Abstract

To extend drain intervals and improve efficiency, new engine oils with increased dispersant concentration and reduced viscosity are required. Low viscosity engine oils can increase the prevalence of boundary friction at low temperature and increase its severity at higher temperatures. As a result, combinations of organic and inorganic friction modifiers (FM) will be used to reduce boundary friction across a range of temperatures, also preventing damage to vehicle catalysts. This paper presents an experimental case study of such a new generation of fully formulated engine lubricants with varying concentrations of polyisobutylene succinimide dispersant, organic, and inorganic FM. Representative conditions pertaining to those encountered at the top dead center reversal of the piston compression ring-cylinder liner contact are created, and the generated friction measured through use of a sliding-strip tribometry. Subsequently, X-ray photoelectron spectroscopy (XPS) is used to determine the composition of the formed surface tribofilms in order to explain the observed frictional characteristics. The key interactions and frictional behavior of the dispersant and friction modifiers are highlighted across a range of operating temperatures.

References

1.
Holmberg
,
K.
,
Andersson
,
P.
, and
Erdemir
,
A.
,
2012
, “
Global Energy Consumption Due to Friction in Passenger Cars
,”
Tribol. Int.
,
47
, pp.
221
234
. 10.1016/j.triboint.2011.11.022
2.
Uras
,
H. M.
, and
Patterson
,
D. J.
,
1983
, “
Measurement of Piston and Ring Assembly Friction Instantaneous IMEP Method
,”
SAE Technical Paper 830416
, pp.
1
14
.
3.
Spikes
,
H.
,
2015
, “
Friction Modifier Additives
,”
Tribol. Lett.
,
60
(
1
), p.
5
. 10.1007/s11249-015-0589-z
4.
Zhang
,
J.
, and
Spikes
,
H.
,
2016
, “
On the Mechanism of ZDDP Antiwear Film Formation
,”
Tribol. Lett.
,
63
(
2
), p.
24
. 10.1007/s11249-016-0706-7
5.
Umer
,
J.
,
Morris
,
N.
,
Leighton
,
M.
,
Rahmani
,
R.
,
Balakrishnan
,
S.
, and
Rahnejat
,
H.
,
2019
, “
Nano and Microscale Contact Characteristics of Tribofilms Derived From Fully Formulated Engine Oil
,”
Tribol. Int.
,
131
, pp.
620
630
. 10.1016/j.triboint.2018.11.007
6.
Leighton
,
M.
,
Nicholls
,
T.
,
De La Cruz
,
M.
,
Rahmani
,
R.
, and
Rahnejat
,
H.
,
2016
, “
Combined Lubricant–Surface System Perspective: Multi-Scale Numerical–Experimental Investigation
,”
Proc. Inst. Mech. Eng. Part J: J. Eng. Tribol.
,
231
(
7
), pp.
910
924
. 10.1177/1350650116683784
7.
Forder
,
M.
,
Umer
,
J.
,
Morris
,
N.
,
Rahmani
,
R.
,
Howell-Smith
,
S.
, and
Rahnejat
,
H.
,
2020
, “
Asperity Level Frictional Interactions of Cylinder Bore Materials and Lubricant Composition
,”
Proc. Inst. Mech. Eng. Part J: J. Eng. Tribol.
, pp.
1
8
.
8.
King
,
J.
,
2007
,
The King Review of Low-Carbon Cars Pt. 1., The Potential for CO2 Reduction
,
HMSO
,
London
.
9.
Holmberg
,
K.
, and
Erdemir
,
A.
,
2017
, “
Influence of Tribology on Global Energy Consumption, Costs and Emissions
,”
Friction
,
5
(
3
), pp.
263
284
. 10.1007/s40544-017-0183-5
10.
Gohar
,
R.
, and
Rahnejat
,
H.
,
2008
,
Fundamentals of Tribology
,
Imperial College Press
,
London
.
11.
Lenauer
,
C.
,
Tomastik
,
C.
,
Wopelka
,
T.
