Composites: Part A 38 (2007) 87–93

www.elsevier.com/locate/compositesa

Solid freeform fabrication of epoxidized soybean oil/epoxy

composite with bis or polyalkyleneamine curing agents q
a,*
Z.S. Liu , S.Z. Erhan a, P.D. Calvert b

a
Food and Industrial Oil Research, NCAUR, ARS, USDA, 1815 N. University Street, Peoria, IL 61604, United States
b
Arizona Materials Laboratories, Department of Materials Science and Engineering, University of Arizona, 4715 E. Fort Lowell Road,
Tucson, AZ 85712, United States

Received 13 June 2005; received in revised form 22 December 2005; accepted 13 January 2006

Abstract

Extrusion freeform fabrication has been used to make bars of fiber-reinforced epoxidized soybean oil (ESO)/epoxy resin. Freeform
fabrication methods build materials by the repetitive addition of thin layers. The mixture of epoxidized soybean oil (ESO) and epoxy
resin are modified with a gelling agent to solidify the materials until curing occurs. The high strength and stiffness composites are formed
through fiber reinforcement. Glass, carbon and mineral fibers are used in the formulations. It is shown that the fiber orientation follows
the direction of motion of the write head that deposits the resins and has a large influence on the properties of the composite. In addition,
the effects of curing agents, curing temperature, epoxy/ESO ratio, and fiber loading on mechanical properties of composites are studied
and reported.
 2006 Elsevier Ltd. All rights reserved.

Keywords: A. Fibres; A. Polymer-matrix composites (PMCs); Solid freeform fabrication; B. Mechanical properties

1. Introduction with increasing social emphasis on issues of the environ-

Fiber-reinforced composites offer great potential for use
in aircraft and automotive primary structure. They are gen-
erally manufactured by using fibers as reinforcement and
polymeric resin as a matrix. During the last few years, there
has been a growing interest in the use of polymers obtained
from renewable resources because advantages of these
polymers include their biodegradable properties and, in
many cases, lower cost [1]. The importance of natural prod-
ucts for industrial applications also becomes very clear
q
Names are necessary to report factually on available data; however,
the USDA neither guarantees nor warrants the standard of the product,
and the use of the name by USDA implies no approval of the products to
the exclusion of other that may also be suitable.
*
Corresponding author. Tel.: +1 309 681 6104; fax: +1 309 681 6340.
E-mail address: liuz@ncaur.usda.gov (Z.S. Liu).
ment, waste disposal, and the depletion of non-renewable
resources. United States agriculture produces over 20 bil-
lion pounds of soybean oil annually, only 590 million
pounds used in industrial application, and frequently
carry-over exceeds one billion pounds. The major use of
soybean oil is directed to food products such as salad
and cooking oil, shortening, and margarine. Less than
3% of soybean oil is utilized in non-food applications since
a number of former vegetable oil markets were lost to
petroleum products. Development of economically feasible
new industrial products from soybean oil or commercial
processes is highly desirable. In our previous paper [2],
we reported the preparation of epoxidized soybean oil
(ESO) based composites. These composites reinforced with
glass, short carbon, Franklin Fiber H-45, and Fillex 17-
AF1 fibers demonstrated thermophysical and mechanical
properties comparable to petroleum-based soft rubbery
polymeric materials. In order to obtain a variety of viable

