Tribofilm Formation & Friction Modification in Engine Oils

ENERGY TECHNOLOGIES
Tribofilm Formation & Friction Modification in Engine Oils

David Gillespie
TM
Smart Science to Improve Lives
2
TODAY’S PRESENTER
Dr David Gillespie
Lead Applications Scientist
ENERGY TECHNOLOGIES
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CONTENTS
1 Sustainability drivers
2 Friction modifiers
3 Experimental techniques
4 Interaction of PFMs and MoDTC
5 Conclusions and Q&A
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UN 17 SUSTAINABLE DEVELOPMENT GOALS

1st January 2016, 2030 Agenda for Sustainable Development
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CARBON FOOTPRINT
Scope 1, 2 and 3 Carbon
Scope 1
Direct emissions that result
from activities within the
organisation’s control
Scope 2
Indirect emissions from any
electricity, heat or steam
purchased and used
Scope 3
Any other indirect emissions
from sources outside of an
organisation’s direct control
ENERGY TECHNOLOGIES
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CARBON FOOTPRINT
Scope 1, 2 and 3 Carbon
Scope 1
Direct emissions that result
from activities within the
organisation’s control
Scope 2 Friction
Indirect emissions from any modifiers
electricity, heat or steam
purchased and used
Scope 3
Any other indirect emissions
from sources outside of an
organisation’s direct control
ENERGY TECHNOLOGIES
7
IMPORTANCE OF FRICTION MODIFIERS
• Vital in reducing friction…leading to improvements in fuel economy.
• Various types exist – with advantages and disadvantages
FM class Examples Pros Cons

Depletes in use: friction
Excellent sliding friction
Inorganic/organometallic MoDTC reduction potentially lost
reduction
in aged oil
Not as potent as
Organic GMO, oleamide Does not deplete in use
MoDTC
• But we are interested in…
ENERGY TECHNOLOGIES
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POLYMERIC FRICTION MODIFIERS

• Polymeric friction modifier (PFM) – 3 studied here
PFM 1 PFM 2 PFM 3
Previous studies have shown excellent fuel economy benefits.

ENERGY TECHNOLOGIES
9
PFMS AND FUEL ECONOMY IMPROVEMENT
• Sequence VIE test – 0W20 model reference oil

• Ad-pack was an ACEA C2/C3 package (5W30 and 5W40)
• Not optimised for the test or the friction modifiers
• Demonstration to allow basic evaluation of PFMs 1 and 2
• Both polymeric friction modifiers gave significant fuel economy benefit
PFM
FEI 1 % FEI 2 % FEI sum %
contribution
0W20 reference oil 1.09 1.32 2.41 -

0W20 + 0.5% PFM1 1.69 1.42 3.11 0.70
0W20 + 0.5% PFM2 2.02 1.35 3.37 0.96
ENERGY TECHNOLOGIES
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BENEFITS IN USE - CO2 SAVINGS
• Assumptions:
• 0.5% PFM treat-rate
• 20,000km per annum
• 4 kg oil per year
• 2.31kg CO2 produced per
litre of fuel (gasoline)
• CO2 emission savings

can be in the range of 1
– 2 tonnes of CO2 per
kg of PFM
ENERGY TECHNOLOGIES
Aims
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AIMS…
1. Rationalise PFM frictional performance through tribofilm analysis

2. Understand interactions between PFM and MoDTC
3. Boost MoDTC performance by design and selection of correct PFM
Correct PFM will be different depending on the formulation
PFM for MoDTC-free Maximum possible friction Greatest CO2 emission

formulation reduction reduction
Extension of MoDTC durability
PFM for MoDTC- Extension of oil drain interval or
(better FEI 2), no antagonism
containing formulation lower MoDTC content
with MoDTC
ENERGY TECHNOLOGIES
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1. EVALUATE FRICTIONAL PERFORMANCE

MTM Test Conditions
Parameter Value Parameter Ball Disc
80ºC Material AISI 52100 steel AISI 52100 steel

Temperature
50ºC
Roughness < 0.02 µm Ra < 0.01 µm Ra
36N (1.01 GPa initial Hertzian contact
Load
pressure) Hardness 720-780 HV 720-780 HV
Slide-roll ratio 200% (pure sliding) Diameter 19.05 mm 46mm

