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

2. 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 The Degradation of Lubricants in Gasoline Engines Part 1: Introduction, Lubricant Flow in Engine, Effects of Detergents 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 Sump Ring Pack Small Volume Short Residence Time Large Volume Long Residence Time Flow Rate S. Yasutomi, Y. Maeda, T. Maeda, Ind. Eng. Chem. Prod. Res. Dev., 20, 530, 1981

13. Ring Pack Residence Time 1-e -1  RingPac k 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 Submitted to Tribology Letters: M. S. Stark, R. J. Gamble, C. J. Hammond et al., 2004 Conditions : 1500 rpm, 50 % Load. Lubricant : XHVI TM 8.2 only

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

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

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

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

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

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

25. Oxidation in Ring Pack Comparison 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. Ring Pack Residence Time 60 ± 15 seconds Volume of Oil 0.30 ± 0.08 cm 3 Temperature  200 °C Flow Rates Into Ring Pack 0.32 ± 0.03 cm 3 min -1 Returning to Sump 0.27 ± 0.03 cm 3 min -1 Oil Loss 0.05 cm 3 min -1 Sump Residence Time 62 ± 6 hours/litre Temperature 70 °C Conditions: 1500 rpm, 50% Load. Lubricant, XHVI TM 8.2 only Characterisation of Ricardo Hydra Engine Submitted to Tribology Letters: M. S. Stark, R. J. Gamble, C. J. Hammond et al., 2004

33. Flow Rates Sump Residence Time (cm 3 min -1 ) (hours/litre) 50 % Load, No Detergent0.27 ± 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, XHVI TM 8.2 (Detergent: 2 % w/w Sulfonate) Lubricant Flow : Effect of Detergent 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. Institute of Tribology University of Leeds Peter M. Lee,* Martin Priest School of Mechanical Engineering, University of Leeds, Leeds, LS2 9JT, UK John R. Lindsay Smith, Moray S. Stark, Julian J. Wilkinson Department of Chemistry, University of York, York YO10 5DD, UK R. Ian Taylor Shell Global Solutions, Chester, CH1 3SH, UK Simon Chung Infineum UK Ltd., Milton Hill, Abingdon, Oxfordshire, OX13 6BB, UK The Degradation of Lubricants in Gasoline Engines STLE Annual Meeting : Toronto 17 th - 20 th May 2004

37. Part 2: A Study of the Link Between Base Oil Degradation and its Changing Rheological Properties Peter Leeefy7pml@leeds.ac.ukweb?? Peter M. Lee,* Martin Priest School of Mechanical Engineering, University of Leeds, Leeds, LS2 9JT, UK John R. Lindsay Smith, Moray S. Stark, Julian J. Wilkinson Department of Chemistry, University of York, York YO10 5DD, UK R. Ian Taylor Shell Global Solutions, Chester, CH1 3SH, UK Simon Chung Infineum UK Ltd., Milton Hill, Abingdon, Oxfordshire, OX13 6BB, UK The Degradation of Lubricants in Gasoline Engines

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

39. 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 The Degradation of Lubricants in Gasoline Engines Julian Wilkinson jjw102@york.ac.uk www.york.ac.uk/res/gkg Part 3: Chemical Mechanisms for the Oxidation of Branched Alkanes

40. Abstract for STLE Conference Toronto, May 2004 The Degradation of Lubricants in Gasoline Engines: Part 1: A Combined Tribological, Rheological and Chemical Model for Lubrication Degradation in the Piston Ring Pack Moray S. Stark*, John R. Lindsay Smith, 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, Shell Research Ltd, PO Box 1, Chester, CH1 3SH, UK Simon Chung Infineum UK Limited, PO Box 1, Milton Hill, Abingdon, Oxfordshire, OX13 6BB, UK The automotive industry requires lubricants that will have longer drain intervals and higher performance (such as lower component wear and increased fuel economy) and this must be achieved within ever tightening compositional constraints, for example, reduced phosphorus levels. To help the design of the next generation of lubricants, this project is studying the fundamental behaviour of lubricants in gasoline engines. A detailed tribological model of the oil flow in the piston ring pack has been constructed. This is combined with a detailed chemical model describing the oxidation of the hydrocarbon base fluid and a rheological model that describes how lubricant degradation products affect the viscosity of the oil. The predicted viscosity change of the lubricant during use feeds back into the tribological model to give a prediction of the change in performance of the lubricant in the engine as the oil degrades. This talk will discuss the progress made on this project, and experiments that have been done to verify the models. * Biography for Presenting Author Moray Stark has a BSc and PhD in Physics, but has been working as a Chemist for longer than he can remember. The past few years have been spent specialising in the study of the oxidation mechanisms of hydrocarbon and ester lubricant base fluids, and the effects that oxidation products have on the rheology of lubricants. This work is sponsored by Shell Global Solutions (UK) and Infineum.

41. 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, Shell Research Ltd., Chester, CH1 3SH, UK Simon Chung Infineum UK Ltd., Milton Hill, Abingdon, Oxfordshire, OX13 6BB, UK The Degradation of Lubricants in Gasoline Engines Part 1: A Combined Tribological, Rheological and Chemical Model for Lubrication Degradation in the Piston Ring Pack STLE Annual Meeting : Toronto 16 th - 20 th May 2004

42. Sedimentation of XHVI 8.2 + Detergent Department of Chemistry