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Advances in Materials Science and Engineering
Volume 2013 (2013), Article ID 230216, 4 pages
Direct Synthesis of (K0.5Na0.5)NbO3 Powders by Mechanochemical Method
Institute of Materials Science, Vietnam Academy of Science and Technology, 18 Hoang Quoc Viet, Hanoi 10000, Vietnam
Received 30 May 2013; Accepted 17 July 2013
Academic Editor: Wen-Hua Sun
Copyright © 2013 Nguyen Duc Van. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
The synthesis and structural properties of lead-free piezoelectric (K0.5Na0.5)NbO3 powders prepared by mechanochemical method using Nb2O5, K2CO3, and Na2CO3 as starting materials were reported. X-ray diffraction, infrared spectroscopy, Raman spectroscopy, and scanning electron microscopy were used to characterize the prepared samples. Results showed that, for the first time, by selecting the milling speed of 600 rpm and the ball-to-powder weight ratio of 35 : 1 as milling parameters, pure (K0.5Na0.5)NbO3 crystalline phase was obtained directly in the as-milled samples after 5 h of milling time. The existence of a carbonato complex between and Nb5+ ions as an intermediate species of the formation of (K0.5Na0.5)NbO3 was also found.
Lead-free potassium sodium niobate piezoceramics, (K,Na)NbO3, have been studied intensively due to their attractive piezoelectric and ecofriendly properties [1–4]. It is, however, difficult to obtain this material with high density and stoichiometry by traditional solid-state reaction. By using this method, undoped alkali niobate-based samples were reported to be nonstoichiometric, and their density, due to their phase stability that is limited to only about 1140°C, is significantly lower than the theoretical value [5–8]. Besides, if K2O was produced from solid-state reaction mixture, this compound began to be volatile at 800°C and led to the change in chemical stoichiometry of obtained niobates [2–4, 9]. Therefore, different synthesis routes for alkali niobate-based piezoceramics were employed such as sol-gel, Pechini, or hydrothermal synthesis [10–12]. One of the most expected alternatives to solid-state reaction route is the mechanochemical method due to the fact that it requires only widely used commercial chemicals like oxides or carbonates as starting materials and its ability of providing the preparative product at large scale comparable with that of solid-state reaction one. However, no preparative procedures of (K,Na)NbO3 by this method have been reported to date although many efforts were carried out . Recently, for the synthesis of alkali niobate-based materials, mechanochemical method was used only as an assistance step to activate the reaction mixture before calcination for solid-state reaction method [14, 15].
This paper presents the synthesis and structural property of (K0.5Na0.5)NbO3 powders prepared directly by mechanochemical method.
2. Materials and Methods
All analytical grade chemicals used as starting materials for mechanochemical method, namely, K2CO3, Na2CO3, and Nb2O5, were purchased from Aldrich. Prior to usage, all these reagents were dried at 200°C for 2 h to remove moisture. They were mixed with desired stoichiometric composition and placed in a stainless steel vial of the planetary mill, Fritsch Pulverisette 6, with a ball-to-powder weight ratio of 35 : 1. The mechanochemical reaction was operated with rotational speed of 600 rpm for different milling times of 3, 4, 5, and 10 h. The as-milled samples were then calcined at 700, 800, 900, 950, and 1000°C. Phase identification was performed by using an X-ray powder diffractometer, Siemens D 5000 with CuKα radiation. For lattice parameter calculation, Si was used as an internal standard. A field-emission scanning electron microscope, Hitachi S 4800, an Infrared spectrometer (GX-Perkin-Elmer), and a Raman spectrometer Labram-1B (Horiba) were used to characterize the studied samples.