1359-835X/$ - see front matter  2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.compositesa.2006.01.009
88 Z.S. Liu et al. / Composites: Part A 38 (2007) 87–93
polymeric materials ranging from elastomers to rigid plas-
tics meeting a wide variety of market demand, a combina-
tion of ESO and epoxy resin is considered.
Epoxy resins are widely used as polymeric matrix in
composites. However, epoxy resins are similar to other
engineering resins in that they are either brittle, notch-sen-
sitive, or both. For load-bearing purposes, this means that
the product may be subject to catastrophic failure. A major
effort over the years focused on improving the toughness of
epoxy structural systems. As a result, epoxy resins have
been used for structural applications such as adhesives,
encapsulation of electronic devices, and composites such
as electrical laminates, aerospace parts and automotive
parts.
Sue et al. [3] have reviewed rubber-toughening of epoxy
resins. This method has been most effective and can improve
toughness substantially. Qureshi et al. [4] reported that the
use of 25% epoxidized crambe oil (ECO) as reactive diluents
in bisphenol A and cycloaliphatic epoxy compounds gave
improvement in resistance to fatigue crack propagation
without significant sacrifice in tensile or impact strength
and Young’s modulus. Raghavachar et al. [5] recently
reported rubber-toughening epoxy thermosets with epoxi-
dized crambe oil. They reported the phase separation in
thermoset matrices of diglycidyl ether bisphenol
(DGEBA)-4,4 0 -diaminodiphenylmethane (DDM)-ECO
and improvement in toughness of the epoxy matrices. Frac-
ture toughness values of the epoxy thermosets were
increased approximately 100% by both 5% and 10% epoxi-
dized crambe oil. It is clear that a combination of epoxi-
dized vegetable oil, epoxy resin and curing agents can be
formulated to meet a wide variety of market demands.
Soy-based polymers will support global sustainability and
provide an alternative to synthetic polymers for many man-
ufacturing applications [6].
Solid freeform fabrication (SFF) is a method of making
shapes without molds. It is best known in its stereolitho-
graphy forms as a method of rapid prototyping. In stereo-
lithography a laser photopolymerizes successive thin layers
of monomer to build up a solid object. Extrusion solid free-
form fabrication was developed by the University of Ari-
zona in collaboration with Advanced Ceramic Research
(Tucson, AZ) [7]. It functions essentially as a three-dimen-
sional (3D) pen plotter. A fine stream of liquid resin or
slurry is pumped from a syringe as it moves over the sur-
face of a hot-plate to trace out a layer of materials. The syr-
inge then moves up one step and writes the next lager as the
first continues to cure (Fig. 1). The shape to be produced
may be derived from a 3D CAD program or from standard
drawing packages. This method has the potential to pro-
duce new materials and complex composites that could
not be made in any other way.
In this work, we report the preparation of ESO/epoxy
based composites by extrusion solid freeform fabrication
method. High strength and stiffness parts can be obtained
through fiber reinforcement. These high performance com-
posites will be tested in agriculture equipment, the automo-
Fig. 1. Sketch of the extrusion freeform fabrication apparatus.
tive industry, civil engineering, marine infrastructure, rail
infrastructure, and the construction industry. Recent
advances in genetic engineering, natural fiber development,
and composite science offer significant opportunities for
improved materials from renewable resources with
enhanced support for global sustainability.
2. Experimental
2.1. Materials
The resin used as a co-matrix is EPON 828, provided
by the Shell Chemical Company (Houston, Texas).
EPON 828 is a bisphenol A/epichlorohydrin based epoxy
resin, which is the most widely used epoxy. ESO (7.0% oxi-
rane oxygen) was purchased from Alf Atochem Inc. (Phil-
adelphia, PA). Calcium sulfate microfiber, Franklin Fiber
H-45 used in the experiments was provided by the United
States Gypsum Company, (Chicago, IL). Wollastonite
mineral fiber, Fillex 17-AF1 fiber is surface-modified wol-
lastonite, an inorganic mineral reinforcement. The Fillex
17-AF1 fiber was provided by Intercorp Inc. (Milwaukee,
WI). Glass fiber is milled E-glass (electric glass) fiber with
a nominal length of 1/32 in. Fiber diameter of 10 lm was
used in all experiments. All above fibers were used as
received. Short carbon fiber was purchased from Dupont
Co. (Wilmington, DE) and chopped in a coffee grinder
for 20 s to reduce the length. Optical microscopy gave aver-
age length from 0.25 to 0.12 mm. A previous study [8] char-
acterized length distributions, diameter distributions and
aspect ratios obtained for fibers chopped in this way. Cur-
ing agents, 2,2 0 -(ethylenedioxy)-bisethylamine, Jeffamine
EDR-148, polyalkyleneamine, Jeffamine D-230, and Jeff-
amine T-403 were provided by Huntsman Corporation,
(Houston, Texas), and used as received. Diethylenetria-
mine (DETA) and triethylenetetramine (TETA) 60% tech
were purchased from Aldrich Chemical Inc., (Milwaukee,
WI), and used without further purification. The chemical
structures of curing agents are shown in Scheme 1. Thixo-
tropic agent, Aerosil R805 was obtained from Degussa
Corp. (Ridgefiled Park, NJ).
 Z.S. Liu et al. / Composites: Part A 38 (2007) 87–93 89

