Thermodynamic aspects of the glass transition of silicates

The marked increase in second-order thermodynamic properties observed at the glass-transition signals the onset of configurational changes in viscous liquids. Experimental determinations in the glass-transition range will illustrate this point for thermal expansivity and demonstrate that the kinetics of volume, enthalpy and structural relaxation are identical for silicate liquids. Within the framework of the Adam–Gibbs theory, heat capacity and viscosity data may be combined to calculate configurational entropies and gain insights into the potential energy barrier to viscous flow. Finally, the considerable effect of water on the glass transition temperature of geologically relevant silicates is presented.     

Configurational energetics in ice ih probed by compton scattering

Temperature-induced changes in the ground-state electron momentum density of polycrystalline ice Ih are studied with high accuracy by Compton scattering utilizing synchrotron radiation. A unique feasibility of the technique to provide direct experimental information on configurational enthalpies and heat capacities is demonstrated. The configurational enthalpy, obtained with an accuracy of 1.5 meV, evolves linearly with temperature above T=100 K. Consequently the configurational heat capacity is found to be constant, c{p}{config}=(0.44+/-0.11) J g{-1} K-1, in this temperature regime. Obtaining these quantities experimentally is fundamentally important for evaluating the accuracy of molecular-dynamics simulations schemes.     

Quantum diffusion in solid H2?Ne solutions

Quantum diffusion in solid hydrogen containing 0.02–0.25 mol.% neon has been investigated by the calorimetric method in temperature range 1–3 K. The concentrations of orthohydrogen were 0.23; 0.5 and 1 mol. %. The parameter studied was characteristic configurational relaxation time τ. Heat capacity is very sensitive to space distribution of orthohydrogen molecules. Therefore, the determination of configuration relaxation rate has been performed by observing the time dependence of heat capacity. A neon impurity in the indicated concentration is observed to accelerate quantum diffusion in hydrogen. The magnitude of the effect diminishes as the temperature increases.     

Heating liquid dielectrics by time dependent fields

Steady state and time-resolved dielectric relaxation experiments are performed at high fields on viscous glycerol and the effects of energy absorption from the electric field are studied. Time resolution is obtained by a sinusoidal field whose amplitude is switched from a low to a high level and by recording voltage and current traces with an oscilloscope during this transition. Based on their distinct time and frequency dependences, three sources of modifying the dynamics and dielectric loss via an increase in the effective temperature can be distinguished: electrode temperature, real sample temperature, and configurational temperatures of the modes that absorbed the energy. Isothermal conditions that are desired for focusing on the configurational temperature changes (as in dielectric hole burning and related techniques) are maintained only for very thin samples and for moderate power levels. For high frequencies, say ν > 1 MHz, changes of the real temperature will exceed the effects of configurational temperatures in the case of macroscopic samples. Regarding microwave chemistry, heating via cell phone use, and related situations in which materials are subject to fields involving frequencies beyond the MHz regime, we conclude that changes in the configurational (or fictive) temperatures remain negligible compared with the increase of the real temperature. This simplifies the assessment of how time dependent electric fields modify the properties of materials.     

Negative heat capacity of Ar55 cluster

The solid–liquid phase transitions of Ar₅₅ cluster was simulated by the microcanonical molecular dynamics and microcanonical parallel tempering methods using Lennard–Jones potential, and thermodynamic quantities were calculated. The caloric curve of cluster has S-bend. To understand this behaviour, configurational and total entropies were evaluated, and the dents on the entropy curves were noticed as the sign of negative heat capacity. The heat capacities were evaluated by using configurational entropy data. The potential energy distributions have bimodal behaviour in the given range at the melting temperature. At the same time by using configurational entropy canonical caloric curve and canonical heat capacity were calculated. To obtain entropy change upon melting, total entropy were calculated from the caloric curve. The microcanonical results melting temperature, latent heat and entropy change upon melting values were reported and compared with the values reported in the literature and the values calculated from the thermodynamic relations offered for bulk matter, consistent values were found.     

Can experiments select the configurational component of excess entropy?

