Physica B 405 (2010) 42564261

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Physica B
journal homepage: www.elsevier.com/locate/physb

X-ray peak broadening studies of nanocrystalline hydroxyapatite by WilliamsonHall analysis

K. Venkateswarlu a,b, A. Chandra Bose b, N. Rameshbabu a,n
a b

Department of Metallurgical and Materials Engineering, National Institute of Technology, Tiruchirappalli 620 015, Tamilnadu, India Department of Physics, National Institute of Technology, Tiruchirappalli 620 015, Tamilnadu, India

a r t i c l e in f o
Article history: Received 4 June 2010 Received in revised form 8 July 2010 Accepted 10 July 2010 Keywords: Hydroxyapatite Microwave synthesis Crystal structure X-ray diffraction Anisotropy

a b s t r a c t
Hydroxyapatite (HA) nanoparticles were prepared by microwave synthesis method and the obtained powder is annealed at 800 1C for 2 h. The annealed HA particles were characterized by X-ray diffraction (XRD) and Fourier transform infrared (FTIR) spectroscopy methods. The HA size and morphology were examined using a transmission electron microscope (TEM). The XRD results reveal that the diffraction peaks of the annealed HA were of well crystalline and correspond to the hexagonal crystal structure. The XRD and FTIR results conrm the absence of secondary phases such as b-tricalcium phosphate (b-TCP) and calcium oxide in annealed HA particles. The TEM result conrms the hexagonal structure of annealed HA and the particles were observed to be of ellipsoid-like shaped morphology with less agglomeration. The lattice strain, crystallite size, lattice deformation stress and deformation energy density for annealed (800 1C) HA nanoparticles were estimated by WilliamsonHall-isotropic strain model (WH-ISM), WH-anisotropic strain model (WH-ASM) and WH-energy density model (WHEDM) based on WilliamsonHall (WH) plot from powder X-ray diffraction data. The results of estimated average crystallite size of annealed HA by Scherrer and WH plot methods were compared with TEM results. It is found that the average crystallite size measured by WH plot methods is in good agreement with TEM results. & 2010 Elsevier B.V. All rights reserved.

1. Introduction Hydroxyapatite [HA, Ca10(PO4)6(OH)2], a major mineral component 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 elds, 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 densication and fracture toughness are higher [3]. It has also been found that nanoscale particles (1100 nm) usually have physical properties different from those of bulk particles (10100 mm). They exhibit a variety of interesting properties including magnetic, optical and other physical properties as well as surface reactivity depending on particle size [4]. Hence for complete understanding of nanoscale material properties, the crystallite size need to be calculated correctly. Out of all the methods available for the calculation of crystallite size Scherrers method is a well known method that uses X-ray diffraction patterns to predict the size of crystallites based on the

Corresponding author. Tel.: +91 431 2503464; fax: + 91 431 2500133. E-mail addresses: rameshrohith@gmail.com, nrb@nitt.edu (N. Rameshbabu).

width of the diffraction peak. But Scherrers formula underestimates 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 Scherrers 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 Scherrers formula. Unlike Scherrers method, X-ray diffraction peak prole 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 [57]. 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 in the nanomaterial affects the crystallite size measurement. In 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

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modications introduced by strain in the properties of nanomaterials, strain calculations are required [11]. However, tting the powder diffraction data completely and accurately is complicated and hence it attracts many indirect methods such as Williamson Hall method and WarrenAverbach analysis for estimating the lattice strain and crystallite size [12,13]. In WarrenAverbach 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 WH analysis is a simplied 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 microstructural parameters such as lattice strain, lattice deformation stress and deformation energy density present in the annealed HA nanoparticles were estimated based on conventional WH plot using WH-ISM, WH-ASM and WH-EDM models. From the crystallite size values obtained from Scherrer and WH methods, it is observed that there is signicant effect of lattice strain on crystallite size estimated from X-ray diffraction data, which is further conrmed by the good agreement between the crystallite size values obtained from WH and TEM analyses.

