RESUMO
The HfV2-HfV2O7 composite is proposed as a material with potentially temperature-independent thermophysical properties due to the combination of anomalously increasing thermoelastic constants of HfV2 with the negative thermal expansion of HfV2O7. Based on literature data, the coexistence of both a near-zero temperature coefficient of elasticity and a coefficient of thermal expansion is suggested for a composite with a phase fraction of approximately 30 vol.% HfV2 and 70 vol.% HfV2O7. To produce HfV2-HfV2O7 composites, two synthesis pathways were investigated: (1) annealing of sputtered HfV2 films in air to form HfV2O7 oxide on the surface and (2) sputtering of HfV2O7/HfV2 bilayers. The high oxygen mobility in HfV2 is suggested to inhibit the formation of crystalline HfV2-HfV2O7 composites by annealing HfV2 in air due to oxygen-incorporation-induced amorphization of HfV2. Reducing the formation temperature of crystalline HfV2O7 from 550 °C, as obtained upon annealing, to 300 °C using reactive sputtering enables the synthesis of crystalline bilayered HfV2-HfV2O7.
RESUMO
We have systematically studied the effect of transition metal valence electron concentration (VEC) of amorphous T 0.75Y0.75B14 (a-T 0.75Y0.75B14, T = Sc, Ti, V, Y, Zr, Nb) on the elastic properties, bonding, density and electronic structure using ab initio molecular dynamics. As the transition metal VEC is increased in both periods, the bulk modulus increases linearly with molar- and mass density. This trend can be understood by a concomitant decrease in cohesive energy. T' = Ti and Zr were selected to validate the predicted data experimentally. A-Ti0.74Y0.80B14 and a-Zr0.75Y0.75B14 thin films were synthesized by high power pulsed magnetron sputtering. Chemical composition analysis revealed the presence of up to 5 at.% impurities, with O being the largest fraction. The measured Young's modulus values for a-Ti0.74Y0.80B14 (301 ± 8 GPa) and a-Zr0.75Y0.75B14 (306 ± 9 GPa) are more than 20% smaller than the predicted ones. The influence of O incorporation on the elastic properties for these selected systems was theoretically studied, exemplarily in a-Ti0.75Y0.75B12.75O1.25. Based on ab initio data, we suggest that a-Ti0.75Y0.75B14 exhibits a very dense B network, which is partly severed in a-Ti0.75Y0.75B12.75O1.25. Upon O incorporation, the average coordination number of B and the molar density decrease by 9% and 8%, respectively. Based on these data the more than 20% reduced Young's modulus obtained experimentally for films containing impurities compared to the calculated Young's modulus for a-Ti0.75Y0.75B14 (without incorporated oxygen) can be rationalized. The presence of oxygen impurities disrupts the strong B network causing a concomitant decrease in molar density and Young's modulus. Very good agreement between the measured and calculated Young's modulus values is obtained if the presence of impurities is considered in the calculations. The implications of these findings are that prediction efforts regarding the elastic properties of amorphous borides containing oxygen impurities on the at.% level are flawed without taking the presence of impurities into account.