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Materials and Manufacturing Processes

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Sintering and Properties of Dense Manganese-Doped

Calcium Phosphate Bioceramics Prepared Using Sol-Gel
Derived Nanopowders
a a b c d c
I. Sopyan , N. A. Nawawi , Q. H. Shah , S. Ramesh , C. Y. Tan & M. Hamdi
a
Department of Manufacturing and Materials Engineering, Faculty of Engineering,
International Islamic University Malaysia, Gombak, Kuala Lumpur, Malaysia
b
Department of Mechanical Engineering, Faculty of Engineering, International Islamic
University Malaysia, Gombak, Kuala Lumpur, Malaysia
c
Department of Engineering Design and Manufacture, Faculty of Engineering, University of
Malaya, Kuala Lumpur, Malaysia
d
Department of Mechanical Engineering, College of Engineering, Universiti Tenaga Nasional
Malaysia, Kajang, Selangor, Malaysia

Available online: 27 Jun 2011

To cite this article: I. Sopyan, N. A. Nawawi, Q. H. Shah, S. Ramesh, C. Y. Tan & M. Hamdi (2011): Sintering and Properties
of Dense Manganese-Doped Calcium Phosphate Bioceramics Prepared Using Sol-Gel Derived Nanopowders, Materials and
Manufacturing Processes, 26:7, 908-914

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 Materials and Manufacturing Processes, 26: 908–914, 2011
Copyright © Taylor & Francis Group, LLC
ISSN: 1042-6914 print/1532-2475 online
DOI: 10.1080/10426914.2011.557285

Sintering and Properties of Dense Manganese-Doped Calcium

Phosphate Bioceramics Prepared Using Sol-Gel Derived Nanopowders
I. Sopyan1 , N. A. Nawawi1 , Q. H. Shah2 , S. Ramesh3 , C. Y. Tan4 , and M. Hamdi3
1
Department of Manufacturing and Materials Engineering, Faculty of Engineering,
International Islamic University Malaysia, Gombak, Kuala Lumpur, Malaysia
2
Department of Mechanical Engineering, Faculty of Engineering, International Islamic University Malaysia,
Gombak, Kuala Lumpur, Malaysia
3
Department of Engineering Design and Manufacture, Faculty of Engineering, University of Malaya,
Kuala Lumpur, Malaysia
4
Department of Mechanical Engineering, College of Engineering, Universiti Tenaga Nasional Malaysia,
Downloaded by [International Islamic Uni Malaysia] at 23:34 27 June 2011

Kajang, Selangor, Malaysia

Dense manganese-doped biphasic calcium phosphate (Mn-BCP) ceramics were fabricated via uniaxial pressing using the sol-gel derived
powders. The compacted discs were sintered in ambient atmosphere with temperatures ranging from 800
C to 1400
C. Manganese (Mn) level was
varied in the range of 0.6, 1.9, 4.3, and 11.9 mol%, and its effect on physical and mechanical properties of the dense samples were investigated. All
dense samples have been proved to show HA and
-TCP phases only. Mn doping has shifted the onset of the sintering temperature of the BCP,
leading to the improved densification of BCP ceramics. The relative density also increased with sintering temperature. Considerable grain growth
has been observed for Mn-doped BCP samples when compared to the undoped BCP. Furthermore, 11.9 mol% Mn-doped BCP dense samples
showed the maximum hardness of 6.66 GPa compared to 2.89 GPa for the undoped BCP. The incorporation of Mn was also found to be beneficial
in enhancing the fracture toughness of BCP throughout the temperature range employed. This study has shown that Mn doping was effective in
improving the sintering properties of BCP without affecting the phase stability.

Keywords Biomaterials; Ceramics; Characterization; Dopant; Manganese; Mechanical; Nanomaterials.