, and
Jech
,
M.
,
2015
, “
Piston Ring Wear and Cylinder Liner Tribofilm in Tribotests With Lubricants Artificially Altered With Ethanol Combustion Products
,”
Tribol. Int.
,
82
, pp.
415
422
. 10.1016/j.triboint.2014.04.034
12.
Bewsher
,
S. R.
,
Leighton
,
M.
,
Mohammadpour
,
M.
,
Rahnejat
,
H.
,
Offner
,
G.
, and
Knaus
,
O.
,
2019
, “
Boundary Friction Characterisation of a Used Cylinder Liner Subject to Fired Engine Conditions and Surface Deposition
,”
Tribol. Int.
,
131
, pp.
424
437
. 10.1016/j.triboint.2018.11.005
13.
Umer
,
J.
,
Morris
,
N.
,
Leighton
,
M.
,
Rahmani
,
R.
,
Howell-Smith
,
S.
,
Wild
,
R.
, and
Rahnejat
,
H.
,
2018
, “
Asperity Level Tribological Investigation of Automotive Bore Material and Coatings
,”
Tribol. Int.
,
117
, pp.
131
140
. 10.1016/j.triboint.2017.08.023
14.
Inoue
,
K.
, and
Watanabe
,
H.
,
1983
, “
Interactions of Engine Oil Additives
,”
Trans. ASLE
,
26
(
2
), pp.
189
199
. 10.1080/05698198308981493
15.
Barcroft
,
F. T.
, and
Park
,
D.
,
1986
, “
Interactions on Heated Metal Surfaces Between Zinc Dialkyldithiophosphates and Other Lubricating Oil Additives
,”
Wear
,
108
(
3
), pp.
213
234
. 10.1016/0043-1648(86)90002-5
16.
Zhang
,
J.
,
Yamaguchi
,
E.
, and
Spikes
,
H.
,
2014
, “
The Antagonism Between Succinimide Dispersants and a Secondary Zinc Dialkyl Dithiophosphate
,”
Tribol. Trans.
,
57
(
1
), pp.
57
65
. 10.1080/10402004.2013.845275
17.
Martin
,
J.
,
Grossiord
,
C.
,
Le Mogne
,
T.
, and
Igarashi
,
J.
,
2000
, “
Role of Nitrogen in Tribochemical Interaction Between Zndtp and Succinimide in Boundary Lubrication
,”
Tribol. Int.
,
33
(
7
), pp.
453
459
. 10.1016/S0301-679X(00)00073-6
18.
Gallopoulos
,
N. E.
, and
Murphy
,
C. K.
,
1971
, “
Interactions Between a Zinc Dialkylphosphorodithioate and Lubricating Oil Dispersants
,”
Trans. ASLE
,
14
(
1
), pp.
1
7
. 10.1080/05698197108983221
19.
Kapsa
,
P.
,
Martin
,
J. M.
,
Blanc
,
C.
, and
Georges
,
J. M.
,
1981
, “
Antiwear Mechanism of ZDDP in the Presence of Calcium Sulfonate Detergent
,”
ASME J. Tribol.
,
103
(
4
), pp.
486
494
. 10.1115/1.3251714
20.
Kasrai
,
M.
,
Fuller
,
M. S.
,
Bancroft
,
G. M.
, and
Ryason
,
P. R.
,
2003
, “
X-Ray Absorption Study of the Effect of Calcium Sulfonate on Antiwear Film Formation Generated From Neutral and Basic ZDDPs: Part 1—Phosphorus Species
,”
Tribol. Trans.
,
46
(
4
), pp.
534
542
. 10.1080/10402000308982660
21.
Najman
,
M.
,
Kasrai
,
M.
,
Bancroft
,
M. G.
, and
Davidson
,
R.
,
2006
, “
Combination of Ashless Antiwear Additives With Metallic Detergents: Interactions With Neutral and Overbased Calcium Sulfonates
,”
Tribol. Int.
,
39
(
4
), pp.
342
355
. 10.1016/j.triboint.2005.02.014
22.