over the 2y range of 20601, using a step radiation (l 1.54056 A) size of 0.021 and step time of 4 s. The diffraction pattern of annealed HA sample consists of well dened 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 WH plot. The functional groups present in assynthesized and annealed HA were ascertained by Fourier transform infrared spectroscopy (FTIR, Perkin Elmer, Spectrum One, USA) over the region 4504000 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 selectedarea 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. 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 ltration is dried at 80 1C for 24 h and the cake obtained after drying was powdered with agate mortar and pestle. The assynthesized HA powder particles were annealed at 800 1C for 2 h. 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 Youngs modulus and strain calculation of annealed HA nanoparticles. hkl Ehkl (GPa) WH-ASM Strain 10 3 0.3909 0.2971 0.3909 0.4333 0.3714 0.5714 WH-EDM Strain 10 3 0.1819 0.1382 0.1819 0.2016 0.1728 0.2659

210 202 310 113 213 004

133 175 133 120 140 91

Fig. 1. X-ray diffraction pattern of hydroxyapatite annealed at 800 1C for 2 h (a) and as-synthesized hydroxyapatite (b).

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The instrumental corrected broadening bhkl [23] corresponding to the diffraction peak of HA was estimated using the equation

bhkl bh

2 2 1=2 k l measured binstrumental

It is well known that the Scherrers formula provides only the lower bound to the crystallite size. Here the crystallite size value is calculated using Scherrers formula to compare with the values obtained from the WH models and TEM analysis results. The crystallite size Dv of annealed HA is estimated from the Scherrers equation [24] as Dv kl bhkl cos yhkl 2

where Dv is the volume weighted crystallite size (nm); k is the shape factor (k 0.9), l is the wave length of the X-rays (l 0.154056 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 Scherrers formula is found to be 65 nm.
Fig. 2. FTIR spectra of as-synthesized hydroxyapatite (a) and hydroxyapatite annealed at 800 1C for 2 h (b).

3.3. Estimation of lattice strain (e) and crystallite size (Dv) by WH-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 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 WH equation [25] for the total peak broadening is given by

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 conrms 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: 9001200 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.

bhkl cos yhkl

Kl 4e sin yhkl 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 WH-ISM model, the strain present in the material and the crystallite size are, respectively, extracted from the slope and the intercept of the linear t 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. WH-ISM plot of annealed nanocrystalline hydroxyapatite.

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Fig. 4. WH-ASM plot of annealed nanocrystalline hydroxyapatite.

Fig. 5. WH-EDM plot of annealed nanocrystalline hydroxyapatite.

WH-ISM model is an appropriate approach for the estimation of lattice strain due to less scatter of data points from the linear t. The better t of the experimental data points conrms the uniformity of the lattice strain. 3.4. Estimation of lattice deformation stress (s) and crystallite size (Dv) by WH-ASM According to Hooks law, within elastic limit, there exists linear proportionality relation between stress and strain and is given by s Ee where E is the constant of proportionality being the modulus of elasticity or Youngs modulus. This equation is merely an approximation that is valid for signicantly small strain. Assuming a small strain to be present in the annealed HA particles, Hooks 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 s/Ehkl and the modied equation is given by

allows the uniformity of the stress to a reasonable approximation. Here, the scatter of data points from the linear t is due to the introduction of anisotropic Youngs modulus in Eq. 4. 3.5. Estimation of deformation energy density by WH-EDM In Eq. (3), it is considered the homogeneous isotropic nature of the crystal which, in many cases, is not fullled. Moreover, all the constants proportionality associated with the stressstrain relation are no longer independent when the lattice strain energy density u is considered. According to Hooks law u e2 Ehkl =2, and therefore, the modied WH-ASM equation can be expressed as "   # Kl 2 1=2 1=2 bhkl cos yhkl 4 sin yhkl 6 u Ehkl Dv The graph drawn between bhkl cos yhkl and 4sin yhkl 2=Ehkl 1=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 t made to the graph. From Eqs. (4) and (6), the deformation stress and energy density are related asu 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, WH plots drawn using Eqs. (4) and (6) are virtually the same. For a given sample, WH plots can be plotted using Eqs. (3), (4) and (6) and the appropriate model can be chosen based on the best t 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 t for WH-ISM (Fig. 3), WH-ASM (Fig. 4) and WH-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 WH plots, the standard deviation data show that the scatter from the linear t is of the order of 10 5 in case of the three WH models. This much less signicant SD from the linear t of the three models supports that the assumptions made in the present analysis are acceptable in a reasonable approximation. However, the scattering of the

bhkl cos yhkl

K l 4s sin yhkl Dv Ehkl

Here Ehkl is Youngs modulus in the direction normal to the set of (h k l) crystal lattice planes. The crystallographic direction dependent Youngs modulus in hexagonal crystals [26] is given by
Ehkl h2 h 2k2 =3 al=c2 2 s11 h2 h 2k2 =32 s
4 2 2 2 33 al=c 2s13 s44 h h 2k =3al=c

