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Porous Magnesium-Doped Biphasic Calcium Phosphate

Ceramics Prepared via Polymeric Sponge Method
a a
I. Sopyan & T. A. Rahim
a
Department of Manufacturing and Materials Engineering, Faculty of Engineering ,
International Islamic University Malaysia , Kuala Lumpur , Malaysia
Accepted author version posted online: 09 Sep 2011.Published online: 03 May 2012.

To cite this article: I. Sopyan & T. A. Rahim (2012) Porous Magnesium-Doped Biphasic Calcium Phosphate Ceramics Prepared
via Polymeric Sponge Method, Materials and Manufacturing Processes, 27:6, 702-706, DOI: 10.1080/10426914.2011.602787

To link to this article: http://dx.doi.org/10.1080/10426914.2011.602787

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 Materials and Manufacturing Processes, 27: 702–706, 2012
Copyright # Taylor & Francis Group, LLC
ISSN: 1042-6914 print=1532-2475 online
DOI: 10.1080/10426914.2011.602787

Porous Magnesium-Doped Biphasic Calcium Phosphate Ceramics

Prepared via Polymeric Sponge Method
I. Sopyan and T. A. Rahim

Department of Manufacturing and Materials Engineering, Faculty of Engineering, International Islamic University
Malaysia, Kuala Lumpur, Malaysia
Downloaded by [International Islamic University Malaysia IIUM] at 16:47 01 January 2014

Porous magnesium-doped biphasic calcium phosphate (Mg-BCP) scaffolds were prepared through polymeric sponge method by employ-
ing sol-gel derived Mg-BCP powders of 5 and 10 mol% Mg concentrations doped. Magnesium-free porous biphasic calcium phosphate
(BCP) was also prepared as the reference. Morphological analysis showed that the doping of magnesium caused accelerated crystal growth
of BCP particles leading to more progressive particle fusion and densification. All porous samples showed good pore interconnectivity with
the macropores of 100–1,000 m m in average size. Magnesium free porous BCP has 0.39 MPa compressive strength, and it increased with the
doped Mg level to 2.17 MPa at 10 mol% Mg doping. This was attributed to the increased density from 1.98 g/cm3 (Mg free porous BCP) to
2.19 g/cm3 (10 mol% porous Mg-BCP) thus reflecting denser porous structure as the consequence of more progressive densification. It can
be concluded that magnesium acted as the sintering additive of the fabricated porous calcium phosphates leading to improved mechanical
properties.

Keywords Biomaterials; Ceramics; Characterization; Dopant; Magnesium; Mechanical; Physical; Porosity; Properties.

INTRODUCTION various metal ions. Several groups have attempted to

Porous calcium phosphate ceramics have been applied
for cell loading, drug releasing agents, chromatography
analysis, and most extensively, for bone implants [1–4].
In bone engineering, pore characteristics are crucial
due to its close correlation to the degree of bone
in-growth. In particular, porosity, pore-size distribution,
pore morphology, and orientation, as well as the degree
of pore interconnectivity significantly affect bone pen-
etration in macropores of implants, thus mediating
implant-tissue osseointegration. Pore interconnectivity
allows circulation and exchange of body fluids, ion dif-
fusion, nutritional supply, osteoblast cell penetration,
and vascularization. Surface roughness of the pores is
also required for the attachment of cells.
Dimension and morphology of pores are important
for a successful osteointegration. The minimum pore
size required to enable in-growth of the surrounding
bone together with blood supply is about 50–150 mm
for macropores. Even bigger pores of 200–500 mm are
needed for colonization of osteoblast in the pores, fibro-
vascular in-growth, and finally the deposition of the new
bone [1, 2]. Increasing porosity leads to reduced strength
which may hamper its application for bone implants due
to difficult handling. Several strategies have been there-
fore tried to increase the mechanical strength of artificial
porous calcium phosphate including via doping of
Received April 5, 2011; Accepted June 1, 2011
Address correspondence to I. Sopyan, Department of Manufactur-
ing and Materials Engineering, Faculty of Engineering, International
Islamic University Malaysia, 50728 Kuala Lumpur, Malaysia; E-mail:
sopyan@iium.edu.my
incorporate metal ions into calcium phosphate lattice
as a strategic way to improve the densification, mechan-
ical, and biological performances of calcium phosphate
ceramics [5–7].
Doping calcium phosphate materials with magnesium
for biological and mechanical improvement were also
extensively investigated. Various research groups have
attempted to dope calcium phosphate materials with
magnesium [8–11]. Doping of magnesium ions into
biphasic calcium phosphate (BCP) will results in bio-
logical improvement as the ion will cause the acceler-
ation of nucleation kinetics of bone minerals [10].
Magnesium depletion adversely affects all stages of
skeletal metabolism, leading to decrease in osteoblastic
activities and bone fragility. Addition of magnesium
might as well improve thermal stability of tricalcium
phosphate (TCP) which prevents phase transformation
of b-TCP to much resorbable a-TCP phase at high
temperature [12].
We have reported the synthesis of Mg-doped biphasic
calcium phosphate (Mg-BCP) powders at different Mg
concentration through a sol-gel method [13]. In this
work, porous Mg-BCP bodies were prepared via poly-
meric sponge method by employing the sol-gel powders.
The polymeric sponge method is performed by impreg-
nating porous polymeric substrates (sponges) with the
ceramics slurry. Porous ceramics prepared via the poly-
meric sponge method normally have controllable pore
size and complex shapes suitable for different applica-
tions. A proper pore size distribution of porous bioac-
tive ceramics obtained via this method, as required for
osteoconduction, is also characterized by the existence
of micro=meso=macropores with an adequate degree of

