Materials Letters 63 (2009) 1702–1704

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Materials Letters
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / m a t l e t

Highly porous hydroxyapatite scaffolds with elongated pores using stretched

polymeric sponges as novel template
In-Hwan Jo a, Kwan-Ha Shin a, Young-Mi Soon a, Young-Hag Koh a,⁎, Jong-Hoon Lee b, Hyoun-Ee Kim b
a
Department of Dental Laboratory Science and Engineering, Korea University, Seoul 136-703, Republic of Korea
b
Department of Materials Science and Engineering, Seoul National University, Seoul 151-742, Republic of Korea

a r t i c l e i n f o a b s t r a c t

Article history: This study reports a simple way of improving the compressive strength of highly porous hydroxyapatite (HA)
Received 25 March 2009 scaffolds by adopting elongated polymeric sponges as a novel template. In this method, as-received polymeric
Accepted 7 May 2009 sponges with isotropic pores were stretched uniaxially to 50% elongation at 200 °C for 2 h, and then coated with
Available online 14 May 2009
a HA slurry. The HA-coated sponges were heat-treated at 800 °C for 3 h to remove the polymeric sponges and at
1250 °C for 3 h to sinter the HA walls. The fabricated samples showed a highly anisotropic pore structure with
Keywords:
Ceramics
elongated pores parallel to the direction of the elongation of the polymeric sponge. This simple method allowed
Porosity a highly porous scaffold to have a high compressive strength of 3.8 ± 0.1 MPa at a porosity of 76% when tested
Mechanical properties parallel to the direction of pore elongation.
Hydroxyapatite © 2009 Elsevier B.V. All rights reserved.
Sponge replication

1. Introduction would be expected to provide improved mechanical properties [16–

Porous bioceramics have attracted considerable attention for
applications in bone tissue engineering because their interconnected
pores can provide a favorable environment for bone ingrowth and
osseointegration [1]. Thus far, a number of manufacturing methods for
the production of porous materials have been developed [2–6].
Among these methods, the polymeric sponge replication method has
received particular attention because it can provide very high porosity
with good interconnections between pores [2,7–9]. These properties
would be expected to promote bone ingrowth and the vascularization
of newly formed tissue, but would inevitably cause a decrease in the
strength of the materials [10].
Fundamentally, the mechanical properties of porous materials
should be strongly affected not only by the intrinsic strength of the
ceramic walls, but also by the pore structure (e.g., porosity, pore size,
pore shape, and pore orientation) [11]. Therefore, considerable effort
has been made to improve the strength of the porous materials
produced using the polymeric sponge replication method without
sacrificing their high porosity. These methods include the addition of
fibers and whiskers as reinforcement [12], a double-coating process
[13], blunting of the sharp apices of triangular voids [14], and the use
of a carbon coated polymeric sponge as a novel template [15]. In
addition, several attempts have been made to tailor the pore structure
of the starting polymeric foams, particularly in order to produce
functionally-graded materials (FGM) with porosity gradient that
⁎ Corresponding author. Tel.: +82 2 940 2844.
E-mail address: kohyh@korea.ac.kr (Y.-H. Koh).
19].
In this study, we examined the utility of polymeric sponges with
elongated pores as a novel template for improving the mechanical
properties of highly porous hydroxyapatite (HA) scaffolds. First,
templates were prepared by stretching the as-received polymeric
sponges to various levels of elongation, ranging from 33 to 60%, at
200 °C for 2 h. Subsequently, the sponges prepared with elongated
pores were coated with a HA slurry, followed by heat-treatment at
800 °C for 3 h to remove the polymeric sponges and at 1250 °C for 3 h
to sinter the HA walls. The effects of the elongated pores on the
compressive strength of highly porous hydroxyapatite scaffolds as
well as the processability of this method were examined.
2. Experimental procedure
Highly porous hydroxyapatite (HA) scaffolds with elongated pores
were produced using elongated polymeric sponges as a novel
template. The as-received polyurethane sponges (15 pores per inch,
Jeil Urethane Co., Korea) with dimensions of approximately
7 × 35 × 17 mm were stretched to various levels of elongation (0, 33,
50, and 60%) and then kept in an oven at 200 °C for 2 h to induce
plastic deformation of the polyurethane strut, resulting in polymeric
sponges with elongated pores.
A hydroxyapatite (HA) slurry was prepared by dispersing com-
mercial HA powder (Ca10(PO4)6(OH)2; Alfa Aesar Co., Milwaukee, WI,
USA), which was calcined at 900 °C for 3 h, in ethanol containing
triethyl phosphate (TEP; (C2H5)3PO4, Aldrich, USA) as a dispersant,
and polyvinylbutyral (PVB; Aldrich, USA) as a binder. The prepared
polymeric sponges were coated with the HA slurry and then dried in

