Joseph M. Perez, Tribology Group, Chemical Engineering Dept.,

Penn State University, University Park, PA 16802

Diesel Engine Emissions Reduction ConferenceNewport, RI

August 24-28, 2003

Research on Fuels & Lubricants

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Penn State’s Slippery Bunch:

1950’s Dew Line Lubricants, New Base Oil & Additive Technology

1960’s SR 71 Blackbird Hydraulic Fluids, Super Refined Lubricants (Type II)

1970’s Oxidation, Greases, Metals1980’s VPO, Adiabatic Engine, MeOH Oils1990’s Environmentally Friendly Fluids

Extended Drain Oils

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Current Projects

Fuel StudiesDMEBiodieselULSF

Vegetable OilsHigh Temperature Liquid LubricantsCoatings & LubricantsRole of Chemical Structure

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Penn State “Green” Project

1. Over 200 pieces of farm & construction equipment on campus.

2. Conversion to Environmentally Friendly Lubricants initiated.

3. Use of Biodiesel in farm equipment.4. Conversion of waste oils to Biodiesel –

Undergraduate Engineering Project

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FUELSDiesel Fuels

Biodiesel Fuels

Dimethyl Ether

+ ROH catalyst

Hydrocarbon Syngas DME

Distillation Hydrocarbon mixture

Soybeans

Petroleum cut boiling ~ 282-338oC, #2, LSDF and ULSDF

300 ppm S32 ppm SULSD (< 15ppm S)

Blends of methyl esters made from vegetable oils

Converted from Syngas

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DME Methane + H2 + CO

DME Research

DME is environmentally benignDecomposes rapidly Doesn’t harm ozone layer

Reduces diesel engine emissionsAddition of oxygen into combustion zone

Engine and Vehicle TestsProblems include low viscosity (wear), high vapor pressure, and material compatibility

Laboratory TestsViscosity StudiesInjector StudiesO-Ring Studies

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Fuel Injector Studies

Need digital pics of new andDME pins from Plint!

Dr. Perez has pins at Argonne

New DME SCUFFED

Fuel Injector Pin

Modified Cameron –Plint Machine

Test Pins

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Biodiesel Fuel Studies

Previous work involved study of VPO of diesel and biodiesel fuels in pilot plant (10)

(10) Wain, K. Perez, J. “ Oxidation of Biodiesel Fuels for Improved Fuel Lubricity” Proceedings of the Internal Combustion Engine Division, Lubrication and Friction Committee ASME Rockford, IL #2002-ICE-447 (2002)

Demonstrated in laboratory tests that addition of oxygen to biodiesel resulted in improvement in friction

Run #1Temp- 325oC

Feed Rate- 1000 g/hr

O2/Feed Mole Ratio- 1.0

Run #2Temp- 375oC

Feed Rate- 1000 g/hr

O2/Feed Mole Ratio- 1.0

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0.020

0.040

0.060

0.080

0.100

0.120

0.140

0 10 20 30 40 50 60Time (min)

Fric

iton

Coe

ffici

ent (

)

Low Sulfur Diesel

Ox. Diesel Run #1

Ox. Diesel Run #2

Low Sulfur & Oxidized Diesel Fuels

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0.060

0.070

0.080

0.090

0.100

0.110

0.120

0.130

0.140

0 10 20 30 40 50 60

Time (min)

Fric

iton

Coe

ffici

ent (

)

Fuel A

Fuel B

Fuel C

Friction Traces for ULSDFsJMP13@PSU.EDU

Fuel Deposit TestsMicro-oxidation test

10ml of test fuel into glass test tubeOne stainless steel panHeat to 150oC for 7 daysWeigh and characterize deposits on pan

Test Fuels

A,B,C Ultra low sulfur fuels, different manufacturersD Low sulfur dieselE KeroseneG #2 diesel

Fuel also filtered through Al column to remove additives and analyzed

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Fuel Deposits

*Filtered fuel shows little or no deposits on walls of glass micro-oxidation tubes as well as on coupons

Progressively less deposits as B is

filtered

Progressively less deposits as G is filtered (not as dramatic as B)Order of deposit

thickness, most to least: B>>A>D>C G>E

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0

5

10

15

20

25

30

35

6 7 8 9 10 11 12 13 14 15 16 17 18 19 20

Carbon #

Rel

ativ

e %

Fuel AFuel BFuel G

GC Analyses - Fuels

Fuel C, D similar to A

Fuel B significantly different - additive?

