Zeming Chen

Dielectric relaxation of long-chain glass-forming monohydroxy alcohols

The dielectric relaxation of two long-chain glass forming monohydroxy alcohols, 2-butyl-1-octanol and 2-hexyl-1-decanol, is studied at low temperature. Remarkable broadening from the pure Debye relaxation is identified for the slowest dynamics, differing from the dielectric spectra of short-chain alcohols. The broadening of the Debye-like relaxation in the two liquids develops as temperature increases, and the approaching of the Debye-like and structural relaxation widths is shown. Similar results are observed in the dielectric spectra of dilute 2-ethyl-1-hexanol in either 2-hexyl-1-decanol or squalane. The results of the liquids and mixtures reveal a correlation between the broadening and the Debye-like relaxation strength. Molecular associations in monohydroxy alcohols are discussed with the modification of the Debye relaxation.

Glass transition in binary eutectic systems: best glass-forming composition.

The glass transition and glass-forming ability in a binary eutectic system of methyl o-toluate (MOT) versus methyl p-toluate (MPT) are studied across the whole composition range. The phase diagram is constructed to explore the best glass-forming composition as the characteristic temperatures of the glass transition, crystallization, eutectic, and liquidus are determined. The best vitrification region is found to locate between the eutectic and the midpoint compositions of the eutectic line, indicating a remarkable deviation from the eutectic composition. The compilation of various simple binary eutectic systems covering inorganic, metallic, ionic, and molecular glass-forming liquids reproduces the rule. Kinetics and thermodynamics in binary systems are investigated to associate with the rule. The composition dependence of the structural relaxation time and the kinetic fragility are presented with dielectric measurements. It is found that whereas mixing of binary miscible liquids kinetically favors glass formation, thermodynamic contribution to the deviation of the best glass-forming composition from eutectics is implied.

Enthalpy and dielectric relaxations in supercooled methyl m-toluate.

The structural relaxation of a glass forming liquid, methyl m-toluate, is studied in the deeply supercooled region near glass transition with the calorimetric and dielectric techniques. The thermodynamics and kinetics of the enthalpy relaxation are focused, and the kinetic studies are paralleled with dielectric relaxation. Relaxation enthalpies are expressed in two manners, and the numerical determination is based on the quantity of heat involved in the enthalpy recoveries from the relaxed glasses to liquids through glass transition. The correlations between the relaxation enthalpies and fragility are examined, and the remarkable dependence is visible for both cases. The enthalpy and dielectric relaxations in the liquid reveal comparable results of the fragility indices and stretching exponents.

Glass formability in medium-sized molecular systems/pharmaceuticals. I. Thermodynamics vs. kinetics

Scrutinizing critical thermodynamic and kinetic factors for glass formation and the glass stability of materials would benefit the screening of the glass formers for the industry of glassy materials. The present work aims at elucidating the factors that contribute to the glass formation by investigating medium-sized molecules of pharmaceuticals. Glass transition related thermodynamics and kinetics are performed on the pharmaceuticals using calorimetric, dielectric, and viscosity measurements. The characteristic thermodynamic and kinetic parameters of glass transition are found to reproduce the relations established for small-molecule glass formers. The systematic comparison of the thermodynamic and kinetic contributions to glass formation reveals that the melting-point viscosity is the crucial quantity for the glass formation. Of more interest is the finding of a rough correlation between the melting-point viscosity and the entropy of fusion normalized by the number of beads of the pharmaceuticals, suggesting the thermodynamics can partly manifest its contribution to glass formation via kinetics.

Comparative study of dynamics in glass forming mixtures of Debye-type N-ethylacetamide with water, alcohol, and amine

The glass transition and relaxation dynamics in the binary mixtures of a Debye liquid, N-ethylacetamide, with water, monoalcohol, and amine are studied by calorimetric and dielectric measurements in the highly viscous regimes near the glass transition. Calorimetric measurements show the glass transition temperature in the N-ethylacetamide-water mixtures is remarkably enhanced as water is added as high as 70 mol. % before crystallization is detected. A similar increase is also observed in the N-ethylacetamide-rich mixtures with the non-Debye 1,2-propanediamine. However, the dielectric measurements show that the main relaxation in the N-ethylacetamide-water mixtures with water fraction up to 60 mol. % reproduces the dynamic characters of the mixtures constituted by two Debye liquids, N-ethylacetamide and 2-ethyl-1-butanol. The comparison of the calorimetric and dielectric features for the three mixing systems suggests that the Debye relaxation persists in the N-ethylacetamide-water mixtures within the experimentally studied compositions.

