out on a 3-roll calendar. The
calendaring process can also be used to impregnate a textile or
metallic fabric (frictioning). Correct thickness measurement of
calendared stock is important. This is done online using laser or
electromechanical means.
Injection Molding of Rubber - Pages 132 to 240

An injection molding machine consists of a barrel, a compound
reservoir and a mold. When rubber is being cured in the injection
mold, fresh rubber is prepared for the next cycle. Thus, injection
molding is almost a continuous process. For safe injection molding, the
compounds generally need to be scorch safe to 130°C.
Compression & Transfer Molding of Rubber - Pages 140 to 141

In compression molding a pre-weighed, preformed piece is placed in
the mold. Then the mold is closed under pressure to vulcanize the
rubber. Transfer molding is a form of injection molding. The compound
to be cured is held in a heated reservoir, the amount of rubber to fill
the mold is forced through a runner system and the mold cavity by a
piston. In spite of advantages of injection molding, compression and
transfer molding processes are still used worldwide.
ASSIGNMENT 6
Chapter 6: Testing Rubber During Processing & Vulcanization
Pages 142 to 162
Overview - Page 144

The purpose of this chapter is to familiarize the reader with testing
procedures used for evaluating processing and vulcanization
characteristics of rubber. The tests can be put into three groups: 1)
materials processing characteristics, 2) vulcanization characteristics
and 3) final properties.
Terms & Definitions - Page 145

This section (Table I) provides a list of terms and definitions related to
processing and vulcanization. This table also lists ASTM designation
test standards for additional information on these tests.
Processability Testing - Pages 145 & 155

This type of test measures properties, which determine how the rubber
will behave during processing (milling, extrusion, calendaring, etc.).
Mooney Viscosity Test - Pages 149 & 150

This section gives details of procedures for Mooney viscosity testing.
The rubber sample is put in a Mooney viscometer, warmed for 1
minute, then tested for 4 minutes. Viscosity at the end of the 4-minute
test is considered Mooney viscosity. Two standard rotors are used for
this test - a large rotor for general use and a small rotor for stiffer
material.
Extrusion Testing - Pages 151 & 152

Generally, the Garvey Die test method is used to test extrudability of
uncured compound. The extruded sample is rated normally for
smoothness and sharpness of edges. Results from this are correlated
with the factory extrusion process.
Scorch Testing - Pages 154 to 156

Scorch is defined as premature vulcanization. Longer scorch time
means greater processing safety in production. The most common
measure of scorch is the time to a 5-point rise above the minimum at
temperatures between 120°C and 135°C. Scorch may occur during
processing of a compound due to accumulated effects of heat and
time.
Vulcanization Testing - Pages 156 to 162

During vulcanization, chemical bonds are created between long
molecules and this makes the product elastic. A rubber product should
be cured for optimum cure time. Excess cure may result in reversion or
marching modulus (i.e. modulus continues to rise with cure time).
The physical changes during vulcanization occur in three stages: 1) the
induction or pre-cure period, 2) the crosslinking stage and 3) the over-
cure or reversion stage. These are illustrated in Figure 7.
Proper balance between maximum scorch safety and fast cure rate is
obtained by adjusting the cure system.
Cure characteristic parameters and their symbols are listed in the text.
The rate of vulcanization is affected by temperature. The effect of

temperature on vulcanization is normally expressed by the Arhenius
Equation. A simple rule of thumb is that the rate doubles for every
10°C rise in temperature. This, however, assumes that the cure is
done under isothermal conditions. However, in reality, often rubber
products are of different thickness and rubber is a poor heat
conductor.
ASSIGNMENT 7
Chapter 7a: Sulfur and Non-Peroxides
Pages 65 to 190
Definition - Pages 165 to 167

When a rubber compound containing curing agents is heated at certain
temperatures, it changes from soft an high permanent set material to
a hard and elastic one. This curing process is irreversible as chemical
crosslinks are formed between polymer chains to provide a network.
Currently, the vulcanization is measured by cure meters or

rheometers. Detailed descriptions of such instruments are provided in
Chapter 6 of this book.
Effect of Vulcanization on Rubber Properties - Pages 170 to 172

Vulcanization improves properties of rubber compounds. The
improvement is related to the degree of chemical crosslinking and the
length of these crosslinks. Hardness and modulus increase with degree
of crosslinking Tensile strength, fatigue life and tear strength first
increase, reach maximum values, then decrease with crosslink density.
Vulcanization with Sulfur - Pages 173 to 175

During vulcanization long chains of rubber molecules are linked
together by crosslinks of one or more sulfur atoms. The change in
properties resulting from vulcanization is due to intermolecular
crosslinking. Sulfur vulcanization crosslinks include mono-, di- and
polysulfidic (up to 8 sulfur atoms) structures. For unaged conditions,
polysulfidic crosslinks give high tensile strength, elongation and flex
properties in natural rubber. However, after aging, when polysulfidic
crosslinks convert to mono-, di- and some polysulfidic forms, tensile
strength and fatigue life drop.
\r\nAccelerators, Secondary Accelerators - Pages 175 to 181

Curing with sulfur alone takes a long time. Use of our accelerators
speed up the cure rate. See Figure 12 for examples. The type of
accelerator affects the scorch time and cure rate. A combination of
zinc oxide and stearic acid is used to further activate the cure rate.
Secondarily, accelerators such as dithiocabanates, diarylguanidines
and thiuram disulfides are used as "kickers" to further activate the
primary accelerators. Conversion of a properly formulated uncured
stock into a cured rubber requires the use of correct temperature and
cure time.
Conventional as well as efficient vulcanization systems can be used.
Typically, conventional cure systems use higher sulfur amounts (2 to
2.5 phr) with suitable amounts of accelerators. Efficient vulcanization
cure systems us low (< 1 phr) to zero sulfur contents and higher
accelerator contents.
Non-Sulfur Vulcanization - Pages 186 to 188

