Supercooled Research Articles

Dynamical Facilitation Governs the Equilibration Dynamics of Glasses

Convincing evidence of domain growth in the heating of ultrastable glasses suggests that the equilibration dynamics of supercooled liquids could be driven by a nucleation and growth mechanism. We investigate this possibility by simulating the equilibration dynamics of a model glass during both heating and cooling between poorly and well-annealed states. Though we do observe the growth of domains during heating, we find that domains are absent during cooling. This absence is inconsistent with classical nucleation theory. By comparing the equilibration dynamics of our glass with that of two models with kinetic constraints, we demonstrate that dynamical facilitation generically leads to heating driven by domain growth and cooling without domains. Our results provide strong evidence that dynamical facilitation, not nucleation and interfacial-tension-driven domain growth, is the driving mechanism for the equilibration dynamics of glass formers. Published by the American Physical Society 2024

A method to assess the quality of additive manufacturing metal powders using the triboelectric charging concept

A new method to assess the quality of additive manufacturing (AM) metal powders using the triboelectric charging concept is demonstrated using CpTi, Ti6Al4V, AlSi10Mg, IN 738, and SS 316L powders. For each powder tested, the surface chemical composition was first analyzed using X-ray photoelectron spectroscopy (XPS) to determine the composition of the passivation layer. Some modifications to the current GranuCharge™ setup, developed by GranuTools™, were then performed by incorporating a flow rate measuring tool to assess how tribocharging is affected as a function of flow rate. Variations in the tribocharging response have been found with the flow rate of CpTi, AlSi10Mg and SS 316L powders. Moreover, results suggest that the tribocharging behavior might not be the same even with powders fabricated with the same passivation process. Finally, the compressed exponential model of Trachenko and Zaccone was used to reproduce the tribocharging behavior of the powders. The models were found to work best when the stretch constant β = 1.5, which is identical to the value found in other systems such as structural glasses, colloidal gels, entangled polymers, and supercooled liquids, which experience jamming when motion of individual particles become restricted, causing their motion to slow down.

Early prediction of spinodal-like relaxation events in supercooled liquid water.

Several computational studies on different water models reported evidence of a phase transition in supercooled conditions between two liquid states of water differing in density: the high-density liquid (HDL) and the low-density liquid (LDL). Yet, conclusive experimental evidence of the existence of a phase transition between the two liquid water phases could not be obtained due to fast crystallization in the region where the phase transition should occur. For the same reason, the investigation of possible transition mechanisms between the two phases is committed to computational investigations. In this work, we simulate an out-of-equilibrium temperature-induced transition from the LDL to the HDL-like state in the TIP4P/2005 water model. To structurally characterize the system relaxation, we use the node total communicability (NTC) we recently proposed as an effective order parameter to discriminate the two liquid phases differing in density. We find that the relaxation process is compatible with a spinodal-like scenario. We observe the formation of HDL-like domains in the LDL phase and we characterize their fluctuating behavior and subsequent coarsening and stabilization. Furthermore, we find that the formation of stable HDL-like domains is favored in the regions where the early formation of small patches of highly connected HDL-like molecules (i.e., with very high NTC values) is observed. Besides characterizing the LDL- to HDL-like relaxation from a structural point of view, these results also show that the NTC order parameter can serve as an early-time predictor of the regions from which the transition process initiates.

Measurement of the depth-dependent local dynamics in thin polymer films through rejuvenation of ultrastable glasses

The depth dependence of structural relaxation dynamics is a key part of understanding thin glassy films. Despite this importance and decades of research, a method to provide this information has proved elusive. We measure the isothermal rejuvenation of stable glass films of poly(styrene), and demonstrate that the propagation of the front responsible for the transformation to a supercooled-liquid state serves as a highly localized probe of the local dynamics of the supercooled liquid. We use this connection to probe the depth-dependent relaxation rate with nanometric precision for a series of polystyrene films over a range of temperatures near the bulk glass transition temperature. The analysis shows the spatial extent of enhanced surface mobility and reveals the existence of an unexpected large dynamical length scale in the system. The results are compared with the cooperative-string model for glassy dynamics. The data reveals that the film-thickness dependence of whole film properties arises mainly from the volume fraction of the near-surface region. While the dynamics farthest from the free surface shows the expected bulk-like temperature dependence, the dynamics in the near-surface region shows very little dependence on temperature. This technique can be used in a broad range of thin film materials to gain previously unattainable information about localized structural relaxation.

