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基于组分Ca2Pr2Cu5O10三元固溶区的范围和晶体结构

DOI: 10.11858/gywlxb.2004.01.006, PP. 27-35

Keywords: Ca2Pr2Cu5O10,三元固溶区,X射线衍射,Rietveld结构精修,晶体结构

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Abstract:

利用X射线衍射分析和Rietveld结构精修方法研究了基于组分Ca2Pr2Cu5O10三元固溶区的范围和晶体结构。根据X射线分析结果和相消失法,为了保持Ca2+xPr2-xCu5O10结构单位晶胞中恒定的氧含量和电价平衡,基于组分Ca2Pr2Cu5O10的三元固溶区的范围可确定为:在Ca2+xPr2-xCu5O10固溶区的富Ca区(Ca/Pr>1),其表达式仍可以表示为一般的化学计量式Ca2+xPr2-xCu5O10(x=0.4,0.2,0);在富Pr区(Ca/Pr<1),其表达式为Ca1.7Pr2.2·Cu5O10、Ca1.4Pr2.4Cu5O10,即:Ca2+xPr2-xCu5O10固溶区范围从Ca2.4Pr1.6Cu5O10至Ca1.4Pr2.4·Cu5O10。研究表明:基于组分Ca2Pr2Cu5O10的三元固溶体晶体结构可以看作是正交晶系NaCuO2型亚晶胞的无公度相;Ca2.4Pr1.6Cu5O10亚晶胞的点阵常数为a0=0.28246(7)nm,b0=0.63693(1)nm,c0=1.06794(1)nm;其正交超结构的点阵常数为a=5a0,b=b0,c=5c0。Ca2.4Pr1.6Cu5O10的结构也可以用单斜超晶胞来表述,该单斜超晶胞的空间群为P21/c,Z=4,a=5a0,b=b0,c=c0/sinβ,β=104.79°或136.60°,V=5a0b0c0。在基于组分Ca2Pr2Cu5O10的三元固溶体晶体结构中,Ca和Pr之间在一定范围内是可以相互替代的,而且它们在结构中的占位是无序的。

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