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Reinforcing hydroxyapatite/thermosetting
epoxy composite with 3-D carbon fiber fabric
through RTM processing

Article in Materials Letters · January 2004

DOI: 10.1016/S0167-577X(03)00437-3

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 Materials Letters 58 (2003) 163 – 168
www.elsevier.com/locate/matlet

Reinforcing hydroxyapatite/thermosetting epoxy composite with 3-D

carbon fiber fabric through RTM processing
Jun-Liang Zhao, Tao Fu, Yong Han, Ke-Wei Xu *
State Key Laboratory for Mechanical Behavior of Materials, Xi’an Jiaotong University, Xi’an 710049, PR China
Received 23 January 2003; received in revised form 29 April 2003; accepted 2 May 2003

Abstract

Bioactive ceramic/polymer composites have been developed in the orthopaedic field in recent years. In this work, three-dimensional (3-D)
carbon fiber fabric is used to reinforce hydroxyapatite (HA)/thermosetting epoxy composite and epoxy resin through resin transfer molding
(RTM) processing. It is found that the 3-D carbon fiber fabric can be impregnated with epoxy and HA-containing epoxy resin, and HA is
distributed gradually along the depth direction in fiber-reinforced HA/epoxy composite, although HA is dispersed evenly in epoxy resin by
surface modification of silane coupling agent. The impact toughness and flexural strength of fiber-reinforced epoxy and fiber-reinforced HA/
epoxy composites are much higher than those of epoxy and HA/epoxy composite. The impact toughness of both fiber-reinforced composites
decreases while the flexural strength and the flexural modulus increase with fiber volume ratio. The impact toughness of the fiber-reinforced
HA/epoxy composite is higher, while the flexural strength and modulus are lower than those of the fiber-reinforced epoxy composite at the
same fiber volume ratio. The flexural strength of the both composites is higher than, and their flexural modulus is close to, those of the human
cortical bone. The in vitro cytotoxicity test with L929 fibroblasts shows that the addition of HA diminished the toxicity of epoxy resin.
D 2003 Elsevier B.V. All rights reserved.

Keywords: Carbon fiber; 3-D fabric; Hydroxyapatite; Epoxy resin; Resin transfer molding

1. Introduction cused on the problems caused by modulus mismatch, both

Bone can be regarded as a composite consisting mainly
of an inorganic phase, apatite, and an organic phase,
collagen. In recent years, bioactive ceramic/polymer com-
posites have been developed in the orthopaedic field for
their bone analog design as well as good biological and
mechanical performances [1– 6]. Bioactive ceramic such as
hydroxyapatite (HA) is combined with polymers which are
generally bioinert to provide the composite bioactivity. The
composite implants thus are able to form chemical bond
with the host tissue, and the fixation of implants is accel-
erated. Moreover, the elastic modulus of the composite can
be adjusted to approach that of the human bone by altering
the content of ceramic. It is known that the match of elastic
modulus between implants and the human bone favors the
avoidance of ‘‘stress shielding’’ and the sequent bone
absorption, which is often caused by implants with high
elastic modulus [6– 8]. Sufficient attention should be fo-
* Correspondence author. Tel.: +86-29-2668614; fax: +86-29-3237910.
E-mail address: kwxu@mail.xjtu.edu.cn (K.-W. Xu).
in research and in the clinic setting. However, the current
medical applications of HA/polymer composites are limited
to minor load bearing situations such as orbital floor
reconstruction, because of their lower mechanical strength
than that of the human bone.
In industrial fields, carbon fiber has been successfully
used to reinforce polymers. The three-dimensional (3-D)
carbon fiber fabric-reinforced polymer composites are wide-
ly utilized because of their good mechanical properties, such
as high tolerance to damage and high fracture toughness [9].
The available techniques for producing this kind of com-
posite are press molding, extruding, vacuum impregnating,
resin transfer molding (RTM), and so on. Among these
methods, RTM is the most widely used due to the advan-
tages it offers: (1) close-mold forming, (2) accurate control
on composition, (3) simple processing procedure, and (4)
one-time net forming. However, most of the resins for RTM
are thermosetting polymers, among which epoxy is the most
often used.
In this work, we attempted to use 3-D carbon fiber fabric
to reinforce HA/epoxy composite through RTM processing,

