Trends Biomater. Artif.

Organs, Vol 22(3),

PolymerppCeramic
169-178Composites
(2008) for Orthopedic Applications 165
http://www.sbaoi.org

Development and Characterization of Polymer Ceramic Composites for

Orthopedic Applications

K. Janaki, S. Elamathi, D. Sangeetha*

Department of Chemistry,
Anna University Chennai,
Chennai-600025, India.
*Corresponding author, sangeetha@annauniv.edu

Received 01 July 2008; Accepted 25 November 2008; published online 23 December 2008

In the present work, synthetic composites were prepared using Polyether ether ketone (PEEK) and Poly
styrene (ethylene-butylene) polystyrene (PSEBS) as polymer matrices and Hydroxyapatite as the ceramic. In
order to have chemical interactions possible with-OH group of Hydroxyapatite, the polymers were sulphonated.
By doing so, the drawback of Hydroxyapatite, i.e., its migration from the site of implant in the body can be
avoided. Thus a better interface of Hydroxyapatite with the polymer matrix can be expected. In order to study
the effect of biocompatibility of HAP in sulphonated PEEK and PSEBS, a series of two sets of composites
(each having 5 different proportions) were prepared. Then, the water swelling studies, biocompatibility tests
were performed. Biocompatibility tests include clot formation test, % Haemolysis and protein adsorption test.
Then the prepared composites were characterized by FT-IR, XRD and TGA. © Society for Biomaterials and
Artificial Organs (India), 20080701-21.

Introduction spread interest from both the orthopedic and

Biomaterials play a key role in the replacement
of body parts and restoration of human
anatomical structures. Among these, the
metallic materials occupy a leading role
besides the availability of ceramics and
polymers for hard tissue replacement. The
material suited for bone joint replacement in
the human body should satisfy features like
tissue tolerance, resistance to corrosion or wear,
biocompatibility and nit producing and adverse
body reactions. (1-3). Due to density and elastic
modulus mismatch of commonly used metallic
implants with bone, material scientists are
trying to develop composite as a bone substitute
material using a synthetic polymer as a matrix
and different ceramic material as a reinforcing
agent (4).Hydroxyapatite Ca10(PO 4 )6(OH) 2 ,
commonly referred to as HAP, has attracted wide
dental fields due to its excellent biocompatibility
and tissue bioactivity properties. Hydroxyapatite
is particularly attractive as a biomedical surface
modifier used to increase the rate and longevity
of implant fixation. Calcium phosphate ceramics
and Hydroxyapatite in particular could be used
to manufacture ideal biomaterials due to their
biocompatibility and Osseo integration, as well
as being the materials most similar to the
mineral component of the bone.
Hydroxyapatite is chemically similar to the
mineral component of bones and hard tissues
in mammals. It is one of the few materials that
are classed as bioactive, meaning that it will
support bone in growth and Osseo integration
when used in orthopaedic, dental and
maxillofacial applications. The chemical nature
of hydroxyapatite is to lend it for substitution.
170 K. Janaki, S. Elamathi, D. Sangeetha

The most common substitutions involve
carbonate, fluoride and chloride substitutions
for hydroxyl groups, while defects can also exist
resulting in deficient hydroxyapatites. Seventy
percent of bone is made up of hydroxyapatite, a
calcium phosphate mineral. The process of
bone resorption by the osteoclasts releases
stored calcium into the systemic circulation and
is an important process in regulating calcium
balance. As bone formation actively fixes
circulating calcium in its mineral form, removing
it from the bloodstream, resorption actively
unfixes it thereby increasing circulating calcium
levels.
Hydroxyapatite is a regarded to be a bioactive
material (5). It seems to be the most appropriate
ceramic material for artificial bones or teeth due
to its excellent biocompatibility and bioactivity.
Also, HAP actively encourages bone
regeneration at the surface of the implant. (6).
Although, surface modification is the key to
altering the surface properties of the polymer
without changing its physical and mechanical
properties, the method has inherent
disadvantages in that the modification has to
be performed on the finished product. This is
often undesirable and modification of the
polymer prior to processing would be more
advantageous if the desirable surface
properties are retained to a significant extent in
the finished product. (7)
of load bearing orthopedic applications. Based
o the bone like stiffness of PEEK polymer, it is
anticipated that by incorporating bioactive HAP
an varying the amount would result in composite
with elastic modulus comparable to that of
natural bone and at the same time make the
PEEK polymer bioactive. (11). However, the
migration of individual particles from the implant
site before tissue in growth cause
inconvenience, difficult to fill the surface of
irregular bone defect and reconstruction. To
avoid the migration of HAP from polymer matrix
and produce the possible chemical interaction
between polymer and HAP, the polymers were
sulphonated.
Experimental
Sulphonation of PEEK
About 10g of dry PEEK powder was taken in a
500ml round bottom flask. About 150ml of
concentrated sulphuric acid was added and the