Peroxides
Peroxide crosslinking takes place via free radical mechanisms initiated
by the cleavage of O-O bonds in peroxide. Crosslinks are C-C bonds
and are very stable. See more details in the second part of this
chapter dealing with peroxide cures.
Metal Oxides
Halogen-containing elastomers such as neoprene and chlorosulfonated
polyethylene are commonly crosslinked by metal oxides. The common
ones are zinc and magnesium oxides. Crosslinking eliminates ZnCl2
and MgCl2 .
Phenolic Resins
Resins based on phenol and formaldehyde are used to cure elastomers
with relatively low unsaturation such as butyl rubber. The crosslinks
are C-C bonds and therefore are more stable.
ASSIGNMENT 8
Chapter 7b: Vulcanization of Rubber - Peroxides
Pages 191 to 207
History
Initially, peroxide cures were not very common because peroxide
cures had low strength and poorer aging. In the 1930s, peroxide cures
got renewed interest when polyethylene was discovered because sulfur
cures were ineffective. Because of better heat aging, compression set
properties and their ability to crosslink saturated polymers, peroxide
cures are common today.
Vulcanization - Pages 192 to 196

Peroxide vulcanization takes place via a free radical mechanism.
Peroxides on decomposition form alkoxy radicals which absract
hydrogen from polymer chains leaving a radical on these chains. Twp
such polymer radicals combine to give polymer-polymer crosslinks.
Comparison with Sulfur Vulcanization - Pages 196 & 197

The C-C bonds formed in peroxide cures are more rigid and stronger
than the C-S and S-S bonds formed in sulfur vulcanization. Thus,
peroxide cures provide lower compression set and improved heat
resistance. Sulfur crosslinks give higher tear strength and abrasion
resistance. See Table I for examples comparing sulfur and peroxide
cures in EPDM formulations showing the nces of peroxide cures.
Compounding - Pages 197 to 203

Acidic ingredients cause ionic decomposition of peroxides creating no
free radicals for crosslinking. If a peroxide radical can abstract hydrogen
not only from polymers, but also from other compounding ingredients,
such as antioxidants, the peroxide crosslinking efficiency will be
reduced. Among the oils used in rubber compounding, paraffinic oils
are preferred for peroxide vulcanization (See Figure 8). Coagents, on
the other hand, increase the cure efficiency of peroxides. In the
presence of coagents, hardness and modulus of peroxide vulcanizates
are increased whereas elongation and compression set are reduced.
General compounding recommendations are given on page 201.
ASSIGNMENT 9
Chapter 8: Physical Testing of Rubber
Pages 208 to 234
Purpose
To offer a general discussion on types of common tests run and their
procedures for rubber compounds, both cured and uncured.
Basic Concepts of Testing - Pages 209 to 211

The are four basic concepts of testing:
• Validity
• Accuracy
• Precision
• Reproducibility
Types of tests Applied to Rubber - Pages 211 to 213

This section lists major tests run on dumbbell or ring specimens. Table
2 gives the listing and purpose of each test. The ASTM standard
designation is given for each test so that the reader can get more
details on test procedures on their own.
Tensile Test Data - Pages 213 to 215

Tensile tests are usually performed on dumbbell or ring specimens.
Specimens can also be cut from rubber products and tested. In tensile
(stress-strain) testing, stress per unit area at a given elongation is
called modulus at that elongation, e.g. 100% modulus means stress at
100% elongation. Tensile strength is stress per unit area at break.
Elongation at break is the total elongation of the sample when it
breaks.
Compression Test - 216 & 217

Compression tests are run to determine the ability of rubber
compounds to retain their shape and dimensions when subjected to
constant load and constant deformation. The procedure is described in
the text. Usually the lower the set, the better the rubber compound.
Compression set also depends on aging conditions (e.g. heat, fluid).
Heat Resistance Test - Page 217

It is also known as accelerated aging test. Properties of unaged rubber
are measured. Then specimens are aged in hot air over time. After
cooling, the same properties of aged samples are measured. Percent
reduction in a property (e.g. tensile strength) is a good indicator of
heat resistance. Of course, minimum reduction is considered best.
Fluid Resistance Test - Pages 218 & 219
This is another heat resistance test run by immersing rubber
specimens in fluids at elevated various temperatures. Changes in
hardness, tensile strength, volume and mass are measured after
aging.
Low Temperature Test - Pages 219 to 221

This test is meant to determine low temperature flexibility of rubber.
This is especially useful when rubber products are used in cold weather
or for low temperature applications. Different test methods are
described in this section.
Ozone Resistance Test - Page 221

Ozone degrades rubber if not properly protected. Therefore it is
important to know the ozone resistance of rubber products that are
exposed to ozone. Ozone degradation results in cracks in cured
rubber. In an ozone test, rubber is exposed to 20 to 100 pphm ozone
and initiation of cracks is monitored as a function of ozone exposure
time.
Tear Test - Pages 221 & 222

Rubber products usually fail due to some form of tearing. ASTM D624
describes four different types of specimens that are used for tear
testing. These tests are done on a tensile tester and the force required
to either initiate a crack or produce continuous tearing is measured.
There is a significant variability in each of these tests.
Rheometer Test - Pages 225 to 227

Figure 4 is a typical rheometer curve/ More details of this procedure
are given in Chapter 6. T90 and maximum torque are usually
considered good indicators of optimum cure.
Dynamic Properties of Rubber & Applicable Test Methods -

Pages 227 to 231
This section briefly describes how dynamic responses of rubber are
measured. The evaluation of elastic and damping forces can be
determined with dynamic tests. Such information is important to
determine performance and service lives of such rubber products as
tires, belts, shock mounts, diaphragms, tank track pads, etc.
Some Other Tests - Pages 231to 233

Two other major tests discussed here are abrasion test and flex fatigue
test. ASTM standards are included here for references and more
detailed information
ASSIGNMENT 10
Chapter 9a: General Purpose Elastomers - Natural Rubber
Pages 235 to 256
History - Pages 235 & 236

