pushing the boundaries with high-performance lubricants · elas tomer c ompatibility of el evanc e...
TRANSCRIPT
Pushing the Boundaries with
High-Performance Lubricants
STLE Frontiers WorkshopOctober 25, 2015
Selim M. Erhan
Copyright 2015, Elevance Renewable Sciences, Inc. All rights reserved.
Key Discussion Points
2
No more blending esters and PAOs for additive solubility.
New Elevance Aria™ WTP 40 combines the functionality of
synthetic esters and PAOs into a single, high-performance
lubricant base stock with significantly improved additive
solubil ity. With the high viscosity, shear stabil ity and
elastomer compatibility of Elevance Aria™ WTP 40, you can
formulate the wear-resistant, low-foaming solutions your
customers need in high-viscosity gear and compressor
lubricants. Seize the fr eedom.
Learn more and request field trial support at
elevance.com/aria
UNLOCK THE FORMULATION FREEDOM YOU’VE BEEN WAITING FOR.One revolutionary molecule makes
it possible. Elevance Aria™ WTP 40.
• A look at high molecular weight, additives with high polarity.
• Comparisons of alphaolefin/alphaolefin ester synthetic, base stock (ERS 40): properties and performance
• Neat base stock (ERS 40) versus PAO
• Base stock bound (ERS 40) versus blended PAO/ester
• Fully formulated lubricants
• Rig test data and model study ERS 40 gear oil formulations
Copyright 2015, Elevance Renewable Sciences, Inc. All rights reserved.
Boundary Regime (1) is where
surface interactions dominate
Tribologist’s Description of Lubrication
Elastohydrodynamic Regime (3)
is where fluid rheology
dominates
Thin-Film Friction (2)
Also called mixed lubrication, this
consists of both Boundary and EHD,
however it is not simply an average
of the two regimes
Copyright 2015, Elevance Renewable Sciences, Inc. All rights reserved.
Mixed Regime
Pressure
Movement
Movement
Overcoming Friction
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Boundary Regime
Severe
Pressure
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Friction generates heat, which causes a chemical reaction
on the surface of the metal.
EP Mechanism
Copyright 2015, Elevance Renewable Sciences, Inc. All rights reserved.7
Do we have alternatives?
Copyright 2015, Elevance Renewable Sciences, Inc. All rights reserved.
FUNCTIONAL GROUPSFunctional Groups are like hands and feet
Copyright 2015, Elevance Renewable Sciences, Inc. All rights reserved.
FUNCTIONAL GROUPS
Copyright 2015, Elevance Renewable Sciences, Inc. All rights reserved.
In very slow starts and very heavy loads oil-starved regions will be vulnerable.
10
Copyright 2015, Elevance Renewable Sciences, Inc. All rights reserved.
FUNCTIONAL GROUPS
Copyright 2015, Elevance Renewable Sciences, Inc. All rights reserved.
If fluids can not be squeezed into a smaller volume if it can not escape
12
General vegetable oil polymerization
Microtap – Forming Tap
98
99
100
101
102
103
104
105
MCCP Dimer Trimer Polymer
% Efficiency on 1018 CRS
Oxidized oils
Oil
Gardner- Holdt
Viscosity
@ 25 oCCentiStokes
Gardner - Holdt
Viscosity
@ 25 oC CentiStokes
Soybean K 275 Z-3 4630
Canola K 275 Z-3 4630
Rapeseed K 275 Z-3 4630
Castor - Z-3 4630
CentiStokes x Specific Gravity = Centipoise
Oscillating Arm with
Steel Ball
Temperature-Controlled
Sample Cell with Steel
Disk Surface
Load Applied by
Hanging Weights
Force Detector
Boundary Friction
Ball Oscillates Across Disk
Measure Force to move ball
High Frequency Reciprocating Rig (HFRR) –Boundary Regime
Boundary Friction – oxidized veg oils
The friction coefficient for base oil alone is 0.159
The friction for 5% of the Z viscosity oil is lower
than for 10% of the same oil at K viscosity
Mini Traction Machine (MTM)
A ball and disk in contact are driven
independently to create a mixed
rolling/sliding contact.
The frictional force between the ball and disk is
measured by a force transducer.
