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Reinforcing hydroxyapatite/thermosetting
epoxy composite with 3-D carbon fiber fabric
through RTM processing
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Ke-Wei Xu
Xi'an Jiaotong University
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Materials Letters 58 (2003) 163 – 168
www.elsevier.com/locate/matlet
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
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- using an Instron-1195 pull tester. The support span was 60
patibility and bioactivity as well as carbon fiber fabric that mm and the cross-head speed was 1 mm/min. The flexural
offers enhanced mechanical properties. This composite strength and flexural modulus were calculated with the
material may enable such load-bearing applications as hip- following equation, respectively:
joint replacement and plates for fixing fractured bone.
3PL L3 DP
rf ¼ ; E¼
2bh2 4bh3 Dx
2. Experimental
where rf is the flexural strength (MPa), E is the flexural
2.1. Material preparation modulus (GPa), P is the maximum flexural load (N), DP/Dx
is the slope of the initial linear section of the flexural load –
WSR618 epoxy resin with epoxy value of 0.48– 0.54 eq/ displacement curve (N mm 1), L is the support span (mm),
100 g and the solidifying agent phthalic anhydride with low b and h are the width and thickness of the sample (mm),
toxicity (Wuxi Resin Factory, China) were used to minimize respectively. The cross-section and the fracture were exam-
the toxicity of the resultant epoxy resin [10]. Silane coupling ined with S-2700 scanning electron microscope (SEM) after
agent KH-570 was obtained from Shuguang Chemical coating with a thin gold film to increase the conductance.
Factory (Nanjing, China). HA powder was synthesized via The element distribution was analyzed with energy-disper-
the wet method, heated at 650 jC for 1 h, sieved to attain a sive of X-ray (EDX).
grain size of 3 –4 Am. The 3-D carbon fiber fabric beams
were made of T-300 carbon fiber through the weaving 2.3. Cytotoxicity test
method, with fiber volume ratios of 25%, 35% and 45%.
Silane coupling agent was diluted by acetone, and the Two kinds of materials, HE1 and HE3, were tested with
mixture was stirred for 30 min for complete dispersion, L929 fibroblasts. Samples were cut into slices of
added with HA powder and stirred for another 30 min, then 10 10 1 mm, polished, cleaned and sterilized by ultra-
dried. HA powder, with or without silane treatment, was violet light for 2 h. The culture is RMPI1640 culture + 10%
added into the stirred epoxy at the HA/epoxy weight ratio of fetus bovine serum. The slices were soaked in the culture at
20% and 40%. The mixtures were then heated at 130 jC for the ratio (culture volume/slice surface area) of 6 ml/cm2 at
1 h before the solidifying agent, dilute agent and anti-foam 37 jC. The culture was filtered and the original leach was
agent were added. The even mixture was then cast into the obtained after being soaked for 24 h. The original leach with
mold, solidified according to the specified procedure and 100% concentration was diluted to obtain 50%, and diluted
samples HE2 and HE3 were obtained (Table 1). Pure epoxy again to obtain 25% of the original leach concentration. The
resin sample without HA was also prepared (HE1). The positive control is the original leach of pure lead, and the
mixture with HA/epoxy weight ratio of 20% and pure epoxy negative control is the cell culture without soaking samples.
resin were used to prepare 3-D carbon fiber fabric-rein- L929 fibroblasts were inoculated to 96-pore culture plate
forced HA/epoxy (FHE) and carbon fiber fabric-reinforced with a cell concentration of 1 104/ml and culture volume
epoxy (FE) samples (Table 1) via RTM processing. The of 0.1 ml for each pore. The culture was replaced by 0.1 ml
sample size was 10 15 75 mm for all samples. leaches (for the tested groups and positive control) or culture
(for negative control) after being cultured for 24 h. After a
2.2. Mechanical test and characterization culture period of another 3 and 6 days, the cell activity was
checked according to the MTT method [11].
