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


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_at_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_at_york.ac.uk
www.york.ac.uk/res/gkg
36
The Degradation of Lubricants in Gasoline Engines
STLE Annual Meeting Toronto 17th- 20th May 2004
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
Institute of Tribology
University of Leeds
37
The Degradation of Lubricants in Gasoline Engines
Part 2 A Study of the Link Between Base Oil
Degradation and its Changing Rheological
Properties
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
Peter Lee efy7pml_at_leeds.ac.uk web??

38
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
39
The Degradation of Lubricants in Gasoline Engines
Part 3 Chemical Mechanisms for the Oxidation of
Branched Alkanes
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
Julian Wilkinson jjw102_at_york.ac.uk
www.york.ac.uk/res/gkg
40
Abstract for STLE Conference Toronto, May 2004
The Degradation of Lubricants in Gasoline
EnginesPart 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
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 16th- 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, Shell Research
Ltd., Chester, CH1 3SH, UK Simon Chung Infineum
UK Ltd., Milton Hill, Abingdon, Oxfordshire, OX13
6BB, UK
42
Sedimentation of XHVI 8.2 Detergent
Department of Chemistry
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