XIAO Chang-jiang1,2, JIN Chang-qing2, WANG Xiao-hui3
1. Department of Material Science and Engineering, Henan University of Technology, Zhengzhou 450007, China 2. Institute of Physics, Chinese Academy of Sciences, Beijing 100080, China 3. State Key Laboratory of New Ceramics and Fine Processing，Department of Materials Science and Engineering，Tsinghua University，Beijing 100084, China
Abstract：High pressure can significantly increase the densification. Further, during the high pressure assisted sintering, the nucleation rate is increased due to reduced energy barrier and the growth rate is suppressed due to the decreased diffusivity. Thus high pressure enables the specimen to be fabricated with relatively lower temperature and shorter sintering period that assures to obtain dense nanocrystalline ceramics. Dense nanocrystalline BaTiO3 ceramics with uniform grain sizes of 60 and 30 nm, respectively, were obtained by pressure assisted sintering. The crystal structure and phase transitions were investigated by Raman scattering at temperatures ranging from -190 to 200 ℃. The Raman results indicated that the evolution of Raman spectrum with grain size is characterized by an intensity decrease, a broadening of the line width, a frequency shift, and the disappearance of the Raman mode. With increasing temperature, similar to 3 mm BaTiO3 normal ceramics, the successive phase transitions from rhombohedral to orthorhombic, orthorhombic to tetragonal, and tetragonal to cubic were also observed in nanocrystalline BaTiO3 ceramics. In addition, when particle size is reduced to the nanoscale, one will find some unusual physical properties in nanocrystalline ceramics, compared with those of coarse-grained BaTiO3 ceramics. The different coexistences of multiphase were found at different temperature. Especially, the ferroelectric tetragonal and orthorhombic phase can coexist at room temperature in nanocrystalline BaTiO3 ceramics. The phenomenon can be explained by the internal stress. The coexistences of different ferroelectric phases at room temperature indicate that the critical grain size for the disappearance of ferroelectricity in nanocrystalline BaTiO3 ceramics fabricated by pressure assisted sintering is below 30 nm.
[1] Zhao Z，Buscaglia V，Viviani M，et al. Phys. Rev. B，2004, 70: 024107. [2] Lin S, Lü T Q, Jin C Q, et al. Phys. Rev. B，2006, 74: 134115. [3] Wang X H, Deng X Y, Wen H, et al. Appl. Phys. Lett.，2006, 89: 162902. [4] LI Ying, DUAN Yu-ran, LI Wei-hua(李 颖, 段玉然, 李维华). Spectroscopy and Spectral Analysis(光谱学与光谱分析), 2002, 22(5): 783. [5] Poniatowski E H, Jouanne M, Morhange J F, et al. Phys. Rev. B，1999, 60(14): 10080. [6] Fujii M, Nagareda T, Hayashi S, et al. Phys. Rev. B，1991, 44(12): 6243. [7] Fujii M, Kanzawa Y, Hayashi S, et al. Phys. Rev. B，1996, 54(12): R8373. [8] Skandao G. Nanostruct. Mater.，1995, 5(2): 111. [9] Liao S C, Chen Y J, Kear B H, et al. Nanostruct. Mater.，1998, 10(6): 1063. [10] Li B R, Wang X H, Li L T. Mater. Chemistry and Physics, 2002, 78: 292. [11] Perry C H, Hall D B. Phys. Rev. Lett., 1965, 15: 700. [12] Venkateswaran U D, Naik V M, Naik R. Phys. Rev. B, 1998, 58(21): 14256. [13] Du Y L，Zhang M S, Chen Q, et al. Appl. Phys. A，2003, 76: 1099. [14] Arlt G, Hennings D, With G de. J. Appl. Phys., 1985, 58(4): 1619. [15] Arlt G. Ferroelectrics，1990, 104: 217. [16] Frey M H, Payne D A. Phys. Rev. B, 1996, 54(5): 3158.
