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Scripta Materialia 64 (2011) 426–429

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Porous hydroxyapatite ceramics fabricated

by an ice-templating method
Kechao Zhou,a Yan Zhang,a Dou Zhang,a,⇑ Xiaoyong Zhang,a Zhiyou Li,a Gang Liub and
Tim W. Buttonb
a
State Key Laboratory of Powder Metallurgy, Central South University, Changsha, Hunan 410083, People’s Republic of China
b
School of Metallurgy and Materials, University of Birmingham, Edgbaston, Birmingham B15 2TT, UK
Received 11 October 2010; accepted 1 November 2010
Available online 4 November 2010

Porous hydroxyapatite (HA) ceramics with lamellar structures have been fabricated by an ice-templating process using as-syn-
thesized and commercial HA powders. The viscosities of the suspensions prepared using the as-synthesized powders were 9–11 times
higher than those of the suspensions prepared using the commercial powders. Finer particle size resulted in larger lamellar pore
width and a thinner porous ceramic wall, while a much denser ceramic wall, as well as lower porosity and higher compressive
strength, was obtained with the commercial powder.
Ó 2010 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Keywords: Porous; Directional solidification; Hydroxyapatite; Ice-templating

Porous hydroxyapatite (HA, Ca5 (PO4)3OH) has
received much attention due to its strong bonding to
bone, and because it is more resorbable and osteocon-
ductive than its dense counterpart. It is essential to sat-
isfy certain criteria in the development of pore structures
for the application of bone tissue engineering, including
the appropriate mechanical strength and the pore char-
acteristics i.e. porosity, pore size, pore shape and pore
orientation, in order to promote the migration of cells
through the pores, with appropriate space for the nutri-
ent transportation, tissue infiltration and, ultimately,
vascularization [1]. Several techniques have been devel-
oped for fabricating porous HA scaffolds, including
gel casting [2], gas foaming [3], slip casting [4], polymer
foam replication [5] and solid free-form fabrication [6].
In general, these methods are only able to provide an
isotropic microstructure by employing a template or
porogen. It would be beneficial to develop scaffolds with
oriented microstructure and controlled architecture to
fulfill the various requirements needed for bone replace-
ment applications.
Directional freezing has recently attracted much
interest for the fabrication of porous ceramics with
lamellar architectures [7,8]. The porosity, lamellar
⇑ Corresponding
author. Fax: +86 731 88877196; e-mail:
dzhang@mail.csu.edu.cn
thickness, pore width and pore orientation have been
shown to be strongly correlated with the processing con-
ditions, including the suspension parameters [9,10] and
the freezing conditions [11,12].
The aim of our work was to explore the influence
of different particle sizes on the rheological properties
of aqueous HA suspensions and the microstructures
of freeze-cast HA ceramics, and to characterize
the mechanical properties of porous HA ceramics.
Understanding the relationships between the particle
sizes and the rheological properties of the aqueous
suspensions, as well as the microstructure, porosity
and the mechanical strength of the freeze-cast HA
ceramics are useful for controlling the microstructure
and properties of the HA scaffolds for bone repair
and replacement applications.
The precipitation method [13,14] was utilized to pro-
duce HA powder from reagent-grade Ca (NO4)2 and
(NH4)2HPO4 (Tianjin Guangfu Fine Chemical Research
centre, PR China). Commercial HA powder (Nanjing
Emperor Nano Material Co. Ltd., PR China) was em-
ployed for comparison purposes. HA suspensions were
prepared by mixing HA powders, 1 wt.% PVA binder
(420, Kuraray Co. Ltd., Japan), and the dispersant,
ammonium polyacrylate (HydroDisper A160, Shenzhen
Highrun Chemical Industry Co. Ltd., PR China) in
deionized water, followed by ball-milling for 24 h.

1359-6462/$ - see front matter Ó 2010 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.scriptamat.2010.11.001
 K. Zhou et al. / Scripta Materialia 64 (2011) 426–429 427

Figure 1. (A) TEM micrograph of synthesized powder prepared by the precipitate method. (B) SEM micrograph of the commercial powder. (C)
XRD patterns of both types of HA powders.

