The Degradation of Lubricants in Gasoline Engines Additives 2005

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

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 [email protected] www.york.ac.uk/res/gkg

The Degradation of Lubricants in Gasoline Engines nderstand Increase in Engine Friction with Oil Degradation Department of Chemistry

The Degradation of Lubricants in Gasoline Engines nderstand Increase in Engine Friction with Oil Degradation Sampling of Lubricant from Piston Assembly Department of Chemistry

The Degradation of Lubricants in Gasoline Engines nderstand Increase in Engine Friction with Oil Degradation Sampling of Lubricant from Piston Assembly Measurement of Lubricant Flow in Engine Department of Chemistry

The Degradation of Lubricants in Gasoline Engines 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 Department of Chemistry

The Degradation of Lubricants in Gasoline Engines 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 Department of Chemistry

The Degradation of Lubricants in Gasoline Engines Viscosity Increase in a Paris Taxi Fleet Vk100 (cSt) 15 10 5 Oil Change 0 0 10 20 30 Oil Change 40 Distance (1000 km) Department of Chemistry 50 60

The Degradation of Lubricants in Gasoline Engines Engine Oil Stress Factor for Gasoline Cars : 1950 - 2000 -2 Oil Stress Factor (kW km litre ) Oil Drain Interval Engine Power Oil Stress Factor Engine Displacement Sump Volume 500 400 300 200 100 0 1940 1950 1960 1970 1980 1990 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 2000 BP Castrol

Engine : Ricardo Hydra Institute of Tribology School of Mechanical Engineering ,The University of Leeds Fuel Injected Gasoline Single Cylinder 0.5 litre Capacity Department of Chemistry

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)

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)

Lubrication of Engine Sump 1 Valve Train 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)

Lubrication of Engine Sump 1 Valve Train Sump 2 Piston Assembly Crank Shaft 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)

Lubrication of Engine Sump 2 Piston Assembly Crank Shaft 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)

Degradation of Lubricant Piston Assembly Sump 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)

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 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)

Oil Flow in Engine Piston Small Volume Short Residence Time Flow Rate Sump Large Volume Long Residence Time 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 Residence Time: Method Piston Sump Sample Lubricant from Piston Assembly Add Marker to 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 [ marker]ringpack [marker]sump (1 exp Time RingPack ) 100 Marker (%) 75 1-e-1 50 25 0 0 10RingPack 20 30 40 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 50

Piston Assembly Residence Time : 60 sec [marker]ringpack [marker]sump (1 exp Time delay RingPack ) 100 Marker (%) 75 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 Sump Large Volume Long Residence Time 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

Oxidation Chemistry Hydrocarbon Base Fluid (schematic) Department of Chemistry

Oxidation Chemistry Hydrocarbon Base Fluid Hydroperoxides O O H Department of Chemistry

Oxidation Chemistry Hydrocarbon Base Fluid Hydroperoxides O O H O Alcohols Department of Chemistry H

Oxidation Chemistry Hydrocarbon Base Fluid Hydroperoxides O O H O O Alcohols Department of Chemistry H O H Carboxylic Acids O Ketones

Oxidation Chemistry Hydrocarbon Base Fluid Hydroperoxides O O H O O Alcohols H O H Carboxylic Acids O Ketones Infrared Spectroscopy of Carbonyl Group Department of Chemistry

Comparison of Sump and Ring Pack 0.3 8 6 0.2 4 0.1 2 Ring Pack Sump (x10) 0 0 60 120 TAN (Calculated) Carbonyl (10-3 mol / litre) 10 0.0 180 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, Proceedings of the 31st Leeds-Lyon Symposium on Tribology, Sept 2004, Elsevier, 2005 (in press)

Comparison of Sump and Ring Pack 0.3 8 6 0.2 4 0.1 2 Ring Pack Sump (x10) 0 0 60 120 TAN (Calculated) Carbonyl (10-3 mol / litre) 10 0.0 180 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, Proceedings of the 31st Leeds-Lyon Symposium on Tribology, Sept 2004, Elsevier, 2005 (in press)

