Beyond the Average: Spatial and Temporal Fluctuations in Oxide Glass-Forming Systems.

Atomic structure dictates the performance of all materials systems; the characteristic of disordered materials is the significance of spatial and temporal fluctuations on composition-structure-property-performance relationships. Glass has a disordered atomic arrangement, which induces localized distributions in physical properties that are conventionally defined by average values. Quantifying these statistical distributions (including variances, fluctuations, and heterogeneities) is necessary to describe the complexity of glass-forming systems. Only recently have rigorous theories been developed to predict heterogeneities to manipulate and optimize glass properties. This article provides a comprehensive review of experimental, computational, and theoretical approaches to characterize and demonstrate the effects of short-, medium-, and long-range statistical fluctuations on physical properties (e.g., thermodynamic, kinetic, mechanical, and optical) and processes (e.g., relaxation, crystallization, and phase separation), focusing primarily on commercially relevant oxide glasses. Rigorous investigations of fluctuations enable researchers to improve the fundamental understanding of the chemistry and physics governing glass-forming systems and optimize structure-property-performance relationships for next-generation technological applications of glass, including damage-resistant electronic displays, safer pharmaceutical vials to store and transport vaccines, and lower-attenuation fiber optics. We invite the reader to join us in exploring what can be discovered by going beyond the average.

Understanding Glass through Differential Scanning Calorimetry.

Differential scanning calorimetry (DSC) is a powerful tool to address some of the most challenging issues in glass science and technology, such as the nonequilibrium nature of the glassy state and the detailed thermodynamics and kinetics of glass-forming systems during glass transition, relaxation, rejuvenation, polyamorphic transition, and crystallization. The utility of the DSC technique spans across all glass-forming chemistries, including oxide, chalcogenide, metallic, and organic systems, as well as recently discovered metal-organic framework glass-forming systems. Here we present a comprehensive review of the many applications of DSC in glass science with focus on glass transition, relaxation, polyamorphism, and crystallization phenomena. We also emphasize recent advances in DSC characterization technology, including flash DSC and temperature-modulated DSC. This review demonstrates how DSC studies have led to a multitude of relevant advances in the understanding of glass physics, chemistry, and even technology.

Why does B2O3 suppress nepheline (NaAlSiO4) crystallization in sodium aluminosilicate glasses?

The uncontrolled growth of nepheline (NaAlSiO4) crystals during the manufacturing of sodium aluminosilicate glasses via the fusion draw or float techniques and during the vitrification of some of the sodium- and alumina-rich nuclear waste glasses is a well-known problem. The addition of B2O3 to suppress the crystallization in these glasses is well documented in the literature. Another advantage of B2O3 is that it lowers the viscosity of the glass melt and, if incorporated in its trigonal coordination state, will improve the intrinsic damage resistance of the final glass product. Hence, B2O3 has been an integral component of glass compositions for advanced industrial applications and for nuclear waste vitrification. However, one major disadvantage of adding B2O3 to alkali aluminosilicate based glasses is its adverse impact on their chemical durability due to the rapid hydrolysis of B[3,4]-O-B[3,4] bonds in comparison to (Si, Al)-O-(Si, Al) bonds. Therefore, designing a boron-containing alkali aluminosilicate based functional glass with minimal tendency towards crystallization and high chemical durability requires an in-depth fundamental understanding of the mechanism through which B2O3 tends to suppress crystallization in these glasses. There is no current consensus on the fundamental mechanism through which B2O3 tends to suppress nepheline crystallization in these glasses. Based on the mechanisms described and the questions raised in the preceding literature, the present study focuses on addressing the ongoing debate through a detailed structural and thermo-kinetic investigation of glasses designed in the Na2O-Al2O3-B2O3-SiO2 based quaternary system over a broad composition space. Using a combination of Raman and (1D and 2D) nuclear magnetic resonance spectroscopies along with equilibrium and non-equilibrium viscosity, and liquidus temperature measurements, it has been shown that the substitution of Si-O-Al by Si-O-B linkages in the glass structure results in a significant increase in the glass forming ability as well as an increase in the liquidus viscosity (slower diffusivity), thereby suppressing the nepheline crystallization.

Optical properties of a melt-quenched metal-organic framework glass.

Metal-organic framework (MOF) glasses are characterized by the possession of both inorganic and organic components, linked in a continuous network structure by coordination bonds. To the best of our knowledge, the optical properties of MOF glasses have not been reported until now. In this work, we prepared a transparent bubble-free bulk MOF glass, namely, the ZIF-62 glass (ZnIm2-xbImx), using our newly developed hot-pressing technique, and measured its optical properties. The ZIF-62 glass has a high transmittance (up to 90%) in the visible and near-infrared wavelength ranges, which is comparable to that of many oxide glasses. Using the Becke line nD method, we found that the ZIF-62 glass exhibits a refractive index (1.56) similar to most inorganic glasses, though a lower Abbe number (∼31).

