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We study multicomponent liquids by increasing the mass of 15% of the particles in a binary Kob–Andersen model. We find that the heavy particles have dual effects on the lighter particles. At higher temperatures, there is a significant decoupling of the dynamics between heavier and lighter particles, with the former resembling a pinned particle to the latter. The dynamics of the lighter particles slow down due to the excluded volume around the nearly immobile heavier particles. Conversely, at lower temperatures, there is a coupling between the dynamics of the heavier and lighter particles. The heavier particles' mass slows down the dynamics of both types of particles. This makes the soft pinning effect of the heavy particles questionable in this regime. We demonstrate that as the mass of the heavy particles increases, the coupling of the dynamics between the lighter and heavier particles weakens. Consequently, the heavier the mass of the heavy particles, the more effectively they act as soft pinning centers in both high and low-temperature regimes. A key finding is that akin to the pinned system, the self-dynamics and collective dynamics of the lighter particles decouple from each other as the mass of the heavy particles has a more pronounced impact on the latter. We analyze the structure–dynamics correlation by considering the system under the binary and modified quaternary framework, the latter describing the pinned system. Our findings indicate that whenever the heavy mass particles function as soft pinning centers, the modified quaternary framework predicts a higher correlation. [ABSTRACT FROM AUTHOR]

As the temperature decreases, the dynamics of supercooled liquids significantly slow down and become increasingly heterogeneous in space. Many previous studies have found that static structures also become heterogeneous and are spatially correlated with the dynamical heterogeneity. However, there are still debates on whether the dynamical heterogeneity is controlled by the structures, and which structural order parameters should be used to describe the structural heterogeneities (if exist) in amorphous systems. The appropriate order parameter depends on the specific details of the system and needs to be determined for each system. To address this difficulty, here, we use a machine-learning-based method that was trained solely by the static structures. This method combines convolutional neural networks and gradient-weighted class activation mapping, providing interpretable characteristic structures, which can quantify the degrees of liquid-like and solid-like structures in every local part of the system. We apply this method to a canonical glass-forming system and demonstrate that particles in the liquid-like structures are mobile, while those in the solid-like structures are immobile. The present work develops a novel approach to accurately characterize amorphous structures, which will be particularly useful for systems where appropriate structural order parameters have not yet been identified. [ABSTRACT FROM AUTHOR]

We combine the use of molecular dynamics simulations and the generalized Langevin equation to study the diffusion of a fluid adsorbed within kerogen, the main organic phase of shales. As a class of microporous and amorphous materials that can exhibit significant adsorption-induced swelling, the dynamics of the kerogen's microstructure is expected to play an important role in the confined fluid dynamics. This role is investigated by conducting all-atom simulations with or without solid dynamics. Whenever the dynamics coupling between the fluid and solid is accounted for, we show that the fluid dynamics displays some qualitative differences compared to bulk fluids, which can be modulated by the amount of adsorbed fluid owing to adsorption-induced swelling. We highlight that working with the memory kernel, the central time correlation function of the generalized Langevin equation, allows the fingerprint of the dynamics of the solid to appear on that of the fluid. Interestingly, we observe that the memory kernels of fluid diffusion in kerogen qualitatively behave as those of tagged particles in supercooled liquids. We emphasize the importance of reproducing the velocity–force correlation function to validate the memory kernel numerically obtained as confinement enhances the numerical instabilities. This route is interesting as it opens the way for modeling the impact of fluid concentration on the diffusion coefficient in such ultra-confining cases. [ABSTRACT FROM AUTHOR]

Monte Carlo simulations are widely employed to measure the physical properties of glass-forming liquids in thermal equilibrium. Combined with local Monte Carlo moves, the Metropolis algorithm can also be used to simulate the relaxation dynamics, thus offering an efficient alternative to molecular dynamics. Monte Carlo simulations are, however, more versatile because carefully designed Monte Carlo algorithms can more efficiently sample the rugged free energy landscape characteristic of glassy systems. After a brief overview of Monte Carlo studies of glass-formers, we define and implement a series of Monte Carlo algorithms in a three-dimensional model of polydisperse hard spheres. We show that the standard local Metropolis algorithm is the slowest and that implementing collective moves or breaking detailed balance enhances the efficiency of the Monte Carlo sampling. We use time correlation functions to provide a microscopic interpretation of these observations. Seventy years after its invention, the Monte Carlo method remains the most efficient and versatile tool to compute low-temperature properties in supercooled liquids. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

