Engine Oil Training

HJ Soo
September 12, 2018

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Agenda for September 12 to 13

Day Time Topics

September 12 3.00 pm to 4.30 pm What is inside an Engine Oils
4.30 pm to 5.00 pm Open Discussion
September 13 10.00 am to 12.00 pm Why we need Engine Oil Specs
12.00 pm to 1.00 pm Lunch
1.00 pm to 2.30 pm Afton Mainstream HDEO Update
– HiTEC 12200
2.30 pm to 3.00 pm Break
3.00 pm to 3.30 pm API SN Plus and TGDI
3.30 pm to 4.00 pm Open Discussion
End of 2 days Training

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Before We start the Training

 Tell me who you are?

 Tell me what do you want to learn from the Trainings?
 Tell me what do you know about engine and engine oils?

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Engine Types

Internal Combustion Engines

(ICE)
 Mobile Fuels
 Stationary  Diesel
Compression Ignition  Biodiesel
 High Speed Heavy-Duty Diesel  Gasoline
Oils (HDDEO)
 Ethanol
 Light-Duty Diesel Oils (LDDO)
 Natural Gas
Spark Ignition
(LPG/LNG/CNG)
 Passenger Car Motor Oils
(PCMO)
 Motor-cycle Oils (MCO)
Engines with after treatment
devices

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Flow of next 1 hour Training

The The key

What makes
importance of components in
up an engine
base oils additive
oil?
quality package

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What is an engine oil?
Engine Oil is a balanced
complex product that is an
integral part of an engine
In fact the engine oil is as much
a part of the vehicles engineering
as the pistons and valve gear.
The oil is an often-neglected part
of your vehicle, but is literally the
life-blood of the engine
It is a sophisticated piece of
modern technology costing
millions of dollars to develop,
and can mean the difference
between years of smooth
running or catastrophic failure.
Image courtesy EPC

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 To function effectively, the engine oil needs
chemical additives as well as base oils to meet
Chemistry the required performance levels

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 What Makes Up an Engine Oil?

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What Makes Up an Engine Oil?

Base Oil
5 - 20% 4 - 10%
Performance Additives DI Package VII/PPD
 DI Package
Viscosity Modifier (VM)
 Thickens at high temperatures
Pour Point Depressant (PPD) 75 - 95% Base Oil
 Lowers the pour point, prevents thickening at
low temperatures
PCMO oils typically have lower
additive treat rates than HDEO oils
 PCMO ~ 5-13% wt. DI Engine Oil Composition
 HDEO ~ 12-20% wt. DI

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Base Oil

Abundant
Inexpensive (relatively)
Good lubricant
Stable
Wide operating temperature range

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 General Properties of Base Stock “Chemistry”

Chemical Type Structure VI Pour Point Oxidation Additive

Resistance Solubility
n-Paraffin (Wax) Very High ~175 Solid @ 50C Excellent Low
iso-Paraffins with High ~ 150 Good Excellent Low
branched chains

iso-Paraffins with Good ~ 130 Good Excellent Low

highly branched
chains (PAO’s)
cyclo-Paraffin-single Good ~ 130 Good Good Medium
ring with long chains

Naphthenes, Poor ~ 60 Good Medium Medium

polycondensed

Monoaromatics, long Poor ~ 60 Good Medium High

chains

Polyaromatics Very Poor < 0 Good Very Poor High

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 API 1509, Annex E -- Base Stock Definitions (E.1.2) and
Categories (E.1.3)
Viscosity
Type % Saturates % Sulfur
Definitions (E.1.2.1 – E.1.2.3): Index
Base Stock – produced by single VI  80
Manufacturer, meeting manufacturer’s Group I < 90 > 0.03
VI < 120
specification
VI  80
Base Stock Slate – Base stocks of Group II  90  0.03
different viscosities but same VI < 120
Base Stock Grouping Group III  90  0.03  120
Base Oil – Base Stock or Blend of Base Group IV PAO n/a n/a
Stocks
All other
Group V n/a n/a
base stocks
100 Group II Group III
90 Analytical Methods (Table E-1):
Saturates [wt%]

