Adam-Gibbs model in the density scaling regime and its implications for the configurational entropy scaling

To solve a long-standing problem of condensed matter physics with determining a proper description of the thermodynamic evolution of the time scale of molecular dynamics near the glass transition, we extend the well-known Adam-Gibbs model to describe the temperature-volume dependence of structural relaxation times, ${\tau}_{\alpha} (T,V)$. We employ the thermodynamic scaling idea reflected in the density scaling power law, ${\tau}_{\alpha}=f(T^{-1} V^{-\gamma } )$, recently acknowledged as a valid unifying concept in the glass transition physics, to discriminate between physically relevant and irrelevant attempts at formulating the temperature-volume representations of the Adam-Gibbs model. As a consequence, we determine a straightforward relation between the structural relaxation time ${\tau}_{\alpha}$ and the configurational entropy $S_c$, giving evidence that also $S_c (T,V)=g(T^{-1} V^{-\gamma} )$ with the exponent {\gamma} that enables to scale ${\tau}_{\alpha} (T,V)$. This important finding has meaningful implications for the linkage between thermodynamics and molecular dynamics near the glass transition, because it implies that ${\tau}_{\alpha}$ can be scaled with $S_c$

Hidden parameters in open-system evolution unveiled by geometric phase

We find a class of open-system models in which individual quantum trajectories may depend on parameters that are undetermined by the full open-system evolution. This dependence is imprinted in the geometric phase associated with such trajectories and persists after averaging. Our findings indicate a potential source of ambiguity in the quantum trajectory approach to open quantum systems.Comment: QSD analysis added; several stylistic changes; journal reference adde

An equation for the description of volume and temperature dependences of the dynamics of supercooled liquids and polymer melts

A recently proposed expression to describe the temperature and volume dependences of the structural (or alpha) relaxation time is discussed. This equation satisfies the scaling law for the relaxation times, tau = f(TV^g), where T is temperature, V the specific volume, and g a material-dependent constant. The expression for the function f is shown to accurately fit experimental data for several glass-forming liquids and polymers over an extended range encompassing the dynamic crossover, providing a description of the dynamics with a minimal number of parameters. The results herein can be reconciled with previously found correlations of the isochoric fragility with both the isobaric fragility at atmospheric pressure and the scaling exponent g.Comment: to be published in the special edition of J. Non-Crystalline Solids honoring K.L. Nga

Improving FEM crash simulation accuracy through local thickness estimation based on CAD data

ManuscriptIn this paper, we present a method for estimating local thickness distribution in finite element models, applied to injection molded and cast engineering parts. This method features considerable improved performance compared to two previously proposed approaches, and has been validated against thickness measured by different human operators. We also demonstrate that the use of this method for assigning a distribution of local thickness in FEM crash simulations results in a much more accurate prediction of the real part performance, thus increasing the benefits of computer simulations in engineering design by enabling zero-prototyping and thus reducing product development costs. The simulation results have been compared to experimental tests, evidencing the advantage of the proposed method. Thus, the proposed approach to consider local thickness distribution in FEM crash simulations has high potential on the product development process of complex and highly demanding injection molded and cast parts and is currently being used by Ford Motor Company.FCT – Fundação para a Ciência e a Tecnologia (Portuguese Foundation for Science and Technology) through projects PEst-C/CTM/LA0025/2013 and PEst-OE/EEI/UI0752/201

Mechanical and dielectric relaxation spectra in seven highly viscous glass formers

Published dielectric and shear data of six molecular glass formers and one polymer are evaluated in terms of a spectrum of thermally activated processes, with the same barrier density for the retardation spectrum of shear and dielectrics. The viscosity, an independent parameter of the fit, seems to be related to the high-barrier cutoff time of the dielectric signal, in accordance with the idea of a renewal of the relaxing entities after this critical time. In the five cases where one can fit accurately, the temperature dependence of the high-barrier cutoff follows the shoving model. The Johari-Goldstein peaks, seen in four of our seven cases, are describable in terms of gaussians in the barrier density, superimposed on the high-frequency tail of the $\alpha$-process. Dielectric and shear measurements of the same substance find the same peak positions and widths of these gaussians, but in general a different weight.Comment: Contribution to the Ngai Fest issue of J. Non-Cryst. Solids; 8 pages, 8 figures, 30 reference

Glassy dynamics in mono-, di-, and tri-propylene glycol: From the alpha- to the fast beta-relaxation

We present a thorough characterization of the glassy dynamics of three propylene glycols (mono-, di- and trimer) by broadband dielectric spectroscopy. By covering a frequency range of more than 15 decades, we have access to the entire variety of dynamic processes typical for glassy dynamics. These results add three more molecular glass formers to the sparse list of materials for which real broadband spectra, including the region of the fast beta-process, are available. Some first analyses of the various observed dynamic processes are provided

More than one dynamic crossover in protein hydration water

Studies of liquid water in its supercooled region have led to many insights into the structure and behavior of water. While bulk water freezes at its homogeneous nucleation temperature of approximately 235 K, for protein hydration water, the binding of water molecules to the protein avoids crystallization. Here we study the dynamics of the hydrogen bond (HB) network of a percolating layer of water molecules, comparing measurements of a hydrated globular protein with the results of a coarse-grained model that has been shown to successfully reproduce the properties of hydration water. With dielectric spectroscopy we measure the temperature dependence of the relaxation time of protons charge fluctuations. These fluctuations are associated to the dynamics of the HB network of water molecules adsorbed on the protein surface. With Monte Carlo (MC) simulations and mean--field (MF) calculations we study the dynamics and thermodynamics of the model. In both experimental and model analyses we find two dynamic crossovers: (i) one at about 252 K, and (ii) one at about 181 K. The agreement of the experiments with the model allows us to relate the two crossovers to the presence of two specific heat maxima at ambient pressure. The first is due to fluctuations in the HB formation, and the second, at lower temperature, is due to the cooperative reordering of the HB network

Wear Analysis of Discs and Balls on a Micro-Scale

Surface topographies of discs and balls after wear process were analysed. Discs were made from 42CrMo4 steel with hardness of 42 HRC, but balls from 100Cr6 steel of hardness 64 HRC. They were measured using white light interferometer Talysurf CCI Lite. Procedures for minimizing errors of wear loss determination were discussed. They can be applied thanks to software TalyMap. It was found that application of wear analysis of discs and balls on a micro scale allowed us precise determination of their wear after tribological tests, however this analysis should be careful, particularly for surfaces of high roughness

Effect of entropy on the dynamics of supercooled liquids: New results from high pressure data

We show that for arbitrary thermodynamic conditions, master curves of the entropy are obtained by expressing S(T,V) as a function of TV^g_G, where T is temperature, V specific volume, and g_G the thermodynamic Gruneisen parameter. A similar scaling is known for structural relaxation times,tau = f(TV^g); however, we find g_G < g. We show herein that this inequality reflects contributions to S(T,V) from processes, such as vibrations and secondary relaxations, that do not directly influence the supercooled dynamics. An approximate method is proposed to remove these contributions, S_0, yielding the relationship tau = f(S-S_0).Comment: 10 pages 7 figure