Physica B 405 (2010) 4256–4261

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Physica B
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X-ray peak broadening studies of nanocrystalline hydroxyapatite

by Williamson–Hall analysis
K. Venkateswarlu a,b, A. Chandra Bose b, N. Rameshbabu a,n
a
Department of Metallurgical and Materials Engineering, National Institute of Technology, Tiruchirappalli 620 015, Tamilnadu, India
b
Department of Physics, National Institute of Technology, Tiruchirappalli 620 015, Tamilnadu, India

a r t i c l e in f o a b s t r a c t

Article history: Hydroxyapatite (HA) nanoparticles were prepared by microwave synthesis method and the obtained
Received 4 June 2010 powder is annealed at 800 1C for 2 h. The annealed HA particles were characterized by X-ray diffraction
Received in revised form (XRD) and Fourier transform infrared (FTIR) spectroscopy methods. The HA size and morphology were
8 July 2010
examined using a transmission electron microscope (TEM). The XRD results reveal that the diffraction
Accepted 10 July 2010
peaks of the annealed HA were of well crystalline and correspond to the hexagonal crystal structure.
The XRD and FTIR results confirm the absence of secondary phases such as b-tricalcium phosphate
Keywords: (b-TCP) and calcium oxide in annealed HA particles. The TEM result confirms the hexagonal structure of
Hydroxyapatite annealed HA and the particles were observed to be of ellipsoid-like shaped morphology with less
Microwave synthesis
agglomeration. The lattice strain, crystallite size, lattice deformation stress and deformation energy
Crystal structure
density for annealed (800 1C) HA nanoparticles were estimated by Williamson–Hall-isotropic strain
X-ray diffraction
Anisotropy model (W–H-ISM), W–H-anisotropic strain model (W–H-ASM) and W–H-energy density model (W–H-
EDM) based on Williamson–Hall (W–H) plot from powder X-ray diffraction data. The results of
estimated average crystallite size of annealed HA by Scherrer and W–H plot methods were compared
with TEM results. It is found that the average crystallite size measured by W–H plot methods is in good
agreement with TEM results.
& 2010 Elsevier B.V. All rights reserved.

1. Introduction width of the diffraction peak. But Scherrer’s formula under-

Hydroxyapatite [HA, Ca10(PO4)6(OH)2], a major mineral com-
ponent of natural bone, has been successfully applied in
orthopedic and dental implant applications for several years due
to its excellent biocompatibility [1]. It has also been applied in
non-medical fields, such as gas sensors, catalysis and host
material for lasers [2]. In most of the cases in nanomaterials
(such as hydroxyapatite), in comparison with micron size
materials, the densification and fracture toughness are higher
[3]. It has also been found that nanoscale particles (1–100 nm)
usually have physical properties different from those of bulk
particles (10–100 mm). They exhibit a variety of interesting
properties including magnetic, optical and other physical proper-
ties as well as surface reactivity depending on particle size [4].
Hence for complete understanding of nanoscale material proper-
ties, the crystallite size need to be calculated correctly. Out of all
the methods available for the calculation of crystallite size
Scherrer’s method is a well known method that uses X-ray
diffraction patterns to predict the size of crystallites based on the
n in the nanomaterial affects the crystallite size measurement. In
Corresponding author. Tel.: +91 431 2503464; fax: + 91 431 2500133.
E-mail addresses: rameshrohith@gmail.com, nrb@nitt.edu (N. Rameshbabu).
estimates or provides only lower bound to the crystallite size
because it has not taken account of peak broadening resulting
from other important factors such as inhomogeneous strain and
instrumental effects. If the peak broadening contributions from
these other factors were zero, then the peak width would be
determined solely by the crystallite size and the Scherrer’s
formula would be applicable. If the other contributions to the
width were non-zero, then the crystallite size can be larger than
that predicted by the Scherrer’s formula. Unlike Scherrer’s
method, X-ray diffraction peak profile analysis takes into account
peak broadening resulting from the above said other important
factors and has been widely used to calculate the grain size, lattice
distortion, twinning, stacking fault probabilities and long-range
and root mean square stresses in nanocrystalline materials [5–7].
Apart from these, various analytical methods are being used to
estimate the crystallite size and lattice strain present in the
material from X-ray peak broadening [8].
In nanomaterials both crystallite size and lattice strain have
their own contribution to X-ray diffraction peak broadening and
the peak broadening contributed by lattice strain is due to
large volume of grain boundaries [9,10]. Hence the strain present
order to measure the crystallite size correctly and to study the