Introduction out in enhancing the mechanical properties of dense BCP

Calcium phosphate bioceramics have widely been
developed for biomedical applications due to excellent
biocompatibility, bioactivity, and osteoconduction
characteristics. Among various phases of calcium
phosphate, hydroxyapatite [Ca10 PO4 6 OH2 , HA] and
beta-tricalcium phosphate [Ca3 PO4 2 ,
-TCP], with
similar composition and crystal structure to natural bone,
are the two most common calcium phosphate ceramics
applied for medical purposes [1]. These materials have
been fabricated in porous [2], coating [3], granular [4],
paste [5], and dense forms [6].
Dense HA is described as HA that has porosity less
than 5 vol% with micropores size diameter less than 1 m
and grain size bigger than 02 m. The microporosity is
unintentionally introduced and is dependent on compaction
parameters as well as temperature and duration of sintering.
It is important to note that dense HA has a compressive
strength four times that of cortical bone, but yet it shows a
significantly lower tensile strength and fracture toughness.
Hence, multiple development efforts have been carried
Received October 3, 2010; Accepted January 8, 2011
Address correspondence to I. Sopyan, Department of Manufacturing
and Materials Engineering, Faculty of Engineering, International Islamic
University Malaysia, Gombak 50728, Kuala Lampur, Malaysia; E-mail:
sopyan@iium.edu.my
908
including: a) varying the powder processing technique to
manipulate powder properties such as particle size and
shape, distribution, and morphology of the starting powders,
b) control of sintering process, and c) incorporation of metal
as sintering additive into the BCP.
Inclusion of trace metal elements has a significant
role in improving the physical and biological properties
of bioactive ceramics. Many trace metal elements like
Mg, Sr, and Na have been incorporated into the CaP
phase. However, the inclusion of Mn in BCP has not
been studied extensively although numerous works have
reported the significant role of manganese oxide in
promoting densification in other ceramics systems [7]. The
incorporation of manganese (Mn) as sintering additive into
apatite structure has been of great interest as it improves
its bonelike mechanical properties [7]. In addition, the
influence of Mn on stability and particle growth of HA have
also been recognized [8].
It is reported that Mn physically functioned as calcination
additive of BCP powders without producing other secondary
phases like -TCP and CaO which possibly inducing
microcracks [7, 9, 10]. Doping of Mn into BCP, hence,
is expected to show better mechanical performance of
the dense bodies. Biologically, it was found that divalent
Mn2+ has influenced the activation of integrins, a family of
receptors that mediate cellular interactions with extracellular
matrix and cell surface ligands [8, 11]. The ligand affinity
 MANGANESE-DOPED CALCIUM PHOSPHATE BIOCERAMICS
increases in the presence of Mn, resulting in the promotion
of cell adhesion. Moreover, manganese in the bone was also
found to cause a decrease in bone resorption [12].
Various research groups have attempted to dope calcium
phosphate materials with manganese [7–10, 13, 14] through
the solid-state reaction [8, 10] and precipitation method
[8]. In this work, manganese has been doped into BCP
powder via the sol-gel technique. No work on sol-gel
derived Mn-doped BCP powders reported by other groups.
Sol-gel synthesis allows the preparation of materials not
easily accessible by other methods yet using mild and low
energy conditions. The obtained sol-gel powders were then
compacted and sintered to obtain dense BCP compacts
with optimum mechanical properties. We have reported
the synthesis of manganese doped BCP powder elsewhere
[15, 16]. This report presents the effect of Mn content
and sintering condition on phase behavior and mechanical
properties of the BCP dense samples.
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Experimental
Preparation of Dense Undoped BCP and Mn-Doped
BCP Ceramics
Undoped (Mn-free) BCP and Mn-doped BCP powders
used to produce dense compacts were synthesized via
a sol-gel technique and have been reported elsewhere
[15, 16]. The sol-gel undoped BCP and Mn-doped
BCP powders with four different molar concentrations
ranging from 0.6 mol%, 1.9 mol%, 4.3 mol%, and 11.9 mol%
were synthesized. Manganese level in the BCP powder
samples was determined on a Perkin Elmer atomic
absorption spectrometer (AAS), model AAnalyst 400. The
undoped BCP and Mn-doped BCP powders were uniaxially
compacted at 2.5 MPa pressure into disc shapes (20 mm
diameter × 5 mm thickness) using hardened steel mould and
die set. For each powder concentration, seven samples were
fabricated. Cleanliness of the mould and die set was strictly
controlled to ensure that samples are not contaminated,
and it was also cleansed with WD-40 to prevent powder