Korcek
,
S.
,
Jensen
,
R. K.
,
Johnson
,
M. D.
, and
Sorab
,
J.
,
1999
, “
Fuel Efficient Engine Oils, Additive Interactions, Boundary Friction, and Wear
,”
Tribol. Ser.
,
36
, pp.
13
24
. 10.1016/S0167-8922(99)80024-8
23.
Ratoi
,
M.
,
Niste
,
V. B.
,
Alghawel
,
H.
,
Suen
,
Y. F.
, and
Nelson
,
K.
,
2014
, “
The Impact of Organic Friction Modifiers on Engine Oil Tribofilms
,”
RSC Adv.
,
4
(
9
), pp.
4278
4285
. 10.1039/C3RA46403B
24.
Tung
,
S. C.
, and
McMillan
,
M. L.
,
2004
, “
Automotive Tribology Overview of Current Advances and Challenges for the Future
,”
Tribol. Int.
,
37
(
7
), pp.
517
536
. 10.1016/j.triboint.2004.01.013
25.
Tang
,
Z.
, and
Li
,
S.
,
2014
, “
A Review of Recent Developments of Friction Modifiers for Liquid Lubricants (2007–Present)
,”
Curr. Opin. Solid State Mater. Sci.
,
18
(
3
), pp.
119
139
. 10.1016/j.cossms.2014.02.002
26.
De Barros
,
M. I.
,
Bouchet
,
J.
,
Raoult
,
I.
,
Le Mogne
,
T.
,
Martin
,
J. M.
,
Kasrai
,
M.
, and
Yamada
,
Y.
,
2003
, “
Friction Reduction by Metal Sulfides in Boundary Lubrication Studied by XPS and XANES Analyses
,”
Wear
,
254
(
9
), pp.
863
870
. 10.1016/S0043-1648(03)00237-0
27.
Grossiord
,
C.
,
Varlot
,
K.
,
Martin
,
J.-M.
,
Le Mogne
,
T.
,
Esnouf
,
C.
, and
Inoue
,
K.
,
1998
, “
MoS2 Single Sheet Lubrication by Molybdenum Dithiocarbamate
,”
Tribol. Int.
,
31
(
12
), pp.
737
743
. 10.1016/S0301-679X(98)00094-2
28.
Miklozic
,
K. T.
,
Graham
,
J.
, and
Spikes
,
H.
,
2001
, “
Chemical and Physical Analysis of Reaction Films Formed by Molybdenum Dialkyl-Dithiocarbamate Friction Modifier Additive Using Raman and Atomic Force Microscopy
,”
Tribol. Lett.
,
11
(
2
), pp.
71
81
. 10.1023/A:1016655316322
29.
Levine
,
O.
, and
Zisman
,
W. A.
,
1957
, “
Physical Properties of Monolayers Adsorbed at the Solid–Air Interface. I. Friction and Wettability of Aliphatic Polar Compounds and Effect of Halogenation
,”
J. Phys. Chem.
,
61
(
8
), pp.
1068
1077
. 10.1021/j150554a008
30.
Graham
,
J.
,
Spikes
,
H.
, and
Korcek
,
S.
,
2001
, “
The Friction Reducing Properties of Molybdenum Dialkyldithiocarbamate Additives: Part I—Factors Influencing Friction Reduction
,”
Tribol. Trans.
,
44
(
4
), pp.
626
636
. 10.1080/10402000108982504
31.
Gosvami
,
N. N.
,
Bares
,
J. A.
,
Mangolini
,
F.
,
Konicek
,
A. R.
,
Yablon
,
D. G.
, and
Carpick
,
R. W.
,
2015
, “
Mechanisms of Antiwear Tribofilm Growth Revealed In Situ by Single-Asperity Sliding Contacts
,”
Science
,
348
(
6230
), pp.
102
106
. 10.1126/science.1258788
32.
Lundgren
,
S. M.
,
Eriksson
,
K.
, and
Rossenaar
,
B.
