Preparation of porous alumina for biomedical

applications through protein foaming–

consolidation method
A. Fadli and I. Sopyan*
The present work reports a novel method for preparation of porous alumina using egg yolk both as
consolidator and foaming agent. Suspensions with an alumina to yolk ratio of 1 in weight were
prepared by stirring for 3 h and the resulting slip was poured into cylindrical shaped moulds
followed by foaming and consolidation by drying at temperatures of 110 and 180uC. The dried
green bodies were then burned to remove the pore creating agent at 600uC for 1 h, followed by
sintering at 1550uC for 2 h. The density of the porous bodies was 2?27 g cm23 when foamed at
110uC and it decreased to 1?80 g cm23 at 180uC foaming temperature. The compressive strength
was found to drop from 5?72 MPa at 43?6% porosity to 4?57 MPa at 50?4% porosity. Macropores
of the porous bodies were found to fall in the range of 100–500 mm, showing promising
applicability for scaffold devices.
Keywords: Protein foaming–consolidation, Porous ceramics, Porosity, Characterisation

Introduction properties. These groups are the key to understanding

Porous alumina has been attracting considerable atten-
tion for scaffold applications, especially for cell loading
and bone grafts. Its biomedically interesting character-
istics are contributed by biocompatibility, inertness and
chemical stability. Many methods have been employed
to produce alumina porous bodies. All methods
commonly used organic substances merely as a pore
creating agent or as a template for pores generation.
Different particles such us poppy seed, camphene, wheat
particles, starch were used as a pores generation for
producing porous alumina.1–4 Preparation of the porous
ceramics with trimodal pores structure has been
reported using foaming and starch consolidation
method.5 Recently, proteins such as ovalbumine and
bovine serum albumin have been used for the foaming
and setting of aqueous ceramic powder suspensions for
preparation of porous ceramics.6,7 Mao et al. reported a
water soluble epoxy resin combined with a polyamine
hardener was developed to consolidate foamed suspen-
sions to manufacture alumina foams.8 Thus various
methods have been developed to produce porous
alumina with a big variety in pore distribution, which
finally determine its suitability for many applications.9
Proteins are high molecular compounds, which are
formally understood as condensation products of amino
acids. Their amino acid R groups are responsible for the
great variety of proteins in their physical and chemical
Department of Manufacturing and Materials Engineering, Faculty of
Engineering, International Islamic University Malaysia, P.O. Box 10,
50728 Kuala Lumpur, Malaysia
*Corresponding author, email sopyan@iiu.edu.my
the chemical interactions with the ceramic material, on
the good binder properties of proteins are based, such as
adhesion on the surface of the used alumina oxide
particles or to dispersant molecules. Proteins are prone
to foaming because of their amphiphilic character.10 The
usage of ovalbumine as foaming agent have been tried
by some research groups.6,7 However, its high foaming
capacity makes it unsuitable for making porous ceramics
with controlled porosity.
Egg yolk is a complex association of water (50%),
lipids (33%) and proteins (17%).11 The lipids phase in
egg yolk would reduce the foaming capacity of protein
in making pores. Setup of proper composition between
yolk and alumina powder will be able to make porous
alumina with controlled pore size distribution accord-
ingly. In this paper, the authors would like to present a
novel method for preparation of porous alumina using
egg yolk both as consolidator and foaming agent. The
effect of time and temperature of foaming on physical
properties such as pore size, density, porosity and
strength of sintered products will be reported as well.
Experimental
Commercial alumina powder (Al2O3) (Sigma-Aldrich
Chemie, USA), with a characteristic mean diameter of
0?25 mm (measured using a Nano-S, Malvern, UK) and
a surface area 0?39 m2 g21 (measured by N2 adsorption,
Autosorb-1 model, Quantachrome, USA) was used in
the present study. Protein used was yolk that freshly
isolated from chicken egg procured from local market.
Slip was prepared by dispersing the alumina powder in
yolk with an alumina to yolk ratio of 1 in weight. The
slurry was magnetically stirred with rate of

