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 A
2M
3O
12 family (A = trivalent cation, M = Mo, W). The expansion
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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 A
2M
3O
12 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, AlScMo
3O
12, was successfully synthesized using non-hydrolytic sol-gel chemistry. Depending on the reaction conditions, phase separation into Al
2Mo
3O
12 and Sc
2Mo
3O
12 or single-phase AlScMo
3O
12 could be obtained. Optimized conditions for the reproducible synthesis of stoichiometric, homogeneous AlScMo
3O
12 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 Sc
2W
3O
12 structure at 100 to 460 K. In contrast to all previously-reported A
2M
3O
12 compositions, AlScMo
3O
12 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.
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