Unveiling winter survival strategies: physiological and metabolic responses to cold stress of Monochamus saltuarius larvae during overwintering.

Monochamus saltuarius is a destructive trunk-borer of pine forest and an effective dispersal vector for pinewood nematode (PWN), a causative agent of pine wilt disease (PWD), which leads to major ecological disasters. Cold winter temperatures determine insect survival and distribution. However, little is known about the cold tolerance and potential physiological mechanisms of M. saltuarius. We demonstrated that dead Pinus koraiensis trunks do not provide larvae with insulation. The M. saltuarius larvae are freeze-tolerant species. Unlike most other freeze-tolerant insects, they can actively freeze extracellular fluid at higher subzero temperatures by increasing their supercooling points. The main energy sources for larvae overwintering are glycogen and the mid-late switch to lipid. The water balance showed a decrease in free and an increase in bound water of small magnitude. Cold stress promoted lipid peroxidation, thus activating the antioxidant system to prevent cold-induced oxidative damage. We found eight main pathways linked to cold stress and 39 important metabolites, ten of which are cryoprotectants, including maltose, UDP-glucose, d-fructose 6P, galactinol, dulcitol, inositol, sorbitol, l-methionine, sarcosine, and d-proline. The M. saltuarius larvae engage in a dual respiration process involving both anaerobic and aerobic pathways when their bodily fluids freeze. Cysteine and methionine metabolism, as well as alanine, aspartate, and glutamate metabolism, are the most important pathways linked to antioxidation and energy production. The implications of our findings may help strengthen and supplement the management strategies for monitoring, quarantine, and control of this pest, thereby contributing to controlling the further spread of PWD. © 2024 Society of Chemical Industry.

High-speed cryo-microscopy reveals that ice-nucleating proteins of Pseudomonas syringae trigger freezing at hydrophobic interfaces.

Ice-nucleating proteins (INpro) trigger the freezing of supercooled water droplets relevant to atmospheric, biological, and technological applications. The high ice nucleation activity of INpro isolated from the bacteria Pseudomonas syringae could be linked to the aggregation of proteins at the bacterial membrane or at the air-water interface (AWI) of droplets. Here, we imaged freezing onsets, providing direct evidence of these proposed mechanisms. High-speed cryo-microscopy identified the onset location of freezing in droplets between two protein-repellent glass slides. INpro from sterilized P. syringae (Snomax) statistically favored nucleation at the AWI of the droplets. Removing cellular fragments by filtration or adding surfactants increased the frequency of nucleation events at the AWI. On the other hand, cultivated intact bacteria cells or lipid-free droplets nucleated ice without an affinity to the AWI. Overall, we provide visual evidence that INpro from P. syringae trigger freezing at hydrophobic interfaces, such as the AWI or the bacterial membrane, with important mechanistic implications for applications of INpro.

Technical note: Retrieval of the supercooled liquid fraction in mixed-phase clouds from Himawari-8 observations

Abstract. The supercooled liquid fraction (SLF) in mixed-phase clouds (MPCs) is an essential variable of cloud microphysical processes and climate sensitivity. However, the SLF is currently calculated in spaceborne remote sensing only as the cloud phase–frequency ratio of adjacent pixels, which results in a loss of the original resolution in observations of cloud liquid or ice content within MPCs. Here, we present a novel method for retrieving the SLF in MPCs based on the differences in radiative properties of supercooled liquid droplets and ice particles at visible (VIS) and shortwave infrared (SWI) channels of the geostationary Himawari-8. Liquid and ice water paths are inferred by assuming that clouds are composed of only liquid or ice, with the real cloud water path (CWP) expressed as a combination of these two water paths (SLF and 1-SLF as coefficients), and the SLF is determined by referring to the CWP from Cloud-Aerosol Lidar and Infrared Pathfinder Satellite Observations (CALIPSO). The statistically relatively small cloud phase spatial inhomogeneity at a Himawari-8 pixel level indicates an optimal scene for cloud retrieval. The SLF results are comparable to global SLF distributions observed by active instruments, particularly for single-layered cloud systems. While accessing the method's feasibility, SLF averages are estimated between 74 % and 78 % in Southern Ocean (SO) stratocumulus across seasons, contrasting with a range of 29 % to 32 % in northeastern Asia. The former exhibits a minimum SLF around midday in summer and a maximum in winter, while the latter trend differs. This novel algorithm will be valuable for research to track the evolution of MPCs and constrain the related climate impact.