(SRR) 50%
Entrainment Stribeck curve: 50mms-1 - 4000mms-1

speed Rubbing: 500mms-1
ENERGY TECHNOLOGIES
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MTM @ 80OC / PFM1 PFM2 50% SRR

0.16
0W20
0.14 0.5% PFM1
0.5% PFM 2 • Initial friction is same for all
0.12 test oils
Coefficient of friction
0.10 • Increase in friction is due to

tribofilm build up
0.08
• PFM 1 reduced friction by 15%
0.06
• PFM 2 reduced friction by 25%
0.04
• Same ranking as Sequence
0.02 VIE engine test result
0.00
0.01 0.1 1
Speed / ms-1
ENERGY TECHNOLOGIES
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2. TRIBOFILM ANALYSIS
Concept of “tribofilm” – what is it?
• Generally: a film formed

tribochemically on a surface
• Combined effect of: heat, contact
pressure, asperity contact etc.
• In engine oils:
• Formed of anti-wear and other
additives in the lubricant
• Composed primarily of various zinc,
phosphorous, and sulphur
compounds
Lubricants 2013, 1(4), 132-148
ENERGY TECHNOLOGIES
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XPS ANALYSIS OF THE TRIBOFILM
X-ray source Detector
• X-ray photoelectron spectroscopy

• Gives information of the chemical composition of a surface
• Here the surface is progressively etched using an ion beam 1-10nm
• Build up a depth profile of the tribofilm
Substrate
ENERGY TECHNOLOGIES
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Substrate
First measurement (100 s)
Tribofilm
ENERGY TECHNOLOGIES
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Substrate
Second measurement (500 s) Tribofilm
ENERGY TECHNOLOGIES
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Substrate
Tribofilm
Third measurement (900 s)
ENERGY TECHNOLOGIES
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BASIC TRIBOFILM CHEMISTRY – 0W20 REFERENCE

XPS profile Tribofilm structure
100 C 1s 285 - 286 %

Ca 2p %
Fe 2p3/2 Metal %
80 P 2p % Organic carbon – oil layer
S 2p %
Residual oil
Atomic %
Zn 2p3/2 %
60 Additive elements – mixed in
with Fe from steel substrate
and organic carbon Zn, P, S, Ca, C, Fe
40
20
MTM disc surface Steel substrate
0
0 200 400 600 800 1000
Etch Time / s
ENERGY TECHNOLOGIES
But what are the effects seen when PFM is combined with
a commonly used MoDTC?
We see both ANTAGONISTIC and SYNERGISTIC effects.
TM
ENERGY TECHNOLOGIES Smart Science to Improve Lives
PFM-MoDTC
Antagonism
23
MTM - 80OC 250PPM MO 50% SRR

0.16
0W20
250ppm Mo
0.14
250ppm Mo + 0.5% PFM1
250ppm Mo + 0.5% PFM2
• MoDTC reduces 0W20 friction by
0.12
>70%
0.10
• MoDTC + PFM is lower friction than
0.08
0W20 + PFM but…
• MoDTC + PFM 1 or PFM 2 is higher
0.06 friction than only MoDTC - antagonism
0.04
0.02
0.01 0.1 1
Speed / ms-1
ENERGY TECHNOLOGIES
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RAMAN SPECTROSCOPY – OF MTM BALL SURFACE
• Friction is a function of [MoS2] in the contact zone

• Raman is a surface sensitive analytical technique
250ppm Mo + 0.5% PFM2
250ppm Mo + 0.5% PFM1
250ppm Mo
ENERGY TECHNOLOGIES
PFM-MoDTC
Synergism
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MTM – 50% SRR, 800PPM MO
0.14 0.16
0W20 engine oil 0W20 engine oil
0.5% PFM3 0.5% PFM3
0.12 800ppm Mo 0.14 800ppm Mo
800ppm Mo + 0.5% PFM3
800ppm Mo + 0.5% PFM3
0.12
0.10
0.10
0.08
0.08
0.06
0.06
0.04
0.04
0.02 0.02
50C 80C
0.00 0.00
0.01 0.1 1 0.01 0.1 1
Speed / ms-1 Speed / ms-1