Hydroxyapatite has been used clinically as

substitute for autografts in filling bone defects.
Unlike, other implant materials, HAP is
biocompatible, nontoxic, resorbable,
possesses excellent osteo conductive ability,
Figure 1: Sulphonation of PEEK to SPEEK
possesses structure similar to bone mineral
and forms direct bond with bone. (8). Bone is
the natural composite in the body, bone serves
as a number of functions, such as providing the CH 2 CH
x
CH 2 CH 2 CH 2 CH CH 2 CH
z
cells found in the marrow that differentiate in to CH 2 y

blood cells and also act as a calcium reservoir.

CH 3
Nevertheless, its primary purpose is to provide
ClSO 3 H
mechanical support for soft tissues and serves
as an anchor for the muscles that generate
motion (9, 10).
CH CH 2 CH 2 CH 2 CH CH 2 CH
CH 2 z
x
Polyether ether ketone is a rigid semi-crystalline CH 2 y

polymer possessing excellent mechanical

CH 3
properties and bone like stiffness. In recent SO 3 H
years, PEEK polymer has gained much attention
Figure 2: Sulphonation of PSEBS to SPSEBS
in the biomedical field, particularly in the area
 Polymer Ceramic Composites for Orthopedic Applications 171

contents of the flask were vigorously stirred. The
reaction was carried out under nitrogen
atmosphere. After the prescribed time, the
contents of the flask were poured into a trough
containing a large excess of crushed ice. The
sulphonated polymer obtained in the form of
innumerable fibers was recovered by filtering.
It was then washed for 10 - 15 times with the
distilled water, until the last trace of acid was
removed. The product obtained was
sulphonated PEEK. It was then dried in an oven
at 80ºC overnight.
and quickly weighed after carefully wiping out
the excess liquid. This process is done at
different soaking period to determine the
amount of absorption at particular time “t”. The
samples were then quickly placed back in the
solvent. The process was repeated until films
attained saturation as indicated by constant
weight after a certain period of soaking time.
Then the swelling percentage was calculated
using the following formula.
% Swelling = (Wwet - Wdry/Wdry) x 100

