Hydrate formation and its effects on the thermal expansion properties of HfMgW3O12

Abstract

HfMgW₃O₁₂ is a representative material with negative thermal expansion in the ABM₃O₁₂ (A = Zr, Hf; B = Mg, Mn, Zn, M = W, Mo) family. Herein we report a novel feature of hydration in HfMgW₃O₁₂ and its effect on the thermal expansion and its structures which have not been determined previously. It is found that hydrate formation in HfMgW₃O₁₂ occurs under ambient or moisture conditions and restrain the low energy librational and translational and even high energy bending and stretching motions of the polyhedra. The coefficient of thermal expansion could be tailored from negative to zero and positive depending on the hydration levels. The unhydrated HfMgW₃O₁₂ adopts an orthorhombic structure with space group Pna2₁ (33) without phase transition at least from 80 K to 573 K, but pressure-induced structure transition and amorphization are found to occur at about 0.19 Gpa and above 3.93 GPa, respectively.