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Porous hydroxyapatite ceramics

fabricated via starch consolidation
technique

Article in Journal of Ceramic Processing Research

January 2015

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Journal of Ceramic Processing Research. Vol. 16, No. 00, pp. 1~10 (2015)
J O U R N A L O F

Ceramic
Processing Research

Porous hydroxyapatite ceramics fabricated via starch consolidation technique

*
Ahmed Y.M.Z.a, , Ewais E.M.M.a and El-Sheikh S.M.b

a
Ceramic and Refractory Materials Division bNano-Structured Materials Division.Central Metallurgical Research and
Development Institute, CMRDI P.O. Box: 87 Helwan, 11421 , Helwan, Egypt

The starch consolidation technique was regarded as a versatile route for fabricating both dense and porous ceramics. Porous
hydroxyapatite ceramics would be processed via applying this technique. There are various parameters controlling this technique
such as the suspension solid loading, the amount and type of starch added as well as the sintering regime of the samples in terms
of temperatures and time. The influence of both potato starch amounts and the sintering temperature upon the chemical, physical
and mechanical properties of porous hydroxyapatite samples produced via this technique was investigated. The XRD and FT-IR
analysis of the sintered sample prove the decomposition of the parent hydroxyapatite phase into tricaclium phosphate upon
increasing of both starch amount and sintering temperature. The high apparent porosity of 57% was found to produce for samples
containing 30 Wt.% potato starch and sintered at 1250 oC. While the pore size was found to be also highly affected by both starch
amount and sintering temperature, that confirmed from SEM investigation and porosimeter analysis. The increasing of starch
amounts and the decreasing of sintering temperature lead to a high retardation in the compressive strength of the sintered HA
sample.

Key word: Hydroxyapatite, Potato starch, Starch consolidation technique, Sintering, Porosity, Compressive strength.

Introduction replacement, according to the fact that they do not

There is a considerable demand in oral
surgery [1-3] and orthopedic medicine [4,
5] for inorganic scaffolds suitable for repair or
replacement of human bone tissue. Calcium
phosphate-based ceramic materials, mainly
hydroxyapatite (HA), is regards as the most
appropriate ceramic material for hard tissue
exhibit any cytotoxic effect, show excellent
biocompatibility with the hard tissues and also skin
and muscle tissues [5]. On the other hand, its
bioactivity promotes both tissue bonding and new
tissue formation. For this application porous HA
bioceramic with open pore structures are of
particulate interest and importance since they have
excellent permeability and a large surface area [6,
7]. The preferred method of fabricating such
bioceramic should be capable of tailoring their porosity,
offering perfect and large interconnections and
achieving dense ceramic networks. Unfortunately, due
to low mechanical reliability, HA ceramic cannot be
used for heavy load bearing area applications [8]. Thus,
in recent years, many works were concentrated on
finding a processing technique capable of achieving
more reliable bioceramic bodies. A numbers of
fabrication techniques have been developed for
producing porous bioceramic, including
*Corresponding
author: Tel : +202-
25010642 Fax:
+202-25010639
E-mail: ahmedymz@hotmail.com
1 mechanical properties. This process is based on the
the incorporation of pore-forming fugitives materials [9],
hydrothermal conversion from coral [10], bulk ceramic
processing technique [11], foaming [12-14], the replication
of polymer foams by impregnation [15, 16], the dual phase
mixing technique [17] and limiting densification during the
sintering process [18]. However, none of these methods
can satisfy all the above mentioned requirements, namely
high porosity, perfect interconnection, and high mechanical
properties of the produced bodies. For instance, the
polymer foam replication method can produce a body with
ultra high porosity with large interconnection. But the
reticulated porous ceramic produced by this method often
have very poor mechanical properties because of the
defects generated during the pyrolysis of the polymer foam
[16]. Generally speaking, all the above mentioned
approaches are suffering from a lack of control over the
final architecture and distribution of porosity within the
HA body.
A key step in the processing of advanced ceramics is the
control of microstructure of the green bodies with
minimizes defects, so that high strength and reliable
products are obtained after sintering [19]. It has been well
established that the present of agglomerate in the green
compacts is difficult to eliminate through conventional dry
powder consolidation processes as like uniaxial pressing
[20]. Consequently wet processing forming routes
involving a colloidal dispersion of fine powder particle in a
liquid medium and their consolidation into homogeneous
green body with minimum defects (both in size and
numbers) has gained wide acceptance.
