Performance you can rely on.

Additive components

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Outline

• Overview of Additives
• Why they’re used
• Functions of engine oil
• The Challenge
• Basic Concepts
• Polarity, Surfactants, and Micelles
• Colloids and Emulsions
• Radicals and Reactions
• Engine Processes and Additives
• Oxidation and Antioxidants
• Acids and Detergents
• Deposits and Dispersants
• Wear and Anti-Wear
• Friction and Friction Modifiers
• Formulation
• Putting it all together
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What’s in the bottle*?

Ensures fluidity and
Base Stock
adds performance
Viscosity Changes
Modifier temperature response Hydraulic
Oils &
Monograde
Dispersant Keeps everything soluble Engine Oils
don’t have

=
VM
Detergent Neutralizes acids and
prevents deposits
Anti-
Oxidant Reduces and delays
oxidation
Anti-Wear
Reduces abrasive wear
Friction
Modifiers Reduces (or increases)
**Many other, more
friction
specialized additives
Others As needed for specialized
*Not all oils have Additive products
all components Package
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Functions of additives

• Make “oil” work

• Base stock by itself is not good enough for most applications
• Tailor base oils for different applications
• The same base stock can become PCEO, HDDO,
ATF, Industrial Oil, etc., depending which additives are used
• There are some limitations
• Perform two critical functions:
• Minimize destructive processes
• Oxidation, wear, friction, corrosion, etc.
• Confer beneficial properties
• Lubricity, cleaning, etc.

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The challenge

• Engine lubricating oils are non-polar

• Hydrocarbons
• Engines and their contents are polar
• Metal surfaces
• Oxidation products
• Soot
• Sludge
• Varnish
• etc.
• How to make them mix?

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Surfactants

• Molecules with both polar and non-polar sections

Polar ‘head’ Non-polar ‘tail’

• Will orient based on polarity of medium

• Interface
• Where two phases meet
• e.g., oil and water
• Polar ends in water
• Non-polar ends in oil
• In bulk liquid 

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Micelles
In Oil In Water
Polar core

Non-polar core
• In three dimensions these form a spherical environment
• Solid in the middle = colloid
• Liquid in the middle = emulsion
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Oxidation

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Chemically, what is oxidation?

• Destruction of molecules by exposure to oxygen at

elevated temperatures
• Technically, oxidation can occur without oxygen, but we don’t need
to consider those cases
• Initiated by Radicals
• Molecular fragments with an unpaired electron
• Very unstable and reactive
• Radicals attack and “pull apart” the base stock molecules
• To pair their lone electron
• The process can be catalyzed by metals
• Catalyzed = Accelerated
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How to measure oxidation

1. Oxygen Uptake H
2. Infrared C
3. Acid Number H
4. Insolubles +O2
5. Viscosity Growth

C •OH H
Carbonyl C
O

+O2 •OH
Polar H
C OH C Radical Larger molecule
O H (higher viscosity)
Acid
Chain Breaking Chain Growth
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Indicators of oxidation

Aluminum Beaker Oxidation Test (ABOT)

50 Acid 5
Number
40 Infrared 4

Change (Pentane, Acid)

Change (IR, Viscsosity)

30 Viscosity 3

20 2

Pentane
10 Insolubles 1

0 0

-10 -1
0 50 100 150 200 250 300 350
Test Hours

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Viscosity changes due to oxidation

Polymer Thickened Fluid

NOT TO SCALE
Relative sizes and
timings of
decrease and
increase will vary
Break Point
Viscosity

Oxidation
Inhibitor
Consumed

Chain
breaking of Chain growth of base Runaway
VM stock oxidation

Time

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Anti-oxidant example

• Anti-oxidant displays “Induction Time” to delay onset of oxidation

– Followed by “Break Point” and resumption of oxidation
80
Light paraffin oil at 160C
5.0 mM tetralin hydroperoxide
Extent of Oxidation

60

40

20 Plus
hindered phenol
anti-oxidant
0
0 500 1000 1500 2000 2500 3000 3500
Time, seconds
Source: E. A. Haidasz, et. al., J. Am. Chem. Soc. 2016, 138 (16), pp. 5290-5298
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Effect of temperature
Test
Aluminium Beaker Oxidation Test (ABOT)
Temperature