Configurational entropy is frequently used to rationalize the structural dynamics of glass-forming liquids. The main problem with this concept is that it is not directly accessible to experiments. We introduce a procedure to estimate the configurational component of the excess entropy of a liquid --specifically, the configurational-entropy contribution from the structural relaxation process-- through a combined investigation of dynamic and thermodynamic properties as functions of temperature and pressure. We test our method on orthoterphenyl, salol, and glycerol, and find that the fraction of excess entropy that arises from structural configurations is about 70% for all three materials.Received: 29 April 2004, Published online: 29 June 2004PACS: 64.70.Pf Glass transitions - 78.35. + c Brillouin and Rayleigh scattering; other light scattering - 77.22.Gm Dielectric loss and relaxation     

Mosaic multistate scenario versus one-state description of supercooled liquids

According to the mosaic scenario, relaxation in supercooled liquids is ruled by two competing mechanisms: surface tension, opposing the creation of local excitations, and entropy, providing the drive to the configurational rearrangement of a given region. We test this scenario through numerical simulations well below the Mode Coupling temperature. For an equilibrated configuration, we freeze all the particles outside a sphere and study the thermodynamics of this sphere. The frozen environment acts as a pinning field. Measuring the overlap between the unpinned and pinned equilibrium configurations of the sphere, we can see whether it has switched to a different state. We do not find any clear evidence of the mosaic scenario. Rather, our results seem compatible with the existence of a single (liquid) state. However, we find evidence of a growing static correlation length, apparently unrelated to the mosaic one.     

Dynamic scaling approach to glass formation

Experimental data for the temperature dependence of relaxation times are used to argue that the dynamic scaling form, with relaxation time diverging at the critical temperature T(c) as (T-T(c))(-nuz), is superior to the classical Vogel form. This observation leads us to propose that glass formation can be described by a simple mean-field limit of a phase transition. The order parameter is the fraction of all space that has sufficient free volume to allow substantial motion, and grows logarithmically above T(c). Diffusion of this free volume creates random walk clusters that have cooperatively rearranged. We show that the distribution of cooperatively moving clusters must have a Fisher exponent tau=2. Dynamic scaling predicts a power law for the relaxation modulus G(t) approximately t(-2/z), where z is the dynamic critical exponent relating the relaxation time of a cluster to its size. Andrade creep, universally observed for all glass-forming materials, suggests z=6. Experimental data on the temperature dependence of viscosity and relaxation time of glass-forming liquids suggest that the exponent nu describing the correlation length divergence in this simple scaling picture is not always universal. Polymers appear to universally have nuz=9 (making nu=3 / 2). However, other glass-formers have unphysically large values of nuz, suggesting that the availability of free volume is a necessary, but not sufficient, condition for motion in these liquids. Such considerations lead us to assert that nuz=9 is in fact universal for all glass- forming liquids, but an energetic barrier to motion must also be overcome for strong glasses.     

Heat capacity of isolated clusters

The character of interaction between thermal (vibrational) and configurational cluster excitations is considered under adiabatic conditions when a cluster is a member of a microcanonical ensemble. The hierarchy of equilibration times determines the character of atomic equilibrium in the cluster. The behavior of atoms in the cluster can be characterized by two effective (mean) temperatures, corresponding to the solid and liquid aggregate states, because the typical time for equilibration of atomic motion is less than the transition time between aggregate states. If the cluster is considered for a time much longer than the typical dwell time in either phase, then it is convenient to characterize the system by only one temperature, which is determined from the statistical-thermodynamic long-time average. These three temperatures are not far apart, nor are the cluster heat capacities evaluated on the basis of these definitions of temperature. The heat capacity of a microcanonical ensemble may be negative for two coexisting phases if the mean temperature is defined in terms of the mean kinetic energy, rather than as the derivative of energy with respect to microcanonical entropy. However, if the configurational excitation energy is smaller than the total excitation energy separating the phases, then the two-state model predicts a positive heat capacity under either definition of temperature. Moreover, if the cluster is sufficiently large, then the maximum values of the microcanonical and canonical heat capacities are equal.     

Spin–lattice relaxation phenomena in the magnetic state of a suggested Weyl semimetal CeAlGe

ABSTRACT

In this work, we report the results of DC susceptibility, AC susceptibility and related technique, resistivity, transverse and longitudinal magnetoresistance and heat capacity on polycrystalline magnetic semimetal CeAlGe. This compound undergoes antiferromagnetic type ordering around 5.2 K (T¹). Under the application of external magnetic fields, parallel alignment of magnetic moments is favoured above 0.5?T. At low field and temperature, frequency and AC field amplitude response of AC susceptibility indicate the presence of spin–lattice relaxation phenomena. The observation of spin–lattice interaction suggests the presence of the Rashba–Dresselhaus spin–orbit interaction which is associated with inversion and time-reversal symmetry breaking. Additionally, the presence of negative and asymmetric longitudinal magnetoresistance indicates anomalous velocity contribution to the magnetoresistance due to the Rashba–Dresselhaus spin–orbit interaction which is further studied by heat capacity.     