Freeze-casting was carried out by pouring the suspen-
sions into a transparent cylindrical polydimethylsilox-
ane (PDMS) mould (10 mm diameter  15 mm high),
which was then transported to a copper cold finger
placed in a liquid nitrogen container. Frozen samples
were then demoulded and the ice was sublimated in a
freeze-drier (FD-1A-50, Beijing Boyikang Medical
Equipment Co., PR China) for 24 h. The dried samples
were heated at 600 °C for 3 h and sintered at 1250 °C for
3 h.
The specific surface area of the HA powder was mea-
sured using a Monosorb surface area analyzer (Quanta-
chrome, USA). The rheological properties of the
suspensions were investigated using a rheometer (AR
2000, TA Instruments, USA) at 20 °C. X-ray diffraction
(XRD, Rigaku D/max-2550) was used to evaluate the
phases of the as-synthesized and commercial powders.
The apparent porosity was derived from the density
data. The microstructures of the powders and sintered
HA ceramics were examined by environmental scanning
electron microscopy (ESEM, Quanta 200, JEOL,
Tokyo, Japan) and transmission electron microscopy
(TEM, JEM-2100F, JEOL, Tokyo, Japan). Compres-
sive strength tests were performed at a crosshead speed
of 0.2 mm min–1 using an Electronic Universal Testing
Machine (KD11-2, Shenzhen KEJALI Technology Co.
Ltd., PR China).
Two types of HA powders were employed in this
work in order to investigate the effects of particle sizes
on the rheological properties and the microstructures

Figure 2. Viscosity vs. solids loading of the HA suspensions. (A) HA suspension using the commercial powder with 1 wt.% dispersant concentration.
(B) HA suspension using the synthesized powder with 5 wt.% dispersant concentration.
428 K. Zhou et al. / Scripta Materialia 64 (2011) 426–429

of the freeze-cast ceramics. Figure 1A shows a TEM
micrograph of the synthesized HA powder obtained by
the precipitation method. The average particle size was
about 0.2–0.3 lm, close to the result of Kong et al.
[13] obtained using the same preparation method. The
surface area of the synthesized powder was 65.8 m2 g–1,
indicating the existence of amorphous particles.
Figure 1B shows an SEM micrograph of commercial
powder prepared by a spray-drying process. The surface
area of the commercial powder was 15.42 m2 g–1. The
large spherical powders were composed of much finer
HA powders with a primary particle size of 1 lm.
The XRD patterns (Fig. 1C) show that both types of
HA powders are single phase. However, the commercial
powder exhibited a higher degree of crystallinity, and
the broad diffractive peaks of the synthesized powder
suggest it has a smaller grain size and the existence of
the amorphous HA powders.
Figure 2 shows the relationship between the viscosity
and the shear rate of the HA suspension with a range of
solids loading from 10 to 40 vol.% for both types of HA
powders. With the increase in the solids loading, the vis-
cosity of both HA powders increased at all shear rates.
The viscosity curves of all the suspensions showed the
shear thinning behaviour. At the same shear rates and
solids loading, the viscosities of the suspensions pre-
pared using the synthesized powder were around 9–
11 times higher than those of the suspensions prepared
using the commercial powder, although the dispersant
concentration in the synthesized powder suspension
was 5 times higher than that in the commercial powder
suspension. At a shear rate of 100 s 1, the viscosity of
40 vol.% solids loading suspension prepared using the
commercial powder was 37 mPa
s, similar to the value
of 29 mPa
s obtained for the suspension of 20 vol.% sol-
ids loading prepared using the synthesized powder, as
shown in Figure 2A and B, respectively. This indicates
an obvious effect of particle size on the rheological prop-
erties of HA suspensions. The decrease in the particle
size and the existence of amorphous particles can lead
to an increase in the viscosity. This trend became more
obvious as the solids loading of HA suspensions
increased.
Figure 3 shows cross-sectional SEM micrographs of
porous HA ceramics obtained from suspensions of
20 vol.% solids loading for both types of HA powders.
Both samples exhibited porous structures with clear
lamellar channels of long-range order. As regards the
pore structures, a smaller pore width and a thicker
lamellar were obtained in the sample prepared using
the commercial powder, and a larger pore width and a
thinner lamellar were obtained in the sample prepared
using the synthesized powder, as shown in Figure 3A
and B, respectively. The sample prepared using the com-
mercial powder showed a smooth and dense lamellar
surface with a grain size of 2–6 lm, as shown in Fig-
ure 3C, while the sample prepared using the synthesized
powder exhibited a rough and porous lamellar structure
with a smaller grain size of 0.8–1.6 lm, as shown in
Figure 3D. During the freezing process, the particle
surfaces act as nucleation sites. The finer particle size
of the synthesized powder can lead to lower degree of
supercooling which is unfavourable to the nucleation
of ice crystals, resulting in thicker ice in the freeze-cast
sample and larger pore width in the sublimated porous
HA ceramic.

