Journal of Dispersion Science and Technology

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Evaluation of the experimental parameters for the

morphological tunning of monodispersed calcium
hydroxyapatite

Khalida Akhtar & Cynthia Pervez

To cite this article: Khalida Akhtar & Cynthia Pervez (2020): Evaluation of the experimental
parameters for the morphological tunning of monodispersed calcium hydroxyapatite, Journal of
Dispersion Science and Technology, DOI: 10.1080/01932691.2020.1724798

To link to this article: https://doi.org/10.1080/01932691.2020.1724798

Published online: 17 Feb 2020.

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JOURNAL OF DISPERSION SCIENCE AND TECHNOLOGY
https://doi.org/10.1080/01932691.2020.1724798

Evaluation of the experimental parameters for the morphological tunning

of monodispersed calcium hydroxyapatite
Khalida Akhtar and Cynthia Pervez
National Centre of Excellence in Physical Chemistry, University of Peshawar, Khyber Pakhtunkhwa, Pakistan

ABSTRACT ARTICLE HISTORY

The new era of science and technology signifies the control over the size and shape of materials. Received 29 October 2019
The size and shape variation plays a crucial role in determining the properties of the material and Accepted 25 January 2020
promises a potential application of these materials. The present study focuses on the fabrication
KEYWORDS
of the most important inorganic biomaterial, namely, calcium hydroxyapatite (Ca10(PO4)6(OH)2)
Calcium hydroxyapatite;
(HA) in a nano range having uniform morphology and high surface to volume ratio. HA particles monodispersed; monetite;
were successfully synthesized by the hydrothermal homogenous precipitation, having whiskers tricalcium phosphate
and cubic shaped particle morphology with high crystallinity in size range of 6.1 nm and 9.7 nm,
respectively. The morphological features of the particles were further analyzed by Scanning elec-
tron microscope (SEM), and the structural evolution was studied by Fourier transform infrared
spectroscopy (FT-IR) and X-Ray diffraction analysis (XRD). Urea was used as a precipitating agent
to raise pH and promote nucleation & rapid growth of HA crystals at low supersaturation. The
effect of different reaction parameters on HA particle morphology was also investigated. Aging
time showed a sensitive dependence on the morphological features of HA particles, and the pH
of a solution had a vital role in the formation of various crystal phases of calcium phosphate,
which served as a precursor in HA formation.

GRAPHICAL ABSTRACT

1. Introduction
Nanomaterials over the recent years have flourished
immensely[1] as they possess remarkable and distinct proper-
ties such as high surface to volume ratio, size, shape, geom-
etry, and morphology of the particles.[2,3] Nanoparticles
have vast applications in the fields of energy, electronics,
catalysis, optics, sensors, electrochemistry,[4] medicine, and
magnetism.[5] In the medical field, they can be used in diag-
nostic imaging, microbial, and biomaterial production.[2,4–6]
Effective biomaterials are further reinforced in biocompo-
sites to improve their properties.[7]
Among the biomaterials, calcium hydroxyapatite has been
used widely.[8] It is generally known as hydroxyapatite
(HA), having the chemical formula (Ca10(PO4)6(OH)2) with
a hexagonal structure. As natural HA forms bones and teeth
major composition, so artificial HA nanoparticles are widely
synthesized[9] and used in orthopedics in bone repair and
implants, as materials substitute in dentistry and as fillers in
composites for medical applications.[10,11] Moreover, HA
possesses exceptional bioactive and osteoconductive features,
non-toxicity and bone attachment ability and biocompatibil-
ity with living tissue.[12,13] Various physical and chemical