Modifier clustering and avoidance principle in borosilicate glasses: A molecular dynamics study.

Oxide glasses are typically described as having a random, disordered skeleton of network-forming polyhedra that are depolymerized by network-modifying cations. However, the existence of local heterogeneity or clustering within the network-forming and network-modifying species remains unclear. Here, based on molecular dynamics simulations, we investigate the atomic structure of a series of borosilicate glasses. We show that the network-modifying cations exhibit some level of clustering that depends on composition-in agreement with Greaves' modified random network model. In addition, we demonstrate the existence of some mutual avoidance among network-forming atoms, which echoes the Loewenstein avoidance principle typically observed in aluminosilicate phases. Importantly, we demonstrate that the degree of heterogeneity in the spatial distribution of the network modifiers is controlled by the level of ordering in the interconnectivity of the network formers. Specifically, the mutual avoidance of network formers is found to decrease the propensity for modifier clustering.

Unusual thermal response of tellurium near-infrared luminescence in phosphate laser glass.

We report an unusual thermal response of tellurium (Te) near-infrared (NIR) luminescence in phosphate laser glass, where the luminescence first increases and then decreases with heat-treatment temperatures increasing from 250°C to the glass transition temperature (Tg). This is followed by a distinct revival of Te NIR luminescence at temperatures above Tg. This result differs from the scenario in conventional rare-earth (Er3+, Nd3+, and Yb3+)-doped phosphate glasses, where the rare-earth NIR emission decreases with increasing heat-treatment temperature. The difference may originate from conversion between Te4 and other Te species, which depends on the evolution of the glass structure and molecular motion during the reheating processes, leading to unusual thermal response of Te NIR luminescence. The increase in Te4 clusters enhances Te NIR emission, indicating that Te NIR luminescence is assigned to the Te4 cluster, in contrast to previous studies. Heating and cooling cycles between 50°C and 250°C reveal strong dependence of the thermal degradation on glass structure. Te-doped phosphate laser glass with zero thermal degradation can be realized by stabilizing NIR luminescence center Te4 by adjusting the glass structure with reduced network crosslinking. The superior optical performance has been confirmed in our previous study that the NIR luminescence properties can be well maintained in Te-doped fiber. The findings indicate that Te-doped phosphate glass with unusual thermal responses can potentially be used in fiber laser devices.

Comment on "Glass Transition, Crystallization of Glass-Forming Melts, and Entropy" Entropy 2018, 20, 103.

In a recent article, Schmelzer and Tropin [Entropy 2018, 20, 103] presented a critique of several aspects of modern glass science, including various features of glass transition and relaxation, crystallization, and the definition of glass itself. We argue that these criticisms are at odds with well-accepted knowledge in the field from both theory and experiments. The objective of this short comment is to clarify several of these issues.

Thermometer Effect: Origin of the Mixed Alkali Effect in Glass Relaxation.

Despite the dramatic increase of viscosity as temperature decreases, some glasses are known to feature room-temperature relaxation. However, the structural origin of this phenomenon-known as the "thermometer effect"-remains unclear. Here, based on accelerated molecular dynamics simulations of alkali silicate glasses, we show that both enthalpy and volume follow stretched exponential decay functions upon relaxation. However, we observe a bifurcation of their stretching exponents, with ß=3/5 and 3/7 for enthalpy and volume relaxation, respectively, in agreement with Phillips's topological diffusion-trap model. Based on these results, we demonstrate that the thermometer effect is a manifestation of the mixed alkali effect. We show that relaxation is driven by the existence of stressed local structural instabilities in mixed alkali glasses. This driving force is found to be at a maximum when the concentrations of each alkali atom equal each other, which arises from a balance between the concentration of each alkali atom and the magnitude of the local stress that they experience.

Variability in the relaxation behavior of glass: Impact of thermal history fluctuations and fragility.

Glasses are nonequilibrium materials that continuously relax toward the metastable supercooled liquid state. As such, the properties of a glass depend on both its composition and thermal history. When an initially cooled glass is subjected to additional thermal cycles, relaxation during the heat treatment is accelerated, leading to changes in the macroscopic properties of the glass. This relaxation behavior is intrinsic to the glassy state and of critical interest to the high-tech glass industry. In many practical cases, the magnitude of the relaxation is less important than the variability of the relaxation effects due to slight variations in the thermal history experienced by the glass. These fluctuations in thermal history can occur either during the initial glass formation or during the subsequent heat treatment cycle(s). Here we calculate the variation in relaxation behavior using a detailed enthalpy landscape model, showing that the relaxation variability can be reduced dramatically by increasing the fragility of the system.