Large-amplitude thermal excursions imposed on deeply supercooled liquids modulate the nonlinear time evolution of their structural rearrangements. The consequent aftereffects are treated within a Wiener–Volterra expansion in laboratory time that allows one to calculate the associated physical-aging and thermal response functions. These responses and the corresponding higher-harmonic susceptibilities are illustrated using calculations based on the Tool–Narayanaswamy–Moynihan (TNM) model. The conversion from laboratory to material time is thoroughly discussed. Similarities and differences to field-induced higher-harmonic susceptibilities are illustrated using Lissajous and Cole–Cole plots and discussed in terms of aging nonlinearity parameters. For the Lissajous plots, banana-type shapes emerge, while the Cole–Cole plots display cardioidic and other visually appealing patterns. For application beyond the regime in which conventional single-parameter aging concepts work, the Wiener–Volterra material-time-series is introduced as the central tool. Calculations and analyses within this general framework in conjunction with suitable choices of higher-order memory kernels and employing correspondingly extended TNM models yield at least qualitative agreement with recent large-perturbation physical aging experiments. Implications for differential scanning calorimetry and related methods are discussed. The introduced concepts and analyses provide a solid foundation for a generalized description of nonlinear thermal out-of-equilibrium dynamics of glass forming materials, differing from the nonlinear responses known from rheology and dielectric spectroscopy. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

Cavitation in supercooled water has been induced by the short ultrasound pulses of an ultrasonic horn driven at 20 kHz. The cavitation during the ultrasonic pulses and occasionally the crystallization events thereafter have been imaged by a high-speed camera. The probability of ice crystallization in dependence on the pulse duration and temperature showed a high chance for the water to remain liquid if sufficiently short bursts of moderate acoustic power were applied. This regime has been used for the assessment of sonoluminescence (SL) from the generated cavitation bubbles in the supercooled liquid state. To this end, light emitting events were summed up over a number of ultrasonic pulses by an image intensifier. SL appeared mostly directly under the tip of the ultrasonic horn and sometimes also a few millimeters below the tip. The intensity of SL events showed a slight rise for a decrease in temperature, i.e., for an increase in supercooling. This behavior is in accord with the SL dependence on temperature above the freezing point and might be attributed to a further lowering of vapor pressure. An increase in the bubble collapse peak temperature for increased supercooling is calculated on the basis of spherical bubble model calculations, which supports the findings. The simulations predict further that the peak temperature will fall off again beyond a certain supercooling level. [ABSTRACT FROM AUTHOR]

Water shows anomalous properties that are enhanced upon supercooling. The unusual behavior is observed in both H2O and D2O, however, with different temperature dependences for the two isotopes. It is often noted that comparing the properties of the isotopes at two different temperatures (i.e., a temperature shift) approximately accounts for many of the observations—with a temperature shift of 7.2 K in the temperature of maximum density being the most well-known example. However, the physical justification for such a shift is unclear. Motivated by recent work demonstrating a "corresponding-states-like" rescaling for water properties in three classical water models that all exhibit a liquid–liquid transition and critical point [Uralcan et al., J. Chem. Phys. 150, 064503 (2019)], the applicability of this approach for reconciling the differences in the temperature- and pressure-dependent thermodynamic properties of H2O and D2O is investigated here. Utilizing previously published data and equations-of-state for H2O and D2O, we show that the available data and models for these isotopes are consistent with such a low temperature correspondence. These observations provide support for the hypothesis that a liquid–liquid critical point, which is predicted to occur at low temperatures and high pressures, is the origin of many of water's anomalies. [ABSTRACT FROM AUTHOR]