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0.14 0.16
0.5% PFM3 0.5% PFM3
0.12 800ppm Mo 0.14 800ppm Mo
800ppm Mo + 0.5% PFM3
800ppm Mo + 0.5% PFM3
0.12
0.10
0.10
0.08
0.08
0.06
0.06
0.04
0.04
0.02 0.02
50C 80C
0.00 0.00
0.01 0.1 1 0.01 0.1 1

ENERGY TECHNOLOGIES
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TRIBOFILM CHEMISTRY - 50% SRR 50C 800PPM MO 10
60 Fe 8
Zn
• 0W20
Atomic %
Atomic %
6
40
• Thinnest tribofilm (more Fe)
4 • Lowest additive
20 concentration
2
• PFM 3
0
100s 500s 900s 100s 500s 900s 100s 500s 900s 100s 500s 900s
0
100 500 900 100 500 900 100 500 900 100 500 900 • Thickest tribofilm
0W20 PFM3 MoDTC MoDTC + PFM3 0W20 PFM3 MoDTC MoDTC + PFM3
1.0 • Highest Zn concentration
15
Ca 0.8 MoS2 • Additive elements
Atomic %
relatively high in
0.6
Atomic %
10
presence of MoDTC &
0.4 MoDTC/PFM 3
5
0.2
0 0.0
100s 500s 900s 100s 500s 900s 100s 500s 900s 100s 500s 900s 100 500 900 100 500 900 100 500 900 100 500 900
0W20 MoDTC MoDTC + PFM3 PFM3 0W20 MoDTC MoDTC + PFM3 PFM3
ENERGY TECHNOLOGIES
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0.14 0.16
0.5% PFM3 0.5% PFM3
0.12 800ppm Mo 0.14 800ppm Mo
800ppm Mo + 0.5% PFM3
800ppm Mo + 0.5% PFM3
0.12
0.10
0.10
0.08
0.08
0.06
0.06
0.04
0.04
0.02 0.02
50C 80C
0.00 0.00
0.01 0.1 1 0.01 0.1 1

ENERGY TECHNOLOGIES
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0.14 0.16
0.5% PFM3 0.5% PFM3
0.12 800ppm Mo 0.14 800ppm Mo
800ppm Mo + 0.5% PFM3
800ppm Mo + 0.5% PFM3
0.12
0.10
0.10
0.08
0.08
0.06
0.06
0.04
0.04
0.02 0.02
50C 80C
0.00 0.00
0.01 0.1 1 0.01 0.1 1

ENERGY TECHNOLOGIES
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TRIBOFILM CHEMISTRY – 80C, 50% SRR

1.5
40
Fe Zn
1.0
Atomic %
Atomic %
• MoDTC containing
20
0.5
samples only
0
100s 500s 900s 100s 500s 900s
0.0
100s 500s 900s 100s 500s 900s
• PFM3 = more Zn,
MoDTC MoDTC + PFM3
5
MoDTC MoDTC + PFM3 Ca less Fe - thicker
tribofilm
Ca 4 MoS2
• [MoS2] concentration
10
at 100s etching is
Atomic %
3
Atomic %
5 2
similar – similar
friction profile
1
0 0
100s 500s 900s 100s 500s 900s 100s 500s 900s 100s 500s 900s
MoDTC MoDTC + PFM3 MoDTC MoDTC + PFM3
ENERGY TECHNOLOGIES
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MTM - 200% SRR 800PPM MO

0W20
0.16 0.16 0.5% PFM3
0W20 800ppm Mo
0.5% PFM3 800ppm Mo + 0.5% PFM3
0.14
800ppm Mo
800ppm Mo + 0.5% PFM3
0.12 0.12
0.10
0.08 0.08
0.06
0.04 0.04
0.02
50C 80C
0.00 0.00
0.01 0.1 1 0.01 0.1 1
-1
Speed / ms-1 Sliding speed / m
ENERGY TECHNOLOGIES
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0W20
0.16 0.16 0.5% PFM3
0W20 800ppm Mo
0.5% PFM3 800ppm Mo + 0.5% PFM3
0.14
800ppm Mo
800ppm Mo + 0.5% PFM3
0.12 0.12
0.10
0.08 0.08
0.06
0.04 0.04
0.02
50C 80C
0.00 0.00
0.01 0.1 1 0.01 0.1 1
-1
ENERGY TECHNOLOGIES
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TRIBOFILM CHEMISTRY – 50C, 200% SRR (PURE SLIDING)

