ASIA-PACIFIC JOURNAL OF CHEMICAL ENGINEERING

Asia-Pac. J. Chem. Eng. (2010)

Published online in Wiley InterScience
(www.interscience.wiley.com) DOI:10.1002/apj.480

Special Theme Research Article

Phase behaviour of manganese-doped biphasic calcium
phosphate ceramics synthesized via sol-gel method
Natasha Ahmad Nawawi,1 Iis Sopyan,1 * Singh Ramesh2 and Afzeri1
1
Department of Manufacturing and Materials Engineering, Kulliyyah of Engineering, International Islamic University Malaysia, 50728 Kuala Lumpur,
Malaysia
2
Department of Mechanical Engineering, College of Engineering, Universiti Teknologi Nasional, 43009 Kajang, Malaysia

Received 1 November 2009; Revised 29 April 2010; Accepted 26 May 2010

ABSTRACT: Manganese-doped biphasic calcium phosphate (Mn-doped BCP) powders have been synthesized via sol-
gel technique. The Mn-doped BCP powders were studied for their phase behaviour at different concentrations of Mn
(0, 0.01, 2, 5 and 15 mol%) and calcination temperatures (500–1200 ◦ C). For all the Mn concentrations, the X-ray
diffraction (XRD) revealed that only hydroxyapatite (HA) and β-tricalcium phosphate (β-TCP) phases were present. It
was shown that the HA crystallinity increased with increase in Mn content. Moreover, the weight loss at 700–850 ◦ C
detected by thermogravimetric analysis confirmed the presence of biphasic mixtures in the BCP powders. The study
on effect of calcination temperature was done on the pure BCP and 5 mol% Mn-BCP powder. The XRD revealed
that the decomposition of HA to TCP took place at the temperature range of 700–800 ◦ C. Fourier transform infrared
spectroscopy and XRD measurements found that HA peaks increased with the increasing Mn content and temperature.
This was also accompanied by the enlarging particles at higher calcination temperatures and Mn contents due to fusion
of agglomerated particles. These findings have led to the conclusion that Mn has acted as a calcination additive for the
BCP powder.  2010 Curtin University of Technology and John Wiley & Sons, Ltd.

KEYWORDS: manganese; biphasic calcium phosphate; sol-gel; phase behaviour; calcination