Sulphonation of PSEBS where W wet =weight of wet specimen, W dry=

weight of dry specimen
Polystyrene ethylene butylene polystyrene
(PSEBS) was sulphonated using Blood compatibility tests
chlorosulphonic acid (CSA) as the sulphonating
agent. Weighed polymer was dissolved in A biomaterial is a substance used in medical
chloroform. The solution was allowed to cool in devices for contact with the living body for the
an ice bath. Then the required amount of Tri- intended method of application and for the
butyl phosphate (TBP) (to moderate the intended time period. To acquire
reaction) followed by CSA were added drop wise biocompatibility, the materials used in medical
with continuous stirring. The reaction was applications must meet certain regulatory
carried out in the nitrogen atmosphere. The requirements. The surface of biomaterials is
reaction was terminated using methanol. Then believed to play an important role in determining
the ionomer was washed with water several biocompatibility. Therefore, certain test
times until the pH was neutral. The obtained procedures have been developed and they need
ionomer was dried at 75 0C for one day. to be employed to judge the haemofriendly
nature of materials. The following three tests
Preparation of Composites have been done in order to predict the biological
performance of the composites in living tissues.
The sulphonated PEEK polymer was dissolved
in boiled N-methylpyrrolidone (NMP). The
measured amount of hydroxyapatite was added Table 1: Weight of the clot formed by the
into it and the whole contents were kept for
composites
stirring for 5 hours. Then it was dried in an oven
at 80ºC for 10 hours and the preparation was Sample % of HAP Clot weight
done for different proportions. Name (wt %) (in gram)
SPEEK 1 1 0.0034
The sulphonated PSEBS polymer was SPEEK 3 3 0.0047
dissolved in tetrahydrofuran (THF) and the clear SPEEK 5 5 0.0086
SPSEBS 1 1 0.0081
polymer solution was poured into the dispersed
SPSEBS 3 5 0.0180
hydroxyapatite in THF. It was kept for stirring for SPSEBS 5 10 0.0202
five hours. Then using solvent evaporation
method, the different composition of polymer
composites was prepared. Table 2: % Haemolysis of composites
Sample % of HAP Haemolysis
Swelling studies Name (wt %) %
SPEEK 1 1 1.131
A small portion of previously weighed polymer SPEEK 3 3 1.133
composite was placed in deionized water and SPEEK 5 5 1.28
it was kept for equilibration with water at room SPSEBS 1 1 1.246
temperature. The specimens were taken out SPSEBS 3 5 2.053
SPSEBS 5 10 2.207
172 K. Janaki, S. Elamathi, D. Sangeetha

Clot formation test

20
The anti-thrombogenic potential of the
composite surface was judged by the blood- 15
clot formation test as described by A.Bajpai et

Swelling %
(12). In brief, the specimens were equilibrated 10
with saline water (0.9% w/v NaCl) at 37ºC for 24
hours in a constant temperature. To these 5
swollen samples was added 0.5ml of ACD (Acid
Citrate Dextrose) blood followed by the addition 0
of 0.03ml of CaCl2 solution (4 mol.l-1) to start the 0 1 2 3 4 5 6
thrombus formation. Here, Acid Citrate Dextrose HAPcontent (inwt %)

Solution is a solution of citric acid, sodium citrate

and dextrose in water. It is mainly used as an Figure 3: Swelling % of SPEEK/HAP composites
anticoagulant to preserve blood from clotting.
Adding 4ml of deionized water stopped the
reaction and the thrombus formed was 160
separated by soaking in water for 10 minutes at 140
room temperature and then fixed in 30% 120
Swelling %

formaldehyde solution (2ml) for another 10 100

minutes. The fixed clot was placed in water for
80
10 minutes and after drying its weight was
60
recorded.
40

