JOURNAL OF

COMPOSITE
Article M AT E R I A L S
Journal of Composite Materials
46(15) 1831–1838
! The Author(s) 2011
Synthesis and characterization of porous Reprints and permissions:
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hybrid biomaterials with improved DOI: 10.1177/0021998311426623
jcm.sagepub.com
mechanical properties

M Estevez, AM Escamilla, S Vargas, AR Hernandez-Martinez

and R Rodriguez

Abstract
New ceramic-polymer biomaterials with controlled porosity were synthesized with improved mechanical and tribological
properties. These materials contain synthetic hydroxyapatite (HAp) microparticles and two different ceramic particles at
different concentrations (alumina microparticles and silica nanoparticles) and posses a morphology that matches the real
bone. The particles were agglutinated using solvent-free, mono-component polyurethane. The pores were generated by
a chemical reaction between the OH groups of the hydroxylated resin and the ceramic particles with the blocked
isocyanate. The porosity grows practically linear with the temperature of the thermal treatment. The materials were
characterized using X-ray diffraction (XRD), ICP, dynamic light scattering (DLS), scanning electron microscopy (SEM),
densitometry, abrasion, and mechanical tests.

Keywords
Ceramics, hybrid composites, nanoparticles, material characterization

biomaterials for clinical applications with concentra-

Introduction
One of the most important aspects in the development
of biomaterials is their use as prosthesis or implants in
living organisms, specifically for bone repair or bone
ingrowth (traumatism, bone disease, etc.) applica-
tions.1,2 Synthetic hydroxyapatite (Ca5(PO4)3OH)
(HAp) is the mineral most commonly used to produce
biomaterials because it is chemically very similar to real
bone. However, their acceptance by the living organism
is based not only in the right chemistry, which is
responsible to support cellular activity without eliciting
an inappropriate host response, but also equally impor-
tant is the morphology, which is responsible for pro-
viding the right conditions for vascularization.3–5
In recent years, polymer-ceramic composite mate-
rials with high content of HAp have been designed
for biomedical applications (PA/HAp, PMMA/HAp,
PLA/HAp, PE/HAp, etc.).6–8 The design of these syn-
thetic materials is based on the original constituents of
bones: a structured hybrid composite made of organic
(collagen, etc.) and mineral (HAp) constituents, which
together confer to the final material high mechanical
resistance.9,10 When HAp is included in the design of
tions around 65% wt, the composite is biocompatible
and bioactive to initiate the osteogenesis. However,
most of the studies on these materials showed
either no increase or a slight decrease in compressive
strength of the polymer materials when HAp was
incorporated.11,12
The bioceramics are widely used in bone grafting
and dental devices because HAp has the ability to
favor the presence of osteoblasts required for bone
tissue engineering.13,14 The chemical properties of the
ceramic surfaces determine their compatibility with the
resin and the performance of the whole material.15,16
Other ceramic materials are biocompatible, osteocon-
ductive, and bioabsorbable and are commonly used as
Centro de Fisica Aplicada y Tecnologı́a Avanzada (CFATA), Universidad
Nacional Autonoma de Mexico, Campus Juriquilla, Querétaro, CP 76230,
Mexico
Corresponding author:
M Estevez, Centro de Fisica Aplicada y Tecnologı́a Avanzada (CFATA),
Universidad Nacional Autonoma de Mexico, Campus Juriquilla,
Querétaro, CP 76230, Mexico
Email: miries@fata.unam.mx
1832
bone repair, like calcium sulfate (CS), which is used to
fill bone defects and maxillary sinus lifts because it is
well tolerated by the host, is completely re-absorbed
within 3 months, and does not interfere with bone heal-
ing. However, the HAp–polymer composites combine
the excellent biocompatibility, bioactivity, and osteo-
conductivity of HAp with the important mechanical
properties of polymeric materials, producing compos-
ites with improved properties.17–19 It has been reported
that high-purity high-density (>3.9 g/cm3) alumina was
the first bioceramics used for implants, specifically in
load-bearing hip prostheses and dental implants
because of its excellent corrosion and wearing resis-
tance. Alumina is considered as bio-inert material,
safe to use in the human body, but it is not bonded
to living tissue when implanted.20,21
Recently, the fabrication of bioceramics with con-
trolled morphology (porosity) has attracted consider-