0167-577X/$ - see front matter D 2003 Elsevier B.V. All rights reserved.
doi:10.1016/S0167-577X(03)00437-3
164 J.-L. Zhao et al. / Materials Letters 58 (2003) 163–168
with the aim of producing HA powder that offers biocom-
patibility and bioactivity as well as carbon fiber fabric that
offers enhanced mechanical properties. This composite
material may enable such load-bearing applications as hip-
joint replacement and plates for fixing fractured bone.
2. Experimental
2.1. Material preparation
WSR618 epoxy resin with epoxy value of 0.48– 0.54 eq/
100 g and the solidifying agent phthalic anhydride with low
toxicity (Wuxi Resin Factory, China) were used to minimize
the toxicity of the resultant epoxy resin [10]. Silane coupling
agent KH-570 was obtained from Shuguang Chemical
Factory (Nanjing, China). HA powder was synthesized via
the wet method, heated at 650 jC for 1 h, sieved to attain a
grain size of 3 –4 Am. The 3-D carbon fiber fabric beams
were made of T-300 carbon fiber through the weaving
method, with fiber volume ratios of 25%, 35% and 45%.
Silane coupling agent was diluted by acetone, and the
mixture was stirred for 30 min for complete dispersion,
added with HA powder and stirred for another 30 min, then
dried. HA powder, with or without silane treatment, was
added into the stirred epoxy at the HA/epoxy weight ratio of
20% and 40%. The mixtures were then heated at 130 jC for
1 h before the solidifying agent, dilute agent and anti-foam
agent were added. The even mixture was then cast into the
mold, solidified according to the specified procedure and
samples HE2 and HE3 were obtained (Table 1). Pure epoxy
resin sample without HA was also prepared (HE1). The
mixture with HA/epoxy weight ratio of 20% and pure epoxy
resin were used to prepare 3-D carbon fiber fabric-rein-
forced HA/epoxy (FHE) and carbon fiber fabric-reinforced
epoxy (FE) samples (Table 1) via RTM processing. The
sample size was 10
15
75 mm for all samples.
2.2. Mechanical test and characterization
The notched impact test (V-type notch with a depth of 3
mm) was carried out on the composites, using a LOS
pendulum impact tester (maximum impact power 30 kgm).
m). The three-point flexural strength test was conducted
Table 1
Composition of the composite samples
HE group FE group FHE group
HE1 HE2* HE3* FE1 FE2 FE3 FHE1 FHE2 FHE3
Matrix HA 0 16.7 28.6 0 0 0 16.7 16.7
(wt.%)
Epoxy 100 83.3 71.4 100 100 100 83.3 83.3
(wt.%)
Fiber Vol. (%) 0 0 0 25 35 45 25 35
* HA powder without silane treatment was also used for composite
preparation.
using an Instron-1195 pull tester. The support span was 60
mm and the cross-head speed was 1 mm/min. The flexural
strength and flexural modulus were calculated with the
following equation, respectively:
3PL L3 DP
rf ¼ ; E¼
2bh2 4bh3 Dx
where rf is the flexural strength (MPa), E is the flexural
modulus (GPa), P is the maximum flexural load (N), DP/Dx
is the slope of the initial linear section of the flexural load –
displacement curve (N mm 1), L is the support span (mm),
b and h are the width and thickness of the sample (mm),
respectively. The cross-section and the fracture were exam-
ined with S-2700 scanning electron microscope (SEM) after
coating with a thin gold film to increase the conductance.
The element distribution was analyzed with energy-disper-
sive of X-ray (EDX).
2.3. Cytotoxicity test
Two kinds of materials, HE1 and HE3, were tested with
L929 fibroblasts. Samples were cut into slices of
10
10
1 mm, polished, cleaned and sterilized by ultra-
violet light for 2 h. The culture is RMPI1640 culture + 10%
fetus bovine serum. The slices were soaked in the culture at
the ratio (culture volume/slice surface area) of 6 ml/cm2 at
37 jC. The culture was filtered and the original leach was
obtained after being soaked for 24 h. The original leach with
100% concentration was diluted to obtain 50%, and diluted
again to obtain 25% of the original leach concentration. The
positive control is the original leach of pure lead, and the
negative control is the cell culture without soaking samples.
L929 fibroblasts were inoculated to 96-pore culture plate
with a cell concentration of 1
104/ml and culture volume
of 0.1 ml for each pore. The culture was replaced by 0.1 ml
leaches (for the tested groups and positive control) or culture
(for negative control) after being cultured for 24 h. After a
culture period of another 3 and 6 days, the cell activity was
checked according to the MTT method [11].
3. Results and discussion
3.1. The structure of the composites
3.1.1. The structure of HE composite
HA powder without coupling agent treatment is seriously
and unevenly agglomerated in epoxy matrix (Fig. 1a),
showing poor compatibility between HA powder and epoxy
16.7 resin. The silane coupling agent can improve the compati-
83.3
bility between inorganic particles and polymer matrix by
bridging the effect of the two side terminals [12]. The
45 hydrophilic siloxane terminals of KH-570 silane coupling
agent may hydrolyze to form Si– OH groups, which can
react chemically with the –OH groups of HA, and the
 J.-L. Zhao et al. / Materials Letters 58 (2003) 163–168 165