H2N CH CH2 [ O CH2 CH ] x NH2 program written in Microsoft Quick Basic. Solid bar sam-
ples were written as a series of lines.
CH3 CH3

Jeffamine D-230 2.4. Scanning electron microscopy

Scanning electron microscopy (SEM) was performed to

CH2 [O CH2 CH (CH3) ]x NH2 investigate the fracture surface of the composites and inter-
face between the filler and the polymeric matrix. The SEM
CH3CH2 C CH2 [ O CH2 CH (CH3) ]y NH2 photographs were taken with a JEOLJSM 6400 V instru-
ment. The specimens were previously coated with gold.
CH2 [ O CH2 CH (CH3) ]z NH2 The microscope was operated at 5 kV.

Jeffamine T-403 2.5. Mechanical testing

The mechanical properties testing were done using a

H2N CH2 CH2 O CH2 CH2 O CH2 CH2 NH2
three point bending test method with an Instron model
Jeffamine ERD-148 1100 testing machine. The tests were carried out at room
temperature. Because samples for three point bending test
are rectangular shapes, ASTM D-90 test standard was fol-
H2N CH2 CH2 NH CH2 CH2 NH2
lowed. The support span length was modified to 40 mm
Diethylenetriamine (DETA) (according to ASTM-90, the support span length of
50 mm was recommended). The standard formula for the
CH2 CH2 NH2
modulus, E and strength, U in three point bending of a
H2N CH2 NH CH2 CH2 NH CH2
beam was used
Triethylenetetramine (TETA)
E ¼ PL3 =4bd 3 d; U ¼ 3PL=2bd 2
Here P is equal to the break load, L is the support span, d is
H ( NH CH2 CH2 )n NH2 the deformation at the center under load P, d is the sample
Polyethylenimine, linear
height, and b is the sample width.