Accordingly, a technique based on colloidal approach
could be promising for achieving the requirements needed
for implant application [21]. Various colloidal processes,
such as slip casting [22-27], tape casting [12, 28, 29] and
gel casting [30-32] has been reported for the preparation of
HA bodies with different sizes and shapes.
However, the obtained properties results are so far
from promising to fulfill the requirements for using the
produced product as implant. Herein (in this project) a
trial was made for utilizing another approach based on
colloidal processing named starch consolidation
technique for fabricating the 3D HA structure. In this
approach, a well stabilized HA suspension is forced to
consolidate in an impermeable mold without powder
compaction or liquid removal by addition of starches
upon heating. The potential advantageous of this
technique is a good material homogeneity which
promotes control of the shrinkage during sintering and
hence controls the overall features of the final sintered
product.
The starch consolidation technique was applied in
this investigation in order to produce porous
hydroxyapatite objects with homogeneous structure,
controllable porosities as well as satisfied sintered
fundamental property of starches and their gelling
ability in water [33]. Starch is widely present as a
reserve of carbohydrate in the leaves, stems, and fruits
of most land plants [34]. Most starches consist of
mixtures of two polysaccharide types, a linear one,
amylose, and highly branched one, amylopectin.
Amylose gives the starch its gelling property in
aqueous suspensions. The glucose units that build up
the polymeric chains in starch expose a lot of hydroxyl
groups and, therefore, give a strong hydrophilic
character to starch granules.
The water insolubility of starch granules below about
50 oC means that they can be handled and processed at
room temperature without significant impact on the
granule structure. However, when the starch suspension
is heated to a temperature between 55 and 80 oC
(depending on type and concentration), the
intermolecular bonds holding the granules together are
weakened. During this process, the granules undergo a
rapid and irreversible swelling by water uptake which
results in an increased granule size to many times the
original size [33].
By mixing ceramic powders and starch in a water
suspension, pouring it into a mold and heating it up to
60-80 oC the starch particle will swell by water uptake.
This swelling removes water from the slip causing the
ceramic particles stick together and, consequently,
consolidate into a solid body. As the starch granules
swell, they will also act as a binder adding strength to
the consolidated body which enables demoulding prior
to drying. After burn-out of the starch and sintering of
the ceramic matrix, the material is obtained with a
porosity corresponding to the original amount, shape
and size of the starch particles including the allowed
swelling during the consolidation. Besides the
favorable gelling properties of starches, they are
3 Ahmed Y.M.Z., Ewais E.M.M. and El-Sheikh S.M.
environmentally friendly, easy to burn out and not less
important; they are very cheap [35].
There are various parameters controlling the tailoring of
3D porous ceramic body using the starch consolidation
technique. These factors, such as the suspension rheology,
the solid content, the amount and type of added starch and
sintering regime in terms of temperature and time
represents the most important parameters. Herein, the
influence of both different potato starch amounts addition
and the sintering temperature on the various properties of
the sintered HA sample are through investigated. Various
potato starch amounts varied from 10 to 30 Wt% and
various sintering temperatures ranging from 1250 to 1350
o
C were applied. The influence of such variation in both
starch amount and sintering temperature upon the
chemical, physical and mechanical properties of the final
sintered HA sample were studied.
Experimental and Procedures
Materials
Hydroxyapatite powder used in this investigation was
delivered from Riedel-de Haen Co. (Seelze, Germany).
The bulk characteristics, which are taken from the
manufacturer, indicated that the powder only contains
minor amounts of compounds other than calcium and
phosphates. A stock of HA powder was firstly calcined at
1100 oC. The calcined powders were found to have a mean
particle size of ~ 16 m, surface area of ~ 2 m 2/g and
pore volume of 0.002 cc/g.