CONTACT Khalida Akhtar khalidaakhtar@uop.edu.pk National Centre of Excellence in Physical Chemistry, University of Peshawar, Peshawar-25120,
Khyber Pakhtunkhwa, Pakistan.
ß 2020 Taylor & Francis Group, LLC
2 K. AKHTAR AND C. PERVEZ
techniques have been devised in fabricating monodispersed
and uniform nanoparticles.[4,6] Synthesis of uniform HA
particles with specific morphology is easily achieved by
homogenous precipitation technique[8,14] along with the
addition of organic additive such as amide which upon
hydrolysis maintains the pH of the solution and enhances
crystal growth.[15]
Furthermore, HA is used in many industrial operations,
including cancer cells retardant, lightening materials, sen-
sors, carriers, catalysts, as well as agents for drug delivery.[16]
These applications require better adsorption capability,
mechanical strength, and so on. To complement the mech-
anical properties of HA composite, a few features need to be
controlled, like particle size, morphology, surface area, par-
ticle size distribution, agglomeration, structure and crystallite
size.[13] Lack of properties, such as agglomeration, high
aspect ratio, morphology and low surface area, results in
slow reaction kinetics and low density which favor the for-
mation of cracks like voids. The resulted voids caused het-
erogeneity in the structure which, lowers the mechanical
properties of the composite.[17]
HA can be synthesized by practicing numerous techni-
ques,[18–20] but very few can control the morphology of the
HA. Moreover, these methods are time-consuming, compli-
cated, and expensive. Correspondingly additives were also
used in the synthesis of HA particles to control the morpho-
logical features of the end product.[9,15,21,22] Various mor-
phologies of HA particles were prepared by using different
synthesis routes. Like, researchers[23,24] prepared HA par-
ticles in the needle and plate-like morphology by employing
the sol-gel and solid-state reaction method respectively,
while the rod and spherical particle were produced by water
in oil emulsion and microwave radiation assisted proc-
esses.[25,26] However, homogeneous precipitation enables the
synthesis of particles with uniform and specific morphology
by controlling different parameters such as the temperature
of the reaction medium, pH, external environment, and ini-
tial concentration of the reactants.[8,27] Furthermore, this
method is economical and environment-friendly.[28]
The reported findings validate the fact that the morphology
and uniformity of calcium hydroxyapatite particles are affected
by the concentration of the precursor salts, the temperature of
the reaction, chemical additives, aging time, pH, method of
synthesis, etc. These observations pointed to the fact that there
is still room to establish reproducible recipes for the synthesis
of the monodispersed fine particle of HA by an economical
and environmentally friendly simple method.
2. Experimental
2.1. Materials
Analytical reagent grade anhydrous calcium nitrate
(Ca(NO3)2), sodium dihydrogen phosphate dihydrate
(NaH2PO4
2H2O), and urea (NH2)2CO, were purchased from
BDH laboratories, Fluka Granite and Scharlau. No further
purification was done for the reagents. Deionized water was
employed for making all the stock and working solutions dur-
ing the experimentation. Filtration of all the stock solutions
was done through membrane filter paper (approx 0.2 mm pore
size) to remove all the insoluble impurities. Pyrex glassware
was used throughout the course of experimentation.
2.2. Synthesis of calcium hydroxyapatite
Calcium hydroxyapatite nanoparticles were prepared through
homogenous hydrothermal precipitation. To achieve this
objective, a series of aqueous solutions of calcium nitrate
(0.05 M) and sodium dihydrogen phosphate dihydrate (0.1 M)
was prepared. Urea was used as a precipitating agent.
Stoichiometric amounts of the reactant solutions were mixed,
while urea was added in a solid form (1 g) followed by sonic-
ation to ensure complete dissolution of urea. The resulting
mixture was then heated in a water bath in a specially designed
Pyrex glass tube at 70–90  C for diversified predetermined
intervals of time (20–60 min). Furthermore, the resulting solu-
tion mixtures were kept under silent conditions during the
course of the reaction. Finally, the precipitated solids formed
were separated through membrane filters by vacuum filtration
followed by washing with ethanol and a large expanse of dou-
ble-distilled water. The washed powder, free from the remnants
of the precipitant solution was dried and stored in a desiccator
for analysis through characterization.
2.3. Characterization
Selected batches of the synthesized particles were physically
and chemically characterized by various characterization tech-
niques. Scanning Electron Microscopy (SEM; JEOL, JSM-
6490) was used for surface analysis, like determining the
morphology and particle size of hydroxyapatite particles.
Fourier transform infrared spectroscopy of the optimized and
uniform array of calcium hydroxyapatite particles was done
by the FT-IR instrument (Shimadzu, IR Prestige-21, FTIR-
8400S), to obtain infrared spectral profiles of the samples.
Measurements of the FT-IR spectrum were scanned from 400
to 4000 cm1, and approximately 10 scans were recorded.
An analysis by X-ray diffractometer (XRD, JEOL JDX-
3532) was performed to check the crystallinity of the
selected samples of HA by utilizing 0.154 nm Cu Ka radia-
tions, 40 kV operating voltage and current of approximately
20 mA. All the samples were inspected in the 2h range of
10–80 with a step angle of 0.05 at a scan speed of 0.1 /sec.
Surface area analysis (NOVA2200e, Quantachrome) was
required to determine the quality and utility of the particles.
To study the thermal behavior, the synthesized powder sam-
ples were subjected to TGA/DTA analyzer (Perkin Elmer,
Diamond series). The analysis was carried out in the pres-
ence of air, and the heating rate was kept at 10  C/min.
3. Results and discussion
3.1. Synthesis of uniform fine particles of calcium
hydroxyapatite
Monodispersed calcium hydroxyapatite (HA) particles were
prepared by a homogeneous precipitation method. The
 JOURNAL OF DISPERSION SCIENCE AND TECHNOLOGY 3

Figure 1. SEM analysis of the particles precipitated from solution having 1 g urea at 85  C for 40 min (A) 0.4 M Ca(NO3)2/0.6 M NaH2PO4 (B) 0.2 M Ca(NO3)2/0.5 M
NaH2PO4 (C) 0.09 M Ca(NO3)2/0.4 M NaH2PO4(D) 0.07 M Ca(NO3)2/0.3 M NaH2PO4 (E) 0.06 M Ca(NO3)2/0.2 M NaH2PO4 (F) 0.05 M Ca(NO3)2/0.1 M NaH2PO4.