80 Saturates: ASTM D2007

70
60 Viscosity Index: ASTM D2270
50
40 Sulfur (use one): ASTM D1552
30 ASTM D2622
20
10 ASTM D3120
0 ASTM D4294
60 80 100 120 140
ASTM D4927
Viscosity Index
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Naming of Base Oils
Refiners describe a base oil by viscosity and sometimes
by type of processing
 Viscosity designation can come from the SUS (Saybolt Universal Seconds)
or Kinematic Viscosity in cSt (centistokes)
 Processing descriptions include:
• SN = Solvent Neutral; HT = Hydrotreated; N= Neutral;
RHT = Rerefined Hydrotreated; HVI = High Viscosity Index

Phillips 66 Pure Performance 110N = 110 SUS (~ 4.1 cSt); Neutral

Chevron 220R = 220 SUS (~6.3 cSt); R for Richmond
Safety-Kleen 120RHT = 120 SUS (~ 4.2 cSt); Rerefined HT
Motiva STAR 12 = ~ 12 cSt
ExxonMobil EHC-45 = ~ 4.5 cSt ; Exxon Hydrocracked
Ultra-S 4 = ~ 4.0 cSt

Viscosities: Light (4-5 cSt), Medium (6-8 cSt), Heavy (10-12 cSt)

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Base Stock Selection Summary

A wide variety of base stocks are available in the

marketplace
 Group I stocks and Bright Stocks are decreasing in supply
 Group II and Group III base oils are growing
 PAO and other synthetics are very important in all
lubrication areas
• Remain in tight supply
• Expensive
Selection of proper base stocks is application
dependent

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 Typical Engine Oil Composition

Pour-Point Depressant
(< 0.5%)

Viscosity Modifier
(VI Improver)
(0 – 4% neat polymer)

Performance Additives
(Detergent-Inhibitor Package)
(5 – 20%)

Base Oil
(75 – 95%)
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 Common DI Package Components

Pour-Point • Dispersants (Ashless)

Depressant • Detergents (Metallic)
(< 0.5%)
• ZDDP
Viscosity Modifier • Antioxidants
(VI Improver) • Friction Modifiers
(0 – 4% neat polymer)
• Anti-foamers
• Antiwear Agents
Performance Additives
(Detergent-Inhibitor • Corrosion Inhibitors
Package) (5 – 20%) • Rust Inhibitors
• Metal Deactivators
Base Oil • Seal Swell Agents
(75 – 90%)
• Emulsifiers/Demulsifiers

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 Dispersants (30 – 60% in DI Pack)
Structure Chemistry / Type Functions

• Polyalkene long • Succinimides • Maintains

hydrocarbon tail x
O engine
N
N y
H
cleanliness at
H
• Succinic or O
low to moderate
phenolic • Mannichs temperatures
connecting
OH
group • Keeps sludge /
x

H
N

contaminants in
N H
• Typically amine
y
H
suspension
or polyamine • Uncapped
polar head
group • Post-treated
▪ Polyol as ▪ Boric Acid
alternative ▪ Organic
head group Acids

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 Function of Dispersants

Maintains engine cleanliness at low to moderate temperature

and keeps sludge in suspension

Sequence VG M271SL

Good

Poor

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 Negative Attributes of Dispersants

May impact unfavorably on cold cranking simulation

(CCS) viscosity, particularly on low vis grade oils
 Need to adjust trimming base stock usage

High polymer loading in engine oil may affect fuel

economy performance

Uncapped N-based dispersants are generally more

aggressive to fluoroelastomer sealing material
 May be alleviated by post-treatment

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 Detergents (15 – 30% in DI Pack)
Structure Chemistry / Types Functions