lamination. The green bodies were sintered in air using a
heating furnace (Protherm, PLF 160/5) at seven different
temperatures ranging between 800–1400
C and held for 2
hours. The ramp-rate was fixed at 2
C/min for both heating
and cooling process. Conventional pressureless sintering
was used in all processes. It has been well established that,
when the furnace ramp-rate exceeded 5
C/min, thermal and
residual stresses would develop in the HA structure [17, 18].
The reason behind this phenomenon is due to the low heat
conductivity and high shrinkage rate of HA which then led
to the formation of microcracks and macrocracks in the
samples [19].
Characterization of Dense Mn-BCP Ceramics
Prior to characterization, the sintered dense samples were
ground and polished manually on one surface using Mecapol
(Presi, P260). The samples were ground using silicon
carbide (SiC) paper (600–1000 grit) in order to remove the
roughness and refine the surface for characterization. The
samples were then polished using diamond paste (3 m–
1 m) slightly until an optically reflective surface was
obtained. The presence of the crystalline phase in the
909
sintered dense samples was analyzed by X-ray diffraction
(XRD) (Shimadzu Diffractometer, XRD-6000), and the
scans were performed on the surface of the polished dense
samples. The change in color intensity of the produced
dense samples was measured in the range of the visible
light using UV-Vis Spectrometer (Perkin Elmer, Lambda
35) with a diffuse reflectance accessory (AS-00552-210).
The bulk density of the sintered dense samples was
measured by water immersion technique [20–22] based on
the Archimedes principle using a standard densimeter (Alfa
Mirage, MD-300S). The immersion medium used in the
measurement was distilled water. Subsequently, the relative
density was calculated by taking the theoretical density of
HA as 3.156 g/cm3 . For Vickers hardness determination, the
indentations were made using a pyramidal diamond indenter
(Mitutoyo, MHV H-2) with an applied load of 100 g. The
load was applied smoothly, without impact, and held for
10 seconds. In the present work, three indentations were
made for each sample, and the average value was taken.
The fracture toughness (KIc ) of the sintered dense samples
was determined using Vickers indentation method and the
KIc value was calculated using the equation reported by
Niihara [23].
Results and discussion
Detailed characterization of undoped BCP and Mn-doped
BCP powders has been published elsewhere [15, 16]. The
transmission electron microscopy (TEM) measurement of
the undoped BCP powder calcined at 900
C shows spherical
crystals with crystallite size distribution between 10 nm and
20 nm. The nanometric primary particles are globular in
shape and tightly agglomerated into micrometric aggregates.
Field emission scanning electron microscopy (FESEM)
revealed that doping of Mn into BCP particles caused fusion
of particles leading to larger individual particles.
Figure 1 shows UV-vis absorption bands of the dense
samples of undoped and Mn-doped BCP sintered at 1300
C.
It was reported that intensity of the color increased with the
increasing Mn content and calcination temperature [24]. In
this study, the increase in Mn content has also increased the
color intensity of dense BCP to darker shades, as verified by
the increased light absorption for higher Mn content. This
phenomenon was also probably influenced by the natural
appearance of Mn itself as blackish or brown solid. The
origin of the apatite blue color was due to the presence of
Mn5+ or MnO3− 3−
4 ions at the PO4 sites in the apatite crystal
structure [24, 25]. Sintering at higher temperatures increases
the intensity of oxidation in the oxidizing atmosphere and
also provides enough energy for the oxidized manganese ion
(Mn2+ to Mn5+  to migrate within the crystal lattice [24, 25].
Nevertheless, the change in color in the present work was
found to have negligible effect on the phase stability for
both Mn-doped BCP powder and dense samples. This is
confirmed by the XRD phase analysis showing no presence
of other phases other than HA and
-TCP up to the sintering
temperature of 1200
C for the powder and 1400
C for dense
samples [16].
XRD analysis on the dense bodies of undoped and
0.6 mol% and 4.3 mol% Mn-doped BCP are shown in
Fig. 2. All dense compacts showed peaks of HA phase
 910
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Figure 1.—UV-Vis spectra of pure and Mn-doped BCP dense samples
sintered at 1300
C (color figure available online).
that correspond to the standard International Centre for
Diffraction Data (ICDD) card (no: 09-432 for HA) with no
secondary phases such as -TCP, TTCP, or CaO detected.
Within the sintering regime employed, the phase transition
of
-TCP to HA was observed where the presence of
-
TCP peaks disappeared for Mn-doped BCP dense samples