,
2015
, “
Boosting the Friction Performance of Amine Friction Modifiers With MoDTC
,”
SAE Int. J. Fuels Lubr.
,
8
(
1
), pp.
27
30
. 10.4271/2015-01-0684
33.
Morina
,
A.
,
Neville
,
A.
,
Priest
,
M.
, and
Green
,
J. H.
,
2006
, “
ZDDP and MoDTC Interactions and Their Effect on Tribological Performance—Tribofilm Characteristics and Its Evolution
,”
Tribol. Lett.
,
24
(
3
), pp.
243
256
. 10.1007/s11249-006-9123-7
34.
Gandhi
,
H. S.
, and
Shelef
,
M.
,
1991
, “
Effects of Sulphur on Noble Metal Automotive Catalysts
,”
Appl. Catal.
,
77
(
2
), pp.
175
186
. 10.1016/0166-9834(91)80063-3
35.
Yan
,
L.
,
Yue
,
W.
,
Wang
,
C.
,
Wei
,
D.
, and
Xu
,
B.
,
2012
, “
Comparing Tribological Behaviors of Sulfur- and Phosphorus-Free Organomolybdenum Additive With ZDDP and MoDTC
,”
Tribol. Int.
,
53
, pp.
150
158
. 10.1016/j.triboint.2012.04.002
36.
Muraki
,
M.
,
Yanagi
,
Y.
, and
Sakaguchi
,
K.
,
1997
, “
Synergistic Effect on Frictional Characteristics Under Rolling-Sliding Conditions Due to a Combination of Molybdenum Dialkyldithiocarbamate and Zinc Dialkyldithiophosphate
,”
Tribol. Int.
,
30
(
1
), pp.
69
75
. 10.1016/0301-679X(96)00025-4
37.
Kasrai
,
M.
,
Cutler
,
J. N.
,
Gore
,
K.
,
Canning
,
G.
,
Bancroft
,
G. M.
, and
Tan
,
K. H.
,
1998
, “
The Chemistry of Antiwear Films Generated by the Combination of ZDDP and MoDTC Examined by X-ray Absorption Spectroscopy
,”
Tribol. Trans.
,
41
(
1
), pp.
69
77
. 10.1080/10402009808983723
38.
Miklozic
,
K. T.
,
Forbus
,
T. R.
, and
Spikes
,
H. A.
,
2007
, “
Performance of Friction Modifiers on ZDDP-Generated Surfaces
,”
Tribol. Trans.
,
50
(
3
), pp.
328
335
. 10.1080/10402000701413505
39.
Rounds
,
F.
,
1989
, “
Effect of Detergents on ZDP Antiwear Performance as Measured in Four-Ball Wear Tests
,”
Lubr. Eng.
,
45
(
12
), pp.
761
769
.
40.
Minami
,
I.
,
2017
, “
Molecular Science of Lubricant Additives
,”
Appl. Sci.
,
7
(
5
), p.
445
. 10.3390/app7050445
41.
Sniderman
,
D.
,
2017
, “
The Chemistry and Function of Lubricant Additives
,”
Tribol. Lubr. Technol.
,
73
(
11
), pp.
18
29
.
42.
Li
,
W.
,
Kumara
,
C.
,
Luo
,
H.
,
Meyer, III
,
H. M.
,
He
,
X.
,
Ngo
,
D.
,
Kim
,
S. H.
, and
Qu
,
J.
,
2020
, “
Ultralow Boundary Lubrication Friction by Three-Way Synergistic Interactions Among Ionic Liquid, Friction Modifier, and Dispersant
,”
ACS Appl. Mater. Interfaces
,
12
(
14
), pp.
17077
17090
. 10.1021/acsami.0c00980
43.
Johansson
,
S.
,
Nilsson
,
P. H.
,
Ohlsson
,
R.
, and
Rosén
,
B. G.
,
2011
, “
Experimental Friction Evaluation of Cylinder Liner/Piston Ring Contact
,”
Wear
,
271
(
3–4
), pp.
