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Lubricant Additives-Heverly-2012 - 2 - 8 PDF
Lubricant Additives-Heverly-2012 - 2 - 8 PDF
STLE Houston
February 8, 2012
Rob Heverly
R. T. Vanderbilt Co.
1
Overview
2
Functions of Lubricants
3
Lubricant additives
4
Lubrication Regimes
Lubricant Lubricant
Film Film
Lubricant
Film
MIXED-FILM LUBRICATION
Both the bulk lubricant and
the boundary film play a role
6
Additive Response
7
Additive Dosage
8
Three general categories
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%
10
10
Dispersants
Non-metallic or ashless cleaning agents
Solubilize and disperse contaminants
Soot
Sludge
Deposit precursors
Structure
11
11
Dispersants
Action Mechanism
Sludge
Sludge Dispersant Micelle
Types
Succinimides
Succinate Esters
Mannich types
Phosphorus types
Polymeric Dispersants
Combinations
12
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
O CH3
S
PIB CH C O R OH
PIB P (OCH2 CH OH)2
CH2 C O R OH
O
13
13
Typical Dispersant Structures
Mannich Base
OH OH
-CH2NHRNHCH2-
R R
Phenate
R R
OMO
Salicylate
OH OH
O O
C O M O C (MCO3)
Phosphonate
M = metal ion 16
16
Typical Detergent Structures
Sulfonates
SO3 SO
SO3 3
++ Ca++
SO3 Ca SO 3
CaCO3
SO3 Ca++ Ca++ SO
3
SO3
SO SO3
3
17
17
Boundary Lubrication Additives
Friction Modifiers Upper Surface
Lubricant
Boundary
Antiwear Additives Asperity Contacts Layers
Lower Surface
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, phosphorous , and chlorine compounds are
elements found in most EP additives
Used under highly loaded conditions to prevent welding
19
19
EP Additives
Activation Temperature
EP1
EP2
Reaction Rate
T1
T2
20
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
But; can poison the catalyst in the catalytic
converter
21
Antioxidants
22
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
23
RO2: peroxide free radical 23
Oxidation Mechanism
Typical oxidation products:
Peroxides, alcohols, acids, esters, aldehydes, and ketones; all oil soluble
Further reactions resulting in high molecular weight products that are
not oil soluble
24
24
Antioxidant Types
Radical Scavengers
Peroxide Decomposers
Metal Passivators
OH CH2 OH
25
25
Antioxidant Types
Radical Scavengers (continued)
Aromatic Amines
R N R
H
26
26
Antioxidant Types (continued)
27
27
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,
28
28
Viscosity Index (VI) Improvers
Viscosity
Determines lubricant film thickness and flow properties
Changes with:
200
Temperature 50
VI
Viscosity, cSt
100 100
Pressure 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
29
29
VI Improver Structure
.
Viscosity Index (VI) Improvers
Improve viscosity-temperatures properties of lubricants
Thickening Efficiency
Ba
se
oil
+po
Viscosity
lym
Ba er
se
Oi
l
Shear Stability
Shear stability
Temporary viscosity loss
(moderate shear stress)
Permanent viscosity loss
(high shear stress)
Molecular Weight
32
32
Pour Point Depressants (PPD)
Modify crystal morphology of wax structures
Improve flow properties at low temperatures
Mainly polymeric compounds
Wax modifier
Blocked wax
molecule
The growing
wax crystal
33
33
Corrosion Inhibitors
Protect metal surfaces against chemical attack
Form surface films by adsorption
Solid
Surface
Compete with other polar additives (FM, AW, EP) for surface
Two types of corrosion inhibitors
Rust inhibitors ferrous metals
Metal passivators nonferrous metals
34
34
Corrosion Inhibitors
Typical Rust Inhibitors
Sulfonates
Carboxylic acid derivatives
Phosphoric acid derivatives
Fatty acid amides
R
Si O
R n
Concentration ~ 0.001%
Silicone-free Defoamers (cutting fluids, hydraulic fluids)
Polyethers
Organic copolymers
36
36
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
Steve Swedberg, Building Blocks for Lubes,
LubesnGreases, November 2011, Pages 35 to 40.
37
Questions?
Rob Heverly
R. T. Vanderbilt Co. Inc.
Rheverly@rtvanderbilt.com
281-474-7444