Light and heavy water show similar anomalies in thermodynamic and dynamic properties, with a consistent trend of anomalies occurring at higher temperatures in heavy water. Viscosity also increases faster upon cooling in heavy water, causing a giant isotope effect, with a viscosity ratio near 2.4 at 244 K. While a simple temperature shift apparently helps in collapsing experimental data for both isotopes, it lacks a clear justification, changes value with the property considered, and requires additional ad hoc scaling factors. Here, we use a corresponding states analysis based on the possible existence of a liquid–liquid critical point in supercooled water. This provides a coherent framework that leads to the collapse of thermodynamic data. The ratio between the dynamic properties of the isotopes is strongly reduced. In particular, the decoupling between viscosity η and self-diffusion D, measured as a function of temperature T by the Stokes–Einstein ratio Dη/T, is found to collapse after applying the corresponding states analysis. Our results are consistent with simulations and suggest that the various isotope effects mirror the one on the liquid–liquid transition. [ABSTRACT FROM AUTHOR]

The bulk water density data are studied in a very large temperature–pressure range, from stable liquid to glass in the frame of water polymorphism. Because this thermodynamic variable evidences a crossover T*, above which the hydrogen bond (HB) is unable to arrange tetrahedral networks, the T-dependence of their isobars was considered. Such an analysis also shows pressure, P*, around which their thermal behaviors are completely different: concave below P* (with maxima and minima) and convex above (without extremes). Having ρ's measured values of the bimodal structures of the liquid phase, HDL (ρHDL), made of not-bonded monomers (ρNHB) and partially bonded dimers plus trimers (ρNHB), and LDL tetramers (ρLDL) the isobars of the relative distributions [W(P, T)] of the three species (WLDL, WPHB, and WNHB) have been evaluated. The results were studied by means of a logistic function (LF) that details the evolutions of the relative polpulations of the water LDL and HDL phases by decreasing T (for the isobars, in the range of 0.1–400 MPa). The LFs analysis obtained by proposing a full connection between liquid water from its supercooled metastable phase to the stable up to the boiling temperature identifies the Widom line quite satisfactorily and fully supports the presence of the liquid–liquid critical point in the deep supercooled region, located at about 190 K and in the range 200 > P > 180 MPa. [ABSTRACT FROM AUTHOR]

In a recent work, we have briefly introduced a new structural index for water that, unlike previous indicators, was devised specifically for generic contexts beyond bulk conditions, making it suitable for hydration and nanoconfinement settings. In this work, we shall study this metric in detail, demonstrating its ability to reveal the existence of a fine-tuned interplay between the local structure and energetics in liquid water. This molecular principle enables the establishment of an extended hydrogen bond network, while simultaneously allowing for the existence of network defects by compensating for uncoordinated sites. By studying different water models and different temperatures encompassing both the normal liquid and the supercooled regime, this molecular mechanism will be shown to underlie the two-state behavior of bulk water. In addition, by studying functionalized self-assembled monolayers and diverse graphene-like surfaces, we shall show that this principle is also operative at hydration and nanoconfinement conditions, thus generalizing the validity of the two-liquid scenario of water to these contexts. This approach will allow us to define conditions for wettability, providing an accurate measure of hydrophobicity and a reliable predictor of filling and drying transitions. Hence, it might open the possibility of elucidating the active role of water in the broad fields of biophysics and materials science. As a preliminary step, we shall study the hydration structure and hydrophilicity of graphene-like systems (parallel graphene sheets and carbon nanotubes) as a function of the confinement dimensionality. [ABSTRACT FROM AUTHOR]

A method for characterizing the topological fluctuations in liquids is proposed. This approach exploits the concept of the weighted gyration tensor of a collection of particles and permits the definition of a local configurational unit (LCU). The first principal axis of the gyration tensor serves as the director of the LCU, which can be tracked and analyzed by molecular dynamics simulations. Analysis of moderately supercooled Kob–Andersen mixtures suggests that orientational relaxation of the LCU closely follows viscoelastic relaxation and exhibits a two-stage behavior. The slow relaxing component of the LCU corresponds to the structural, Maxwellian mechanical relaxation. Additionally, it is found that the mean curvature of the LCUs is approximately zero at the Maxwell relaxation time with the Gaussian curvature being negative. This observation implies that structural relaxation occurs when the configurationally stable and destabilized regions interpenetrate each other in a bicontinuous manner. Finally, the mean and Gaussian curvatures of the LCUs can serve as reduced variables for the shear stress correlation, providing a compelling proof of the close connection between viscoelastic relaxation and topological fluctuations in glass-forming liquids. [ABSTRACT FROM AUTHOR]