625
633
. 10.1016/j.wear.2010.08.028
44.
Umer
,
J.
,
Morris
,
N.
,
Rahmani
,
R.
,
Balakrishnan
,
S.
, and
Rahnejat
,
H.
,
2020
, “
Nanoscale Frictional Characterisation of Base and Fully Formulated Lubricants Based on Activation Energy Components
,”
Tribol. Int.
,
144
, p.
106115
. 10.1016/j.triboint.2019.106115
45.
Gore
,
M.
,
Morris
,
N.
,
Rahmani
,
R.
,
Rahnejat
,
H.
,
King
,
P. D.
, and
Howell-Smith
,
S.
,
2017
, “
A Combined Analytical-Experimental Investigation of Friction in Cylinder Liner Inserts Under Mixed and Boundary Regimes of Lubrication
,”
Lubr. Sci.
,
29
(
5
), pp.
293
316
. 10.1002/ls.1369
46.
Leighton
,
M.
,
Morris
,
N.
,
Rahmani
,
R.
, and
Rahnejat
,
H.
,
2017
, “
Surface Specific Asperity Model for Prediction of Friction in Boundary and Mixed Regimes of Lubrication
,”
Meccanica
,
52
(
1–2
), pp.
21
33
. 10.1007/s11012-016-0397-z
47.
ASTM standard D445
,
1996
,
Standard Test Method for Kinematic Viscosity of Transparent and Opaque Liquids
,
West Conshohocken, PA
.
48.
Morris
,
N.
,
Leighton
,
M.
,
De la Cruz
,
M.
,
Rahmani
,
R.
,
Rahnejat
,
H.
, and
Howell-Smith
,
S.
,
2015
, “
Combined Numerical and Experimental Investigation of the Micro-Hydrodynamics of Chevron-Based Textured Patterns Influencing Conjunctional Friction of Sliding Contact
,”
Proc. Inst. Mech. Eng. Part J: J. Eng. Tribol.
,
229
(
4
), pp.
316
335
. 10.1177/1350650114559996
49.
Wakuri
,
Y.
,
Hamatake
,
T.
,
Soejima
,
M.
, and
Kitahara
,
T.
,
1992
, “
Piston Ring Friction in Internal Combustion Engines
,”
Tribol. Int.
,
25
(
5
), pp.
299
308
. 10.1016/0301-679X(92)90027-K
50.
Diaby
,
M.
,
Sablier
,
M.
,
Le Negrate
,
A.
,
El Fassi
,
M.
, and
Bocquet
,
J.
,
2009
, “
Understanding Carbonaceous Deposit Formation Resulting From Engine Oil Degradation
,”
Carbon
,
47
(
2
), pp.
355
366
. 10.1016/j.carbon.2008.10.014
51.
Liu
,
W.
, and
Chen
,
S.
,
2000
, “
An Investigation of the Tribological Behaviour of Surface-Modified ZnS Nanoparticles in Liquid Paraffin
,”
Wear
,
238
(
2
), pp.
120
124
. 10.1016/S0043-1648(99)00344-0
52.
Bogunovic
,
L.
,
Zuenkeler
,
S.
,
Toensing
,
K.
, and
Anselmetti
,
D.
,
2015
, “
An Oil-Based Lubrication System Based on Nanoparticular TiO2 With Superior Friction and Wear Properties
,”
Tribol. Lett.
,
59
(
2
), pp.
1
12
. 10.1007/s11249-015-0557-7
53.
Humphrey
,
E.
,
Morris
,
N.
,
Leighton
,
M.
,
Rahmani
,
R.
, and
Rahnejat
,
H.
,
2018
, “
Multiscale Friction in Lubricant-Surface Systems for High-Performance Transmissions Under Mild Wear
,”
Tribol. Lett.
,
66
(
3
), pp.
1
13
. 10.1007/s11249-018-1032-z
54.
Spiller
,
S.
,
Lenauer
,
C.
,
Wopelka
,
T.
, and
Jech
,
M.