Fig. 1. Cross-sections of sample HE2 (a) without and (b)with KH-750

silane coupling agent treatment. Fig. 2. Cross-section of FE2 observed at different resolutions.

hydrophobic methyl acrylate groups can be tangled with the 3.2. The impact toughness of the composites
chains of epoxy resin. Therefore, the dispersion of HA
powder in epoxy matrix is obviously improved (Fig. 1b). The impact toughness of HE, FE and FHE is shown in
Fig. 4. The impact toughness of HE2 is higher than that of
3.1.2. The structure of FE and FHE composites HE1 (pure epoxy), and the impact toughness of HE3 is
Epoxy resin and HA-containing resin can be impreg- lower than that of HE1. This indicates that HA powder can
nated into carbon fiber fabric by means of RTM. It can be slightly toughen epoxy resin at a low weight ratio.
seen from the cross-section of FE2 at a lower resolution The impact toughness of FE and FHE is much higher
(Fig. 2a) that the resin is homogeneously distributed than that of HE, showing the significant toughening effect of
among fibers, and fibers intersected in the composite— 3-D carbon fiber fabric. And the impact toughness of FE
which is quite different from the structure of one-direc- and FHE increases with a decrease in fiber volume ratio. It
tional fiber-reinforced polymer composite. However, a few is shown in the fractographs that the fracture of FE1 is very
defects such as gas cavities in epoxy matrix and non- rough compared with those of FE2 and FE3 (Fig. 5). The
impregnation between fibers are found at the higher
resolution (Fig. 2b), which indicates that RTM processing
needs further improvement.
EDX analysis was applied along the cross-section of
FHE2 from the surface to the center to investigate the
distribution of HA in the composite. The detected elements
are C, O, Ca, P and Cl; Ca and P are enriched at the surface
(Fig. 3). The gradual distribution of HA in FHE may be due
to the hindrance posed by the fabric to HA powder during the
flow of epoxy resin in the RTM processing. Fortunately, HA
would concentrate evenly around the whole surface of the
fabric rather than only around the resin injection site because
of a small gap between the die and fabric, through which HA
would not confront any hindrance during the resin flowing.
The gradual distribution of HA will affect the mechanical and Fig. 3. Concentrations of Ca and P in FHE2 from the surface to the center
biological performances of the FHE composite. along the depth direction.
166 J.-L. Zhao et al. / Materials Letters 58 (2003) 163–168
Fig. 4. Impact toughness of HE, FE and FHE. (a) HE1, (b) FE1, (c) FHE1,
(d) HE2, (e) FE2, (f) FHE2, (g) HE3, (h) FE3, (i) FHE3.
rougher fracture is always related to more energy absorption
during impact process, and consequently higher impact
toughness is obtained.
Fig. 5. Impact fractographs of (a) FE1, (b) FE2 and (c) FE3.
The impact toughness of FHE is higher than that of FE at
the same fiber volume ratio (Fig. 4). It can be seen from
themacro-fractographs that FE has more extracted fibers
attached with resin, exhibiting strong resin –fiber interface,
while FHE has some extracted fibers without resin encap-
sulation. This suggests that the addition of HA in epoxy resin
weakens the resin– fiber interface. However, the weak resin–
fiber interface can absorb more energy by fiber extracting,
and this leads to higher impact toughness of FHE.
3.3. The flexural load – displacement curves of the compo-
sites
The typical flexural load – displacement curves of HE, FE
and FHE are shown in Fig. 6. The curve of HE keeps linear
until fracture occurs, which is the feature of a brittle
material. The curve of FE at the initial stage is linear, but