Cooling rate effects in sodium silicate glasses: Bridging the gap between molecular dynamics simulations and experiments.

Although molecular dynamics (MD) simulations are commonly used to predict the structure and properties of glasses, they are intrinsically limited to short time scales, necessitating the use of fast cooling rates. It is therefore challenging to compare results from MD simulations to experimental results for glasses cooled on typical laboratory time scales. Based on MD simulations of a sodium silicate glass with varying cooling rate (from 0.01 to 100 K/ps), here we show that thermal history primarily affects the medium-range order structure, while the short-range order is largely unaffected over the range of cooling rates simulated. This results in a decoupling between the enthalpy and volume relaxation functions, where the enthalpy quickly plateaus as the cooling rate decreases, whereas density exhibits a slower relaxation. Finally, we show that, using the proper extrapolation method, the outcomes of MD simulations can be meaningfully compared to experimental values when extrapolated to slower cooling rates.

Response to "Comment on 'A model for phosphate glass topology considering the modifying ion sub-network"' [J. Chem. Phys. 142, 107103 (2015)].

In our recent paper [C. Hermansen, J. C. Mauro, and Y.-Z. Yue, J. Chem. Phys. 140, 154501 (2014)], we applied temperature-dependent constraint theory to model the glass transition temperature (Tg) and liquid fragility index (m) of alkali phosphate glasses. Sidebottom commented on this paper concerning the m values obtained by differential scanning calorimetry (DSC) [D. L. Sidebottom, J. Chem. Phys. 142, ⬛ (2015)]. We have considered Sidebottom's comments carefully and conclude that the m values of phosphate liquids obtained by DSC are reliable, except for the NaPO3 and possibly P2O5 compositions. Based on his dynamic light scattering measurements, Sidebottom has found that P2O5 is a strong liquid with m ≈ 20. However, based on the heat capacity jump at Tg and the stretching exponent of the relaxation function, P2O5 should be classified as an intermediate fragile liquid with m ≈ 40. We also argue that m cannot be universally related to the average connectivity of the network and point out several inconsistencies with this view.

Unique effects of thermal and pressure histories on glass hardness: Structural and topological origin.

The properties of glass are determined not only by temperature, pressure, and composition, but also by their complete thermal and pressure histories. Here, we show that glasses of identical composition produced through thermal annealing and through quenching from elevated pressure can result in samples with identical density and mean interatomic distances, yet different bond angle distributions, medium-range structures, and, thus, macroscopic properties. We demonstrate that hardness is higher when the density increase is obtained through thermal annealing rather than through pressure-quenching. Molecular dynamics simulations reveal that this arises because pressure-quenching has a larger effect on medium-range order, while annealing has a larger effect on short-range structures (sharper bond angle distribution), which ultimately determine hardness according to bond constraint theory. Our work could open a new avenue towards industrially useful glasses that are identical in terms of composition and density, but with differences in thermodynamic, mechanical, and rheological properties due to unique structural characteristics.

Structure-topology-property correlations of sodium phosphosilicate glasses.

In this work, we investigate the correlations among structure, topology, and properties in a series of sodium phosphosilicate glasses with [SiO2]/[SiO2 + P2O5] ranging from 0 to 1. The network structure is characterized by (29)Si and (31)P magic-angle spinning nuclear magnetic resonance and Raman spectroscopy. The results show the formation of six-fold coordinated silicon species in phosphorous-rich glasses. Based on the structural data, we propose a formation mechanism of the six-fold coordinated silicon, which is used to develop a quantitative structural model for predicting the speciation of the network forming units as a function of chemical composition. The structural model is then used to establish a temperature-dependent constraint description of phosphosilicate glass topology that enables prediction of glass transition temperature, liquid fragility, and indentation hardness. The topological constraint model provides insight into structural origin of the mixed network former effect in phosphosilicate glasses.

Mixed alkaline earth effect in the compressibility of aluminosilicate glasses.