INTRODUCTION extensively used as substitution materials for artificial

Synthetic calcium phosphate has been used as bone
grafts since the 1970s. Its chemical composition which
is close to the mineral phase of bone is the origin of
its excellent biocompatibility to tissue bone. Moreover,
calcium phosphate ceramic does not exhibit any cytoxic
effect and it can directly bond to the bone.[1] However,
the stability of crystal structure of calcium phosphate
is higher than that of natural apatite.[2] Most natural
apatite is non-stoichiometric because of the presence of
minor constituents which have an effect on the lattice
parameters, the crystallinity, the dissolution kinetics and
other physical properties of apatite.[2] Along with this,
biphasic calcium phosphate (BCP) has raised much
attention, especially in the field of biomaterials. The
BCP ceramic comprises a mixture of hydroxyapatite
[HA, Ca10 (PO4 )6 (OH)2 ] and β-tricalcium phosphate
[β-TCP, β-Ca3 (PO4 )2 ]. This material is regarded as
suitable for synthetic bone applications and has been
*Correspondence to: Iis Sopyan, Department of Manufacturing
and Materials Engineering, Kulliyyah of Engineering, International
Islamic University Malaysia, 50728 Kuala Lumpur, Malaysia.
E-mail: sopyan@iiu.edu.my
 2010 Curtin University of Technology and John Wiley & Sons, Ltd.
bone grafts for nearly three decades.[3] This mixture
is considered better when compared with either the
single-phase HA or β-TCP component, because of its
unique dissolution characteristics promoting new bone
formation at the implant site.[4] Although HA is a more
stable phase, HA alone is not favoured, as it is a non-
biodegradable bone replacement materials. As known,
good implant materials should be biodegradable, as they
can degrade inside the bone and defect simultaneously
with the formation of a new bone. Apart from this,
application of β-TCP alone as a biomaterial for alveolar
ridge augmentation resulted in high rate of β-TCP
degradation,[5] which is unlikely not favoured too. In
conjunction to balance the non-biodegradablity of more
stable phase HA and to slow the rate of biodegradation
of β-TCP, the interest in the BCP characteristics has
recently risen and consequently, BCP materials have
been well studied. In addition, BCP often exhibits a
combination of enhanced bioactivity and mechanical
stability that is difficult to achieve in a single-phase
material.[6]
Although bone mineral is essentially calcium phos-
phate, it also contains significant concentrations of other
N. A. NAWAWI et al.
ions that can substitute for the different cations and
anions present in the apatitic structure.[7] Besides that,
inclusion of trace metal elements has a significant role
in improving the physical and/or chemical properties
of bioceramic. Trace ions such as Mg2+ , Mn2+ , Zn2+ ,
Na+ , Sr2+ and K+ can be replaced with Ca2+ in the
HA or TCP structure within the body fluid or during
fabrication due to their similarity in chemical affin-
ity and/or ionic radius. Along with this, through com-
prehensive and continuous research, it was found that
incorporation of metal as sintering additive[8 – 10] is a
simple and economical way to improve the densifica-
tion and mechanical performance of BCP. The effect
of Mn on the stability and particle growth of HA has
been recognized.[11] It has been added and doped to
calcium phosphate-based materials through solid-state
reaction[11,12] and precipitation method.[11,13] The moti-
vation for the addition of Mn2+ ions to HA was due to
the fact that divalent Mn2+ has influenced the activation
of integrins, a family of receptors that mediate cellular
interactions with extracellular matrix and cell surface
ligands.[11,14] The ligand affinity increases in the pres-
ence of Mn, resulting in the promotion of cell adhesion.
In one study, Mn in the bone was found to cause a
decrease in bone resorption.[15] It is also reported that
Mn functioned as calcination and sintering additives
of BCP powders without producing other secondary
phases such as α-TCP and CaO.[16] The formation of the
α-TCP phase during the sintering process is not
preferable, as it induces microcracks, which eventu-
ally reduces the mechanical properties of the sintered
specimens.
In this research, the doping process was carried out
chemically via adapted sol-gel technique rather than
via physical method, as reported by other researchers
such as wet milling,[11] ball milling[16] and mixing in
agate mortar.[17] Sol-gel method affords greater control
over the formation of particular phases and the purity of
the formed phases and lower processing temperatures.
These contribute to good homogeneity of powder due
to good mixing of the starting materials,[1,18] nano-size
dimensional of the primary particles[1,7,19,20] and high
reactivity.[1,21]
This report presents the synthesis of pure BCP
and Mn-doped BCP powders (varied from 0.01 to
15 mol%) via colloidal sol-gel method and the as-
synthesized powders were calcined at the temperatures
of 500–1200 ◦ C to reach the optimum crystalline phase
and to ensure complete removal of organic and inor-
ganic substances. Their physicochemical characteriza-
tions will be reported as well.
EXPERIMENTAL
A total of 250 ml of ammonium solution (11%, R&M
Chemicals, UK) was heated at 60 ◦ C and 90.5 g of
 2010 Curtin University of Technology and John Wiley & Sons, Ltd.