The slow Arrhenius process (SAP) is a dielectric mode connected to thermally activated equilibration mechanisms, allowing for a fast reduction in free energy in liquids and glasses. The SAP, however, is still poorly understood, and so far, this process has mainly been investigated at temperatures above the glass transition. By employing a combination of methods to analyze dielectric measurements under both isochronal and isothermal conditions, we were able to quantitatively reproduce the dielectric response of the SAP of different polymers and to expand the experimental regime over which this process can be observed down to lower temperatures, up to 70 K below the glass transition. Employing thin films of thicknesses varying between 10 and 800 nm, we further verified that the peak shape and activation energy of the SAP of poly(4-bromostyrene) are not sensitive to temperature, nor do they vary upon confinement at the nanoscale level. These observations confirm the preliminary trends reported for other polymers. We find that one single set of parameters—meaning the activation barrier and the pre-exponential factor, respectively, linked to the enthalpic and entropic components of the process—can describe the dynamics of the SAP in both the supercooled liquid and glassy states, in bulk and thin films. These results are discussed in terms of possible molecular origins of the slow Arrhenius process in polymers. [ABSTRACT FROM AUTHOR]

In this paper, we demonstrate that the weak temperature dependence of the structure factor of supercooled liquids, a defining feature of the glass transition, is a consequence of the averaging of the scattering intensity due to angular averaging. We show that the speckle at individual wavevectors, calculated from a simulated glass former, exhibits a Debye–Waller factor with a sufficiently large temperature dependence to represent a structural order parameter capable of distinguishing liquid from glass. We also extract from the speckle intensities a quantity proportional to the variance of the local restraint, i.e., a direct experimental measure of the amplitude of structural heterogeneity. [ABSTRACT FROM AUTHOR]

Highly acidic protic ionic liquids (PILs) are promising materials for potential electrochemical applications due to their high proton conductivity and excellent thermal stability. Still, little is known about the correlation between charge transport and structural dynamics as well as the proton transport mechanism despite the large body of literature on this topic. Here, we have examined the charge transport and structural dynamics by employing broadband dielectric spectroscopy in two highly acidic PILs in their supercooled liquid and glassy states, which included the same anion [TfO]− and different cations, [Tau]+ vs [Ahs]+. Unlike many other ionic liquids, the conductivity relaxation time τe of two studied PILs is substantially faster than the structural relaxation time τα. The decoupling behavior between charge transport and structural dynamics of two materials, which is manifested by a decoupling index Rτ, varies between 0.3 and 2.3 over the temperature range above Tg. Moreover, "Walden" plots of the molar conductivity vs the viscosity qualify both compounds as "Super ILs." All findings support the physical picture of large, polar, and orientationally correlated ion clusters, where the slow α-relaxation can be identified as structural relaxation associated with cooperative reorientations of the cluster macrodipole. In contrast, the shortest timescale for diffusive charge transport, τe, is 1–2 decades shorter than τα, implying that proton hopping is triggered by "single particle" (ions or ion pair) rotations and jumps on a sub-length scale of the cluster size, a dynamics being present even in the glassy state as indicated by a strong β-relaxation. These results demonstrate the practicality of employing highly acidic PILs in electrochemical fields. [ABSTRACT FROM AUTHOR]