able attention because organic tissue can grow in the
interior of the interconnected pores allowing the vascu-
larization of the implant and enhancing the implant-
tissue interaction. The colonization of the pores takes
place when the pore size is in the range from 100
to 300 mm and the pore volume fraction higher than
50% vol.22–24
In the last decades, an increasing demand for high-
durability biomaterials has been observed; then, it is
important to provide biomaterials with the right prop-
erties to stay for longer times into the living organism.
It is known that the addition of hard ceramic particles
improves the mechanical and tribological properties of
polymers: the hardness and size of ceramic particles
strongly affect these properties in the final hybrid mate-
rial.25,26 In this case, the mechanical properties and the
abrasion and the scratching resistance were increased
by the addition of two different types of particles
with different sizes: alumina microparticles and silica
nanoparticles.27 The use of ceramic particles with dif-
ferent sizes allows the filling, with nanoparticles, of the
interstitial space left by the microparticles; the use of
micro- and nanoparticles produces a reinforcement of
the composite that renders in materials with improved
mechanical and tribological properties.28,29
The mixture of polyisocyanate with the resin and the
ceramic particles is a reactive system because the poly-
isocyanate reacts with all OH groups present in the
system. If the silica nanoparticles are added first,
because their surface area is considerably larger with
respect to the alumina microparticles, the number of
OH groups that can react with the isocyanate is also
larger, producing a highly cross-linked material in a
short time (i.e., a fast cure process); this increases signif-
icantly, and in a short time, the system viscosity reducing
the possibility to obtain a homogeneous mixture; addi-
tionally, in this case, the amount of ceramic particles
Journal of Composite Materials 46(15)
that can be introduced into the polymer is low respect
to the case where the alumina microparticles are intro-
duced first.30,31 In this last case, the number of OH
groups that can react with the isocyanate is considerably
lower, allowing a slow curing process with an associated
slow increment in viscosity that allows a good homoge-
nization of the composite. When the silica nanoparticles
are added after the alumina microparticles, the nanopar-
ticles fill the interstitial spaces left by the largest parti-
cles, producing an increment in the mass density that
renders in an improvement in the mechanical and tribo-
logical properties. In this case, the amount of ceramic
particles that can be introduced into the polymer is
larger with respect to the former case.27 In this work,
new ceramic-polymers porous hybrid materials were
synthesized with the appropriated morphology to be
used as prosthesis or implants in living organism. The
materials were added with two different types of ceramic
particles of different sizes to improve the mechanical and
tribological properties of the final material.
Experimental
HAp preparation
The hydroxyapatite was synthesized as reported else-
where:32 aqueous solutions of Ca(NO3)2 (J.T. Baker
at 99%) at 0.431 M and of H3PO4 (J.T. Baker at
99.9%) at 0.258 M were prepared and mixed together
at room temperature in a closed reactor with strong
agitation for few minutes reaching a pH ¼ 11. After
this, the system was slowly agitated allowing the sedi-
mentation of the insoluble component; the precipitate
was separated, washed with distilled water three times,
and stored for 1 day. The sediment was dried at 110 C
for 24 h and pressed to form pellets, which were subse-
quently heated in air at 800 C at a rate of 5 C/min
during 1 h at reduced pressure (10 Torr). The hydroxy-
apatite obtained was characterized by X-ray diffraction
(XRD). The XRD patterns were obtained using a
Rigaku D500 machine with a radiation source of
1.54 Å (Cu Ka line) and the angle 2Q was varied from
5 to 80 at a scan of 2 /min. The Ca/P molar ratio was
determined digesting the HAp in an acid medium and
using an ICP-OES Thermo iCAP 6500 Duo apparatus;
the Ca/P molar ratio obtained was 1.653.
Samples preparation
The samples were prepared using solvent-free mono-
component polyester polyurethane containing a malo-
nate-blocked polyisocyanate and three different types
of ceramic particles with different sizes. A total of 8 g
of the mono-component polyester polyurethane were
mixed with the corresponding concentration of ceramic
Estevez et al.