0921-4526/$ - see front matter & 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.physb.2010.07.020
 K. Venkateswarlu et al. / Physica B 405 (2010) 4256–4261 4257

modifications introduced by strain in the properties of nanoma-
terials, strain calculations are required [11]. However, fitting the
powder diffraction data completely and accurately is complicated
and hence it attracts many indirect methods such as Williamson–
Hall method and Warren–Averbach analysis for estimating the
lattice strain and crystallite size [12,13]. In Warren–Averbach
analysis the intensity of the diffracted X-ray beam is calculated in
Fourier space and this intensity is considered as a value given by
the convolution of size and strain broadening [14]. Whereas W–H
analysis is a simplified method that clearly differentiates between
size induced and strain induced peak broadening by considering
the peak width as a function of 2y [15].
The objective of this work is to calculate the crystallite size of
nanocrystalline annealed HA particles more accurately from
powder X-ray diffraction data by considering the contributions
of other important factors, namely instrumental and lattice strain
effects to the X-ray peak broadening. In addition, other micro-
structural parameters such as lattice strain, lattice deformation
stress and deformation energy density present in the annealed HA
nanoparticles were estimated based on conventional W–H plot
using W–H-ISM, W–H-ASM and W–H-EDM models. From the
crystallite size values obtained from Scherrer and W–H methods,
it is observed that there is significant effect of lattice strain on
crystallite size estimated from X-ray diffraction data, which is
further confirmed by the good agreement between the crystallite
size values obtained from W–H and TEM analyses.
2. Experimental
2.1. Synthesis of HA nanoparticles
Analytical grade calcium hydroxide [Ca (OH)2, E. Merck,
Germany] and di-ammonium hydrogen phosphate [DAP,
(NH4)2HPO4, E. Merck, Germany] were used for the preparation of
HA nanoparticles by microwave synthesis method. The amount of
the reactants is calculated based on the Ca/P molar ratio of 10/6. The
0.3 M DAP solution in a glass beaker is added to the 0.3 M calcium
hydroxide aqueous suspension in 1000 ml glass beaker in 1 min
under high-speed stirring conditions. This 1000 ml glass beaker
containing the precursor mixture with pH of about 11 (Orion 3 star,
Thermo electron, USA) is immediately subjected to the microwave
irradiation for an optimized time of 30 min [16] in a domestic
microwave oven (Samsung India, 2.45 GHz, 850 W power). The
mixing, crystallization of HA and its aging occur under the
microwave irradiation in a shorter period. The product obtained
after filtration is dried at 80 1C for 24 h and the cake obtained after
drying was powdered with agate mortar and pestle. The as-
synthesized HA powder particles were annealed at 800 1C for 2 h.
radiation (l ¼ 1.54056 Å) over the 2y range of 20–601, using a step
size of 0.021 and step time of 4 s. The diffraction pattern of
annealed HA sample consists of well defined peaks. The isolated
and preferred high intensity peaks (shown in Table 1)
corresponding to higher diffraction angle were chosen to
estimate crystallite size and lattice strain by various models
based on the W–H plot. The functional groups present in as-
synthesized and annealed HA were ascertained by Fourier
transform infrared spectroscopy (FTIR, Perkin Elmer, Spectrum
One, USA) over the region 450–4000 cm  1 in pellet form for the
powder samples of 1 mg mixed with spectroscopic grade KBr
(Merck) of 200 mg. Spectra were recorded at 4 cm  1 resolution,
averaging 80 scans. The size and the crystal structure of the
annealed HA powders were analyzed by transmission electron
microscope (TEM, Philips, CM12 STEM, Netherlands). For TEM
analysis, the powder sample was ultrasonically dispersed in
ethanol to form dilute suspensions, and then few drops were
deposited on the carbon-coated copper grids. Electron diffraction
patterns were obtained in microprobe mode with 10 mm selected-
area aperture.
3. Results and discussion
3.1. XRD and FTIR analyses of HA nanoparticles
The XRD pattern of annealed HA sample is shown in Fig. 1(a).
The annealed HA sample exhibits several diffraction peaks, which
can be indexed as hexagonal HA. Since the HA nanoparticles were
prepared using precursor materials with stoichiometric Ca/P
molar ratio of 10/6 and in favorable synthesis conditions
[17,18], such as basic pH (pH  11), temperature above 90 1C,
suitable microwave irradiation power (850 W) and irradiation
time (30 min), no impurity peaks such as calcium oxide (CaO) or
b-TCP were detected in the diffraction pattern after annealing.
The presence of impurities, if any, was below the detection limit
and hence the annealed HA is greater than 95 wt% phase pure and
is acceptable for surgical implant applications as per standards
(ASTM F 1185-03). Generally the favorable synthesis conditions
increase the Ca/P molar ratio of the precipitated HA, which in turn
increases its thermal stability at high temperatures. This suggests
that the prepared HA particles were thermally stable under the
performed annealing conditions. As compared to the broad X-ray