Calculation of Sump Residence Time SUMP [Product]RingPack d [Product ]Sump dt -3 0.3 8 6 0.2 4 0.1 2 Ring Pack Sump (x10) 0 0 60 120 TAN (Calculated) Carbonyl (10 mol / litre) 10 0.0 180 Time (mins) M. S. Stark, J. J. Wilkinson, P. M. Lee, J. R. Lindsay Smith, M. Priest, R. I. Taylor and S. Chung, Proceedings of the 31st Leeds-Lyon Symposium on Tribology, Sept 2004, Elsevier, 2005 (in press)

Calculation of Sump Residence Time SUMP [Product]RingPack d [Product ]Sump dt SUMP 49 5 hours -3 0.3 8 6 0.2 4 0.1 2 Ring Pack Sump (x10) 0 0 60 120 TAN (Calculated) Carbonyl (10 mol / litre) 10 0.0 180 Time (mins) M. S. Stark, J. J. Wilkinson, P. M. Lee, J. R. Lindsay Smith, M. Priest, R. I. Taylor and S. Chung, Proceedings of the 31st Leeds-Lyon Symposium on Tribology, Sept 2004, Elsevier, 2005 (in press)

Calculation of Sump Residence Time SUMP [Product]RingPack d [Product ]Sump dt SUMP 19 2 hours litre-1 -3 0.3 8 6 0.2 4 0.1 2 Ring Pack Sump (x10) 0 0 60 120 TAN (Calculated) Carbonyl (10 mol / litre) 10 0.0 180 Time (mins) M. S. Stark, J. J. Wilkinson, P. M. Lee, J. R. Lindsay Smith, M. Priest, R. I. Taylor and S. Chung, Proceedings of the 31st Leeds-Lyon Symposium on Tribology, Sept 2004, Elsevier, 2005 (in press)

Sump Residence Time (hours/litre) Sump Residence Time : Engine Speed 40 30 20 10 0 0 1000 Engine Speed (rpm) 2000 Conditions : 1000 - 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, Proceedings of the 31st Leeds-Lyon Symposium on Tribology, Sept 2004, Elsevier, 2005 (in press)

Characterisation of Gasoline Engine Piston Assembly Residence Time Volume of Oil Flow Rates Returning to Sump Oil Loss 1 cm3 min-1 cylinder-1 0.05 cm3 min-1 cylinder-1 Sump Residence Time 60 seconds 1 cm3 cylinder-1 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 Volume of Oil Temperature 60 seconds 1 cm3 cylinder-1 200 C Flow Rates Returning to Sump Oil Loss 1 cm3 min-1 cylinder-1 0.05 cm3 min-1 cylinder-1 Sump Residence Time Temperature 20 hours litre-1 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) Department of Chemistry XHVI 8.2 (average) 39

Models of Hydrocarbon Base-Fluids No. of Carbons (random example) Department of Chemistry XHVI 8.2 (average) 39 Hexadecane 16

Traditional Alkane Oxidation Mechanism Department of Chemistry ROO . . ROOH

Traditional Alkane Oxidation Mechanism . Department of Chemistry ROO . . O O2 O ROOH

Traditional Alkane Oxidation Mechanism ROO . . O . ROOH O O2 H O O O Department of Chemistry RH O R .

Traditional Alkane Oxidation Mechanism ROO . . O . ROOH O O2 H O O O RH O . R HO H O O Department of Chemistry O

Traditional Alkane Oxidation Mechanism ROO . . O . ROOH O O2 H O O O O RH . R HO R H O O O H O O Department of Chemistry RH .