In order to prepare a well stabilized suspension from
calcined HA, Acumer 9400 as a dispersing agent is
applied. Acumer 9400 was supplied from The Dow
Chemical Company, Midland, Michigan, USA. It is a
water-soluble sodium salt polymer used to disperse and
stabilize high-solids mineral slurries. It is an anionic
dispersant of sodium polyacrylate polymer (SPA) of
solid content 41-43 Wt% with a molecular weight of
3000-4000 g/mole.
The potato commercial starch used in this work was
supplied by El-Gomhoria Company, Egypt. This starch
had not any physical or chemical modification. It was
chosen mainly due to its low cost and easy
reproducibility.
Processing
Suspensions produced from calcined hydroxyapatite
powders were prepared by adding the predetermined
amount of powder gradually to a predetermined amount
of bi-distilled water with a continuous stirring. The
bidistilled water pH was adjusted to 11 and contain 3.6
weight% of Acumar 9400 dispersant. The solid loading
of suspensions was adjusted at 59 Vol.%. The
suspensions are then ball milled in a planetary mill for
24 hrs using the zirconia ball as milling media. Chosen
of 24 hrs milling time was based on the fact that it is
the
Porous hydroxyapatite ceramics fabricated via starch consolidation technique 4
minimum time to promote deagglomeration by ball
milling [36]. On the other hand to avoid grinding of
powder during milling, the volume of suspension was
maintained at twice the total volume of the balls [37].
After preparation of all suspensions, a predetermined
amount of potato starch was then added to it with
vigorous mechanical stirring for 3 hrs. It is important to
mention that the total solid loading of suspensions
(with adding various potato starch amounts) was kept
constant at 59 Vol.%. Taking into consideration that the
density of potato starch is ~ 1.45 g/cm3, which is much
lower than that of hydroxyapatite of 3.156 g/cm3. This
was achieved via the addition of predetermined
amounts of distilled water during the addition of potato
starch. After 3 hrs of vigorous mechanical stirring for
homogenization and conditioning the suspensions were
then ready for casting.
In order to prepare a green HA sample, the prepared
suspension (with various starch contents) was poured
into the non-porous moulds and the moulds with
suspension were heated in a dryer at 80 oC for 24 hrs.
The produced green samples were then subjected firstly
to binder removal prior to sintering step. The removal
of starch was performed in a muffle furnace
(Nabertherm, Germany) at a controlled heating rate to
prevent blistering, cracking, or delamination that would
be caused by (i) a mismatch of thermal expansion
between the HA and the organic phase or (ii) the
expansion of exhaust gases. Then the sintering of the
green samples was performed in the same furnace.
Sintering in the conventional programmable furnace is
the most practical and simple procedure. The main
problem associated with this method is the generation
of thermal and residual stress fields due to low heat
conductivity and high shrinkage of the HA. It may lead,
in particular, to the formation of micro- and
macrocracks in the specimen. To avoid this problem,
the temperature ramp (depending on the sample size)
usually should not exceed 5C/min. The green samples
were sintered at different sintering temperatures
starting from 1250 to 1350 oC with 50 oC intervals
while the furnace reaches these sintering temperatures
with a heating rate of 5 oC/min.
Characterizations
X-ray diffraction (XRD, Bruker axs D8, Karlsruhe,
Germany) with Cu-K ( = 1.5406) radiation and
secondary monochromator in the range 2 from 20 to
100 o was used to identify the formed phases and
determine the crystallite size of the produced powder.
The functional group analysis was performed by
Fourier Transform Infrared Spectroscopy (FT-IR). The
measurements were carried out in the transmission
mode in the mid-infrared range (400-4000 cm-1) at the
resolution of 4 cm1. The studies were performed using
the instrument of JASCO 3600, Tokyo, Japan. For
FTIR measurements, KBr pellets containing the exact
weighted amount of the substance examined were
prepared.
Morphology of sintered samples was examined using
scanning electron microscope (JEOL-JSM-5410 Tokyo,
Japan) equipped with EDX unit (England, Oxford,
ANCK).
The bulk density and apparent porosity for a both
green and sintered samples were determined by
Archimedes immersion techniques, whereas, the linear
change of sintered samples was determined by common
means [38]. The pore size distribution of the porous
HA ceramic was determined by Hg-intrusion
porosimeter ( Poresizer 9320, Micrometrics, USA ).