reaction mixture containing an appropriate amount of cal- under a silent condition for different intervals of time
cium nitrate Ca(NO3)2, sodium dihydrogen phosphate (20–60 min) and various temperatures (80–95  C).
NaH2PO4, and urea CO(NH2)2 were heated in a water bath Precipitates of white color were produced, which were
4 K. AKHTAR AND C. PERVEZ

Figure 2. SEM analysis of particles prepared from 0.05 M Ca (NO3)2/0.1M NaH2PO4 aged for 40 min with various concentration of urea (A) 0.6 g at 85  C(B) 0.8 g at
85  C (C) 1 g at 85  C (D) 1.2 g at 85  C (E) 1 g at 90  C (F) 1 g at 95  C.

further immersed in NaOH solution for 30 minutes to form precipitating agent and NaOH was used to provide the
HA. During the course of the reaction, urea was used as a required basic medium for the progression of the reaction.
 JOURNAL OF DISPERSION SCIENCE AND TECHNOLOGY 5

Figure 3. SEM analysis of the particles formed from reactant solutions heated at 85  C containing 1 g urea, 0.05 M Ca(NO3)2 and 0.1 M NaH2PO4 aged for (A) 20 min
(B) 25 min (C) 32 min (D) 40 min (E) 45 min (F) 50 min. (G) & (H) particles formed respectively in “C & F” were immersed in NaOH solution for 30 min at 60  C.
6 K. AKHTAR AND C. PERVEZ
Figure 4. Growth mechanism of monetite crystals based on aging time.
The progression of HA formation was a consequence of
various chemical reactions, among which urea initiated the
equilibrium reactions[29] as follows;
COðNH2 Þ2 þ H2 O ! NH2 COONH4
NH2 COONH4 ! 2NH3 þ CO2
NH3 þ H2 O ! NH4 þ OH þ
Urea hydrolysis yields carbamate (Equation (1)), which is
an endothermic reaction. Carbamate further decomposes to
produce ammonia and carbon dioxide (Equation (2)) in an
endothermic process, which ceases in the absence
of heat.[30,31]
The proposed stoichiometric reactions employed in the
synthesis of HA are as follows:
CaðNO3 Þ2 ! Ca2þ þ NO3 2
NaH2 PO4 ! Na1þ þ H2 PO4 1
The products of reactions 3–5 (Ca2þ, H2PO41, OH1) as
reactants (Equation (6)) led to the formation of CaHPO4,
which is commonly known as monetite. It acts as a precur-
sor in the formation of HA.[15,31,32]
Ca2þ þ H2 PO4 1 þ OH1 ! CaHPO4 þ H1þ þ H2 O
Monetite is further immersed in aqueous NaOH
(Equation (7)) as high pH is required for the production of
HA.[32]
10CaHPO4 þ OH1 ! Ca10 ðPO4 Þ6 ðOHÞ2 #
þ 4ðPO4 Þ3 þ 7Hþ þ H2 O
3.2. Optimization of reaction conditions
SEM analysis of the synthesized powder revealed that con-
trolled stepwise experimentation was needed, in which dif-
ferent parameters, i.e., reaction time, initial concentration,
pH, and temperature of the reaction medium were adjusted
to obtain monodispersity and uniformity in the particle
shape and size. It also pointed out the fact that these
parameters greatly influenced the particle morphological
features. Hence for tailoring the particle morphology and
uniformity, extensive optimization of the operational param-
[1] eters was carried out, and an experimental array was set up
to follow the basic mechanism required for particle growth.
[2] In the initial stages of experimentation, either irregular par-
[3] ticle morphology or gel was formed in abundance. But con-
trolled optimization led to homogeneous, monodispersed,
and uniform HA systems.
The concentration of reactants regulates the degree of
supersaturation and precipitation of particles from aqueous
solution and determines the particle morphology. Therefore,
to prepare uniform HA particles of various morphologies,
the effect of concentration of reactants was studied, while
keeping all other parameters constant. For the trial experi-
[4] ments, various reactant mixtures containing a different con-
centration of Ca(NO3)2 (0.04–0.4 M) and NaH2PO4 (0.1–0.6
[5] M) were prepared, whereas urea (1 g), temperature (85  C)
and aging time (40 min) were kept constant. The resulted
particles were evaluated by SEM (Figure 1). SEM micro-
graphs (Figure 1A, B) revealed that very high concentrations
of both reactants i.e., (0.2–0.4M) Ca(NO3)2 and (0.5–0.6M)
[6] NaH2PO4, initiated the chemical reaction, but particles of
irregular morphology were obtained due to high nuclei pro-
duction. More nuclei resulted in an increased bulk precipita-
tion rate, which favored the formation of the agglomerate
and diminished crystal size.[33] When the concentration of
the reactants was slightly decreased to (0.09–0.06M) for
[7] Ca(NO3)2 and (0.4–0.2 M) for NaH2PO4, a mixture of cubes
and whiskers like particle morphology was observed (Figure
1C–E) in the same system. So, the concentration was further
decreased regularly, under optimized controlled conditions.
At a very low concentration of Ca(NO3)2 (0.05 M) and
NaH2PO4 (0.1 M), particles of both morphologies (whiskers
and cubes) got smooth, as shown in Figure 1F. It revealed
that low concentration resulted in a low supersaturation of
the reactants and caused fewer nuclei formation, which fur-
ther grew large enough to form discrete particles. Further
decrease in the concentration of Ca(NO3)2 (˂ 0.05 M) and

