Thermal behaviour of Pd40Cu30Ni10P20 bulk metallic glass

The thermal behaviour of differently milled Pd40Cu30Ni10P20 bulk metallic glass through the glass transition has been investigated by in situ high-energy synchrotron X-ray diffraction. Repeated heating and cooling were performed between the glassy and the supercooled liquid state. The changes in positions and intensities of the first and second diffraction maxima of the as-milled powder indicate irreversible changes during first heating up to the glass transition temperature Tg due to structural relaxation. After annealing, reversible structural changes with temperature are observed upon heating and cooling in the glassy phase, and in the supercooled liquid state respectively. The shift in the position of the first maximum scales approximately with the linear thermal expansion for the glassy state; however, this relation does not hold for the supercooled liquid. The structural transition from the glass to the supercooled liquid at the glass transition temperature is reflected by the intensity of the diffraction maxima and by a reversed temperature dependence of the position of the second diffuse maximum below and above Tg. The changes of the glass structure for the decrease of free volume by annealing are found to be different from those observed for the reversible volume expansion or shrinkage by varying the temperature. Therefore, the shift of the first diffuse maximum position of bulk metallic glasses cannot be used as a measure of the change in free volume.