3. Results and Discussion
X-ray diffraction (XRD) diagrams of the as-milled samples with different milling times were shown in Figure 1. (K0.5Na0.5)NbO3 phase occurred with the strongest peaks at 2-θ values of 22.37, 31.82, 45.58, and 56.69° after only 3 h of milling time together with diffraction peaks of Nb2O5 phase (PDF card no. 27–1003) at 28.30, 36.62, and 55.06°, while the remaining Na2CO3 and K2CO3 were amorphous. By increasing the milling time further than 5 h, (K0.5Na0.5)NbO3 phase became a unique observable crystalline phase (orthorhombic, Å; Å; Å) with all diffraction peaks shifted distinctly from those of either KNbO3 (PDF card no. 32-0822, Å, Å, Å) or NaNbO3 (PDF card no. 33-1270, Å, Å, Å). To our knowledge, it is the first time that this (K,Na)NbO3 phase was formed directly by mechanochemical route after many efforts have been made by researchers. Rojac et al., for example, reported that no crystalline phase of (K,Na)NbO3 was formed by mechanochemical reaction between Na2CO3, K2CO3, and Nb2O5 even after as long as 40 hours of milling time with the milling speed of 300 rpm and the ball-to-powder weight ratio of 25 : 1 . Thus, in our opinion, with our selected milling parameters, a suitable milling energy was produced to facilitate for all starting materials to react mechanochemically at atomic scale simultaneously. The formation of (K0.5Na0.5)NbO3 phase was also confirmed by the presence of NbO6 octahedra in the as-milled sample with three bands in Raman spectrum (Figure 2). The first band at 245 cm−1 was corresponding to a symmetric O–Nb–O bending vibration ( mode), while the second one at 613 cm−1 originated from a symmetric O–Nb–O stretching vibration ( mode). The third band at 862 cm−1 denotes the () mode. This result is in good agreement with those reported in previous works [16, 17]. The infrared (IR) spectra of the as-milled mixtures after different milling times of 3, 4, 5, and 10 h were shown in Figure 3. Similar to the case of NaNbO3 synthesized mechanochemically , the adsorption band at 1467 cm−1, which is assigned for the asymmetrical C–O stretching vibration of the free , disappeared by increasing in milling time over 4 h, and three new bands were observed at 1633, 1507, and 1338 cm−1 instead. The symmetrical C–O stretching vibration band at 1055 cm−1, which is inactive for the free in alkali carbonates [18, 19], was also detected in all studied samples. The existence of these new bands in milled samples was due to the lowering in symmetry of the anion with the formation of a carbonato complex between and Nb5+ ions as an intermediate species during the mechanochemical synthesis of (K0.5Na0.5)NbO3.
XRD diagrams of calcined samples were shown in Figure 4. The orthorhombic phase of (K0.5Na0.5)NbO3 began to be observed for the sample calcined at 900°C with two peak splittings (1 1 0)/(0 0 1) and (2 2 0)/(0 0 2) at 2θ values of 23 and 45°, respectively. Thus, the calcination temperature for these peak splittings to start is higher than that for the case of solid-state reaction method (800–850°C) [20, 21]. It should be noted that, from the field-emission scanning electron microscopy (FESEM) image of the optimized as-milled sample as shown in Figure 5, the average grain size of about 10 nm was obtained and was significantly smaller than that (about 0.4 μm) of the samples prepared by solid-state reaction . In addition, it is well known that the samples synthesized by mechanochemical method have more defects than those received by the solid-state reaction method. As a result, during the calcination of an as-milled sample, a certain heating energy was required to remove the defects and to grow up the grain and that led to these abovementioned peak splittings that occurred at higher calcination temperature.
For the first time, by selecting the milling speed of 600 rpm and ball-to-powder weight ratio of 35 : 1 as milling parameters, pure (K0.5Na0.5)NbO3 phase was formed directly by mechanochemical method in the as-milled product after 5 h of milling time. The results showed that the orthorhombic phase of (K0.5Na0.5)NbO3 began to be observed for the sample calcined at 900°C. In addition, the existence of a carbonato complex between and Nb5+ ions as an intermediate species of the formation of (K0.5Na0.5)NbO3 prepared by mechanochemical method was confirmed by means of infrared spectroscopy.
This work was financially supported by Vietnam’s National Foundation for Science and Technology Development (NAFOSTED) with Project Code 103.02-2011.06. The author is also grateful to the Third World Academy of Sciences (TWAS) under Research Grant Agreement no. 10-156 RG/CHE/AS_I for scientific equipment.
- Y. Saito, H. Takao, T. Tani et al., “Lead-free piezoceramics,” Nature, vol. 432, no. 7013, pp. 84–87, 2004.
- P. K. Panda, “Review: environmental friendly lead-free piezoelectric materials,” Journal of Materials Science, vol. 44, no. 19, pp. 5049–5062, 2009.
- T. Takenaka, H. Nagata, and Y. Hiruma, “Current developments and prospective of lead-free piezoelectric ceramics,” Japanese Journal of Applied Physics, vol. 47, no. 5, pp. 3787–3801, 2008.
- J. Rödel, W. Jo, K. T. P. Seifert, E.-M. Anton, T. Granzow, and D. Damjanovic, “Perspective on the development of lead-free piezoceramics,” Journal of the American Ceramic Society, vol. 92, no. 6, pp. 1153–1177, 2009.
