Wear - Croda Lubricants

A Novel Zero SAPS
Antiwear Component
SAPS = Sulphated Ash, Phosphorous, & Sulphur
Dr Andy Oldfield
Acknowledments:
Trevor Blease, John Gamwell & Andy Oldfield, Uniqema, Wilton, UK
Rudi ter Haar, Vincent Wortel & Cock Verboom, Uniqema, Gouda, Netherlands
Why a New Product ?
• Europe, US and Japan are introducing a
series of increasingly tighter controls over
tailpipe emissions (e.g. Euro V, US 2007)
• Focus on Particulate Matter (PM), NOx,
Hydrocarbons (HC), and CO
• To meet these requirements, new exhaust
after treatment devices are needed
• These devices are very sensitive to at least
one of SAPS in the lubricant
SAPS – Overview
• Sulphated Ash
– From: ZDDP, Metal containing detergents
– Implications: Antioxidancy, Antiwear, TBN,
corrosion, engine cleanliness, soot handling
• Phosphorous
– From: ZDDP
– Implications: Antioxidancy, Antiwear
• Sulphur
– From: ZDDP, detergents, mineral oil, antioxidants
– Implications: Antioxidancy, Antiwear, engine
cleanliness, low S base oils
Why a New Product ?
• Major source of lubricant SAPS is ZDDP
• Engine wear performance needs to be
maintained
Introducing our New Product
EMKARATE DE 10479
• Novel ester based technology which has
been optimised for anti-wear boosting effect
• Zero SAPS
• New product in “Launch Phase”
– Product has been been successfully “scaled-up”
– Registered in major territories
Uniqema Screening Tests
• Uniqema’s tribology department has spent
considerable time developing screening
tests which discriminate in wear
performance between industry standard
reference oils with good and poor wear
performance
• Quite a few antiwear tests do not screen
real life antiwear performance e.g. Falex, 4ball, some HFRR conditions
Our Approach to Wear Tests
• Need a multi-dimensional approach
– End of test wear scar
– Film Thickness
– Changes in “Wear Regime” transition
• Checked for repeatability and discrimination
using well known reference oils
• Uniqema has used experimental design to
optimise test conditions
– Load, Speed, Test Length, Metallurgy, Surface
Pre-conditioning, etc.
General Testing Protocol
• Uniqema has taken reference oils from the
standard CEC high temperature wear test
and demonstrated the performance benefit by
top treating the poor oil.
• “Good” (i.e. low wear) reference oil (CEC
194/6)
• “Poor” (i.e. high wear) reference oil (CEC
142/10)
• These oils are ranked on wear performance
not SAPS levels
HFRR – Wear Test Method 1
•
•
•
•
High Frequency Reciprocating Rig (HFRR)
Ball on Flat
Average of five runs
Run
2hr, pause,
2hr, pause,
1hr
• HFRR equipment also measures resistance
between contacting surfaces (Electrical
Contact Resistance, ECR)
– Measures insulating film formation
– Indirect measurement of wear
CEC Ref Oil 142/10 (Poor Oil)
HFRR – Film Thickness and Friction Plot
0.18
100
Av Scar Size = 0.277
90
0.16
80
0.14
0.12
60
0.1
50
Friction
Film Thickness
70
0.08
40
0.06
30
0.04
20
0.02
10
0
0
2000
4000
6000
8000
10000
12000
14000
16000
0
18000
Time data points (1 data per 5sec)
100 per. Mov. Avg. (Friction1)
100 per. Mov. Avg. (Friction2)
100 per. Mov. Avg. (Film Thickness1)
100 per. Mov. Avg. (Film Thickness2)
CEC Ref Oil 142/10 (Poor Oil) +
0.5% Emkarate DE 10479
HFRR – Film Thickness and Friction Plot
100
0.16
90
0.14
80
Av Scar Size = 0.240
0.12
0.1
60
50
0.08
40
0.06
30
0.04
20
0.02
10
0
0
2000
4000
6000
8000
10000
12000
Time data points (1 data per 5sec)
Film Run 1
Film Run 2
Friction Run 1
Friction Run 2
14000
16000
0
18000
Friction
Film Thickness
70
CEC Ref Oil 142/10 (Poor Oil) +
0.25% 2ryZDDP
HFRR – Film Thickness and Friction Plot
100
0.2
Av Scar Size = 0.255
0.18
80
0.16
70
0.14
60
0.12
50
0.1
40
0.08
30
0.06
20
0.04
10
0.02
0
0
2000
4000
6000
8000
10000
12000
14000
16000
0
18000
Time data points (1 data per 5sec)
100 per. Mov. Avg. (Friction1)
100 per. Mov. Avg. (Friction2)
100 per. Mov. Avg. (Film Thickness1)
100 per. Mov. Avg. (Film Thickness2)
Friction
Film Thickness
90
CEC Ref Oil 142/10 (Poor Oil) +
0.25% 2ryZDDP + 0.25% DE10479
HFRR – Film Thickness and Friction Plot
100
0.2
0.18
80
0.16
70
0.14
60
0.12
50
0.1
40
0.08
30
0.06
20
0.04
10
0.02
0
0
2000
4000
6000
8000
10000
12000
14000
16000
Friction
Film Thickness
Average Scar Size = 0.238
90
0
18000
Time data points (1 data per 5sec)
100 per. Mov. Avg. (Friction1)
100 per. Mov. Avg. (Friction2)
100 per. Mov. Avg. (Film Thickness1)
100 per. Mov. Avg. (Film Thickness2)
CEC Ref Oil 142/10 (Poor Oil) +
0.25% 2ryZDDP
HFRR – Film Thickness and Friction Plot
100
0.2
Av Scar Size = 0.255
0.18
80
0.16
70
0.14
60
0.12
50
0.1
40
0.08
30
0.06
20
0.04
10
0.02
0
0
2000
4000
6000
8000
10000
12000
14000
16000
0
18000
Time data points (1 data per 5sec)
100 per. Mov. Avg. (Friction1)
100 per. Mov. Avg. (Friction2)
100 per. Mov. Avg. (Film Thickness1)
100 per. Mov. Avg. (Film Thickness2)
Friction
Film Thickness
90
CEC Ref Oil 142/10 (Poor Oil) +
0.25% 2ryZDDP + 0.25% DE10479
HFRR – Film Thickness and Friction Plot
100
0.2
0.18
80
0.16
70
0.14
60
0.12
50
0.1
40
0.08
30
0.06
20
0.04
10
0.02
0
0
2000
4000
6000
8000
10000
12000
14000
16000
Friction
Film Thickness
Average Scar Size = 0.238
90
0
18000
Time data points (1 data per 5sec)
100 per. Mov. Avg. (Friction1)
100 per. Mov. Avg. (Friction2)
100 per. Mov. Avg. (Film Thickness1)
100 per. Mov. Avg. (Film Thickness2)
Film Formation - Overview
• Poor European reference oil (CEC 142/10)
gives no film
• Emkarate DE 10497 inclusion leads to film
formation after 3 hours
• Emkarate DE 10497 accelerates film
formation of secondary ZDDP alone
Wear Scar Method 2
Modified Reichert test (Cylinder on Ring).