702
 POROUS Mg-DOPED BCP CERAMICS 703

interconnection [2]. This report presents the effect of

magnesium doping on physical properties and phase
behavior of the porous Mg-BCP bodies.

EXPERIMENTAL
Preparation of Porous Ceramic Scaffolds via
Polymeric Sponge Method
The sol-gel synthesis of pure BCP and Mg-BCP pow-
ders has been reported elsewhere [13]. The doped Mg
levels were fixed at 5 and 10 mol%. By using the synthe-
sized powder, slurries were prepared with an adjusted
loading of Mg-BCP powders, using Duramax of
D-3005 type (Rohm and Haas, USA) as the dispersant.
Commercial cellulosic sponge (Spontex, Verniano Co., FIGURE 1.—XRD patterns of porous bodies of pure BCP and Mg-BCP
Downloaded by [International Islamic University Malaysia IIUM] at 16:47 01 January 2014

Italy) was used; it is able to recover to its original shape
after impregnation and is fully eliminated at a tempera-
ture of about 600 C. The suspensions of BCP and
Mg-BCP powders were prepared by dissolving the pow-
ders into distillated water, little by little, in stirring con-
dition followed by the addition of the dispersant.
Stirring was continued for 24 h to assure slurry hom-
ogeneity and stability. After soaking into the slurry,
the sponges were dried in ambient air and then subjected
to heat-treatment at 600 C for 3 h to eliminate the
organic matrix. Sintering was conducted at 1,250 C for
3 h. The dimension and mass of all the samples were
measured before and after heat treatment.
Characterization of Porous Bodies
The degree of crystallinity and the presence of b-TCP
and HA phases was identified by X-ray diffractometer
(XRD) (Shimadzu, XRD 6000). X-ray diffraction spec-
tra were collected over the 2 h range of 20–50 using cop-
per Ka radiation with a step scan rate of 2 in 2 h min 1.
The phase identification of the powders was done by
comparing the obtained XRD patterns with JCPDS card
No. 09-432 for HA and 09-169 for b-TCP. Morphologi-
cal analyses were performed on a field emission scanning
electron microscope (JEOL, JSM6700 F).
The density of the sintered porous bodies was mea-
sured by using Archimedes principles method. Com-
pression test is used to characterize the prepared
porous BCP and Mg-BCP scaffolds. The compressive
strength of the porous samples was measured using a
mechanical testing machine (Instron 8874). The com-
pressive load of 500 N was applied at a crosshead speed
of 6.67  10 6 m=s on the cylindrical samples of
12 mm  10 mm (height  diameter) dimension until
failure.
sintered at 1250 C.
sintered bodies with 10 mol% of MgO addition [7]. Dur-
ing the phase transition, calcium was expelled from
b-TCP by Mg substitution which, in turn, reacts with
b-TCP phase to form HA phase [14]. As a consequence,
the HA peaks were observed to increase with the
decreasing b-TCP. The appearance of MgO peak at
43 for 10 mol% Mg porous bodies indicates that Mg
ions were expelled from b-TCP. However, there is no
peak of a-TCP detected in these porous samples which
pointing out that the phase transition temperature from
b-TCP to a-TCP was found to take place above 1,250 C.
This shows that at high sintering temperature (1,250 C),
b-TCP and Mg-doped b-TCP become unstable and con-
tribute to a decrease in solubility limit of Mg in the
b-TCP [14]. Another possible factor that contributes to
the loss of b-TCP during the sintering process is the
presence of moisture during the thermal treatments car-
ried out in an ambient air. Because the characteristic of
TCP is an unstable phase at elevated temperature, it
might react with the moisture to form stable HA.
The decomposition of b-TCP can be explained in
details with thermogravimetric and differential analysis
(TG=DTA) analysis performed on the as synthesized
powder, as shown in Fig. 2. The results from the