0167-577X/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.matlet.2009.05.017
 I.-H. Jo et al. / Materials Letters 63 (2009) 1702–1704 1703

Fig. 1. Optical photographs of the samples produced using various polymeric sponges with elongations of (A) 0%, (B) 33%, (C) 50, and (D) 60%.

Fig. 2. SEM micrographs of the fabricated sample showing (A) the pore structure parallel to the direction of pore elongation, (B) the surface morphology of the HA wall, (C) the pore
structure normal to the direction of pore elongation, and (D) the fracture surface of the HA wall with an internal void.

an oven at 60 °C for 30 min. The coating/drying step was repeated highly porous hydroxyapatite (HA) scaffolds. Fig. 1(A)–(D) shows the
several times until the sample had sufficient strength. Subsequently, typical optical photographs of porous HA scaffolds produced using the
three layers of the HA-coated sponges were stacked and then coated polymeric sponges with various elongations (0, 33, 50, and 60%). As
again with the HA slurry to produce larger samples as a scaffold. The expected, the sample produced using the as-received polymeric
HA-coated sponges were heated slowly to 800 °C at a heating rate of
150 °C/h and maintained at this temperature for 3 h to burn out the
polymeric sponge and binders used in the HA slurry. This was
followed by sintering at 1250 °C for 3 h to densify the HA struts. The
procedure was repeated to reduce the porosity of the sample.
The pore structures and microstructures of the sintered HA walls of
the fabricated samples were evaluated using optical and scanning
electron microscopy (FE-SEM, JSM-6701F, JEOL Techniques, Tokyo,
Japan). The compressive strengths of the samples with dimensions of
~ 10 × 9 × 20 mm were examined using a universal testing machine
(Model 5565, Instron Corp., Danvers, MA) at a crosshead speed of
5 mm/min. The samples were compressed either parallel or normal to
the direction of pore elongation. The stress and strain responses of the
samples were monitored during the compressive strength tests. More
than five samples were tested to obtain average values and their
standard deviation.