Scheme 1. Chemical structures of curing agents. 3. Results and discussion

3.1. Composite morphology

2.2. Forming of composites
ESO and EPON 828 were mixed well in the ratio of
1:0.3. Vacuum was applied to remove air bubbles at
55 C for 30 min. Then mixture was mixed with Aerosil
R805, 10 g /100 g (ESO + EPON), and fibrous fillers. The
mixture was degassed in vacuum system at 55 C for
30 min. The fiber filled slurries showed a yield point, such
that formed parts hold their shape until cured. The mixture
was removed from the oven, and cooled to room tempera-
ture. Curing agent, 23.3 g/100 g (ESO + EPON) was then
added, and after proper mixing, the paste was put into
20 cc plastic syringe. Bars 75 mm · 8 mm · 4 mm were
formed by deposition of five layers, and subsequently cured
at 100 C for 24 h, then at 180 C (Jeffamine curing agents)
for 48 h, or at 150 C (TETA or DETA curing agent) for
48 h.
2.3. Solid freeform fabrication
Solid freeform fabrication was conducted using an
Asymtek model 402 fluid dispensing system, equipped with
small stepper motors (Oriel stepper mike) to drive the deliv-
ery syringe. The Asymtek and syringes were controlled by a
Scanning electron microscopy (SEM) was performed to
characterize the morphology of soybean oil-based filled
composite materials. In our previous paper [2], we reported
SEM micrographs of four different kinds of fibers: (1) the
commercial milled glass fibers with a nominal length of
1/32 in. and fiber diameter of 10 lm, the aspect ratio distri-
bution reported according to Peng [9] shows two main
peaks at values of 3 and 7; (2) calcium sulfate microfiber,
Franklin Fiber H-45 with average length of 60–75 lm,
average diameter of 1.5–2 lm, average aspect ratio of 40;
(3) Wollastonite mineral fiber, Fillex 17-AF1 with average
aspect ratio of 20, diameter of 2.5 lm; (4) the carbon fiber
was grounded for 20 s in coffee ground, giving an average
length from 0.25 to 0.12 mm. Those fibers were used in
all the experiments. Fig. 2 shows SEMs of freshly fractured
surface for ESO/EPON composite filled with four types of
fibers. Fig. 2(a) corresponds to milled glass fiber. Fig. 2(b)
corresponds to Franklin Fiber H-45. Fig. 2(c) corre-
sponds to Fillex 17-AF1 fiber. Fig. 2(d) corresponds to
carbon fiber. SEM photographs show the well-developed
interfacial interaction between fiber (Franklin Fiber
H-45 or Fillex 17-AF1 fiber) and matrix. Clearly, for glass
fiber and carbon fiber, there are fiber breakages due to the
90 Z.S. Liu et al. / Composites: Part A 38 (2007) 87–93

of triglycidyl epoxy with amine curing agents by FTIR and

found that the intensity of secondary amine peaks signifi-
cant increased at lower temperature, compared to primary
amine peaks. Hydroxyl group intensity also increased with
time. At higher temperatures, the reaction of both primary
and secondary amines was initially simultaneous, but as the
reaction proceeds further, higher epoxy-hydroxyl etherifi-
cation reaction dominated the reaction. This etherification
reaction indicates the formation of network structure of
composites. As the crosslinking increases, the mechanical
properties of the composites are improved.

