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John R. Lindsay Smith, Moray S. Stark,* Julian J. WilkinsonDepartment of Chemistry, University of York, York YO10 5DD, UK
Peter M. Lee, Martin PriestSchool of Mechanical Engineering, University of Leeds, Leeds, LS2 9JT, UK
R. Ian TaylorShell Global Solutions, Chester, CH1 3SH, UK
Simon ChungInfineum UK Ltd., Milton Hill, Abingdon, Oxfordshire, OX13 6BB, UK
Additives 2005 : Dublin 5th- 7th April 2005
The Degradation of Lubricants in Gasoline Engines
Department of Chemistry
John R. Lindsay Smith, Moray S. Stark,* Julian J. WilkinsonDepartment of Chemistry, University of York, York YO10 5DD, UK
Peter M. Lee, Martin PriestSchool of Mechanical Engineering, University of Leeds, Leeds, LS2 9JT, UK
R. Ian TaylorShell Global Solutions, Chester, CH1 3SH, UK
Simon ChungInfineum UK Ltd., Milton Hill, Abingdon, Oxfordshire, OX13 6BB, UK
The Degradation of Lubricants in Gasoline Engines
mss1@york.ac.uk www.york.ac.uk/res/gkg
Additives 2005 : Dublin 5th- 7th April 2005
Understand Increase in Engine Friction with Oil Degradation
Department of Chemistry
The Degradation of Lubricants in Gasoline Engines
Understand Increase in Engine Friction with Oil Degradation
Sampling of Lubricant from Piston Assembly
Department of Chemistry
The Degradation of Lubricants in Gasoline Engines
Understand 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
Understand 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
Understand 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
The Degradation of Lubricants in Gasoline Engines
Department of Chemistry
0
5
10
15
0 10 20 30 40 50 60
Distance (1000 km)
Vk1
00 (
cSt)
Oil Change Oil Change
0
100
200
300
400
500
1940 1950 1960 1970 1980 1990 2000
Oil
Str
ess
Fac
tor
(kW
km
litr
e-2)
Engine Oil Stress Factor for Gasoline Cars : 1950 - 2000
The Degradation of Lubricants in Gasoline Engines
VolumeSump
IntervalDrainOil
ntDisplacemeEngine
PowerEngineFactorStressOil
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
© BP Castrol
Engine : Ricardo Hydra
Institute of Tribology
School of Mechanical Engineering ,The University of Leeds
Department of Chemistry
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)
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)
Sump 1
Valve Train
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 2
Piston Assembly
Crank Shaft
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 2
Piston Assembly
Crank Shaft
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
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
Sump
Piston
Sump
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
R. Gamble, Influence of Lubricant Degradation on Piston Assembly Tribology, PhD Thesis, University of Leeds, 2002
PTFE Tube
Piston
Connecting Rod
Top Ring Groove
Sample Collection
Top Ring Groove
Screw with 1mm Diameter Hole
1.2mm Diameter Hole
PTFE Tube
Collar
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
Small VolumeShort Residence Time
Large VolumeLong Residence Time
Flow Rate
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
Sump
Piston
Piston Assembly Residence Time: Method
Sump
Piston
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
Sample Lubricant from Piston Assembly
0
25
50
75
100
0 10 20 30 40 50
Time (arb)
Ma
rke
r (%
)Piston Assembly Residence Time: Method
)exp1(]marker[]marker[ RingPack
Time
sumpringpack
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
Piston Assembly Residence Time : 60 sec
M. S. Stark, R. J. Gamble, C. J. Hammond et al., Measurement of Lubricant Flow in a Gasoline Engine,Tribology Letters (in press) 2005
