Beijing Synchrotron Radiation Facility (BSRF), Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049, China.
Inorg Chem. 2013 Jan 7;52(1):431-4. doi: 10.1021/ic302245x. Epub 2012 Dec 14.
The structural phase transition of gadolinium-scandium-gallium garnet (Gd(3)Sc(2)Ga(3)O(12), GSGG) has been studied at high pressure and high temperature using the synchrotron X-ray diffraction technique in a laser-heated diamond anvil cell. The GSGG garnet transformed to an orthorhombic perovskite structure at approximately 24 GPa after laser heating to 1500-2000 K. The garnet-to-perovskite phase transition is associated with an ∼8% volume reduction and an increase in the coordination number of the Ga(3+) or Sc(3+) ion. The orthorhombic perovskite GSGG has bulk modulus B(0) = 194(15) GPa with B(0)' = 5.3(8), exhibiting slightly less compression than the cubic garnet structure of GSGG with B(0) = 157(15) GPa and B(0)' = 6.5(10). Upon compression at room temperature, the cubic GSGG garnet became amorphous at ∼65 GPa. Coupled with the amorphous-to-perovskite phase transition in Y(3)Fe(5)O(12) and Gd(3)Ga(5)O(12) at high-pressure-temperature conditions, we conclude that amorphization should represent a new thermodynamic state resulting from hindrance of the garnet-to-perovskite phase transition, whereas the garnet-to-amorphous transition in rare-earth garnets should be kinetically hindered at room temperature.
采用同步辐射 X 射线衍射技术在激光加热金刚石压腔中研究了钆-钪-镓石榴石(Gd(3)Sc(2)Ga(3)O(12),GSGG)的高压高温结构相变。在激光加热到 1500-2000 K 后,GSGG 石榴石转变为正交钙钛矿结构,约在 24 GPa 时发生相变。石榴石-钙钛矿相变伴随着约 8%的体积收缩和 Ga(3+)或 Sc(3+)离子配位数的增加。正交钙钛矿 GSGG 的体弹模量 B(0) = 194(15) GPa,B(0)’= 5.3(8),与 B(0) = 157(15) GPa 和 B(0)’= 6.5(10)的立方石榴石结构相比,压缩性稍低。在室温下压缩时,立方 GSGG 石榴石在约 65 GPa 时变为非晶态。结合 Y(3)Fe(5)O(12)和 Gd(3)Ga(5)O(12)在高温高压条件下的非晶-钙钛矿相变,我们得出结论,非晶态可能代表一种新的热力学状态,这是由于抑制了石榴石-钙钛矿相变,而在室温下,稀土石榴石中的石榴石-非晶转变应该受到动力学的抑制。