Can Place Steel Ball
Or Piece of Friction
Material on Arm
Disk is Immersed
in Oil
Friction is Measured
by Force Detector
Attached to Shaft
Holding the Friction
Material
Thin Film Friction at 75 °C with MTM
2012 © Afton Chemical Corporation, All Rights Reserved. Not to be copied, shared, or reproduced in
any media without the express written permission of Afton Chemical Corporation
5% conc 10% conc
At a concentration of 5 wt%, canola oil, rapeseed oil, and
soybean oil reduce friction. Castor oil and the chlorinated
paraffin slightly increase friction.
Increasing the concentration from 5 to 10 wt% maintains friction
reduction with canola oil, rapeseed oil, and soybean oil, while
the chlorinated paraffin still increases friction.
The major fatty acids in both canola oil (18 carbon) and
rapeseed oil (22 carbon) is mono-unsaturated.
The significant reduction in the castor oil is most likely a result
of an increase in the soluble, friction-reducing component.
Thin Film Friction at 125 °C with MTM
2012 © Afton Chemical Corporation, All Rights Reserved. Not to be copied, shared, or reproduced in any media without the
express written permission of Afton Chemical Corporation
At a concentration of 5 wt%, canola oil, rapeseed oil, and
soybean oil reduce friction. Castor oil and the chlorinated
paraffin slightly increase friction.
Increasing the concentration from 5 to 10 wt% maintains friction
reduction with canola oil, rapeseed oil, and soybean oil, while
the chlorinated paraffin still increases friction.
The major fatty acids in both canola oil (18 carbon) and
rapeseed oil (22 carbon) is mono-unsaturated.
The significant reduction in the castor oil is most likely a result
of an increase in the soluble, friction-reducing component.
5% conc 10% conc
6. Leveling Bearing
Moment arm
Transmitted
Torque
1. Tool Specimen
2.Workpiece Specimen
4. Applied Force
5. Rotation
3. Lubricant
Contact Pattern (Squeeze-film)
Twist Compression Lubricant Starvation Conditions
Twist Compression Test ResultsTime until failure
Lubricant Breakdown
Static coefficient of friction
Average Coefficient of
Friction
Coefficient of Friction at
Specific Time
Friction Factor(s) /
Weighted avg.
Sheet Damage
Tool Damage / Galling
Tribochemical
Residues
Lubricity additives in naphthenic oil @ 10% on TCT
0
0.05
0.1
0.15
0.2
0.25
CO
F in
itia
l
0.145
0.15
0.155
0.16
0.165
0.17
0.175
0.18
0.185
0.19
CO
F av
era
ge
Copyright 2015, Elevance Renewable Sciences, Inc. All rights reserved.
PAOs
24
No more blending esters and PAOs for additive solubility.
New Elevance Aria™ WTP 40 combines the functionality of
synthetic esters and PAOs into a single, high-performance
lubricant base stock with significantly improved additive
solubil ity. With the high viscosity, shear stabil ity and
elastomer compatibility of Elevance Aria™ WTP 40, you can
formulate the wear-resistant, low-foaming solutions your
customers need in high-viscosity gear and compressor
lubricants. Seize the fr eedom.
Learn more and request field trial support at
elevance.com/aria
UNLOCK THE FORMULATION FREEDOM YOU’VE BEEN WAITING FOR.One revolutionary molecule makes
it possible. Elevance Aria™ WTP 40.
• New building blocks and derivatives for the lubricants market
• Comparison of alphaolefin/alphaolefin ester synthetic, base stock (ERS 40): properties and performance
• Neat base stock (ERS 40) versus PAO
• Base stock bound (ERS 40) versus blended PAO/ester
• Fully formulated lubricants
• Rig test data and model study ERS 40 gear oil formulations
Copyright 2015, Elevance Renewable Sciences, Inc. All rights reserved.
Differentiated Catalyst Technology
25
Traditional Catalyst Our Proprietary Catalyst
Propylene
Ethylene 2-butene
Propylene
A
B
C
D
B DA C 1-decene
9-decenoic acid methyl ester
Methyl oleate
ethylene
A
BC D
BD
C
A
Allows for conversion of complex molecules such as fatty acids and esters
Copyright 2015, Elevance Renewable Sciences, Inc. All rights reserved.