Figure 3. Cross-sectional SEM micrographs of sintered HA porous ceramics obtained from the suspension incorporating different particle sizes: (A)
and (C) from suspension prepared using commercial powder with 1 wt.% dispersant concentration; (B) and (D): from suspension prepared using
synthesized powder with 5 wt.% dispersant concentration. The solidification direction was parallel to the page and the lamellar orientation.
 K. Zhou et al. / Scripta Materialia 64 (2011) 426–429
Figure 4. Compressive strengths and the porosity of porous HA
ceramics obtained from the suspensions with different particle sizes as a
function of the initial solids loading. The compressive tests were
carried out parallel to the solidification direction.
Figure 4 shows the effects of particle size and solids
loading on the porosity and compressive strength of
the sintered HA ceramics. A finer particle size resulted
in higher porosity for all the solids loadings investigated,
while the difference became less when the solids loading
was above 30 vol.%. For the compressive strength, the
trend was reversed. A finer particle size resulted in smal-
ler compressive strength for all the solids loadings, while
the difference became larger and larger with increasing
solids loading. With the increase in the solids loading
from 10 to 40 vol.%, the porosities decreased from
75.8% to 43.5% for the samples prepared using the com-
mercial powder, and from 86% to 47.9% for the samples
prepared using the synthesized powder, while the com-
pressive strengths increased from 1.3 to 5.6 MPa for
the samples prepared using the commercial powder
and from 0.7 to 3.1 MPa for the samples prepared using
the synthesized powder.
As the viscosity of the 20 vol.% solids loading suspen-
sion prepared using the synthesized powders was much
higher than that of the suspension prepared using the
commercial powder, the freezing front experienced
higher resistance in the ice-templating process, making
it difficult to achieve a densely packed structure of the
ceramic wall when the solidification process ceased.
After sublimation, the ice bonds between ceramic parti-
cles were lost, leaving rather large pore structures in the
ceramic wall, which were not eliminated by the sintering
process. The interactions between the particle size, the
viscosity of the suspension and the freezing kinetics
429
exhibit complex effects on the pore characteristics of
porous HA ceramic. Further investigation on the utiliza-
tion of nanosized powder in the preparation of HA por-
ous ceramic is needed for better understanding of the
particle size effects in the ice-templating process.
Porous HA ceramics with well-aligned lamellar struc-
ture have been successfully fabricated by an ice-templat-
ing method using as-synthesized and commercial HA
powders of different particle sizes, i.e. 0.2–0.3 lm and
1 lm, respectively. The utilization of HA powder of fi-
ner particle size resulted in 9–11 times higher viscosity
of the suspension, larger pore width, thinner and less
dense ceramic wall of the lamellar structures. With the
increase of the solids loading from 10 to 40 vol.%, the
porosities decreased accordingly, and the compressive
strengths increased from 1.3 to 5.6 MPa for the samples
prepared using the commercial powder, and from 0.7 to
3.1 MPa for the samples prepared using the synthesized
powder.
The authors are grateful to the New Century
Excellent Talents program funded by the Ministry of
Education in the People’s Republic of China (NCET-
10-0802) for the financial support.
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