- H. Yang, Y. Lin, J. Zhu, and F. Wang, “An efficient approach for direct synthesis of K0.5Na0.5NbO3 powders,” Powder Technology, vol. 196, no. 2, pp. 233–236, 2009.
- V. Lingwal, B. S. Semwal, and N. S. Panwar, “Dielectric properties of Na1-xKxNbO3 in orthorhombic phase,” Bulletin of Materials Science, vol. 26, no. 6, pp. 619–625, 2003.
- D. H. Cho, M. K. Ryu, S. S. Park et al., “A study of ferroelectric properties in NaxK1-xNbO3 ceramic compounds,” Journal of the Korean Physical Society, vol. 46, no. 1, pp. 151–154, 2005.
- S. C. Lee, H.-G. Yeo, J. H. Cho et al., “Alkali metal non-stoichiometric effects in (K0.5Na0.5)NbO3 based piezoelectric ceramics,” Journal of the Korean Physical Society, vol. 56, no. 12, pp. 453–456, 2010.
- S. Zhang, R. Xia, and T. R. Shrout, “Lead-free piezoelectric ceramics versus PZT?” Journal of Electroceramics, vol. 19, no. 4, pp. 251–257, 2007.
- J. Hao, Z. Xu, R. Chu et al., “Characterization of (K0.5Na0.5)NbO3 powders and ceramics prepared by a novel hybrid method of sol-gel and ultrasonic atomization,” Materials and Design, vol. 31, no. 6, pp. 3146–3150, 2010.
- A. Chowdhury, S. O'Callaghan, T. A. Skidmore, C. James, and S. J. Milne, “Nanopowders of Na0.5K0.5NbO3 prepared by the pechini method,” Journal of the American Ceramic Society, vol. 92, no. 3, pp. 758–761, 2009.
- Y. Zhou, M. Guo, C. Zhang, and M. Zhang, “Hydrothermal synthesis and piezoelectric property of Ta-doping K0.5Na0.5NbO3 lead-free piezoelectric ceramic,” Ceramics International, vol. 35, no. 8, pp. 3253–3258, 2009.
- T. Rojac, M. Kosec, B. Malič, and J. Holc, “Mechanochemical synthesis of NaNbO3, KNbO3 and K0.5Na0.5NbO3,” Science of Sintering, vol. 37, no. 1, pp. 61–67, 2005.
- K. C. Singh and C. Jiten, “Lead-free piezoelectric ceramics manufactured from tantalum-substituted potassium sodium niobate nanopowders,” Materials Letters, vol. 65, pp. 85–88, 2011.
- T. Rojac, A. Benčan, and M. Kosec, “Mechanism and role of mechanochemical activation in the synthesis of (K,Na,Li)(Nb,Ta)O3 ceramics,” Journal of the American Ceramic Society, vol. 93, no. 6, pp. 1619–1625, 2010.
- Z. Wang, H. Gu, Y. Hu et al., “Synthesis, growth mechanism and optical properties of (K,Na)NbO3 nanostructures,” CrystEngComm, vol. 12, no. 10, pp. 3157–3162, 2010.
- C. Wang, Y. Hou, H. Ge, M. Zhu, H. Wang, and H. Yan, “Sol-gel synthesis and characterization of lead-free LNKN nanocrystalline powder,” Journal of Crystal Growth, vol. 310, no. 22, pp. 4635–4639, 2008.
- T. Rojac, M. Kosec, P. Šegedin, B. Malič, and J. Holc, “The formation of a carbonato complex during the mechanochemical treatment of a Na2CO3-Nb2O5 mixture,” Solid State Ionics, vol. 177, no. 33-34, pp. 2987–2995, 2006.
- T. Rojac, Ž. Trtnik, and M. Kosec, “Mechanochemical reactions in Na2CO3–M2O5 (M = V, Nb, Ta) powder mixtures: influence of transition-metal oxide on reaction rate,” Solid State Ionics, vol. 190, no. 1, pp. 1–7, 2011.
- H. Birol, D. Damjanovic, and N. Setter, “Preparation and characterization of (K0.5Na0.5) NbO3 ceramics,” Journal of the European Ceramic Society, vol. 26, no. 6, pp. 861–866, 2006.
- P. Bomlai, P. Wichianrat, S. Muensit, and S. J. Milne, “Effect of calcination conditions and excess alkali carbonate on the phase formation and particle morphology of Na0.5K0.5NbO3 powders,” Journal of the American Ceramic Society, vol. 90, pp. 1650–1655, 2007.