Since, bioceramic are very brittle, it is very difficult
to make the desired shape needed for mechanical
characterization by different machining method.
Therefore, conventional methods of mechanical
characterization such as biaxial, tensile, and impact
testing are not applicable to porous bioceramics.
Instead, the compression test has been widely applied
for characterization of porous scaffolds. For this
purpose, samples consisting of cylindrical bars (12 mm
in diameter and 12 mm in length) were selected and the
compressive tests were performed at a crosshead speed
of 0.5 mm/min using a universal testing machine. The
compressive strength was evaluated from the maximum
point of the stress/ strain graph, which occurs when the
first crack appeared in the samples. The average of
three samples was taken as the measure of the
compressive strength of the sample.
Results and Discussion
XRD analysis
Figure 1 shows the X-ray diffraction patterns for
porous hydroxyapatite samples produced with different
amount addition of potato starch and sintered at various
sintering temperatures. After sintering, specimens had
been crushed and the powders were examined by X-ray
diffraction method. For comparison, the XRD pattern
of the starting powder was introduced in all graphs. The
starting HA powder (which was calcined at
Fig. 1. XRD diffraction patterns of samples with different
potato starch contents and sintered at various temperatures.
1100 oC) shows a diffraction pattern in which all peaks
is corresponded solely to the hydroxyapatite phase
(JCPDS 9-432). However, for samples produced with
different potato starch amounts (10 and 30 Vol.%), at
any sintering temperature (1250, 1300, 1350 oC), the
produced patterns have additional peaks (assigned by
the black arrow in the figure) beside the parent HA
phase. The additional peaks were identified as
corresponding to -TCP phase (JCPDS 9-169).
Moreover, the intensity of the additional peaks is
slightly increased with increasing both the amount of
potato starch added during green sample formation as
well as sintering temperature. On the other hand, the
patterns indicated that the crystallinity of the main
phase (HA) is improved with increasing sintering
temperature. This could be indicated from sharpen of
the HA peaks with increasing sintering temperature.
This last observation is in good agreement with various
authors [39, 40] who dictated that increasing sintering
5 Ahmed Y.M.Z., Ewais E.M.M. and El-Sheikh S.M.
temperature is responsible for enhancing the
crystallinity of HA.
Nevertheless, the appearance of the additional peaks
corresponding to -TCP is believed to be according to
the decomposition of the HA sample during sintering.
This decomposition may result from two main reasons.
Firstly, it could be related to the temperature which is
extensively control such decomposition. Several
authors [41, 42] have reported on the temperature
dependency of HA stability; which could lead to the
dissociation of the HA according to the
dehydroxylation behavior of HA forming a
nonstoichiometric phase according to the following
reaction:
Ca10(PO4)6(OH)2 Ca10(PO4)6Ox(OH)2(1-x)
+xH2O
In this reaction, the water is liberated from
hydroxyapatite gradually and hydroxyoxyapatite
Ca10(PO4)6Ox(OH)2(1-x) (HOA) with a gradually
decreasing content of OH groups is formed before
oxyaptite. This dehydroxylation process has no
significant effect on the crystal structure of HA [43],
which are in good agreement with the XRD results.
This dehydroxylation process is reversible and upon
attainment of the critical temperature, 75-80% of the
bonded water remained. If the critical point is
exceeded, complete and irreversible dehydroxylation
occurs, resulting in the decomposition of the HA to
anhydrous TCP [44]. However, there are disagreements
about this critical temperature of HA decomposition,
the reasons mainly involving different powder
characteristics and firing conditions [41]. Generally
speaking, the sintering of HA is highly complicated,
while some authors revealed that HA will decompose to
anhydrous calcium phosphates such as tricalcium
phosphate (TCP) in the range of 12001450 oC [44, 45].
This explains the appearance of the TCP in all
sintering temperatures applied, with increasing its peak
intensity with increasing temperature. Secondly, the
presence of carbonate ions in the reaction media could
enhance the decomposition of HA. During the
evaporation of starch, a considerable amount of
carbonate ions is released. The presence of carbonate in
the apatite structure weakens the bonds, increases the
dissolution rate and the solubility [46]. So the higher
amount of carbonate content seems to destabilize the
apatite structure leading to the formation - TCP phase
with the presence of HA phase [47]. Increasing the
amount of starch added during green sample formation
leads to a slight increase in the amount of carbonate
released during sintering, which interpret the slight
increase in the formation of -TCP phase with
increasing potato starch amount in the green sample.