多元可激发气体声弛豫频率的环境影响分析

推导多元可激发气体中声弛豫频率和环境温度、压强的解析关系.理论分析和仿真计算表明：声弛豫频率线性反比于主弛豫过程的弛豫时间,正比于主弛豫过程的振动耦合热容,反比于外自由度热容;温度升高导致振动耦合热容增加、内外自由度能量转移速率增大引起弛豫时间减少,进而造成声弛豫频率正比于环境温度;压强增加使得分子碰撞速率增加引起弛豫时间减少,进而使得声弛豫频率线性正比于环境压强.     

An interstitialcy theory of structural relaxation and related viscous flow of glasses

A theory of isothermal structural relaxation and creep of glasses below the glass transition temperature is given. According to the interstitialcy theory, the supercooled liquid state does not exist below a Kauzmann "pseudocritical" temperature T(k), which lies above the temperature T(K), commonly called the "Kauzmann temperature." Structural relaxation is simply a reduction with time of the interstitialcy concentration to the crystalline state for TT(k). The predicted viscosity eta is universal, given by eta=eta(0) + eta(T)t, in agreement with experiment. eta is continuous in T, with eta discontinuous at T(k) but linear in 1/T above and below T(k). The dependence of eta on the shear modulus directly connects kinetic and thermodynamic properties of glasses and liquids.     

Modeling phase transition for compressible two-phase flows applied to metastable liquids

The seven-equation model for two-phase flows is a full non-equilibrium model, each phase has its own pressure, velocity, temperature, etc. A single value for each property, an equilibrium value, can be achieved by relaxation methods. This model has better features than other reduced models of equilibrium pressure for the numerical approximations in the presence of non-conservative terms. In this paper we modify this model to include the heat and mass transfer. We insert the heat and mass transfer through temperature and Gibbs free energy relaxation effects. New relaxation terms are modeled and new procedures for the instantaneous temperature and Gibbs free energy relaxation toward equilibrium is proposed. For modeling such relaxation terms, our idea is to make use of the assumptions that the mechanical properties, the pressure and the velocity, relax much faster than the thermal properties, the temperature and the Gibbs free energy, and the ratio of the Gibbs free energy relaxation time to the temperature relaxation time is extremely high. All relaxation processes are assumed to be instantaneous, i.e. the relaxation times are very close to zero. The temperature and the Gibbs free energy relaxation are used only at the interfaces. By these modifications we get a new model which is able to deal with transition fronts, evaporation fronts, where heat and mass transfer occur. These fronts appear as extra waves in the system. We use the same test problems on metastable liquids as in Saurel et al. [R. Saurel, F. Petitpas, R. Abgrall, Modeling phase transition in metastable liquids: application to cavitating and flashing flows, J. Fluid Mech. 607 (2008) 313–350]. We have almost similar results. Computed results are compared to the experimental ones of Simões-Moreira and Shepherd [J.R. Simões-Moreira, J.E. Shepherd, Evaporation waves in superheated dodecane, J. Fluid Mech. 382 (1999) 63–86]. A reasonable agreement is achieved. In addition we consider the six-equation model with a single velocity which is obtained from the seven-equation model in the asymptotic limit of zero velocity relaxation time. The same procedure for the heat and mass transfer is used with the six-equation model and a comparison is made between the results of this model with the results of the seven-equation model.     

Surface nuclear magnetic relaxation and dynamics of water and oil in granular packings and rocks

Low field proton nuclear spin-relaxation at variable magnetic field strength and temperature provides surface dynamical parameters such as surface diffusion coefficients, activation energies, time of residence and coefficient of surface affinity. These parameters were extracted from measurements on grain packs and natural oil-bearing rocks. On grain packs, we show first that changing the amount of surface paramagnetic impurities leads to striking different relationships between the pore-size and the relaxation times T1 and T2. These relationships are well supported by fast-diffusion (surface-limited) or slow-diffusion relaxation models. Surface relaxivity parameters rho1 and rho2 are deduced from the pore size dependence in the fast-diffusion regime. Then, we evidence the frequency and temperature dependence of the surface relaxivity rho1 by field cycling NMR relaxation and relevant theoretical models. The typical frequency dependence found allows an experimental separation of the surface and bulk microdynamics in granular packings and petroleum rocks and the determination of the above mentioned surface dynamical parameters. Finally, we present the first field cycling nuclear spin relaxation experiments performed in water/oil saturated petroleum rocks. We believe that these experiments give new information about the surface localization of these two saturating liquids in pores.     