ß W. S. Maney & Son Ltd. 2009

DOI 10.1179/143307509X440668 Materials Research Innovations 2009 VOL 13 NO 3 327
Fadli and Sopyan Preparation of porous alumina for biomedical applications
1 Viscosity versus shear rate for slurry with alumina to
yolk ratio of 1 in weight
150 rev min21 for 3 h at room temperature. The viscosity
of the slurry was measured in a ThermoHaake VT 550
viscotester using sensor type of SV-DIN. The slurry was
cast in cylindrical open stainless steel mould and heated in
an air oven with varying temperature 110 and 180uC for
1 h. Castor oil was used as lubricant for easy mould
removal. The dried samples were heated in a furnace at a
rate of 10uC min21 up to 600uC for removal of the yolk
and then at rate of 2uC min21 up to 1550uC. Density of
sintered samples was measured in an Electronic densi-
meter (MD300S Alfa Mirage, Thermochem, Brazil).
Microstructure of sintered samples was observed by a
SEM (JEOL 5600, Japan). Mechanical strength of the
sintered samples was measured in a universal testing
machine (Lloyd LR10K plus) by diametrical compression
at a loading rate of 2?5 mm min21. Sintered samples of
10 mm diameter and 10 mm length were used for
diametrical compression testing.
Results and discussion
Figure 1 shows the viscosity versus shear rate for slurry
with an alumina to yolk ratio of 1 in weight. The
viscosity measurements were carried out within 3 h after
mixing. The slurry showed pseudoplastic flow beha-
viour. Pseudoplasticity in ceramics slurry usually arises
because of the existence of an interparticles network,
2 Image (SEM) of cross-section of porous alumina with drying times of a 8, b 12 and c 60 min at drying temperature of
180uC
Table 1 Characteristics of alumina samples after sintering at 1550uC for 2 h with drying time of 60 min
Sample Drying temperature, uC Apparent density, g cm23
A 110 2.27
B 180 1.80
328 Materials Research Innovations 2009 VOL 13 NO
which undergoes a gradual breakdown with increasing
shear rate, causing the typically observed decrease in
viscosity of slurries. These suspensions show a slight
shear thinning behaviour for a lower range of shear rates
(up to 400 s21) whereas at higher shear rates (1000 s21),
they show slight shear thickening. The viscosity value of
the slurries at high shear rate (1000 s21) is in the range
0?6–1?1 Pa s, thus indicating that the slurries are
pourable under shear.3
The effect of drying temperature on physical proper-
ties (average apparent density, shrinkage, porosity and
compressive strength) of the porous bodies can be seen
by comparing samples A and B as shown Table 1. Both
samples A and B with an alumina to yolk ratio of 1 in
weight were stirred for 3 h. Sample A was heat treated at
temperature of 110uC, whereas sample B at 180uC.
When dried at 110uC, the alumina slurry could not
foam, thus the created pores of sintered bodies were
merely attributed to protein removal. On the other
hand, when dried at 180uC, protein foaming took place
uniformly, producing big pores in the porous bodies. As
the drying temperature increased from 110 to 180uC, the
volume shrinkage of sintered alumina bodies increased
from 7?83 to 29?3%. So did porosity; the porosity
changed from 43?5 to 50?4%.
The apparent density of porous body can influence its
mechanical strength, permeability, and presence of
structural defects.12 Porosity characterisation is based
on the presence of open pores which are related to
properties such as permeability and surface area of the
porous structure. High porosity usually means a high
surface/volume ratio, and thus favours cell adhesion to
the porous body and promotes bone regeneration.13
Figure 2 shows the SEM cross-section of porous
alumina samples prepared from different drying times.
The macrostructures show an increase in the pore size of
alumina bodies when drying time increased. This
foaming has provided big pores so the pores size of
sintered bodies was in the range of 100 to 1200 mm.
After sintering at 1550uC for 2 h, porous alumina
prepared in this work exhibited apparent density
decreased from 2?27 to 1?80 g cm23 as the drying
temperature increased from 110 to 180uC. It can be
Strength, MPa Shrinkage, vol.-% Porosity, %
5.72 7.83 43.6
4.57 29.3 50.4
3