Cold tolerance and metabolism of red-haired pine bark beetle Hylurgus ligniperda (Coleoptera: Curculionidae) during the overwintering period.

Hylurgus ligniperda invaded Shandong, China, through imported forest timber, posing a threat to China's forest health. Exotic insects with broad environmental tolerance, including low temperatures, may have a better chance of surviving the winters and becoming invasive. Understanding the cold-tolerance strategies of H. ligniperda may help to design sustainable pest management approaches. In this study, we aim to investigate the cold-tolerance ability and relevant physiological indicators in overwintering H. ligniperda adults to determine any possible overwintering strategies. Supercooling points (SCPs) for adults H. ligniperda differed significantly across months and reached the lowest level in the mid- and post-overwintering period, the minimum SCPs -6.45 ± 0.18 °C. As the cold exposure temperature decreased, the survival rate of adults gradually decreased, and no adult survived more than 1 day at -15 °C, and the LLT50 for 1 day was -7.1 °C. Since H. ligniperda adults can survive internal ice formation, they are freeze-tolerant insects. Throughout the overwintering period, the SCPs and the water, protein, sorbitol, and glycerol content in adults decreased initially and then increased. We reported significant correlations between total protein, sorbitol, trehalose, and glycerol content in the beetles and SCPs. Glycogen, lipid, protein, trehalose, and sorbitol content in adult beetles may directly affect their cold-tolerance capacity and survival during winter. This study provides a physiological and biochemical basis for further study of metabolism and cold-tolerance strategies in H. ligniperda adults, which may help predict population dynamics and distribution potential of pests.

Lidar–radar synergistic method to retrieve ice, supercooled water and mixed-phase cloud properties

Abstract. Mixed-phase clouds are not well represented in climate and weather forecasting models, due to a lack of the key processes controlling their life cycle. Developing methods to study these clouds is therefore essential, despite the complexity of mixed-phase cloud processes and the difficulty of observing two cloud phases simultaneously. We propose in this paper a new method to retrieve the microphysical properties of mixed-phase clouds, ice clouds and supercooled water clouds using airborne or satellite radar and lidar measurements, called VarPy-mix. This new approach extends an existing variational method developed for ice cloud retrieval using lidar, radar and passive radiometers. We assume that the lidar attenuated backscatter β at 532 nm is more sensitive to particle concentration and is consequently mainly sensitive to the presence of supercooled water. In addition, radar reflectivity Z at 95 GHz is sensitive to the size of hydrometeors and hence more sensitive to the presence of ice particles. Consequently, in the mixed phase the supercooled droplets are retrieved with the lidar signal and the ice particles with the radar signal, meaning that the retrievals rely strongly on a priori and error values. This method retrieves simultaneously the visible extinction for ice αice and liquid αliq particles, the ice and liquid water contents IWC and LWC, the effective radius of ice re,ice and liquid re,liq particles, and the ice and liquid number concentrations Nice and Nliq. Moreover, total extinction αtot, total water content (TWC) and total number concentration Ntot can also be estimated. As the retrieval of ice and liquid is different, it is necessary to correctly identify each phase of the cloud. To this end, a cloud-phase classification is used as input to the algorithm and has been adapted for mixed-phase retrieval. The data used in this study are from DARDAR-MASK v2.23 products, based on the Cloud-Aerosol Lidar with Orthogonal Polarization (CALIOP) and Cloud Profiling Radar (CPR) observations from the CALIPSO and CloudSat satellites, respectively, belonging to the A-Train constellation launched in 2006. Airborne in situ measurements performed on 7 April 2007 during the Arctic Study of Tropospheric Aerosol, Clouds and Radiation (ASTAR) campaign and collected under the track of CloudSat–CALIPSO are compared with the retrievals of the new algorithm to validate its performance. Visible extinctions, water contents, effective radii and number concentrations derived from in situ measurements and the retrievals showed similar trends and are globally in good agreement. The mean percent error between the retrievals and in situ measurements is 39 % for αliq, 398 % for αice, 49 % for LWC and 75 % for IWC. It is also important to note that temporal and spatial collocations are not perfect, with a maximum spatial shift of 1.68 km and a maximum temporal shift of about 10 min between the two platforms. In addition, the sensitivity of remote sensing and that of in situ measurements is not the same, and in situ measurement uncertainties are between 25 % and 60 %.