Natural Rubber (NR) comes from the tree species hevea brasiliensis in
latex form. In the 17th century, Mexico made waterproofed fabric with
latex. Later, Charles MacIntosh made waterproof fabric by dissolving
NR in tar naptha. In 1838, Charles Goodyear discovered vulcanization
which converted soft, sticky rubber to a hard, strong and elastic form.
In the early 1900s the development of rubber products started rapidly
with the widespread use of pneumatic tires.
Tapping - Pages 237 & 238

Latex is collected in a ceramic or glass blowl placed at the bottom of a
diagonal cut in the tree bark. Common practice is to tap the tree every
second day. The latex is brought to the collection station and rubber
content measured. Ammonia is added as a preservative. At that point,
dry rubber content may be 30% to 40%.
Characteristics of NR - Pages 241 to 244

NR has very high electrical resistivity. It can be made more conductive
by adding conductive carbon blacks. The cubical coefficient of NR is
about 15 to 20 times that of steel. Uncured NR can dissolve in a good
solvent like toluene. Cured rubber will only swell when in contact with
toluene. NR crystallizes when stretched or stored at low temperature
which is the reason for its high tensile strength. Chemical analysis of
NR shows that, on an average, NR contains about 93.6% rubber
hydrocarbon. The rest is comprised of acetone extractables, protein
and ash.
Modified Rubbers - Pages 244 to 246

NR can be modified to yield different types of rubber. The most
common ones are constant viscosity (CV) rubber, deproteinized rubber
(DPNR), epoxidized rubber and oil-extended rubber (OENR). Peptized
NR has peptizer in it. These rubbers break down more rapidly to make
it an easier processing rubber.
Grading of NR - Pages 246 to 248

Ribbed smoke sheet (RSS) comes in six types: 1X, 1, 2, 3, 4 and 5.
Number 5 is the darkest and possibly the dirtiest. Technically specified
rubbers (TSRs) have ASTM standards on dirt, ash, nitrogen and
volatile matter content.
Compounding of NR - Pages 248 to 255
Compounding of NR is similar to SPR and polybutadiene using common
filler/oils, activators and sulfur/accelerators or peroxide cure systems.
The type of NR to be used depends on the cured properties desired.
For example, for good flex resistance, one would need lower diret
content NR. Because of the high level of unsaturation content, NR is
more susceptible to degratdation due to hot air and ozone. Therefore,
antioxidants and antiozonants are added as stabilizers to NR
compounds.
Like other diene rubbers, NR can be cured with high sulfur/low

accelerator or low sulfur/relatively high accelerator cure systems.
Typical NR Compounds - Pages 255 & 256

This section provides formulations for typical NR products. Products
listed are acid hose tube, heavy-duty tire sidewall, red printing plate
rubber, conveyor belt cover and transparent shoe soles.
Future Trends - Pages 257 & 258

NR is environmentally friendly. It is compatible with most diene
rubbers. Because of these reasons, NR consumption and production
will continue to rise.
ASSIGNMENT 11
Chapter 9b: Styrene Butadiene Rubbers (SBR)
Pages 259 to 269
History of SBR - Pages 259 & 260

Emulsion SBR was discovered as a replacement for NR during WWII.
At that time, NR was in short supply and prices were very high. Two
German scientists developed the formulation to polymerize styrene
and butadiene monomers in emulsion/ Under licensing agreements,
Firestone, Goodyear, Goodrich, Goodrich US Rubber and Standard Oil
started manufacturing emulsion SBR (ESBR) in the United States.
Emulsion SBR can be made at 5°C (cold) and 50 °C (hot). Cold ESBR
offers several advantages over hot SBR.
With the discovery of the Ziegler-Natta catalyst, production of solution

SBR (SSBR) began. Large consumption of SSBR started when tire
companies started using it in tire treads.
Raw Materials & Manufacture of SBR - Pages 264 & 265

Styrene and butadiene are two monomers used in the manufacture of
SBR. ESBR is polymerized in water whereas SSBR is polymerized in
solvent.
Schematic diagrams of manufacturing methods for ESBR and SSBR are

on page 261 and 263. Oil-extended and oil-black-SBR masterbatches
are normally made from higher viscosity SBRs. Antioxidants are added
to both types of SBR to protect the rubber during storage.
ESBR has a broader molecular weight distribution than SSBR and

better processability. SSBR is more difficult to process because of its
narrow molecular weight distribution.
Compounding & Processing - Pages 264 & 265

SBR compounding is similar to that of natural rubber (NR). It can use
the same compounding ingredients. SBR, however, requires additional
accelerator and less sulfur. ESBR shows higher heat build-up than NR
in a comparable formulation. SBR has better tread wear resistance
than NR.
Table III lists properties of SBR and NR that explain the usefulness of
these rubbers for specific product applications.
Table IV lists compounds where only the amount of carbon black (N-
330) is varied from 10 to 70 phr in ESBR. Properties are listed as a
function of cure times and carbon black loading. With increased carbon
black loading, hardness and modulus increase. Tensile strength
reaches its optimum values around 50 to 60 phr loading. Elongation is
reduced as a function of black loading. Also, Firestone flexometer heat
build-up increases with increased carbon black content, This type of
information can be used to optimize a formulation to meet certain
properties requirements.
SSBR vs. ESBR - Pages 265 to 268

Because of its narrower MWD (molecular weight distribution), SSBR is
more difficult to process. This can be improved either by blending with
different Mooney or branched SSBR. High vinyl SSBR has slower cure
rates and lower hysteresis. SSBR has lower heat build-up (in general).
Chemically modified coupled SSBR has improved resilience at 50°C

(low rolling resistance) and improved wet traction than non-modified
SSBR. This is explained to be due to the higher bound rubber content
of modified coupled SSBR.
ASSIGNMENT 12
Chapter 9c: Polybutaiene & Polyisprene Rubber
Pages 270 to 286

Although polybutadiene has been produced since the 1930s in Europe,
it was not used extensively until the 1960s following the discovery that
sterospecific catalyst systems used in inert solutions would produce
polymers with controlled structures having better physical properties
than those produced with emulsion polymerization.
The high cis polyisoprene polymer has only been available since 1954
and its development was also due to the discovery of sterospecific
polymerization catalysts.
Solution Polymerization - Pages 271 to 273

