JMP13@PSU.

EDU

Research on Fuels &

Lubricants

Joseph M. Perez,
Tribology Group, Chemical Engineering Dept.,
Penn State University, University Park, PA 16802

Diesel Engine Emissions Reduction Conference

Newport, RI
August 24-28, 2003
 JMP13@PSU.EDU

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, Metals
„ 1980’s VPO, Adiabatic Engine, MeOH Oils
„ 1990’s Environmentally Friendly Fluids
Extended Drain Oils
 JMP13@PSU.EDU

Current Projects

„ Fuel Studies
„ DME
„ Biodiesel
„ ULSF
„ Vegetable Oils
„ High Temperature Liquid Lubricants
„ Coatings & Lubricants
„ Role of Chemical Structure
 JMP13@PSU.EDU

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
 JMP13@PSU.EDU

FUELS
Diesel Fuels
Petroleum cut boiling ~ 282-
338oC, #2, LSDF and ULSDF
300 ppm S
32 ppm S Distillation Hydrocarbon mixture
ULSD (< 15ppm S)

+ ROH
catalyst Biodiesel Fuels
Blends of methyl esters made
from vegetable oils
Soybeans

Dimethyl Ether
Converted from Syngas Hydrocarbon Syngas DME
 DME Research
JMP13@PSU.EDU

DME is environmentally benign DME Methane + H2 + CO

Decomposes rapidly
Doesn’t harm ozone layer

Reduces diesel engine emissions

Addition of oxygen into combustion zone

Engine and Vehicle Tests

Problems include low viscosity (wear), high vapor
pressure, and material compatibility
Laboratory Tests
Viscosity Studies
Injector Studies
O-Ring Studies
 Fuel Injector Studies
JMP13@PSU.EDU

Test Pins

Fuel Injector
Pin

New DME SCUFFED

Modified Cameron – Need digital pics of new and

Plint Machine DME pins from Plint!

Dr. Perez has pins at Argonne

 JMP13@PSU.EDU

Biodiesel Fuel Studies

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

Demonstrated in laboratory tests that addition

of oxygen to biodiesel resulted in improvement
in friction
Run #1 Run #2
Temp- 325oC Temp- 375oC
Feed Rate- 1000 g/hr Feed Rate- 1000 g/hr
O2/Feed Mole Ratio- 1.0 O2/Feed Mole Ratio- 1.0

(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)
Low Sulfur & Oxidized Diesel Fuels
0.140

0.120
Friciton Coefficient ( )

0.100

0.080

0.060
Low Sulfur Diesel

0.040 Ox. Diesel Run #1

Ox. Diesel Run #2
0.020
0 10 20 30 40 50 60
Time (min)
JMP13@PSU.EDU
 JMP13@PSU.EDU

Friction Traces for ULSDFs

0.140

0.130

0.120
Friciton Coefficient ( )

0.110

0.100

0.090
Fuel A
0.080
Fuel B
0.070 Fuel C

0.060
0 10 20 30 40 50 60
Time (min)
 Fuel Deposit Tests
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Micro-oxidation test

10ml of test fuel into glass test tube

One stainless steel pan
Heat to 150oC for 7 days
Weigh and characterize deposits on pan

Fuel also filtered through Al

column to remove additives and
analyzed

Test Fuels
A,B,C Ultra low sulfur fuels, different manufacturers
D Low sulfur diesel
E Kerosene
G #2 diesel
 JMP13@PSU.EDU

Fuel Deposits

Progressively less Progressively less

deposits as B is
filtered
Order of deposit
thickness, most to least:
B>>A>D>C#G>E
deposits as G is
filtered (not as
dramatic as B)

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

as well as on coupons
 GC Analyses - Fuels
JMP13@PSU.EDU

35

30 Fuel B significantly Fuel A

different - additive?
Fuel B
25
Relative %

Fuel G
20

15

10

0
6 7 8 9 10 11 12 13 14 15 16 17 18 19 20

Carbon #
Fuel C, D similar to A
 Lubricant Research

Does the Chemical Structure of the

Base Fluid affect its effectiveness in
protecting the surface against wear?

JMP13@PSU.EDU
 Effect of Structure
„ Alcohol + Acid Ester + Water
catalyst, heat

To evaluate structure effect use same acid (2-

ethylhexanoic) and different alcohols

„ Neopentyl Glycol (CH3)2C(CH2OH)2

„ Trimethylol propane CH3CH2C(CH2OH)3

„ Pentaerytritol C(CH2OH)4
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 Effect of Acid Chain Length on Wear

„ Trimethylol propane = alcohol

0.3 Acids:
0.25
D = nC5
0.2
∆ SCAR

0.15
E = nC7
0.1 F = mixture of
0.05 nC8 & C10
0
Wear

Ester D Ester E Ester F

JMP13@PSU.EDU
 JMP13@PSU.EDU
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.
 WEAR INDEX vs WEAR RATE
TEST COND: 40kg, 75C, 600rpm, 30min
60
WEAR RATE, mm3/NmX10-9

Wear Rate
50
Log. (Wear Rate)
40 R2 = 0.7934

30

20

10

0
0 50 100 150 200 250 300
WEAR INDEX
JMP13@PSU.EDU
 EFFECT of CHAIN LENGTH on FRICTION COEF.
TEST CONDITIONS: 40 kg, 75 C., 600 rpm , 30
0.2

0.18
2
R = 0.9622
0.16

0.14
FRICTION COEF.

0.12

0.1

0.08

0.06

0.04

0.02

0
0 5 10 15 20 25

ESTER ACID CHAIN LENGTH, CARBON No.