RESULTS AND DISCUSSION

Characterization of Porous Mg-Free and Mg-BCP
After sintered at 1,250 C, porous bodies of pure and
Mg-BCP are mainly composed of HA phase, as XRD
patterns in Fig. 1 show. However, b-TCP peak appeared
for the porous bodies with Mg-doping and disappeared
for that with no Mg-doped. It was reported that b-TCP FIGURE 2.—TG=DTA curve of pure BCP and 10 mol% Mg-BCP powders
and HA are the existing phases in calcium phosphate (color figure available online).
 704
FIGURE 3.—Surface morphology of pure BCP (a) and 10 mol% Mg-BCP
(b) porous bodies sintered at 1,250 C.
TG=DTA analysis suggest that the presence of Mg has
shifted the onset of the sintering temperature of
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the BCP, indicating that the presence of magnesium
improves the densification of the b-TCP phase in the
BCP mixture. This analysis revealed that the Mg is an
effective sintering additive for b-TCP, as it delayed
the phase transformation of b-TCP to other phases
like HA or a-TCP. Sintering of Mg-BCP might thus
produce denser compacts with better mechanical
properties [15].
Figure 3 shows surface morphology of Mg-free (a)
and 10 mol% Mg-doped (b) BCP porous bodies. The fig-
ure confirms that porous sample of 10 mol% Mg-BCP
showed better sintering behavior and densification due
to particle coarsening at high level Mg-doping. Figure 4
displays microporous structure of pure BCP (a) and
10 mol% Mg-BCP (b) porous bodies. It is clear that
the microstructure of porous 10 mol% Mg-BCP shows
fully-densified pore walls structure as the result of sinter-
ing at 1,250 C. However, the micrograph of porous pure
BCP shows residual porosity due to incomplete densifi-
cation of structure during the sintering process. This
residual porosity adversely influenced the mechanical
performance of the porous ceramics. The presence of
Mg as sintering additive also contribute to the improve-
ment of grain boundary properties of BCP thereby
improving the compression strength of 10 mol %
Mg-BCP [5].
Figure 5 presents the compression test result of porous
10 mol% Mg-BCP ceramics. All samples displayed a
linear-elastic region followed by a collapse until rupture.
The result of compressive tests, along with porosity and
density, is presented in Table 1. The table clearly indi-
cates that incorporation of magnesium has increased
FIGURE 4.—Microstructure of pure BCP (a) and 10 mol% Mg-BCP (b)
porous bodies sintered at 1,250 C.
I. SOPYAN AND T. A. RAHIM
FIGURE 5.—Graph of compressive strength vs. strain of porous 10 mol%
Mg-BCP sample (color figure available online).
the compressive strength. Porous Mg-free BCP sample
registered a 0.39 MPa compressive strength and its
strength increased to 0.64 MPa and 2.17 after doping
of 5 and 10 mol% Mg, respectively. One possible reason
is the amount of b-TCP phases present in 10 mol%
Mg-BCP is the highest compared to other samples.
The occurrence of b-TCP phase together with HA phase,
which is known as BCP, was believed to give better
strength characteristics compared to HA porous cer-
amics alone, while b-TCP porous ceramics is extraordi-
narily brittle [8]. In addition, incorporation of
magnesium as sintering additive into BCP has improved
its densification, thus leading to improved mechanical
behavior. This more progressive densification is presum-
ably due to higher thermal stability of BCP phase as
shown by the XRD patterns in Fig. 1. The thermal stab-
ility of the starting powder allowed the samples densify
further at higher sintering temperature [16].
It has been reported that the noticeable enhancement
of compression strength is also considered as the pro-
motion of densification due to the formation of liquid
phases between separated MgO and BCP and to the sta-
