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Effect of crosslinking on the friction

and wear behavior of soybean and


tung oil-based polymeric materials
Satyam Bhuyan, Sam Holden,
Sriram Sundararajan
Department of Mechanical
Engineering
Dejan Anjelkovic, Richard Larock
Department of Chemistry
Iowa State University, Ames, IA

Multiscale Surface Engineering


and Tribology Laboratory

Outline
Background and motivation
Objectives
Materials and methods
Results and discussion
Conclusion

119th Annual Meeting of the Iowa Academy of Sciences

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Multiscale Surface Engineering


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Background and Motivation


World Marketed Energy Use by Fuel, 1980-2030 (quadrillion Btu)
300

History

Projections

33%

250
Oil

200

27%

38%
Coal

26%

150

Share of
World
Total

24%
Natural Gas

100
24%
8%

50

5%
Nuclear

6%

0
1980

9%

Renewables

1985

1990

1995

2000

2005

2010

2015

2020

2025

2030

www.eia.doe.gov
119th Annual Meeting of the Iowa Academy of Sciences

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Multiscale Surface Engineering


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Background and Motivation

Strong need to find viable alternatives to petroluem based


feedstock
The benefits of using agricultural feedstock as sources for
engineering materials includes:

The desire to improve environmental quality


Taking advantage of excess agricultural production
The potential for rural development
Concern over national security over dependence on foreign oil

Bio-based products include transportation fuels, chemicals,


and natural fibers derived from bio-renewable resources
Characterization of relevant properties of bio-based
materials are needed to evaluate their potential in replacing
existing materials.
Brown, Robert C., Biorenewable Resources. 2003
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Objectives
A new type of thermosetting polymers can be prepared through cationic
copolymerization of soybean oil and other types of biodegradable oil.
Changing the concentration of its constituents these polymers can range
from elastomer to tough and rigid plastic.

The objective of this study is to evaluate the


tribological (friction and wear) properties of the
soybean and tung oil-based polymeric materials
as a function of the crosslinking density.

119th Annual Meeting of the Iowa Academy of Sciences

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Materials
Three low saturated soybean (LSS) oil based-polymers with
styrene (ST) as the monomer and divinyl benzene (DVB) as
the crosslinking agent. Boron triflouride diethyl etherate
(BFE) modified with Norway fish oil ethyl ester (NFO) is used
as the initiator1.
Samples are designated as LSS DVB 10, LSS DVB 15 and
LSS DVB 20.

Three tung oil based-polymers with styrene (ST) as the


monomer and divinyl benzene (DVB) as the crosslinking
agent2.
Samples are designated as TUN DVB 20, TUN DVB 30 and
TUN DVB 40.
1 F.

2 F.

119th Annual Meeting of the Iowa Academy of Sciences

Li, et al., Polymer 42 (2001), 1567-1579


Li and R. Larock, Biomacromolecules, 4 (2003), 1018-1025
6

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Materials Bulk mechanical


properties of soybean oil-based
samples

Samples

Tg
(oC)

e
(moles/m3)

E (MPa)

u (MPa)

b (%)

RMS
Roughnessa
(nm)

LSS DVB 10

48

2.0 x 102

20

2.7

96.1

99 11

LSS DVB 15

61

5.3 x 102

90

6.0

64.1

102 9

LSS DVB 20

71

9.0 x 102

116

7.6

19.9

80 1

TUN DVB20

77

3.5 x 103

170

44

10.6 0.6

TUN DVB30

82

6.1 x 103

390

89

10.4 0.2

TUN DVB40

71

17 x 103

460

110

11.6 0.7

1698

21.3

Epoxy (EP) resin


a Measured

2.4

111 19

using AFM, 15 m X 15 m scan size.


F. Li and R. Larock, Journal of Polymer Science: Part B: Polymer Physics, 39 (2001), 60-77
F. Li and R. Larock, Biomacromolecules, 4 (2003), 1018-1025

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Experimental details
Reciprocating microtribometer

Friction (ramped load) tests Si3N4


ball of radius 1.2 mm

Dry sliding wear tests


Reciprocating tests with
Si3N4 ball

Load range: 0.2 800 mN


Stroke length: 40 mm

Load: 800 mN

Stroke speed: 10 mm/s

Stroke speed: 5 mm/s

Scratch tests with a diamond probe


of radius 100 m and 900 cone angle
Load range: 0.2 700 mN

Reciprocating tests with


diamond probe
Load: 700 mN

Conditions similar to ramped load


test for stroke length and stroke
speed

119th Annual Meeting of the Iowa Academy of Sciences

Stroke length: 60
mm/cycle for 500 cycles

Stroke speed: 10 mm/s


Stroke length: 60
mm/cycle for 10 cycles

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Experimental details
miscellaneous

Samples were cleaned in an ultrasonic bath for 10 mins


with de-ionized water and dried with compressed
nitrogen
Tests were performed at a controlled humidity( RH ~
20%) and temperature (25 0C)
Four sets of friction measurements were performed for
each sample.