Proof of concept for a nonadditive stochastic model of supercooled liquids.

The recently proposed nonadditive stochastic model (NSM) offers a coherent physical interpretation for diffusive phenomena in glass-forming systems. This model presents nonexponential relationships between viscosity, activation energy, and temperature, characterizing the non-Arrhenius behavior observed in supercooled liquids. In this work, we fit the NSM viscosity equation to experimental temperature-dependent viscosity data corresponding to 25 glass-forming liquids and compare the fit parameters with those obtained using the Vogel-Fulcher-Tammann (VFT), Avramov-Milchev (AM), and Mauro-Yue-Ellison-Gupta-Allan (MYEGA) models. The results demonstrate that the NSM provides an effective fitting equation for modeling viscosity experimental data in comparison with other established models (VFT, AM, and MYEGA), characterizing the activation energy in fragile liquids, presenting a reliable indicator of the degree of fragility of the glass-forming liquids.

Universal mechanism of shear thinning in supercooled liquids

Soft glassy materials experience a significant reduction in viscosity η when subjected to shear flow, known as shear thinning. This phenomenon is characterized by a power-law scaling of η with the shear rate γ°\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\dot{\\gamma }$$\\end{document}, η∝γ°−ν\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\eta \\propto {\\dot{\\gamma }}^{-\ u }$$\\end{document}, where the exponent ν is typically around 0.7 to 0.8 across different materials. Two decades ago, the mode-coupling theory (MCT) suggested that shear thinning occurs due to the advection. However, it predicts too large ν = 1 ( > 0.7 to 0.8) and overestimates the onset shear rate by orders of magnitude. Recently, it was claimed that a minute distortion of the particle configuration is responsible for shear thinning. Here we extend the MCT to include the distortion, and find that both advection and distortion contribute to shear thinning, but the latter is dominant. Our formulation works quantitatively for several different glass formers. We explain why shear thinning is universal for many glassy materials.

Relationship between Synoptic Weather Patterns and Topography on Snowfall in the Idaho Mountainous Regions during the SNOWIE Project

Abstract Snowpack melting is a crucial water resource for local ecosystems, agriculture, and hydropower in the Intermountain West of the United States. Glaciogenic seeding, a method widely used in mountain regions to enhance precipitation, has been subject to numerous field studies aiming to understand and validate this mechanism. However, investigating precipitation distribution and amounts in mountainous areas is complicated due to the intricate interplay of synoptic circulation patterns and local complex topography. These interactions significantly influence microphysical processes, ultimately affecting the amount and distribution of surface precipitation. To address these challenges, this study leverages Weather Research and Forecasting (WRF) Model simulations, providing high-resolution (900 m), hourly data, spanning the Payette region of Idaho from January to March 2017. We applied the self-organizing map approach to categorize the most representative synoptic circulation patterns and conducted a multiscale analysis to explore their associated environmental conditions and microphysical processes, aiming to assess the cloud seeding potential. The analysis identified four primary synoptic patterns: cold zonal flow (CZF), cold southwesterly flow (CSWF), warm zonal flow (WZF), and warm southwesterly flow (WSWF), constituting 21.3%, 23.1%, 30.0%, and 25.5%, respectively. CSWF and WSWF demonstrated efficiency in generating natural precipitation. These patterns were characterized by abundant supercooled liquid water (SLW) and ice particles, facilitating cloud droplet growth through seeder–feeder processes. On the other hand, CZF exhibited the least SLW and limited potential for cloud seeding, while WZF displayed a lower ice water content but substantial SLW in the diffusion/dendritic growth layer, suggesting a favorable scenario for cloud seeding. Significance Statement Understanding snowfall amounts and distribution in the mountains and how it is linked to topography, synoptic flow, and microphysical processes will help in the development of effective strategies for cloud seeding operations, managing runoff, reservoir, and mitigating flood risks, garnering substantial interest from stakeholders and the government agencies.