Wear Performance Data
0.32
0.3
W ear S car m m
2
0.28
0.26
0.24
0.22
0.2
Poor Oil (CEC 142/10)
Poor Oil + 0.5% wt/wt DE 10479
Advanced Reichert
Extended HFRR Test
Good Oil (CEC 194/6)
Wear Regimes - Schematic
1800
•
•
1600
1400
Critical load defines I-II / III transition
Normal camshaft operation in regime I
Fn [N]
1200
1000
III
800
II
600
BL, moderate
scuffing wear
400
200
I
0
0
0.5
1
1.5
2
2.5
3
3.5
v [m/s]
EHL/ML/BL, very low wear
Severe wear, virtually unlubricated,
adhesive transfer type wear
4
Wear “Regime Change” Method 3
• TNO Tribometer used
– Measures ball-on-ring wear
• Wear rate measured for various contact
velocities and loads.
• Determines a critical load above which a
dramatic increase in wear rate is observed i.e.
wear regime changes
• The higher the critical load, the higher contact
pressure can be tolerated without catastrophic
wear
• Test under development in co-operation with
industrial an academic partners
Comparison of Critical Loads for
Reference Oils
600
Critical load ( N)
500
II
400
300
I
200
100
0
0.1
0.25
0.5
1
2
4
Contact velocity ( m /s)
RL148 (bad oil)
RL 195 (good oil)
Test is validated since good oil has higher critical loads
than bad oil (Ref. Oils OM602A Soot induced wear test)
Critical Loads for Base Oil + ZDDP
600
Critical load ( N)
500
Base oil ( SN150)
400
II
300
Base oil + 1% sec-ZDDP
Base oil + 0.5% secZDDP + 0.5% DE10479
200
I
100
0
0.1
0.25
0.5
1
2
4
Contact velocity ( m /s)
Results show that 0.5% sec-ZDDP + 0.5% DE10479
gives better wear performance than 1% sec-ZDDP.
Further Test Data
• Good Results obtained at formulators on
engine tests
– Proven performance
– Data is covered by confidentiality agreements so
can not be shown
• No detrimental effects to stability
• No detrimental effects on seal compatibility
Suggestions for Use
• 0.5% DE 10479 with 0.5% ZDDP
• Blending into addpack
• Add at the end
• Blending into oils
• Add on top of addpack
Theories on Zero-SAPS Mechanism
• Physical vs Chemical
• Polarity
• Viscosity
ZDDP
Organic rich ZDDP film
Hard Polyphosphate Chemisorbed – ZDDP reacted layer
Metal oxide
Metal
Next Steps
• Good performance indicated in HFRR and
Reichert tests verified by engine testing
– Test programs underway to provide publishable
data
• “Soot induced wear” protection evaluation
underway
• Further work ongoing to understand the
mechanism in more details
Conclusions
• Emkarate DE 10479 is a zero SAPS antiwear additive
booster
• Proven performance
• Very effective at low treat rates (<1%)
– 50 : 50 mix with ZDDP
• Provides the formulator with ultimate flexibility in
meeting SAPS limits and wear targets
• Available now
Disclaimer
Although the information and recommendations in this publication are believed to be accurate and
are given in good faith UNIQEMA TM makes no representation or warranty as to the completeness or
accuracy of any information given. Suggestions made concerning uses or applications are only the
opinion of Uniqema and users should undertake their own Tests and analysis to determine the
suitability of these products for their own particular purpose. However because of numerous factors
affecting results, Uniqema MAKES NO REPRESENTATION OR WARRANTY, EXPRESS OR
IMPLIED, AS TO MERCHANTABILITY, FITNESS FOR PARTICULAR PURPOSE OR OF ANY
OTHER NATURE WITH RESPECT TO INFORMATION OR THE PRODUCT TO WHICH THE
INFORMATION REFERS.
Nothing contained herein is to be construed as a recommendation to use any product, process,
equipment or formulation in conflict with any patent or other intellectual property right and Uniqema
makes no representation or warranty, express or implied, that the use thereof will not infringe any
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Uniqema is an international business of Imperial Chemical Industries PLC. Uniqema operates
through ICI affiliated companies in the relevant countries such as ICI Americas Inc, Unichema, a
division of Indopco Inc., and Mona Industries in the USA.
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