,
2017
, “
Real Time Durability of Tribofilms in the Piston Ring–Cylinder Liner Contact
,”
Tribol. Int.
,
113
, pp.
92
100
. 10.1016/j.triboint.2016.12.002
55.
Willermet
,
P. A.
,
1998
, “
Some Engine oil Additives and Their Effects on Antiwear Film Formation
,”
Tribol. Lett.
,
5
(
1
), pp.
41
47
. 10.1023/A:1019148415074
56.
Plaza
,
S.
,
1987
, “
The Effect of Other Lubricating Oil Additives on the Adsorption of Zinc Di-Isobutyldithiophosphate on Fe and γ-Fe2O3 Powders
,”
ASLE Trans.
,
30
(
2
), pp.
241
247
. 10.1080/05698198708981754
57.
Ramakumar
,
S. S. V.
,
Rao
,
A. M.
, and
Srivastava
,
S. P.
,
1992
, “
Studies on Additive-Additive Interactions: Formulation of Crankcase Oils Towards Rationalization
,”
Wear
,
156
(
1
), pp.
101
120
. 10.1016/0043-1648(92)90147-Z
58.
Morina
,
A.
,
Neville
,
A.
,
Priest
,
M.
, and
Green
,
J. H.
,
2006
, “
ZDDP and MoDTC Interactions in Boundary Lubrication—The Effect of Temperature and ZDDP/MoDTC Ratio
,”
Tribol. Int.
,
39
(
12
), pp.
1545
1557
. 10.1016/j.triboint.2006.03.001
59.
Morina
,
A.
, and
Neville
,
A.
,
2007
, “
Understanding the Composition and Low Friction Tribofilm Formation/Removal in Boundary Lubrication
,”
Tribol. Int.
,
40
(
10–12
), pp.
1696
1704
. 10.1016/j.triboint.2007.02.001
60.
Bouchet
,
M. D. B.
,
Martin
,
J. M.
,
Le Mogne
,
T.
,
Bilas
,
P.
,
Vacher
,
B.
, and
Yamada
,
Y.
,
2005
, “
Mechanisms of MoS2 Formation by MoDTC in Presence of ZnDTP: Effect of Oxidative Degradation
,”
Wear
,
258
(
11–12
), pp.
1643
1650
. 10.1016/j.wear.2004.11.019
61.
Martin
,
J. M.
,
Grossiord
,
C.
,
Varlot
,
K.
,
Vacher
,
B.
, and
Igarashi
,
J.
,
2000
, “
Synergistic Effects in Binary Systems of Lubricant Additives: A Chemical Hardness Approach
,”
Tribol. Lett.
,
8
(
4
), pp.
193
201
. 10.1023/A:1019147520893
62.
Khaemba
,
D. N.
,
Neville
,
A.
, and
Morina
,
A.
,
2016
, “
New Insights on the Decomposition Mechanism of Molybdenum DialkyldiThioCarbamate (MoDTC): A Raman Spectroscopic Study
,”
RSC Adv.
,
6
(
45
), pp.
38637
38646
. 10.1039/C6RA00652C
63.
Wei
,
J.
,
Xue
,
Q.
, and
Wang
,
H.
,
1993
, “
Effects of Anti-Wear Additives on Friction and Wear Properties of Cr2O3 Coating
,”
Tribol. Int.
,
26
(
4
), pp.
241
244
. 10.1016/0301-679X(93)90004-K
64.
Ghanbarzadeh
,
A.
,
Piras
,
E.
,
Nedelcu
,
I.
,
Brizmer
,
V.
,
Wilson
,
M. C. T.
,
Morina
,
A.
,
Dowson
,
D.
, and
Neville
,
A.
,
2016
, “
Zinc Dialkyl Dithiophosphate Antiwear Tribofilm and Its Effect on the Topography Evolution of Surfaces: A Numerical and Experimental Study
,”
Wear
,
362–363
, pp.
186
198
. 10.1016/j.wear.2016.06.004
You do not currently have access to this content.