Calorimetric measurements on some undercooled metals and alloys

Undercooling was achieved directly in the cell of a high temperature calorimeter (Setaram HTDSC) for Ni, Fe, Cu, Pd and several alloys, using cooling rates between 1 and 15 K min⁻¹. The samples were immersed in alumina powder inside a standard alumina crucible under flowing helium. Ag, Au and Al were not undercooled significantly. The reproducibility of the measurements was within 1.5%. The heat of solidification of Ni at an undercooling of ΔT = 220 K was −17.5 ± 0.2 kJ mol⁻¹, which is the same absolute value of the heat of fusion at the equilibrium melting point T_m. This implies that the specific heat of the undercooled liquid is very close to that of the crystalline solid in this temperature range. Fe appears to display a similar behavior at ΔT = 220 K. The difference between the heat of fusion at T_m and the heat of solidification at an average value of ΔT = 95 K is significant for a Pd_77.5Cu₆Si_16.5 glass-forming alloy. From these data, we calculated an average specific heat difference between the liquid and crystal phases of 7 ± 5 J mol⁻¹ K⁻¹. The enthalpy data for Pd₈₂Si₁₈ comply with those of the ternary Pd---Cu---Si.