Additive 05 Moray Stark

The Degradation of Lubricants in Gasoline Engines
Additives 2005 : Dublin 5th- 7th April 2005
John R. Lindsay Smith, Moray S. Stark,* Julian J. Wilkinson

Department of Chemistry, University of York, York YO10 5DD, UK
Peter M. Lee, Martin Priest

School of Mechanical Engineering, University of Leeds, Leeds, LS2 9JT, UK
R. Ian Taylor
Shell Global Solutions, Chester, CH1 3SH, UK
Simon Chung
Infineum UK Ltd., Milton Hill, Abingdon, Oxfordshire, OX13 6BB, UK
Department of Chemistry
Additives 2005 : Dublin 5th- 7th April 2005
John R. Lindsay Smith, Moray S. Stark,* Julian J. Wilkinson

Department of Chemistry, University of York, York YO10 5DD, UK
Peter M. Lee, Martin Priest

School of Mechanical Engineering, University of Leeds, Leeds, LS2 9JT, UK
R. Ian Taylor
Shell Global Solutions, Chester, CH1 3SH, UK
Simon Chung
Infineum UK Ltd., Milton Hill, Abingdon, Oxfordshire, OX13 6BB, UK
mss1@york.ac.uk www.york.ac.uk/res/gkg
nderstand Increase in Engine Friction with Oil Degradation
Sampling of Lubricant from Piston Assembly
Measurement of Lubricant Flow in Engine
Measurement of Lubricant Degradation in Engine
Measurement of Lubricant Degradation in Engine
Chemical Mechanisms of Base Fluid Oxidation
Viscosity Increase in a Paris Taxi Fleet
15
10
Vk100 (cSt)
Oil Change Oil Change

0
0 10 20 30 40 50 60
Distance (1000 km)
Engine Oil Stress Factor for Gasoline Cars : 1950 - 2000

 Engine Power  Oil Drain Interval 
Oil Stress Factor    
 Engine Displacement  Sump Volume 
Oil Stress Factor (kW km litre )
500
-2
400
300
200
100
0
1940 1950 1960 1970 1980 1990 2000 © BP Castrol
R. I. Taylor, R. Mainwaring, R. M. Mortier, Engine Lubricant Trends Since 1990,

Proc. I. Mech. E. Vol 219, Part J: J. Engineering Tribology, p 1-16, 2005
Engine : Ricardo Hydra
Institute of Tribology
School of Mechanical Engineering ,The University of Leeds
 Fuel Injected Gasoline

 Single Cylinder
 0.5 litre Capacity
Lubrication of Engine
P. M. Lee, M. Priest, J. R. Lindsay Smith, M. S. Stark, J. J. Wilkinson, R. I. Taylor and S. Chung,

Proceedings of the 31st Leeds-Lyon Symposium on Tribology, Sept 2004, Elsevier, 2005 (in press)

Sump 1
Valve Train

Sump 1
Valve Train
Sump 2
Piston Assembly
Crank Shaft

Sump 2
Piston Assembly
Crank Shaft

Degradation of Lubricant
Piston Assembly
Sump

Degradation of Lubricant
Piston
Piston Assembly
Sump
Sump
S. Yasutomi, Y. Maeda and T. Maeda, Kinetic Approach To Engine Oil .2.

Antioxidant Decay of Lubricant in Engine System, Ind. Eng. Chem. Prod. Res. Dev. 20 (1981) 536
Piston Assembly
R. Gamble, Influence of Lubricant Degradation on Piston Assembly Tribology,

PhD Thesis, University of Leeds, 2002
Piston Assembly
M. S. Stark, R. J. Gamble, C. J. Hammond et al., Measurement of Lubricant Flow in a Gasoline Engine,

Tribology Letters (in press) 2005
Extraction of Oil from Top Piston Ring
Top Ring Groove
1.2mm Diameter Hole

Screw with 1mm
Diameter Hole
Collar Piston
PTFE
Tube
Top Ring Groove
PTFE Tube
Connecting
Sample Collection Rod
R. Gamble, Influence of Lubricant Degradation on Piston Assembly Tribology,