sintered at higher temperatures. For undoped BCP dense
samples,
-TCP was still detected at the temperature of
900
C but disappeared at higher temperatures. For 4.3 mol%
Mn-doped BCP,
-TCP phase started to disappear at a
higher temperature, 1200
C. The phase transition occurred
as free Ca, which was expelled from
-TCP by Mg
substitution, which in turn reacts with
-TCP phase to
form HA phase [26]. As a consequence, the HA peaks
were observed with the increasing sintering temperatures.
This result shows that at high sintering temperature
> 1200
C,
-TCP and Mn-doped
-TCP becomes unstable
and contributes to a decrease in solubility limit of Mn in
the
-TCP. Other possible factors that contributed to the
disappearing of
-TCP during the sintering process is the
presence of moisture [27] in the suspension and the fact
that also during the thermal treatments which was carried
out in air atmosphere [28]. Because of the characteristic of
TCP as unstable phase at elevated temperature, it may react
with the moisture present in the furnace atmosphere to form
stable HA.
No peak of alpha-tricalcium phosphate (-TCP),
tetracalcium phosphate (TTCP), and calcium oxide (CaO)
was detected in these dense samples throughout the sintering
regime to 1400
C, which points out that the phase transition
temperature from
-TCP to -TCP probably happened
above 1400
C. However, previous researches reported that
HA ceramics started to decompose into secondary phases
when sintered beyond 1350
C [29–31] and some even
reported that it started at about 1300
C [32–37]. Hence, it
could be deduced that in this research work, sol-gel derived
HA phase stability was not disrupted by the fabrication
of dense samples parameters such as the initial pressing
conditions, sintering cycle, and temperature employed.
I. SOPYAN ET AL.
Wang et al. reported that sintering can lead to the
partial thermal decomposition of HA into TCP and/or
TTCP [38]. The decomposition is accompanied in two
steps: dehydroxylation and decomposition. It was also
stated that dehydroxylation to oxyhydroxyapatite proceeds
at temperatures about 850–900
C by the fully reversible
reaction in accordance to Eq. (1) [38]:
Ca10 PO4 6 OH2 → Ca10 PO4 6 OH2−2x Ox + H2 Ogas 
(1)
The decomposition to TCP and TTCP occurs at a
temperature greater than 900
C according to the reaction
given in Eq. (2):
Ca10 PO4 6 OH2 → 2Ca3 PO4 2 + Ca4 P2 O9 + H2 Ogas 
(2)
According to these equations, both the dehydroxylation and
decomposition reactions include water vapor as a product.
The rates at which these reactions proceed would depend
on the partial pressure of H2 O in the sintering atmosphere
[39]. Besides that, the high humidity content present in the
sintering atmosphere has the tendency to slow down the
decomposition rate by preventing the dehydration of the OH
group from the HA matrix [16]. Thus, the secondary phases
could be suppressed by controlling the moisture content in
the sintering atmosphere.
In addition, it was observed from Fig. 2 that the HA
crystallinity of the dense samples similar to the HA
crystallinity of the corresponding powder [Fig. 2(d)] used
for their fabrication. At 900
C, the crystallinity of undoped
BCP dense samples was higher than the 4.3 mol% Mn dense
sample due to higher crystallinity of its powder at that
temperature.
The decomposition of
-TCP can be explained in details
via the TG/DTA analysis performed on the as synthesized
powder (Fig. 3). The presence of Mn caused a change
in the sintering behavior of dense BCP. The results from
the TG/DTA study suggest that the presence of Mn has
shifted the onset of the sintering temperature of the BCP,
indicating that the presence of manganese improves the
densification of the
-TCP phase in the BCP mixture [9].
This analysis revealed that the Mn is an effective sintering
additive for
-TCP, as it delayed the phase transformation
of
-TCP to other phases, which are HA or -TCP. This
characteristic allows Mn-doped
-TCP to be sintered at
higher temperatures which can produce denser materials
with possibly better properties [9].
Densification behavior of the sintered samples can be
affected by the difference in powder characteristics and
morphologies. Moreover, in this study, the densifications are
studied in terms of Mn content and sintering temperatures.
From the effect of sintering temperature on the relative
density, it was likely that the increase in relative density
was irrespective of Mn content. For undoped BCP
dense samples, the relative density also increased with
the increasing sintering temperature, as Fig. 4 shows.
 MANGANESE-DOPED CALCIUM PHOSPHATE BIOCERAMICS 911
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Figure 2.—XRD patterns of (a) dense pure BCP; (b) dense 0.6 mol% Mn-doped BCP; (c) dense 4.3 mol% Mn-doped BCP calcined at various temperatures; and
(d) BCP powders of different levels of Mn doping calcined at 900
C.