A flow diagram for the polymerization of these monomers is shown in
Figure 1 and the criteria necessary for solution polymerization are
listed on page 272 along with the commercial elastomers that are
available (Table I).
Polymer Structure - Pages 273 to 275

Tables II through V illustrate how different catalyst combinations
produce different polybutadiene structures. Tables XII and XIII show
the structural characteristics obtained with polyisoprene. Table XIV
lists the properties of a commercial polyisoprene (Natsyn 2200).
Processing & Vulcanization - Pages 275 to 285

The processing of both elastomers is similar in that it varies with
microstructure, molecular weight, molecular weight distribution and
branching. For polybutadiene, these characteristics are shown in
Tables VI and VII, with typical valcanizate properties in Table VIII.
Tables IX and X illustrate the use of cis-polybutadiene in several tire
tread applications.
The physical properties obtained with solution polyisoprene are similar

to those obtained with NR, i.e. high gum strength, high resilience, low
heat build-up and good mechanical strength in filled stocks. Tables XV
through XVII show examples of cis-polyisoprene in gum and filled
stocks. These recipes and their properties should be studied to show
the range of uses that polyisoprene has as a replacement for NR.
ASSIGNMENT 13
Chapter 9d: Ethylene-Propylene287 to 311
Introduction - Pages 287 to 28

Ethylene-propylene rubber is known as EPM or EPR and ethylene-
propylene-diene rubber is known as EPDM. The most widely used
procedure for synthesizing these elastomers is a solution process. This
section gives brief details on elastomer synthesis.
The diene monomer in EPDM is on side chains, thus the backbone

structure is completely saturated and not subject to oxidation and
ozone attack. Termonomers commonly used are ENB, DCPD and 1,4
hexadiene.
Compounding Principles - Pages 296 to 301

EPDM is compounded the same way as diene rubbers except EPDMs
can be loaded with larger quantities of black and oil. Commonly used
carbon blacks are N500, N600 and N700. N550 and N660 favor
reinforcement and increase hardness and tensile strength. Napthenic
and paraffinic oils are preferred in EPDM compounds.
For EPR, peroxides are used to vulcanize rubber. EPDM compounds can
be cured either by peroxide or sulfur/accelerator systems. Organic
peroxides are used for high heat resistance and low compression set.
Applications - Pages 306 to 310

Because of their resistance to high heat, oxidation, ozone and
ultraviolet light, EPDMs are used in roof sheeting; automotive sponge
and seals; hoses and tubing, and wire and cable. Examples of
formulations and their properties are listed in this section.
ASSIGNMENT 14
Chapter 9e: Isobutylene Based Elastomers
Pages 312 to 357
Introduction & History - Pages 312 & 313

Note what properties have contributed to the success of these
elastomers, the most common usage and when they were introduced
as vulcanizable after copolymerization with isoprene.
Butyl Rubber - Pages 313 to 317

A flow diagram for the production of butyl rubber is shown in Figure 1.
Note the definition of "mole percent" unsaturation and how it is used in
describing the molecular weight between unsaturation points (Figures
2 & 3).
Typical Mooney viscosities and their related mole percent unsaturation

is given in Table I with a list of suppliers.
Butyl Vulcanization - Pages 317 to 320

The three methods for vulcanization are sulfur, dioxime and resin
cures. Figure 5 illustrates the relative cure rates obtained with these
systems and shows the reversion obtained with sulfur cures. The
dioxime and resin cures are illustrated on pages 318 and 319.
Properties and Applications - Pages 321 to 324

The properties obtained with butyl vulcanizates are discussed and the
characteristics produced by this elastomer are: gas permeability;
thermal stability; ozone & weather resistance; vibration resistance;
chemical and moisture resistance, and are illustrated with typical
compounding recipes.
Polyisobutylene - Pages 324 & 325

Note the differences between polyisobutylene and butyl rubbers. A
comparison is given showing how the two commercial groups vary in
molecular weight and what they are used for in the applications shown
on page 325.
Halogenated Butyl - Pages 325 to 329

The incorporation of 1 to 2 percent halogen element in the butyl chain
increases the possibility of obtaining reversion-resistant vulcanizates
when they are blended with the highly unsaturated elastomers. The
reactions are quite fast and are shown on pages 326 and 327. A flow
diagram shows the process in Figure 17 with a listing of the
commercial grades in Table IX. Note the problems involved in
stabilizing these products and the criteria needed for this type of
stabilization and what chemical serves this purpose.
Compounding Halogenated Butyl - Pages 329 & 330

The compounding ingredients used are briefly discussed on pages 329
and 330. Note the properties obtained by the use of each group of
materials.
Processing Halobutyl - Pages 320 to 331

The mixing, calendaring, extrusion and molding conditions for both
chloro and bromo butyl are briefly discussed.
Chlorobutyl Vulcanization & Applications - Pages 331 to 337

Chlorobutyl can be vulcanized with sulfur, the use of zinc oxide and
bis-alkylation. These are discussed in detail including information on
resin cures. Scorch limit with zinc oxide systems is controlled by the
use of magnesium oxide (Table X). Stress relaxation characteristics of
both butyl and chlorobutyl are shown in Figure 12. Applications using
chlorobutyl include innerliners, sidewall components, truck inner tubes
and are discussed with other uses shown on page 337.
Bromobutyl Vulcanization & Applications - Pages 338 to 344

Note the difference in the reactivity of the bromo group when
compared to chlorobutyl as discussed on page 338. A comparison of
bromobutyl systems and their characteristics are shown in Table XIII.
The use of compounding ingredients and their effects on scorch, cure
rate and curemeter modulus are shown in Table XIV. Other
characteristics and uses are discussed with typical recipes on pages
334 through 344.
Star Branched Butyls -- Pages 344 to 346

