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

The Degradation of Lubricants in Gasoline Engines. STLE Annual Meeting : Toronto 17 th - 20 th May 2004. 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

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

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  1. The Degradation of Lubricants in Gasoline Engines STLE Annual Meeting : Toronto 17th- 20th May 2004 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

  2. The Degradation of Lubricants in Gasoline Engines Part 1: Introduction, Lubricant Flow in Engine, Effects of Detergents 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 Moray Stark mss1@york.ac.uk www.york.ac.uk/res/gkg

  3. Aims • To Predict Increase in Piston Friction with Oil Degradation • Chemical Model for Base Fluid Oxidation • Rheological Model for Increase in Viscosity • Tribological Model for Piston Friction • To Develop Bench-top Reactors that Mimic • the Piston Ring Pack Department of Chemistry

  4. Introduction to Project • This Talk: • Introduction to Project • Fluid Flow in Engine • Effects of Detergent • Next Talk: (Peter Lee) • Tribology of Project • Engine Modifications • Enhanced Degradation Tests • Third Talk: (Julian Wilkinson) • Chemical Models of Hydrocarbon Base Fluids • Chemical Mechanisms of Base Fluid Oxidation Department of Chemistry

  5. Engine : Ricardo Hydra • Fuel Injected Gasoline • Single Cylinder • 0.5 litre Capacity Department of Chemistry

  6. Engine : Ricardo Hydra • Fuel Injected Gasoline • Single Cylinder • 0.5 litre Capacity Engine Conditions • 1000 - 2000 rpm • 33% - 75% Load Department of Chemistry

  7. Engine : Ricardo Hydra • Fuel Injected Gasoline • Single Cylinder • 0.5 litre Capacity Engine Conditions • 1000 - 2000 rpm • 33% - 75% Load • Engine Modifications • External Sump (70 - 80 ºC) • Sampling of Ring Pack Lubricant Department of Chemistry

  8. Lubricant Specification Build up complexity of Lubricant Base Fluid only Base Fluid : Shell XHVI ™ 8.2 Department of Chemistry

  9. Lubricant Specification Build up complexity of Lubricant Base Fluid only Base Fluid + Detergent (2 % w/w) Base Fluid : Shell XHVI ™ 8.2 Detergent : Neutral Alkyl Sulfonate Department of Chemistry

  10. Lubricant Specification Build up complexity of Lubricant Base Fluid only Base Fluid + Detergent (2 % w/w) Base Fluid + Detergent (2 % w/w) + Dispersant (2 % w/w) Base Fluid : Shell XHVI ™ 8.2 Detergent : Neutral Alkyl Sulfonate Dispersant : Alkyl Succinimide Department of Chemistry

  11. Extraction of Oil from Top Piston Ring Department of Chemistry

  12. Oil Flow in Engine Small Volume Short Residence Time Ring Pack Flow Rate Large Volume Long Residence Time Sump S. Yasutomi, Y. Maeda, T. Maeda, Ind. Eng. Chem. Prod. Res. Dev., 20, 530, 1981

  13. Ring Pack Residence Time 1-e-1 RingPack 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

  14. Ring Pack Residence Time : 60 sec Conditions : 1500 rpm, 50 % Load. Lubricant : XHVITM 8.2 only Submitted to Tribology Letters: M. S. Stark, R. J. Gamble, C. J. Hammond et al., 2004

  15. Oxidation Chemistry Hydrocarbon Base Fluid Department of Chemistry

  16. Oxidation Chemistry Hydrocarbon Base Fluid Hydroperoxides Department of Chemistry

  17. Oxidation Chemistry Hydrocarbon Base Fluid Hydroperoxides Alcohols Department of Chemistry

  18. Oxidation Chemistry Hydrocarbon Base Fluid Hydroperoxides Alcohols Carboxylic Acids Ketones Department of Chemistry

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

  20. Oil Flow and Chemistry in Engine High Temperature Small Volume Short Residence Time Ring Pack Low Temperature Large Volume Long Residence Time Sump Department of Chemistry

  21. Oxidation in Ring Pack : Carbonyl IR Conditions : 1500 rpm, 50 % Load. Lubricant : XHVITM 8.2 only Submitted to Tribology Letters: M. S. Stark, R. J. Gamble, C. J. Hammond et al., 2004

  22. Oxidation in Ring Pack : Carbonyl IR vs TAN Conditions : 1500 rpm, 50 % Load. Lubricant : XHVITM 8.2 only Submitted to Tribology Letters: M. S. Stark, R. J. Gamble, C. J. Hammond et al., 2004

  23. Effect of Detergent on Ring Pack Oxidation Conditions : 1500 rpm, 33 - 75 % Load Lubricant : XHVITM 8.2 (Detergent: 2 % w/w Sulfonate)

  24. Effect of Engine Conditions : Load Conditions : 1500 rpm, 33 - 75 % load Lubricant : XHVITM 8.2. Detergent: 2 % w/w Sulfonate

  25. Oxidation in Ring PackComparison with Previous Work 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

  26. Sump Residence Time and Oil Flow Rates Department of Chemistry

  27. Sump Residence Time and Oil Flow Rates Department of Chemistry

  28. Sump Residence Time and Oil Flow Rates Department of Chemistry

  29. Sump Residence Time and Oil Flow Rates Department of Chemistry

  30. Sump Residence Time and Oil Flow Rates Department of Chemistry

  31. Sump Residence Time and Oil Flow Rates

  32. Characterisation of Ricardo Hydra Engine Ring Pack Residence Time 60 ± 15 seconds Volume of Oil 0.30 ± 0.08 cm3 Temperature  200 °C Flow Rates Into Ring Pack 0.32 ± 0.03 cm3 min-1 Returning to Sump 0.27 ± 0.03 cm3 min-1 Oil Loss 0.05 cm3 min-1 Sump Residence Time 62 ± 6 hours/litre Temperature 70 °C Conditions: 1500 rpm, 50% Load. Lubricant, XHVITM 8.2 only Submitted to Tribology Letters: M. S. Stark, R. J. Gamble, C. J. Hammond et al., 2004

  33. Lubricant Flow : Effect of Detergent Flow Rates Sump Residence Time (cm3 min-1) (hours/litre) 50 % Load, No Detergent 0.27 ± 0.03 62 ± 6 33 % Load, 2 % Detergent 0.69 ± 0.07 24 ± 3 50 % Load, 2 % Detergent 0.74 ± 0.08 22 ± 2 75 % Load, 2 % Detergent 0.54 ± 0.06 30 ± 3 Conditions: 1500 rpm, 33 % - 75 % Load Lubricant, XHVITM 8.2 (Detergent: 2 % w/w Sulfonate) Department of Chemistry

  34. Conclusions • Lubricant Flow in Gasoline Engine Measured • Effects of Detergent Established Department of Chemistry

  35. Conclusions • Lubricant Flow in Gasoline Engine Measured • Effects of Detergent Established • Acknowledgements • Shell Global Solutions Moray Stark mss1@york.ac.uk www.york.ac.uk/res/gkg

  36. Sedimentation of XHVI 8.2 + Detergent Department of Chemistry

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