2.2. Characterization of prepared powder

The X-ray diffraction is carried out for these powder particles

using a Rigaku Ultima III X-ray diffractometer with Cu Ka1

Table 1
Young’s modulus and strain calculation of annealed HA nanoparticles.

hkl Ehkl (GPa) W–H-ASM W–H-EDM

Strain  10  3 Strain  10  3

210 133 0.3909 0.1819

202 175 0.2971 0.1382
310 133 0.3909 0.1819
113 120 0.4333 0.2016
213 140 0.3714 0.1728
004 91 0.5714 0.2659 Fig. 1. X-ray diffraction pattern of hydroxyapatite annealed at 800 1C for 2 h
(a) and as-synthesized hydroxyapatite (b).
4258 K. Venkateswarlu et al. / Physica B 405 (2010) 4256–4261
Fig. 2. FTIR spectra of as-synthesized hydroxyapatite (a) and hydroxyapatite
annealed at 800 1C for 2 h (b).
diffraction peaks of HA nanoparticles in as-synthesized condition
(Fig. 1(b)), the diffraction peaks of the annealed HA particles
(Fig. 1(a)) were narrow and well separated. It confirms that the
sample is of improved crystallanity and increased crystallite size.
The absence of impurities and an increase in crystallinity of
annealed HA nanoparticles are also proved by FTIR analysis. The
FTIR spectra of as-synthesized and annealed HA were shown in
Fig. 2(a) and (b), respectively. The characteristic bands for HA
were exhibited in both the spectra: 900–1200 cm  1 for
phosphate bending and stretching; 602 cm  1 for phosphate
bending; and 632 cm  1 and 3571 cm  1 for librational and
stretching modes of hydroxyl vibrations. The intensities of both
the hydroxyl bands and the band at 962 cm  1 for phosphate can
be used to indicate the crystallinity of HA [19]. The intensities of
these bands increased with annealing treatment and this result
coincides with the XRD results as shown in Fig. 1. In addition, the
absence of the broad bands at 1630 and 3400 cm  1 in annealed
HA is due to the removal of adsorbed water with the annealing
treatment. The broadening of the phosphate characteristic bands
near 1040 and 1090 cm  1 is due to low crystallinity and small
dimensional effect of as-prepared HA particles [20]. In the case of
annealed HA particles, the phosphate characteristic bands near
962, 1040 and 1090 cm  1 and hydroxyl band at 632 cm  1 are
comparatively sharp, which indicates improved crystallinity. No
absorption bands at 873, 1421 and 1455 cm  1 corresponding to
the presence of carbonate ions, which may come from a reaction
between carbon dioxide in air and high pH precursor solution
[21], were found in the annealed HA compared to as-synthesized
HA particles. It is found that the human bone or synthetic HA
when heated above 700 1C readily lose their carbonate ions [22].
The absence of carbonate bands in sample, annealed at 800 1C in
the present study, is also due to the loss of carbonate ions during
heating in air.
3.2. Determination of crystallite size by Scherrer analysis
Generally, the X-ray diffraction peak broadening is due to the
instrumental broadening, broadening due to crystallite size and
lattice strain present in the material. The contributions of each of
these effects are convoluted causing an overall broadening of the
diffraction peaks. Before estimating the crystallite size and
lattice strain, it is necessary to correct the instrumental effect.
The instrumental corrected broadening bhkl [23] corresponding
to the diffraction peak of HA was estimated using the equation
2 2 1=2
bhkl ¼ ½ðbh k l Þmeasured ðbÞinstrumental  ð1Þ
It is well known that the Scherrer’s formula provides only the
