Loosing thermodynamic stability in amorphous materials

The primary relaxation dynamics near the glass transformation temperature T g exhibits universal features in all glass formers, when showing two-level tunneling states (Low Temp. Phys. 35, 282 (2009)). Researchers have long searched for any signature of the underlying “true” ergodic–nonergodic transition emerging at a certain thermodynamic instability temperature Te . Here, the relaxation timescale for glass-forming materials is analyzed within a self-consistent thermodynamic cluster description combined with the cluster percolation concept. Exploring the ergodic hypothesis, its violation is found near a crossover from the Gaussian to non-Gaussian (Poisson) cluster-volume fluctuations, describing the finite-size fractal-cluster distributions. The transformation of the compact-structure “ergodic” clusters into hole-like glassy nanoclusters is attributed to the critical-size thermal fluctuations. The ergodic–nonergodic phase diagram showing Te is predicted in the model-independent form through the glass fragility parameter known for organic and inorganic liquids and amorphous solids. In all cases the ergodic-instability temperature is located below and close to the glass transformation temperature, whereas the distance between the two characteristic temperatures decreases with growing the material fragility

Cluster relaxation dynamics in liquids and solids near the glass-transformation temperature

The structural relaxation in glass forming materials is studied near the glass transformation temperature Tg indicated by the heat capacity maximum. The late-time asymptote of the Kohlrausch–Williams–Watts form of the relaxation function is rationalized via the mesoscopic-scale correlated regions in terms of the Debye-type clusters following the dynamic scaling law. It is repeatedly shown that regardless of underlying microscopic realizations in glass formers with site disorder the structural relaxation is driven by local random fields, described via the directed random walks model. The relaxation space dimension ds = 3 at Tg is suggested for relaxing units of fractal dimension d f = 5/2 for quadrupolar-glass clusters in ortho–para hydrogen mixtures, that is compared with entangled-chain clusters in polymers (d f = 1) and solid-like clusters relaxing in supercooled molecular liquids (with ds = 6 and d f = 3). The relaxation dynamics of orientational-glass clusters in plastic crystals is attributed to the model of continuos time random walks in space ds = 6. As a by-product, the expansivity in polymers, molecular liquids and networks is predicted

Orientational ordering in monolayers of ortho–para hydrogen

We discuss orientational ordering in monolayers of solid hydrogen in view of recent experimental findings in NMR studies of (ortho)c–(para)₁–c-hydrogen mixtures on boron nitride substrate. Analysis of the temperature-concentration behavior for the observed NMR frequency splitting is given on the basis of a two-dimensional (J = 1)c–(J = 0)₁–c-rotor model with the quadrupolar coupling constant Г₀ = (0.50 ± 0.03) K and the crystalline field amplitude V₀ = (0.70 ± 0.10) K derived from experiment. The two distinct para-rotational short-range ordered structures are described in terms of the local alignment and orientation of the polar principal axis, and are shown to be due to the interplay between the positive and negative crystalline fields. It is shown that the local structures observed below the 2D site-percolation threshold cp = 0.72 are rather different from the ferromagnetic-type para-rotational ordering suggested earlier by Harris and Berlinsky

Slow relaxation in weakly open vertex-splitting rational polygons

The problem of splitting effects by vertex angles is discussed for nonintegrable rational polygonal billiards. A statistical analysis of the decay dynamics in weakly open polygons is given through the orbit survival probability. Two distinct channels for the late-time relaxation of type 1/t^delta are established. The primary channel, associated with the universal relaxation of ''regular'' orbits, with delta = 1, is common for both the closed and open, chaotic and nonchaotic billiards. The secondary relaxation channel, with delta > 1, is originated from ''irregular'' orbits and is due to the rationality of vertices.Comment: Key words: Dynamics of systems of particles, control of chaos, channels of relaxation. 21 pages, 4 figure

Generic features of the primary relaxation in glass-forming materials (Review Article)

We discuss structural relaxation in molecular and polymeric supercooled liquids, metallic alloys and orientational glass crystals. The study stresses especially the relationships between observables raised from underlying constraints imposed on degrees of freedom of vitrification systems. A self-consistent parametrization of the α-timescale on macroscopic level results in the material-and-model independent universal equation, relating three fundamental temperatures, characteristic of the primary relaxation, that is numerically proven in all studied glass formers. During the primary relaxation, the corresponding small and large mesoscopic clusters modify their size and structure in a self-similar way, regardless of underlying microscopic realizations. We show that cluster-shape similarity, instead of cluster-size fictive divergence, gives rise to universal features observed in primary relaxation. In all glass formers with structural disorder, including orientational-glass materials (with the exception of plastic crystals), structural relaxation is shown to be driven by local random fields. Within the dynamic stochastic approach, the universal subdiffusive dynamics corresponds to random walks on small and large fractals

THERMAL EXPANSION OF METHANES AND CONVERSION PROCESSES

On a étudié la dilatation thermique du méthane solide, contenant de l'oxygène et de l'azote comme impuretés, dans la gamme de température entre 2 et 14 K.The thermal expansion of solid methane, containing O2 and N2 impurities, was studied in the temperature range from 2 K to 14 K