5 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 t made to the plot. The crystallite size estimated by WH-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 s=Ehkl . From Fig. 4, it can be observed that though there is a small scatter of experimental data points nearer to the linear t, it

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experimental data pointing away from the linear t is very much less signicant in WH-ISM (Fig. 3) compared to WH-ASM (Fig. 4) and WH-EDM (Fig. 5). This conrms that the uniformity of the lattice strain is more than that of lattice deformation stress and deformation energy density. Since the data points are close to the linear t in all the three models, the estimated crystallite size is in agreement with the TEM results as discussed in Section 3.6. The crystallite size, lattice strain, deformation stress and deformation energy density are estimated by following the linear t procedure in all the three models. Especially the crystallite size is estimated from the intercept made by the linear t with Y-axis. The intercept value depends on the distribution of the data points, which in turn affects the crystallite size to be estimated. Also, the distribution of data points with respect to the linear t depends on its number of points. It suggests that the estimation of the crystallite size by linear t procedure depends on the number of peaks taken for the analysis [23]. The calculated anisotropic Youngs modulus and lattice strain values are listed in Table 1 and the estimated crystallite size, lattice strain, lattice deformation stress and deformation energy density values from WH analysis are listed in Table 2.

the electron beam interacts with matter. Elastic scattering can be both coherent with a phase relationship and incoherent without a phase relationship among the scattered electrons. Elastic scattering occurring from well-ordered arrangements of atoms as in a crystal results in coherent scattering and gives spot pattern. If the crystals in the material were randomly oriented as in the case of a polycrystalline material, the elastic scattering results in a ring pattern. The TEM micrograph and the selected area electron diffraction (SAED) pattern of annealed HA particles were shown in Fig. 6(a) and (b), respectively. It is observed that the annealed HA is of ellipsoid-like shaped morphology. The crystallite size of annealed HA is estimated from TEM images by image analysis done with a freely available IMAGE J software and the estimated average crystallite size is 95 7 10 nm (mean 7 SD). The SAED pattern conrms the crystalline structure of hexagonal HA and is in agreement with the XRD results.

4. Conclusions Pure nanocrystalline HA is successfully synthesized by microwave method using precursor materials with calcium:phosphorous molar ratio of 10:6. There is a signicant difference between obtained crystallite size value by the Scherrer analysis and the TEM analysis. There is a good agreement between the crystallite size values obtained by WH-ISM, WH-ASM and WH-EDM models and that obtained by TEM analysis. Hence, WH analysis by the three models results in more accurate estimation of crystallite size compared to Scherrer analysis. Therefore it is suggested that the contribution from instrumental effects and lattice strain effect to the X-ray peak broadening need to be considered while calculating the crystallite size value of nanomaterials. Within the materials elastic limit, the WH models can be applied to estimate other microstructural parameters such as lattice strain, lattice deformation stress and lattice deformation energy density in a reasonable approximation. The crystallite size and the lattice strain values obtained from the WH-ISM model can be further extended to estimate the dislocation densities present in the material with more accuracy.

3.6. TEM analysis of nanocrystalline hydroxyapatite In TEM, the transmitted electron beam is used to create an image of the sample. Elastic or inelastic scattering occurs when
Table 2 The estimated microstructural parameters of annealed HA nanoparticles. Method Scherrer analysis WH-ISM WH analysis WH-ASM WH-EDM TEM analysis Parameter (unit) Dv (nm) Dv (nm) e 10 3(no unit) Dv (nm) s (MPa) Dv (nm) u (kJ m 3) Dv (nm) Estimated values 65 97 0.4943 92 52 95 12 95 7 10

Fig. 6. TEM micrograph (a) and SAED pattern (b) of annealed nanocrystalline hydroxyapatite.