Table 1. Composition of all prepared materials
Sample PU HAp Al2O3 SiO2
50Si-50HAp 8.0 g 3.8 g 0g 3.8 g
70A-30HAp 8.0 g 2.3 g 5.3 g 0g
80A-20HAp 8.0 g 1.5 g 6.1 g 0g
particles (Table 1). Because the ceramic particles have
different sizes, the largest particles (HAp) were added
first, followed by the alumina microparticles (3.2
microns; Cabot, USA) and finally by the silica nano-
particles (16 nm; Degussa, Ger). Each type of ceramic
particles was well incorporated before the addition of
the next type. The incorporation was carried out with
strong and high-shear rate agitation until a smooth and
homogeneous paste was obtained. The addition of the
ceramic particles unstabilizes the polymer emulsion and
the chemical reaction between the ciano groups of poly-
isocianate and the hydroxyls groups of the resin and
ceramic particles starts releasing part of the malonate
blocking structure as CO2 that generates the pores into
the material; this reaction is temperature dependent.
A change in the temperature of the thermal treatment
allows to control the pore size and the pore volume
fraction.
Samples of different sizes and geometries were pre-
pared according to the corresponding test. A sample of
each formulation was kept into the mould for 24 h at
room temperature to finish the curing reaction. Samples
of each formulation were thermally treated at different
temperatures and times: 50 C (12 h), 80 C (8 h), 110 C
(2 h), and 150 C (1 h); three samples were prepared for
each composition and for each temperature.
Samples characterization
The size of the ceramic particles was determined using a
dynamic light scattering (DLS) apparatus Brookhaven
Instruments Corp. model BI-APD equipped with a He-
Ne laser at 632.8 nm and a digital correlator. The aver-
age particle size of the ceramic particles was 16 nm for
silica and 3.2 microns for alumina.
The mass densities were determined weighting the
samples in an analytical balance with a resolution of
105 g and measuring the sizes using a micrometer with
resolution of 0.01 mm and an accuracy of 0.001 mm.
The pore size was obtained using the scanning electron
microscopy (SEM) images and the pore volume frac-
tion was determined using the formula reported
elsewhere33
rp
fp ¼ 1  ð1Þ
rs
1833
where fp, rp, and rs are the pore volume fraction, the
density of the porous material, and the density of the
non-porous material (prepared using no-blocking
isocyanate).
The mechanical tests were performed according to
the norm ASTM D-695-02 a in an Adamel Lhomargy
machine model DY.22 in compression mode with a
compression rate of (1.3  0.3) mm/min. The cell load
was of 5000 N with a resolution of 0.1 N. For this test,
cylindrical samples were prepared of each formulation
using a Teflon mould of 20 mm high and 10 mm
diameter.
The wearing resistance was determined using the
Taber Method according to the norm ASTM-D-1242-
95a;34 the weight lost was obtained by sanding the
flat surface of the samples with a F-400 Fandeli sand-
paper mounted on a steel plate rotating at 76 rpm in
dry conditions; the samples, with dimensions
2.0  1.0  0.5 cm, were loaded with a weight of 20 g.
Five experiments were performed for each sample, all at
room temperature. The weight lost was determined
every 20 s with an accuracy of 1  105 g. After
each sanding procedure and before the weight determi-
nation, the scratched surface was cleaned with a dry
soft cloth wipe to remove the dust and the sand paper
was also cleaned with a soft brush. The abrasion resis-
tance,34 defined as the time required to remove a unit
mass of the material, corresponds to the inverse of the
weight lost.
The water absorption (WA) was determined immers-
ing completely the samples, of known weight, in dis-
tilled water for 21 days and determining the final
weight; after the immersion time, the samples were
superficially dried with a tissue paper and immediately
weighted. The WA was obtained according to the
expression
Wf  Wi
WA ¼ ð2Þ
Wi
where Wi and Wf are the initial and final weights.
The SEM was performed in a JEOL JSM-6060 at
20 kV in secondary electron mode with different mag-
nifications; the samples were frozen in liquid N2,
broken, and the new exposed surface covered with a
gold film. The average pore size was determined using
the SEM images.
Results
The mass densities of all prepared materials are reported
in Figure 1. In all cases, the density decreases practically
linear with temperature, reducing from near 1 g/mL to
0.4 g/mL when the temperature was varied from room
temperature to 150 C. The pore size and the pore volume
1834 Journal of Composite Materials 46(15)