Conformational temperature characterizing the folding of a protein

The time sequences of the molecular dynamics simulation for the folding process of a protein is analyzed with the inherent structure landscape which focuses on the configurational dynamics of the system. Time-dependent energy and entropy for inherent structures are introduced, and from these quantities a conformational temperature is defined. The conformational temperature follows the time evolution of a slow relaxation process and reaches the bath temperature when the system is equilibrated. We show that the nonequilibrium system is described by two temperatures, one for fast vibration and the other for slow configurational relaxation, while the equilibrium system is described by one temperature. The proposed formalism is applicable widely for systems with many metastable states.     

Metastable states,relaxation mechanisms,and fracture of liquids under severe loading conditions

The relaxation properties and fracture of glycerol, silicone oil, transformer oil, and water have been studied experimentally under shock wave loading. The power-law strain rate dependences of the stress amplitude and spall strength were found for the compression and rarefaction fronts, respectively. It was shown that temperature has a strong influence on the spall strength of glycerol near the phase transformation temperature. The power laws reflect a self-similar nature of the momentum transfer and fracture mechanisms of liquids that are conventionally observed in solids and governed by the mechanisms of defect-induced structural relaxation. The mechanisms of viscoelasticity are related to the metastable states that may give rise to a collective behavior of displacement field fluctuations (microshearing) in liquids and thus provide a viscoplastic response of liquids under high strain rate loading.     

Phenomenological theory of structural relaxation based on a thermorheologically complex relaxation time distribution

The aim of this work is to explore the consequences on the kinetics of structural relaxation of considering a glass-forming system to consist of a series of small but macroscopic relaxing regions that evolve independently from each other towards equilibrium in the glassy state. The result of this assumption is a thermorheologically complex model. In this approach each relaxing zone has been assumed to follow the Scherer-Hodge model for structural relaxation (with the small modification of taking a linear dependence of configurational heat capacity with temperature). The model thus developed contains four fitting parameters. A least-squares search routine has been used to find the set of model parameters that fit simultaneously four DSC thermograms in PVAc after different thermal histories. The computersimulated curves are compared with those obtained with Scherer-Hodge model and the model proposed by Gómez and Monleón. The evolution of the relaxation times during cooling or heating scans and also during isothermal annealing below the glass transition has been analysed. It has been shown that the relaxation times distribution narrows in the glassy state with respect to equilibrium. Isothermal annealing causes this distribution to broaden during the process to finally attain in equilibrium the shape defined at temperatures above T _g .     

A quantum field theory of the liquid-glass transition in multi-component liquids

An established unified theory of the liquid-glass transition in one-component liquids is extended to multi-component liquids. The universal features such as the Kauzmann paradox, the Vogel-Tamman-Fulcher (VTF) law on the relaxation times and the transport coefficients, the jump of the specific heat at the glass transition temperature and the Boson peaks are elucidated. The Kauzmann entropy in a form of a Curie law with a negative sign comes from the mixing between the sound and the intra-band fluctuation entropies, where the critical temperature corresponds to the sound instability temperature at a reciprocal particle distance. The VTF law is constructed from the Einstein relation on entropy and probability so that the Kauzmann entropy is included as a normal form in exponent of the VTF law. The Kauzmann entropy explains the Kauzmann paradox and the jump of the specific heat so that the universal features of the glass transition are elucidated consistently.     

‘Monte Carlo’ computer simulation of chain molecules III. Simulation of n-alkane molecules

Considering a realistic model for isolated n-alkane molecules, their configurational behaviour has been explored employing a ‘Monte Carlo’ method. The present study shows that the behaviour of the short molecules is unlike that of the longer molecules in regard to the variation with temperature of the mean-square end-to-end distance and radius of gyration. For the short molecules the mean-square end-to-end distance and the radius of gyration are decreasing functions of temperature, but they increase with temperature in the case of the longer molecules. The macromolecules assume random-walk behaviour at approximately 600 K. The computed heat capacity versus temperature curves disclose configurational transitions in the chains.