Materials Chemistry and Physics 130 (2011) 8489

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Materials Chemistry and Physics

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Nanostructured Nb2 O5 natural hydroxyapatite formed by the mechanical alloying method: A bulk composite
W.J. Nascimento , T.G.M. Bonadio, V.F. Freitas, W.R. Weinand, M.L. Baesso, W.M. Lima
Universidade Estadual de Maring, Departamento de Fsica, Av. Colombo, 5790, 87020-900 Maring, PR, Brazil

a r t i c l e

i n f o

a b s t r a c t
The aim of this study was to develop a nanostructured Nb2 O5 natural hydroxyapatite bulk composite to serve as an alternative biocompatible bulk material for implants. A set of samples of hydroxyapatite from sh bones with different concentrations of Nb2 O5 were designed. They were prepared through a milling process, compacted under different pressures (350, 450, 550 and 650 MPa) and sintered in air atmosphere at 1000 C for 1 h. The results revealed that the prepared composites presented strong interactions between the two elements and showed improvement in the sinterability with signicant densication and microstructure changes, suggesting that they are promising for implants meant to replace bone tissues. 2011 Elsevier B.V. All rights reserved.

Article history: Received 14 September 2010 Received in revised form 6 April 2011 Accepted 26 May 2011 Keywords: Biomaterials Sintering Nanostructures Mechanical properties

1. Introduction The search for biocompatible materials for implants in the human body is an important area of research. Up to now, the bioactive calcium phosphates, among them hydroxyapatite (HAp) with the composition Ca10 (PO4 )6 (OH)2 , have been widely used for the reconstruction and/or replacement of tissues, allowing medicine and modern dentistry to offer new options for patients, thus improving their quality of life with the partial or total replacement of fractured bones. It is well known that these materials present osteoconductibility and intrinsically osteoinductibility characteristics that are similar to those of mineral bone matrices and have been associated with their chemical and structural similarities [17]. However, due to their low mechanical strength compared with natural bones, particularly regarding fragility and low resistance, there are restrictions for their use, especially in implants intended for high mechanical efforts. The main challenge, therefore, has been the development of alternative compounds with improved mechanical resistances and biocompatibilities. Because of its excellent biocompatibility and bioactivity, HAp has been used as a coating on materials with high mechanical strength, such as titanium, niobium and their alloys, resulting in improved bioactive properties, thus contributing to a higher level of osteointegration between the metal and the bone. This has been done to overcome the undesirable low biocompatibility of those metals when used in the restoration of anatomical structures. In

Corresponding author. E-mail address: Walter@d.uem.br (W.J. Nascimento). 0254-0584/$ see front matter 2011 Elsevier B.V. All rights reserved. doi:10.1016/j.matchemphys.2011.05.069

other words, the metallic component contributes to improving the mechanical resistance, and the HAp coating facilitates the biological osteointegration between the implant and the bone tissue. In addition, it is known that an ideal alloy for implants should have a low density, excellent mechanical strength, high resistance against corrosion, and it must be free of toxic elements. Among the suitable metals, the most resistant in terms of corrosion is titanium and its alloys, followed by niobium, tantalum and stainless steel. Several studies have focused on the development of biocompatible composites based on these metals aiming to improve their characteristics in terms of their use in implants [813]. The choice element depends on various factors that enable their use. Sometimes this choice is focused on the materials cost or availability. Niobium is abundant in Brazil, and it is known that niobium pentoxide (Nb2 O5 ) is simple to obtain. Moreover, this oxide is biocompatible and resistant to corrosion [1418]. The low density of this oxide associated with the biocompatibility and nontoxicity suggests its use to improve the biomechanical properties of the intended composites. Thus, the combination of a natural HAp with Nb2 O5 is promising for the development of biomaterials with improved gures of merits in terms of their use in implants. In addition, the possibility of developing a bulk and homogeneous composite with these two compounds may improve the biocompatible characteristics compared with those of existing implants that are usually made with a biocompatible coating deposited on a metal surface. Therefore, the aim of this study was to develop, through powder metallurgy, a nanostructured Nb2 O5 natural hydroxyapatite composite, to serve as an alternative biocompatible bulk material for implants. The inuence of compaction pressure and sinter-