Figure 5. pH Vs time plots showing synthesis of montite whiskers (WM) in
30 min (A) and cubes (CM) in 50 min (B) and their conversion to hydroxyapatite
when immersed in a solution of NaOH for further 30 min at 60  C (C) WHA and
(D) CHA.
NaH2PO4 (˂ 0.1 M) produced no significant effect on the
particle morphology.
Urea, as a precipitating agent affected the process of
hydrolysis to a large extent, therefore the concentration
effect of urea was also taken into consideration. The opti-
mized reactant mixtures of Ca(NO3)2 (0.05 M) and
NaH2PO4 (0.1 M) having different concentrations of ure-
a(0.6 g–1.5 g) were heated at 85  C for 40 min. SEM results
(Figure 2) revealed that sufficient addition of urea was
required for the nucleation and growth in a steady supersa-
turated condition.[29] It was observed that agglomerates were
formed at 0.6 g and 0.8 g of urea (Figure 2A, B), while regu-
lar whiskers and cubes were produced when the quantity
increased to 1 g (Figure 2C). It may be due to the fact that
the reaction proceeded at a high concentration of urea (1 g)
as a result of the continuous rise of pH, time and tempera-
ture, which resulted in the formation of monetite, an excel-
lent precursor for HA.[8] Further increase in the
concentration of urea (1.5 g) led to the formation of a gelat-
inous precipitate (Figure 2D).
In the synthesis of HA, it is also crucial to control the
reaction temperature to study the thermal effect on particle
morphology. For this purpose, the temperature was varied
from (85–95  C) while all the other parameters were kept
constant. SEM results showed that heating of a reaction
mixture at 85  C led to the formation of whiskers and cubes
(Figure 2C). However, above this temperature (90–95  C),
gelatinous precipitates were obtained as shown in Figure 2D,
E. It may be a consequence of the high reaction rate, which
increased the production of nuclei in a short life span and
enhanced the particle surface growth and aggregation.[34]
Reaction time is a master variable in the determination of
particle morphology, which can only be implicated by a
well-developed theory, i.e., Ostwald’s ripening theory and
Oriented attachment theory as two morphologies were pro-
duced simultaneously in the same reaction mixture by fol-
lowing the optimized condition (Figure 2C). Therefore, it
was essential to quench the reaction at a different time
JOURNAL OF DISPERSION SCIENCE AND TECHNOLOGY 7
interval to separate the two morphologies and also allow the
facilitated growth to obtain uniform particles of definite size
and shape of each morphology. SEM analysis (Figure 3A–F)
showed that uniform full-grown whiskers were produced at
a residence time of 32 min (Figure 3C) while cubic shape
particles required more time to attain full growth as com-
pared to whiskers and finally precipitated after 50 min of
aging (Figure 3F).
Reaction time-dependent results were further compared
with Ostwald ripening theory and oriented attachment the-
ory[33] as shown in Figure 4 to explain the growth of nano-
crystals as:
1. Initially, the particles nucleated from the clear precursor
solution, and gradually the fusion of the nanoparticles
occurred to reduce the overall energy (Step I & II in
Figure 4).
2. The aggregation of small nanoplatelets appeared as a
result of the continuous consumption of the nutrients
(Step III in Figure 4).
3. Finally, large whiskers were formed by the self-assembly
of the nanoplatelets by an oriented attachment mechan-
ism. In this mechanism, two single crystals are formed
by self-organization of two particles by sharing common
crystallographic orientation (Step IV in Figure 4).
4. Furthermore, layer by layer growth of thin whiskers
formed thick nanocubes (Step V in Figure 4). Large
crystallites grew on account of small ones, which can be
explained by Ostwald ripening. The formation of nano-
cubes can also be attributed to the low driving force for
the motion of the growing interface. As a result of the
kinetically low driving force, monetite as the precursor
phase was formed.
Many precursor phases were formed before pure HA for-
mation due to variation in pH; therefore, the study of pH
effect was of vital importance in the synthesis of calcium
phosphates. The initial pH of the reactant mixture contain-
ing Ca(NO3)2 (0.05 M), NaH2PO4 (0.1 M), and urea (1 g)
was 4.2, which gradually increased to pH 4.8 upon urea
hydrolysis on heating at 85  C. Finally, at high temperature
when urea completely decomposed, monetite whiskers and
cubes (Figure 3C, F) were formed at 32 min and 50 min of
aging, respectively. Monetite served as an excellent precur-
sor, which reacted with the hydroxyl ions and completely
changed into HA.[8]
In order to increase pH of the reaction mixture and to
make hydroxyl ions available for HA, monetite particles
comprising of whiskers and cubes (Figure 3C, F) were dis-
persed in 0.1 mol/L NaOH solution for 30 min at 60  C in a
water bath. Monetite was converted to HA in 1–4 hour,
respectively, by using the same method,[32] while in this
study, the complete conversion was observed in 30 min.
Monetite crystals were transformed entirely into HA at pH
12.48, which were confirmed by XRD and FT-IR and their
SEM micrographs are shown in Figure 3G, H. The basic
mechanism of conversion of monetite into HA proceeded
through the continuous process of dissolution and
8 K. AKHTAR AND C. PERVEZ