3. Results and discussion

We herein employed to use polymeric sponges with elongated Fig. 3. The typical stress versus strain responses of the porous HA scaffolds, compressed
pores as a novel template to improve the mechanical properties of (A) parallel and (B) normal to the direction of pore elongation.
1704 I.-H. Jo et al. / Materials Letters 63 (2009) 1702–1704
Table 1
Characteristics of the porous HA scaffolds produced using the single and double-coating
processes.
Porous HA scaffolds Porosity [vol.%] Compressive strength [MPa]
Single coating 82 1.7 ± 0.3
Double coating 76 3.8 ± 0.1
The compressive strength of the sample was measured parallel to the direction of pore
elongation.
sponge contained isotropic pores (Fig. 1(A)). On the other hand, the
stretched polymeric sponges produced porous HA scaffolds with
highly elongated pores, that resembled the original pore structure of
the polymeric template (Fig. 1(B)–(D)). In addition, the pores became
narrower with increasing magnitude of elongation. However, the
highest elongation of 60% caused fracturing of some polymeric struts,
resulting in broken HA walls, as marked by arrows, which would
deteriorate the mechanical properties of the porous HA scaffolds
(Fig. 1(D)). These results suggest that the optimum elongation of an
as-received polymeric sponge that would allow the production of a
highly porous HA scaffold with elongated pores should be 50%.
The pore structure of the fabricated HA scaffold and densification
of HA struts produced using a polymeric sponge with an elongation of
50% were examined more closely by scanning electron microscopy
(SEM), as shown in Fig. 2(A)–(D). Elongated pores were formed well
throughout the sample (Fig. 2(A)). In addition, the ceramic dip-
coating process used in this study allowed the HA walls to be densified
well without noticeable defects, such as pores and cracks (Fig. 2(B)).
On the other hand, slightly distorted pores were formed normal to
the direction of elongation (Fig. 2(C)). In addition, the HA strut con-
tained internal voids formed by the removal of the polymeric strut
(Fig. 2(D)), which is often the case with reticulated ceramics [5]. The
ranges of pore size obtained parallel and normal to the direction of
pore elongation roughly measured from SEM micrographs were 700–
950 µm and 750–1100 µm, respectively. It should be noted that the
size of the internal voids might be large enough to provide a favorable
environment for bone ingrowth within the voids.
The compressive strength of the porous HA scaffolds with elongated
pores was measured by compressing them either parallel or normal to
the direction of pore elongation. Both samples exhibited a similar
fracture behavior, as shown in Fig. 3(A) and (B). In other words, the
stress increased linearly with an elastic response and then decreased
rapidly due to fast fracture. It should be noted that the densification
behavior of the fractured sample might be also observed, when a
relatively low crosshead speed is employed during compression [7]. The
sample showed a very high compressive stress of 1.86 MPa at a porosity
of 82 vol.%, when compressed parallel to the direction of pore elongation
(Fig. 3(A)). On the other hand, a relatively low compressive stress of
0.36 MPa was achieved, when compressed normal to the direction of
pore elongation (Fig. 3(B)). The measured compressive strengths of the
samples tested parallel and normal to the direction of elongation were
1.7± 0.25 MPa and 0.37 ± 0.11, respectively.
Several factors should be considered when interpreting the
improvement in compressive strength of the porous HA scaffolds
with the elongated pores. Firstly, an increase in the fraction of HA
struts along the pore elongation would result in a higher compressive
strength [20]. Secondly, a decrease in the edge length (l) would
increase the compressive strength of the porous HA scaffold because
brittle collapse stress of porous ceramic foams (σcr) is inversely
proportional to the edge length (l) [11]. In addition, although the
major deformation mode of the porous HA scaffolds should be
bending of the thin HA struts [11,21], HA struts preferentially oriented
parallel to the loading direction may fail due to the tensile stress
generated by compression, which would eventually split the sample
into several parts, which occurs in a similar manner to that of a porous
ceramic with an oriented pore structure [22,23].
The compressive strength of the porous HA scaffolds was further
improved by decreasing the porosity, which was achieved by simply
coating them with the HA slurry again, followed by heat-treatment at
1250 °C for 3 h. It was possible to fabricate a sample with a lower
porosity, while preserving interconnections between pores. The
sample produced using the double-coating process had a much
higher compressive strength than that of the sample produced using
the single coating process, as summarized in Table 1. The measured
compressive strength was as high as 3.8 ± 0.1 MPa at a porosity of
76 vol.%. The values obtained in this study were much higher than
those reported in the literature [7,24]. It should be noted that this
method can be applied to any materials that can be produced using a
conventional sponge replication method, such as hydroxyapatite,
bioactive glass, alumina, zirconia, and titanium, and so forth.
4. Conclusions
Highly porous HA scaffolds with elongated pores were fabricated
successfully using stretched polymeric sponges as a novel template. The
fabricated samples exhibited a highly anisotropic pore structure with
good interconnections between the elongated pores, which would be
expected to provide a favorable environment for bone ingrowth. The
construction of the elongated pores allowed the highly porous HA
scaffolds to have a high compressive strength of 3.8 ± 0.1 MPa at a
porosity of 76 vol.%, when tested parallel to the direction of pore
elongation. These results indicate that a polymeric sponge with
elongated pores can be used as a novel to produce highly porous
ceramic scaffolds with improved strengths.
Acknowledgment
This research was supported by a grant from the Fundamental R&D
Program for Core Technology of Materials funded by the Ministry of
Knowledge Economy, Republic of Korea.
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