Haemolysis test
Haemolysis experiments were performed on the
surfaces of prepared composites as described
by R.Saini etal (13). In a typical experiment, dry
composite pieces were equilibrated in normal
saline water (0.9% w/v NaCl) at 37ºC for 24
hours and human ACD blood (0.25 ml) was
added into the composites after 20 minutes 2
ml of saline water was added into the
specimens to stop haemolysis and the
samples were incubated for 60 minutes at 37ºC.
Positive and negative controls were obtained
by adding 0.25 ml of human ACD blood and
0.9% w/v NaCl respectively to 2 ml of deionized
water. Incubated samples were centrifuged for
45 minutes, and its absorbance at 545 nm was
recorded using a spectrophotometer. The
percentage haemolysis was calculated using
the following relationship,
Hemolysis (%) = (Atest - A(-)control)/(A(+)control - A(-)control)
Where, A is absorbance. The absorbance of
positive and negative controls was found to be
1.35 and 0.0875 respectively.
Protein Adsorption
The batch contact process performed
adsorption of BSA onto the polymer composite
20
0
0 1 2 5 7.5 10
HAP content (in t%)
Figure 4: Swelling % of SPSEBS/HAP compos-
ites
materials as described by A. Bajpai (14). For
protein adsorption experiment, protein (BSA-
Bovine Serum albumin) solution was prepared
in 0.5M PBS (Phosphate buffer saline) at
physiological pH 7.4. A fresh solution of BSA
was always prepared prior to adsorption
experiments. The polymer composites of
definite weights were equilibrated with PBS for
24 hours. The adsorption was taken then
carried out by gently shaking a BSA solution of
known concentration containing preweighed
and fully swollen composites. By taking fully
swollen samples, the possibility of soaking of
BSA solution within the composite becomes
minimum. Shaking was performed so gently
that no froth was produced, otherwise BSA would
absorb in air-water interface. After 24 hours, the
samples were removed and the adsorbed
protein was assayed for the remaining
concentration of BSA by recording absorbance
at 660 nm on a UV-Vis spectrophotometer.
 Polymer Ceramic Composites for Orthopedic Applications
FT-IR studies
FT-IR studies of the powdered specimens were
recorded on a FTIR spectrophotometer. Prior to
analysis KBr pellets were prepared by mixing
of sample and KBr followed by uniaxial pressing
the powders under vacuum. FT-IR
characterization was done in order to predict
any bonding that has been developed between
the sulphonated polymer and ceramic.
XRD studies
To know the level of dispersion of the inorganic
content in the specimens and to know the
amount of crystallinity, XRD measurements
were performed using X’ pert pro diffractometer.
Thermo Gravimetric Analysis
This is the technique in which the change in
weight of a substance with temperature over a
period of time is followed. Thermal stability and
decomposition temperature can be assessed
easily. From the results, the increased or
decreased thermal stability of the composites
compared to the polymers and the ceramic can
be found. To evaluate thermal stability of the
composites, TGA was performed in the
temperature range of 0–800°C, in nitrogen
atmosphere at a heating rate of 10°C min–1.
Mechanical testing
Tensile strength of the specimens was
measured using a Universal Testing Machine
(UTM) possessing a load cell of 5 kN, at room
temperature. The gauge length and diameter
of all specimens were 50 mm and 5 mm
respectively. Tests were conducted with a
constant strain rate of 10 mm per minute and
up to failure of the material. The increase or
decrease in tensile strength of the composites
was recorded.
Results and discussion
Swelling studies
Blood is a specialized body fluid that is
composed of blood cells suspended in a liquid
called blood plasma. Plasma, which comprises
55% of blood fluid, is 90% of water by volume.
So, the composite we are using for a biomedical
173
application should not show the property of
absorbing water.
One of the prime factors to contribute to
biocompatible nature of synthetic biomaterials
is the amount of water content which imparts
several unique physiochemical properties to
the material. A polymer matrix imbibing an
adequate of water, shows living tissue like
membrane, physiological stability, low
interfacial tension, permeability to
biomolecules etc. Thus realizing the unusual
significance of water sorption capacity of a
material, the composites have been
investigated for water sorption capacity and the
influence of chemical composition of the
composites on their water intake has been
investigated as discussed below.
The polymers PSEBS and PEEK are
hydrophobic in nature. When it gets
sulphonated, the polymers become more
hydrophilic and hence absorption of water
increases. The water absorption behaviour of
the polymer composite is influenced by the
incorporation of the HAP in the polymer material.
The results are shown in Figure 3 and 4, which
clearly reveals that the water absorption ratio
constantly decreases with increasing HAP
content in the polymer composite material. The
results are quite expected and may be explained
by the fact that due to relatively lower
hydrophilicity of the apatite in comparison to
sulphonated polymer, its increasing fraction in
the composite results in a lower water sorption
by the composite. Alternatively, the increasing
polymer-HAP interaction with increasing
concentration of HAP results in a slower
relaxation of polymer chains, which also
decreases the swelling ratio.
While increasing the amount of HAP in the
polymer material, the water absorption gets
decreased. This can be explained by the fact
that while increasing the amount of HAP in the
composite, the HAP molecules can occupy the
gaps between the polymer molecule and
interactions are possible between the sulphonic
acid group and the hydroxyl group of the HAP.
This makes it less hydrophilic.
When the water absorption behaviour of the
SPEEK/HAP was compared with SPSEBS/HAP
174 K. Janaki, S. Elamathi, D. Sangeetha
Figure 5: FT-IR of HAP
Figure 6 FT-IR spectra of (A) SPEEK and (B)
SPEEK/HAP composite membranes
composites, SPEEK/HAP composites shows
lower water absorption than SPSEBS/HAP
composites. So the composite made from
SPEEK can be expected to be more compatible
when compared with the composite made from
SPSEBS as far as their water absorption
behavior is concerned.
Blood Compatibility Tests
Clot formation test
The results reveal the fact that the weight of
blood clot constantly increases with increasing
amount of HAP in the feed mixture. The values
are shown in table 1. The results may be
explained on the basis of the fact that both PEEK
and PSEBS became hydrophilic polymers,
when they were sulphonated and therefore, are
not expected to provoke any damage to blood
cells or any change in the structure of the
plasma proteins. It has also been realized that
with increasing concentrations of ceramic, the
composite acquires less smoothness of their
surfaces and this consequently results in an
improvement in antithrombogenic property of
Figure 7: FT-IR spectra of (A) SPSEBS and (B)
SPSEBS/HAP composite membranes
material. The results obtained suggested that
the composite shows decreasing blood
compatibility with the increase in HAP content.
Here, the clot formed by SPEEK with 5% of HAP
is almost equal to that of the SPSEBS with 1%
of HAP. Thus, when compared to SPSEBS/HAP
composites the SPEEK/HAP composites are
more blood compatible.
Percentage Haemolysis test
The prepared composites were tested for
haemolytic activity and the results obtained are
quite satisfactory. Percent haemolysis is
maximum (100%) for distilled water–saline
water-added blood sample (positive control).
The results obtained clearly indicate that, with
increasing HAP content, the extent of
haemolysis steadily increases. The observed
results may be attributed to the reason that, with
the increase in polymer weight fractions in the
composite, the surface composition favorably
changes, which improves the blood compatible
quality of the material. The results are shown in
Table 2.
Protein Adsorption test
From the protein adsorption test, the
absorbance values were obtained for both sets
of composites. It is observed that the protein
adsorption is not taking place. The results
conclude that a material surface showing
reluctance to BSA adsorption proves to be more
 Polymer Ceramic Composites for Orthopedic Applications 175