In this paper, we apply a theoretical model for fluid state thermodynamics to investigate simulated water in supercooled conditions. This model, which we recently proposed and applied to sub- and super-critical fluid water [Zanetti-Polzi et al., J. Chem. Phys. 156(4), 44506 (2022)], is based on a combination of the moment-generating functions of the enthalpy and volume fluctuations as provided by two gamma distributions and provides the free energy of the system as well as other relevant thermodynamic quantities. The application we make here provides a thermodynamic description of supercooled water fully consistent with that expected by crossing the liquid–liquid Widom line, indicating the presence of two distinct liquid states. In particular, the present model accurately reproduces the Widom line temperatures estimated with other two-state models and well describes the heat capacity anomalies. Differently from previous models, according to our description, a cluster of molecules that extends beyond the first hydration shell is necessary to discriminate between the statistical fluctuation regimes typical of the two liquid states. [ABSTRACT FROM AUTHOR]

Recent studies have provided conclusive evidence for the existence of a liquid–liquid critical point in numerical models of water. Such a scenario implies the competition between two local molecular arrangements of different densities: a high-density liquid (HDL) and a low-density liquid (LDL). Within this context, the development of accurate structural indicators to properly characterize the two interconverting local structures is demanded. In a previous study, we introduced a reliable energy-based structural descriptor that properly discriminates water molecules into tetrahedrally arranged molecules (T molecules) and distorted molecules (D molecules). The latter constitute defects in terms of hydrogen bond (HB) coordination and have been shown to represent a minority component, even at high temperatures above the melting point. In addition, the D molecules tend to form high-quality HBs with three T molecules and to be surrounded by T and D molecules at further distances. Thus, it became evident that, while the LDL state might consist of a virtually pure T state, the HDL state would comprise mixed molecular arrangements including the D molecules. Such a need to abandon the single-molecule description requires the investigation of the degree of structural information to be incorporated in order to build an appropriate multi-molecule indicator. Hence, in this work, we shall study the effect of the local structural constraints on the water molecules in order to discriminate the different molecular arrangements into two disjoint classes. This will enable us to build a multi-molecule structural indicator for water whose performance will then be investigated within the water's supercooled regime. [ABSTRACT FROM AUTHOR]

The use of depolarization lidar to measure atmospheric volume depolarization ratio (VDR) is a common technique to classify cloud phase (liquid or ice). Previous work using a machine learning framework, applied to peak properties derived from co-polarized attenuated backscatter data, has been demonstrated to effectively detect supercooled-liquid-water-containing clouds (SLCCs). However, the training data from Davis Station, Antarctica, include no warm liquid water clouds (WLWCs), potentially limiting the model's accuracy in regions where WLWCs are present. In this work, we apply the same framework used on the Davis data to a 9-month micro-pulse lidar dataset collected in Ōtautahi / Christchurch, Aotearoa / New Zealand, a location which includes WLWC. We then evaluate the results relative to a reference VDR cloud-phase mask. We found that the Davis model performed relatively poorly at detecting SLCC with a recall score of 0.18, often misclassifying WLWC as SLCC. The performance of our new model, trained using data from Ōtautahi / Christchurch, displays recall scores as high as 0.88 for identification of SLCC, although it generally underestimates SLCC occurrence. The overall performance of the new model highlights the effectiveness of the machine learning technique when appropriate training data relevant to the location are used. [ABSTRACT FROM AUTHOR]

Supercooled liquid water (SLW) refers to droplets in clouds that remain unfrozen at temperatures below 0 °C. SLW is an important intermediate hydrometeor in the processes of snowfall and rainfall that can modulate the radiation budget. This study investigates the distribution of supercooled cloud water over mainland China using the East Asia–Pacific cloud macro- and microphysical properties dataset (2016), derived from Himawari-8 observations. The results show that the highest frequency of SLW in liquid-phase stratus clouds occur at the eastern slope of the Tibetan Plateau, the western side of the Sichuan Basin. Additional SLW is mostly found in liquid-phase clouds over the Sichuan Basin and its adjacent areas in southern China. In the region with the highest frequency of SLW, the mechanical forcing of the Tibetan Plateau causes the convergence of low-level airflow within the basin, which also carries moisture that is forced to ascend stably, creating a favorable condition for the formation of supercooled clouds. As the airflow continues to ascend, it encounters the mid-to-upper-level westerlies and temperature inversion. At the mid-to-upper level, the westerlies exhibit stronger wind speeds, directing flow towards the basin. Concurrently, the temperature inversion stabilizes the atmospheric stratification, limiting the further ascent of airflow. This inversion can also restrain convection and upward motion within the clouds, allowing for SLW to exist and persist for an extended period. [ABSTRACT FROM AUTHOR]

