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In this article, we investigate the structural relaxation of lithium silicate glass during isothermal physical aging by monitoring the temporal evolution of its refractive index and enthalpy following relatively large (10–40 °C) up- and down-jumps in temperature. The Kohlrausch–Williams–Watts function aptly describes the up- and down-jump data when analyzed separately. For temperature down-jumps, the glass exhibits a typical stretched exponential kinetic behavior with the non-exponentiality parameter β < 1, whereas up-jumps show a compressed exponential behavior (β > 1). We analyzed these datasets using the non-exponential and non-linear Tool–Narayanaswamy–Moynihan (TNM) model, aiming to provide a comprehensive description of the primary or α-relaxation of the glass. This model described both up- and down-jump datasets using a single value of β ≤ 1. However, the standard TNM model exhibited a progressively reduced capacity to describe the data for larger temperature jumps, which is likely a manifestation of the temperature dependence of the non-exponentiality or non-linearity of the relaxation process. We hypothesize that the compressed exponential relaxation kinetics observed for temperature up-jumps stems from a nucleation-growth-percolation-based evolution on the dynamically mobile regions within the structure, leading to a self-acceleration of the dynamics. On the other hand, temperature down-jumps result in self-retardation, as the slow-relaxing denser regions percolate in the structure to give rise to a stretched exponential behavior. [ABSTRACT FROM AUTHOR]

Until quite recently, in almost all papers on crystal nucleation in glass-forming substances, it was assumed that nucleation proceeds in a completely relaxed supercooled liquid and, hence, at constant values of the critical parameters determining the nucleation rate for any given set of temperature, pressure, and composition. Here, we analyze the validity of this hypothesis for a model system by studying nucleation in a lithium silicate glass treated for very long times (up to 250 days) in deeply supercooled states, reaching 60 K below the laboratory glass transition temperature, Tg. At all temperatures in the considered range, T < Tg, we observed an enormous difference between the experimental number of nucleated crystals, N(t), and its theoretically expected value computed by assuming the metastable state of the relaxing glass has been reached. Analyzing the origin of this discrepancy, we confirmed that the key parameters determining the nucleation rates change with time as a result of the glass relaxation process. Finally, we demonstrate that, for temperatures below 683 K, this particular glass almost fully crystallizes prior to reaching the ultimate steady-state nucleation regime (e.g., at 663 K, it would take 176 years for the glass to reach 99% crystallization, while 2600 years would be needed for complete relaxation). This comprehensive study proves that structural relaxation strongly affects crystal nucleation in deeply supercooled states at temperatures well below Tg; hence, this phenomenon has to be accounted for in any crystal nucleation model. [ABSTRACT FROM AUTHOR]

Until quite recently, in almost all papers on crystal nucleation in glass-forming substances, it was assumed that nucleation proceeds in a completely relaxed supercooled liquid and, hence, at constant values of the critical parameters determining the nucleation rate for any given set of temperature, pressure, and composition. Here, we analyze the validity of this hypothesis for a model system by studying nucleation in a lithium silicate glass treated for very long times (up to 250 days) in deeply supercooled states, reaching 60 K below the laboratory glass transition temperature, Tg. At all temperatures in the considered range, T < Tg, we observed an enormous difference between the experimental number of nucleated crystals, N(t), and its theoretically expected value computed by assuming the metastable state of the relaxing glass has been reached. Analyzing the origin of this discrepancy, we confirmed that the key parameters determining the nucleation rates change with time as a result of the glass relaxation process. Finally, we demonstrate that, for temperatures below 683 K, this particular glass almost fully crystallizes prior to reaching the ultimate steady-state nucleation regime (e.g., at 663 K, it would take 176 years for the glass to reach 99% crystallization, while 2600 years would be needed for complete relaxation). This comprehensive study proves that structural relaxation strongly affects crystal nucleation in deeply supercooled states at temperatures well below Tg; hence, this phenomenon has to be accounted for in any crystal nucleation model. [ABSTRACT FROM AUTHOR]

Metadynamics (MetaD) is a useful technique to study rare events such as crystallization. It has been only recently applied to study nucleation and crystallization in glass-forming liquids such as silicates, but the optimal set of parameters to drive crystallization and obtain converged free energy surfaces is still unexplored. In this work, we systematically investigated the effects of the simulation conditions to efficiently study the thermodynamics and mechanism of crystallization in highly viscous systems. As a prototype system, we used fused silica, which easily crystallizes to β-cristobalite through MetaD simulations, owing to its simple microstructure. We investigated the influence of the height, width, and bias factor used to define the biasing Gaussian potential, as well as the effects of the temperature and system size on the results. Among these parameters, the bias factor and temperature seem to be most effective in sampling the free energy landscape of melt to crystal transition and reaching convergence more quickly. We also demonstrate that the temperature rescaling from T > Tm is a reliable approach to recover free energy surfaces below Tm, provided that the temperature gap is below 600 K and the configurational space has been properly sampled. Finally, albeit a complete crystallization is hard to achieve with large simulation boxes, these can be reliably and effectively exploited to study the first stages of nucleation. [ABSTRACT FROM AUTHOR]