• C12- C24 olefinic • Sulfonates • Maintains engine

hydrocarbon tail cleanliness at
high
• Benzenesulfonic, • Phenates temperatures
phenolic, or
salicylic acid • Keeps deposits /
polar head group • Salicylates insoluble in
suspension
• Neutral salts of
Ca, Mg, Na, Ba • Neutral / Low- • Neutralizes acidic
base (TBN < 180) byproducts
• Overbased with
metal carbonates • Overbased (TBN • Provides
/ hydroxides > 180 – 400+) rust/corrosion
protection

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 Function of Detergents

Maintains engine cleanliness at high temperature and keeps

deposit in suspension

Neutralizes acidic byproducts and provides rust and corrosion

protection
VW TDi
Cat 1K

Good

Poor

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 Negative Attributes of Detergents

Metallic detergents are main sources of sulfated ash

content in engine oil
 Contributes to ash and particulate in exhaust

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 ZDDP (5 – 15% in DI Pack)
Structure Chemistry / Types Functions

• Zinc salts of • Primary • Provides wear

dialkyldithio- protection by
phosphoric acid, • Secondary forming a
a reaction product protective
of phosphorus • Aryl chemical
pentasulfide tribofilm on
(P2S5) and C3 – C8 • Mixed Primary / moving metal
or aryl alcohols Secondary surfaces

• Overbased (with • Functions as

ZnO) effective
antioxidants and
corrosion
inhibitors

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 Function of ZDDPs

Provides wear protection

Functions as effective antioxidant and
corrosion inhibitor
Valve Train Wear
Valve Train Wear TU3
TU3 Roller Follower Wear Test Sequence IVA RFWT
Sequence IVA (RFWT)

Good Poor

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 Negative Attributes of ZDDP

Contributes phosphorus in EO that adversely affects

performance of emission control system overtime
 Formation of a glaze on catalyst substrates impermeable to emission
gases

In general, there are two modes of P transport to emission

catalysts
 Bulk oil consumption
• Hence the industry has imposed P limit in PCMO specifications
 P volatilization
• Implemented P retention requirement from used oil analysis from Sequence IIIG
engine test in GF-5
• ZDDP with longer alkyl chains generally volatilizes less

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 Component Usage

A mixed component system is often used in EO technology to

meet performance requirements and/or product features
 Dispersant
• Hydrocarbon chain lengths (low and high MW)
• Post-treatments (capped and uncapped)

 Detergent
• Metallic elements (Ca, Mg, Na)
• Detergent types (sulfonates, phenates, salicylates)
• TBN levels (neutral and overbased)

 ZDDP
• Types (primary, secondary, aryl)
• Alcohol carbon chain lengths

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 Holistic Approach to EO Formulation Development

Adhere to physical and chemical constraints per specifications and/or

customer requirements
 Physical: e.g. viscosity grades, shear stability
 Chemical: e.g. P, S, sulfated ash levels

Understand engine and bench test appetites and component

responses
 Use design of experiment approaches when feasible
 Identify “big hammer” effects, good and bad
 Categorize secondary, marginal, and “no-harm” effects

Develop a balanced, cost-effective core technology platform

 Use positive “big hammer” components
 Minimize (or avoid, if at all possible) use of bad actors
 Balance out “trade-offs”; compromise only what can be tolerated or overcome

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Viscosity

Classification System Document: SAE J300 (2015-01)

 Purposes:
• Common language to be used by marketers to communicate with
consumers
• Engineering system used during engine development to assure engine
robustness
• System of specifications used by refiners who produce base stocks.

Types of Measurements
 Kinematic
 Cold-Cranking
 Pumpability and Yield Stress
 Gel-forming tendency
 Shear Stability

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SAE J300 – Engine Oil Viscosity Classification

New Viscosity-Grades

Latest version of SAE J300 (2015-01-20) can be downloaded from www.sae.org

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Viscosity Index
Higher VI  less change in viscosity with temperature
 History (SAE, 1929): Calculation based on fluid viscosities at 100°F (37.8°C) and 210°F
(98.9°C) - difference of naphthenic (poor, VI = 0) and paraffinic (good, VI = 100) mineral oils at
100°F = 100 equal parts, same vis at 210°F), based on kinematic viscosity
 Today’s calculation based on fluid viscosities at 40°C and 100°C

