Pressure-induced cubic-to-orthorhombic phase transformation in the negative thermal expansion material HfW2O8

Abstract

The effect of pressure on the crystal structure of HfW2O8 has been investigated by neutron powder diffraction. At a hydrostatic pressure of 0.62 GPa at room temperature the cubic material transforms, with a 5% reduction in volume, to the same orthorhombic phase that is seen in the isostructural compound ZrW2O8 above 0.21 GPa. The transformation is sluggish, requiring about 24 h to complete at constant pressure. Once formed, the orthorhombic phase is retained upon release of pressure. Upon heating to 360 K, the metastable orthorhombic phase transforms back to the cubic phase. The substantially higher pressure for the cubic-to-orthorhombic transition in HfW2O8, compared to ZrW2O8, may be important for the application of this material in composites with controlled thermal expansion because rather large local pressures can occur in such composites.