Elevance Renewable Sciences Building Blocks
26
esterification
metathesis
unsaturated methyl ester
Enable design of unique lubricant base stocks
Copyright 2015, Elevance Renewable Sciences, Inc. All rights reserved.
New Base Stock Technology
27
• Combines the performance of Groups IV and V into one base stock
• Wide range of viscosities and polarities through synthetic versatility
Process: Catalytic polymerization ofLinear a-olefins and linear a-olefin esters Performance Benefits
• Improved additive solvency &
formulation compatibility
• Seal compatibility
• Low-foaming
• Reduced wear
• Lower friction
Copyright 2015, Elevance Renewable Sciences, Inc. All rights reserved.28
ERS 40’s Balanced Solvency Enables Creation of Robust FormulationsA
nili
ne
Po
int
Base StocksTest Method: ASTM D611
0
20
40
60
80
100
120
140
160
180
ERS 40 PAO 40 Ester Group I Proup II
Balanced aniline point for improved formulation compatibility and performance
Formulation Flexibility - Additive Solvency
Formulation Simplicity with ERS 40 Versus PAO 40/Ester Blends
29 Copyright 2015, Elevance Renewable Sciences, Inc. All rights reserved.
PAO 40Base Stock
Conventional LubricantWith PAO 40
Compatibilizing Agent (Ester)
Additive Package
Formulation Freedom –eliminating need to use
ester to blend
additives
ERS 40Base Stock
Lubricant with ERS 40
Additive Package
Performance of PAO/ester blend versus ERS 40 (bound ester) base stocks
ERS 40 Shows Increased Shear Stability Versus PAO/ester blend
30
Rheological performance, 100C
Kv100C=28.60.2cSt
ERS 40
PAO 40/ester
mPAO 40/ester
PAO with bound ester forms thicker film at contact than PAO/ester blends
Copyright 2015, Elevance Renewable Sciences, Inc. All rights reserved.
31
Formulation Comparison: 75W90 GL-5 Lubricant Based on ERS 40 Versus PAO 40
Formulation Composition
ERS 40 PAO 40
ERS 40 (%) 65.5 --
PAO 40 (%) -- 67.0
PAO 4 (%) 28.5 17.0
Ester (%) -- 10.0
Additive package (%) 6.0 6.0
KV @ 100C 17.6 17.7
Copyright 2015, Elevance Renewable Sciences, Inc. All rights reserved.
• ERS 40 has bound ester versus PAO requires ester to be blended in• ERS 40 maintains higher viscosity – provides increased options for
viscosity grade
Improved Performance - Formulated Lubricant
32
PAO 40/10% ester
Copyright 2015, Elevance Renewable Sciences, Inc. All rights reserved.
Compatibilizers added
ERS 40 Unique Molecule Provides Additive Solvency & Compatibility
6% GL-5 Add pack
Base Stocks
Fully FormulatedGL-5 Gear Lubricant
ERS 40PAO 40 PAO 40/
10% ester
No compatibilizers addedCompatibilizers
added
Clarity, brightness and
color demonstrate excellent solubility
of additives
Formulation Flexibility - Additive Solvency
Base Stock Performance: Tribology Bench Tests
MTM
33
Rheometer
EHL
MPRCopyright 2015, Elevance Renewable Sciences, Inc. All rights reserved.
Copyright 2015, Elevance Renewable Sciences, Inc. All rights reserved.
EHL fluid film measurement, 100C*
ERS 40 Shows Increased Film Thickness at Low Speeds Indicating Improved Boundary Lubrication
34
*EHL test was done by Dr. Girma Biresaw, USDA
At 100C; 40NPAO 40 40N (a)’ERS 40 40N’
Improved Performance - Base Stock
Copyright 2015, Elevance Renewable Sciences, Inc. All rights reserved.
