Additive Components

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Additive Components

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1 © INFINEUM INTERNATIONAL LIMITED 2019. All Rights Reserved.
©INFINEUM INTERNATIONAL LIMITED 2020. All Rights Reserved.
© 2020 Infineum International Limited. All rights reserved.
Outline
1 2 3
Overview of Engine Processes Formulation

Additives and Additives Putting it all together
Why they’re used Oxidation and Antioxidants
Functions of engine oil Acids and Detergents
Deposits and Dispersants
Wear and Anti-Wear
Friction and Friction Modifiers
2
What’s in the Bottle*?

Base Stock Ensures fluidity and adds performance
Viscosity Modifier Changes temperature response
Detergent Neutralizes acids and prevents deposits
= Dispersant
Anti-Oxidant
Keeps everything soluble
Reduces and delays oxidation
Anti-Wear Reduces abrasive wear
Friction Modifiers Reduces (or increases) friction

Many other, more
specialized additives
Others As needed for specialized products
3 *Not all oils have all components
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Functions of Additives
Make “oil” work

Base stock by itself is not good
Perform two critical functions:
enough for most applications
1. 2.
Minimize destructive Confer beneficial
Tailor base oils for different applications
processes properties
The same base stock can become PCEO, HDDO,
ATF, Industrial Oil, etc., depending which Oxidation, wear, Lubricity,
additives are used friction, corrosion, cleaning,
etc. etc.
There are some limitations
4
Oxidation
5
What is Oxidation?
Destruction of molecules by exposure Radicals attack and “pull apart”
to oxygen at elevated temperatures the base stock and other molecules
▪ Technically, oxidation can occur without oxygen, ▪ To pair their lone electron
but we don’t need to consider those cases
The process can be catalyzed by metals

Initiated by Radicals ▪ Catalyzed = Accelerated
▪ Molecular fragments with an unpaired electron
▪ Very unstable and reactive
6
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
Breaking of Viscosity Modifier Depletion of Anti-oxidant
Followed by normal oxidation Followed by runaway oxidation
7
Effect of Temperature
Aluminium Beaker
Test
Oxidation Test (ABOT) Temperature
10
170C
8
Acid Number Increase
6 163°C
This data set:
Rule of thumb:
Rate doubles Every 10C increase in
155°C
every 7°C temperature doubles the
4
rate of oxidation
2
140C
0
150 200 250 300
Test Hours
8
Oxidation Inhibitors
(Or Anti-Oxidants)
9
Anti-Oxidant
Oxidation Negative consequences Function of Compositions
of oxidation anti-oxidants
Destruction of ▪ Viscosity increase Reduce and Hindered Phenol
molecules by ▪ Acid formation control Alkylated DiPhenyl Amine (ADPA)
exposure to oxidation
Attack engine surfaces Some sulfur compounds
oxygen at
elevated Particularly copper-lead bearings Certain metal compounds
temperatures ▪ Insolubles (e.g., Molybdenum)
Hydrocarbon
Form deposits “tail” for
solubility
Sludge and varnish
▪ Additive depletion
H
O H
R R
10 R
Hindered Phenol Alkylated DiPhenyl Amine
Anti-Oxidant example
Antioxidant 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
11 Source: E. A. Haidasz, et. al., J. Am. Chem. Soc. 2016, 138 (16), pp. 5290-5298
Detergents
12
Detergents
Functions
Neutralize acids
▪ Combustion products: Sulfur and Nitrogen (strong) acids
▪ Oxidation products: organic (weak) acids
Reduce high-temperature deposits
▪ Prevent piston ring sticking
▪ Prevent 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
▪ Phenate
▪ Salicylate
Deposit prevention
13
Detergent Example
14 Bad Results Good Results

SASH and Ash

Detergents contain metal Typically measured as Note:
“sulfated ash” There is also a test for “ash”
Calcium, magnesium, sodium, etc.
React the oil with sulfuric acid ▪ Without sulfuric acid
When burned,
and burn it
they leave a residue ▪ ASTM D482
▪ Simulates burning in
Called “Ash” the presence of fuel
Metals become metal sulfates
▪ Hydrocarbons burn completely
▪ Indirect method of measuring
metal content
▪ ASTM D874
15
Base Number
Base Number (BN) is a Two test methods
quantitative measure of alkalinity ▪ ASTM D2896
Formerly known as Total Base Number (TBN) – Uses perchloric acid, an extremely strong acid
– Measures “everything”
Concentration of base • Strong bases, weak bases, some salts, etc.
Expressed as equivalent KOH neutralizing ability – Gives higher numbers
(mg KOH/g units)
– Used for fresh oils
Add acid until solution is neutralized
▪ ASTM D4739
– Uses hydrochloric acid, a strong acid
– Measures “effective”
• Strong bases
– Gives lower numbers
– Used for in-service oils
16
Dispersants
17
Dispersants
Definition Composition
▪ Also called “Ashless Dispersants” ▪ Long chain hydrocarbon for solubility
▪ “Ash” (“SASH”) means “contains a metal” Fuel ▪ Small (non-metal) polar “head group”
additives
▪ Sodium, calcium, magnesium, zinc, etc. to stick to soot and deposits
call these
▪ Dispersants don’t contain metals “detergents”
▪ Only carbon, hydrogen, nitrogen, oxygen, boron, etc. Detergent
Functions
Dispersant
▪ Suspend (dissolve) soot Diesel engine oils
▪ Inhibit and suspend sludge Gasoline engine oils
▪ Sludge = oil + water + oxidation + dirt = “black mayonnaise”