Experimental analysis of freezing desalination using gravity and centrifugal methods with economic evaluation of coupled freezing desalination and ice storage system

This study conducted experiments to compare the desalination efficiency of gravity and centrifugal desalination methods for freezing desalination, showing the superiority of centrifugal desalination. Moreover, through experiments on supercooled water production, it was determined that supercooled water can operate stably at an evaporator temperature of −4.5 °C, and its supercooling state can be released using ultrasound. Based on the experimental results, a novel system that combines freezing desalination with ice storage is proposed. The proposed system utilizes supercooled water for ice production and centrifugal post-treatment, using desalinated ice as a cold storage medium to integrate desalination and ice storage. The proposed system showed a 30 % lower total capital cost compared to conventional systems, with a payback period of 38.18 % lower than conventional system (5.42 years). Additionally, the system demonstrated optimal economic performance when utilizing 80 % of its ice storage capacity, with a payback period of 3.38 years, contrasting with 7.62 years when utilizing 20 % storage capacity. The application of this system in four regions with varying peak and off-peak electricity prices, including Guangdong, Fujian, Hainan, and, France revealed that the system demonstrates greater economic viability in areas with significant disparities in electricity pricing.

Diffusion proxies reveal the dynamic process in supercooled and glassy lithium diborate

Understanding the effective diffusion coefficient (D) is crucial for describing atomic transport during crystal nucleation in supercooled liquids and glasses. However, pinpointing the key structural units driving crystallization in intricate, multicomponent glass-formers remains a challenge. This study presents a novel analysis of lithium diborate (Li₂O·2 B₂O₃ - LB₂) crystallization in supercooled and glassy states by using available viscosity and crystallization data for samples of the same batch. An original key feature is that the nucleation rates were measured using a single-stage rather than the traditional double-stage heat treatment. We compared three proxies for D: Dη obtained from viscosity, DU derived from crystal growth rates, and Dτ estimated from nucleation time-lags. Our analysis revealed that at deep supercoolings, below the glass transition temperature, DU and Dτ yield similar steady-state nucleation rate estimates, which significantly exceed those predicted by using Dη (the most frequently used diffusion proxy). This result suggests that the atomic jumps governing crystal nucleation may be comparable to those in crystal growth, but distinct from those associated with cooperative rearrangements controlling viscous flow. Additionally, the estimated kinetic spinodal temperature (Tks) is above the Kauzmann temperature Tk, implying that crystal nucleation precedes relaxation to the supercooled liquid state, circumventing the entropy paradox and corroborating recent MD simulations for other substances. These findings are valuable for refining theoretical models of crystal nucleation and highlight the complexities of the glassy state.

Crystallization Kinetics of Phosphonium Ionic Liquids: Effect of Cation Alkyl Chain Length and Thermal History.

The effects of alkyl chain length on the crystallization kinetics and ion mobility of tetraalkylphosphonium, [P666,n][TFSI], (n = 2, 6, 8, and 12) ionic liquids were studied by differential scanning calorimetry (DSC) and broadband dielectric spectroscopy (BDS) over a wide temperature range. The liquid-glass transition temperature (Tg) and ion dynamics examined over a broad T range were almost insensitive to structural modifications of the phosphonium cation. In contrast, the crystallization kinetics were strongly affected by the length of the fourth alkyl chain. Furthermore, the thermal history of the sample (cold vs melt crystallization) significantly impacted the crystallization rate. It has been found that the nature of crystallization phenomena is the same across the homologous series, while the kinetic aspect differs. Finally, electric conductivity in supercooled liquid and crystalline solid phases was measured for all samples, revealing significant ionic conductivity, largely independent of the cation structure.

Configuration entropy and potential energy landscape in thermodynamics and dynamics of supercooled liquids

In thermodynamics of supercooled liquids, sub-molecular units, referred to as “beads,” are used. It has been reported that all thermodynamic functions as well as the parameters in the empirical distribution functions of the potential energy landscape approach appear to be explicit functions of the number of beads in molecules. This finding opens the possibility of measuring the number of beads from each of these functions and estimating the configuration and vibration components in their formation. An enthalpy factor has been introduced and found that within the temperature domain of the invariable enthalpy factor, the molecules partition to a constant number of beads. A correlation has been observed between temperature dependence of the potential barriers, restricting cooperative rearrangement of beads and heat capacity of liquids. Relations connecting the landscape approach with the number of beads in the molecules have been estimated. The molecular equation for configuration entropy obtained can provide guidance for the development of new materials with a desirable configuration entropy. A method for predicting thermodynamic and statistical quantities of supercooled liquids from kinetics is also suggested.