PhD Thesis, University of Leeds, 2002
Extraction of Oil from Top Piston Ring

Oil Flow in Engine
Piston Small Volume

Short Residence Time
Flow Rate
Large Volume
Sump Long Residence Time

Piston Assembly Residence Time: Method
Piston Sample Lubricant

from Piston Assembly
Add Marker to Sump

Sump
S B Saville, F D Gainey, S D Cupples, M F Fox, D J Picken,

SAE Technical Paper, International Fuels and Lubricants Meeting, Oct 10-13, 1988
Piston Assembly Residence Time: Method
Time

 RingPack
[ marker]ringpack  [marker]sump (1  exp )
100
75
Marker (%)
1-e-1
50
25
0
0 10RingPack 20 30 40 50
Time (arb)
S B Saville, F D Gainey, S D Cupples, M F Fox, D J Picken,

SAE Technical Paper, International Fuels and Lubricants Meeting, Oct 10-13, 1988
Piston Assembly Residence Time : 60 sec
Time  delay

 RingPack
[marker]ringpack  [marker]sump (1  exp )
100
75
Marker (%)
50
25
0
0 1 2 3 4 5
Time (min)
Conditions : 1500 rpm, 50 % Load. Lubricant : XHVITM 8.2 only

M. S. Stark, R. J. Gamble, C. J. Hammond et al., Measurement of Lubricant Flow in a Gasoline Engine,
Tribology Letters (in press) 2005
Piston Flow Rate: Method
Piston Small Volume

Short Residence Time
Flow Rate
Large Volume
Sump Long Residence Time

Oxidation Chemistry
Hydrocarbon
Base Fluid
(schematic)
Oxidation Chemistry
Hydrocarbon
Base Fluid
Hydroperoxides
O
O
H
Oxidation Chemistry
Hydrocarbon
Base Fluid
Hydroperoxides
O
O
H
O
H
Alcohols
Oxidation Chemistry
Hydrocarbon
Base Fluid
Hydroperoxides
O
O
H
O
O
+
O O H
H
Alcohols Carboxylic Acids Ketones
Oxidation Chemistry
Hydrocarbon
Base Fluid
Hydroperoxides
O
O
H
O
O
+
O O H
H
Alcohols Carboxylic Acids Ketones
Infrared Spectroscopy
of Carbonyl Group
Comparison of Sump and Ring Pack
10
Carbonyl (10-3 mol / litre) 0.3
8
TAN (Calculated)
6 0.2
4
0.1
2 Ring Pack
Sump (x10)
0 0.0
0 60 120 180
Time (mins)
Conditions : 2000 rpm, 50 % Load
M. S. Stark, J. J. Wilkinson, P. M. Lee, J. R. Lindsay Smith, M. Priest, R. I. Taylor and S. Chung,
Comparison of Sump and Ring Pack
10
Carbonyl (10-3 mol / litre) 0.3
8
TAN (Calculated)
6 0.2
4
0.1
2 Ring Pack
Sump (x10)
0 0.0
0 60 120 180
Time (mins)
Conditions : 2000 rpm, 50 % Load
Calculation of Sump Residence Time
[Product]RingPack
 SUMP 
 d [Product ]Sump 
 
 dt 
10
0.3
Carbonyl (10 mol / litre)
TAN (Calculated)
6 0.2
-3
4
0.1
2 Ring Pack
Sump (x10)
0 0.0
0 60 120 180
Time (mins)

[Product]RingPack
 SUMP   SUMP  49  5 hours
 
 dt 
10
0.3
TAN (Calculated)
6 0.2
-3
4
0.1
2 Ring Pack
Sump (x10)
0 0.0
0 60 120 180
Time (mins)

[Product]RingPack
 SUMP 
 SUMP  19  2 hours litre-1
 
 dt 
10
0.3
TAN (Calculated)
6 0.2
-3
4
0.1
2 Ring Pack
Sump (x10)
0 0.0
0 60 120 180
Time (mins)