10
170C
8
Acid Number Increase

6 163°C
This data set:
Rate doubles
every 7°C
4 155°C

2
140C

0
150 200 250 300
Test Hours

Rule of thumb - every 10C increase in temperature doubles the

rate of oxidation
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Oxidation inhibitors
(or anti-oxidants)

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Anti-oxidant

• Oxidation
– Destruction of molecules by exposure to oxygen at elevated temperatures
• Negative consequences of oxidation
– Viscosity increase
– Acid formation
• Attack engine surfaces
– Particularly copper-lead bearings
– Insolubles
• Form deposits
– Sludge and varnish
– Additive depletion
• Function of anti-oxidants
– Reduce and control oxidation
• Compositions
– Hindered Phenol
– Alkylated DiPhenyl Amine
– Some sulfur compounds
– Certain metal compounds (e.g., Molybdenum)
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How do hindered phenols work?

• Easily lose a hydrogen to form a stable radical

• Stabilized by aromatic ring
• Further reaction inhibited by molecular structure
Bulky groups reduce Weakly bonded
Hindered further reactions hydrogen

H H
OH H
H
C
H .
H
H
C
H H
H C O C H
Is really H H
C C
H H H H
H H
R
R

Hydrocarbon tail for solubility Aromatic ring stabilizes radical

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Detergents

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Detergents

• Functions
• Neutralize acids
• Combustion products: Sulfur and Nitrogen (strong) acids
• Oxidation products: organic (weak) acids
• Reduce high-temperature deposits
• Prevent piston ring sticking
• Lacquer, varnish, and carbon
• Prevent bore polish (abrasive or corrosive liner wear)
• Mechanisms
• Basic (alkaline) to neutralize acids
• Surface-active to reduce deposits
Ca, Mg, Na, Ba, ….
• Composition
• Basic metal with organic “tail”
• Sulfonate Deposit prevention
• Phenate
• Salicylate
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Detergent example
• Acid neutralization

0%
Base Number Decrease by D4739

-20%

-40%
Oil C

-60% Oil B

Oil A
-80%
Time Hours

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Detergent example

Exhibit A Exhibit B
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Detergents
Strong
Li, Na, K, Rb, Cs H– O – M – O –H Inorganic
Base

M (OH)
H– O – M – O –H Neutral
M (OH)2

Mg, Ca, Sr, Ba

H– O – M – O –H Basic

'Soap'

CaCO3
Mg(OH)2 Overbased

'Core'
(metal carbonate)
(metal hydroxide)

“M” is a metal, such as calcium, magnesium, sodium, etc.

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SASH and ash

• Detergents contain metal

– Calcium, magnesium, sodium, etc.
• When burned, they leave a residue
– Called “Ash”
• Typically measured as ”sulfated ash”
• React the oil with sulfuric acid and burn it
• Simulates burning in the presence of fuel
• Metals become metal sulfates
• Hydrocarbons burn completely
• Indirect method of measuring metal content
• ASTM D874
• Note: There is also a test for ”ash”
• without sulfuric acid
• ASTM D482
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Base number

• Base Number (BN) is a quantitative measure of alkalinity

• Formerly known as Total Base Number (TBN)
• Concentration of base
• Expressed as equivalent KOH neutralizing ability (mg KOH/g units)
• Add acid until solution is neutralized
• Two test methods
• ASTM D2896
• Uses perchloric acid, an extremely strong acid
• Measures “everything”
– Strong bases, weak bases, some salts, etc.
• Gives higher numbers
• Used for fresh oils
• ASTM D4739
• Uses hydrochloric acid, a strong acid
• Measures “effective”
– Strong bases
• Gives lower numbers
• Used for in-service oils
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Dispersants

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Dispersants

• Definition Common Dispersant

PolyIsoButylene Succinic Anhydride/PolyAMine
– Also called “Ashless Dispersants”
– “Ash” (“SASH”) means “contains a metal” PIBSA/PAM
• Sodium, calcium, magnesium, zinc, etc.
• Dispersants don’t contain metals Fuel additives call
• Only carbon, hydrogen, nitrogen, oxygen, boron, etc. these “detergents”
• Functions
• Suspend (dissolve) soot Diesel engine oils
• Inhibit and suspend sludge Gasoline engine oils
• Sludge = oil + water + oxidation + dirt = “black mayonnaise”
• Reduce formation of deposits
• Keep things clean
• Engine oil is a trash collector Detergent
• Oil change is “taking out the garbage”
• Composition Dispersant
• Long chain hydrocarbon for solubility
• Small (non-metal) polar “head group” to stick to soot and deposits

