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

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


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

Additives 2005 : Dublin 5th- 7th April 2005

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



Viscosity Increase in a Paris Taxi Fleet



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


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


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)





Sump 1

Valve Train



Sump 1

Valve Train

Sump 2

Piston Assembly

Crank Shaft



Sump 2

Piston Assembly

Crank Shaft

Degradation of Lubricant

Piston Assembly

Sump


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


Oil Flow in Engine

Small VolumeShort Residence Time

Large VolumeLong Residence Time

Flow Rate


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


Sump

Piston

Oxidation Chemistry

Hydrocarbon Base Fluid(schematic)


Oxidation Chemistry

Hydrocarbon Base Fluid

HydroperoxidesO

O

H


Oxidation Chemistry


Hydroperoxides

Alcohols

OO

H

OH


Oxidation Chemistry


Hydroperoxides

Alcohols Carboxylic Acids Ketones

OO

H

OH

O

O H

O

+


Oxidation Chemistry

Infrared Spectroscopyof Carbonyl Group


Hydroperoxides

Alcohols Carboxylic Acids Ketones

OO

H

OH

O

O H

O

+


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)


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[



dt

d Sump


]Product[ hours 549 SUMP


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


]Product[ -1litre hours 219 SUMP


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

)


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


No. of Carbons

XHVI™ 8.2 (average) 39

Hexadecane 16

(random example)

Models of Hydrocarbon Base-Fluids


+ ROO. .

+ ROOH


Traditional Alkane Oxidation Mechanism

+ ROO. .

+ ROOH

.+ O2

OO



+ ROO. .

+ ROOH

.+ O2

OO

OO

+ RH

OO

H

+ R.



+ ROO. .

+ ROOH

.+ O2

OO

OO

+ RH

OO

H

+ R.

OO

H

O

O + H



+ ROO. .

+ ROOH

.+ O2

OO

OO

+ RH

OO

H

+ R.

OO

H

O

O + H

O

+ RH

OH

+ R.



+ ROO. .

+ ROOH

.+ O2

OO

OO

+ RH

OO

H

+ R.

OO

H

O

O + H

O

+ RH

OH

+ R.

O

+ H2O

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

+ RO2. + O2

OO

H

.



OO H

+ RO2. + O2

OO

H

OO

+ O2



OO H

+ RO2. + O2

OO

H

OO

+ O2

OO

H

OO

H

+ RH



OO H

+ RO2. + O2

OO

H

OO

+ O2

OO

H

OO

H

+ RH

O OH

No. of Carbons


Hexadecane 16

Pristane 19

(random example)



No. of Carbons


Hexadecane 16

Pristane 19

Squalane 30

(random example)



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

Bench-Top Reactors


time (min)OH OH

OH

OH

Solvent (CH3OH)

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

time (min)


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

time (min)

OKetones

impurity


Oxidation of Pristane : Ketones

time (min)

O

O

O

O


impurity

Oxidation of Pristane : Ketones

time (min)

Alkane


Oxidation of Pristane : Alkanes

time (min)

O

O

+ .

RH


Oxidation of Pristane : Fragmentation

O

time (min)

O



+

O

time (min)

O



+


Reactions of Alkyl Radicals

.+ RH .+ R



.+ RH .+ R

OO

+ O2 .



.+ RH .+ R

OO

+ O2 . OO

H+ RH



.+ RH .+ R

OO

+ O2 . OO

H+ RH

O

H + H2O


Formation of Carboxylic Acids

.+ RH .+ R

OO

+ O2 . OO

H+ RH

O

H + H2O

O

H

+ RO2.

O.



.+ RH .+ R

OO

+ O2 . OO

H+ RH

O

H + H2O

O

H

+ RO2.

O. O

OO.

+ O2



.+ RH .+ R

OO

+ O2 . OO

H+ RH

O

H + H2O

O

H

+ RO2.

O. O

OO.

+ O2 O

OO

H

+ RH



.+ RH .+ R

OO

+ O2 . OO

H+ RH

O

H + H2O

O

H

+ RO2.

O. O

OO.

+ O2 O

OO

H

+ RH

O

OH

time (min)


Oxidation of Pristane : Alkenes


Possible Mechanisms of Alkene Formation

+ H2O

OH



OH

O

O

H

+



O

O

OH

O

O

H

+

+ H2O



O

O

OH

O

O

H

+

+ H2O

O

O

H



O

O

OH

O

O

H

+

+ H2O

O

O

H

O

O

H

Very Easy

.Monomer


Alkenes and Polymerisation

(+ ROO.)

.+ .

Very Easy

.Monomer



(+ ROO.)

.+ .

Very Easy

.Monomer



(+ ROO.)

+

.

R

R.+

Conclusions




Chemical Mechanisms of Base Fluid Oxidation


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


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

Documents

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