The branching of IIR with styrene-block copolymers improves the
green strength and reduces cold flow and affects other processing
characteristics of tehse elastomers when compared to the normal
types of isobutylene polymers as illustrated in Figure 14.
Brominated Isobutylene-p-methylstyrene Elastomers - Pages

346 to 355
The preparation and properties of these copolymers (BIMS) is
described with emphasis on the improvement over the normal
bromated butyls. Detailed information on the use of compounding
ingredients and resulting properties and uses are shown in Figures 20
through 23. Typical recipes and properties are given in Tables XXI and
XXIV. Note how these elastomers improve certain physical properties
when compared to the normal bromated IIRs.
ASSIGNMENT 15
Chapter 10a: Nitrile & Hydrogenated Nitrile Rubbers
Pages 358 to 381
Nitrile Elastomers (NBR)
Introduction & History - Pages 358 & 359

The first nitrile rubber was not available until 1935 in Germany under
the trade name of Perbunan. By 1940, several American companies
produced nitriles under the trade names of "Hycar," Chemigum,"
"Butaprene" and "Perbunan." All of the nitriles were utilized for military
purposes during World War II. Currently there are several major
producers in the United States.
Manufacture & Composition - Pages 359 & 360

All nitrile polymers are produces with varying ratios of acrylonitrile and
butadiene (or isoprene) in an emulsion polymerization system. The
molecular weight is controlled during polymerization to produce
elastomers with different Mooney viscosities. A terpolymer is made
using a small amount of carboxylic acid which permits vulcanization
with metal oxides. Much of the nitrile produced is used in the latex
form for many applications requiring oil resistance.
Processing - Pages 360 to 363

A basic recipe for NBR compound is given in Table I and mixing using
mills and internal mixers is discussed (Tables II through IV).
Information on calendaring, extrusion and molding is discussed with
information on conditions and results.
Vulcanization - Page 364

The two main vulcanization systems, sulfur and peroxide, are
discussed with examples given in Tables V and VI, with information on
the use of metal oxides for vulcanization of carboxylated nitriles.
Properties - Pages 364 to 366

The general, mechanical, electrical and permeation properties of these
elastomers and their uses are discussed and examples are given in
Tables VII through XII.
Applications - Pages 367 & 368

In addition to their usage where oil and fuel resistance is required,
there are many other applications where these elastomers are used. A
listing of some of the other applications is given.
Hydrogenated Nitriles (HNBR)

Note that these elastomers were not commercially available until
1984. Currently there are two companies supplying these: Zeon
Corporation (Japan) and their subsidiary Zeon Chemicals, L.P. (Texas)
and Bayer Corporation (Texas).
Basic Structure - Page 371

The same emulsion polymerization and monomers used to prepare
nitrile rubbers furnishes the polymer which is coagulated and dissolved
in a solvent where the hydrogenation takes place. (See Figure 1.) The
amount of hydrogenation can vary from about 85% to 100% with the
majority of elastomers hydrogenated around 90%.
As with the unsaturated nitiriles, the acrylonitrile content can be varied

to give different degrees of solvent resistance. The heat and oxidation
resistance is greatly increased as the percent of saturation increases.

Note that similar ingredients are used for compounding with the
exception that the cure systems utilize peroxides with coagents to
vulcanize the highly hydrogenated elastomers. Sulfur can be used
where the saturation is in the 8% to 10% range. A recipe showing the
range of ingredients is shown in Table I.
Processing & Vulcanization - Pages 375 & 376

Note how these processes vary when compared to unsaturated nitrile.
Properties & Applications - Pages 375 & 376

Table II lists the most common uses of HBNR. Tables III through VII
illustrate automotive and seal uses for various compounds. Other uses
are discussed.
ASSIGNMENT 16
Chapter 10b: Neoprene, Hypalon™ and Chlorinated
Polyethylene
Pages 382 to 417
History - Page 383

Note that polychloroprene (Neoprene) was introduced in 1931 while
chlorosulfonated polyethlylene (Hypalon™) and chlorinated
polyethylene were both commercially available in 1951.
Neoprene - Pages 383 to 387

Neoprene is prepared by polymerizing chloroprene, with or without a
co-monomer, in an emulsion system. The resulting polymer can be
coagulated into solid rubber or stabilized for use as latex. The types
available from nine manufacturers are shown in Table I (solid types)
and Table II (latex types).
Basic Structures & Properties - Pages 387 to 391

The main structural unit in the polymer chain is the trans configuration
shown on page 387. The type of repeating unit (86% to 91%) is
responsible for the ability of Neoprene to crystallize rapidly.
To reduce this tendency, copolymers are made with either sulfur (G

types) or 2,3-dichloro-1,3-butadiene. The rate of crystallization is
shown in Table III. Note the importance of crystallization on polymer
properties and its comparison to thermal stiffening and how it affects
certain properties.
Compounding, Processing & Vulcanization - Pages 391 to 398

The typical ingredients for Neoprene compounds are shown on page
391 and discussed on pages 392 through 394. Note that Neoprene is
vulcanized with metal oxides, usually a combination of zinc and
magnesium oxides. Processing and vulcanization of the solid polymer
and the latex types are quite similar to those used for other
elastomers. Tables VII through X give examples of these procedures.
Commercial Applications - Pages 398 to 403

A list of the various uses appears on pages 398 and 399. Note the
wide variation of uses, i.e. automotive, construction, wire and cable.
Hypalon™ (CSM) and Chlorinated PE (CM) - Pages 304 to 417

Note that both elastomers were prepared originally from polyethylene
dissolved in a solvent and either chlorinated (CM) or chlorosulfonated
(CSM) to form various combinations (%Cl or %SO2Cl) respectively.
The newer methods are also briefly discussed. Figures 3 and 4 show
the repeating structures of these polymers.
Synthesis & Cure Chemistry - Pages 404 to 406

Note the different methods used to cure these elastomers.
Basic Properties - Pages 406 to 407

Tables XIII through XVII show the properties for many applications.
Compounding & Vulcanization - Pages 408 to 412