Asia-Pacific Journal of Chemical Engineering
ethylenedinitrilotetraacetic acid (Titriplex II) (Merck
kGaA, Germany) was added while stirring until it dis-
solved and gave clear solution. Then, 100 ml aqueous
solution of 65 g of calcium precursor, Ca(NO3 )2 · 4H2 O
(Merck kGaA, Germany), was poured into the mixture.
The dopant, 50 ml of Mn(NO3 )2 · 4H2 O (Merck kGaA,
Germany) was subsequently added with the exception
for the synthesis of pure BCP. The dopant was added
at molar percentage (mol%) of 0.01, 2, 5 and 15 mol%
with respect to Mn-to-Ca molar ratio. Then, phospho-
rus precursor made of 20 g of diammonium hydrogen
phosphate [(NH4 )2 HPO4 ] (Merck kGaA, Germany) and
22.6 g of urea (R&M Chemicals, UK) that act as gelling
agent are subsequently added. The mixture was then
refluxed at 100 ◦ C for 3–5 h while stirring until a white
gel was obtained. The white gel was then dried at
340 ◦ C, which then turned into black dried gel. The
black gel was subjected to calcination at the tempera-
tures of 500–1200 ◦ C; the gel was heated from room
temperature to the respective temperature with a heat-
ing rate of 10 ◦ C/min followed by a holding time of 3 h
before being cooled to room temperature in the furnace.
MATERIAL CHARACTERIZATION
X-ray diffraction (XRD) studies on the calcined pow-
ders were carried out using the Shimadzu, XRD600
series, diffractometer. Diffraction spectra were collected
over the 2θ range of 20–50 ◦ C using monochromated
Cu Kα radiation (λ = 0.15406 Å) ´ with a step size of
◦ −1
0.02 in 2θ s and a step scan rate of 2◦ in 2θ
−1
min . Phases were identified with MDI Jade7 soft-
ware (Materials Data, Inc.). The degree of crystallinity
of the calcined powders and the presence of β-TCP
and HA phases were also identified. The crystalline
phases were determined by a comparison of the regis-
tered standard Joint Committee on Powder Diffraction
File (JCPDF) cards (HA: 09–0432, β-TCP: 09–0169)
with the obtained powder diffraction files. The inten-
sity ratio between HA and TCP in all calcined powder
was determined using relative intensity ratio method.[22]
The crystallite size in HA was evaluated according to
Scherrer’s formula via XRD. Infrared spectroscopy for
chemical characterization was performed by the atten-
uated total reflectance (ATR) method, using Fourier
transform infrared (FTIR) spectroscopy (Perkin Elmer
FTIR, Spectrum 100 Series). The measurements were
carried out in transmission mode in the mid-infrared
range (380–2000 cm−1 ) at the resolution of 4 cm−1 ,
where the powders were directly placed onto the ATR
holder, and 16 scans were performed at a resolution
of 2 cm−1 in order to determine the various functional
groups in the samples and to determine the presence of
anions partially substituting PO4 3− and/or OH− groups.
Surface morphology of the powder was evaluated using
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Asia-Pacific Journal of Chemical Engineering
Figure 1. TG/DTA analysis of BCP white gel.
Figure 2. XRD patterns of pure BCP and various Mn-doped BCP powders calcined at
900 ◦ C.
the field emission scanning electron microscope (JEOL,
JFM 6700F). Prior to imaging, the BCP powders were
subjected to sputter coating (JEOL, JFC-1600) with a
thin layer of platinum to improve their conductivity.
Thermogravimetric analysis (TGA) was performed on
the black gel of the as-synthesized powders in ambient
air using the Perkin Elmer apparatus (Pyris Diamond
TG/DTA) with 2 ◦ C/min heating rate.
RESULTS AND DISCUSSION
White gel started to form after 4–5 h of the reflux
process of the reaction mixture at 100 ◦ C. The reac-
tion of HA formation has been expressed in Eqn 1.
The Thermogravimetric and Differential Thermal Anal-
ysis(TG/DTA) analysis was done on the white gel to
study its thermal transformation, and the result is pre-
sented in Fig. 1. A total multi-step weight loss of ∼70%
 2010 Curtin University of Technology and John Wiley & Sons, Ltd.
PHASE BEHAVIOUR OF MANGANESE-DOPED BCP CERAMIC
was recorded. The drop of the first 100 ◦ C shows ca.
10% of weight loss which was attributed to the removal
of water from the gel. Up to 300 ◦ C, the weight drop
reached approximately 50%, and it can be attributed to
the removal of urea. In addition, finally at temperatures
higher than 300 ◦ C, the decomposition of nitrate and
hydroxide occurred. At this temperature, the white gel
experienced exothermic process as the calcination took
place. The calcination has converted the amorphous gel
to crystalline phase of BCP.
(5 − x )Ca(NO3 )2 + x Mn(NO3 )2 + 3(NH4 )2 HPO4
+ 4NH4 OH −−→ Ca(5−x ) Mnx (PO4 )3 OH
+ 10NH4 NO3 + 3H2 O (1)
Figure 2 presents the XRD patterns of the Mn-doped
BCP powders at different Mn mol% calcined at 900 ◦ C.
Calcination of the powders at this temperature has
indicated the formation of β-TCP phase together with
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N. A. NAWAWI et al.
HA phase as the main phases. As there is no extra
diffraction peak observed in the BCP powders with
all Mn concentrations, there is no precipitate presented
in the Mn-doped BCP powder.[17] The diffraction pat-
terns showed exclusively sharp clear reflections that
confirmed the phase purity and high-crystallinity degree
of the powder produced. All the detected peaks are in
accordance with the standards complied by the Interna-
tional Centre for Diffraction Data of powder diffraction