lower bound to the crystallite size. Here the crystallite size value
is calculated using Scherrer’s formula to compare with the values
obtained from the W–H models and TEM analysis results.
The crystallite size Dv of annealed HA is estimated from the
Scherrer’s equation [24] as
kl
Dv ¼ ð2Þ
bhkl cos yhkl
where Dv is the volume weighted crystallite size (nm); k is the
shape factor (k¼ 0.9), l is the wave length of the X-rays
(l ¼0.154056 nm for Cu Ka radiation); yhkl is Bragg diffraction
angle (1) and bhkl is the broadening of the hkl diffraction peak
measured at half of its maximum intensity (in radians). The
volume weighted crystallite size Dv measured using Scherrer’s
formula is found to be 65 nm.
3.3. Estimation of lattice strain (e) and crystallite size (Dv)
by W–H-ISM
In addition to the instrumental X-ray peak broadening, lattice
strain and crystallite size are the other two independent factors
that contribute to the total peak broadening. The strain induced
line broadening bs is given by the relationbs ¼ 4e tan yhkl . Now the
total peak broadening is represented by the sum of the
contributions of crystallite size and strain present in the material.
Assuming that the strain present in the material is uniform, thus
considering the isotropic nature of the crystal, the W–H equation
[25] for the total peak broadening is given by
Kl
bhkl cos yhkl ¼ þ4e sin yhkl ð3Þ
Dv
where K is the shape factor and Dv is volume weighted crystallite
size. A plot is drawn by taking 4sin yhkl along X-axis and
bhkl cos yhkl along Y-axis as shown in Fig. 3. In W–H-ISM model,
the strain present in the material and the crystallite size are,
respectively, extracted from the slope and the intercept of the
linear fit made to the plot. The estimated values of the strain
and the crystallite size are given by 4.9436  10  4 and 97 nm,
respectively. From Fig. 3, it seems that the conventional
Fig. 3. W–H-ISM plot of annealed nanocrystalline hydroxyapatite.
 K. Venkateswarlu et al. / Physica B 405 (2010) 4256–4261
Fig. 4. W–H-ASM plot of annealed nanocrystalline hydroxyapatite.
W–H-ISM model is an appropriate approach for the estimation of
lattice strain due to less scatter of data points from the linear fit.
The better fit of the experimental data points confirms the
uniformity of the lattice strain.
3.4. Estimation of lattice deformation stress (s) and crystallite size
(Dv) by W–H-ASM
According to Hook’s law, within elastic limit, there exists linear
proportionality relation between stress and strain and is given by
s ¼Ee where E is the constant of proportionality being the modulus
of elasticity or Young’s modulus. This equation is merely an
approximation that is valid for significantly small strain. Assuming
a small strain to be present in the annealed HA particles, Hook’s
law can be applied to estimate the lattice deformation stress to a
reasonable approximation. Beyond the elastic limit or with a
further increase in strain, the stress in the particles deviate from
this linear proportionality. Hence by assuming that the lattice
deformation stress is uniform in all crystallographic directions, the
strain factor in the second term of Eq. (3) is replaced by e ¼ s/Ehkl
and the modified equation is given by
K l 4s sin yhkl
bhkl cos yhkl ¼ þ ð4Þ
Dv Ehkl
Here Ehkl is Young’s modulus in the direction normal to the set of
(h k l) crystal lattice planes.
The crystallographic direction dependent Young’s modulus in
hexagonal crystals [26] is given by
