Liquid dynamics in partially crystalline glycerol

We present a dielectric study on the dynamics of supercooled glycerol during crystallization. We explore the transformation into a solid phase in real time by monitoring the temporal evolution of the amplitude of the dielectric signal. Neither the initial nucleation or the crystal growth influence the liquid dynamics visibly. For one of the samples studied, a tiny fraction of glycerol remained in the disordered state after the end of the transition. We examined the nature of the alpha relaxation in this frustrated crystal and find that it is virtually identical to the bulk dynamics. In addition to that, we have found no evidence that supercooled glycerol transforms into a peculiar phase where either a new solid amorphous state or nano-crystals dispersed in a liquid matrix are formed.Comment: 7 pages, 7 figure

Communication: High pressure specific heat spectroscopy reveals simple relaxation behavior of glass forming molecular liquid

The frequency dependent specific heat has been measured under pressure for the molecular glass forming liquid 5-polyphenyl-4-ether in the viscous regime close to the glass transition. The temperature and pressure dependence of the characteristic timescale associated with the specific heat is compared to the equivalent timescale from dielectric spectroscopy performed under identical conditions. It is shown that the ratio between the two timescales is independent of both temperature and pressure. This observation is non-trivial and demonstrates the existence of specially simple molecular liquids in which different physical relaxation processes are both as function of temperature and pressure/density governed by the same underlying "inner clock". Furthermore, the results are discussed in terms of the recent conjecture that van der Waals liquids, like the measured liquid, comply to the isomorph theory.Comment: 6 pages, 3 figure

Generalized single-parameter aging tests and their application to glycerol

Physical aging of glycerol following temperature jumps is studied by dielectric spectroscopy at temperatures just below the glass transition temperature. The data are analyzed using two single-parameter aging tests developed by Hecksher et al. [J. Chem. Phys. 142, 241103 (2015)]. We generalize these tests to include jumps ending at different temperatures. Moreover, four times larger jumps than previously are studied. The single-parameter aging tests are here for the first time applied to a hydrogen-bonded liquid. We conclude that glycerol obeys single-parameter aging to a good approximation.Comment: 20 pages, 8 figure

Dynamic thermal expansivity of liquids near the glass transition

Based on previous works on polymers by Bauer et al. [Phys, Rev. B (2000)], this paper describes a capacitative method for measuring the dynamical expansion coefficient of a viscous liquid. Data are presented for the glass-forming liquid tetramethyl tetraphenyl trisiloxane (DC704) in the ultraviscous regime. Compared to the method of Bauer et al. the dynamical range has been extended by making time-domain experiments and by making very small and fast temperature steps. The modelling of the experiment presented in this paper includes the situation where the capacitor is not full because the liquid contracts when cooling from room temperature down to around the glass-transition temperature, which is relevant when measuring on a molecular liquid rather than polymer

A systematic study of the isothermal crystallization of the mono-alcohol n-butanol monitored by dielectric spectroscopy

Isothermal crystallization of the mono-hydroxyl alcohol n-butanol was studied with dielectric spectroscopy in real time. The crystallization was carried out using two different sample cells at 15 temperatures between 120 K and 134 K. For all temperatures, a shift in relaxation times to shorter times was observed during the crystallization process, which is characterized by a drop in relaxation strength. The two different sample environments induced quite different crystallization behaviors, consistent and reproducible over all studied temperatures. An explanation for the difference was proposed on the background of an Avrami and a Maxwell-Wagner analysis. Both types analysis suggest that the morphology of the crystal growth changes at a point during the crystallization. The differences between the cells can be explained by this transition taking place at different times for the two cells

Physical ageing studied by a device allowing for rapid thermal equilibration

Ageing of organic glasses to the equilibrium liquid state is studied by measuring the dielectric loss utilizing a microregulator where temperature is controlled by means of a Peltier element. Compared to conventional equipment the new device adds almost two orders of magnitude to the span of observable ageing times. Data for five organic glass-forming liquids are presented. The existence of an "inner clock" is confirmed by a model-free test showing that the ageing of structure is controlled by the same material time that controls the dielectric properties. At long times relaxation is not stretched, but simple exponential, and there is no "expansion gap" between the limits of the relaxation rates following up and down jumps to the same temperature

Communication:Two measures of isochronal superposition

A liquid obeys isochronal superposition if its dynamics is invariant along the isochrones in the thermodynamic phase diagram (the curves of constant relaxation time). This paper introduces two quantitative measures of isochronal superposition. The measures are used to test the following six liquids for isochronal superposition: 1,2,6 hexanetriol, glycerol, polyphenyl ether, diethyl phthalate, tetramethyl tetraphenyl trisiloxane, and dibutyl phthalate. The latter four van der Waals liquids obey isochronal superposition to a higher degree than the two hydrogen-bonded liquids. This is a predic- tion of the isomorph theory, and it confirms findings by other groups.Comment: 14 pages (article 4 pages, supplementary 10 pages), 42 figure