1.1
fraction are reported in Figures 2 and 3. As a conse- 80A-20HAp

quence of the reduction in density, the pore size and the 1

70A-30HAp
50S-50HAp
pore volume fraction increase with temperature; the pore
0.9
volume fraction is directly related to the density, and then
grows also practically linear with temperature with 0.8

Density (g/mL)
slopes in the range from 0.3 to 0.45 ( C)1.
0.7
Figure 4(a) through (c) shows the results of the
mechanical properties. In Figure 4(a) is reported the 0.6

Young modulus as a function of the temperature while 0.5

in Figure 4(b) and (c) the force and the deformation to
rupture, respectively. Figure 5 shows the abrasion resis- 0.4

tance (the inverse of the rate the weigh is lost) as a func- 0.3
20 40 60 80 100 120 140 160
tion of temperature; here it is possible to see that for all Temperature (°C)
samples the highest abrasion resistance was obtained for
samples treated at 110 C. The weight percentage of the Figure 1. Mass density as a function of temperature.
water absorption is reported in Figure 6 where, as
expected, this quantity increases with the porosity and
consequently with temperature. Typical SEM images of
the samples are shown in Figure 7(a) through (d). 160
80A-20HAp
70A-30HAp
50S-50HAp
140
Discussion
120
The reduction in density when the temperature was
Pore Size (µm)

increased (Figure 1) modifies all properties of the sam- 100

ples: the morphology, the mechanical and the abrasion

80
properties, and the water absorption. The reduction in
density (from 1.0 to 0.4 g/mL) follows a linear depen- 60
dence with temperature where the slopes are in the
range from 0.003 to 0.004 g/mL C depending on the 40

type and concentration of the ceramic particles. It is

20
important to note that, for a given temperature, the 20 40 60 80 100 120 140 160
Temperature (°C)
higher densities were obtained for the sample contain-
ing silica nanoparticles. The chemical reaction between Figure 2. Average pore size obtained from the scanning
the blocked isocyanate and the hydroxyls groups of the electron microscopy (SEM) images.
resin and the ceramic particles is responsible for the
CO2 production, that is, the pore generator. This reac-
tion is temperature dependent as evidenced by
Figures 2 and 3, where the pore size and the pore
60
volume fraction are reported as a function of tempera- 80A-20HAp
70A-30HAp
ture. The pore size (Figure 2) increases with tempera- 50S-50HAp
50
ture because this accelerates the chemical reaction
producing more and more rapidly CO2 gas into the
Pore Volume Fraction (%)

material; additionally, the pressure of the CO2 is also 40

temperature dependent, increasing linearly with tem-

perature (ideal gas law). These two effects reinforce 30
each other to increase the pore size and the pore
volume fraction with temperature; this is in full agree-
20
ment with the results shown in Figures 2 and 3. These
pore size profiles show the presence of two regimes: the
10
first one at low temperature where the pore size grows
slowly with the temperature, and the second one start-
ing between 80 and 110 C and characterized by a faster 0
20 40 60 80 100 120 140 160
increment in the pore size with temperature.
Temperature (°C)
The change in regime (inflection) happens at tempera-
tures between 80 and 110 C depending on the type of Figure 3. Pore volume fraction obtained using Equation (1).
Estevez et al. 1835

the ceramic particles: for alumina-containing particles (a) 450 80A-20HAp

70A-30HAp
the transition happens at a lower temperature (80 C), 50Si-50HAp
400
while for the silica-based sample the inflection happens
at higher temperature (110 C). 350
The pore volume fraction was calculated using

Young Modulus (MPa)

Equation (1) and the results are reported in Figure 3. 300
As mentioned, a non-porous reference sample was pre-
pared using a non-blocked isocyanate in order to avoid 250
the CO2 generation; for this material the density was
1.04 g/mL. Because the pore volume fraction is directly 200

related to the mass density, this increases with the tem-

150
perature in a practically linear way. At low temperature
(bellow 50 C), the pore volume fraction is below the
100
percolation threshold and consequently the pores are 60 80 100 120 140
not interconnected. Temperature (°C)

As mentioned, porous materials possess generally (b) 5

80A-20HAp
weak mechanical properties essentially because the 70A-30HAp
50Si-50HAp
pores act as stress concentrators on a thin wall favoring 4
the presence of cracks and fissures and diminishing the