Since calcium phosphate is a biodegradable and
bioactive phase. The presence of other calcium
phosphate phases together with HA can change
biological properties (cellular response and solubility in
human blood); for example, the solubility of calcium
phosphate materials increases in the order of HA <-
TCP <-TCP [48]. HA is stable in a body fluid,
whereas TCP is rather soluble in the fluid [49]. Many
studies have indicated that the dissolution of well-
crystallized HA in the human body after implantation is
too low to achieve optimum results. On the other hand,
the dissolution rate of -TCP ceramics are too fast for
bone bonding [50]. According to Ducheyne and Qiu
[51], how stated that the more soluble the material, the
higher the tendency to induce precipitation of bone-like
apatite, which effectively contributes to bone
formation. This is a consequence of the body fluid
enrichment on calcium and phosphorus due to the
calcium phosphate dissolution [51]. Consequently, the
presence of TCP in the sintered sample is not
undesirable and even in bone tissue engineering and
drug delivery is a benefit phase [52]. Many researchers
have focused mainly on biphasic calcium phosphate
ceramics composed of HA and TCP to achieve an
optimum dissolution rate of bone-graft materials [41].
FT-IR analysis
However, FT-IR experiments for all samples
produced with various potato starch contents and
sintered at various temperatures were carried out and
the produced spectra were carefully analyzed. It was
earlier stated that the functional groups that normally
observed in the FT-IR of calcium phosphate based
materials are PO43, OH, HPO42 and CO3 in the
range of 4000-300 cm1 [53]. There are four modes of
PO43; 1, 2, 3, and 4 which gives bands at around
958 cm1, 500400 cm1, 1100-1019 cm1 and 605-530
cm1, respectively [53]. On the other hand, there are
three modes of OH ions; stretching, vibration and
translation, which give bands at 3700-250, 630, and
390 cm1, respectively [54].
Figure 2 shows the FT-IR spectra of samples
produced with various potato starch contents and
sintered at various temperatures. In this sense, the FT-
IR spectra of HA powder calcined at 1100 oC were
introduced as a matter of comparison. The pattern
brought out that there are some
Fig. 2. FT-IR Spectra of samples containing different Potato
starch contents and sintered at different temperature.
common characteristics of the spectra produced from
diverse samples. Whereas, some differences between
these spectra are clearly detectable.
The common features between the five spectra of
different samples (as received and calcined at different
temperatures) are:
1- Appearance of absorption bands in the range of ~ 964,
1045, and 570 cm1 are characteristic bands of
crystallized apatite phase [55].
2- All vibration modes of PO43- (n1, n2, n3, and n4) are
clearly identified in all spectra. Bands appeared at ~
964, 470, 1045-1095, and 570-605 cm1 are
characteristic bands for n1, n2, n3, and n4 starching
modes of PO43 ions, respectively.
3- Bands at 3444 and 1635 cm-1 are relevant to the
bending modes of the hydroxyl group in the absorbed
water. While bands at 3571 cm-1, as well as 633 cm-1,
Porous hydroxyapatite ceramics fabricated via starch consolidation technique 6
are assigned to the tretching vibration of the hydroxyl
group in the crystal structure of hydroxyapatite [56-58].
However, the most important differences between the
observed spectra are that the peak area of the band ~
3571 cm-1 (assigned for stretching mode of the
hydroxyl group) is highly decreased with increasing
both the sintering temperature, as well as the amount of
potato starch content. Not only this band, but the other
stretching hydroxyl band which should appear at 630
cm1 is completely disappear with increasing the
sintering temperatures at higher potato starch content.
These two observations confirm the formation of tri-
calcium phosphate, the dehydrated version of
hydroxyapatite, leading to the formation of bi-phasic
calcium phosphate [47].