Figure 3.—TGA curve of the synthesized BCP powder.

Moreover, it was observed that the density curve showed second stage of sintering would correspond to the onset of
small increment before the onset of densification. This densification and the removal of the majority of porosity
corresponds to the first stage of sintering in which necks [17], as indicated by the dramatic increase in the sintered
are formed between powder particles [40]. Furthermore, the dense samples density between 1000
C and 1300
C.
 912
Figure 4.—Effect of sintering temperature on the relative density of sintered
BCP samples.
Downloaded by [International Islamic Uni Malaysia] at 23:34 27 June 2011
Generally, all the compositions studied exhibited a
similar trend in the bulk density variation as the sintering
temperature increased. Figure 4 shows that all the samples
showed relative density of above 82% of theoretical density
at all temperatures. However, the undoped BCP achieved
the highest value of only 91% after 1300
C sintering, which
could be achieved by 4.3 mol% Mn-doped BCP at a lower
temperature of 1200
C. For 0.6 mol% Mn and 1.9 mol% Mn,
the maximum densification of 92% and 93%, respectively,
was attained at 1300
C. Meanwhile, 11.9 mol% Mn only
attained the highest of 98% relative density when sintered at
1400
C as compared to 4.3 mol% Mn which attained 99%
densification at 1300
C and 1400
C.
Sintering at 1300
C resulted in a further increase in
density to 99% for 4.3 mol% Mn compared to 91% and 92%
relative densities for undoped and 1.9 mol% Mn-doped BCP
compacts, respectively. This improvement in densification
observed for the 4.3 mol% Mn-doped sample is believed
to be influenced by the higher amount of stable
-TCP
phase present in the starting powder as shown in Fig. 2(d).
The stability of the
-TCP phase has been reported to
have an influence on the densification of the material at
higher temperatures [41]. In addition, it was found that the
4.3 mol% Mn-doped BCP has lower HA crystallinity and the
smallest particle size among the synthesized powders [17]. It
is well documented that smaller particle size would provide
a higher heat transfer area and thus accelerate densification
upon sintering [34, 42]. These features probably contributed
to the highest densification achieved by the 4.3 mol% Mn-
doped BCP in the present work.
The effects of sintering temperature on the Vickers
hardness, Hv , of both the undoped BCP and Mn-doped BCP
are shown in Fig. 5. It can be seen that the Mn doped
samples exhibited superior hardness compared to those of
undoped BCP throughout the sintering regime. For undoped
BCP, the Hv was 051 ± 004 GPa and 053 ± 002 GPa
at 800
C and 900
C, respectively. These results were
detrimental as the sample exhibited the lowest hardness
throughout the sintering temperatures employed. The
hardness continuously increased with sintering temperature
and reached the maximum of 305 ± 002 GPa at 1300
C.
I. SOPYAN ET AL.
Figure 5.—Effect of sintering temperature and Mn doping on the Vickers
hardness of BCP (color figure available online).
Further sintering at 1400
C, however, resulted in a decrease
in hardness for all samples except for the 11.9 mol% Mn
doped sample. The maximum values of 348 ± 002 GPa
and 458 ± 002 GPa were obtained for the 0.6 mol% and