Figure 9: XRD pattern of (A) SPEEK and (B) SPEEK/

Figure 8: XRD pattern of HAP
HAP composite

biocompatible. The positive results shows a observed at 1403 cm-1. Characteristic carbonyl
lower water sorption by the composite. group peak was observed at 1620cm-1.

The blood compatibility of the composites with Figure 6 (B) shows the IR spectrum of SPEEK/
increasing HA content showed a decrease, i.e. HAP composite. A shift of the peak from 3397
both the weight of the clot formed and % cm-1 to 3523 cm-1 is due to the bonding of the -
Haemolysis were increased. The reason for the OH group of HAP with –SO 3H group of the
observed more thrombogenicity is that the ionic sulphonated polymer. Another shift in the
groups of HAP may react with the blood sulphonic acid group peak was observed from
components and produced greater blood- 1124 cm- 1 and 1018 cm-1 in the case of SPEEK
surface interactions. This was likely to cause to 1159 cm-1 and 1059 cm-1 in the synthesized
thrombogenic behavior of the composite. The SPEEK/HAP composites. Appearance of peak
above discussion clearly suggests that a less at 1706.3 cm-1 is due to the attributed –C=O
crosslinked composite with more polymer and group.
low HAP content may prove to be more
biocompatible. The FT-IR spectrum of SPSEBS is shown in the
Figure 7 (A). Appearance of a broad envelope
FT-IR around 3000-3600 cm-1 was assigned to –OH
stretch of sulphonic acid group. Appearance of
Figure 5 shows the IR spectrum of raw HAP
powder. The broad peak ranging from 3300-
3600 cm- 1 is explained owing to O-H group
stretch vibration. The band at 1450 cm- 1 is
assigned to the CO32- stretching. An intense PO4
3-
peak appeared at 1031 cm - 1 . Additional
phosphate group bands are found in the region
866.1 cm- 1, 604 cm- 1and 565 cm- 1 as confirmed
in literature.