Calorimetric determination of fragility in glass forming liquids: T f vs. T g-onset methods

The calorimetric determination of the fragility m-index is compared using the Tf and Tg-onset methods for typical metallic and molecular glass forming systems of Pd39Ni10Cu30P21, glycerol, triacetin and propylene carbonate. The results are evaluated by referring to the standard m-values determined from the kinetic measurements of the viscosity or structural relaxation time in the supercooled liquid regimes. The m-indexes derived from the Tf method are found to generally agree well with the kinetic measurements for all the systems. However, a large deviation is shown between the m-indexes calculated with the Tg-onset method and the kinetic results for the fragile liquids of triacetin and propylene carbonate, indicating the calorimetric determination of the fragility m-indexes in terms of the Tf method produces less uncertainty.Graphical abstract

Anomaly in dielectric relaxation dispersion of glass-forming alkoxy alcohols

The dielectric relaxations in six primary and secondary alkoxy alcohols with varying molecular size and different separation between -O- and hydroxyl group are studied at temperatures around glass transition. The analyses of the apparent full width at half maximum of the main relaxations of the alkoxy alcohols reveal minima in the temperature dependence of the relaxation dispersions. The stretching exponents for the main relaxations of the alkoxy alcohols are also found not to follow the empirical correlations with other dynamic quantities established for generic liquids. A comparison of the relaxation dispersions in the alkoxy alcohols with those in Debye and non-Debye (generic) liquids is presented. The impacts of the β-relaxations on the apparent main relaxation widths are reviewed for molecular glass formers.

Relaxation dynamics in the strong chalcogenide glass-former of Ge22Se78

The enthalpy relaxation is performed in the glassy Ge22Se78 to understand the dynamic behaviors. The structure of the glass is examined by X-ray diffraction and Raman spectra. The dynamic parameters such as the fragility, stretching exponent and non-linear factor are determined. A low fragility of m = 27 is exhibited for the chalcogenide, however, the stretching exponent is found not to have a larger value. The enthalpy relaxation spectra are constructed for various glass formers, and a relationship between the fragility and the symmetry of the spectra is demonstrated. The dynamic results are used to evaluate the structure of the Ge22Se78 glass.

Revisiting the glass transition and dynamics of supercooled benzene by calorimetric studies

The glass transition and dynamics of benzene are studied in binary mixtures of benzene with five glass forming liquids, which can be divided into three groups: (a) o-terphenyl and m-xylene, (b) N-butyl methacrylate, and (c) N,N-dimethylpropionamide and N,N-diethylformamide to represent the weak, moderate, and strong interactions with benzene. The enthalpies of mixing, ΔH(mix), for the benzene mixtures are measured to show positive or negative signs, with which the validity of the extrapolations of the glass transition temperature T(g) to the benzene-rich regions is examined. The extrapolations for the T(g) data in the mixtures are found to converge around the point of 142 K, producing T(g) of pure benzene. The fragility m of benzene is also evaluated by extrapolating the results of the mixtures, and a fragility m ∼ 80 is yielded. The obtained T(g) and m values for benzene allow for the construction of the activation plot in the deeply supercooled region. The poor glass formability of benzene is found to result from the high melting point, which in turn leads to low viscosity in the supercooled liquid.

Probing the Debye dielectric relaxation in supercooled methanol

The explanation of the dielectric dynamics in methanol would offer knowledge of the Debye relaxation in supercooled monoalcohols. However, due to the fast crystallization, it is hard to attain the dynamics of pure methanol in the deeply supercooled region. In this paper we studied the dynamics of methanol - 2-ethyl-1-hexanol mixtures with methanol concentration up to 80 mol% using dielectric and calorimetric measurements. Two main relaxations are detected in the dielectric spectra of the mixtures, and the slower one generally reproduces the Debye relaxation features reported in earlier studies of other monoalcohols. The validity of the ideal mixing law is verified for the relaxation time of the slower dynamics in the mixtures. The results suggest that the Debye relaxation is present in the dielectric spectra of methanol. The temperature dependence of the Debye relaxation time is constructed for the supercooled methanol.