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Acknowledgements The authors would like to acknowledge the grants from Department of Biotechnology, New Delhi (BT/PR-11731/MED/ 32/99/2008, dated 19-08-2009) and Department of Science and Technology, New Delhi (SR/NM/NS-27/2008, dated 25-02-2009). The authors would also like to thank Dr. M. Chidambaram, Director, National Institute of Technology, Tiruchirappalli, for his constant support and encouragement. References
[1] M. Afshar, N. Ghorbani, M. Ehsani, M.R. Saeri, C.C. Sorrel, Mater. Des. 24 (2003) 197. [2] R.E. Riman, W.L. Suchanek, K. Byrappa, C.W. Chen, P. Shuk, C.S. Oakes, Solid State Ionics 151 (2002) 393. [3] S.A. Edward, J.G. Nathaniel, N. Atsushi, Y.Y. Jackie, Nano Lett. 1 (2001) 149. [4] K.H. Wu, C.H. Yu, Y.C. Chang, D.N. Horng, J. Solid State Chem. 177 (2004) 4119. [5] R.W. Siegel, G.E. Fougere, Nanophase Materials, Kluwer Academic Publ., Netherlands, 1994. [6] G.W. Nieman, J.R. Weertman, R.W. Siegel, J. Mater. Res. 6 (1991) 1012. [7] P.G. Sanders, A.B. Witney, J.R. Weertman, R.Z. Valiev, R.W. Siegel, Mater. Sci. Eng. A 204 (1995) 7. [8] B.E. Warren, B.L. Averbach, J. Appl. Phys. 21 (1950) 595.

[9] [10] [11] [12] [13] [14] [15] [16] [17] [18] [19] [20] [21] [22] [23] [24] [25] [26] [27]

B.D. Hall, D. Zanchet, D. Ugarte, J. Appl. Cryst. 33 (2000) 1335. H.G. Jiang, M. Ruhle, E.J. Lavernia, J. Mater. Res. 14 (1999) 549. V. Biju, N. Sugathan, V. Vrinda, S.L. Salini, J. Mater. Sci. 43 (2008) 1175. B.E. Warren, B.L. Averbach, B.W. Roberts, J. Appl. Phys. 22 (1951) 1493. G.K. Williamson, W.H. Hall, Acta Metall. 1 (1953) 22. B.E. Warren, X-ray Diffraction, Dover Publications, New York, 1969. C. Suryanarayana, M.G. Norton, X-ray Diffraction: A Practical Approach, Plenum Press, New York, 1998. N. Rameshbabu, T.S. Sampath Kumar, K.Prasad Rao, Mater. Res. Innov. 14 (2010) 45. S. Raynaud, E. Champion, D. Bernache-Assollant, P. Thomas, Biomaterials 23 (2002) 1065. Y. Zhengwen, J. Yinshan, W. Yu Jie, M. Li Yan, L. Fangfei, Mater. Lett. 58 (2004) 3586. R.N. Panda, M.F. Hsiech, R.J. Chung, T.S. Chin, J. Phys. Chem. Solids 62 (2003) 193. Y. Zhang, L. Zhou, D. Li, N. Xue, X. Xu, J. Li, Chem. Phys. Lett. 376 (2003) 493. P.N. Kumta, C. Sfeir, D.H. Lee, D. Olton, D. Choi, Acta Biomater. 1 (2005) 65. S. Jalota, A.C. Tas, S.B. Bhaduri, J. Mater. Res. 19 (2004) 1879. R. Srinivasan, R. Yogamalar, R.J. Josephus, A.C. Bose, Funct. Mater. Lett. 2 (2009) 1. M.R. Panigrahi, S. Panigrahi, Physica B 405 (2010) 1787. A.W. Burton, O. Kenneth, R. Thomas, I.Y. Chan, Microporous Mesoporous Mater. 117 (2009) 75. R. Yogamalar, R. Srinivasan, A. Vinu, K. Ariga, A.C. Bose, Solid State Commun. 149 (2009) 1919. D.E. Gray, American Institute of Physics Handbook, McGraw-Hill Book Company, New York, 1972.