ERS 40 Demonstrated Excellent Friction and Wear Performance
35
Wear performance at 100C
0
100
200
300
400
500
600
PAO 40 mPAO 40 ERS 40
Bal
l wea
r sc
ar, d
iam
eter
um
Wear of neat base stocks, Kv100C=38.10.5
PAO 40 mPAO 40 ERS 40
Friction properties at 100C
0
0.005
0.01
0.015
0.02
0.025
0.03
0.035
0 20 40 60 80 100
Co
effi
cien
t o
f fr
icti
on
Slide/roll ratio, %
Friction of base stocks, Kv100C=38.10.5
PAO 40mPAO 40ERS 40
cSt
MTM – mini traction machine test
Wear Tracks
Benefits of Bound Versus Blended Ester
ERS 40 shows improved wear and friction results when compared to blended PAO 40/Ester and mPAO 40/Ester Base Oil
Micropitting Rig (MPR) Test Conditions: Mimic Wind Turbine
• Realistic Contact Pressure & Film Thickness• Temperature = RT - 135C• Velocity = 0 - 4m/s• Load= 0 – 1250N (3GPa)• SRR = 0 - 200% • ~1x10^6 contact cycles/hour
*MPR test was done by Dr. Aaron Greco, ANL
Copyright 2015, Elevance Renewable Sciences, Inc. All rights reserved.
Copyright 2015, Elevance Renewable Sciences, Inc. All rights reserved.
MPS Predicts Reduced Micropitting with ERS 40 as a Base Stock
37
PAO 40 ERS 40
Sample: Pure ERS 40 and PAO 40, Kv100C of 38.1cStMPR Micropitting test: 90C, 300N, 3m/s, SRR=20%, 4hr
*MPR test was done by Dr. Aaron Greco, ANL
Improved Performance - Base Stock
ERS 40 shows reduced micropitting as evidenced by no horizontal and diagonal blue wear scars
Copyright 2015, Elevance Renewable Sciences, Inc. All rights reserved.
No Foaming Seen in Formulated Lubricant Containing ERS 40
38
ASTM D892 Foaming Tendency Foam Stability
Base Stock in API GL-5 Foam Volume, ml Foam Volume, ml
Formulated API GL-5 Gear Lubricant
Seq I24°C
Seq II93°C
Seq III24°C
Seq I24°C
Seq II93°C
Seq III24°C
PAO 40/ester 590 0 160 230 0 0
mPAO 65/ester 430 160 210 200 0 10
ERS 40 0 0 0 0 0 0
Copyright 2015, Elevance Renewable Sciences, Inc. All rights reserved.39
GL-5 Spec PAO 40/ester ERS 40
Adipate TMP
Sludge >9.4 9.7 9.7 9.7
% Visc Inc. <100 7 8 14
Varnish >7.5 7.5 7.7 9.5
Increased cleanliness with ERS 40 based API GL-5 formulations Versus PAO 40/ester (adipate or TMP) blends
Improved Performance – Formulated Lubricant
Automotive Gear Oil Oxidation Test, L-60-1 (ASTM D 5704)
Copyright 2015, Elevance Renewable Sciences, Inc. All rights reserved.
Key Application Performance Insights
40
No more blending esters and PAOs for additive solubility.
New Elevance Aria™ WTP 40 combines the functionality of
synthetic esters and PAOs into a single, high-performance
lubricant base stock with significantly improved additive
solubil ity. With the high viscosity, shear stabil ity and
elastomer compatibility of Elevance Aria™ WTP 40, you can
formulate the wear-resistant, low-foaming solutions your
customers need in high-viscosity gear and compressor
lubricants. Seize the fr eedom.
Learn more and request field trial support at
elevance.com/aria
UNLOCK THE FORMULATION FREEDOM YOU’VE BEEN WAITING FOR.One revolutionary molecule makes
it possible. Elevance Aria™ WTP 40.
• Market drivers for high performance lubricant technology
• New building blocks and derivatives for the lubricants market
• Comparison of synthetic high viscosity base stocks -properties and performance
• Neat base stock
• Base stock blends with compatibilizers
• Fully formulated lubricants
• Rig test data and model study of formulated gear oils
41
Formulation Comparison: 75W90 GL-5 Lubricant Based on ERS 40 Versus PAO 40
Formulation Composition
ERS 40 PAO 40
ERS 40 (%) 65.5 --
PAO 40 (%) -- 67.0
PAO 4 (%) 28.5 17.0
Ester (%) -- 10.0
Additive package (%) 6.0 6.0
KV @ 100C 17.6 17.7
Copyright 2015, Elevance Renewable Sciences, Inc. All rights reserved.