Simulations of primary and secondary ice production during an Arctic mixed-phase cloud case from the Ny-Ålesund Aerosol Cloud Experiment (NASCENT) campaign

Abstract. The representation of Arctic clouds and their phase distributions, i.e., the amount of ice and supercooled water, influences predictions of future Arctic warming. Therefore, it is essential that cloud phase is correctly captured by models in order to accurately predict the future Arctic climate. Ice crystal formation in clouds happens through ice nucleation (primary ice production) and ice multiplication (secondary ice production). In common weather and climate models, rime splintering is the only secondary ice production process included. In addition, prescribed number concentrations of cloud condensation nuclei or cloud droplets and ice-nucleating particles are often overestimated in Arctic environments by standard model configurations. This can lead to a misrepresentation of the phase distribution and precipitation formation in Arctic mixed-phase clouds, with important implications for the Arctic surface energy budget. During the Ny-Ålesund Aerosol Cloud Experiment (NASCENT), a holographic probe mounted on a tethered balloon took in situ measurements of number and mass concentrations of ice crystals and cloud droplets in Svalbard, Norway, during fall 2019 and spring 2020. In this study, we choose one case study from this campaign that shows evidence of strong secondary ice production and use the Weather Research and Forecasting (WRF) model to simulate it at a high vertical and spatial resolution. We test the performance of different microphysical parametrizations and apply a new state-of-the-art secondary ice parametrization. We find that agreement with observations highly depends on the prescribed cloud condensation nuclei/cloud droplet and ice-nucleating particle concentrations and requires an enhancement of secondary ice production processes. Lowering mass mixing ratio thresholds for rime splintering inside the Morrison microphysics scheme is crucial to enable secondary ice production and thereby match observations for the right reasons. In our case, rime splintering is required to initiate collisional breakup. The simulated contribution from collisional breakup is larger than that from droplet shattering. Simulating ice production correctly for the right reasons is a prerequisite for reliable simulations of Arctic mixed-phase cloud responses to future temperature or aerosol perturbations.

Mode coupling behavior and fragile to strong transition of trehalose in a binary mixture with water upon supercooling.

We perform molecular dynamics simulations of a binary mixture of water and trehalose with the TIP4P/Ice water model. We analyze the slow dynamics of trehalose molecules in the mildly supercooled region for concentrations of 3.66 and 18.57 wt. %. We previously studied the dynamics of water in the same mixtures. Supercooled TIP4P/Ice water solvating trehalose molecules was found to follow the Mode Coupling Theory (MCT) and to undergo a transition from a fragile to a strong behavior for both concentrations. Here, we show that also the dynamics of trehalose molecules follows the MCT and displays a fragile to strong crossover (FSC). The results show that trehalose in binary mixtures with water shares with it the dynamical behavior typical of glass forming liquids. Moreover, the FSC for trehalose structural relaxation times is found to occur at temperatures close to those previously obtained for water in the same solutions, showing that the dynamics of the solute is strongly coupled to that of the solvent. We also perform a MCT test showing that the trehalose dynamics obeys the MCT time-temperature superposition principle and that the exponents derived from the theory and the ones obtained from fitting procedure of the relaxation times are comparable, confirming that trehalose molecules in supercooled water solutions follow the MCT of glassy dynamics. Moreover, as predicted by the theory, trehalose particles have MCT parameters comparable to those of water in the same mixtures. This is an important result, given that MCT was originally formulated for monoatomic particles.

Structure and rheological behavior of mixed-alkali molybdate and tungstate glasses and liquids

The structure of mixed-alkali (Li,Na,K) molybdate and tungstate glasses with 55-62.5 mol% MoO3 and 53-65 mol% WO3 is studied using Raman spectroscopy, while the rheological behavior of the corresponding supercooled liquids is measured using parallel plate rheometry. The M-O (M = Mo,W) polyhedral units in these glasses are found to be similar to those characteristic of the crystalline alkali ortho- and pyro- molybdate and tungstate phases. The structure of glasses with ≤55 % MO3 is dominated by isolated [MO4]2− tetrahedra. Increasing MO3 content results in the formation of chain-like moieties of corner- and edge- sharing MO6 octahedra and MO4 tetrahedra. This compositional evolution of the glass structure is found to be consistent with the corresponding variation in Tg and viscosity of the parent supercooled liquids. Moreover, the low degree of structural connectivity of these liquids is manifested in rather high kinetic fragility index that is somewhat unprecedented in archetypal oxide systems.

Formation and Migration Enthalpy from Elemental and Cooperative Diffusion in Lead Silicate Supercooled Liquid and Glass

Formation and Migration Enthalpy from Elemental and Cooperative Diffusion in Lead Silicate Supercooled Liquid and Glass