Sump Residence Time : Engine Speed
Sump Residence Time (hours/litre)

40
30
20
10
0
0 1000 2000
Engine Speed (rpm)
Conditions : 1000 - 2000 rpm, 50 % Load
Characterisation of Gasoline Engine
Piston Assembly
Residence Time  60 seconds
Volume of Oil  1 cm3 cylinder-1
Flow Rates
Returning to Sump  1 cm3 min-1 cylinder-1
Oil Loss  0.05 cm3 min-1 cylinder-1
Sump
Residence Time  20 hours litre-1
M. S. Stark, R. J. Gamble, C. J. Hammond, et al., Tribology Letters, (in press) 2005

M. S. Stark, et al., Proceedings of the 31st Leeds-Lyon Symposium on Tribology, Sept 2004, (in press) 2005
Characterisation of Gasoline Engine
Piston Assembly
Residence Time  60 seconds
Volume of Oil  1 cm3 cylinder-1
Temperature  200 °C
Flow Rates
Returning to Sump  1 cm3 min-1 cylinder-1
Oil Loss  0.05 cm3 min-1 cylinder-1
Sump
Residence Time  20 hours litre-1
Temperature  70 °C
M. S. Stark, R. J. Gamble, C. J. Hammond, et al., Tribology Letters, (in press) 2005