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ing on the physico-mechanical and microstructural properties of the HApNb2 O5 composites is discussed, and their properties are compared with those of existing biocompatible materials used for implants.
2. Materials and methods Natural HAp powder was obtained via the calcinations of sh bone at 900 C for 8 h. This calcination procedure was shown to be capable of inducing nanoparticles in the powder [1921]. Subsequently, this natural HAp powder and Nb2 O5 were mixed and milled for 3 h with the mechanical alloying technique. The milling was performed on a Fritsch Pulverisette 6 planetary ball mill. The process was made with a stainless steel crucible and balls with mass ratios of 6/1 and a rotational speed of 300 rpm. The composites were designed in ve compositions dened in (vol.%) by (100 x) HAp + x Nb2 O5 , in which x varied from 50 to 90%. Samples compacted into cylindrical forms of 10 mm in diameter and 2 mm thickness were obtained with a uniaxial press at 350, 450, 550 and 650 MPa without using lubrication. The sintering was performed in air atmosphere at 1000 C for 1 h. The (Nb2 O5 HAp) powder was examined using CuK radiation on Shimadzu 6000 X-ray diffractometer source at a scan speed of 0.5 min1 and step scan of 0.02 , performed at the nal stage of the milling. The crystallite size (Lc ) of composites after milling was estimated from the Scherrers equation [22,23]: Lc = k h k l cos (1)

55 50

(100 - x) HAp + x Nb2O5 hkl = 110 hkl = 211

Crystallite size (nm)

45 40 35 30 25 20

Crystallite size Pure - HAp: 61.4 0.7 nm Pure - Nb2O5: 51.7 0.9 nm
50 60 70 80 90

Nb2O5 content (vol. %)

Fig. 2. Variation of crystallite sizes with Nb2 O5 quantitys (vol.%) for lines (h k l) = (1 1 0) ( ) and (h k l) = (2 1 1) ( ) of composite powders (100 x) HAp + x Nb2 O5 , milled for 3 h. x = 50, 60, 70, 80 and 90%.

in which Lc is the average crystallite size (nm), h k l is the full width of the peak at half of the maximum intensity, is the wavelength of X-ray radiation and k is the shape coefcient (value between 0.9 and 1). The instrumental corrected broadening h k l corresponding to the diffraction peak was estimated using the following equation [24]: hkl =
2 2 exp inst

(2)

in which exp corresponds to the experimental half width and inst the instrumental half width related to the powder standard LaB6 (SRM 660-NIST). The crystallite size is a measure of the size of coherently diffraction domain and is not the same as particle size as whole due to polycrystalline aggregates [25]. The mass densities were determined by the Archimedes method and following the standard norm MPIF 42 [26]. The porosity was evaluated by comparing the mass density of the sintered material ( S ) with the theoretical mass density ( T ) of the obtained composite. The linear dimensional change was evaluated through comparison between the dimensions (diameter) of the parts in green with the sintered ones. The measures were done with a micrometer with a precision of 0.01 mm. The morphological evolution of the porosity and the microstructure of the sintered samples were analysed by employing techniques of metallography and a scanning electron microscope (SEM) using a Shimatzu-SS-Supercan system. Transmission electron microscopy (TEM) observation was performed on a JEM 1400 (JEOL) instrument operating at 120 kV. For TEM analysis, the powder sample was ultrasonically dispersed in ethanol and drops were deposited on 300 carbon lm square mesh copper grids. The Vickers hardness was evaluated by employing the techniques of indentation on a microdurometer, Display Microhardeness Tester HVS 1000, following the 38489 ASTM norm [27]. Average hardness value was determined from 10 indentations in each sample at a load of 1000 g for 15 s.

4.0 3.9 3.8 3.7 3.6 3.5 3.4 3.3

Compacting pressure: 350 MPa 550 MPA

450 MPa 650 MPa

Mass density (g/cm )

50

60

70

80

90

Nb2O5 content (vol. %)

24 22

Composite: Cx = (100 - x) HAp + x Nb2O5

x = 50, 60, 70, 80 and 90 (vol. %)
C50

Compacting pressure: 350 MPa 450 MPa 550 MPa 650 MPa

20

Porosity (%)

C60

18 16 14 12 10 8 6 50 60 70 80 90

Intensity (a.u.)