• ERS 40 has bound ester versus PAO requires ester to be blended in• ERS 40 maintains higher viscosity – provides increased options for
viscosity grade
Improved Performance - Formulated Lubricant
42
0
200
400
600
800
Dia
me
ter
of b
all
we
ar
sca
r, u
m
MTM Wear
0
0.005
0.01
0.015
0.02
0.025
0.03
0 10 20 30 40 50
Co
effi
cien
t o
f fr
icti
on
Slide/roll ratio, %
COF versus slide/roll ratio, 100 C
Copyright 2015, Elevance Renewable Sciences, Inc. All rights reserved.
A 75W90 gear lubricant formulation tested at 100C on MTM
ERS 40 Improved Friction and Reduced Wear in Formulated Gear Oils
PAO 40/esterGL-5 (75W90)
ERS 40GL-5 (75W90)
ERS 40GL-5 (75W90)
PAO 40/esterGL-5 (75W90)
Improved Performance - Formulated Lubricant
Copyright 2015, Elevance Renewable Sciences, Inc. All rights reserved.
Strong L-37 (ASTM D6121) Load Evaluation Pass Showing Performance Under Extreme Pressure and Load
Gear Rating API GL-5 MT-1 LimitsPinion Ring
Wear 7.0 8.0 5 min.
Rippling 9.4 10.0 8 min.
Ridging 9.4 10.0 8 min.
Pitting + Spalling
9.9 9.9 9.3 min.
Scoring 10.0 10.0 10
Deposits 10 10 Report
Corrosion 10 10 Report
Discoloration 9 8 Report
Overall Rating PASS PASS
43
Improved Performance – Formulated Lubricant
Copyright 2015, Elevance Renewable Sciences, Inc. All rights reserved.
ERS 40 Increased Rate and Thickness of Additive Deposition
44
Improved molecular architecture and polarity contribute to faster and increased additive deposition
MTM-SLIM additive film measurement (ZDDP model system)
ERS 40+1%ZDDP
PAO 40/ester+1%ZDDP
0
40
80
120
0 30 60 90 120
Ad
dit
ive
Film
th
ickn
ess,
nm
Rubbing time, min
Series1 Series2
Improved Performance - Formulated Lubricant
Copyright 2015, Elevance Renewable Sciences, Inc. All rights reserved.
Key Take-Aways
45
No more blending esters and PAOs for additive solubility.
New Elevance Aria™ WTP 40 combines the functionality of
synthetic esters and PAOs into a single, high-performance
lubricant base stock with significantly improved additive
solubil ity. With the high viscosity, shear stabil ity and
elastomer compatibility of Elevance Aria™ WTP 40, you can
formulate the wear-resistant, low-foaming solutions your
customers need in high-viscosity gear and compressor
lubricants. Seize the fr eedom.
Learn more and request field trial support at
elevance.com/aria
UNLOCK THE FORMULATION FREEDOM YOU’VE BEEN WAITING FOR.One revolutionary molecule makes
it possible. Elevance Aria™ WTP 40.
• Polymeric molecules with multiple polar points are very effective in the mixed regime moving into the boundary regime
• The form stronger and thicker adsorbed fluid films and intramolecular interactions
• The molecular design with chemically bound ester shows advantages over the PAO/ester blends in additive compatibility, seal compatibility, foam control, friction, wear, excellent cleanliness and tribological performance
Copyright 2015, Elevance Renewable Sciences, Inc. All rights reserved.
Acknowledgments
46
• Colleagues at Elevance Renewable Sciences
• Dr. Ali Erdemir and Dr. Aaron Greco at Argonne National Laboratory Tribology Group
• Dr. Girma Biresaw at USDA National Center for Agricultural Utilization Research
• Dr. Mark Devlin and Dr. Carl Bennett at Afton Chemical
Thank you.
Copyright 2015, Elevance Renewable Sciences, Inc. All rights reserved.
ERS 40: A High-Performing Base Stock
Base Stock Property ERS 40
KV 100°C, cSt (ASTM D445) 39
KV 40°C, cSt (ASTM D445) 349
Viscosity Index (ASTM D2270) 162
Pour Point, °C (ASTM D97) -30
Aniline Point, °C (ASTM D611) 99
Dielectric Constant 25°C (ASTM D294) 2.53
48
Combines chemical and physical properties of PAO and ester into one high-performing base stock