later yield occurs when load increases. The matrix and fibers
at the outermost layer are first cracked by tensile stress and
therefore the load drops. Initially, the unbroken part sustains
the load, which then induces the curve to expand until the
sample is destroyed.
The curve of FHE is also linear at the initial stage, but
there is no obvious yield point for the whole curve (Fig. 6).
This indicates that the failure of FHE in the case of tensile
stress is due to continuous fiber extracting, not due to the
abrupt crack of matrix and fibers. The weak resin – fiber
interface may function here. The outermost layer of FHE
has the highest tensile stress, and at the same time, the
highest concentration of HA and the weakest interface.
Therefore, the layer is the first place to fail.
The maximum flexural load and deformation of FE and
FHE are much higher than those of HE; FE and FHE did not
fracture after they were destroyed, indicating the strength-
ening and toughening effects of the 3-D carbon fiber fabric
on epoxy resin and HA/epoxy composite.
3.4. The flexural strength of the composites
The flexural strength of HE, FE and FHE is shown in
Fig. 7. The flexural strength of HE2 is higher than that of
Fig. 6. Typical flexural load – displacement curves of HE, FE and FHE.
 J.-L. Zhao et al. / Materials Letters 58 (2003) 163–168
Fig. 7. Flexural strength of HE, FE and FHE compared with that of several
commonly used implant materials and human cortical bone [13]. (a) HE1,
(b) FE1, (c) FHE1, (d) HE2, (e) FE2, (f) FHE2, (g) HE3, (h) FE3, (i) FHE3,
(j) human cortical bone, (k) titanium alloy, (l) stainless steel, (m) CoCr
alloy.
HE1, and the flexural strength of HE3 is lower than that of
HE1. This implies that HA powder can slightly strengthen
epoxy resin at a low weight ratio. But the flexural strength is
rather too low compared with that of the human cortical
bone (about 180 MPa) for HE to be effectively used as a
bone implant material for load bearing.
The flexural strength of FE and FHE is 504 –552 and
408 –513 MPa, respectively. The flexural strength of FE and
FHE increases with the fiber volume ratio; the same is not
true of FHE2, which has the lowest flexural strength. The
reason for the exception may be attributed to the fact that
there are more unexpected defects in FHE2 observed with
SEM, which may constitute the part of the RTM process that
is not controlled very well. The flexural strength of FHE is
lower than that of FE at the same fiber volume ratio, which
may be also due to the weakened fiber – matrix interface by
HA powder. In spite of that, the flexural strength of FHE is
still high compared with the values obtained from common-
ly used implant materials, and is much higher than that of
the human cortical bone (Fig. 7j).
It is observed from the aforementioned mechanical
results that the fiber – resin interface plays an important role
in the failure mode. A strong interface can effectively
transfer load from matrix to fibers, as is required for high
strength. But if the interface is strong, the stress concentra-
tion in front of an approaching crack cannot be instantly
relieved, so the crack will propagate into fibers from the
matrix, and fibers will fail. A weak interface, however, can
suppress crack propagation by fiber extraction, and results
in high toughness but low strength [14,15].
3.5. The flexural modulus of the composites
The flexural modulus of HE, FE and FHE are shown in
Fig. 8. The flexural modulus of HE approaches the lower
bound of the human cortical bone’s modulus, which varies
from 7 to 25 GPa, with an average of 20 GPa [6,13]. The
167
Fig. 8. Flexural modulus of HE, FE and FHE compared with that of several