½h2 þ ððh þ2kÞ2 =3Þ þðal=cÞ2 2
Ehkl ¼
s11 ðh2 þðh þ2kÞ2 =3Þ2 þs 4 2
33 ðal=cÞ þð2s13 þ s44 Þðh þðh þ2kÞ =3Þðal=cÞ
Here s11, s33, s44 and s13 are the elastic compliances and their
standard hand book values are 7.49  10  12, 10.9  10  12,
15.1  10  12 and  4.0  10  12, respectively [27]. A plot is drawn
by taking 4 sin yhkl =Ehkl along X-axis and bhkl cos yhkl along Y-axis as
shown in Fig. 4. The lattice deformation stress and crystallite size
were, respectively, extracted from the slope and intersection of
the linear fit made to the plot. The crystallite size estimated by
W–H-ASM is 92 nm and the estimated deformed stress is 52 MPa.
Under the assumption of uniform lattice deformation stress made
earlier, the anisotropic strain can be estimated using the relation
ehkl ¼ s=Ehkl . From Fig. 4, it can be observed that though there is a
small scatter of experimental data points nearer to the linear fit, it
4259
Fig. 5. W–H-EDM plot of annealed nanocrystalline hydroxyapatite.
allows the uniformity of the stress to a reasonable approximation.
Here, the scatter of data points from the linear fit is due to the
introduction of anisotropic Young’s modulus in Eq. 4.
3.5. Estimation of deformation energy density by W–H-EDM
In Eq. (3), it is considered the homogeneous isotropic nature of
the crystal which, in many cases, is not fulfilled. Moreover, all the
constants proportionality associated with the stress–strain rela-
tion are no longer independent when the lattice strain energy
density u is considered. According to Hook’s law u ¼ e2 Ehkl =2, and
therefore, the modified W–H-ASM equation can be expressed as
"   #
Kl 2 1=2 1=2
bhkl cos yhkl ¼ þ 4 sin yhkl u ð6Þ
Dv Ehkl
The graph drawn between bhkl cos yhkl and 4½sin yhkl ð2=Ehkl Þ1=2 
is shown in Fig. 5.
The uniform lattice deformation energy density u is estimated
from the slope and the crystallite size is estimated from the
intersection of the linear fit made to the graph. From Eqs. (4) and
(6), the deformation stress and energy density are related
asu ¼ s2 hkl =2Ehkl . It can be noted that in both Eqs. (4) and (6)
the anisotropic nature of the elastic constants has been taken into
account. In Eq. (4), it is assumed that the lattice deformation
stress has the same value in all crystallographic directions
allowing the deformation energy to be anisotropic whereas in
Eq. (6), the deformation energy density is assumed to have
the same value in all crystallographic directions allowing the
deformation stress to be anisotropic. However, W–H plots drawn
2
2
using Eqs. (4) and (6) are virtually the same. For a given sample,
ð5Þ W–H plots can be plotted using Eqs. (3), (4) and (6) and the
appropriate model can be chosen based on the best fit of the
experimental data. In the present study the root mean square
error (RMSE) or standard deviation (SD) of experimental data
points from the ideal linear fit for W–H-ISM (Fig. 3), W–H-ASM
(Fig. 4) and W–H-EDM (Fig. 5) is given by 1.44  10  5, 8.32  10  5
and 7.54  10  5, respectively. Though the data points seem to be
visually scattered from the W–H plots, the standard deviation
data show that the scatter from the linear fit is of the order
of 10  5 in case of the three W–H models. This much less signifi-
cant SD from the linear fit of the three models supports that
the assumptions made in the present analysis are acceptable in
a reasonable approximation. However, the scattering of the
4260 K. Venkateswarlu et al. / Physica B 405 (2010) 4256–4261