C70 C80 C90 Nb2O5 HAp

20

30

40

50

60

70

80

2 (degree)
Fig. 1. X-ray diffraction patterns of HAp and Nb2 O5 precursors, and of the composite powders (100 x) HAp + x Nb2 O5 , milled for 3 h. x = 50, 60, 70, 80 and 90 (vol.%).

Nb2O5 content (vol. %)

Fig. 3. Effect of Nb2 O5 quantities (vol.%) and compacting pressures on (a) mass density and (b) porosity of the sintered composites (100 x) HAp + x Nb2 O5 , sintered in air atmosphere at 1000 C for 1 h. x = 50, 60, 70, 80 and 90%.

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Compacting pressure (MPa)

0.0 -0.8 -1.6 350 450 550 650

1.4

Nb2O5content (vol. %):

1.2

50% 80%

60% 90%

70%

Microhardness (GPa)
Nb2O5 content (vol.%): x = 90% x = 60% x = 80% x = 50% x = 70%

1.0

Dimensional change (%)

-2.4 -3.2 -4.0 -4.8 -5.6 -6.4

0.8

0.6

0.4 350 400 450 500 550 600 650

Compacting pressure (MPa)

Fig. 5. Vickers hardness values as a function of compacting pressures and Nb2 O5 quantities (vol.%) of sintered composites (100 x) HAp + x Nb2 O5 , sintered in air atmosphere at 1000 C for 1 h. x = 50, 60, 70, 80 and 90%. Average hardness value was determined from 10 indentations in each sample at a load of 1000 g for 15 s.

Fig. 4. Effect of Nb2 O5 quantities (vol.%) and compacting pressures on linear dimensional change of the sintered composites (100 x) HAp + x Nb2 O5 , sintered in air atmosphere at 1000 C for 1 h. x = 50, 60, 70, 80 and 90%.

3. Results and discussion To verify the formation of composites, X-ray diffraction spectra were obtained. The results for both the starting materials and the composites are presented in Fig. 1. Despite the fact that the program X-Pert High Score permitted only the identication of the Nb2 O5 (JCPDS N 037-1468 and N 027-1313) and HAp (JCPDS N 09-0432) phases, the diffraction spectra after the milling process showed that the peaks (3 1 2), (4 1 1) and (3 1 5) of the Nb2 O5 powder overlap with peaks (2 1 1), (1 1 2) and (3 0 0) of the hydroxyapatite, which suggests the formation of nanostructured composites. These results indicate that, during the mechanical alloying process, the powder particles of HAp and Nb2 O5 are repeatedly attened, cold-welded, fractured and re-welded. As described before [22], the impact forces plastically deform the powder particles leading to work hardening and fracture.

Fig. 6. TEM photomicrographs of the powder particles from the composite 50 HAp + 50 Nb2 O5 (vol.%), after milling for 3 h.

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Table 1 Vickers hardness values of the HApNb2 O5 composites pressed at 650 MPa and sintered at 1000 C. Results reported in the literature for HA, HAp, BHA, BHATi and EHATi, all of them also sintered at 1000 C, are also presented. T ( C) 1000 1000 1000 1000 1000 1000 1000 1000 Material HApNb2 O5 HApNb2 O5 HApNb2 O5 HApNb2 O5 HApNb2 O5 HA [33] HA [34] HAp [35] (50) (60) (70) (80) (90) Hardness (GPa) 1.27 0.14 1.06 0.07 1.05 0.10 0.8 0.1 0.6 0.1 1.17 0.07 1.16 0.9 0.1 Material BHA [36] BHA [37] BHA [38] BHATi (5) [39] BHATi (10) [39] EHATi (5) [39] EHATi (10) [39] Hardness (GPa) 0.311 0.41 0.02 0.43 0.05 0.14 0.13 0.39 0.39

HApNb2 O5 (50), (60), (70), (80) and (90) (vol.%), composites in this work; HA, hydroxyapatite commercial [33]; HA, hydroxyapatite synthetic [34]; HAp, hydroxyapatite from sh bones [35]; BHA, hydroxyapatite from bovine bones [3638]; EHATi (5) and (10) (vol.%), composites [39]; and BHATi (5) and (10) (vol.%), composites [39].

