Pushing the Boundaries with High-Performance Lubricants · elas tomer c ompatibility of El evanc e Aria WTP 40, y ou c an formulat e the w ear-r esis tant, l ow-foaming solutions

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


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


Mixed Regime

Pressure

Movement

Movement

Overcoming Friction


Boundary Regime

Severe

Pressure


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?


FUNCTIONAL GROUPSFunctional Groups are like hands and feet


FUNCTIONAL GROUPS


In very slow starts and very heavy loads oil-starved regions will be vulnerable.

10


FUNCTIONAL GROUPS


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


PAOs

24











elevance.com/aria



• 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


• Rig test data and model study ERS 40 gear oil formulations


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


Elevance Renewable Sciences Building Blocks

26

esterification

metathesis

unsaturated methyl ester

Enable design of unique lubricant base stocks


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


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


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


• 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


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.


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


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



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


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


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)


Key Application Performance Insights

40











elevance.com/aria



• 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


• 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


• ERS 40 has bound ester versus PAO requires ester to be blended in• ERS 40 maintains higher viscosity – provides increased options for

viscosity grade


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


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)



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


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



Key Take-Aways

45











elevance.com/aria



• 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


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.


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

Documents

Pushing the Boundaries with High-Performance Lubricants · elas tomer c ompatibility of El evanc e Aria WTP 40, y ou c an formulat e the w ear-r esis tant, l ow-foaming solutions