![]() |
|
The dynamics of hydrogen atoms and the local structure of the metal framework in disordered Ti-V alloys were investigated by 1H NMR and incoherent inelastic neutron scattering (IINS) methods to characterize the types of the hydrogen sites and to quantitatively evaluate metal-hydrogen interaction in beta-Ti1-yVyHx(x`1; 0.2 1E y 1E 0.9). A cluster model with Ti6-iVi type octahedrons was constructed to describe the local structure of metal framework around a hydrogen atom in the Ti-V alloy. This model was applied to analyses of composition dependence of hydrogen site population and activation energy for hydrogen diffusion. In incoherent inelastic neutron scattering (IINS) spectra of beta-Ti1-yVyHx(x`1; 0.2 1E y 1E 0.9) at 50 K, four scattering peaks were observed in the energy ranges of 13 meV < epsIlon < 16 meV, 36 meV < epsIlon < 44 meV, 97 meV < epsIlon < 110 meV, and 134 meV < rpsIlon < 152 meV. These peaks were assigned to the lattice vibrations of the metal framework and the local vibrations of hydrogen atoms occupying the octahedral site (O-site) and two kinds of tetrahedral sites (T1- and T2-sites, respectively). From the composition dependence of the site population, the short range order parameter of metals in the Ti-V alloy was determined to be 0.43 } 0.05. Temperature and frequency dependence of 1H spin-lattice relaxation times (T1) were measured over the temperature range 105`400 K and at frequencies 9, 22.5, 52, and 90 MHz to study dynamics of hydrogen atoms in disordered metal hydrides beta -Ti1-y VyHx (x`1; 0.2 1E y 1E 0.8). All the hydrides had a minimum value caused by the hydrogen diffusion in the T1 vs. 1/T curves. The activation energies (Ea) of the hydrogen diffusion gradually decreased from 24 kJmol-1 for y = 0.2 to 21.8 kJmol-1 for 0.4, and then rapidly decreased to 17.5 kJmol-1 for y = 0.8. The metal-hydrogen interactions were evaluated to be -50.5 kJmol-1 for Ti-H and -34.0 kJmol-1 for V-H, respectively, by applying above cluster model to the composition dependence of Ea. The short range order parameter of metals in the Ti-V alloy was sIgma = 0.4, which was in good agreement with one determined by incoherent inelastic neutron scattering (sIgma = 0.43 } 0.05).