80 5
60
Fe 4
Zn
Atomic %
3
Atomic %
40
2
• Pure sliding
20
1
conditions
0 0
• PFM3 – thin but
100s 500s 900s 100s 500s 900s 100s 500s 900s 100s 500s 900s 100s 500s 900s 100s 500s 900s 100s 500s 900s 100s 500s 900s
0W20 MoDTC MoDTC + PFM3 PFM3 0W20 MoDTC MoDTC + PFM3 PFM3 additive rich tribofilm
1.0
• MoDTC provides a
15
Ca 0.8 MoS2 thicker tribofilm
• MoDTC + PFM3 =
Atomic %
10 Atomic % 0.6
0.4 thin tribofilm yet

5 friction still low?
0.2
0 0.0
100s 500s 900s 100s 500s 900s 100s 500s 900s 100s 500s 900s 100s 500s 900s 100s 500s 900s 100s 500s 900s 100s 500s 900s
0W20 MoDTC MoDTC + PFM3 PFM3 0W20 MoDTC MoDTC + PFM3 PFM3
ENERGY TECHNOLOGIES
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0W20
0.16 0.16 0.5% PFM3
0W20 800ppm Mo
0.5% PFM3 800ppm Mo + 0.5% PFM3
0.14
800ppm Mo
800ppm Mo + 0.5% PFM3
0.12 0.12
0.10
0.08 0.08
0.06
0.04 0.04
0.02
50C 80C
0.00 0.00
0.01 0.1 1 0.01 0.1 1
-1
ENERGY TECHNOLOGIES
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0W20
0.16 0.16 0.5% PFM3
0W20 800ppm Mo
0.5% PFM3 800ppm Mo + 0.5% PFM3
0.14
800ppm Mo
800ppm Mo + 0.5% PFM3
0.12 0.12
0.10
0.08 0.08
0.06
0.04 0.04
0.02
50C 80C
0.00 0.00
0.01 0.1 1 0.01 0.1 1
-1
ENERGY TECHNOLOGIES
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60
TRIBOFILM CHEMISTRY – 80C, 200% SRR (PURE SLIDING) 6
Fe Zn
40 4
Atomic %
Atomic %
20 2 • MoDTC containing
samples only
0
100s 500s 900s 100s 500s 900s
0
100s 500s 900s 100s 500s 900s
• [MoS2] only present
15
MoDTC MoDTC + PFM3
2.0
MoDTC MoDTC + PFM3 near surface for
MoDTC alone
Ca MoS2
10
1.5
• PFM3 contributes to a
thicker tribofilm –
Atomic %
Atomic %
1.0
higher Zn, Ca content
5
0.5 • How can we exploit
this synergy?
0 0.0
100s 500s 900s 100s 500s 900s 100s 500s 900s 100s 500s 900s
MoDTC MoDTC + PFM3 MoDTC MoDTC + PFM3
ENERGY TECHNOLOGIES
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PFM 3 FOR FRICTION DURABILITY – SRV, RECIPROCATING

200N (211MPa), Cylinder on Disc (st-st), 80OC, 1mm stroke
0.20
0.18
800ppm Mo
800ppm Mo + 0.5% PFM3
0.16
• PFM 3 has the potential to
0.14
extend the durability of
0.12
engine oils formulated with
0.10 MoDTC
0.08 Or
0.06
• Allow for the use of lower
0.04 levels of MoDTC
0.02
0.00
0 20000 40000 60000 80000 100000 120000 140000 160000
Time / s
ENERGY TECHNOLOGIES
Summary
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SUMMARY AND CONCLUSIONS
• Tribofilm is not only composed of ZDDP (and MoDTC)

• Tribofilm structure and composition is heavily dependent on:
• Temperature
• Contact conditions
• Interactions between friction modifiers and other additives
• Better understanding of tribofilm chemistry can enable better
PFM selection for a given formulation
• PFMs for MoDTC formulations
• PFMs for MoDTC-free formulations
ENERGY TECHNOLOGIES
Thank You!
315 Cherry Lane

New Castle, DE 19720
PTIC.NAM@croda.com
@CrodaPlc
in Croda Lubricants

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