SEM of sintered sample
Figure 3 shows the scanning electron micrographs of
HA samples produced from suspensions containing
different amounts of potato starches and sintered at
various sintering temperatures. The micrographs
revealed that the sample porosity, as well as the pore
size, is largely affected by both the sintering
temperatures as well as the
Fig. 3. Effect of both starch amount and sintering temperature
on the microstructure of sintered samples. [a] and [b] samples
containing 10 and 30% P.S. and sintered at 1250 oC, [c], [ d ]
samples containing 10 and 30% P.S. and sintered at 1300 oC, [e]
and [f] samples containing 10 and 30% P.S. and sintered at 1350
o
C.
content of the potato starch in the green sample.
Increasing potato starch content (at fixed sintering
temperature) leads to a higher increase in both sample
porosity and size of pores produced. While, the
increasing sintering temperature has the opposite effect
compared to that of increasing potato starch content. It
could be observed qualitatively that the number density
of individual pores decreased along with a
simultaneous increase in characteristic grain size with
increasing sintering temperature.
All of the sintered samples preserved their highly
porous structures having pore diameters of several tens
of microns as shown in Fig. 3(a)-(f). Moreover, in each
case, the porous structure was uniform throughout the
entire sample, although, obviously, a higher sintering
temperature with lower potato starch content gave rise
to a lower porosity. In addition, the pore channels
became smaller with these circumstances. It is easily
noticed that the pore diameter is highly increased with
both decreasing sintering temperature and increasing
starch contents. The highest porous sample could be
easily regarded for sample containing 30 Vol.% potato
starch and sintered at the lowest sintering temperature
of 1250 oC.
However, the shape of the pore is highly changed
from the spherical shape at lower potato starch contents
into irregular ones with increasing potato starch
contents whatever the sintering temperature. Sphericity
has been adopted as a measure of the presence of
agglomeration or interconnections between pores. The
lower the sphericity the higher the level of isolated
pores interaction leads to the formation of bigger
cavities or channels [59]. As can be observed in Fig. 3,
this level of interconnectivity between pores increases
with increasing starch added. Higher interconnectivity
will open paths and channels between pores, which
finally result in open porosity. On the other hand, if a
comparison is made between the microstructures of
samples containing 10% potato starch to that contained
30 % one, it will enable us to conclude that the starch
granules are responsible for the interconnections among
the larger pores and that the extension of the
interconnection depends on the amount of starch added
[60].
Porosity and pore size distribution
The apparent porosity, as well as the linear change of
samples produced with various potato starch contents
and sintered at different temperatures, is shown in
Table 1.
It is clear that increasing the amount of potato starch
leads to an abrupt increase in the apparent porosity.
Whereas, increasing sintering temperature is
responsible for decreasing the apparent porosity. On the
other hand it is interesting to note that at a given
sintering condition (1350 oC for 2 hr), the shrinkage of
the specimens is irrelevant to the potato starch content
in the study range, i.e. the shrinkage is relatively
constant for all potato starch contents. It is known from
the sintering theory [61] that when large pores are
present in a fine-grained ceramic green body, these
large pores do not exhibit significant shrinkage, since
they are thermodynamically stable or even show a
tendency to grow [62]. Davis et al. [63] studied the
sintering behavior of alumina with starch and showed
sintering was essentially the same as for starch free
material suggesting that the added pores from the starch
are too large to contribute to the shrinkage [59].
However, increasing porosity with increasing potato
starch content could be attributed to the creation of
cavities resulted from burning out of potato starch.
These cavities are acting as the sites for pores
generations, leading to increasing in the apparent
porosity [64]. It is worthy to mention that the apparent
porosity is even higher than the volume fraction of the
added starch. This may be due to the fact that starch
particles are highly expanded in water and absorb
Table 1. Effect of both sintering temperature and potato starch
amount on the apparent porosity of sintered HA samples.