Figure 7. FT-IR spectra of the as-prepared HA particles synthesized in different

morphologies (A) WHA, (B) CHA, as shown in SEM Figure 3G and 3H,
respectively.
Figure 6. FT-IR spectra of the as-synthesized monetite particles prepared in dif-
ferent shapes as WM (A) and CM (B) shown in SEM Figure 3C and 3F,
respectively. Table 1. Wave number position and IR absorption of different chemical
groups on solid surfaces shown in Figure 7 for the particles presented in SEM
reprecipitation. At thermodynamic equilibrium, the disinte- Figure 3G (WHA) and Figure 3H (CHA).
gration of monetite took place at a high pH of 12.5, and Band position (cm1)
during this process, the continuous dissolution of monetite WHA CHA Group Vibration
occurred at its interface where Caþ2 and H2PO43 accumu- (Figure 7A) (Figure 7B) species mode References
[41]
lated. At the attainment of thermodynamic equilibrium, HA 1017 1017 P–O–H Bending
962 – PO43 Bending [42]
was reprecipitated at the monetite surface, forming nano- 597 597 PO43 Stretching [43]

sized HA crystallites.[32] The variation of pH with respect to 561 561 PO43 Stretching [43]

time of the particle dispersion in NaOH for the transform-

ation of monetite to HA is shown in Figure 5.
The achieved recipes for the synthesis of monodispersed
whiskers and cubic particle systems of monetite (Figure 3C,
F) and HA (Figure 3G, H) were reproducible, and the fabri-
cation route was simple, economical and environmen-
tally friendly.
3.3. Characterization
Monetite whiskers and cubic particle systems designated as
WM and CM (SEM, Figure 3C, F) respectively whereas, HA
particles synthesized in whiskers and cubic shape named as
WHA and CHA (SEM, Figure 3G, H) respectively were fur-
ther analyzed by using different characterization techniques.
3.3.1. FT-IR spectroscopy
The FT-IR spectra of the synthesized monodispersed par-
ticles (WM, CM, and WHA, CHA) are shown in Figure 6
and Figure 7, respectively. The spectra clearly demonstrated
the presence of relevant functional groups such as sharp
peaks of O–H and P–O, which clearly depicted the phase
purity of monetite and HA powder.
The spectra shown in Figure 6 demonstrated the exten-
sive OH stretching band of absorbed water at 3474 cm1
and 3431 cm1, respectively,[35] whereas OH band located at
2816 cm1 in both samples and 2376 cm1 in CM corre-
sponds specifically to stretching of HPO42 ions.[36]
Similarly, the weak band observed at 1644 cm1 in both
spectra contributed to H–O–H bending and rotation of free
residual water.[37] Moreover, the degree of hydrogen bond-
ing accompanying the adjacent OH group corresponded to
the band broadness.[38]
Furthermore, the characteristic bands of monetite sym-
bolized by both stretching and bending of P–O–H were
observed in both samples at 891 cm1, 1355 cm1,[39] while
only bending mode of P–O–H is present in samples at
567 cm 1.[36] In contrast, an intense peak located at
1120 cm1 in WM (Figure 6A) and 1130 cm1 in CM
(Figure 6B) contributed specifically to P–O stretching.[37]
Similarly, in the study of the PO43 functional group, the IR
band centered at 1027 cm1 in WM and 1062 cm1&
987 cm1 in the spectra of CM particles were accredited to
PO43 stretching.[40]
The hydroxyapatite (WHA, CHA) shown in Figure 3G,
H were also analyzed by the FT-IR spectra (Figure 7), and
the observed bands are listed in Table 1. The characteristic
band of the crystalline HA symbolized by a sharp P–O–H
peak was observed at 1017 cm1 for both whiskers and cubic
particles of HA.[41] Similarly, the IR spectra centered at
about 561 cm1and 597 cm1 in both samples indicated the
characteristic stretching vibration of PO43.[43] Moreover,
the bending vibration of PO43 was well presented in WHA
at 962 cm1 (Figure 7A), whereas it was diminished entirely
in CHA particles (Figure 7B) as reported elsewhere.[42]
3.3.2. XRD diffractometry
The selected as-synthesized particles (WM, CM, WHA, and
CHA) were further investigated by X-ray diffraction (XRD)
for the phase purity, crystallinity, and composition, as
shown in Figures 8 and 9. The XRD spectra (Figure 8) for
the as-prepared monetite particles shows the peaks corre-
sponding to 2h values occurred at 13.65 , 26.8 , 30.6 , 33.4 ,
and 40.75 with their respective planes of (001), (200),
(120), (202) and (030). Monetite was the only observable