The peak broadening of the XRD reection can be used to estimate the crystallite sizes along the direction perpendicular to the crystallographic plane, what was performed using the Scherrers equation [2325,28]. For this purpose the most intense peaks were selected, near 23.80 and 31.84 , corresponding to the peaks (h k l) = (1 1 0) and (h k l) = (2 1 1) of the phases Nb2 O5 and HAp, respectively. Fig. 2 shows the variation in crystallite size with quantity (vol.%) of Nb2 O5 , after milling by 3 h, and also the val-

ues of the starting powders, using the mentioned reections. It can be observed that increasing Nb2 O5 content (vol.%) the crystallite sizes for the reection (1 1 0) remains virtually constant, between 42.1 0.6 and 43.9 0.5 nm, while for the reection (2 1 1) they progressively decreases from 51.7 0.9 to 22.5 1.2 nm. These reductions may be caused by the impact forces that plastically deform the powder particles leading to work hardening and fractures. Fragments generated by this mechanism may continue

Fig. 7. Microstructural fracture analysis of the composites (100 x) HAp + x Nb2 O5 (vol.%), pressured at 650 MPa and sintered in air atmosphere at 1000 C for 1 h. (a) x = 50%, (b) x = 60%, (c) x = 70%, (d) x = 80%, (e) x = 90%.

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reducing the particle sizes and, consequently, can reduce the crystallite sizes [22]. The shape of the peaks of X-ray diffraction of Nb2 O5 HAp composites indicates that the milling process may not have changed the crystalline structure, despite reducing the particle size and crystallite size. The effects of the composition and compaction pressure on the density and porosity of the composites are shown in Fig. 3(a) and (b), respectively. The solid and dashed lines are only visual guides. It can be observed that, after sintering, the density of the samples increased with compaction pressure for all compositions. For a single compaction pressure, the density shows signicant growth up to a composition of 70 (vol.%) of Nb2 O5 , but for higher amounts of the added reinforcement, the compression tends to minimise the changes thus reaching a region of stabilisation. The maximum variation was on the order of 7% and occurred for the composite containing 70 (vol.%) of Nb2 O5 and compressed at 650 MPa. The highest porosity values as a function of compacting pressure were observed for the sample with 90 (vol.%) of Nb2 O5 . Again, as occurred for the mass density results, the maximum variation in porosity for a specic compaction pressure was around 8%. These results indicated that the processing procedure via mechanical milling in the high energy regime induced a reduction in particle sizes, thus increasing the area of contact between them, a factor that produced a considerable decrease in the porosity, which resulted in better sintering [2931]. It is important to mention that the porosity of a material is one of the factors that control the osteointegration process [32]. Fig. 4 shows the samples linear dimensional variation, indicating that the composites undergo greater contraction when the concentration of Nb2 O5 is reduced. For example, the sample with 90 (vol.%) Nb2 O5 presented a maximum contraction variation on the order of 1.0%, while that with 50 (vol.%) Nb2 O5 presented a contraction variation of about 5.5%. This comparison was made for a pressure of 550 MPa. In relation to the compaction pressure itself, it was noted that no substantial change in contraction was observed, indicating that the effect of the composition of the sam-