Force to Rupture (N)

mechanical properties. This behavior was observed in
Figure 4(a) where the Young modulus is reported as a 3

function of temperature; here it is possible to see that the

Young modulus was reduced with the temperature for 2
low temperatures; however, at higher temperatures, this
reduces slowly, and in some cases increases, having
values larger than expected. This is because at higher 1

temperatures there are two effects that are in opposition:

on one side the weakness of the material produced by the 0
increment in porosity and on the other the increment in 60 80 100 120 140
Temperature (°C)
the chemical links between the ceramic particles and the
(c) 1
polymeric resin which improves the mechanical proper- 80A-20HAp
70A-30HAp
ties. Due to this, samples treated at higher temperatures 50Si-50HAp

showed a reduction in the rate of diminishing (sample 0.9

Deformation to Rupture (mm)

80A-20HAp) or even an increment (samples 70A-

30HAp and 50Si-50HAp) in the Young modulus for tem-
0.8
peratures higher than 110 C. The profile for the sample
containing silica is different possibly due to the densifi-
cation process (Figure 1) produced by the filling of the 0.7
interstitial space left by the HAp micro-particles with the
silica nanoparticles. As mentioned, in all cases the Young
0.6
modulus have higher and similar values at 150 C.
It is also expected a reduction in the force to rupture for
samples synthesized at higher temperatures which possess 0.5
60 80 100 120 140
higher porosities. However, Figure 4(b) shows that this
Temperature (°C)
quantity is less sensitive to the thermal treatment, having
similar values in the whole range of temperatures. This Figure 4. Mechanical properties: (a) Young modulus, (b) force
means that the increment in porosity produced by the to rupture, and (c) deformation to rupture.
thermal treatment is compensated by the increment in
the chemical links in the ceramic-resin interface. Figure 5 shows the abrasion resistance as a function
Something similar happens with the deformation to rup- of temperature. As can be noticed, the samples treated
ture (Figure 4(c)): the temperature has not a strong effect at 110 C showed the highest abrasion resistance,
in the deformation to rupture for all samples, meaning followed by a reduction at 150 C. This behavior is
that this is practically controlled by the polymeric phase consistent with the explanation provided before
and the polymer-ceramic interface: at 150 C the deforma- the weakening produced by the increment in porosity
tion to rupture is the same for all samples. is partially compensated by an increment in the
1836 Journal of Composite Materials 46(15)

100 40
80A-20HAp 80A-20HAp
70A-30HAp 70A-30HAp
50Si-50HAp
50Si-50HAp
35
80
Abrasion Resistance (s/mg)

30

Water Absorption (wt %)

60

25

40
20

20 15

10
0 60 80 100 120 140
60 80 100 120 140
Temperature (°C) Temperature (°C)

Figure 5. Abrasion resistance as a function of temperature. Figure 6. Percentage of water absorption obtained using
Equation (2).

(a) (b)

(c) (d)

Figure 7. A typical series of scanning electron microscopy (SEM) images for the sample 80A-20HAp at different temperatures:
(a) 150 C; (b) 110 C; (c) 80 C; (d) 50 C.