Apparent porosity, %
Potato starch Linear change, amount,
o
Vol.% Sintering temperature, C % for 1350 oC
7 Ahmed Y.M.Z., Ewais E.M.M. and El-Sheikh S.M.
1250 1300 1350
10 30.13 28 25.7 11.13
20 44.4 41 38 11.2
30 57 53 50 11.18
Fig. 4. Pore size distribution of sintered sample containing
various potato starch content and sintered at various
temperatures. (a) & (b) sintering temperature = 1250 o C, (c) &
(d) sintering temperature = 1300 oC, (e) & (f) sintering
temperature = 1350 oC.
much of it during green sample formation, which could
be the reason of higher porosity obtained [65]. It is well
known that not only the sample porosity is the factor
deciding the suitability of the produced sample for
being used as an implant, but also the pore size
distribution is a high important factor. Accordingly the
pore size distribution of samples produced with various
potato starch contents and sintered at different
temperature were determined. The pore size
distribution of sintered samples was determined in
terms of cumulative volume and incremental volume as
obtained from the Mercury porosimetry study. The data
(Figure 4) for all tested samples showed a narrow pore
size distribution, with pore widths in the range 1-10 m
which in good agreement with the pore widths found in
the SEM images (Figure 3).
The data revealed that as the starch content decreases,
the measured pore content (in terms of incremental
volume) decreases. This evolution is not surprising
since the Hg-porosimetry technique measures pore
sizes corresponding to the contact areas or necks
between larger spherical shaped pores [66] created by
the original starch granules. A number of these contacts
per unit volume and the area of each mutual contact
gradually decrease with decreasing amounts of starch,
resulting in smaller pore content [67, 68]. However, the
amount of starch content seemed to be ineffective in
affecting the pore diameter produced in the final
sample whatever the sintering temperature. While,
sintering temperature seems to be an effective
parameter in this concern. When the sintering
temperature increased to 1350 oC a slight shifting of the
pore diameter to higher value is observed. This could
be explained considering that the sinterization process
takes place between the small crystallites of HA that
form the particles. In general, it can be observed a
small displacement to higher values for higher size pore
with increasing sintering temperature. This could be
due to the small contraction of the particles, during the
sintering process, which would produce an increase of
the inetrparticle pores [63]. On the other hand, the
amount of pores (indicating by incremental volume)
seems to be considerably contracting with increasing
sintering temperature. This is could be attributed to
increasing sintering temperature leads to increase the
sample sinterability which is responsible for increasing
sample density as well as decreasing sample porosity.
Also, it could interpret the observation of increasing the
pore diameter of the sample at a higher sintering
temperature. As the sintering temperature highly
increased this leads to force the small pores to be
migrated to each other, forming larger one with
decreasing its total volumes.
Generally, the result of incremental intrusion in Fig. 4
showed that most of the interpore connections ranged
from 1 m to 10 m in diameter. A maximum peak was
found to be at ~ 2 m for samples sintered at 1250 and
1300 oC and shifted to ~ 5 m at 1350 oC sintering
temperature. These data showed that almost all the
open pores in the sample were in this narrow range,
indicating the good homogeneity of the microstructure
produced by the present process [69]. The obtained
pore diameter seems to be very small compared to
many researchers who declare that porous sample with
an interconnecting pore of diameter ~ 100 m is the
criteria for using these samples in implant application
for promoting bone generation. While, many others like
Chang et al. [70] described new bone formation in
hydroxyapatite scaffolds with pore size 50 m; Lu et
al. [71] concluded that an interconnection size of >50
m can ensure mineralized bone formation, and Tamai
et al. [72] showed bone ingroWth in -TCP scaffolds
with average pore diameter 40 m. Moreover, it has
been demonstrated recently that BCP scaffolds with
interconnected pores of ~ 10 m allow the ingroWths
of new bone [73]. Therefore, the interconnected
macropores of the produced samples could fulfill the
requirements necessary to promote new bone
formation.
Compressive strength
Sintered hydroxyapatite is well known to be a very
brittle ceramic, which is more or less strong in
compression and weak in tension [74]. The changes in
the mechanical properties of the sintered HA are
correlated with grain sizes, bonding between the grains,
density of the specimen, and pore shapes. The presence
Table 2. Effect of both sintering temperature and potato starch
amount on the compressive strength of sintered HA samples.
Potato starch amount, Compressive strength, MPa
Vol.% Sintering temperature, oC
1250 1300 1350
10 26.8 33 39.5
20 22.5 30 36.7
30 12.6 16 19
of fugitive materials in the green sample influences to a
large extent all these parameters. Moreover, the
 Porous hydroxyapatite ceramics fabricated via starch consolidation technique 8
sintering temperature enters as a factor influencing all
of the mentioned parameters [75-76].
