Low Temperature Synthesis and Characterization of AlScMo₃O12

Materials (Basel). 2015 Feb 16;8(2):700-716. doi: 10.3390/ma8020700.

Abstract

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 αa = 1.7 × 10-6 K-1, αb = 6.2 × 10-6 K-1, αc = 2.9 × 10-6 K-1 and αV = 10.8 × 10-6 K-1, respectively.

Keywords: A2M3O12; high resolution diffraction; negative thermal expansion; non-hydrolytic sol-gel chemistry; scandium aluminum molybdate.