Abstract: Effects of Ge, Si addition on energy and electronic structure of ZrO2 and Zr(Fe,Cr)2 related to the corrosion of zirconium alloy were studied by First-principles calculations based on the density functional theory. The calculated heats of formation and cohesive energies show that ZrO2 tetragonal phase is not stable, cubic phase is easily formed and has the highest structural stability, thus the change occurs from tetragonal phase to cubic phase for crystal structure of oxidation, which affects the corrosion resistance of zirconium alloy. Ge, Si can reduce the forming ability and structural stability of ZrO2 cubic phase, Si can easily replace Cr atoms of Zr(Fe, Cr)2 systems, thus Fe/Cr atomic ratio of the second phase in zirconium alloy is improved. The calculations of the density of states (DOS) and Mulliken electronic populations show that hybrid resonant phenomenon and more ionic bonds are both seen between Zr and O of ZrO2, and the reason of reduced structural stability of ZrO2 cubic phase attributes to the weakened ionic bonds between Zr and O with the addition of Ge, Si. It is considered as ZrO2 and Zr(Fe,Cr)2 phase for affecting the corrosion resistance of zirconium alloy. In the case of adding Si, Si contained second phase Zr(Fe,Cr)2 is harmful to corrosion resistance of zirconium alloy, if the change of ZrO2 crystal structure is dominated, the corrosion resistance of zirconium alloy will be improved. As far as Ge is concerned, it is difficult for the formation of Ge contained second phase Zr(Fe,Cr)2, thus the influence of second phase on corrosion resistance of zirconium alloy is less than that of adding Si. If the change tendency from tetragonal phase to cubic phase has slowed down, the corrosion resistance of zirconium alloy will be improved.
周惦武,何蓉,刘金水,彭平. Ge、Si元素对ZrO2和Zr(Fe,Cr)2能量与电子结构的影响*[J]. 材料导报编辑部, 2017, 31(22): 146-152.
ZHOU Dianwu, HE Rong, LIU Jinshui, PENG Ping. Effects of Ge, Si Addition on Energy and Electronic Structure of ZrO2 and Zr(Fe,Cr)2. Materials Reports, 2017, 31(22): 146-152.
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2017, Vol. 31 