file #09-432 for HA and #09-0169 for β-TCP.[17,23]
Here, the presence of β-TCP phase is crucial, as it ver-
ified the formation of biphasic mixtures in the calcined
powder.[24] From this figure, it can be observed that
doping of Mn has greatly increased the crystallinity of
BCP powder even at doping of only 0.01 mol% Mn;
thus, HA crystallinity increased with the increased Mn
content. However, the lack of TCP in the 0.01 mol%
can be attributed to the correct stoichiometric ratio of
Ca : P that is present during the synthesis.[25] In addi-
tion, from 0.01 up to 5 mol% of Mn content, it can be
clearly seen that β-TCP peak intensity increased and
at 5 mol%, Mn-BCP showed the highest intensity of
β-TCP peak. This powder, with the largest amount of
β-TCP in the biphasic mixtures, might possess the high-
est Ca deficiency among all.[23] The presence of Mn
ions has stabilized the β-TCP structure, as the β-TCP
peak increased as percentage of Mn doped into the BCP
increased. Moreover, the increase in β-TCP intensity
with Mn content can be correlated with the incorpora-
tion of Mn into the β-TCP phase via replacement of
the Ca ion by Mn ion.[11,12] This preference was sup-
ported by the ionic size consideration, as the size of
Mn ion (0.83 Å)´ is smaller than Ca ion (0.99 Å).
´ [17,26]
Moreover, it was also observed that further increase
in the intensity of the β-TCP peak is compensated by
an associated decrease in HA intensity and vice versa.
Hence, it can be deduced here that the appearance of
β-TCP phase has suppressed the formation of HA
phase. The 5 mol% Mn-doped BCP powder showed a
shift in the β-TCP peaks to smaller 2θ angles. How-
ever, the HA peaks did not show any changes in their 2θ
angle positions. This also supported the findings that Mn
substitution favours TCP phase rather than HA phase.
This phenomenon might be attributed to the solubil-
ity limit of Mn in HA. As β-TCP contains a cation
site of octahedral coordination which is smaller than
cation site of HA, it is more suitable for the smaller ion
Mn2+ , for example, than the Ca2+ ion.[25] Hence, it can
be inferred that the presence of the Mn concentration
below 5 mol% generated β-TCP as a secondary phase,
but at 5 mol% and above, the solubility limit of the Mn
in the β-TCP phase decreased, leading to the decreasing
portion of β-TCP in the powder.
Table 1 lists the ratio of intensity of HA to TCP.
The intensity quantitative values obtained are in good
agreement with the observation made in Fig. 2 where
the HA intensity increased with Mn content and
 2010 Curtin University of Technology and John Wiley & Sons, Ltd.
Asia-Pacific Journal of Chemical Engineering
Table 1. Ratio of HA/TCP in Mg-doped BCP powders.
Mn-doped BCP (mol%) HA : TCP
Pure BCP 93 : 7
0.01 96 : 4
2 90 : 10
5 72 : 28
15 94 : 6
β-TCP peak appearance has been at its most intense at
5 mol% Mn-doped BCP. The indefinite appearance of
β-TCP peak for 0.01 Mn powder could be correlated to
nearly 100% presence of HA in the powder itself, which
is 96%. These quantitative values have also confirmed
the observation of the suppression of HA intensity with
appearance of β-TCP phase in the mixture.
The FTIR spectra of various Mn-BCP powders cal-
cined at 900 ◦ C are displayed in Fig. 3. Calcined pow-
der’s spectra show vibrational bands characteristic of
calcium phosphate compounds. The fundamental vibra-
tion modes of PO4 3− group were spotted at 574 cm−1
(mode υ4 ), 609 cm−1 (mode υ4 ), 966 cm−1 (mode υ1 ),
1024 cm−1 (mode υ3 ) and 1086 cm−1 (mode υ3 ).[23,27]
Among these bands, the strong band at 1086 cm−1 is
attributed to a TCP.[28] Meanwhile, the band observed
at 630 cm−1 could be attributed to the presence of the
hydroxyl (OH− ) group in a HA environment.[23,28] It
was observed that the band of OH− increased in inten-
sity with Mn content. This is parallel with the XRD
analysis showing the increase in HA crystallinity with
Mn content. Besides that, all the BCP powder is also
characterized by a broad band at 1380–1550 cm−1 ,
which indicates the presence of carbonate (CO3 ) groups.
However, as the amount of Mn increased, the decrease
in the intensity of the corresponding peaks has clearly
pronounced the gradual loss of CO3 bands from the
FTIR spectra.[23]
Referring to XRD pattern of 5 mol% Mn-BCP in
Fig. 2, it can be seen that the powder contains greatest
amount of TCP in its compound among all the pow-
ders. This is confirmed with its FTIR spectra where the
OH− band at 630 cm−1 which belongs to HA phase
has less intensity than 2 and 15 mol% powders. The
presence of HPO4 2− detected at 875 cm−1 in the FTIR
spectra for Mn-doped BCP powders shows that these
powders behave similar to calcium-deficient apatites
without any substituted elements.[23] It was observed
that the decrease in HPO4 2− band intensity is compen-
sated by the appearance of P2 O7 4− band (715 cm−1 ).
With increase in Mn content, the decrease in HPO4 2−
band became intense, corresponding to the increase in
P2 O7 4− band. This phenomenon is verified as the con-
densation of HPO4 2− to yield P2 O7 4− .[27,29] This led
to the conclusion that the anion HPO4 2− exists in less
crystalline phase, and its condensation is completed as
some amount of dopant was added into BCP.
Asia-Pac. J. Chem. Eng. (2010)
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Asia-Pacific Journal of Chemical Engineering PHASE BEHAVIOUR OF MANGANESE-DOPED BCP CERAMIC

