Recent interest in low and negative thermal expansion materials has led to significant research on compounds that exhibit this property, much of which has targeted the A₂M₃O₁₂ family (A = trivalent cation, M = Mo, W). The expansion and phase transition behavior in this family can be tuned through the choice of the metals incorporated into the structure. An undesired phase transition to a monoclinic structure with large positive expansion can be suppressed in some solid solutions by substituting the A-site by a mixture of two cations. One such material, AlScMo₃O₁₂, was successfully synthesized using non-hydrolytic sol-gel chemistry. Depending on the reaction conditions, phase separation into Al₂Mo₃O₁₂ and Sc₂Mo₃O₁₂ or single-phase AlScMo₃O₁₂ could be obtained. Optimized conditions for the reproducible synthesis of stoichiometric, homogeneous AlScMo₃O₁₂ were established. High resolution synchrotron diffraction experiments were carried out to confirm whether samples were homogeneous and to estimate the Al:Sc ratio through Rietveld refinement and Vegard's law. Single-phase samples were found to adopt the orthorhombic Sc₂W₃O₁₂ structure at 100 to 460 K. In contrast to all previously-reported A₂M₃O₁₂ compositions, AlScMo₃O₁₂ exhibited positive thermal expansion along all unit cell axes instead of contraction along one or two axes, with expansion coefficients (200-460 K) of α_a = 1.7 × 10^-6 K^-1, α_b = 6.2 × 10^-6 K^-1, α_c = 2.9 × 10^-6 K^-1 and α_V = 10.8 × 10^-6 K^-1, respectively.

Alyssa Main

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