The mixed modifier effect (MME) in oxide glasses manifests itself as a non-additive variation in certain properties when one modifier oxide species is substituted by another one at constant total modifier content. However, the structural and topological origins of the MME are still under debate. This study provides new insights into the MME by investigating the effect of isostatic compression on density and hardness of mixed MgO/CaO sodium aluminosilicate glasses. This is done using a specially designed setup allowing isostatic compression of bulk glass samples up to 1 GPa at elevated temperature. A mixed alkaline earth effect is found in the compressibility and relative change of hardness, viz., a local maximum of density as a function of Mg/Ca ratio appears following compression, whereas a local minimum of hardness in the uncompressed glasses nearly disappears after compression. Moreover, the densification of these glasses is found to occur at temperatures much below the glass transition temperature, indicating that a non-viscous mechanism is at play. This is further supported by the fact that density relaxes in a stretched exponential manner upon subsequent annealing at ambient pressure with an exponent of ∼0.62. This is close to the Phillips value of 3/5 for relaxation in three dimensions when both short- and long-range interactions are activated.

The unexplored role of alkali and alkaline earth elements (ALAEs) on the structure, processing, and biological effects of bioactive glasses.

Bioactive glass has been employed in several medical applications since its inception in 1969. The compositions of these materials have been investigated extensively with emphasis on glass network formers, therapeutic transition metals, and glass network modifiers. Through these experiments, several commercial and experimental compositions have been developed with varying chemical durability, induced physiological responses, and hydroxyapatite forming abilities. In many of these studies, the concentrations of each alkali and alkaline earth element have been altered to monitor changes in structure and biological response. This review aims to discuss the impact of each alkali and alkaline earth element on the structure, processing, and biological effects of bioactive glass. We explore critical questions regarding these elements from both a glass science and biological perspective. Should elements with little biological impact be included? Are alkali free bioactive glasses more promising for greater biological responses? Does this mixed alkali effect show increased degradation rates and should it be employed for optimized dissolution? Each of these questions along with others are evaluated comprehensively and discussed in the final section where guidance for compositional design is provided.

Dynamics of glass relaxation at room temperature.

The problem of glass relaxation under ambient conditions has intrigued scientists and the general public for centuries, most notably in the legend of flowing cathedral glass windows. Here we report quantitative measurement of glass relaxation at room temperature. We find that Corning® Gorilla® Glass shows measurable and reproducible relaxation at room temperature. Remarkably, this relaxation follows a stretched exponential decay rather than simple exponential relaxation, and the value of the stretching exponent (ß=3/7) follows a theoretical prediction made by Phillips for homogeneous glasses.

Statistics of modifier distributions in mixed network glasses.

The constituents of any network glass can be broadly classified as either network formers or network modifiers. Network formers, such as SiO2, Al2O3, B2O3, P2O5, etc., provide the backbone of the glass network and are the primary source of its rigid constraints. Network modifiers play a supporting role, such as charge stabilization of the network formers or alteration of the network topology through rupture of bridging bonds and introduction of floppy modes. The specific role of the modifiers depends on which network formers are present in the glass and the relative free energies of modifier interactions with each type of network former site. This variation of free energy with modifier speciation is responsible for the so-called mixed network former effect, i.e., the nonlinear scaling of property values in glasses having fixed modifier concentration but a varying ratio of network formers. In this paper, a general theoretical framework is presented describing the statistical mechanics of modifier speciation in mixed network glasses. The model provides a natural explanation for the mixed network former effect and also accounts for the impact of thermal history and relaxation on glass network topology.

Relaxation of enthalpy fluctuations during sub-T(g) annealing of glassy selenium.

The relaxation behavior of glass is influenced by the presence of dynamical heterogeneities, which lead to an intrinsically non-monotonic decay of fluctuations in density and enthalpy during isothermal annealing. This is apparently a universal feature of fragile glass forming systems associated with localized spatial variations in relaxation time. Here we present direct experimental observation of the nonmonotonic evolution of enthalpy fluctuations in glassy selenium annealed near room temperature. The nonmonotonic change in the distribution of enthalpy fluctuations measured by heat capacity spectroscopy offers direct evidence for the presence of dynamical heterogeneity in this glass. An enthalpy landscape model of selenium is then used to simulate annealing under identical conditions. The simulation results closely follow the evolution of enthalpy fluctuations observed experimentally. The close match between model and experiment demonstrate that enthalpy and density fluctuations are sources of dynamical heterogeneities in glassy materials.

Are the dynamics of a glass embedded in its elastic properties?

The low temperature dynamics of glass are critically important for many high-tech applications. According to the elastic theory of the glass transition, the dynamics of glass are controlled by the evolution of shear modulus. In particular, the elastic shoving model expresses dynamics in terms of an activation energy required to shove aside the surrounding atoms. Here, we present a thorough test of the shoving model for predicting the low temperature dynamics of an oxide glass system. We show that the nonequilibrium viscosity of glass is governed by additional factors beyond changes in shear modulus.