chemical links between the ceramic particles and the
polymeric resin.
The morphology of the materials has an important
effect on the water absorption; this is reported in
Figure 6. As can be noticed, samples treated at higher
temperatures absorb more water; this is expected
because when the porosity is increased, more water
can be trapped into the pores in the interior of the
material; additionally, at high temperature (i.e. at
higher porosity) the pores are percolated allowing the
Estevez et al.
water penetrates deeper in the interior of the material,
increasing its absorption. As can be noticed at 150 C,
all samples have practically the same amount of
absorbed water (between 32 and 34%). As before,
there are two regimes in the water-absorbed profiles:
for temperatures lower than 110 C a considerable frac-
tion of pores are blind reducing the amount of water
that can be absorbed by the sample, on the other hand
at temperatures higher than 110 C the pore volume
fraction exceed the percolation threshold allowing the
water to be absorbed deeply into the sample.
A typical series of SEM images for the sample con-
taining 80% of alumina and 20% HAp is reported in
Figure 7(a) through (d): (a) 150 C; (b) 110 C; (c) 80 C;
(d) 50 C. Images for other samples, not reported here,
are similar.
Conclusions
It was possible to produce hybrid porous materials with
good mechanical and tribological properties to be used
as biomaterial for bone substitution. The porosity was
controlled with the temperature of the thermal treat-
ment: increasing the temperature from ambient to
150 C allows to increase the porosity reducing the den-
sity from 1 to 0.4 g/mL. The addition of ceramic parti-
cles of different sizes allows to produce highly porous
biomaterials with improved mechanical and tribologi-
cal properties. When the temperature of the thermal
treatment was 110 C or higher, it was possible to
obtain porosities larger than 40% (for 70A-30HAp
and 50Si-50HAp), allowing the vascularization through
biomaterial without a significant reduction in the
mechanical properties.
Funding
This research received no specific grant from any funding
agency in the public, commercial, or not-for-profit sectors.
Acknowledgments
The authors are indebted to M. in S. Alicia del Real for her
valuable help in the SEM micrograph and Gerardo Fonseca
for their support in mechanical testing.
Conflict of interest
None declared.
References
1. Lasprilla AJR, Martinez GAR, Lunelli BH, Jardini AL
and Maciel Filho R. Biomaterials for application in bone
tissue engineering. J Biotechnol 2010; 150: 455–459.
2. Ashok Kumar. New generation of polymeric biomaterials
for biotechnological and bioengineering applications.
J Biotechnol 2008; 136: S118.
1837
3. Xu JL and Khor KA. Chemical analysis of silica doped
hydroxyapatite biomaterials consolidated by a spark
plasma sintering method. J Inorganic Biochem 2007;
101: 187–195.
4. Chandran P, Azzabi M, Miles J, Andrews M and Bradley
J. Hydroxyapatite – coated hip prosthesis vs the charnley
cemented hip prosthesis. J Arthroplasty 2010; 25: 52–57.
5. Descamps M, Hornez JC and Leriche A. Manufacture of
hidroxyapatite beads for medical applications. J Eur
Ceramic Soc 2009; 29: 369–375.
6. Kumar GS, Girija EK, Thamizhavel A, Yokogawa Y and
Kalkura SN. Synthesis and characterization of bioactive
hydroxyapatite-calcite nanocomposite for biomedical
applications. J Coll Interface Sci 2010; 349: 56–62.
7. Jin-long LIU, Yuan-yuan ZHU, Qing-liang WANG and
Shi-rong GE. Biotribological behavior of ultra high
molecular weight polyethylene composites containing
bovine bone hydroxyapatite. J China Univ Mining
Technol 2008; 18: 606–612.
8. Descamps M, Hornez JC and Leriche A. Manufacture of
hydroxyapatite beads for medical applications. J Eur
Ceramic Soc 2009; 29: 369–375.
9. Katti DR, Pradhan SM and Katti KS. Directional depen-
dence of hydroxyapatite – collagen interactions on
mechanics of collagen. J Biomech 2010; 43: 1723–1730.
10. Kruzic JJ, Kim DK, Koester KJ and Ritchie RO.
Indentation techniques for evaluating the fracture tough-
ness of biomaterials and hard tissues. J Mech Behavior
Biomed Mater 2009; 2: 384–395.
11. Zhao K, Tang YF, Qin YS and Luo DF. Polymer tem-