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Does the Chemical Structure of the Base Fluid affect its effectiveness in protecting the surface against wear?

Lubricant Research

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Effect of Structure

Alcohol + Acid Ester + Watercatalyst, heat

To evaluate structure effect use same acid (2-ethylhexanoic) and different alcohols

Neopentyl Glycol

Trimethylol propane

Pentaerytritol

(CH3)2C(CH2OH)2

CH3CH2C(CH2OH)3

C(CH2OH)4JMP13@PSU.EDU

0

0.05

0.1

0.15

0.2

0.25

0.3

Wear

∆ S

CA

R

Ester D Ester E Ester F

Effect of Acid Chain Length on Wear

Trimethylol propane = alcohol

Acids:

D = nC5

E = nC7

F = mixture of nC8 & C10

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Wear Index =

(Total Carbons)(Effective Chain Length)(Polar Value + Branching Value)

where:Total Carbons = total carbons in the molecule

Effective Length = longest free chain of carbons available to form a film.

Polar Value = No. of carboxyl groups + No. of hydroxyl groups

Branching Value = ( 0.5 x No. of branches) + No. of double bonds.

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WEAR INDEX vs WEAR RATE

R2 = 0.7934

0

10

20

30

40

50

60

0 50 100 150 200 250 300WEAR INDEX

WEA

R R

ATE

, mm

3/N

mX1

0-9 Wear Rate

Log. (Wear Rate)

TEST COND: 40kg, 75C, 600rpm, 30min

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EFFECT of CHAIN LENGTH on FRICTION COEF.

R2 = 0.9622

0

0.02

0.04

0.06

0.08

0.1

0.12

0.14

0.16

0.18

0.2

0 5 10 15 20 25

ESTER ACID CHAIN LENGTH, CARBON No.

FRIC

TIO

N CO

EF.

TEST CONDITIONS: 40 kg, 75 C., 600 rpm, 30

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Test Methods

Load

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Test ConditionsFour Ball Wear Tester:

ANSI 52100 stainless steel balls

Test Time:30 min Run-in30 min Steady State 30 min Surface Eval’n

Test temp. = RT, 60oC, 75oC

Speed = 600, 1200 RPM

Loads = 1,10, 40 Kg

Pin – on – Disc:

Variable SpeedVariable Load

This study: 10 RPM20 NRoom Temp.

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254

91

66.8

8.29

Oil C

>>200226219Flash Point, oC(ASTM D 92)

12097123Viscosity Index(ASTM D2270)

21528.816.9cSt Visc @ 40oC

24.44.993.9cSt Visc @ 100oC (ASTM D 445)

OIL DOil BOil AOilProperties

Properties of Test Oils

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0

0.05

0.1

0.15

0.2

0.25

0.3

∆ w

ear,

mm

Run-in St.State Film Eval

Test Segment

Oil AOil BOil COil D

Effect of “Chain Length” of Hydrocarbon Oils on Wear – 4Ball Test

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0

1

2

3

4

5

6

7W

ear

Rat

e m

m/N

m x

10-

09

Wear f x 100

Oil AOil BOil COil D

Effect of Oil “Chain Length” –Tribometer (CSEM)

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Fric t ion coeffic ient of HMW Synth - Veg O il without ant iwear addit ive

0.0000

0.0200

0.0400

0.0600

0.0800

0.1000

0.1200

0.1400

0 30 60 90

T ime (min )