3.3. Effect of curing agent

Table 2 presents flexural strength and flexural modulus

data for a composite consisting of ESO, 52.0 vol%, EPON
828, 13.5 vol%, Franklin Fiber H-45, 18.7 vol%, Aerosil
R805, 10 g/100 g (ESO + EPON) and various curing agent,
23.3 g/100 g (ESO + EPON). To investigate the effect of
curing agents, the better method is to cure the composites
Fig. 2. Scanning electron micrograph of the freshly fractured surface of at the same temperature with various curing agents. In this
soybean oil-based composites filled with four kinds of fiber. (a) Composite
case, Jeffamine curing agents, EDR-148, D-230, and T-403
filled with E-glass fiber, (b) composite filled with Franklin Fiber H-45, (c)
composite filled with wollastonite, Fillex 17-AF1 fiber, (d) composite do not provide composites with better mechanical proper-
filled with carbon fiber. ties at lower temperature, such as 150 C. The samples are
soft, like rubber materials, they are not suit for three point
bending test. Therefore, the composites were cured at
existence of better adhesion between both components. higher temperature for all Jeffamine curing agents, and at
However, holes and spacing occur along the fiber, resulting 150 C DETA and TETA curing agents. It can be seen
in poor contact and inferior stress transfer between the from Table 2 that when Jeffamine D-230 was used as the
phases. curing agent, the composite has lower mechanical proper-
ties. This is presumably due to the reactivity of the amine
3.2. Effect of curing temperature groups in the Jeffamine D-230 (polyoxypropylenediamine),
where the amine groups are located on secondary carbon
Effect of temperature on the mechanical properties is atoms at the ends of an aliphatic polyether chain. Com-
presented in Table 1. It clearly can be seen that the flexural pared to Jeffamine EDR-148, triethyleneglycoldiamine, its
modulus increases as curing temperature increases. This amine groups are located on primary carbon atoms at
trend was also observed in neat ESO with curing agent sys- the ends of an aliphatic polyether chain. Jeffamine EDR-
tem, reported in our previous paper [2]. An explanation 148 is an unhindered diamine miscible in a wide variety
presumably is that at lower temperature, the epoxy groups of solvents. It is much more reactive than Jeffamine D-
are mainly consumed by primary amine hydrogen atoms, 230. Jeffamine T-403, polyoxypropylenetriamine is a tri-
secondary amine reaction was negligible, because primary functional primary amine. Its amine groups are located
amine hydrogen atoms are more reactive than secondary on secondary carbon atoms at the ends of aliphatic
amine hydrogen atoms. The reactivity of primary and sec-
ondary amine hydrogen atoms are studied by Padma and
coworkers [10]. They investigated the cure reaction kinetics
Table 2
Effect of curing agents
Curing agent Flexural Flexural Strain at
Table 1
strength (MPa) modulus (GPa) break (%)
Effect of curing temperature for Jeffamine EDR-148
Jeffamine D-230 10.5 0.27 3.78
Curing Flexural Flexural Strain at
Jeffamine T-403 14.2 0.25 5.95
temperature (C) modulus (GPa) strength (MPa) break (%)
Jeffamine EDR-148 21.0 0.97 2.22
160 0.13 13.0 4.3 DETAa 65.0 3.93 1.54
170 0.35 13.7 3.4 TETAa 110.0 4.00 2.11
180 0.97 21.0 2.2
Conditions: ESO, 52.0 vol%, EPON 828, 13.5 vol%, Franklin Fiber H-
190 0.98 23.0 2.4
45, 18.7 vol%, curing agent, 23.3 g/100 g and fumed silica, 10.0 g/100 g
Conditions: ESO, 47.6 wt.%, EPON 828, 14.5 wt.%, Franklin Fiber H- (ESO + EPON).
a
45, 23.4 wt.%, Jeffamine EDR-148, 23.3 g/100 g (ESO + EPON) and Curing temperature, 150 C for TTA and DTA, 180 C for all
fumed silica, 10.0 g/100 g (ESO + EPON). Jeffamines.
 Z.S. Liu et al. / Composites: Part A 38 (2007) 87–93
polyether chains. The reactivity of amines located on sec-
ondary carbon atoms is lower than that of amines located
on primary carbon atoms. That is the reason the reactivity
of Jeffamine curing agents in the order of EDR-148 > T-
403 > D230. By comparison of triethylenetetramine
(TETA) and diethylenetriamine (DETA) to Jeffamine cur-
ing agents, TETA and DETA curing agents provide com-
posites with better mechanical properties. This is because
that three are two primary amine groups located on pri-
mary carbon atoms at the ends of an aliphatic polyimine
chain in TETA and DETA molecules. At the same time,
there is one secondary amine group in DETA molecule
and two secondary amine groups in TETA molecule. Those
secondary amine groups also take part in reaction and for-
mulate a network structure of composites. The network
structure of composites would show the stronger mechani-
cal properties.
3.4. Effect of fiber type
The incorporation of disperse fibers into polymers can
improve the mechanical and thermal properties of materi-
als required for engineering applications. This change in
the mechanical and thermal behavior is due to several fac-