plate fabrication of porous hydroxyapatite scaffolds with
interconnected spherical pores. J Eur Ceramic Soc 2011;
31: 225–229.
12. Zhao C-X and Zhang W-D. Preparation of waterborne
polyurethane nanocomposites: polymerization from func-
tionalized hydroxyapatite. Eur Polymer J 2011; 44:
1988–1995.
13. Hing KA, Wilson LF and Buckland T. Comparative per-
formance of three ceramic bone graft substitutes. Spine J
2007; 7: 475–490.
14. Best M, Porter AE, Thian ES and Huang J. Bioceramics:
past, present and for the future. J Eur Ceramic Soc 2008;
28: 1319–1327.
15. Landi E, Celotti G, Logroscino G and Tampieri A.
Carbonated hydroxyapatite as bone substitute. J Eur
Ceramic Soc 2003; 23: 2931–2937.
16. Apaydin ES and Torabinejad M. The effect of calcium
sulfate on hard- tissue healing after periradicular surgery.
J Endodontics 2004; 30: 17–20.
17. Wang ML, Massie J, Allen RT, Lee Y-P and Kim CW.
Altered bioreactivity and limited osteoconductivity of
calcium sulfate- based bone cements in the osteoporotic
rat spine. Spine J 2008; 8: 340–350.
18. Swetha M, Sahithi K, Moorthi A, Srinivasan N,
Ramasamy K and Selvamurugan N. Biocomposites con-
taining natural polymer and hydroxyapatite for bone
tissue engineering. Int J Biol Macromol 2010; 47: 1–4.
19. Lee HJ, Kim SE, Choi HW, Kim CW, Kim KJ and Lee
SC. The effect of surface-modified nano- hydroxyapatite
1838
on biocompatibility of poly(e-caprolactone)/hydroxyapa-
tite nanocomposites. Eur Polymer J 2007; 43: 1602–1608.
20. Sariali E, Stewart T, Mamoudy P, Jin Z and Fisher J.
Undetected fracture of an alumina ceramic on ceramic
hip prosthesis. J Arthroplasty 2010; 25: 658.e1–658.e5.
21. Firkins PJ, Tipper JL, Ingham E, Stone MH, Farrar R
and Fisher J. A novel low wearing differential hardness,
ceramic-on-metal hip joint prosthesis. J Biomech 2001;
34: 1291–1298.
22. Teng S, Chen L, Guo Y and Shi J. Formation of nano-
hydroxyapatite in gelatin droplets and the resulting
porous composite microspheres. J Inorganic Biochem
2007; 101: 686–691.
23. Lu G, Sheng B, Wei Y, Wang G, Zhang L, Ao Q, et al.
Collagen nanofiber-covered porous biodegradable car-
boxymethyl chitosan microcarriers for tissue engineering
cartilage. Eur Polymer J 2008; 44: 2820–2829.
24. Holmes R and Hagler H. Porous hydroxyapatite as bone
graft substitute in maxillary augmentation: an histometric
study. J Cranio-Maxillofacial Surg 1988; 16: 199–205.
25. Kes M, Polat H, Kelesoglu S, Polat M and Aksoy G. The
particle interactions, rheology and the surface roughness
relationship for dental restorative ceramics. J Eur
Ceramic Soc 2009; 29: 2959–2967.
26. Torrey JD and Bordia RK. Mechanical properties of
polymer- derived ceramic composite coatings on steel.
J Eur Ceramic Soc 2008; 28: 253–257.
27. Estevez M, Fonseca G, Vargas S and Rodrı́guez R.
Hybrid porous materials for dental applications.
J Compos Mater 2010; 44: 2667–2678.
Journal of Composite Materials 46(15)
28. Homaeigohar SSh, Sadi AY, Javadpour J and Khavandi
A. The effect of reinforcement volume fraction and par-
ticle size on the mechanical properties of b-tricalcium
phosphate–high density polyethylene composites. J Eur
Ceramic Soc 2006; 26: 273–278.
29. Yang CH, Huh H and Hahn HT. Investigation of effec-
tive material properties in composites with internal defect
or reinforcement particles. Int J Solids Struct 2005; 42:
6141–6165.
30. Modesti M and Lorenzetti A. An experimental method
for evaluating isocyanate conversion and trimer forma-
tion in polyisocyanate - polyurethane foams. EurPolymer
J 2001; 37: 949–954.
31. Bistričić L, Baranović G, Leskovac M and Bajsić EG.
Hydrogen bonding and mechanical properties of thin
films of polyether-based polyurethane-silica nanocompo-
sites. Eur Polymer J 2010; 46: 1975–1987.
32. Mobasherpour I, Soulati Heshajin M, Kazemzadeh A
and Zakeri M. Synthesis of nanocrystalline hydroxyapa-
tite by using precipitation method. J Alloys Comp 2007;
430: 330–333.
33. Gărăjeu M and Suquet P. On the influence of local fluc-
tuations in volume fraction of constituents on the effec-
tive properties of nonlinear composites. J Mech Phys Sol
2007; 55: 842–878.
34. Kennedy DM and Hashmi MSJ. Methods of wear testing
for advanced surface coatings and bulk materials.
J Mater Proc Technol 1998; 77: 246–253.