立方ZrW2O8结构类型化合物是一类在很宽的温度范围内都具有优良的各向同性热收缩性质的化合物，其中以立方ZrW2O8和立方HfW2O8为典型化合物。热收缩化合物的研究在固体氧化物化学方面具有重要理论意义；在调节有机-无机杂化材料的热膨胀系数及制备膨胀系数可控的超低膨胀系数复合材料方面有重要的应用意义。对立方ZrW2O8结构类型化合物的同价和异价取代，不仅可以进一步丰富该热收缩化合物的元素相容性，还能够调整负热膨胀系数、相变温度以及提高加工性能等，为实际应用该类材料积累重要的基础数据。对取代固溶体的晶体结构及性质进行详细地研究，可以深入认识它们的微观结构和宏观性质之间的关系，为优化材料的性能提供必要的理论支持和依据。本论文主要有以下几部分： 1 首次用高温固相法合成了立方Zr1-xMxWMoO8-x/2 (M= Er, Tm, Yb, Sc, In, Ga, Al) 和立方Zr1-xMxW2O8-x/2 (M = Eu, Er, Yb, Sc, In, Ga, Al)两个系列的固溶体，通过DSC测试确定了其立方相形成的温度。对XRD图指标化的结果表明，前者具有b-ZrW2O8结构类型(简称b相)；后者具有a-ZrW2O8结构类型(简称a相)。建立了b相和a相的晶胞参数与M3+离子浓度的Vegard方程，测定了上述固溶体的固溶度。通过对M3+离子的化学性质与Vegard斜率关系的分析，揭示了两个系列固溶体的晶胞参数与基质的晶体结构的关系；还揭示了晶胞参数与基质-取代杂质的离子半径差、元素电负性有关。对于a相固溶体晶胞参数还与晶体取向的有序度有关。 2 采用酸蒸汽水热法首次成功合成了V异价取代的一系列四方水合前驱物HfW2-xVxO7-x/2(OH)2(H2O)2(x = 0, 0.10, 0.15, 0.20, 0.25, 0.30, 0.34, 0.38, 0.40)。通过ICP、红外光谱和热重差热分析对四方水合前驱物进行了表征。研究了以HfW2-xVxO7-x/2(OH)2(H2O)2(x = 0, 0.10, 0.15, 0.20, 0.25, 0.30, 0.34, 0.38, 0.40)为前驱物，随着温度升高脱水，生成相应的正交HfW2-xVxO8-x/2和立方HfW2-xVxO8-x/2固溶体的过程。 3 合成了一系列立方HfW2-xVxO8-x/2固溶体。根据组成不同，立方HfW2-xVxO8-x/2的结构可以看成是a-或b-HfW2O8结构类型。当x < 0.34，它们的结构是a-HfW2O8结构类型(空间群：P213)，而当x = 0.34，其结构则是b-HfW2O8结构类型(空间群：Pa3—)。立方固溶体的晶胞参数随着V含量的增加而线性减小，由此可以测得V元素在立方HfW2-xVxO8-x/2固溶体中的固溶度为34 mol%。 4 测定了立方HfW2-xVxO8-x/2固溶体的拉曼光谱，观察到HfW2-xVxO8-x/2固溶体拉曼光谱中的V-O多重键振动模式和V-O-V振动模式。由此判断V元素以[VO4]配位四面体和[V2O7]配位多面体形式溶入b-HfW2O8的晶体结构中。以此为基础建立了晶体结构模型，精修了b-HfW1.66V0.34O7.83的平均晶体结构。结果表明，V元素更多地偏向于占据W2的晶体学位置；[V2O7]配位多面体与b-HfW2O8的晶体结构重叠，氧空位占据O4的位置；[VO4]配位四面体既占据W2的位置，又占据W1的位置。与[VO4]配位四面体中的VW’缺陷相平衡的氧离子空位平均分布在O1和O3的位置。 5 利用变温XRD和TMA方法测定了立方HfW2-xVxO8-x/2固溶体的热膨胀系数。结果表明，该系列固溶体都具有优良的负热膨胀性质，其有序无序相变温度和负热膨胀系数随着V含量的增加而减小。 6 用酸蒸汽-相转变法合成了富钼区立方Zr(W1-yMoy)2-xVxO8-x/2(y = 0.6, 0.7; x < 0.30 )固溶体。分析表明无论是V含量还是Mo含量的增加都会使正交相中的W-O键个数减少，正交相的总体能量降低，因此正交相的To-c随着V含量或Mo含量的增加都呈现出逐渐减小的趋势；而机理复杂的脱水、相变温度Tt-o不随组成变化。用晶胞参数随组成变化的线性关系和Vegard’s规则确定了固溶体的固溶度；V元素在ZrW2-yMoyO8中的最大浓度随着Mo的增加而减小。测定了所有组分固溶体陶瓷片尺寸变化随温度的曲线，实验结果表明，所有组分固溶体都保持了优良的负热膨胀性质。通过调节Mo/V含量的不同，可以调节固溶体的平均线膨胀系数和有序-无序相转变温度。值得注意的是，在200 K-573 K相当宽的温度范围内，热收缩固溶体Zr(W1-yMoy)2-xVxO8-x/2(y = 0.5, 0.6; x < 0.30)的平均线负热膨胀系数保持为常数，在该温度区间没有发生相变，为制备良好的抗热冲击性能的近零热膨胀复合陶瓷提供了必要条件。

Cubic ZrW2O8 structure type compounds are well-known as a class of materials of considerable isotropic negative thermal expansion (NTE) over a wide temperature range, from 0.3 K up to their decomposition temperature of approximately 1050 K. Among them, ZrW2O8 and HfW2O8 are the typical ones. The NTE materials have attracted considerable research attention in solid oxide chemistry, inorganic-organic hybrid materials and production of composite bodies with precisely controllable positive, negative or zero coefficients of thermal expansion. The equivalent and aliovalent substitutions for cubic ZrW2O8 structure type compounds not only enlarge more negative thermal expansion compounds, but also play a very important part in the modifying of negative thermal expansion property. Studying on the crystal structure and property of the substituted solid solutions can understand the relationship between the microstructure and macroproperties deeply. Moreover, this has scientific significance and broad applications. Investigating the impacts of different cations on the solid solutions can grasp the regularity of the substitutions. Furthermore, discussing the phase transition process from the precursors to cubic ZrW2O8 structure type solid solutions can guide the synthesis of