Wear Scar = 0.44 mm

∆ Wear Scar= 0.140 mmFC= 0.0902

Wear Scar = 0.61 mm

∆ Wear Scar= 0.12 mmFC= 0.0926

Wear Scar = 0.490 mm

∆ Wear Scar= 0.05 mmFC= 0.0832

Pin-on-Disc Avg f =0.066

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R2 = 0.7764

00.05

0.10.15

0.20.25

0.30.35

0.40.45

0 2 4 6 8

Pin on Disc Wear

Four

-bal

l Wea

r

Effect of “Chain Length” of Hydrocarbon Oils on Wear – 4Ball Test vs Tribometer

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Before Cleaning After Cleaning

Fixed Ball:

Chuck (Rotating) Ball

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0

0.05

0.1

0.15

0.2

0.25

0.3

∆ W

ear,

mm

Run-in Steady State Film Eval

ESBOSBOHOSBO

Effect of Double Bonds – Veg Oils

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0

0.05

0.1

0.15

0.2

0.25

0.3

0.35

∆ W

ear,

mm

Run-in Steady State Film Eval.

SBO+ Add AESBO+ Add A

Additive Effectiveness - Additive A

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00.020.040.060.08

0.10.120.140.160.18

0.2

∆ W

ear,

mm

Run-in Steady State Film Eval.

SBO+ Add AHOSBO+ Add A

Effect of Unsaturation - Additive A

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0

0.05

0.1

0.15

0.2

0.25

0.3

∆ W

ear,

mm

Run-in Steady State Film Eval.

SBO+ Add BESBO+ Add B

Additive Effectiveness - Additive B

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00.020.040.060.08

0.10.120.140.160.18

0.2

∆ W

ear,

mm

Run-in Steady State Film Eval.

SBO+ Add BHOSBO+ Add B

Effect of Unsaturation - Additive B

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0

0.05

0.1

0.15

0.2

0.25

0.3

∆ W

ear,

mm

Run-in Steady State Film Eval.

SBO+ Add CESBO+ Add C

Additive Effectiveness - Additive C

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00.020.040.060.08

0.10.120.140.160.18

0.2

∆ W

ear,

mm

Run-in SteadyState

Film Eval.

SBO+ Add CHOSBO+ Add C

Effect of Unsaturation - Additive C

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SummaryEFF & L - research studies & demonstration projects. Oxygenated Alternative Fuels - reduce particulates. DME - potential wear problems. VPO Biodiesel - effective f & wear additive.ULSF’s – wear, deposits, filter plugging. Chemical structure of base fluids and additives -significant factor in future lubricant formulation. New test methods - key to understanding surface interactions. (Optical, Advanced Photon Source, etc.)Surface engineering–materials, coatings & lubricants.

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AcknowledgementAppreciation is given for partial funding of these projects by Air Products; Cargill Corp; Caterpillar, Inc.; Cummins Engine Co.;USDA Laboratory (Peoria, Il) and Valvoline, Inc. Their financial support is appreciated.

A special thanks to Dr. George Fenske and the Tribology Group at Argonne National Laboratory for their continued interest and support of this research.

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The research contributions of the following Graduate Students is acknowledged:

Penn State University: Kimberly Wain – Biodiesel Fuels, DMEElana Chapman–DME, Oxygenated FuelsWaleska Castro – Veg. Oils, f & wear testsKraipat Cheenkachorn – Vegetable OilsDavid Weller – Chemical Characterization

Northwestern University: Ashlie Martini - Pin-on-disc studies, Mark Sturino - Pin-on-disc studies, Optical Microscopy

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No Not JOEPA

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Is Tribology Important?

Lack of Tribological Solutions results in Big Business:

1980 Survey - Over 20 Billion lost due to friction and wear annually

ASME Research Committee, circa 1980

1995 - Over 1.5% of the gross national product is lost due to friction and wear

Amato, Ivan, “ Better ways to Grease Industry’s Wheels” Fortune, Sept 1995; 256 [B]-256[K]

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