Details are give for these two elastomers.
Properties & Applications - Pages 412 and 413

Note the uses of these chlorinated elastomers.
ASSIGNMENT 17
Chapter 10c: Polyvinyl Chloride
Pages 418 to 435

Note that poly(vinyl chloride) can be plasticized or modified to produce
products with a wide range or properties. It is easily processed and its
relatively low cost makes the polymer ideal for the replacement of more
expensive materials.
Production & Synthesis - Pages 419 to 413

Table I shows the capacity of the various resin manufacturers, which
have a total capacity of 14.9 billion pounds per year in 1997 with an
estimate of 17 billion in 2001. this Amount greatly exceeds the
production of any elastomer.
The four methods for the polymerization of vinyl chloride are discussed
with an explanation of the properties of the polymer formed.
Note the importance of molecular weight, porosity, particle size and

shape as well as flow properties for characterizing PVC resins.
Properties and Compounding - Pages 423 to 429

The basic polymer properties and the role of the various ingredients
used for compounding PVC is discussed. Note the functions, types and
properties of the materials used as plasticizers, fillers, stabilizers,
colorants, lubricants, modifiers and retardants in these resins.
Fabrication - Pages 429 to 434

Before use, PVC resins must be mixed before shaping with the usual
methods used both in the rubber and plastics industries. These
include: calendaring, extruding, molding, coating and thermoforming -
and example of which is shown in Table IV.
The blending of resins with plasticizers and other ingredients to form

plastisols and organosols is described. These are used for rotational and
slush molding, fabric coating and dip and spray coating. See Table V.
Markets - Pages 434 & 435

Table VII shows the usage of PBC by market category in 1998. Note
that construction represents 73% of the total.
ASSIGNMENT 18
Chapter 11a: Polysulfide Rubber
Pages 436 to 457

Note that these elastomers have excellent solvent resistance and have
been in use since 1920. Table I lists the current polysulfides and their
suppliers.
Synthesis - Pages 438 to 440

These elastomers are prepared by suspension polymerization methods.
The reactions take place in water with a dichloride compound reacting
with sodium plysulfide in the presence of a dispersing agent. The
reaction product is a dispersion of the polymer in water.
The reaction of several different types of dichloride compounds results

in either mercaptan terminals (SH), hydroxy terminals (OH) or epoxy
terminals (-CH-CH2).
Table II shows their types and properties.
Basic Recipes - Pages 440 to 443

The uses of various polysuflides are explained and displayed with
typical recipes in Tables III, IV and V.
Processing - Pages 443 to 446

Note that Thiokol FA and ST types are processed using typical rubber
processing equipment, internal mixers and mills. Thiokol FA requires a
peptizition step usually requiring MBTS (a rubber accelerator), which
cleaves the sulfur linkages. The liquid type must be compounded
(mixed) with planetary type mixers.

All three types (FA, ST and liquids) require different curatives.
Examples include FA with zinc oxide, ST with zinc peroxide or dioxime
and liquid types with oxidizing agents (magnesium dioxide, lead
peroxide).

The physical properties obtained with the Thiokols are shown in Tables
VI and VII. Several recipes showing the uses of Thiokol are given in
Tables VIII Through XVI.
ASSIGNMENT 19
Chapter 11b: Polyepichlorohydrin Elastomer
Pages 458 to 470
Introduction - Page 458

These elastomers have properties, which are suitable for automotive
uses. These properties include high temperature resistance; resistance
to oil, fuel and ozone; resistance to permeation and are electrically
dissipative.

Polyepichlorohydrin was first commercialized by BF Goodrich and later
sold to Nippon Zeon (1989). The trade names and producers are listed
in Table II.
Synthesis - Pages 460 & 461

The steps in the solution polymerization of these polymers are shown
in Figure 1 and the ASTM designation as well as the polymer
description for homopolymer (CO), copolymers (GCO, ECO) and
terpolymers (GECO) are listed in Table III.
Compounding & Processing - Pages 461 to 463

Compounds are formulated much the same as common elastomers.
Table IV lists a typical formulation. The major difference is in the
curatives: ECH (homopolymer) and its copolymer are saturated and
require unique cure packages (see Tables V and VI). The GCO and
GECO types are sulfur curable. Mills or internal mixers can mix these
compounds. Products are usually formed by extrusion or molding.
Physical Properties - Pages 465 to 469

The basic property ranges are shown in Table IX, dynamic properties
in Figures 2 and 3, heat/oil resistance, temperature resistance and gas
permeability in Figures 4 through 6. Electrical properties such as
volume resistivity are illustrated in Figures 7 and 8.
Applications - Page 469

A summary of polyepichlorohydrin uses is given on page 469.
ASSIGNMENT 20
Chapter 11c: Polyacrylates (ACM)
Pages 471 to 482
History & Commercial Status - Page 471

Note that these elastomers were first introduced in 1947. There are
currently seven suppliers of the various types of acrylic elastomers.
They are saturated, oil resistant and serviceable from 40°C to 190°C.
Manufacture & Composition - Pages 471 to 473The common

methods for polymerization are suspension and emulsion systems.
The backbone (common monomer) monomer can be n-butyl, ethyl or

2-methoxy ethyl acrylate combined with a small amount of cure site
monomer. Cure site monomers usually contain a carboxyl, chloro,
hydroxyl or epoxide group.
Compounding & Processing - Pages 473 to 477

A general recipe (Table I) shows the various components of an ACM
compound. It consists of an elastomer, filler, a retarder, a process aid,
an antioxidant, a plasticizer and curatives.
Note that each cure site may require different combinations for a
specific type of vulcanizing agent. Examples are discussed and shown
in Tables II through IV.
Mixing is usually done in an internal mixer.
Physical Properties - Page 477

Table VI lists the range of physical properties normally obtained with
these elastomers. A post cure is usually required to obtain optimum
results.