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Test Methods

Load

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 Test Conditions
Four Ball Wear Tester: Pin – on – Disc:
ANSI 52100 stainless steel balls
Variable Speed
Test Time: Variable Load
30 min Run-in
30 min Steady State
30 min Surface Eval’n This study:
10 RPM
Test temp. = RT, 60oC, 75oC 20 N
Speed = 600, 1200 RPM Room Temp.
Loads = 1,10, 40 Kg

JMP13@PSU.EDU
 Properties of Test Oils
Oil Oil A Oil B Oil C OIL D
Properties
cSt Visc @ 100oC 3.9 4.99 8.29 24.4
(ASTM D 445)
cSt Visc @ 40oC 16.9 28.8 66.8 215

Viscosity Index 123 97 91 120

(ASTM D2270)
Flash Point, oC 219 226 254 >>200
(ASTM D 92)
JMP13@PSU.EDU
 Effect of “Chain Length” of Hydrocarbon
Oils on Wear – 4Ball Test

0.3 Oil A
0.25 Oil B
Oil C
∆ wear, mm

0.2
Oil D
0.15

0.1

0.05

0
Run-in St.State Film Eval
Test Segment
JMP13@PSU.EDU
 Effect of Oil “Chain Length” –
Tribometer (CSEM)

7 Oil A
Oil B
Wear Rate mm/Nm x 10-09

6
Oil C
5 Oil D
4
3
2
1
0
Wear f x 100
JMP13@PSU.EDU
 Friction coefficient of HMW Synth - Veg Oil without antiwear additive

0.1400

Wear Scar = 0.490 mm

0.1200
∆ Wear Scar= 0.05 mm
FC= 0.0832
0.1000

0.0800 Wear Scar = 0.61 mm

∆ Wear Scar= 0.12 mm

Wear Scar = 0.44 mm

∆ Wear Scar= 0.140 mm

0.0600 FC= 0.0926
FC= 0.0902
0.0400

Pin-on-Disc Avg f =0.066

0.0200

0.0000
0 30 60 90
T ime (min )

JMP13@PSU.EDU
Effect of “Chain Length” of Hydrocarbon Oils on
Wear – 4Ball Test vs Tribometer

0.45
0.4
0.35
Four-ball Wear

2
0.3 R = 0.7764
0.25
0.2
0.15
0.1
0.05
0
0 2 4 6 8
Pin on Disc Wear
JMP13@PSU.EDU
 Chuck (Rotating) Ball

Fixed Ball:

Before Cleaning After Cleaning

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 Effect of Double Bonds – Veg Oils

0.3
ESBO
0.25 SBO
HOSBO
∆ Wear, mm

0.2

0.15

0.1

0.05

0
Run-in Steady State Film Eval
JMP13@PSU.EDU
 Additive Effectiveness - Additive A

0.35
SBO
0.3 + Add A
0.25 ESBO
∆ W ear, m m

+ Add A
0.2
0.15
0.1
0.05
0
Run-in Steady State Film Eval.
JMP13@PSU.EDU
 Effect of Unsaturation - Additive A

0.2
SBO
0.18
0.16 + Add A
0.14 HOSBO
∆ W ear, m m

0.12 + Add A
0.1
0.08
0.06
0.04
0.02
0
Run-in Steady State Film Eval.
JMP13@PSU.EDU
 Additive Effectiveness - Additive B

0.3
SBO
0.25 + Add B
ESBO
∆ W ear, m m

0.2 + Add B
0.15

0.1

0.05

0
Run-in Steady State Film Eval.
JMP13@PSU.EDU
 Effect of Unsaturation - Additive B

0.2
SBO
0.18
0.16 + Add B
0.14 HOSBO
∆ W ear, m m

0.12 + Add B
0.1
0.08
0.06
0.04
0.02
0
Run-in Steady State Film Eval.
JMP13@PSU.EDU
 Additive Effectiveness - Additive C

0.3
SBO
0.25 + Add C
ESBO
∆ W ear, m m

0.2 + Add C
0.15

0.1

0.05

0
Run-in Steady State Film Eval.
JMP13@PSU.EDU
 Effect of Unsaturation - Additive C

0.2 SBO
0.18
+ Add C
0.16
HOSBO
0.14
∆ W ear, m m

0.12 + Add C
0.1
0.08
0.06
0.04
0.02
0
Run-in Steady Film Eval.
State
JMP13@PSU.EDU
 Summary
„ EFF & 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.
JMP13@PSU.EDU
Acknowledgement
„ Appreciation 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.
JMP13@PSU.EDU
 The research contributions of the following
Graduate Students is acknowledged:

„ Penn State University:

„ Kimberly Wain – Biodiesel Fuels, DME
„ Elana Chapman–DME, Oxygenated Fuels
„ Waleska Castro – Veg. Oils, f & wear tests
„ Kraipat Cheenkachorn – Vegetable Oils
„ David Weller – Chemical Characterization
„ Northwestern University:
„ Ashlie Martini - Pin-on-disc studies,
„ Mark Sturino - Pin-on-disc studies, Optical
Microscopy
JMP13@PSU.EDU
 No Not
JOEPA

JMP13@PSU.EDU
 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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