M. S. Stark, et al., Proceedings of the 31st Leeds-Lyon Symposium on Tribology, Sept 2004, (in press) 2005
Hydrocarbon Degradation Chemistry
No. of Carbons
(random example) XHVI™ 8.2 (average) 39
Models of Hydrocarbon Base-Fluids
No. of Carbons
Hexadecane 16
Traditional Alkane Oxidation Mechanism
. .
+ ROO + ROOH
. .
+ ROO + ROOH
O
O
.
+ O2
. .
+ ROO + ROOH
O
O
.
+ O2
H
O O
O O
+
.
RH + R
. .
+ ROO + ROOH
O
O
.
+ O2
H
O O
O O
+
.
RH + R
H
O
O O
+ HO
. .
+ ROO + ROOH
O
O
.
+ O2
H
O O
O O
+
.
RH + R
H
O
O O
+ HO
H
O O
+ RH + R
.
. .
+ ROO + ROOH
O
O
.
+ O2
H
O O
O O
+
.
RH + R
H
O
O O
+ HO
H
O O
+ RH + R
.
H
O
O O
+ H2O
Hexadecane Oxidation
+ RO2. + O2
O H
O
Jensen et al, J. Am. Chem. Soc., 103, 1742 1981 and 101, 7574 1979 (Conditions : 120 – 180 °C)
+ RO2. + O2
O H
O
.
O
O
H
+ RO2. + O2
O H
O
+ O2
O O
O O
H
+ RO2. + O2
O H
O
+ O2
O O
O O
H
+ RH
O O
O O
H H
+ RO2. + O2
O H
O
+ O2
O O
O O
H
+ RH
O O
O O
H H
O O
H
No. of Carbons
Hexadecane 16
Pristane 19
No. of Carbons
Hexadecane 16
Pristane 19
Squalane 30
Tertiary Carbons in Base-Fluids
25
20
tertiary C (%)
15
10
0
isodewaxed
hydrocracked
Group I
Group II
PAO
Group III
Group III
range
S. McKenna, M. Casserino, K. Ratliff, Comparing the Tertiary Carbon Content of PAO’s and Mineral Oils
Presentation, STLE Annual Meeting, Houston, 2002
Tertiary Carbons in Base-Fluids
25
20
tertiary C (%)
15
10
Squalane
isodewaxed
hydrocracked
Group II
Group I
Pristane
PAO
Group III
Group III
range
S. McKenna, M. Casserino, K. Ratliff, Comparing the Tertiary Carbon Content of PAO’s and Mineral Oils
Presentation, STLE Annual Meeting, Houston, 2002
Bench-Top Reactors
Oxidation of Pristane : GC Analysis (polar)
Micro-reactor conditions: 1000 mbar O2, 200 ºC, 1 minute
GC conditions: Carbowax column, 50-250 ºC, 4 ºC min-1
OH
OH
Solvent (CH3OH)
time (min)
OH OH
Oxidation of Pristane : GC (non-polar)
Micro-reactor conditions: 1000 mbar O2, 200 ºC, 1 minute
GC conditions: ZB-5 column, 50-300 ºC, 6 ºC min-1
time (min) impurity
Oxidation of Pristane : Ketones
O
Ketones
time (min) impurity
Oxidation of Pristane : Ketones
O
O
time (min) impurity
Oxidation of Pristane : Alkanes
Alkane
time (min)
Oxidation of Pristane : Fragmentation
O + .
RH
time (min)
O +
time (min)
+ O
time (min)
Reactions of Alkyl Radicals
+ RH + .
R
+ RH + R .
.
+ O2 O
O .
+ RH + R .
.
+ O2 + RH
O
O . O
O
H
+ RH + R .
.
+ O2 + RH
O
O . O
O
H O
H + H2O
Formation of Carboxylic Acids
+ RH + R .
.
+ O2 + RH
O
O . O
O
H O
H + H2O
O + RO2.
O
.
H
+ RH + R .
.
+ O2 + RH
O
O . O
O
H O
H + H2O
+ RO2.
O O + O2
. O
H
O
.
O
+ RH + R .
.
+ O2 + RH
O
O . O
O
H O
H + H2O
+ RO2.
O O + O2 + RH
. O O
H
O
.
O
O
O
H
+ RH + R .
.
+ O2 + RH
O
O . O
O
H O
H + H2O
+ RO2.
O O + O2 + RH
. O O
H
O
.
O
O
O
H
O
H
Oxidation of Pristane : Alkenes
time (min)
Possible Mechanisms of Alkene Formation
+ H2O
O
H
O
H
H
O
+
O
O
H
H
O
+
O
+ H2O O
O
H
H
O
+
O
O O
H
+ H2O O O
O
H
H
O H
O
+
O
O
O O
H
+ H2O O O
Alkenes and Polymerisation
(+ ROO.)
Very Easy
.
Monomer
(+ ROO.)
Very Easy
.
Monomer
.
+ .
(+ ROO.)
Very Easy
.
Monomer
.
+ .
+ + R.
Conclusions
 Sampling of Lubricant from Piston Assembly
 Measurement of Lubricant Flow in Engine
 Measurement of Lubricant Degradation in Engine
 Chemical Mechanisms of Base Fluid Oxidation
Project Posters
 Peter Lee
Lubricant Degradation Studies Using a Single Cylinder Research Engine
• Engine Set-up and Modifications
 Julian Wilkinson
Understanding Lubricant Degradation in Gasoline Engines
• Oxidation Mechanisms of Model Base Fluids
• Viscosity Change During Hydrocarbon Oxidation
Acknowledgements
University of Leeds Richard Gamble, Chris Taylor, D. Desmonteix

University of York Chris Hammond, David Waddington, Trevor Dransfield
Shell Harold Gillespie, Eiji Nagatomi, Richard Dixon
Infineum Bénédicte Menguy
Financial Support
Shell Global Solutions, Infineum, EPSRC
Moray Stark mss1@york.ac.uk www.york.ac.uk/res/gkg

Additive 05 Moray Stark

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The Degradation of Lubricants in Gasoline Engines