tors such as variation in the mobility of the macromole-
cules in the boundary layers, the orientation influence of
the fiber surface, effect of fibers on the structure of the
polymers, as well as the different types of fiber-polymer
interactions. In order to study the effect of different types
of fibers on the mechanical properties, the experiments
were carried out to make test bars. The composite formu-
lation is ESO, 52.0 vol%, EPON, 13.5 vol%, and fiber,
18.7 vol% with Jeffamine EDR-148 curing agent, 23.3 g/
100 g (ESO + EPON). The mechanical properties measure-
ment results are presented in Table 3. Among the different
fibers, glass and carbon fibers show better reinforcing
effects than mineral fibers. These results are probably due
to glass and carbon fibers themselves having high strength.
For example, E glass fiber has a tensile strength of about
3 GPa and a modulus that approaches 100 GPa. They exhi-
bit the large contribution to the strength and rigidity of the
reinforced composites. The principal advantages of glass
fibers commonly used as reinforcing fibers for polymer
matrix are their high strength and their low cost. Franklin
Fiber H-45 used in this study has average 60–75 lm
Table 3
Effect of different types of fibers
Fiber Flexural Flexural Strain at
modulus (GPa) strength (MPa) break (%)
E-glass 1.28 22.3 3.2
Carbon 1.06 21.0 6.6
Franklin 0.97 21.0 2.2
Wollastonite 0.77 19.5 4.2
Conditions: ESO, 52.0 vol%, EPON 828, 13.5 vol%, and fiber, 18.7 vol%,
in the composite formulations with Jeffamine EDR-148, 23.3 g/100 g
(ESO + EPON).
91
length. Specific gravity is 2.45–2.55 g/cc. As a microfiber,
it shows moderate reinforcement. Advantages of this min-
eral fiber are their cheap price and good temperature stabil-
ity. Wollastonite is a semi-reinforcing mineral fiber. The
surface of the fiber is modified. Their properties of bonding
at the interface between resin matrix and inorganic miner-
als are improved. Their mechanical properties, such as ten-
sile strength and modulus have not been presented, but it is
probably similar to most microfibers with a modulus of
approximately 100 GPa, but relatively low tensile strength.
Wollatonite provides many processing performance bene-
fits, including increased stiffness and strength, improved
heat distortion temperature, low coefficient expansion,
and ease processibility at considerably lower cost.
3.5. Influence of fiber orientation on flexural modulus
The strength and moduli of fiber-reinforced composites
depends on fiber volume fraction, aspect ratio, and orienta-
tion. There are good theoretical treatment for the effect of
aspect ratio and volume fraction on modulus [11], but ori-
entation is more difficult to control. It is strongly influenced
by processing methods and by local flow conditions in, for
instance, injection-molded parts. As a result, changes in vol-
ume fraction and aspect ratio will change the degree of ori-
entation. Also, theoretical treatments are not very
satisfactory. Peng and Calvert [12,13] studied orientation
effects in freeformed short-fiber composites. They sectioned
and polished samples of epoxy/glass composites cross the
write direction. Optical microscopy was used to measure
the major and minor axes of the elliptical fiber sections.
They discovered that fiber orientation corresponds closely
to the machine direction during sample preparation. In
glass fiber/epoxy composites, they found that 90% of fibers
are within 10 of the machine’s write direction. By writing a
series of test bars with write axes at different angles to the
long axis, they can vary the modulus by approximately a
factor of three. In ESO/epoxy system, we prepared test bars
by writing at varying angles relative to the axis of the test
bars to investigate effects of fiber orientation on the proper-
ties of composites. The composites’ formulation is ESO/
EPON/Jeffamine EDR-148 reinforced with 23.4 wt.% of
Franklin Fiber H-45. The effect of this orientation on flex-
ural modulus is shown in Table 4. It can be seen that mod-
ulus is much greater parallel to the writing direction than
cross this direction. The modulus can be varied by approx-
imately a factor of three and a half. Peng [13] discussed dis-
tribution of fiber orientation. There is a distribution of fiber
orientation from small to major depending on the write
speed. At lower write speed, such as 250 step s1, and pump
speed at 16 lm s1, there is a major distribution. But at
higher writ speed of 750 step s1 there is a small fiber distri-
bution. In this fiber orientation study, higher writing speed
of 750 step s1 used, we expected that there is a small distri-
bution of fiber orientation. An increase in modulus as
shown in Table 4, is resulted in increasing fiber orientation.
This is significant because the composite modulus is at least
92 Z.S. Liu et al. / Composites: Part A 38 (2007) 87–93