Figure 8. XRD spectra of the as-prepared monetite particles, (A) WM, and (B) CM.
Figure 9. XRD spectra of the as-prepared particles HA particles (A) WHA
and (B)CHA.
crystalline phase in CM particles (Figure 8B), whereas the
sample WM showed impurity (Figure 8A). Moreover, the
peaks were well-coordinated with JCPDS card num-
ber 70–360.[37]
Furthermore, the diffractograms identified the monetite
having a triclinic structure with lattice parameters a ¼ 6.9,
b ¼ 6.65, c ¼ 7.[44] The whisker shape monetite particles
(WM) showed an additional 2h peak at 12.9 having (100) as
a plane value in contrast to cubic particles of monetite, CM,
which confirmed the presence of brushite (CaHPO4.2H2O)
as impurity due to less aging time.[35]
Similarly, the XRD patterns for the synthesized HA par-
ticles, represented as WHA and CHA, are portrayed in
Figure 9, which illustrated the peaks accredited to the for-
mation of HA. The 2h values were found to be 25.85 ,
31.78 , 32.22 , 34.04 , 39.81 , 46.69 , and 49.52 and the
corresponding planes of the depicted values of 2h were
(002), (211), (112), (202), (130), (222) and (213). These
peaks were well-coordinated with the card no. ICDD (09-
0432) for hydroxyapatite (HAP).[45] The observed
JOURNAL OF DISPERSION SCIENCE AND TECHNOLOGY 9
Figure 10. Adsorption isotherm of WHA (A) and CHA (B) at 77 K, using nitrogen
gas as an adsorbate.
diffractograms identified the material as HA with a hex-
agonal phase having lattice parameters of a ¼ b ¼ 0.9407 nm
and c ¼ 0.6873 nm.[46]
The XRD results revealed that the peak intensity of CM
and CHA increased as compared to their respective
whisker’s morphology due to the increasing aging time,
which powerfully depicted high crystallinity and purity of
the particles of the sample.[45] However, the 2h peaks at 26.9
and 12.9 corresponding to the plane values (200) and
(100)[20] were well pronounced in sample WHA (Figure
9A), whereas these peaks were wholly diminished in CHA
(Figure 9B). These were the residual monetite and brushite
peaks, respectively, which was a precursor phase in the for-
mation of HA. It may be due to the increase in pH during
the synthesis, which produced pure CHA as compared to
WHA as a result of the complete decomposition of urea in
the reaction mixture at a longer aging time.[47]
Furthermore, the average crystallite size of the synthe-
sized particle system was calculated from a well known
Debye- Scherer’s equation (Equation (8)) by using their
XRD spectra (Figures 8 and 9):
Xs ¼ Kk=b cos h [8]
where
Xs is the crystallite size(nm),
And h the diffraction angle,
k the wavelength of monochromatic X-ray beam (nm)
(k ¼ 1.5418 Å) for Cu Ka radiation
b is the full-width half maximum (FWHM) for the diffrac-
tion peak under consideration
The average crystallite size of WM and CM determined
was 11.561 nm and 12.94 nm, respectively. Similarly, 6.1 nm
and 9.71 nm were observed for WHA and CHA, respect-
ively.[43] The crystallite size of hydroxyapatite particle sys-
tems was smaller than their monetite partners, which were
also confirmed from the peak broadness of the HA particles.
10 K. AKHTAR AND C. PERVEZ

