RESUMEN
Fluctuations confined to local regions in the structure of a glass are observed as the Johari-Goldstein (JG) relaxation. Properties of these regions and their atomic configuration are currently studied by relaxation techniques, by electron microscopy, and by high-energy X-ray scattering and extended x-ray absorption fine structure methods. One expects that these fluctuations (i) would kinetically freeze on cooling a glass, and the temperature coefficient of its enthalpy, dH/dT, would consequently show a gradual decrease with decrease in T, (ii) would kinetically unfreeze on heating the glass toward the glass-liquid transition temperature, Tg, and dH/dT would gradually increase, and (iii) there would be a thermal hysteresis indicating the time and temperature dependence of the enthalpy. Since no such features have been found, thermodynamic consequences of these fluctuations are debated. After searching for these features in glasses of different types, we found it in one of the most stable metal alloy glasses of composition Pd40Ni10Cu30P20. On cooling from its Tg, dH/dT decreased along a broad sigmoid-shape path as local-region fluctuations kinetically froze. On heating thereafter, dH/dT increased along a similar path as these fluctuations unfroze, and there is hysteresis in the cooling and heating paths, similar to that observed in the Tg-endotherm range. After eliminating other interpretations, we conclude that local-region fluctuations seen as the JG relaxation in the non-equilibrium state of a glass contribute to its entropy, and we suggest conditions under which such fluctuations may be observed.
RESUMEN
Consequences of increase in structural fluctuations on heating Pd40Ni10Cu30P20 and Zr46.75Ti8.25Cu7.5Ni10Be27.5 through their glass to liquid transition range were investigated by measuring the electrical resistivity, ρ, an electron scattering property. The temperature coefficient of resistivity (TCR = (1/ρ) dρ/dT) of the liquid and glassy states is negative. The plots of their ρ against T in the Tg (glass to liquid transition) range show a gradual change in the slope similar to the change observed generally for the plots of the density, elastic modulus, and refractive index. As fluctuations in the melt structure involve fewer configurations on cooling, ρ increases. In the energy landscape description, the melt's structure explores fewer minima with decrease in T, vibrational frequencies increase, and electron scattering and ρ increase. Plots of (-dρ/dT) against T resemble the plot of the specific heat of other glasses and show a sub-Tg feature and a rapid rise at T near Tg. Analysis shows that the magnitude of negative TCR is dominated by change in the phonon characteristics, and configurational fluctuations make it more negative. The TCR of the liquid and glassy states seems qualitatively consistent with the variation in the structure factor in Ziman's model for pure liquid metals as extended by Nagel to metal alloys and used to explain the negative TCR of a two-component metal glass.
RESUMEN
To investigate the effects of added molecular heterogeneity on the hysteretic features of liquid-glass-liquid transition, we studied acetaminophen, sulfathiazole, and three of their mixtures by calorimetry, and determined the T(g) and the fictive temperature, T(f), from changes in the enthalpy and entropy on the cooling and heating paths, as well as the non-exponential parameter, ß(cal). We find that, (i) T(f) for cooling is within 1-3 K of T(f) for heating and both are close to T(g), (ii) the closed loop entropy change in the liquid-glass-liquid range is negligibly small, (iii) T(g) and T(f) increase on increasing sulfathiazole in the mixture, (iv) ß(cal) first slightly increases when the second component is added and then decreases, and (v) ageing causes deviations from a non-exponential, nonlinear behavior of the glass. In terms of fluctuations in a potential energy landscape, adding a solute heterogeneity would shift the state point to another part of the landscape with a different distribution of barrier heights and a different number of minima accessible to the state point. Part of the change in ß(cal) is attributed to hydrogen-bond formation between the two components. Ageing changes the relaxation times distribution, more at short relaxation times than at long relaxation times, and multiplicity of relaxation modes implied by ß(cal) < 1 indicates that each mode contributing to the enthalpy has its own T(g) or T(f). ß(cal) differs from ß(age) determined from isothermal ageing, and the distribution parameter of α-relaxation times would differ from both ß(cal) and ß(age).
RESUMEN
Johari-Goldstein or ß relaxation, persisting down to glassy state from a supercooled liquid, is a universal phenomenon of glassy dynamics. Nevertheless, the underlying micromechanisms leading to the relaxation are still in debate despite great efforts devoted to this problem for decades. Here we report experimental evidence on the structural origins of Johari-Goldstein relaxation in an ultra-quenched metallic glass. The measured activation energy of the relaxation (~26 times of the product of gas constant and glass transition temperature) is consistent with the dynamic characteristics of Johari-Goldstein relaxation. Synchrotron X-ray investigations demonstrate that the relaxation originates from short-range collective rearrangements of large solvent atoms, which can be realized by local cooperative bonding switch. Our observations provide experimental insights into the atomic mechanisms of Johari-Goldstein relaxation and will be helpful in understanding the low-temperature dynamics and properties of metallic glasses.
RESUMEN
In studies of ultraviscous liquids and glasses, (i) the relaxation time and its temperature dependence are generally compared without regard to its asymmetric distribution and (ii) the calorimetric relaxation time at T(g,DSC), the onset temperature of the specific heat rise in a heating scan at 20 K/min, is arbitrarily chosen as 100 s and compared against the relaxation time determined by spectroscopy. We propose that the relaxation time and its derivatives should be compared in a fixed frame of reference, preferably by using its average value that takes into account the asymmetric distribution, and we show that the relaxation time at T(g,DSC) is a material characteristic. It varies with the extent of nonexponential and nonlinear relaxation and the activation energy.