The temperature at which the classical critical nucleus size is equal to the average size of the cooperatively rearranging regions (CRR) in a supercooled liquid has been referred to as a "cross-over" temperature. We show, for the first time, using published nucleation rate, viscosity, and thermophysical data, that the cross-over temperature for the lithium disilicate melt is significantly larger than the temperature of the kinetic spinodal and is equal or close to the temperature corresponding to the maximum in the experimentally observed nucleation rates. We suggest that the abnormal decrease in nucleation rates below the cross-over temperature is most likely because, in this regime, the CRR size controls the critical nucleus size and the nucleation rate. This finding links, for the first time, measured nucleation kinetics to the dynamic heterogeneities in a supercooled liquid. [ABSTRACT FROM AUTHOR]

In several nano-porous materials and their composites, enhancement of ionic conductivity has been reported and several mechanisms having different origins have been proposed so far. In the present work, ionic motion of Li ions in porous lithium disilicates is examined by molecular dynamics simulation in the constant volume conditions and the enhancement of the dynamics is predicted. Structures and dynamics of ions in a nano-porous system were characterized and visualized to clarify the mechanism of the enhancement. The diffusion coefficient of Li ions has shown the maximum in the medium density (and porosity) region, and near the maximum, shortening of the nearly constant loss region in the mean squared displacement of ions as well as changes of the structures of the coordination polyhedra, LiOx is found. It suggests that the loosening of the cage, which increases the jump rate of ions, is an origin of the enhancement. When larger (but still in a nano-scale) voids are formed with a further decrease of density, more tight cages are reconstructed and the diffusion coefficient decreases again. These behaviors are closely related to the residual stress in the system. It is noteworthy that the explanation is not based on the percolation of the path only or formation of boundaries, although the former also affects the dynamics. [ABSTRACT FROM AUTHOR]

Using first principle calculations, we uncover the underlying mechanisms explaining the brittle-toductile transition of LixSi electrodes in lithium ion batteries with increasing Li content. We show that plasticity initiates at x = ~0.5 with the formation of a craze-like network of nanopores separated by Si-Si bonds, while subsequent failure is still brittle-like with the breaking of Si-Si bonds. Transition to ductile behavior occurs at x ≥ 1 due to the increased density of highly stretchable Li-Li bonds, which delays nanopore formation and stabilizes nanopore growth. Collapse of the nanopores during unloading of the LixSi alloys leads to significant strain recovery. [ABSTRACT FROM AUTHOR]

Molecular dynamics simulations have been performed to study the structures along the pressure-volume diagram of network-glasses and melts exemplified by the lithium disilicate system. Experimentally, densification of the disilicate glass by elevated pressure is known and this feature is reasonably reproduced by the simulations. During the process of densification or decompression of the system, the statistics of Qn (i.e., SiO4 tetrahedron unit with n bridging oxygen linked to the silicon atom where n = 0, 1, 2, 3, or 4) change, and the percentage of the Q3 structures show the maximum value near atmospheric pressure at around Tg. Changes of Qn distribution are driven by the changes of volume (or pressure) and are explained by the different volumes of structural units. Furthermore, some pairs of network structures with equi-volume, but having different distributions of Qn (or different heterogeneity), are found. Therefore, for molecular dynamics simulations of the Qn distributions, it is important to take into account the complex phase behavior including poly-structures with different heterogeneities as well as the position of the system in the P-V-T diagram. [ABSTRACT FROM AUTHOR]

The breakdown of the Stokes–Einstein relation was investigated for three glass-forming models composed of mixtures of Lennard-Jones A-B particles, which have been constructed by modifying the shape of the interaction potential between A particles. By performing molecular dynamics simulations, we show that these mixtures intrinsically possess different organizations. The breakdown of the Stokes–Einstein relation particularly occurs at different temperatures for each type of particles and it is directly related to the dynamical decoupling between A and B particles and the formation or not of paths where fast particles show jumplike motions. The effective size of each particles and the fraction of slow and fast particles were also determined. Similarity with silicate glasses including mixed alkali effect is discussed. [ABSTRACT FROM AUTHOR]

Nonlinear ionic conductivity effects are studied via molecular dynamics simulations. We present numerical results for the field dependence of the current density as well as the second moment of the ion displacements. Furthermore we check whether structural changes occur upon application of strong electric fields. We obtain a complex picture of the field-dependent ion dynamics of a disordered system that is beyond simple model descriptions. [ABSTRACT FROM AUTHOR]

Examines the structure of lithium silicate glasses through hyperfine sublevel correlation (HYSCORE) spectroscopy. Nature of HYSCORE; Measurements of lithium spectra; Description of spectra simulation.