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). 3. Results and discussion
m). The three-point flexural strength test was conducted
3.1. The structure of the composites
Table 1
Composition of the composite samples 3.1.1. The structure of HE composite
HE group FE group FHE group
HA powder without coupling agent treatment is seriously
and unevenly agglomerated in epoxy matrix (Fig. 1a),
HE1 HE2* HE3* FE1 FE2 FE3 FHE1 FHE2 FHE3
showing poor compatibility between HA powder and epoxy
Matrix HA 0 16.7 28.6 0 0 0 16.7 16.7 16.7 resin. The silane coupling agent can improve the compati-
(wt.%)
Epoxy 100 83.3 71.4 100 100 100 83.3 83.3 83.3
bility between inorganic particles and polymer matrix by
(wt.%) bridging the effect of the two side terminals [12]. The
Fiber Vol. (%) 0 0 0 25 35 45 25 35 45 hydrophilic siloxane terminals of KH-570 silane coupling
* HA powder without silane treatment was also used for composite agent may hydrolyze to form Si– OH groups, which can
preparation. react chemically with the –OH groups of HA, and the
J.-L. Zhao et al. / Materials Letters 58 (2003) 163–168 165
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. 5. Impact fractographs of (a) FE1, (b) FE2 and (c) FE3. Fig. 6. Typical flexural load – displacement curves of HE, FE and FHE.
J.-L. Zhao et al. / Materials Letters 58 (2003) 163–168 167
Fig. 7. Flexural strength of HE, FE and FHE compared with that of several Fig. 8. Flexural modulus of HE, FE and FHE compared with that of several
commonly used implant materials and human cortical bone [13]. (a) HE1, commonly used implant materials and human cortical bone [13]. (a) – (m)
(b) FE1, (c) FHE1, (d) HE2, (e) FE2, (f) FHE2, (g) HE3, (h) FE3, (i) FHE3, are the same as (a) – (m) in Fig. 7.
(j) human cortical bone, (k) titanium alloy, (l) stainless steel, (m) CoCr
alloy.
flexural modulus of FE and FHE is 27– 36 and 21– 27 GPa,
respectively, which is quite close to that of the human
HE1, and the flexural strength of HE3 is lower than that of cortical bone and much lower than that of the commonly
HE1. This implies that HA powder can slightly strengthen used implant materials (Fig. 8). For example, the flexural
epoxy resin at a low weight ratio. But the flexural strength is modulus of titanium alloy is approximately 120 GPa, which
rather too low compared with that of the human cortical is five times that of human cortical bone. Titanium alloy
bone (about 180 MPa) for HE to be effectively used as a plates to fix broken bone will sustain the major stress (stress
bone implant material for load bearing. shielding), and the existing bone will degenerate and the
The flexural strength of FE and FHE is 504 –552 and new bone formation will be retarded for lack of appropriate
408 –513 MPa, respectively. The flexural strength of FE and mechanical stimulation. The match of elastic modulus
FHE increases with the fiber volume ratio; the same is not between implants and human bone is expected to have good
true of FHE2, which has the lowest flexural strength. The biomechanical compatibility between them [6 – 8].
reason for the exception may be attributed to the fact that
there are more unexpected defects in FHE2 observed with 3.6. The cytotoxicity of the composite samples
SEM, which may constitute the part of the RTM process that
is not controlled very well. The flexural strength of FHE is Carbon fiber offers good biocompatibility [16], so only
lower than that of FE at the same fiber volume ratio, which HE samples are subjected to the cytotoxicity test. The
may be also due to the weakened fiber – matrix interface by absorbance values of HE1 and HE3 at various leach con-
HA powder. In spite of that, the flexural strength of FHE is centrations are shown in Fig. 9. Statistical analysis was
still high compared with the values obtained from common- carried out via one-way analysis of variance (ANOVA), at
ly used implant materials, and is much higher than that of the significant level of 0.05. It can be concluded that there is
the human cortical bone (Fig. 7j). a significant difference among the test groups ( p < 0.01).
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].