Traditional Alkane Oxidation Mechanism ROO . . O . ROOH O O2 H O O O O RH . R HO R H2O H O O O H O O H O O Department of Chemistry RH . O

Hexadecane Oxidation RO2. O2 O Jensen et al, J. Am. Chem. Soc., 103, 1742 1981 and 101, 7574 1979 O H (Conditions : 120 – 180 C)

Hexadecane Oxidation RO2. O2 O O H . O O H Jensen et al, J. Am. Chem. Soc., 103, 1742 1981 and 101, 7574 1979 (Conditions : 120 – 180 C)

Hexadecane Oxidation RO2. O2 O O H O2 O O O O H Jensen et al, J. Am. Chem. Soc., 103, 1742 1981 and 101, 7574 1979 (Conditions : 120 – 180 C)

Hexadecane Oxidation RO2. O2 O O H O2 O O O O O O H RH O H Jensen et al, J. Am. Chem. Soc., 103, 1742 1981 and 101, 7574 1979 O H (Conditions : 120 – 180 C)

Hexadecane Oxidation RO2. O2 O O H O2 O O O O O O H RH O O H H O O H Jensen et al, J. Am. Chem. Soc., 103, 1742 1981 and 101, 7574 1979 (Conditions : 120 – 180 C)

Models of Hydrocarbon Base-Fluids No. of Carbons (random example) Department of Chemistry XHVI 8.2 (average) 39 Hexadecane 16 Pristane 19

Models of Hydrocarbon Base-Fluids No. of Carbons (random example) Department of Chemistry XHVI 8.2 (average) 39 Hexadecane 16 Pristane 19 Squalane 30

Tertiary Carbons in Base-Fluids tertiary C (%) 25 20 15 10 5 Group I Group II Group III hydrocracked Group III isodewaxed PAO 0 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 tertiary C (%) 25 20 15 10 5 Pristane Squalane Group I Group II Group III hydrocracked Group III isodewaxed PAO 0 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 Department of Chemistry

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 Department of Chemistry 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) Department of Chemistry impurity

Oxidation of Pristane : Ketones O Ketones time (min) Department of Chemistry impurity

Oxidation of Pristane : Ketones O O O O time (min) Department of Chemistry impurity

Oxidation of Pristane : Alkanes Alkane time (min) Department of Chemistry

Oxidation of Pristane : Fragmentation O O . RH time (min) Department of Chemistry

Oxidation of Pristane : Fragmentation O O time (min) Department of Chemistry

Oxidation of Pristane : Fragmentation O O time (min) Department of Chemistry

Reactions of Alkyl Radicals . RH Department of Chemistry . R

Reactions of Alkyl Radicals . RH O2 Department of Chemistry O . R O .

Reactions of Alkyl Radicals . RH O2 Department of Chemistry O . R O . RH O O H

Reactions of Alkyl Radicals . RH O2 O . R O . RH O O O H H Department of Chemistry H2O

Formation of Carboxylic Acids . RH O2 O . R O . RH O O O H H O RO2. H Department of Chemistry . O H2O

Formation of Carboxylic Acids . RH O2 O . R O . RH O O O H H O RO2. H Department of Chemistry . O O2 O O . O H2O

Formation of Carboxylic Acids . RH O2 O . R O . RH O O O H H O RO2. H Department of Chemistry . O O2 O O . O RH O O O H H2O

Formation of Carboxylic Acids . RH O2 O . R O . RH O O O H H O RO2. H . O O2 O O . O RH O O O O O Department of Chemistry H H H2O

Oxidation of Pristane : Alkenes time (min) Department of Chemistry

Possible Mechanisms of Alkene Formation O Department of Chemistry H H2O

Possible Mechanisms of Alkene Formation O H O Department of Chemistry H O

Possible Mechanisms of Alkene Formation O H O O H2O O Department of Chemistry H O

Possible Mechanisms of Alkene Formation O H O O O H2O H O Department of Chemistry H O O

Possible Mechanisms of Alkene Formation O H H O O O H2O H O Department of Chemistry O H O O O

Alkenes and Polymerisation ( ROO.) Very Easy . Monomer Department of Chemistry

Alkenes and Polymerisation ( ROO.) Very Easy . Monomer . Department of Chemistry .

Alkenes and Polymerisation ( ROO.) Very Easy . Monomer . . R. R . Department of Chemistry

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 Department of Chemistry

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 Department of Chemistry

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, Moray Stark Infineum, [email protected] EPSRC www.york.ac.uk/res/gkg