▪ Reduce formation of deposits
Common Dispersant
▪ Keep things clean PolyIsoButylene Succinic Anhydride/PolyAMine
▪ Engine oil is a trash collector
PIBSA/PAM
▪ Oil change is “taking out the garbage”
18
Dispersant Example
Bad Results Good Results

19
Friction and Wear
20
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
21
Antiwear Agents
22
Antiwear Agents
Function Mechanism Composition
Reduce surface-on-surface wear ▪ Decompose on the surface to ▪ Zinc-containing (ZDDP) ➔
form protective film ▪ Engine oils
▪ Heat caused by friction ▪ Ashless phosphorus based
▪ “Anti-Flux” – ▪ ATF, gear, aviation
dirty surface prevents adhesion ▪ Ashless non-phosphorus
▪ Railroad and other special cases
▪ Extreme pressure
Consequence: ▪ Gear oils
23
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
More detail about “R” group later ➔
Zinc Dithio Glossary
Alkyl group =
Glossary
hydrocarbon missing one hydrogen
Thio = sulfur in Greek
Can attach to other structures
24 NOTE: Not exact chemical structure; for illustration only

ZDDP alkyl structures
Alkyl type, length, and branching affect ZDDP performance

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
25
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ZDDP Decomposition
ZDDP decomposition temperatures highly dependent on method and conditions
100
Good for passenger car
Thermo-Gravimetric Analysis (TGA) sliding valve trains
80 Good for gas engine ring-

liner wear
Weight Remaining, Percent
Good for marine cylinder

60 oils
40
20
0
150 200 250 300 350
26 Temperature, Celsius
Friction Modifiers
27
What are friction modifiers?

Function Mechanism Composition
▪ Reduce friction between moving ▪ Form a “springy” layer ▪ Straight chain stiff hydrocarbons
surfaces ▪ “Plush carpet” effect with polar end groups
▪ Bond to metal surfaces
Rather than soot, for example
Not to scale!
Friction
Consequence: Modifier
Metal surface

Solid friction modifiers

“Flat plate” molecular geometry Examples Polytetrafluoroethylene
▪ Planes glide over each other ▪ Graphite ▪ PTFE
▪ Molybdenum disulfide ▪ Teflon ®
▪ Strong terminal bonds don’t stick to
other things

Formulation
(Putting It All Together)
30
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
31 “Lubricant Chemistry, Technology, Selection, and Design,” S.Q.A. Rizvi, ASTM MNL59, 2009
©INFINEUM INTERNATIONAL LIMITED 2020. All Rights Reserved. “Automotive Lubricants Reference Book (2e),” R.F. Haycock and J.E. Hillier, SAE PT-111, 2004
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Performance you can rely on.

Performance you can rely on.

Overview of Engine Processes Formulation

What’s in the Bottle*?

Viscosity Modifier Changes temperature response

Detergent Neutralizes acids and prevents deposits

Reduces and delays oxidation

Anti-Wear Reduces abrasive wear

Friction Modifiers Reduces (or increases) friction

Make “oil” work

The process can be catalyzed by metals

Change (Pentane, Acid)

14 Bad Results Good Results

SASH and Ash

▪ Inhibit and suspend sludge Gasoline engine oils

▪ Sludge = oil + water + oxidation + dirt = “black mayonnaise”

Bad Results Good Results

Friction and Wear

Friction and Wear

Both are caused by relative motion between surfaces

▪ Wear is a loss of material

Zinc Dialkyl DithioPhosphate (ZDDP)

Hydrocarbon 'tail' for solubility. Phosphate

24 NOTE: Not exact chemical structure; for illustration only

ZDDP alkyl structures

Alkyl type, length, and branching affect ZDDP performance

80 Good for gas engine ring-

Good for marine cylinder

What are friction modifiers?

©INFINEUM INTERNATIONAL LIMITED 2020. All Rights Reserved.

Solid friction modifiers

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For more information:

©INFINEUM INTERNATIONAL LIMITED 2020. All Rights Reserved. 32

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