Several applications are shown in Tables VIII through XII. Recipes with
typical physical properties are listed for each example.
ASSIGNMENT 21
Chapter 11d: Fluoroelastomers
Pages 483 to 497
History - Page 483

Note that these elastomers are the most expensive of all the synthetic
rubber and that their use is restricted to applications requiring their
unique properties. The first types were introduced in the 1950s.
Commercial Products - Page 484

There are four suppliers of fluorocarbons producing these elastomers
under the following trade names: Technoflon™, Dai-EL™, Viton™ and
Dyneon™ (formerly Fluorel).
Polymerization - Pages 485 & 486

Emulsion polymerization is the method used to prepare these
elastomers. A typical recipe is shown in Table II. Copolymers,
terpolymer and tetrapolymers are produced. Tetrapolymers may also
contain a cure site monomer.
Types of Fluoroelastomers - Pages 486 to 488

The four major types are shown on page 486 and the classification
scheme is discussed in detail.

The three types of cure systems are shown in Table IV. They consist of
diamine cures, biphenol cures and peroxide cure systems.
Properties - Pages 491 to 493

Table V illustrates the advantages and disadvantages obtained with
the three cure systems.
Advantages & Applications - Pages 493 to 496

The strength of fluorine bonds plays an important part in the high and
low temperature characteristics of these elastomers. Some of the
applications are shown in Table VI, included with the recipes and
physical properties.
ASSIGNMENT 22
Chapter 11e: Silicone Elastomers
Pages 498 to 514
Introduction -- Page 499

Note that silicones are elastomeric both at high and low temperatures,
from -150°F to 600°F with long useful lives when compared to organic
rubbers. In addition, they have excellent electrical and weathering
properties.
Synthesis - Pages 499 to 504

The process is shown on page 502. It involves the formation of methyl
chloro silanes, which are distilled into fractions. Dimethyl dichlorosilane
is the starting point for preparing the methyl silanes. Other siloxanes
(mono) act as chain stoppers and the trichloros act as crosslinking
agents. The polymer classes are shown on page 501. They include the
dimethyl (MA), methylphenyl (PMQ), methylvinyl (VMQ) and
fluorovynil (FVMQ).

Fillers are required to reinforce all silicones. The ingredients used in
compounding and their functions are listed in Table II, and the impact
on specific properties is shown in Table III. Fillers suitable for use are
compared in Table IV.

Organic peroxides are used for vulcanization. The cure mechanisms for
both the methyl and methylvinyl polymers are shown on page 508. A
listing of peroxides and their characteristics are compared in tables V
and VI. Additional cures are possible with a silicone hydride.
Applications - Pages 513 & 514

The many uses for these elastomers include automotive, health
industry, aerospace, electrical and numerous miscellaneous
applications.
ASSIGNMENT 23
Chapter 12: Latex & Foam Rubber
Pages 515 to 537

Note how the use of latex was developed. Currently it represents over
10% of total rubber usage. The first use involved natural rubber, then
extended to synthetics when techniques were developed to prepare
high solids, large-particle-size lattices. A listing of all the lattices
available appears in Table I.
Natural Rubber Latex - Pages 517 to 520

The collection and characteristics of NR latex are discussed with
emphasis on measurement of specific tests (KOH number, fatty acid
number and mechanical stability).
Synthetic Lattices - Pages 520 to 523

The types currently available are listed with comments concerning
their usage.
Compounding Latex - Pages 523 to 525

The classification of ingredients used in latex is divided into the
following categories:
• Surfactants
• Liquid phase modifiers
• Elastomer phase modifiers
The methods used to prepare ingredients in order to maintain colloidal

properties, viscosity and foam control are discussed in detail. Note the
use of both wet and dry weights in latex compounds and the
advantages of using latex.

Note how pH and zinc oxide may affect latex stability and
vulcanization. A discussion of the types of accelerators that can be
used in latex is given with reference to a listing in Table IX.
Latex Processes - Pages 530 to 537

Dipping processes are discussed with reference to glove preparation as
summarized in Table XI. Latex foam rubber is discussed comparing the
Dunlp and Talalay processes. Table XII shows two typical foam
recipes.
ASSIGNMENT 24
Chapter 13: Thermoplastic Elastomers
Pages 538 to 553

Thermoplastic elastomers (TPE) allow rubber articles to be produced
using the rapid processing techniques developed by the thermoplastic
industry. Rubber vulcanization is a thermosetting process and takes
place upon heating. For thermoplastic elastomers, transition from
processible melt to solid takes place on cooling. These elastomers
usually contain two or more polymeric phases. At least one soft
elastomeric phase and one hard phase should be present so that it can
offer processability and properties of a thermoplastic elastomer.
Classification & Structure - Pages 539 to 543

TPSs can be divided into three types:
1. Styrene TPE. These are based on molecules such as A-B-A where

A is a polystyrene and B is a polybutadiene, polyisoprene or ply
ethylene-butylene. These are correspondingly known as S-B-S,
S-1-S and S-EB-S.
2. Hard Polymer/Elastomer Combination. These are fine dispersions
of hard thermoplastic polymers and elastomers. These two
materials form co-continuous phases. Polypropylene with EPDM
and EPR are the most common combinations.
3. Multiblock Polymers with Crystalline Hard Segments. These TPEs
have multiblock (A-B)n structures in which "A" segments are
crystalline while "B" segments are amorphous.
Production - Pages 543 to 545

Using an anionic catalyst and adding monomers sequentially produces
styrenic TPEs. The polymerization stem consists of the reaction
between alkyl-lithium and styrene monomer. Blending a hard polymer
with an elastomer, which is crosslinked during the process, produces
hard polymer/elastomer combinations.
One example of multiblock polymers with crystalline hard segments is

polyurethane with polyesters. Here, hard segments are produced by
reacting polyglycols with an excess of diisocyanate and a lower
molecular weight glycol.
Structure-Property Relationship - Pages545 to 548

Most TPEs show many of the characteristics of the individual polymer
constituents. This section describes structure-property relationships for
the three major types of TPE. Table III lists price ranges (1998 to
1999 cost figures), specific gravities and hardness ranges for many
TPEs.