new solid solutions.In this thesis, two series of aliovalent substituted Zr1-xMxWMoO8-x/2(M = Er, Tm, Yb, Sc, In, Ga, Al) and Zr1-xMxW2O8-x/2(M = Eu, Er, Yb, Sc, In, Ga, Al) solid solutions were synthesizedthrough solid state reaction. The XRD patterns of the above solid solutions were characterizedand both of them have cubic structure. The former retained β-ZrW2O8 structure with space groupPa 3 while the latter kept α-ZrW2O8 structure with space group P213. The lower valencesubstitution didn’t destroy the structure of the matrix substance but made the structure a certaindegree of distortion, resulting in the different regularity of the variation for lattice parametersdepending on the different doped elements and compositions. On the basis of the regularity ofthe variation for lattice parameters, the solid solubility of two solid solutions was determined bythe Vegard’s law and the influence factors between the solid solubility and the different radiusand electronegativity of doped ions and Zr4+ ion were studied. Furthermore, the solid solubilityof α-Zr1-xMxW2O8-x/2(M = Eu, Er, Yb, Sc, In, Ga, Al) solid solution was also affected by the orderdegree parameters, which is the biggest difference between the two solid solutions.In this paper, another aliovalent solid solution was also synthesized. The process of acidicsteam hydrothermal (ASH) - thermal dehydrating precursors was chosen to prepare cubicHfW2-xVxO8-x/2(x = 0 – 0.34) solid solutions. XRD data displayed that cubic HfW2-xVxO8-x/2retained α-ZrW2O8 structure with space group P213 when x = 0 – 0.30 at room temperature; thesolid solution kept b-ZrW2O8 structure with space group Pa3 when x = 0.34; whereas a fewreflections of V2O5 and HfV2O7 were observed in the XRD patterns of c-HfW2-xVxO8-x/2 whenx > 0.34, which stated that the solid solution had reached the maximum. In accordance with theregularity of the linear decreasing in lattice parameter with increasing x and the Vegard’s law, thesolid solubility of the cubic HfW2-xVxO8-x/2 solid solutions was determined as 34 mol%, which issignificantly larger than that of aliovalent substituted cubic Zr1-xMxWMoO8-x/2(M = Er, Tm, Yb,Sc, In, Ga, Al) and Zr1-xMxW2O8-x/2(M = Eu, Er, Yb, Sc, In, Ga, Al) and quite equal to that ofcubic ZrW2-xVxO8-x/2. It is demonstrated that synthesizing cubic HfW2-xVxO8-x/2 through ASHtreatment must go through the phase transition process of tetragonal HfW2-xVxO7-x/2(OH)2(H2O)2and orthorhombic HfW2-xVxO8-x/2. The relationship between the phase transitions were discussedin detail in this paper. The properties of cubic HfW2-xVxO8-x/2 were studied deeply, therelationship between the lattice parameters and compositions was established, the phase transitontemperature of the solid solution with different V content was determined. The negative thermal expansion property of cubic HfW2-xVxO8-x/2 was also discussed.Mo-rich equivalent/aliovalent substituted cubic Zr(W1-yMoy)2-xVxO8-x/2 solid solutions were also prepared through ASH treatment. In this part, the influence of Mo/V content on synthesis, properties and structure of the cubic Zr(W1-yMoy)2-xVxO8-x/2 solid solutions was mainly studied. Cubic Zr(W1-yMoy)2-xVxO8-x/2 solid solution show excellent negative thermal expansion property like cubic ZrW2O8 and the negative thermal coefficients were adjusted with different Mo/V proportions.