Additives 2005 : Dublin 5th- 7th April 2005

John R. Lindsay Smith, Moray S. Stark,* Julian J. Wilkinson

Peter M. Lee, Martin Priest

Additives 2005 : Dublin 5th- 7th April 2005

John R. Lindsay Smith, Moray S. Stark,* Julian J. Wilkinson

Peter M. Lee, Martin Priest

nderstand Increase in Engine Friction with Oil Degradation

nderstand Increase in Engine Friction with Oil Degradation

Sampling of Lubricant from Piston Assembly

nderstand Increase in Engine Friction with Oil Degradation

Sampling of Lubricant from Piston Assembly

Measurement of Lubricant Flow in Engine

nderstand Increase in Engine Friction with Oil Degradation

Sampling of Lubricant from Piston Assembly

Measurement of Lubricant Flow in Engine

Measurement of Lubricant Degradation in Engine

nderstand Increase in Engine Friction with Oil Degradation

Sampling of Lubricant from Piston Assembly

Measurement of Lubricant Flow in Engine

Measurement of Lubricant Degradation in Engine

Chemical Mechanisms of Base Fluid Oxidation

Viscosity Increase in a Paris Taxi Fleet

Oil Change Oil Change

Engine Oil Stress Factor for Gasoline Cars : 1950 - 2000

R. I. Taylor, R. Mainwaring, R. M. Mortier, Engine Lubricant Trends Since 1990,

 Fuel Injected Gasoline

P. M. Lee, M. Priest, J. R. Lindsay Smith, M. S. Stark, J. J. Wilkinson, R. I. Taylor and S. Chung,

P. M. Lee, M. Priest, J. R. Lindsay Smith, M. S. Stark, J. J. Wilkinson, R. I. Taylor and S. Chung,

P. M. Lee, M. Priest, J. R. Lindsay Smith, M. S. Stark, J. J. Wilkinson, R. I. Taylor and S. Chung,

P. M. Lee, M. Priest, J. R. Lindsay Smith, M. S. Stark, J. J. Wilkinson, R. I. Taylor and S. Chung,

P. M. Lee, M. Priest, J. R. Lindsay Smith, M. S. Stark, J. J. Wilkinson, R. I. Taylor and S. Chung,

P. M. Lee, M. Priest, J. R. Lindsay Smith, M. S. Stark, J. J. Wilkinson, R. I. Taylor and S. Chung,

S. Yasutomi, Y. Maeda and T. Maeda, Kinetic Approach To Engine Oil .2.

R. Gamble, Influence of Lubricant Degradation on Piston Assembly Tribology,

M. S. Stark, R. J. Gamble, C. J. Hammond et al., Measurement of Lubricant Flow in a Gasoline Engine,

Top Ring Groove

1.2mm Diameter Hole

Top Ring Groove

R. Gamble, Influence of Lubricant Degradation on Piston Assembly Tribology,

P. M. Lee, M. Priest, J. R. Lindsay Smith, M. S. Stark, J. J. Wilkinson, R. I. Taylor and S. Chung,

Piston Small Volume

S. Yasutomi, Y. Maeda and T. Maeda, Kinetic Approach To Engine Oil .2.

Piston Sample Lubricant

Add Marker to Sump

S B Saville, F D Gainey, S D Cupples, M F Fox, D J Picken,

S B Saville, F D Gainey, S D Cupples, M F Fox, D J Picken,

Conditions : 1500 rpm, 50 % Load. Lubricant : XHVITM 8.2 only

Piston Small Volume

S. Yasutomi, Y. Maeda and T. Maeda, Kinetic Approach To Engine Oil .2.

M. S. Stark, J. J. Wilkinson, P. M. Lee, J. R. Lindsay Smith, M. Priest, R. I. Taylor and S. Chung,

M. S. Stark, J. J. Wilkinson, P. M. Lee, J. R. Lindsay Smith, M. Priest, R. I. Taylor and S. Chung,

M. S. Stark, J. J. Wilkinson, P. M. Lee, J. R. Lindsay Smith, M. Priest, R. I. Taylor and S. Chung,

Sump Residence Time (hours/litre)

M. S. Stark, R. J. Gamble, C. J. Hammond, et al., Tribology Letters, (in press) 2005

M. S. Stark, R. J. Gamble, C. J. Hammond, et al., Tribology Letters, (in press) 2005

(random example) XHVI™ 8.2 (average) 39

(random example) XHVI™ 8.2 (average) 39

(random example) XHVI™ 8.2 (average) 39

(random example) XHVI™ 8.2 (average) 39

GC conditions: Carbowax column, 50-250 ºC, 4 ºC min-1

GC conditions: ZB-5 column, 50-300 ºC, 6 ºC min-1

time (min) impurity