In Figure 6 (A), the SPEEK ionomer given for

FT-IR analysis showed characteristic sulphonic
acid group peak at 1124, 1018 cm-1. The peak
at 1018 cm- 1 was assigned to sulphur-oxygen
symmetric vibration O=S=O. The broad peak
appearing at 3397 cm -1 assigned to O-H
Figure 10: XRD pattern of (A) SPSEBS and (B)
vibration from sulphonic acid groups interacting SPSEBS/HAP composite
with molecular water. Aromatic C-C peak was
176
Figure11: Thermogram of (A)SPEEK, (B)SPSEBE,
(C)SPEEK/HAP and (D)SPSEBS/HAP composites
peak around 1174 cm-1, 1027 cm-1, 1116 cm-1
were assigned to the O=S=O (asymmetric
stretch) which is due to the presence of O=S=O
stretching, which confirms that the polymer
PSEBS has been sulphonated. Disappearance
of peak at the frequency of 720 cm-1 and 693 cm-
1 of SPEEK is shown in the Figure 9(A). There is
shows that sulphonic acid group is substituted
in the aromatic ring. Appearance of peak at
around 869 cm -1 shows that sulphonic acid
group is substituted at para position.
Figure 7 (B) shows the IR spectrum of SPSEBS/
HAP composite. In FT-IR characterization of
SPSEBS/HAP composites, the peak at 604.0
cm-1 of HAP was found to be disappeared. This
was due to the disappearance of PO4- group in
its structure which might be happened due to
its interaction with any of the group of the
sulphonated polymer. The peak at 1027.7 cm-1
45
40
35
Tensile strength in MPa
30
25
20
15
10
5
0
0 1 2 3
HAP content (in wt %)
Figure 12: Tensile Strength of SPEEK/HAP
composites
K. Janaki, S. Elamathi, D. Sangeetha
was due to the O=S=O stretching of SPSEBS
was shifted to 1070 cm -1 of SPSEBS/HAP
composites. The shift of the peak from 3437
cm -1 to 3502 cm -1 was also observed. The
intensity of the –OH peak was also reduced.
The interaction between –SO3H group of
SPSEBS with –OH group of HAP has been
confirmed by these peaks. Appearance of peak
at 2924 cm- 1 and 2859 cm -1 is due to the
asymmetric stretching of -CH3 group. Peaks at
1460 cm -1 and 1365 cm -1 are due to the
asymmetric and symmetric deformation of –CH3
and -CH2 groups respectively.
XRD studies
The XRD pattern of the HAP is shown in Figure
8. The HAP exhibits sharp apatite peaks due to
crystal growth, alternatively calcium carbonate
peak at 2q value of about 29o present together
with apatite phase. The X-ray diffraction pattern
an intense pattern at 72.61º and weak patterns
at 43.74º and 50.94º. On comparison of the XRD
patterns of SPEEK and SPEEK/HAP composite,
the later showed an increase in intensity of the
peak at 44.8 and 52.5 due to the formation of
the bond between the –SO 3 H group of the
sulphonated polymer with the –OH of the
inorganic material.
There is an intense pattern at 72.61º and weak
patterns at 45º, 52.8º and 23.1º The X-ray
diffraction pattern of SPSEBS is shown in the
Figure 10(A). The X-ray powder diffraction
2
1.8
Tensile strength in MPa
1.6
1.4
1.2
1
0.8
0.6
0.4
0.2
4 5 0
0 2 HAP
4 content (in
6 wt %) 8 10
Figure 13: Tensile Strength of SPEEK/HAP
composites
 Polymer Ceramic Composites for Orthopedic Applications
patterns of SPSEBS/HAP were shown in the
figure 10(B). There is an intense pattern at
73.52º and weak patterns at 20.9º, 44.5º and
50.94º. When compared the XRD patterns of
SPSEBS and SPSEBS/HAP composite, the
composite showed an increase in intensity of
the peak at 44.8 and 52.5 due to the formation
of the bond between the –SO3H group with –
OH. All the composites and the sulphonated
polymers showed an intense peak near 70 -
72º showed the presence of phenyl ring.
TGA
In order to evaluate thermal stability and
understand the phase transformation in the
prepared polymer composite materials the TGA
studies were performed. The HAP is showed
the thermal stability up to 800ºC. PEEK is a high
thermostable polymer with a Tg value of
approximately 250°C. Sulphonated PEEK
shows glass transition temperature in the range
of 200°C - 220°C, depending on the degree of
sulphonation. The thermogram obtained
between 30 and 800ºC is shown in the Figure
11(A). Three transitions were shown in the
figure. There was a gradual decrease in weight
from 20 - 200ºC. It is due to loss of physically
and chemically bound water in the polymer
matrix. This is followed by a sharp weight loss
