立方ZrW2O8类型化合物是一类在很宽的温度范围内具有各向同性热收缩性质的化合物。制备立方Zr1-xMxW2-yMoyO8-x/2固溶体并对其改性，将进一步优化其性能。本论文采用高温固相法合成了低价离子M3+取代Zr1-xMxWMoO8-x/2 ( M=Yb, Y, In, Al, Fe, Cr )固溶体,用常温XRD对固溶体的结构进行了表征，证明固溶体在常温下和ZrWMoO8具有相同的立方晶胞结构,空间群均为Pa ，用Vegard规则及其参数法确定了Zr1-xMxWMoO8-x/2( M= Yb, Y, In, Al, Fe, Cr )系列固溶体的固溶度，分别为3.3、2.5、2.5、1.5、1.6和1.0 mol%, 低价离子取代导致了固溶体的晶格畸变，使固溶体的晶胞参数随着溶质浓度的增大而减小；Zr1-xMxWMoO8-x/2( M= Yb, Y, In, Al, Fe, Cr )固溶体中电负性相近的元素之间的晶胞参数随溶质浓度变化的Vegard斜率与M3+-Zr4+之间的半径差成线性关系。固溶体的固溶度随着Vegard斜率绝对值的增大而减小，符合晶格弹性能量最小原则。Zr1-xRExW2O8-x/2( RE=Yb, Er, Eu, Sc )固溶体室温下为有序-ZrW2O8结构，空间群为P213，建立了有序度参数随溶质浓度增大线性减小和固溶体的固溶度随Vegard斜率绝对值的增大而增大的关系。通过实验，建立了Zr1-xRExW2O8-x/2( RE=Yb, Er, Eu, Sc )固溶体中的Vegard斜率与M3+-Zr4+之间的半径差的线性关系，从而得到不同溶质的固溶体的晶胞参数与溶质浓度的关系为：a= a0+x ( 1.3Δr-0.33 )，其中a0为25℃下固溶体的晶胞参数，x为溶质浓度，Δr为半径差。对Zr1-xMxWMoO8-x/2( M=Yb, Y, In, Fe, Cr )固溶体的热膨胀性质进行了研究，对溶质一定的固溶体，由于随着掺杂量的增大氧空位逐渐增大，膨胀系数逐渐增大；对于所有固溶体，当取代离子浓度相同时，膨胀系数随着离子半径的增大而增大。对于Zr1-xMxWMoO8-x/2(M=Y, Yb, In, Cr, x=0.00-0.05)固溶体，随着溶质浓度的增加， Zr1-xMxWMoO8-x/2固溶体的热稳定性逐渐增加。

Cubic ZrW2O8 has received considerable attention because of its isotropic negative thermal expansion in a wide temperature range. This makes the investigation of structurally related phases Zr1-xMxW2-yMoyO8-x/2 solid solutions an attractive goal.In this paper, we synthesize Zr1-xMxWMoO8-x/2 ( M=Yb, Y, In, Al, Fe, Cr ) solid solutions by solid-state reaction. The XRD patterns of Zr1-xMxWMoO8-x/2 ( M=Yb, Y, In, Al, Fe, Cr ) solid solutions are indexed with cubic ZrWMoO8 (Space Group: Pa ) structure. Using Vegard's equation and parametric method, the limited solubility of Yb3+, Y3+, In3+, Al3+, Fe3+, Cr3+ in ZrWMoO8 are determined to be about 3.3 mol%、2.5 mol%、2.5 mol%、1.5 mol%、1.6 mol% and 1.0 mol%. The lattice parameter decreases with the substitution concentration increasing. The dependence of lattice parameter on a substitution concentration is expressed by Vegard’s equation, The cationic substitution ranking in a grouping with closed electronegativity has the same Sv. Based on the hypothesis of minimum elastic energy the minimum | Sv | is consistent with the maximum solubility of Zr1-xMxWMoO8-x/2 solid solutions.Zr1-xRExW2O8-x/2( RE=Yb, Er, Eu, Sc ) solid solutions possess -ZrW2O8 structure( Space Group: P213)，The order degree linear decrease with increasing the substitution concentration. the solid solubility of solid solution is direct proportional to Vegard’s slope | Sv | . From the Vegard’s slope Sv’ as a function of r, we can find the expressions for the lattice parameters of those solid solutions is a= a0+x ( 1.3 Δr-0.33 ). For Zr1-xMxWMoO8-x/2 ( M=Yb, Y, In, Fe, Cr ) solid solutions, the thermal expansion coefficient increase with increasing the substituted concentration and the ionic radius. For Zr1-xMxWMoO8-x/2(M=Y, Yb, In, Cr, x=0.00-0.05) solid solutions, the thermal stability increases with increasing the substituted concentration.