10000
Components influencing Viscosity
 Base Stocks
1000
 Viscosity Modifiers

Kinematic Viscosity, cSt

Low VI
 Pour Point Depressants
100
 DI-package components
• Dispersants (unreacted PIB)
have biggest impact 10 High VI

• A dispersant that contributes

too much to viscosity may prevent 1
an economical base stock blend
to be derived to achieve a desired
0.1
viscosity grade -30 -20 -10 0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150
Temperature, °C

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Viscosity Modifier (VM)
also known as Viscosity Index Improver (VII)
improve the characteristics of the base oil
decrease fluid sensitivity towards temperature by stabilising viscosity over a
broader operating range (“Ideal” Lubricant)
used to maintain correct high temperature (KV100) and low temperature
(CCS, @-x°C) balance
 oil thick enough to protect engine parts when warm but thin enough to ensure oil pumps at
low temperature to prevent oil starvation (“hydrodynamic volume”)

"Ideal" Lubricant
Viscosity

Base Stock "A"

Base Stock "B" Base Stock "B" + VM

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 History of Viscosity Modifiers

• Use of Poly-Isobutylenes (PIB) (First multigrade oils in 1953: Amalie 10W-30; RPM
1950’s DELO Supercharged-3)

• Poly-Methacrylates (PMA)
1960’s

• Olefin Copolymers (OCP)

1970’s

• Dispersant Olefin Copolymers (DOCP)

1980’s

• Star Polymers
1990’s

• High-Ethylene Olefin Copolymers (HEOCP)

2000’s

now

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Viscosity Modifiers
Structure Chemistry / Types Functions

• Long-chain, oil- • Olefin Copolymers • Maintains good

soluble (OCP / NDOCP) oil flow at low
hydrocarbon temperatures
polymers with • Polymethacrylates
molecular (PMA) • Prevents
weights from excessive oil
5000 – 100,000 or • Styrene Isoprenes “thinning” at
higher (SIP, Star) high
temperatures
• Thickening • Polyisobutylene
power (TP) and (PIB) • Imparts
shear stability dispersancy to
index (SSI) are • Dispersant VM help engine
critical properties ▪ DOCP cleanliness with
▪ DPMA dispersant VMs

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Parameters influencing Viscosity

Viscosity is dependent on Effects of Viscosity

 Temperature Too little Viscosity
 Pressure  Poor Lubrication
 Flow Rate  Excessive Heat
 Measurement Technique  Increased Wear
 Concentration Too much Viscosity
 Shear Rate (for Non-Newtonian Fluids)  Poor Flow
 Waste of Energy (Fuel Economy)
 Start-up Problems

The “Ideal” Lubricant has a Constant Viscosity (Newtonian),

BUT….

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 What is Shear Stability?

Mechanical shearing device, ie Polymer coil in oil

Diesel Injection Nozzle (“Bosch”)

Deformed by Rupture of
shearing polymer molecules

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Oil Viscometric Properties Affected by VM’s

Shear Rate vs Temperature

Cold Cranking Tapered Bearing

Simulator, Cold Bearing Simulator,
ASTM D5293 Cranking Protection ASTM D4683
CCS TBS

Mini Rotary Low Temp High Temp Kinematic

Viscometer, Pumpability Pumpability Viscometer,
ASTM D4684 MRV Kinematic ASTM D445

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Pour Point Depressants
Structure Chemistry / Types Functions

• Long-chain, oil- • Polymethacrylates • Prevents

soluble (PMA) “structure”
hydrocarbon formation (e.g.
polymers with gelling) in oil at
molecular low temperatures
weights lower
than those of VM • Esters • Lowers pour point
▪ Maleates
• Maintains oil
pumpability at low
temperatures,
▪ Fumarates particularly with
used oils

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By now, do you learn

What makes up an engine oil?

The importance of base oils quality
The key components in additive package

What are the key specifications?

What are the key engine tests?

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