3.3.3. Surface area determination
Surface area is a vital structural characterization of the
nanoparticles, and applications of these particles in different
fields such as catalysts, fillers, drug delivery agents, fuel stor-
age and electrical applications, etc. require particle systems
with high surface area.[48]
The surface area of HA particles was calculated by a well-
known BET (Brunauer, Emmet, and Teller) equation.[49] It
can be seen from the determined data (Figure 10) of the
specific surface area that CHA showed high surface area
(137.461 m2/g) compared to WHA (104.485 m2/g) which
revealed the dependency of the surface area with the particle
Figure 11. TGA/DTA curves of the as-prepared whiskers hydroxyapatite par-
ticles (WHA), as shown in Figure 3G.
Figure 12. TGA/DTA curves of the as-prepared cubic hydroxyapatite particles
(CHA), as shown in Figure 3H.
morphology as well as the synthesis route of the HA
particles.[50]
3.3.4. Thermal gravimetric analysis
The thermal behavior of the synthesized uniform particle
systems of hydroxyapatite (WHA & CHA) was performed in
the air between the temperature range of 40–1000  C and at
the heating rate of 10  C/min. The obtained TGA/DTA
results are given in Figures 11 and 12 and Table 2. TGA
analysis of WHA (Figure 11) pointed out the presence of
three weight-loss steps up to 850  C, which marked the loss
of thermally decomposable constituents. Weight loss of 2.1%
occurred just in the initial stages (140  C) accounted for
the desorption of water absorbed on the HA surface[51] fol-
lowed by an abrupt weight loss (6.6%) in the temperature
range of 140 to 450  C which accounted for the vaporization
of lattice water.[51] The third weight loss (0.7%) took place
gradually from 700 to 850  C, accredited for water loss dur-
ing the transformation of HA to Tricalcium phosphate
(TCP-Ca3(PO4)2) as shown in Equation (9).[40] The total
weight loss obtained experimentally (9.4%) was in good
agreement with the weight loss calculated theoretically
(9.8%) from Equation (9).
wt loss¼9:8%
Ca10ðPO4Þ6ðOHÞ2:3=2H2O ƒƒƒƒƒƒ! 3Ca3ðPO4Þ2
[9]
þ CaO þ 5=2H2O
Similarly, TGA/DTA was performed on CHA particles, as
shown in Figure 12. The analysis showed TGA consisted of
three steps. The first gradual weight loss of 6.0% up to
412  C accounted for the desorption of water absorbed on
the HA surface and vaporization of lattice water,[51] followed
by a rapid weight loss of 1.1% for the evaporation of the
interstitial water. The final weight loss (0.2%) in the range
of 750  C to 850  C was owing to the water loss during the
transformation of HA to TCP, as depicted by Equation
(10).[24] The total weight loss of three steps obtained from
TGA analysis (7.3%) agreed well with the weight loss (7.5%)
calculated from the chemical reaction 10.
weight loss¼7:5%
Ca10ðPO4Þ6ðOHÞ2:1=5H2O ƒƒƒƒƒƒƒƒ! 3Ca3ðPO4Þ2
þ CaO þ 6=5H2O
[10]
The DTA represented in Figures 11 and 12 shows an
endothermic peak in the initial stages (100  C) and gradual
weight loss, having no sharp peaks as reported elsewhere.[52]
WHA and CHA were subjected to another heat treatment
experiment in a programable furnace at 900  C by placing

Table 2. TGA weight losses calculated for the as prepared WHA and CHA particles shown in Figure 3G and H respectively.
Total Weight loss (%)

Sample Temperature ( C) Weight loss (%) Experimental (TGA) Theoretical Calcination References
[51]
WHA 30–71 2.1 9.4 9.79 9.44
71–450 6.6
700–850 0.7
[51]
CHA 31–412 6.0 7.3 7.50 7.37
412–550 1.1
750–850 0.2
 JOURNAL OF DISPERSION SCIENCE AND TECHNOLOGY 11

Table 3. Wave number position and IR absorption of different chemical

groups on solid surfaces WTCP and CTCP particles shown in FT-IR (Figure 13).
Band position (cm1)
WTCP CTCP Group Vibration
(Figure 13A) (Figure 13B) species mode References
542 – PO43 Bending [54]

– 561 PO43 Bending [54]

600 600 PO43 Bending [54]

1023 1023 PO43 Stretching [54,55]

1082 – PO43 Stretching [55]

1120 – PO43 Stretching [55]

[56]
3640 3640 CaO Stretching

Figure 13. FT-IR spectra of TCP particles (A) WTCP (whiskers) and
(B)CTCP (cubes).