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Dispersant example

Exhibit C Exhibit D
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Friction and wear

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Friction and wear

• Both are caused by relative motion between surfaces

• Friction is a loss of energy
• Dissipated as heat
• Heat can do damage
• Wear is a loss of material
• Changes geometry of contacts
• Changes equipment performance
• Introduces metal oxidation catalysts

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Antiwear agents

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Antiwear agents

• Function
• Reduce surface-on-surface wear
• Mechanism
• Decompose on the surface to form protective film
• Heat caused by friction
• “Anti-Flux” – dirty surface prevents adhesion
• Composition
• Zinc-containing (ZDDP) 
• Engine oils
• Ashless phosphorus based
• ATF, gear, aviation
• Ashless non-phosphorus
• Railroad and other special cases
• Extreme pressure 
• Gear oils
Consequence:

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Zinc Dialkyl DithioPhosphate (ZDDP)

RO S S OR

P Zn P Dialkyl

RO S S OR

Hydrocarbon 'tail' for solubility. Phosphate

Can be varied to affect performance Zinc Dithio
More detail about “R” group later 

Note: Not exact chemical structure; for illustration only

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ZDDP “alkyl” structures

Alkyl type, length, and branching affect ZDDP properties
S OR
Zn P Aryl ZDDP – aromatic
S O Z group

S OR
Zn P H
Primary ZDDP – one
S O C X ‘alkyl’ group
H
S OR
Zn P H Secondary ZDDP – two

S O C X ‘alkyl’ groups

Y
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ZDDP decomposition

ZDDP decomposition temperatures highly dependent on method and conditions

100
Good for passenger
Thermo-Gravimetric Analysis (TGA) car sliding valve trains
Weight Remaining, Percent

80 Good for gas engine

ring-liner wear

60 Good for marine

cylinder oils

40

20

0
150 200 250 300 350

Temperature, Celsius

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Extreme pressure (EP) additives

• ‘Extreme’ is a relative term

• ZDDP sometimes called ‘EP’
• EP more commonly refers to
• Additives for high loads in gear oils
• Chlorine-containing molecules
• Highly reactive sulfur or sulfur-phosphorus compounds
• Work similar to ZDDP, but
• More active
• More corrosive
• Balance EP protection with corrosion

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Friction modifiers

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What are friction modifiers?

• Function
• Reduce friction between contacting surfaces in relative motion
• Mechanism
• Form a “springy” layer
• “Plush Carpet” effect Not to scale!
• Composition
• Straight-chain stiff
hydrocarbons with
polar end groups
• Bond to metal surfaces
Friction
• Rather than soot, for example Modifier
Consequence:

Metal surface

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Friction modifier example

• Stribeck curve
• Friction modifier extends the hydrodynamic region
• Enabling protection at lower viscosities
Friction Coefficient (Power Loss)

Without FM

With FM

Viscosity
Ref: Passut, C.A. and Kollman, R.E., SAE paper 780601
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Solid friction modifiers

• ‘Flat Plate’ molecular geometry

• Planes glide over each other
• Graphite (Carbon)
• Molybdenum DiSulphide (MoS2)

• Polytetrafluoroethylene = PTFE
• Teflon®
• Strong terminal bonds don’t stick to other things

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Formulation
(Putting it all together)

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Formulation science

The key is balancing the additives for the application:

Dispersant Detergent FM

Antioxidants LOFI
'The Oil'
ATF
PCMO
Antiwear HDEO VM
Gear
2T
RR
GEO
Antirust Indoil Base Stock

For more information:

“Lubricant Additives, Chemistry and Applications,” L. R. Rudnick (ed.), Marcel Dekker, Inc., 2003
“Lubricant Chemistry, Technology, Selection, and Design,” S.Q.A. Rizvi, ASTM MNL59, 2009
“Automotive Lubricants Reference Book (2e),” R.F. Haycock and J.E. Hillier, SAE PT-111, 2004
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