experimental data pointing away from the linear fit is very much the electron beam interacts with matter. Elastic scattering can be
less significant in W–H-ISM (Fig. 3) compared to W–H-ASM both coherent with a phase relationship and incoherent without a
(Fig. 4) and W–H-EDM (Fig. 5). This confirms that the uniformity phase relationship among the scattered electrons. Elastic scatter-
of the lattice strain is more than that of lattice deformation stress ing occurring from well-ordered arrangements of atoms as in a
and deformation energy density. Since the data points are close to crystal results in coherent scattering and gives spot pattern. If the
the linear fit in all the three models, the estimated crystallite size crystals in the material were randomly oriented as in the case
is in agreement with the TEM results as discussed in Section 3.6. of a polycrystalline material, the elastic scattering results in a ring
The crystallite size, lattice strain, deformation stress and defor- pattern. The TEM micrograph and the selected area electron
mation energy density are estimated by following the linear fit diffraction (SAED) pattern of annealed HA particles were shown in
procedure in all the three models. Especially the crystallite size is Fig. 6(a) and (b), respectively. It is observed that the annealed HA
estimated from the intercept made by the linear fit with Y-axis. is of ellipsoid-like shaped morphology. The crystallite size of
The intercept value depends on the distribution of the data points, annealed HA is estimated from TEM images by image analysis
which in turn affects the crystallite size to be estimated. Also, the done with a freely available IMAGE J software and the estimated
distribution of data points with respect to the linear fit depends average crystallite size is 95710 nm (mean7SD). The SAED
on its number of points. It suggests that the estimation of the pattern confirms the crystalline structure of hexagonal HA and is
crystallite size by linear fit procedure depends on the number of in agreement with the XRD results.
peaks taken for the analysis [23]. The calculated anisotropic
Young’s modulus and lattice strain values are listed in Table 1 and
the estimated crystallite size, lattice strain, lattice deformation 4. Conclusions
stress and deformation energy density values from W–H analysis
are listed in Table 2.
Pure nanocrystalline HA is successfully synthesized by micro-
wave method using precursor materials with calcium:phosphor-
3.6. TEM analysis of nanocrystalline hydroxyapatite ous molar ratio of 10:6. There is a significant difference between
obtained crystallite size value by the Scherrer analysis and the
TEM analysis. There is a good agreement between the crystallite
In TEM, the transmitted electron beam is used to create an
size values obtained by W–H-ISM, W–H-ASM and W–H-EDM
image of the sample. Elastic or inelastic scattering occurs when
models and that obtained by TEM analysis. Hence, W–H analysis
by the three models results in more accurate estimation of
Table 2
The estimated microstructural parameters of annealed HA nanoparticles.
crystallite size compared to Scherrer analysis. Therefore it is
suggested that the contribution from instrumental effects and
Method Parameter (unit) Estimated values lattice strain effect to the X-ray peak broadening need to be
considered while calculating the crystallite size value of nano-
Scherrer analysis Dv (nm) 65
materials. Within the materials elastic limit, the W–H models can
Dv (nm) 97
W–H-ISM e  10  3(no unit) 0.4943 be applied to estimate other microstructural parameters such as
Dv (nm) 92 lattice strain, lattice deformation stress and lattice deformation
W–H analysis W–H-ASM
s (MPa) 52 energy density in a reasonable approximation. The crystallite size
Dv (nm) 95 and the lattice strain values obtained from the W–H-ISM model
W–H-EDM
u (kJ m  3) 12
TEM analysis Dv (nm) 957 10
can be further extended to estimate the dislocation densities
present in the material with more accuracy.

Fig. 6. TEM micrograph (a) and SAED pattern (b) of annealed nanocrystalline hydroxyapatite.
 K. Venkateswarlu et al. / Physica B 405 (2010) 4256–4261 4261

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