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Materials from the A  2  M  3 O 12 family are known for their extensive chemical versatility while preserving the polyhedral-corner-shared orthorhombic crystal system, as well as for their consequent unusual thermal expansion, varying from negative and near-zero to slightly positive. The rarest are near-zero thermal expansion materials, which are of paramount importance in thermal shock resistance applications. Ceramic materials with chemistry Al 2- x  In  x  W 3 O 12 ( x = 0.2-1.0) were synthesized using a modified reverse-strike co-precipitation method and prepared into solid specimens using traditional ceramic sintering. The resulting materials were characterized by X-ray powder diffraction (ambient and in situ high temperatures), differential scanning calorimetry and dilatometry to delineate thermal expansion, phase transitions and crystal structures. It was found that the x = 0.2 composition had the lowest thermal expansion, 1.88 × 10 -6 K -1 , which was still higher than the end member Al 2 W 3 O 12 for the chemical series. Furthermore, the AlInW 3 O 12 was monoclinic phase at room temperature and transformed to the orthorhombic form at ca. 200 °C, in contrast with previous reports. Interestingly, the x = 0.2, x = 0.4 and x = 0.7 materials did not exhibit the expected orthorhombic-to-monoclinic phase transition as observed for the other compositions, and hence did not follow the expected Vegard-like relationship associated with the electronegativity rule. Overall, compositions within the Al 2- x  In  x  W 3 O 12 family should not be considered candidates for high thermal shock applications that would require near-zero thermal expansion properties.

Phase Transition and Coefficients of Thermal Expansion in Al2−xInxW3O12 (0.2 ≤ x ≤ 1)