The effect of both sintering temperatures and potato
starch content on the compressive strength of porous
HA sintered samples was shown in Table 2. It is clearly
noticed that the compressive strength of the produced
porous samples was found to be decreased with both
increasing the amount of potato starch contents and c) The SEM investigation proves the conclusion deduced
decreasing the sintering temperatures. The maximum
compressive strength of about 39.5 MPa was attained at
the lower starch amount of 10 Vol.% and highest
sintering temperature of 1350 oC. The decrease in the
compressive strength with increasing amount of potato
starch as well as decreasing sintering temperature could d) The pore size distribution analysis proves that
attribute to the fact of the highly increased in the
apparent porosity of the produced sample in both cases
(as shown in table 1). These results agreed with the
finding in previous researches that the mechanical
strength of the sample was conversely relative to the
amount of pore former used and final porosity [50,
7779]. Increasing the apparent porosity is a reflection
for decreasing the sample density of the produced green
sample. The low density of the green sample results in
poorer contacts between the particles and, as a
consequence, impedes the sintering process [80].
However, the compressive strength was found to be
slightly decreased with the increasing starch amount
from 10 to 20 Vol.%. While it sharply decreased upon e) The compressive strength of the sintered samples was
increasing starch amounts from 20 to 30 Vol.%,
whatever the sintering temperature. The slight decrease
is owing to that there are two competing mode in this
case, one is responsible for high decrease in
compressive strength via increasing apparent porosity.
The other is increasing compressive strength via
enhancing the rheological properties of the suspension
with an increasing starch amount (as previously
described). Increasing the suspension rheological
properties leads to improve desiccation during firing,
producing stronger denser struts [81]. On the other
hand, although the rheological properties of the slip are
subsequently enhanced by increasing the starch amount
from 20 to 30 Vol.% the higher increase in the apparent
porosity is the effective factor leads to a sharp decrease
in compressive strength. Additionally, the
decomposition of the hydroxyapatite into tri-calcium
phosphate with increasing starch amount could
cooperate in this sharp decrease in compressive
strength. Many researchers [44, 82, 83] have
demonstrated that the decomposition makes the
mechanical strength poorer than pure HA.
Conclusions
This study aims to evaluate the effect of adding
different potato starch amounts and sintering
temperatures on the various physical, chemical and
mechanical properties of sintered porous HA samples.
The following remarks could be deduced from this
study:
a) The phase composition of the sample is affected with
both starch amount and sintering temperatures. A
tricalcium phosphate phase as a new phase resulting
from the decomposition of the parent HA was found to
be produced and even increased with increasing both
the starch amount and sintering temperature. This
conclusion was confirmed from both XRD analysis and
FT-IR analysis.
b) The apparent porosity of the sintered samples was
found to be increased with both increasing potato starch
amount and decreasing the sintering temperature. The
linear change was found to be ineffective with the
change in the starch amount which is an indication of
the large pore size formation in the sample interior. The
high apparent porosity of 57% was found to produce
for samples containing 30 Wt% potato starch and
sintered at 1250 oC.
from the apparent porosity measurements, and show the
increasing in the pore size with increasing both starch
amount and decreasing sintering temperature. Also, the
shape of the pore was found to be largely affected with
both starch amount and sintering temperature.
increasing the amount of potato starch addition leads to
an increase in the measured pore content, as a result, of
increasing of the number ion necks between spherical
pores and increasing the number of contact area. On the
contrary, the opposite phenomenon was found to be
occurring with increasing the sintering temperature.
The peak of maximum pore size was found to be
located at ~ 2 m at different starch amount and
sintering temperature of 1250 and 1300 oC. This peak
maximum was found to be shifted to higher pore size of
~ 5 m for both starch contents (10 and 30 Wt%) for
sintering temperature of 1350oC.
found to be largely affected by both starch amount and
sintering temperature. The compressive strength is
abrupt increased with increasing sintering temperature
and decreasing the starch amount. The highest
compressive strength of 39.5 MPa was found to be
produced for samples with 10 Wt% Potato starch and
sintered at 1350 oC.
Acknowledgments
The authors gratefully acknowledge the financial
support for this research by Science and Technology
Development Fund (STDF), Egypt, Grant No. 806.
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