3 Image (SEM) of a cross-section of porous alumina of sample B after sintering at 1550uC for 2 h and b grain structure
of the porous alumina walls
explained that lower drying temperature of the slurry
gave rise to lower foaming capacity, hence reduced pore
formation.
In order to evaluate the mechanical properties of the
fabricated samples, compressive strength tests were
conducted. The mechanical properties of a porous
material depend on its porosity and density.14 As the
porosity was decreased from 50?4 to 43?6%, the
compressive strength was remarkably increased from
4?57 to 5?72 MPa, as shown in Table 1. Since a higher
density usually leads to higher mechanical strength
meanwhile a high porosity will provides a favourable
biological environment, a balance between the porosity
and density for a porous body must be established for
the specific application.13
Figure 3 shows the SEM images of the macro- and
microstructures of sample B after sintering at 1550uC for
2 h. The macrostructure shows the pores size in the
range from 100 to 500 mm. The grains of porous
alumina walls shown irregular and some small particles
adsorb on the large grains. There is much bonding area
among grains. It is well known that more bonding area
usually leads to higher strength between particles;
consequently the fracture of alumina bodies mainly
happens at the particles boundary.
Conclusions
Porous alumina ceramics were fabricated successfully by
protein foaming–consolidation method using egg yolk
both as consolidator and foaming agent. The porosities
and compressive strengths of the samples were con-
trolled by adjusting the drying temperature of slurry.
Sintered alumina bodies with compressive strength of
4?57–572 MPa at porosities of 43?6–50?4% were
Fadli and Sopyan Preparation of porous alumina for biomedical applications
obtained. Microstructure analysis revealed the existence
of 100–500 mm macropores suitable for medical
application.
Acknowledgement
The authors would like to thanks Faculty of Engineering
and Research Management Center, International
Islamic University Malaysia for their financial support
during implementing this work.
References
1. E. Gregorova and W. Pabst: Ceram. Int., 2007, 33, 1385–1388.
2. B. Yoon, W. Choi, H. Kim, J. Kim and Y. Koh: Scr. Mater., 2008,
58, 537–540.
3. K. Prabhakaran, A. Melkeri, N. M. Gokhale and S. C. Sharma:
Ceram. Int., 2007, 33, 77–81.
4. O. Lyckfeldt and J. M. F. Ferreira: J. Eur. Ceram. Soc., 1998, 18,
131–140.
5. X. Mao, S. Wang and S. Shimai: Ceram. Int., 2008, 34, 107–112.
6. S. Dhara and P. Bhargava: J. Am. Ceram. Soc., 2003, 86, (10),
1645–1650.
7. A. Berthold, A. Haibel, N. Brandes, L. Kroh, U. Gross, L. Uharek
and H. Schubert: J. Mater. Sci., Mater. Med., 2007, 18, 1333–1338.
8. X. Mao, S. Shimai and S. Wang: J. Eur. Ceram. Soc., 2008, 28,
217–222.
9. P. Sepulveda and J. G. P. Binner: J. Eur. Ceram. Soc., 1999, 19,
2059–2066.
10. I. Garrn, C. Reetz, N. Brandes, L. W. Kroh and H. Schubert:
J. Eur. Ceram. Soc., 2004, 24, 579–587.
11. J. M. Aguilar, F. Cordobes, A. Jerez and A. Guerrero: Rheol. Acta,
2007, 44, 731–740.
12. P. Sepulveda, F. S. Ortega, M. D. M. Innocentini and V. C.
Pandolfelli: J. Am. Ceram. Soc., 2000, 83, (120), 3021–3024.
13. H. R. Ramay and M. Zhang: Biomaterials, 2003, 24, 3293–
3302.
14. M. Scheffler and P. Colombo (ed.): ‘Cellular ceramics: structure,
manufacturing, properties and applications’, 291–295; 2005,
Weinheim, Wiley-VCH.
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