producing a maximum at 257ºC. This second
transition is assigned to the loss of sulphonic
acid groups. This sharp weight loss is followed
by another weight loss with a peak maximum at
498ºC. It is also assigned to the degradation of
the polymer matrix, which is the third transition.
The thermogram of SPSEBS, obtained between
30 and 800ºC is shown in the Figure 11(B).
There was a gradual decrease in weight from
30 - 201ºC. It is due to loss of entrapped water
in the polymer matrix. This is followed by a sharp
weight loss producing a maximum at 211ºC. It
is assigned to the loss of sulphonic acid
groups. This sharp weight loss is followed by
another weight loss with a peak maximum at
286ºC. It is also assigned to sulphonic acid
groups buried inside the polymer matrix. Hence
the previous weight loss is ascribed to
decomposition of free, non-bonded sulphonic
acid groups present particularly on the surface
of the matrix. Further, there is a major weight
loss of about 70% with maximum at 424ºC, and
177
it is due to oxidative degradation of the polymer
matrix. This decomposition leaves a residue
that produces a minor weight loss at about
640ºC. The residue was not completely oxidized
in air and the total residue left over is 7.6%.
The thermograms of the composites SPEEK/
HAP and SPSEBS/HAP were shown in Figure
11(C) and 11(D). The temperature of
degradation of water molecules, sulphonic acid
group and polymer matrix were increased,
sufficiently. This can be assigned to the
interactions happened to the –SO3H group of
the sulphonated polymer with the –OH of the
inorganic material. Due to this, the polymer
matrix degradation has been shifted to 540ºC
in SPEEK/HAP composites. In the case of
SPSEBS/HAP composites, the polymer matrix
degradation has been shifted to 484ºC.
Mechanical testing
In order to evaluate the mechanical suitability
of the novel composites, the tensile strength
was measured in the dry condition and the
results were given in Figure 12 and 13. In the
case of SPEEK/HAP composites, a gradual
increase in the tensile strength was observed.
On the other hand, with SPSEBS/HAP, the
tensile strength was found to be almost
constant up to a loading of 7.5% of HAP. After
7.5% loading, there was an increase the in
tensile strength. This type of enhancement in
the tensile strength after 7.5% dosage provides
increased fracture toughness to the samples.
Although the SPEEK/HAP composites
displayed a better mechanical strength than the
SPSEBS/HAP, it was evident that both the
composite materials possess good
mechanical strength for being used in tissue
engineering (TE). Tensile strength of both sets
of composites was increased due to the
chemical bonding between the sulphonic acid
group of the polymers and hydroxyl group of HAP
as evident from the FT-IR spectra.
Conclusion
The prepared SPEEK/HAP composites showed
a tensile strength up to 42.5 MPa with
satisfactory blood compatibility. The clot
formation, % haemolysis in the case of SPEEK/
HAP composite was less when compared to
the SPSEBS/HAP composites and therefore it
178 K. Janaki, S. Elamathi, D. Sangeetha

can be said to be more biocompatible. The
swelling behavior of SPEEK/HAP composite
was not up to the extent of SPSEBS/HAP
composites. Both composites reduce the
migration of HAP and this was confirmed by the
FT-IR analysis. So, it can be said that SPEEK/
HAP composites can be employed for a hard
tissue applications and SPSEBS/HAP
composites can be employed for soft tissue
applications. However, the non- biocompatible
nature of SPSEBS/HAP needs a further focused
study. Among the five different proportions of
SPEEK/HAP composites prepared, the
composite prepared with 99:1 of SPEEK and
HAP shows very good blood compatibility. This
is because of their reduced values in clot
formation test, % Haemolysis and swelling
studies. It also shows a tensile strength around
13 MPa. So, cancellous bone that acquires a
tensile strength about 8 MPa can be replaced
by this particular composite. However, its elastic
modulus needs to be found to confirm its
matching with cancellous bone. Sterilization
process also needs to be done before
employing it inside the body.

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