Lubricant Additives

A formulator’s toolkit

STLE, Toronto
April 8, 2014

Rob Heverly
Vanderbilt Chemicals LLC.
1
 Overview
• General additive comments
• Additives that protect the base oil
• Additives that improve the baseoil performance
• Additives that protect the lubricated surface
• Questions

2
Functions of Lubricants
• Reduce friction and wear
• Remove heat
• Seal
• Reduce corrosion
• Remove and contain wear debris and
contaminants
• Prevent deposits
• Neutralize combustion products
• Transmit power

3
 Lubricant additives

Improve the good properties

Minimize the bad properties

4
 Lubrication Regimes

Lubricant Lubricant
Film Film

FLUID-FILM LUBRICATION BOUNDARY LUBRICATION

Surfaces well separated by Performance essentially
bulk lubricant film depends upon the quality of
the boundary film

Lubricant
Film

MIXED-FILM LUBRICATION
Both the bulk lubricant and
the boundary film play a role

6
 Additive Response
The effectiveness of an additive depends
on the system where it is used.
 An oxidation inhibitor may work well in
one oil and not in another oil
 Polar additives compete with each other
for the same metal surfaces

The final response of the system may not be

the sum of all the components. It will be
greater or lower depending on the
interaction of the components.
7
 Additive Dosage
The ideal treat rate may be different for
different systems.
The additive may be effective at low dosages
and the effectiveness can decrease as the
dosage increases.
The additive may need to reach a specific
dosage before it becomes active.
The performance may continue to increase as
the additive concentration increases.
There may be an ideal treat rate.
The ideal treat rate is influenced by the system
in which it is used.
8
 Three general categories
Protect the baseoil
 Antioxidants
 Antifoam
 Corrosion and rust inhibitors
Improve the baseoil performance
 Pour point depressants
 Viscosity Index improvers
Protect the lubricated surfaces
 Antiwear and extreme pressure additives
 Detergents and dispersants
 Friction Modifiers
 Corrosion and rust inhibitors

9
 Additive Systems
• Additives may be combined to produce well
balanced/optimized additive packages to meet certain
performance criteria.
e.g. Dispersant Inhibitor (DI) Packages for Engine Oils
4% <2%
4%
Dispersant
10%
Detergent
Antiwear Agent
Friction Modifier
Oxidation Inhibitor 60%
Miscellaneous 20%

• Additives may interact with each other (synergism or

antagonism).
• Some additives may have multifunctionality.
10
 Dispersants
• Non-metallic or ashless cleaning agents
• Solubilize and disperse contaminants
– Soot
– Sludge
– Deposit precursors
Structure

Hydrocarbon Tail Polar Head

(Solubilizer) (N and O atoms)

11
 Dispersants

• Mechanism

Types
– Succinimides
– Succinate Esters
– Mannich types
– Phosphorus types
– Polymeric Dispersants
– Combinations
12
 Typical Dispersant Structures
N Substituted Long Chain Alkenyl Succinimides

CH3 O
R CH C CH2 CH C
N [R1 NH]x R1 NH2
CH2 C
O

Succinate Ester Phosphorus Dispersant

O CH3
S
PIB CH C O R OH
PIB P (OCH2 CH OH)2
CH2 C O R OH
O

13
Typical Dispersant Structures
Mannich Base
OH OH

-CH2NHRNHCH2-

R R

Polymeric Dispersant Additives

R R R R R
C CH2 C CH2 C CH2 C CH2 C CH2
O O P O O

Where O = Oleophilic group

P = Polar group
R = Hydrogen or Alkyl group 14
 Detergents

 Metal-containing cleaning agents

 Prevent build-up of deposits from blow by and oxidation on surfaces
 Neutralize acidic products
Structure

Hydrocarbon Tail Polar Head

(Solubilizer) (Metal attachment point)

Two types; high base and low base

– Sulfonates
– Phenates
– Salicylates
Most commonly used metal ions: Ca, Mg
15
 Typical Detergent Structures

Phenate

R R
OMO

Salicylate
OH OH
O O
C O M O C (MCO3)

M = metal ion
16
 Typical Detergent Structures

Overbased Sulfonates

SO3 SO
SO3 3
++ Ca++
SO3 Ca SO3
CaCO3
SO3 Ca++ Ca++ SO
3
SO3
SO SO3
3

17
17
Boundary Lubrication Additives
• Friction Modifiers

• Antiwear Additives

• EP Additives

– Reduce friction and wear at the interface of

rubbing surfaces
– Form surface films
• Adsorbed layers (physical or chemical adsorption)
• Formed by tribochemical reactions

– Prevent/reduce adhesion and interlocking of

surface asperities
18
Antiwear and EP Additives
Form surface films by tribochemical reactions
Typical AW additives:
Sulfur and/or phosphorus-containing compounds
e.g. ZDDP, TCP, amine phosphates
Effective at moderate loads and temperatures
Typical EP additives:
Sulfur and nitrogen compounds, sulfur compounds,
antimony compounds, and chlorine compounds
Used under highly loaded conditions to prevent
welding

19
 EP Additives
Activation Temperature

EP1
EP2
Reaction Rate

T1
T2

50 100 150 200

Temperature, °C

Highly reactive EP additives/high

concentrations may cause corrosive wear
20
 Some additives are
multifunctional
Zinc dithiophosphates
 Protect the metal surfaces from wear by
forming sulfides and phosphates
 Protect Cu, Pb, and Al surfaces from
corrosion
 Protect the baseoil from decomposition
by reducing oxidation, more on that in a
later slide
 But; can poison the catalyst in the
catalytic converter

21
 Antioxidants (Oxidation Inhibitors)

o Oxidation rate determines the useful life of the lubricant

o Reduce oxidation rate of base oil

Oxidation leads to:

Viscosity increase (oil thickening)
Sludge/varnish and deposit formation
Corrosion

22
 Oxidation Mechanism
• Free-radical mechanism
Initiation RH R
O2
Propagation R RO2
O2
RO2 + RH RO2H + R
Branching RO2H RO + OH
O2
RO + RH ROH + RO2
O2
OH + RH H2O + RO2
Termination RO2 + RO2 Neutral non-radical products

RH: hydrocarbon
RO2H: hydroperoxide
R : hydrocarbon free radical
RO2: peroxide free radical 23
 Oxidation Mechanism
• Typical oxidation products:

– Peroxides, alcohols, acids, esters, aldehydes,

and ketones; all oil soluble
– Further reactions
• High molecular weight products that are not oil soluble

• Oxidation rate increases by:

– Oxygen in the oil
– Temperature (rate ~ doubles/10°C or 18 F)
– Light
– Metals that then act as catalysts
24
 Antioxidant Types

 Radical Scavengers
 Peroxide Decomposers
 Metal Passivators

25
Primary Antioxidants
Primary Antioxidants
 Secondary Antioxidants
• Peroxide Decomposers
– Convert hydroperoxides into non-radical
products
– Sulfur and Phosphorus Compounds
e.g. zinc dithiophosphates (ZDP) and
dithiocarbamates
ZDP’s have multifunctional properties:
antioxidant, antiwear, EP, corrosion inhibitor
S S
(RO)2P S Zn S P(OR)2

28
 Antioxidant Types

• Metal Passivators and Rust Inhibitors

– Reduce catalytic effect of metal ions on
oxidation
• Surface film-forming compounds
• Stable complex-forming chelating agents
e.g. benzotriazole, N-salicylidene ethylamine

Synergistic mixtures of different types of antioxidants are

generally used in lubricant formulations.

29
 Friction Modifiers
Function by forming thin monomolecular
layers on metal
long chain (C12-C18) carboxylic acids, fatty acid
esters,
alcohols, …
e.g. CH3-(CH2)7 CH = CH(CH2)7 COOH
sulfurized fatty acids, esters, olefins, …
organometallic compounds: molybdenum
dithiophosphates, molybdenum dithiocarbamate,
copper-containing organic compounds
solid compounds: molybdenum-sulfur compounds,
graphite, PTFE, …

30
Viscosity Index (VI) Improvers (Viscosity Modifiers)

• Viscosity
– Determines lubricant film thickness and flow properties
– Changes with:
• Temperature 200
50
VI

Viscosity, cSt
• Pressure 100 100
VI
50
• Shear rate 30
300 V
I

(for non-Newtonian fluids)

10
• Viscosity Index (VI)
40 60 80 100
– Empirical number measuring the Temperature, °C
temperature response of viscosity
(ASTM D 341, Walter relationship)
– Defined by the gradient between
40 °C and 100 °C
31
 Viscosity Index (VI) Improvers
• Improve viscosity-temperatures properties of lubricants

• Oil soluble polymers

– Typical molecular weights: 10,000 – 250,000

• Effect of polymer on viscosity

Thickening Efficiency
Ba
se
oil
+po
Viscosity

lym
Ba e r
se
Oi
l

0 100 200 300

Temperature, °F Molecular Weight
32
 Viscosity Index (VI) Improvers
• Types of VI Improvers:
– Olefin copolymers
– Polyisobutylene
– Hydrogenated styrene-isoprene copolymers
– Hydrogenated styrene-butadiene copolymers
– Polyalkyl methacrylates
– Dispersant VI improvers (multifunctional)

• Performance influenced by:

Shear Stability
– Shear stability
• Temporary viscosity loss
(moderate shear stress)
• Permanent viscosity loss
Molecular Weight
(high shear stress)
33
Pour Point Depressants (PPD)
• Modify crystal morphology of wax structures
• Improve flow properties at low temperatures
• Mainly polymeric compounds

34
 Corrosion Inhibitors
• Protect metal surfaces against chemical attack
• Form surface films by adsorption

Solid
Surface

• Compete with other polar additives (FM, AW, Detergents,

and EP) for the surface

35
 Corrosion Inhibitors (continued)
• Typical Rust Inhibitors
– Sulfonates
– Carboxylic acid derivatives
– Phosphoric acid derivatives
– Fatty acid amides

• Typical Metal Passivators

– Surface film-forming types (benzotriazole)
– Oil-phase, complex forming chelating agents (N-
Salicylidene-propylenediamine)
– Sulfur scavengers (mercapto-thiadiazole derivatives)
– Zinc dithiophosphates and dithiocarbamates
(multifunctional)
36
 Antifoam Agents
• Destabilize Foam
• Reduce
– Air entrainment, cavitation damage
– Lubricant starvation
• Two types:
– Silicone Polymers
R
Si O
R n
Concentration ~ 0.001%
– Silicone-free Defoamers (cutting fluids, hydraulic fluids)
• Polyethers
• Organic copolymers

37
 References
• Selda Gunsel, “Lubricant Additives,” World
Tribology Congress, Basic Lubricants Course,
September 3, 2001
• C. V. Smalheer and R. K. Smith, “Lubricant
Additives”, Cleveland, Lensins-Hiles Co. 1967
• G. J. Schilling and G. S. Bright, “Fuel and
Lubricant Additives II, “ Lubrication, Vol. 63,
Number 2.
• Fay Linn Lee and John Harris, “Lubricant
Additives: Chemistry and Applications.” page
609 to 636, 2009

38
 Questions?
Rob Heverly
Vanderbilt Chemicals LLC
RHeverly@VanderbiltChemic
als.com
281-474-7444