Both hard and soft segments of styrenic TPEs are amorphous. Such
TPEs can also be compounded with fillers, oils and resins. Common
applications include footwear, wire and cable insulations, adhesives,
sealants and coatings.
Hard polymer/elastomer TPEs are used in automotive and appliance

parts, construction industry and footwear.
Multiblock TPEs are in high performance type applications such as

boots for automobile steering gear assemblies, grease seals, drive
belts and hydraulic hoses.
ASSIGNMENT 25
Chapter 14: Recycling of Rubber
Pages 554 to 571
Introduction - Page 471

In the late 1990s, the United States produced 270 to 280 million scrap
tires per year and about 300 to 350 million pounds of scrap rubber in
the manufacture of rubber goods. The largest consumption of scrap
tires is for tire-derived fuel (TDF) used mostly in cement kilns, power
plants and pulp and paper plants. Table I gives utilization of scrap
tires. Table II gives comparative fuel values.
Recycling Methods - Pages 558 to 563

Major recycling methods include reclaiming, ambient grinding,
cryogenic grinding and wet grinding. Each method is described herein.
Over the years, the use of reclaimed rubber has declined in favor of
ground, recycled rubber. For grinding, tires are shredded to
approximately 2 x 2 or 1 x 1 inch chips which are further reduced in
size either by using ambient grinding mills or frozen, then ground.
Tables VII, VIII and IX show the effect of recycled rubber content on
tensile properties of SBR, butyl rubber and EPDM compounds.
Testing, Storage and Characterization - Pages 564 to 566

Two ASTM standards, ASTM D-5603-96 and ASTM D-5644-96, include
specifications for recycled rubber. Recycled rubber should not be
stored hot. At the crumb manufacturing plants, two samples, each
about 125 grams, are taken from each skid (about 1,000 Kg) at the
time of bagging for shipping. Samples are tested for ash, carbon black,
acetone extract and rubber hydrocarbon content (RHC). Results are
compared with specification (Tables X and XI).
Particle Size Distribution - Pages 566 to 569

ASTM D-5644-96 describes the Ro-Tap method used for determining
particle sizes and particle size distributions of recycled rubber. A set of
six sieves is used on a mechanical shaker. The first two screens are
defines in ASTM D-5603-96 for six particle sizes as listed in Table XII.
Compounding with Recycled Rubber - Pages 569 & 570

This section describes two common procedures on using recycled
rubber in rubber compounds. Explanations are offered for lower scorch
time, higher cure rate and lower maximum torque for recycled rubber
containing compounds than the control compound with no recycled
rubber content.

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BASIC COURSE SUMMARIES GUIDE: Print out and use this PDF booklet with your textbook:

“Basic Elastomer Technology” as you work on each assignment in the course.

“Basic Rubber Technology Course

Copyright © 2005 Rubber Division, ACS

Historical Perspective - Pages 1 to 11

Industrial Growth - Pages 3 to 11

Introduction - Pages 12 & 13

Polymerization Methods - Pages 16 & 17

Structure & Molecular Properties - Pages 18 to 21

Information on Rubber Science and Technology - Pages 24 to

Major Compounding Ingredients & Their Functions - Page 41

Additional Information on Compounding Ingredients - Page 41-

Uses of carbon black and non-black fillers are included on pages 45 to

Definitions and uses of processing aids, vulcanizing agents and

Compound Formulation - Page 52

Selected Compound Properties & Tests - Page 53

Properties & Compound Costs - Page 54

Carbon Black Manufacturing - Pages 58 to 61

Thermal black process is carried out at comparatively lower

Mechanism of Carbon Black Formation - Pages 61 & 62

Carbon Black Classification - Pages 53-64

Carbon Black Characterization - Pages 65-69

Structure is another important characteristic. The parameter defines

Carbon Black in Rubber - Page 69

Rubber Processing Properties - Pages 69 & 70

Dispersion of Carbon Black in Rubber - Pages 70 & 71

Agglomeration occurs on the scale of 1 µm to 1 mm. Filler

Overview of Non-Black Fillers - Pages 83-86

Primary Factors in Polymer Reinforcement - Pages 86 to 89

Naturally Occurring Mineral Fillers - Pages 89 to 94

Synthetic Fillers - Pages 94 to 97

Synthetic silicas have three categories: 1) precipitated silicas, 2)

Surface Chemistry Effects and Silane Modification - Pages 92 to

Silane chemicals are effective in modifying the surface of silicas and

Typical Compounds and Applications - Pages 102 to 110

Overview of Mixing - Page 113

Mixing Operation - (Pages 116 to 119)

• Incorporation - The first stage of mixing during which all

Discharge, Shaping, Cooling & Packaging - Pages 119 and 120

Rubber Extrusion - Pages 121 & 122

Cold Feed vs. Hot Feed Extruders - Page 122

Extruder Operation & Control - Pages 124 to 129

Calendaring of Rubber - Pages 129 to 132

Injection Molding of Rubber - Pages 132 to 240

Compression & Transfer Molding of Rubber - Pages 140 to 141

Overview - Page 144

Terms & Definitions - Page 145

Processability Testing - Pages 145 & 155

Mooney Viscosity Test - Pages 149 & 150

Extrusion Testing - Pages 151 & 152

Scorch Testing - Pages 154 to 156

Vulcanization Testing - Pages 156 to 162

The rate of vulcanization is affected by temperature. The effect of

Definition - Pages 165 to 167

Currently, the vulcanization is measured by cure meters or

Effect of Vulcanization on Rubber Properties - Pages 170 to 172

Vulcanization with Sulfur - Pages 173 to 175

\r\nAccelerators, Secondary Accelerators - Pages 175 to 181

Non-Sulfur Vulcanization - Pages 186 to 188

Vulcanization - Pages 192 to 196

Comparison with Sulfur Vulcanization - Pages 196 & 197

Compounding - Pages 197 to 203

Basic Concepts of Testing - Pages 209 to 211

Types of tests Applied to Rubber - Pages 211 to 213