0
25
50
75
100
0 1 2 3 4 5
Time (min)
Ma
rke
r (%
)
)exp1(]marker[]marker[ RingPack
delayTime
sumpringpack
Conditions : 1500 rpm, 50 % Load. Lubricant : XHVITM 8.2 only
Piston Flow Rate: Method
Small VolumeShort Residence Time
Large VolumeLong Residence Time
Flow Rate
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
Sump
Piston
Oxidation Chemistry
Hydrocarbon Base Fluid
Hydroperoxides
Alcohols Carboxylic Acids Ketones
OO
H
OH
O
O H
O
+
Department of Chemistry
Oxidation Chemistry
Infrared Spectroscopyof Carbonyl Group
Hydrocarbon Base Fluid
Hydroperoxides
Alcohols Carboxylic Acids Ketones
OO
H
OH
O
O H
O
+
Department of Chemistry
Comparison of Sump and Ring Pack
Conditions : 2000 rpm, 50 % Load
0
2
4
6
8
10
0 60 120 180
Time (mins)
Car
bony
l (10
-3 m
ol /
litre
)
0.0
0.1
0.2
0.3TA
N (C
alculated)
Ring Pack
Sump (x10)
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
Conditions : 2000 rpm, 50 % Load
0
2
4
6
8
10
0 60 120 180
Time (mins)
Car
bony
l (10
-3 m
ol /
litre
)
0.0
0.1
0.2
0.3TA
N (C
alculated)
Ring Pack
Sump (x10)
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
0
2
4
6
8
10
0 60 120 180
Time (mins)
Car
bony
l (10
-3 m
ol /
litre
)
0.0
0.1
0.2
0.3TA
N (C
alculated)
Ring Pack
Sump (x10)
dt
d Sump
RingPackSUMP ]Product[
]Product[
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
dt
d Sump
RingPackSUMP ]Product[
]Product[ hours 549 SUMP
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)
0
2
4
6
8
10
0 60 120 180
Time (mins)
Car
bony
l (10
-3 m
ol /
litre
)
0.0
0.1
0.2
0.3TA
N (C
alculated)
Ring Pack
Sump (x10)
Calculation of Sump Residence Time
dt
d Sump
RingPackSUMP ]Product[
]Product[ -1litre hours 219 SUMP
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)
0
2
4
6
8
10
0 60 120 180
Time (mins)
Car
bony
l (10
-3 m
ol /
litre
)
0.0
0.1
0.2
0.3TA
N (C
alculated)
Ring Pack
Sump (x10)
Sump Residence Time : Engine Speed
Conditions : 1000 - 2000 rpm, 50 % Load
0
10
20
30
40
0 1000 2000
Engine Speed (rpm)
Su
mp
Re
sid
en
ce T
ime
(h
ou
rs/li
tre
)
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)
Piston AssemblyResidence Time 60 secondsVolume of Oil 1 cm3 cylinder-1
Flow RatesReturning to Sump 1 cm3 min-1 cylinder-1
Oil Loss 0.05 cm3 min-1 cylinder-1
SumpResidence Time 20 hours litre-1
Characterisation of Gasoline Engine
M. S. Stark, R. J. Gamble, C. J. Hammond, et al., Tribology Letters, (in press) 2005M. S. Stark, et al., Proceedings of the 31st Leeds-Lyon Symposium on Tribology, Sept 2004, (in press) 2005
Piston AssemblyResidence Time 60 secondsVolume of Oil 1 cm3 cylinder-1
Temperature 200 °C
Flow RatesReturning to Sump 1 cm3 min-1 cylinder-1
Oil Loss 0.05 cm3 min-1 cylinder-1
SumpResidence Time 20 hours litre-1 Temperature 70 °C
Characterisation of Gasoline Engine
M. S. Stark, R. J. Gamble, C. J. Hammond, et al., Tribology Letters, (in press) 2005M. S. Stark, et al., Proceedings of the 31st Leeds-Lyon Symposium on Tribology, Sept 2004, (in press) 2005
No. of Carbons
XHVI™ 8.2 (average) 39(random example)
Hydrocarbon Degradation Chemistry
Department of Chemistry
No. of Carbons
XHVI™ 8.2 (average) 39
Hexadecane 16
(random example)
Models of Hydrocarbon Base-Fluids
Department of Chemistry
+ ROO. .
+ ROOH
.+ O2
OO
OO
+ RH
OO
H
+ R.
Department of Chemistry
Traditional Alkane Oxidation Mechanism
+ ROO. .
+ ROOH
.+ O2
OO
OO
+ RH
OO
H
+ R.
OO
H
O
O + H
Department of Chemistry
Traditional Alkane Oxidation Mechanism
+ ROO. .
+ ROOH
.+ O2
OO
OO
+ RH
OO
H
+ R.
OO
H
O
O + H
O
+ RH
OH
+ R.
Department of Chemistry
Traditional Alkane Oxidation Mechanism
+ ROO. .
+ ROOH
.+ O2
OO
OO
+ RH
OO
H
+ R.