Table 4 1.6
Effect of orientation on EPON 828/ESO/Jeffamine EDR-148 Reinforced

Flexural Modulus (GPa)

with 23.4 wt.% Franklin Fiber H-45 1.2
Fiber Flexural Flexural Strain at
orientation modulus (GPa) strength (MPa) break (%) 0.8
0 0.97 21.0 2.2
30 0.42 14.0 5.0 0.4
45 0.34 16.0 5.0
60 0.32 22.0 4.3 0
90 0.29 8.1 2.2 15 20 25 30 35 40 45
Fiber content (wt%)
Conditions: ESO, 47.6 wt.%, EPON, 14.5 wt.%, and Jeffamine EDR-148,
23.3 g/100 g (ESO + EPON). Fig. 3. Flexural modulus of composites as a function of Franklin Fiber
H-45 fiber content.

as sensitive to orientation as to fiber aspect ratio and vol-
ume fraction.
3.6. Effect of EPON 828/ESO ratio
The experiments were carried out for investigating influ-
ence of EPON/ESO ratio on mechanical properties of the
composites. The results are presented in Table 5. It was
found that flexural modulus increases with the EPON con-
centration increases. This indicates that EPON resin has a
determining influence on mechanical properties of the com-
posites. In the two component matrix system, ESO is a soft
segment, and EPON epoxy is a hard segment. An increase
in the EPON resin concentration provides the composite
with a higher flexural modulus. However, when the
EPON/ESO weight ratio is more than 0.3 to 1, phase sep-
aration was observed. This is because EPON has a much
higher reactivity with curing agent Jeffamine EDR-148
than ESO, because of the location of epoxy groups; it
reacts first with curing agent and forms a rigid EPON-Jeff-
amine phase. Peng [12] has studied the physical properties
of composites prepared by pure EPON 828 resin and Jeff-
amine EDR-148 with glass fiber. The flexural modulus
and flexural strength of the composites can reach to
6.3 GPa and 109 MPa, respectively. The composites pre-
pared by pure EPON 828 resin with Franklin fiber would
have better mechanical properties. The brittle and notch-
sensitive properties of epoxy composites need to be
improved. It is well know that soybean oil is a mixture of
triglycerides formed by different saturated and unsaturated
fatty acids. All C@C bonds in the unsaturated fatty acids
are located in the middle of fatty acid chain. Hence, reac-
tivity of internal epoxy group of ESO obtained by the
Table 5
Effect of EPON 828/ESO ratio
EPON/ESO ratio Flexural Flexural Strain at
(weight) modulus (GPa) strength (MPa) break (%)
0.30:1 0.97 21.0 2.2
0.22:1 0.71 16.3 3.3
0.15:1 0.26 12.1 3.6
Conditions: Franklin Fiber H-45, 23.4 wt.%, Jeffamine EDR-148, 23.3
g/100 g (ESO + EPON) and fumed silica, 10.0 g/100 g (ESO + EPON).
epoxidation of double bonds is slower, compared to the
epoxy group on the end of epoxy resin chains. This is
due mainly to the diffusional restrictions.
3.7. Effect of fiber loading
At conditions of EPON/ESO in the ratio of 0.3:1, fumed
silica, 10 g/100 g (ESO + EPON), and Jeffamine EDR-148,
23.3 g/100 g (ESO + EPON), the flexural modulus of com-
posite as a function of Franklin Fiber H-45 loading is pre-
sented in Fig. 3. It is observed that the increase in fiber
content leads to an increase in the flexural modulus. In
the case of fiber-reinforced composites, it is well known
that there exits a critical aspect ratio at which the mechan-
ical properties of the composites are maximized. This crit-
ical aspect ratio depends on the volume fraction of the fiber
and also on the ratio of the modulus of fiber to matrix
modulus [14]. When the volume fraction increases beyond
this limit, the slurry is too viscous and will not flow through
the needle. Therefore data for higher Franklin Fiber H-45
contents are not available.
4. Conclusions
The application of solid freeform fabrication to rein-
forced composites has been explored. Fiber reinforced
epoxidized soybean oil/epoxy composites can be formed
with high strength and stiffness. Different fiber types, E-
glass fiber, carbon fiber, and mineral fibers are used in rein-
forced composites. It was found that glass fiber and carbon
fiber show better reinforcing effects than mineral fibers. By
writing a series of test bars with write axes at different angles
to the long axis, modulus can be varied by approximately a
factor of three and a half. This is significant because com-
posite modulus is at least as sensitive to orientation as to
fiber aspect ratio and volume fraction. By studying the reac-
tivity of different curing agents, it shows the Jeffamine cur-
ing agents in the order of EDR-148 > T-403 > D230. DETA
and TETA curing agents provide the composites with
higher physical properties. The reinforcement is more
marked at elevated temperature. Further, the prospect of
using solid freeform fabrication method for composite fab-
rication from naturally derived matrix materials has many
potential applications in making shapes that cannot be
 Z.S. Liu et al. / Composites: Part A 38 (2007) 87–93 93