Figure 3. FTIR spectra of pure BCP and various Mn-doped BCP powders calcined at 900 ◦ C.

Figure 4. TG/DTA of black gel of pure BCP and Mn-doped BCP powders.

The TGA plot of the pure BCP and Mn-doped BCP
black gels is shown in Fig. 4. From room tempera-
ture to about 250 ◦ C, incorporated water is lost.[26] A
continuous weight loss was observed between 250 and
550 ◦ C, which can be associated with the burning of
organic substances and by-products such as NO3 − and
ammonia which become volatile upon heating. These
by-products are assumed to be absorbed on the sur-
face as there is no evidence that can be found in any
literature indicating that NO3 − is incorporated into the
apatite structure, and the incorporation of ammonia ions
is expected to be at a low level due to their large size.[28]
The weight loss also was described as the oxidation
of the residual solvents and vigorous decomposition
of the organic and inorganic precursors[30] at 440 ◦ C.
In another study,[31] it is stated that at approximately
400 ◦ C, the condensation reaction of hydrogen phos-
phate ions took place. This reaction will increase the
formation of TCP after heating with increase in Mn
doping. This judgement is in good agreement with this
research study. Furthermore, in that temperature range,
all samples showed similar weight loss of about 50%,
which indicated that the calcinations have changed the
amorphous phase of the black gel to the crystalline
phase of BCP.
The steps of weight loss between 700 and 800 ◦ C
show the characteristic of calcium-deficient apatite.
To be exact, at the lowest of 710 up to 800 ◦ C, the

