On the phenomena of partial crystallization of highly undercooled magnesium silicate molten droplets

The present work reports real-time observations of the phenomena of partial crystallization of one of the glass-forming materials, namely enstatite (MgSiO3) from its supercooled liquid droplet. Initially, the molten droplet has been held under purely non-contact conditions using the aerodynamic levitation technique. The desired levels of undercooling have been achieved by deliberately making the levitated molten droplet touch a thin molybdenum wire and hence to initiate heterogeneous nucleation from the point of contact. Influence of thermal parameters like undercooling, cooling rates and recalescence on the process of crystallization is investigated. To understand and report the morphological properties and extent of crystallinity, the solidified enstatite samples have been characterized using optical/scanning electron microscopy (SEM) and X-ray diffraction (XRD) respectively, which confirmed the formation of partially crystallized enstatite spherules and fully glass spherules. XRD showed sharp peaks of enstatite, which confirm crystallinity and a halo profile confirms the amorphous phase of enstatite. Based on the observations of several experiments, we propose the effect of thermal parameters such as levels of undercooling and recalescence on the partial crystallization, as well as partial glass formation from the initially molten droplets of enstatite composition.

Dynamics and Elastic Properties of Glassy Metastable States

By a molecular dynamics (MD) simulation method which ensures the system will be under hydrostatic pressure, dynamic and elastic properties of glassy metatstable states are investigated. In the MD method, the simulation cell fluctuates not only in volume but also in shape under constant hydrostatic pressure and temperature. As observed in experiments for many glass forming materials, metastable states in our simulation show a sharp increase in mean-square-displacement at certain temperatures TD. Dynamic heterogeneity is also observed at TD. Elastic properties are calculated from stress and strain relations obtained from the spontaneous fluctuation of internal stress tensor and simulation cell parameters. Each investigated state shows distinctive dynamics while maintaining solid-like elastic properties. The elastic properties stay intact even above TD. It has been shown that the rigidity and mobility of glassy metastable states are compatible under dynamic heterogeneity.

Integro-Differential Equation for the Non-Equilibrium Thermal Response of Glass-Forming Materials: Analytical Solutions

An integro-differential equation describes the non-equilibrium thermal response of glass-forming substances with a dynamic (time-dependent) heat capacity to fast thermal perturbations. We found that this heat transfer problem could be solved analytically for a heat source with an arbitrary time dependence and different geometries. The method can be used to analyze the response to local thermal perturbations in glass-forming materials, as well as temperature fluctuations during subcritical crystal nucleation and decay. The results obtained can be useful for applications and a better understanding of the thermal properties of glass-forming materials, polymers, and nanocomposites.

Dissecting Dynamics near the Glass Transition

Though the strong transformation in mechanical properties of glass-forming materials near the glass transition, Tg, has been recognized and exploited for millenia, efforts to understand and predict this phenomenon at a molecular level continue to this day. Close to Tg, where relaxation is considerably slower than predicted by the well-known Arrhenius equation, one of the most versatile and widely-used expressions to describe the dynamics or relaxation of glass formers is that of Vogel, Fulcher and Tammann (VFT). The VFT equation, introduced nearly 100 years ago, contains three adjustable fit parameters. In this work the dynamics of the polymer repeat units are related to macroscopic dynamics in polyelectrolyte complexes, which are hydrated amorphous blends of charged polymers. A simple expression, containing no freely adjustable fit parameters, is derived to quantitatively model relaxation from Tg to temperatures well into the Arrhenius region. The new expression, which also fits a selection of three common neutral polymers, will advance the understanding and use of the glass-forming phenomenon.

Quantifying the link between local structure and cellular rearrangements using information in models of biological tissues

Machine learning techniques have been used to quantify the relationship between local structural features and variations in local dynamical activity in disordered glass-forming materials. To date these methods have been...

Dynamic phase transitions in freestanding polymer thin films

After more than two decades of study, many fundamental questions remain unanswered about the dynamics of glass-forming materials confined to thin films. Experiments and simulations indicate that free interfaces enhance dynamics over length scales larger than molecular sizes, and this effect strengthens at lower temperatures. The nature of the influence of interfaces, however, remains a point of significant debate. In this work, we explore the properties of the nonequilibrium phase transition in dynamics that occurs in trajectory space between high- and low-mobility basins in a set of model polymer freestanding films. In thick films, the film-averaged mobility transition is broader than the bulk mobility transition, while in thin films it is a variant of the bulk result shifted toward a higher bias. Plotting this transition’s local coexistence points against the distance from the films’ surface shows thick films have surface and film-center transitions, while thin films practically have a single transition throughout the film. These observations are reminiscent of thermodynamic capillary condensation of a vapor–liquid phase between parallel plates, suggesting they constitute a demonstration of such an effect in a trajectory phase transition in the dynamics of a structural glass former. Moreover, this transition bears similarities to several experiments exhibiting anomalous behavior in the glass transition upon reducing film thickness below a material-dependent onset, including the broadening of the glass transition and the homogenization of surface and bulk glass transition temperatures.

Some Aspects of the Liquid Water Thermodynamic Behavior: From The Stable to the Deep Supercooled Regime

Liquid water is considered to be a peculiar example of glass forming materials because of the possibility of giving rise to amorphous phases with different densities and of the thermodynamic anomalies that characterize its supercooled liquid phase. In the present work, literature data on the density of bulk liquid water are analyzed in a wide temperature-pressure range, also including the glass phases. A careful data analysis, which was performed on different density isobars, made in terms of thermodynamic response functions, like the thermal expansion αP and the specific heat differences CP−CV, proves, exclusively from the experimental data, the thermodynamic consistence of the liquid-liquid transition hypothesis. The study confirms that supercooled bulk water is a mixture of two liquid “phases”, namely the high density (HDL) and the low density (LDL) liquids that characterize different regions of the water phase diagram. Furthermore, the CP−CV isobars behaviors clearly support the existence of both a liquid–liquid transition and of a liquid–liquid critical point.

Non-Markovian Methods in Glass Transition

A model for the heterogeneity of local dynamics in polymer and other glass-forming materials is provided here. The fundamental characteristics of the glass transition phenomenology emerge when simulating a condensed matter open cluster that has a strong interaction with its heterogeneous environment. General glass transition features, such as non-exponential structural relaxations, the slowing down of relaxation times with temperature and specific off-equilibrium glassy dynamics can be reproduced by non-Markovian dynamics simulations with the minimum computer resources. Non-Markovian models are shown to be useful tools for obtaining insights into the complex dynamics involved in the glass transition phenomenon, including whether or not there is a need for a growing correlation length or the relationship between the non-exponentiality of structural relaxations and dynamic heterogeneity.

High-pressure experiments as a novel perspective to study the molecular dynamics of glass-forming materials confined at the nanoscale

We report the pioneering high-pressure dielectric studies on the dynamics of a model van der Waals glass-forming liquid bisphenol-A diglycidyl ether infiltrated into anodic aluminum oxide templates of the mean pore sizes, d = 150 and d = 18 nm.