machined. The resulting composites have sufficient mechan- [5] Raghavachar R, Letasi RJ, Kola PV, Chen Z, Massingill JL. Rubber-
ical properties to be used in a wide variety of areas, such as Toughening Epoxy Thermosets with Epoxidized Crambe Oil. J Am
Oil Chem Soc 1999;76(4):511–6.
agriculture equipment, civil engineering, the automotive [6] Wool P. Development of affordable soy-based plastics, resins, and
industry and the construction industry. adhesives. Chem Technol 1999(June):44–8.
[7] Stuffle K, Mulligan A, Calvert P, Lombardi J. Solid freebody forming
Acknowledgement from polymerizable slurry, solid freeform fabrication symposium
processing, University of Texas, Austin, 1993. p. 60–3.
[8] Freire RS. Short fiber composites with high electrical and thermal
The authors gratefully acknowledge Dr. Arthur Thomp- conductivity, MS Thesis, The University of Arizona, Tucson, 1992.
son for help in SEM, and Ms. Jiong Peng for help in three [9] Peng J. The effect of fiber reinforcement on polymers, MS Thesis, The
point bending test. University of Arizona, Tucson, 1999.
[10] Padma A, Rao RMVGK, Subramaniam C, Nagendrapa G. Cure
References characterization of triglycidyl epoxy/aromatic amine systems. J Appl
Chem Sci 1995;57:401–11.
[11] Hull D, Clyne TW. An introduction to composite materials. Cam-
[1] Kaplan DL. Biopolymers from renewable resources. New York:
bridge: Cambridge University Press; 1996.
Springer; 1998.
[12] Peng J, Lin TL, Calvert P. Orientation effects in freeformed short-
[2] Liu ZS, Erhan SZ, Xu J, Calvert PD. Development of soybean oil-
fiber composites. Composites A 1999;30:133–8.
based composites by solid freeform fabrication method: epoxidized
[13] Calvert P, Peng J, Souvignier C. Solid freeform fabrication of
soybean oil with bis or polyalkyleneamine curing agents systems. J
composites by direct deposition and by in situ mineralization. In:
Appl Poly Sci 2002;85:2100–7.
Dimos D, Danforth SC, Cima MJ, editors. Solid freeform and
[3] Sue HJ, Garcia-Meitin E, Pickelman D. Fracture Behavior of rubber-
additives. Mater Res Soc Symp Proc, vol. 542. Warrendale,
modified high performance epoxies. In: Arends CB, editor. Polymer
PA: Materials Research Society; 1999. p. 3–11.
Toughening. NY: Marcel Dekker; 1996. p. 131–88.
[14] Termonia Y. Theoretical study of the stress transfer in single fibre
[4] Qureshi S, Manson JA, Hertzberg RW, Sperling LH. Mechanical
composites. J Mater Sci 1987;22:504–8.
Behavior of Some Epoxies with Epoxidized Natural Oils as Reactive
Diluents, in ACS Division of ORPL, 1983. Paper 48, p. 576.