OO
H
O
O + H
O
+ RH
OH
+ R.
O
+ H2O
OO
H
Department of Chemistry
Traditional Alkane Oxidation Mechanism
Hexadecane Oxidation
Jensen et al, J. Am. Chem. Soc., 103, 1742 1981 and 101, 7574 1979 (Conditions : 120 – 180 °C)
OO H
+ RO2. + O2
Hexadecane Oxidation
Jensen et al, J. Am. Chem. Soc., 103, 1742 1981 and 101, 7574 1979 (Conditions : 120 – 180 °C)
OO H
+ RO2. + O2
OO
H
.
Hexadecane Oxidation
Jensen et al, J. Am. Chem. Soc., 103, 1742 1981 and 101, 7574 1979 (Conditions : 120 – 180 °C)
OO H
+ RO2. + O2
OO
H
OO
+ O2
Hexadecane Oxidation
Jensen et al, J. Am. Chem. Soc., 103, 1742 1981 and 101, 7574 1979 (Conditions : 120 – 180 °C)
OO H
+ RO2. + O2
OO
H
OO
+ O2
OO
H
OO
H
+ RH
Hexadecane Oxidation
Jensen et al, J. Am. Chem. Soc., 103, 1742 1981 and 101, 7574 1979 (Conditions : 120 – 180 °C)
OO H
+ RO2. + O2
OO
H
OO
+ O2
OO
H
OO
H
+ RH
O OH
No. of Carbons
XHVI™ 8.2 (average) 39
Hexadecane 16
Pristane 19
(random example)
Models of Hydrocarbon Base-Fluids
Department of Chemistry
No. of Carbons
XHVI™ 8.2 (average) 39
Hexadecane 16
Pristane 19
Squalane 30
(random example)
Models of Hydrocarbon Base-Fluids
Department of Chemistry
Tertiary Carbons in Base-Fluids
0
5
10
15
20
25
PA
O
Gro
up
III
iso
de
wa
xed
Gro
up
III
hyd
rocr
ack
ed
Gro
up
II
Gro
up
I
tert
iary
C (
%)
range
S. McKenna, M. Casserino, K. Ratliff, Comparing the Tertiary Carbon Content of PAO’s and Mineral OilsPresentation, STLE Annual Meeting, Houston, 2002
Tertiary Carbons in Base-Fluids
S. McKenna, M. Casserino, K. Ratliff, Comparing the Tertiary Carbon Content of PAO’s and Mineral OilsPresentation, STLE Annual Meeting, Houston, 2002
0
5
10
15
20
25
PA
O
Gro
up
III
iso
de
wa
xed
Gro
up
III
hyd
rocr
ack
ed
Gro
up
II
Gro
up
I
Sq
ua
lan
e
Pris
tan
e
tert
iary
C (
%)
range
time (min)OH OH
OH
OH
Solvent (CH3OH)
Oxidation of Pristane : GC Analysis (polar)
Department of Chemistry
Micro-reactor conditions: 1000 mbar O2, 200 ºC, 1 minute
GC conditions: Carbowax column, 50-250 ºC, 4 ºC min-1
time (min)
Department of Chemistry
Oxidation of Pristane : GC (non-polar)
impurity
Micro-reactor conditions: 1000 mbar O2, 200 ºC, 1 minute
GC conditions: ZB-5 column, 50-300 ºC, 6 ºC min-1
Department of Chemistry
Formation of Carboxylic Acids
.+ RH .+ R
OO
+ O2 . OO
H+ RH
O
H + H2O
O
H
+ RO2.
O.
Department of Chemistry
Formation of Carboxylic Acids
.+ RH .+ R
OO
+ O2 . OO
H+ RH
O
H + H2O
O
H
+ RO2.
O. O
OO.
+ O2
Department of Chemistry
Formation of Carboxylic Acids
.+ RH .+ R
OO
+ O2 . OO
H+ RH
O
H + H2O
O
H
+ RO2.
O. O
OO.
+ O2 O
OO
H
+ RH
Department of Chemistry
Formation of Carboxylic Acids
.+ RH .+ R
OO
+ O2 . OO
H+ RH
O
H + H2O
O
H
+ RO2.
O. O
OO.
+ O2 O
OO
H
+ RH
O
OH
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, Infineum, EPSRC
Moray Stark mss1@york.ac.uk www.york.ac.uk/res/gkg
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