 2010 Curtin University of Technology and John Wiley & Sons, Ltd. Asia-Pac. J. Chem. Eng. (2010)
DOI: 10.1002/apj
N. A. NAWAWI et al.
decomposition of HPO4 2− and P2 O7 4− to biphasic
mixtures has been detected.[22,28] This is verified by the
weight loss of about 2% of all the samples. This result
is derived from the condensation of the HPO4 2− groups
to yield P2 O7 4− , which at higher temperatures react
further with HA to yield Ca3 (PO4 )2 plus the volatile
H2 O according to the following reactions[27,29] :
2HPO4 2− −−→ P2 O7 4− + H2 O
P2 O7 4 + 2OH− −−→ 2PO4 3− + H2 O
Table 2 presents the starting temperature for crystal-
lization of HA and the decomposition temperature of
pyrophosphate to biphasic mixtures of pure BCP and
Mn-doped BCP. The result reveals that doping of Mn up
to 15 mol% has reduced the crystallization temperature
of HA and formation temperature of biphasic mixtures.
From the 15 mol% Mn-doped BCP plot in Fig. 4, it
can be seen that the HA crystallization and TCP forma-
tion have occurred at the temperature of about 381 and
704 ◦ C, respectively. In fact, the 15 mol% Mn-doped
BCP shows the lowest temperatures for both the HA
Table 2. Crystallization and formation temperatures
of pure BCP and Mn-doped BCP at various Mn content.
Starting of HA
crystallization BCP formation
temperature temperature
Mn content (mol%) (◦ C) (◦ C)
Pure BCP 465 754
0.01 416 743
2 439 740
5 433 735
15 380 704
Figure 5. XRD patterns of (a) pure BCP and (b) 5 mol% Mn-doped BCP powders calcined at
different temperatures.
 2010 Curtin University of Technology and John Wiley & Sons, Ltd.
Asia-Pacific Journal of Chemical Engineering
crystallization and TCP formation among all the Mn-
doped BCP samples. Therefore, it can be inferred that
Mn acts as calcination additive to the BCP. In addition,
it was also observed that the 5 mol% Mn-BCP black
gel experienced the sharpest weight drop at 750 ◦ C, as
it was decomposing to biphasic mixtures. This was sup-
ported by XRD result (Fig. 2) and calculated ratio of
HA/β-TCP (Table 1), where highest intensity of β-TCP
(2) phase is portrayed by 5 mol% Mn-doped BCP among
all the samples.
(3) XRD patterns for selected samples, pure BCP and
5 mol% Mn-doped BCP powders calcined at differ-
ent temperatures (500–1200 ◦ C) are presented in Fig. 5.
XRD diffraction pattern for both samples at 500 ◦ C
showed a poorly crystalline apatite, as it is still in amor-
phous state. The transformation from the amorphous
phase with broad peak to crystalline phase was observed
to occur in the range of 600–700 and 500–600 ◦ C
for pure BCP (Fig. 5a) and 5 mol% Mn-doped BCP
(Fig. 5b) powders, respectively. The appearance of
β-TCP was detected starting at 700 and 800 ◦ C for sam-
ple with 5 mol% of Mn and pure BCP, respectively. In
a nutshell, the appearance of β-TCP peak started to be
detected at 700–800 ◦ C for both powders and this is
the evident of the transformation of deficient apatite to
biphasic mixtures of HA and β-TCP. This finding is in
accordance with the TGA in Fig. 4, which inferred that
increase in Mn content resulted in lower crystallization
temperature of BCP. A similar study was also done on
0.01 mol% Mn-doped BCP, and it was observed that the
transition to crystalline phase only occurred between
700 and 800 ◦ C. At 900 ◦ C, all the calcined powders
have showed the existence of β-TCP phase at high-
est resolution of peaks that confirmed the formation of
biphasic mixtures at the optimum temperature. How-
ever, when the calcination temperature was increased
up to 1200 ◦ C, the XRD pattern of the powder showed
Asia-Pac. J. Chem. Eng. (2010)
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Asia-Pacific Journal of Chemical Engineering
Figure 6. FTIR spectra of 5 mol% Mn-doped BCP powder calcined at various temperatures.
increase in peak intensity of HA phases with reduction
in β-TCP phase intensity. This result suggests that at
higher calcination temperature, reversible transforma-
tion of β-TCP phase into HA phase has occurred. For
the doped BCP powder, it was reported by previous
research that the reversible transformation occurred via
the replacement of dopant ion, which in this case is Mn
ion with the Ca ion in β-TCP.[25] Free Ca, which was
expelled from TCP by Mn substitution, in turn, reacts
with the β-TCP phase to form HA phase.[25] This is
also in agreement with the decrease in the intensity of
β-TCP as temperature increased.
Figure 6 shows FTIR spectra of 5 mol% Mn-doped
BCP powders calcined at different temperatures rang-
ing from 500 to 900 ◦ C. The spectra show that C–O
band at 1300–1600 cm−1 decreased in resolution as
the calcination temperature was increased. Besides that,
the decreased in carbonate band has simultaneously
increased the OH− and PO4 3− bands. This finding
shows that the formation of the BCP phase involved
a substitution of carbonate groups for hydroxyl (A
type) and the phosphate (B type) groups. It was also
