Characteristics of the structural and Johari-Goldstein relaxations in Pd-based metallic glass-forming liquids.

The dynamics of Pd-based metallic glass-forming liquids (Pd(40)Ni(10)Cu(30)P(20), Pd(42.5)Ni(7.5)Cu(30)P(20), Pd(40)Ni(40)P(20), and Pd(30)Ni(50)P(20)) was studied by mechanical spectroscopy and modulated differential scanning calorimetry (MDSC). We found that the change in composition has a significant effect on the α relaxation dynamics; the largest difference corresponds to an increase of the glass transition temperature Tg of ∼ 15 K, for materials in which 30% Ni was substituted by 30% Cu (i.e., from Pd(40)Ni(40)P(20) to Pd(40)Ni(10)Cu(30)P(20)). We also found that all Pd-based metallic glasses have very similar fragilities, 59 < m < 67, and Kohlrausch stretched exponents, 0.59 < βKWW < 0.60. It is interesting that the values of m and βKWW correlate well with the general relation proposed by Böhmer et al. for nonmetallic glass formers (Böhmer, R.; et al. J. Chem. Phys. 1993, 99, 4201-4209), which for the observed βKWW values predicts 58 < m < 61. From a linear deconvolution of the α and β relaxations, we find that the substitution of the Ni with Cu induced a large change in the time constant of the Johari-Goldstein relaxation, τβ. The activation energy, Uβ, of the β relaxation was largely independent of chemical composition. In all cases, 25 < Uβ/RT < 28, a range in agreement with results for other glass formers (Kudlik, A.; et al. Europhys. Lett. 1997, 40, 649-654 and Ngai, K. L.; et al. Phys. Rev. E 2004, 69, 031501). From the heat capacity and mechanical loss, estimates were obtained for the number of dynamically correlated units, Nc; we find significantly larger values for these metallic glass-forming liquids than Nc for other glass-forming materials.