ples on their contraction was more signicant than the applied pressure. The variation of Vickers hardness of composites HApNb2 O5 with compaction pressured and quantity (vol.%) of Nb2 O5 is shown in Fig. 5. For comparison purposes, in Table 1 are summarized the results obtained in this work for the samples compressed at 650 MPa with Nb2 O5 contents (vol.%) between 50 and 90%, and also, results reported in the literature for hydroxyapatite [3338] and BHATi and EHATi composites [39], all of them sintered at 1000 C. It is observed in Fig. 5, that the compaction pressure has a signicant bearing on the microhardness, independently of the composition. So, the hardness of the material is greater for higher compaction pressures. Furthermore, the lowest hardness (0.43 0.07 GPa) is observed for the composition with 90 (vol.%) of Nb2 O5 and pressed at 350 MPa. These results are consistent with those of the porosity shown in Fig. 3 (b). It can be noted that the best response to microhardness occurs for the composition of 50 (vol.%) Nb2 O5 , and this effect is evident in the composite compressed at 650 MPa, for which the hardness reached value 1.27 0.14 GPa. These results suggest that the formation of a ceramic composite with a more homogeneous structure occurred as a function of the HAp concentration. This behaviour was evident in the analysis of the microstructure of the composite performed with the SEM data and is related to the continuous evolution of the densication of the material, as will be shown in the photomicrographs latter on. For TEM analysis was selected the sample powder with 50 HAp + 50 Nb2 O5 (vol.%). Micrographs of four regions of this composite are presented in Fig. 6(a)(d). The diagonal image in Fig. 6(a) corresponds to the carbon lm. The statistical analysis provided average particle size of 61 9 nm and average particle aggregate size of 107 29 nm. It is observed that the particles of the composite in the powder form have an irregular shaped morphology as a consequence of the milling process. Comparing with the crystallite size estimated by Scherrers equation (Fig. 2), the average particle size observed in Fig. 6 indicates that these particles consist of one or more crystallites [25,40].

Fig. 8. Microstructure and porosity of the composite 30 HAp + 70 Nb2 O5 (vol.%), sintered in air atmosphere at 1000 C for 1 h, as a function of the compacting pressures: (a) 350 MPa, (b) 450 MPa, (c) 550 MPa, (d) 650 MPa.

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The photomicrographs in Fig. 7(a)(c) show the analysis of the fracture of composites at the compressed pressure of 650 MPa. These composites were chosen because they presented better physical and mechanical responses than the others. It can be seen that the studied samples have signicant intergranular fractures, suggesting the occurrence of fractures along the grain boundaries, which indicates that the cohesive forces that hold the atoms connected to the surface of each particle that forms the necks are not fully effective. Moreover, this analysis shows that the porosities within the sintered samples are interconnected. This was not quantied, but it was observed that some compositions exhibit interconnected porosities that are more pronounced than others. For example, the composites with 50 HAp + 50 Nb2 O5 and 10 HAp + 90 Nb2 O5 (vol.%) have interconnected pores with sizes ranging from 2 to 4 m. The porous morphological evolution was carried out with SEM. The results indicated that the compositions did not affect the shape and distribution of the pores. Then we choose the sample with 30 HAp + 70 Nb2 O5 (vol.%) to show the behaviour of this feature, which is shown in Fig. 8(a)(d). The observed decrease in porosity may be related to the high energy milling process used to obtain the composites, which reduces the particle sizes and increases the area of contact between them, thus facilitating the occurrence of both chemical and/or solid state reactions that may speed up the processes of mass diffusion during the thermal treatment. This is a desirable condition for the formation of composites. It can be seen that the porous shape and distribution conrm the densication of the composites, as shown in Fig. 3. 4. Conclusion In conclusion, the addition of Nb2 O5 to natural hydroxyapatite using the mechanical alloying method favoured the formation of nanostructured composites and improved the sinterability, providing a change in the physical and mechanical properties. The results showed that the milling process reduced the particle sizes, suggesting that the energy of the successive shocks induced chemical and/or solid state reactions that may have facilitated the formation of composites. The low melting point and reactivity of Nb2 O5 enabled the samples to be sintered at temperatures around 1000 C and under an air atmosphere. These sintering conditions and the use of furnaces without atmospheric control capable of producing composites with interconnected porosities and lower densities than those obtained with titanium, niobium and others, reduces the cost production, indicating that this bulk composite is a promising candidate to be used in the development of implants substituting bone tissues. As a nal remark, it is important to remember that Nb2 O5 and HAp are non-toxic compounds. Acknowledgements The authors would like to thank the Brazilian agencies Finep, Capes, Fundaco Araucria and CNPq for their nancial support of this work.

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