observed that the presence of PO4 3− band (1086 cm−1 )
which belongs to the TCP phase has been detected
between the temperature of 700 and 800 ◦ C. This result
is in good agreement with the result of TGA of the
Mn-doped BCP black gels at various Mn concentra-
tions as shown in Fig. 4. The spectrum revealed the
presence of hydrogen phosphate groups (HPO4 2− ) and
pyrophosphate (P2 O7 4− ) bands are evident at 500 ◦ C for
the peak at 875 and 715 cm−1 , respectively. However,
as the temperature increases, the bands of HPO4 2− at
875 cm−1 and P2 O7 4− at 715 cm−1 are viewed with a
decreasing intensity. This led to the conclusion that this
 2010 Curtin University of Technology and John Wiley & Sons, Ltd.
PHASE BEHAVIOUR OF MANGANESE-DOPED BCP CERAMIC
anion, HPO4 2− , exists in less crystalline phase. This
confirms the formation of biphasic mixtures of HA
and conformed that Mn has stabilized β-TCP in the
Mn-doped BCP powder when calcined at higher tem-
perature. Nevertheless, profound change in OH− band
intensity at 630 cm−1 was observed as the temperature
increased from 700 to 900 ◦ C. This can be attributed
to the increase in HA crystallinity with increase in
calcination temperatures,[26] as also supported by the
XRD patterns in Fig. 5. Moreover, the condensation
of CaHPO4 as expressed in Eqn 2 also conforms to
this FTIR result, as it shows a decrease in intensity of
HPO4 2− band with the increase in calcination tempera-
ture, particularly from 700 to 800 ◦ C.
Figure 7 shows (a) transmission electron microscope
picture of 5 mol% Mn-doped BCP powder and scanning
electron microscope images of the powders calcined at
(b) 700 ◦ C and (c) 1000 ◦ C. The powders showed nano-
scale individual particles of diameter between 10 and
20 nm but tightly agglomerated into microscale aggre-
gates. Agglomerates of the crystal are also visible for
the micrograph. Initially, the nano-size crystallites of
the as-synthesized powders are spherical in shape with
size of 16.4 nm as calculated using Scherrer’s equa-
tion. At the calcination temperature of 700 ◦ C, Fig. 7b,
the spherical crystallite still maintained its shape with
crystallite size of 26.7 nm. However, when the cal-
cination temperature was increased up to 900 ◦ C (the
picture is not shown), the spherical-shaped crystals
(40.3 nm) began to exhibit an early stage of sintering
with densification of particles detected at some area of
the agglomerated crystallites. At calcination tempera-
ture of 1000 ◦ C, Fig. 7c, the individual particles tend
to melt together, as more progressive densification of
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N. A. NAWAWI et al.
Figure 7. TEM picture of 5 mol% Mn-doped BCP powder (a) and SEM pictures of the powder calcined at 700 ◦ C (b) and
1000 ◦ C (c).
particles occurred at this temperature and the particle
has enlarged to 60.7 nm. The fusion of particles can be
seen clearly when the 5 mol% Mn-doped BCP powder
was calcined at 1200 ◦ C (64.7 nm) where the crystal-
lites are no longer in their spherical shape but totally
densified, forming flat surface. From the figure, we can
conclude that increasing the calcination temperature has
increased the coarsening of the microstructure of the
powder particles whereby the spherical crystals are well
grown as they melt and diffuse together. This is in good
agreement with the XRD analysis which indicates that
at higher calcination temperatures, the crystallinity of
the 5 mol% Mn-BCP was increased with increase in
crystallite size.
CONCLUSION
Nano-sized particles of pure BCP and Mn-doped BCP
powders with 0.01, 2, 5 and 15 mol% Mn have been
successfully prepared via a novel sol-gel method and
the as-synthesized powder exhibited highly crystalline
BCP characteristic after calcination at 900 ◦ C. How-
ever, as the calcination temperature was increased up
to 1200 ◦ C, the increase in peak intensity of HA phases
with reduction in β-TCP phase intensity was observed.
This result suggests that at higher calcination temper-
ature, reversible transformation of β-TCP phase into
HA phase has occurred. The particle size of the pow-
der was found to enlarge with increased Mn content
and calcination temperature, which was inversely pro-
portional to the obtained specific surface area of the
powders. Presence of BCP characteristic was detected
in the temperature range of 700–800 ◦ C, the diffraction
patterns are consistent with the weight loss experienced
by the powder via the thermal analysis at similar tem-
perature range. The morphology of the samples showed
fusion and densification of the powders with increase in
Mn content and sintering temperature. These findings
 2010 Curtin University of Technology and John Wiley & Sons, Ltd.
Asia-Pacific Journal of Chemical Engineering
have led to the conclusion that Mn acts as calcination
additives for the BCP powder.
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