Pressure-dependence of the phase transitions and thermal expansion in zirconium and hafnium pyrovanadate

Low or negative thermal expansion (NTE) has been previously observed in members of the ZrP2O7 family at temperatures higher than their order-disorder phase transitions. The thermoelastic properties and phase behavior of the low temperature superstructure and high temperature negative thermal expansion phases of ZrV2O7 and HfV2O7 were explored via in situ variable temperature/pressure powder x-ray diffraction measurements. The phase transition temperatures of ZrV2O7 and HfV2O7 exhibited a very strong dependence on pressure (similar to 700 K GPa), with moderate compression suppressing the formation of their NTE phases below 513 K. Compression also reduced the magnitude of the coefficients of thermal expansion in both the positive and negative thermal expansion phases. Additionally, the high temperature NTE phase of ZrV2O7 was found to be twice as stiff as the low temperature positive thermal expansion superstructure (24 and 12 GPa respectively).