1.9 mol% doped BCP, respectively, at 1300
C. As Mn
content increased to 4.3 mol% and 11.9 mol%, sharper
increase in hardness with increasing sintering temperature
between 900
C and 1200
C was observed, with values
of 654 ± 02 GPa and 636 ± 002 GPa, respectively,
being attained at 1300
C. For 4.3 mol% Mn this is the
maximum value but for 11.9 mol% Mn sample, the hardness
continuously increased to a maximum of 666 ± 003 GPa
when sintered at 1400
C. In contrast, the undoped BCP
could only be attained a maximum hardness of 289 ±
001 GPa when sintered at 1400
C. The maximum hardness
achieved in the study is slightly lower than what we had
reported previously, 7.58 GPa, for the precipitation method
derived HA powder wet milled with MnO2 [7].
The effects of sintering temperature and Mn doping on
the fracture toughness of the BCP compacts are shown in
Fig. 6. Similar trend of Vickers hardness was also observed
for the fracture toughness KIc  where the Mn doped
BCP compacts exhibited better properties than the undoped
BCP compacts throughout the sintering regime. For the
undoped BCP sintered compacts, the KIc was observed to
increased from the lowest value of 031 ± 001 MPam1/2
at 800
C to the maximum value of 072 ± 001 MPam1/2
at 1300
C, followed by a decrement to 068 MPam1/2 at
1400
C. Likewise, the fracture toughness of the Mn doped
sintered samples of 0.6 mol%, 1.9 mol%, and 4.3 mol%
showed improvement with sintering temperature up to
1300
C, i.e., 073 ± 001 MPam1/2 , 075 ± 001 MPam1/2 ,
and 097 ± 001 MPam1/2 , respectively. Meanwhile, the
KIc for 11.9 mol% Mn continuously increased to 105 ±
001 MPam1/2 at 1400
C, which was the maximum value of
KIc attained in this research work.
 MANGANESE-DOPED CALCIUM PHOSPHATE BIOCERAMICS
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Figure 6.—Effect of sintering temperature and Mn doping on the fracture
toughness of BCP (color figure available online).
Conclusion
Manganese doped biphasic calcium phosphate dense
bodies with manganese concentrations of 0.6, 1.9, 4.3,
and 11.9 mol% have been fabricated via uniaxial pressing
followed by 800–1400
C sintering using the sol-gel derived
powders. Manganese doping has improved the thermal
stability of dense BCP in all sintering temperatures as no
secondary phases other than HA and
-TCP peaks detected.
The manganese doping also improved the mechanical
properties dense BCP ceramics as investigated in terms of
density, hardness, and fracture toughness. The maximum
relative density of 99% relative density was achieved at
1300
C by the 4.3 mol% Mn doped BCP compact. The
increased density of sintered BCP compacts with sintering
temperature is attributed to the densification of
-TCP phase
in the BCP structure. The hardness tended to increase with
sintering temperature and Mn content and the maximum
hardness of 6.66 GPa was obtained by the 11.9 mol% Mn
doped compact sintered at 1400
C. Similarly, higher level of
Mn doped and sintering temperature has enhanced fracture
toughness of BCP compacts, with the maximum value
was obtained at 11.9 mol% Mn doping showing a fracture
toughness of 105 ± 001 MPam1/2 after 1400
C sintering.
It can be concluded therefore that doping of Mn has
greatly improved the mechanical properties of sintered BCP
compacts.
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