119th Annual Meeting of the Iowa Academy of Sciences

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Surface topography using AFM


15 m X 15 m scan
Soy oil-based polymer

Tung oil-based polymer

Si3N4 Probe

Ra

76 nm

Ra

5.2 nm

Ra

8.6 nm

RMS

93 nm

RMS

11 nm

RMS

11 nm

Peak to Valley

660 nm

Peak to Valley

294 nm

Peak to Valley

244 nm

Skewness
Kurtosis

- 0.42
3.3

Skewness

0.34

Kurtosis

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10

Skewness

- 1.6

Kurtosis

12.4

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Results - Friction response


Soybean oil-based polymer

Tung oil-based polymer

Sample

COF

Sample

COF

LSS DVB 10

0.826

TUN DVB 20

0.078

LSS DVB 15

0.522

LSS DVB 20

0.550

TUN DVB 30

0.397

EP resin

0.701

TUN DVB 40

0.510

119th Annual Meeting of the Iowa Academy of Sciences

The elastomeric LSS DVB 10, showed


higher friction than the brittle LSS DVB
15 and LSS DVB 20 samples.
The coefficients of friction of the soybean
oil-based polymers were comparable to
that of EP resin but the tung oil-based
samples showed much improved friction
performance
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Results Wear tests


Friction Force vs. Sliding Distance with Si3N4 probe

Tung oil-based samples

Soybean oil-based samples

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Wear tracks with Si3N4 ball


Both the LSS DVB
10 and LSS DVB 15
samples exhibited
wear tracks
No wear was
observed on rest of
the samples

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Wear profiles using AFM

Edge of the wear track

LSS DVB 10

LSS DVB 15

Sample

Average wear depth


(nm)

LSS DVB 10

157 14.8

LSS DVB 15

127 13.0

EP resin

2234 1221

119th Annual Meeting of the Iowa Academy of Sciences

LSS DVB 15 showed 19%


less wear depth than LSS
DVB 10 which showed
presence of loose particles
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Transfer Films on Si3N4 ball


The probes for LSS
DVB 10 and LSS
DVB 15 show a
transfer film which
was orientated in the
sliding direction
Presence of transfer
material suggest
adhesive wear
Wear behavior of all
bio-based samples
were significantly
better than the EP
resin

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Scratch test (diamond probe):


LSS DVB 10
Onset of
damage
Cracking

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Scratch test: LSS DVB 15


Onset of
damage
Grooving
Stick slip

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Scratch test: LSS DVB 20


Onset of
damage
Grooving
Stick slip
LSS DVB 10
exhibited
earliest onset
of damage
whereas LSS
DVB 15 and
LSS DVB 20
exhibited
damage at
later stages

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Scratch test: Tung oil- based


polymers
There is an
increase in friction
force after a
certain load
No damage seen
on the surface

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Wear tests with diamond


probe
Choice of normal load
based on scratch test
LSS DVB 10 showed
highest wear depth
followed by LSS DVB 20
and LSS DVB 15

LSS

LSS

Sample

Average wear
depth (m)

LSS DVB 10

27 1.19

LSS DVB 15

7.68 0.44

LSS DVB 20

9.92 0.42

EP resin

9.28 5.96

LSS

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LSS DVB 10 displayed


cracking during the
scratch test (i.e. 1 cycle)
whereas LSS DVB 15
and LSS DVB 20 did not,
suggesting that LSS
DVB 10 underwent
abrasive wear by plastic
deformation whereas the
other samples might
have underwent wear by
fatigue as well
There were no
measurable wear track
seen on the tung oilbased samples

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Summary of tribological tests


Samples

Coeff. of
friction
against
Si3N4a

Coeff. of
friction
against
diamondb

Wear depth
with Si3N4
probec (nm)

Wear depth
with
diamond
probed (m)

Hardnesse
(GPa)

LSS DVB 10

0.826 0.021 0.686 0.058

157 14.76

27 1.19

0.035 0.004

LSS DVB 15

0.522 0.024 0.413 0.015

127 13.08

7.68 0.44

0.060 0.007

LSS DVB 20

0.550 0.019 0.423 0.043

---

9.92 0.42

0.130 0.019

TUN DVB 20

0.078 0.004 0.162 0.015

---

---

0.071 0.001

TUN DVB 30

0.397 0.021 0.201 0.028

---

---

0.091 0.002

TUN DVB 40

0.510 0.063 0.415 0.043

---

---

0.158 0.003

Epoxy (EP)
resin

0.701 0.039 0.830 0.033

2234 1221

9.28 5.96

---

For normal load range of 0.2-800 mN (LSS) and 0.2-400 mN (TUN). b For normal load range of 0.2-100 mN.
c After 500 cycles at 800 mN normal load.
d After 10 cycles at 700 mN normal load.
e Measured using nanoindenter

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Conclusions
Dry friction and wear behavior of soybean oil and tung oil-based polymers
prepared by cationic polymerization of low saturated soy-bean oil (LSS) with
divinyl benzene and polystyrene were evaluated as a function of crosslinking
density.
Crosslinking density has a large impact on friction and wear behavior of soybean
oil-based polymer:
Higher crosslinking density generally resulted in lower friction and adhesive wear.
Increased abrasive wear was observed for the lowest and highest crosslinking
densities.

Crosslinking density has an impact on the friction, but not wear, behavior for tung
oil-based samples
Higher crosslinking resulted in a higher friction
No damage on surface indicates that these brittle materials are wear resisting under
the given loading conditions.

These novel bio-based materials show promise as a replacement for conventional


plastics for use as a structural material (comparison against epoxy resin).
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Acknowledgement
Chris Li, University of South Carolina
Scott Chumbly, SEM group, Iowa State University
Jerry Amenson, Material Analysis and Research Lab,
Iowa State University

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