commonly used implant materials and human cortical bone [13]. (a) – (m)
are the same as (a) – (m) in Fig. 7.
flexural modulus of FE and FHE is 27– 36 and 21– 27 GPa,
respectively, which is quite close to that of the human
cortical bone and much lower than that of the commonly
used implant materials (Fig. 8). For example, the flexural
modulus of titanium alloy is approximately 120 GPa, which
is five times that of human cortical bone. Titanium alloy
plates to fix broken bone will sustain the major stress (stress
shielding), and the existing bone will degenerate and the
new bone formation will be retarded for lack of appropriate
mechanical stimulation. The match of elastic modulus
between implants and human bone is expected to have good
biomechanical compatibility between them [6 – 8].
3.6. The cytotoxicity of the composite samples
Carbon fiber offers good biocompatibility [16], so only
HE samples are subjected to the cytotoxicity test. The
absorbance values of HE1 and HE3 at various leach con-
centrations are shown in Fig. 9. Statistical analysis was
carried out via one-way analysis of variance (ANOVA), at
the significant level of 0.05. It can be concluded that there is
a significant difference among the test groups ( p < 0.01).
Fig. 9. Absorbance value of various concentrations leaches from HE1, HE3,
and the controls. (a) – (c) HE1:100%, 50%, 25%, (d) – (f) HE3:100%, 50%,
25%, (g) positive control, (h) negative control.
168 J.-L. Zhao et al. / Materials Letters 58 (2003) 163–168
Every test group has a significant difference from the
positive control ( p < 0.05). Compared with the negative
control, the 100% concentration leach of HE1 has a signif-
icant difference ( p < 0.05), while every concentration leach
of HE3 did not show a significant difference ( p>0.05). The
aforementioned results indicate that HE1 has a certain
toxicity to L929 fibroblasts at high leach concentrations,
while HE3 has no toxicity at all leach concentrations. This
suggests that the addition of HA powder has diminished the
toxicity of epoxy resin. Current work is underway to
investigate the relevant in-vivo performance of the carbon
fiber fabric-reinforced HA/epoxy composite.
4. Conclusions
The dispersion of HA powder in epoxy resin is obviously
improved by silane coupling agent treatment. HA powder
can slightly reinforce epoxy resin at a limited weight ratio.
Epoxy and HA-containing epoxy have good impregnation
to 3-D carbon fiber fabric, except for a few defects in the
RTM process, and HA is distributed gradually from the
surface to the center of fiber-reinforced HA/epoxy compos-
ite. The impact toughness and flexural strength of both 3-D
carbon fiber fabric-reinforced composites are much higher
than those of the HA/epoxy composite. The impact tough-
ness of both fiber-reinforced composites decreases while
flexural strength and modulus increase with fiber volume
ratio. The impact toughness of fiber-reinforced HA/epoxy
composite is higher, while the flexural strength and modulus
are lower than those of fiber-reinforced epoxy composite at
the same fiber volume ratio. The flexural strength of both
fiber-reinforced composites is higher than, and the flexural
modulus is close to those of human cortical bone. The
cytotoxicity test shows that the addition of HA has dimin-
ished toxicity of epoxy resin.
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Acknowledgements
This work was financially supported by the ‘‘Action
Program’’ of the Education Ministry of China, the National
Natural Science Foundation of China (Grant No.
50002008), and Trans-Century Excellent Personnel Training
Project of the Education Ministry of China.
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