bilization of b-phase [5, 7, 15]. Within the range of
4 mol% MgO addition, the mass transfer appears to be
promoted by the solid solution of MgO into BCP [7].
The presence of a liquid phase can occur at high sinter-
ing temperature or by increasing Mg content more than
5 mol%. The liquid phase formation showed outstanding
change in the microstructure as indicated by the forma-
tion of bimodal microstructure with large grains sur-
rounded by irregular segregation, which in turn
suggests liquid phase sintering and subsequent precipi-
tation of a second phase [15]. Figure 6 shows microstruc-
ture of MgO and BCP liquid phase formation in porous
TABLE 1.—Compressive strength value of porous samples.
Porous BCP Compressive strength (MPa) Density (g=cm3) Porosity (%)
Mg-free 0.39 1.98 36
5 mol% Mg 0.64 2.10 33
10 mol% Mg 2.17 2.19 31
 POROUS Mg-DOPED BCP CERAMICS
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FIGURE 6.—Microstructure of liquid phase formed between BCP and
MgO in porous 10 mol% Mg-BCP sample.
10 mol% Mg-BCP. Addition of Mg has stabilized the
b-TCP from transformation to other phases, and at high
level it seemly produced MgO as a separated phase due
to limited dissolution of Mg in b-TCP phase.
In this study, the macroporous scaffolds with different
pore sizes ranged from 100 to 1,000 mm have been suc-
cessfully fabricated. In polymeric sponge method, the
slurry tends to settle down (aggregate) at the bottom
of the sponge during drying process which results in a
non-homogeneous porous structure after sintering [16].
In order to solve this problem and to maintain a flow-
able slurry, an appropriate amount of the dispersant
agent was added into the slurry. A 70% BCP=Mg-BCP
concentration was selected for this study. The slurry
with high BCP=Mg-BCP concentration gives better den-
sity and mechanical properties of the sintered product.
This preliminary result showed that magnesium doping
has successfully improved mechanical strength of cal-
cium phosphate porous bodies. However, the micro-
structure and the mechanical properties of the porous
samples are also function of the impregnation process
and the starting powder [17, 18]. Further study is in pro-
gress on the effects of impregnation process and sinter-
ing conditions on mechanical and physical properties
of porous Mg-BCP ceramics.
CONCLUSIONS
Porous Mg-BCP scaffolds were fabricated via poly-
meric sponge method using the sol-gel derived Mg-BCP
powders. The sintered porous bodies of pure and
Mg-BCP are mainly composed of HA phase and
b-TCP phase appeared when high level of Mg was
doped. The scaffolds have heterogeneous pore sizes ran-
ging from 100 to 1,000 mm. Compressive test showed
that the increasing concentration of Mg doped into
the BCP has increased the compressive strength of the
scaffolds. The study found that the density of the
porous bodies varied from 1.98 g=cm3 to 2.19 g=cm3
with 31–36% porosities. The measurement of compress-
ive strength of pure and Mg-BCP provided the values
705
of 0.39–2.17 MPa. The results revealed that porous
scaffolds with presence of Mg up to 10 mol% showed
further improvement of compressive strength. The
noticeable enhancement of compression strength is con-
sidered as the promotion of densification, and this is
attributed to the formation of liquid phases between
the separated phase of MgO and BCP and to the stabi-
lization of b-phase. The prepared porous bodies in this
work are physically applicable for human spongy bone
substitutes.
ACKNOWLEDGMENTS
The authors would like to thank Research Manage-
ment Center, International Islamic University, Malaysia
for partial financial support for the work through the
grant No. EDW A11-072-0863.
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