the synthesized particles in a ceramic crucible for 1 hour at

the heating rate of 10  C/min. Weight loss caused by calcin-
ation of WHA was (9.44%) which was in accordance with
the TGA results (9.4%) and theoretical weight loss(9.8%)
interpreted by reaction 9. Similarly, weight loss caused by
calcination of CHA (7.37%) was in accordance with TGA
analysis (7.3%) and the one calculated theoretically from
reaction 10 (7.5%).
The difference in the weight loss of WHA and CHA par-
ticles was due to the fact that WHA particles consisted of
impurity (monetite and brushite), as shown in XRD analysis
(Figure 9A), which are hydrated compounds. Therefore, the
weight loss due to water in the first two steps of TGA for
WHA (Figure 11) and CHA (Figure 12) particles was differ-
ent, which was accounted for the desorption of water mole-
cules from the test material. Moreover, it has been reported
elsewhere that whisker morphology retained high water con-
tent as compared to the structure of the cube.[53]
3.4. Calcination
To authenticate the phase purity and composition of the
final product of reaction 9 & 10, the calcined WHA and
CHA, i.e., WTCP (Whisker Tricalcium Phosphate) and
CTCP (Cube Tricalcium Phosphate) powders respectively
were further characterized by FT-IR and XRD.
The calcined HA particles, designated as WTCP
(whiskers tricalcium phosphate) and CTCP (cubic tricalcium
phosphate), were analyzed by FT-IR spectroscopy and the
obtained spectra are given in Figure 13. It clearly demon-
strated the presence of the relevant PO43 functional group.
The IR spectra centered at 542 and 600 cm1 in WTCP
(Figure 13A) and at 561 and 600 cm1 in CTCP (Figure
13B), which indicated the characteristic bending vibration of
PO43.[54] Moreover, the distinguishing peaks of TCP repre-
senting stretching vibration of the PO43 group ranging
from 1000 to 1120 cm1 [54] were present in both samples.
However, CTCP showed the peak only at 1023 cm1,
whereas WTCP demonstrated peaks at 1023, 1082, and
Figure 14. XRD spectra of TCP particles with different morphology (A) WTCP
(whiskers) and (B) CTCP (cubes).
1120 cm1 falling in the same range (Table 3). The splitting
of the PO43 group has been reported elsewhere, which usu-
ally occurred due to the splitting site-symmetry of the
degenerate modes when PO43 groups arranged itself to
attain structurally ordered symmetry.[55] CaO was formed in
addition to TCP in both samples; therefore, CaO stretching
peak was located at 3640 cm1.[56]
The calcined HA particle samples (WTCP and CTCP)
were further investigated by XRD, as shown in Figure 14.
The peaks corresponding to 2h values at 25.8 , 27.7 , 31.02 ,
32.4 , 34.3 , 46.6 , 49.7 , 53.5 , and their respective planes
were (002), (214), (210), (200), (202), (222), (213) and (301).
bTCP was the only observable crystalline phase noted dur-
ing the XRD analysis of CTCP whereas WTCP particles
showed the trace amount of aTCP. The peak at 2h d-spacing
d210 value in CTCP became intense in Figure 14 showing
the formation of pure bTCP. Whereas four conjugated peaks
appeared at the same position (Figure 14A) pointed to the
presence of small traces of aTCP in WTCP sample[57] as
was observed in its precursors, i.e., WM (XRD, Figure 8A),
and WHA (XRD, Figure 9A). Furthermore, it can be seen
the XRD peaks in WTCP having d-spacing values 002, 214,
202, 222, 301 were broad and ill-defined which were indica-
tive of weak scattering.[14] Also, due to the high-temperature
treatment of WTCP, d values shifted to slightly higher val-
ues as a result of impurity which indicated a reduction of
interlayer spacing values.[58] Moreover, the peaks shown in
Figure 14A, B were well-coordinated with JCPDS card
12 K. AKHTAR AND C. PERVEZ
number 09-0169. Furthermore, the diffractograms identified
bTCP having a rhombohedral structure with lattice parame-
ters a ¼ b ¼ 1.0434, c ¼ 3.7409.[55]
Besides, the XRD results (Figure 14) revealed that CTCP
depicted high crystallinity and purity of the particles.[45]
Therefore, some observable difference was noted in the
intensity of the recorded peaks. For instance, the peaks cor-
responding to 2h at 28.05 and 31.08 (Figure 14B) were
higher in intensity compared to the peaks at the same 2h
position for WTCP (Figure 14A) which demonstrated high
crystallinity of the cubic shape tricalcium phosphate.
However, some active lime CaO appeared in small amounts
corresponding to 2h value at 39.8 with the plane (121) in
the XRD (Figure 14A, B) confirmed the suggested chemical
reactions (Reaction 9-10) for heat treatment.[53] The average
crystallite size of WTCP and CTCP calculated by the
Scherer’s equation (Equation (8)) from the intense peaks of
the XRD (Figure 14) was nearly the same (10.98 nm and
11 nm respectively) which showed that the crystallite size in
case of TCP was unaffected by the particle morphology.
4. Conclusions
Within the limitation of this research, the succeeding con-
clusions were extracted from the preliminary study.
 Synthesis through homogenous precipitation ensured
uniformity, monodispersity, and easy fabrication route.
 Tuning of the technological parameters affected the uni-
formity and morphology of the resulted particles.
 Reproducible recipes for the synthesis of uniform par-
ticles in whiskers and cubic shapes were explored under
extensive optimization of the experimental parameters.
 Aging time showed a sensitive dependence on the
morphology of HA particles, and a tentative mechanism
was deduced to explain its effect.
 The pH of the solution had a vital role in HA formation,
and phase purity as low pH resulted in the formation of
various crystal phases of calcium phosphate, which
served as a precursor.
Acknowledgments
The authors appreciatively acknowledged the National Center of
Excellence in Physical Chemistry, University of Peshawar, and Higher
Education Commission (HEC), Islamabad, Pakistan, for assisting this
research work.
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