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 : D η obtained from viscosity, D U derived from crystal growth rates, and D τ estimated from nucleation time-lags. Our analysis revealed that at deep supercoolings, below the glass transition temperature, D U and D τ yield similar steady-state nucleation rate estimates, which significantly exceed those predicted by using D η (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 (T k s) is above the Kauzmann temperature T k , 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. [ABSTRACT FROM AUTHOR]

Clouds in Antarctica are key elements that affect radiative forcing and thus Antarctic climate evolution. Although the vast majority of clouds are composed of ice crystals, a non-negligible fraction constitutes supercooled liquid water (SLW; water held in liquid form below 0 °C). Numerical weather prediction models have great difficulty in forecasting SLW clouds over Antarctica, favouring ice at the expense of liquid water and therefore incorrectly estimating the cloud radiative forcing. Remote-sensing observations of SLW clouds have been carried out for several years at Concordia Station (75° S, 123° E; 3233 m above mean sea level), combining active lidar measurements (SLW cloud detection) and passive HAMSTRAD microwave measurements (liquid water path, LWP). The present project aimed at in situ observations of SLW clouds using sondes developed by the company Anasphere, specifically designed for SLW content (SLWC) measurements. These SLWC sondes were coupled to standard meteorological pressure–temperature–humidity sondes from Vaisala and released under meteorological balloons. During the 2021–2022 summer campaign, 15 launches were made, of which 7 were scientifically exploitable above a height of 400 m above ground level, a threshold height imposed by the time the SLWC sonde takes to stabilize after launch. The three main outcomes from our analyses are as follows: (a) the first in situ observations so far of SLW clouds in Antarctica with SLWC sondes; (b) on average, the consistency of SLW cloud heights as observed by in situ sondes and remote-sensing lidar; and (c) the liquid water path (vertically integrated SLWC) deduced by the sondes being generally equal to or greater than the LWP remotely sensed by HAMSTRAD. In general, the SLW clouds were observed in a layer close to saturation (U > 80 %) or saturated (U ∼ 100 %–105 %) just below or at the lowermost part of the entrainment zone, or capping inversion zone, which exists at the top of the planetary boundary layer and is characterized by an inflection point in the potential temperature vertical profile. Our results are consistent with the theoretical view that SLW clouds form and remain at the top of the planetary boundary layer. [ABSTRACT FROM AUTHOR]

The molar heat capacity of 1,4-bis(3-methylimidazolium-1-yl)butane bis(trifluoromethylsulfonyl)imide dicationic ionic compound ([C4(MIm)2][NTf2]2) has been studied over the temperature range from 6 to 350 K by adiabatic calorimetry. In the above temperature interval, this compound has been found to form crystal, liquid, and supercooled liquid. For [C4(MIm)2][NTf2]2, the temperature of fusion T°fus = (337.88 ± 0.01) K has been determined by the fractional melting experiments, the enthalpy of fusion ΔfusH° = (52.79 ± 0.28) kJ mol−1 has been measured using the calorimetric method of continuous energy input, and the entropy of fusion ΔfusS° = (156.2 ± 1.7) J K−1 mol−1 has also been evaluated. The standard thermodynamic functions of the studied dicationic ionic compound, namely, the heat capacity Cp°(T), the enthalpy [H°(T) − H°(0)], the entropy S°(T) and the Gibbs free energy [G°(T) − H°(0)] have been calculated on the basis of the experimental data for the temperature range up to 350 K. The results have been discussed and compared with those available in the literature and in the NIST Ionic Liquids Database (ILThermo) for monocationic ionic compounds. [ABSTRACT FROM AUTHOR]

Current general circulation models struggle to capture the phase-partitioning of clouds accurately, both overestimating and underestimating the supercooled liquid substantially. This impacts the radiative properties of clouds. Therefore, it is of interest to understand which processes determine the phase-partitioning. In this study, microphysical-process rates are analysed to study what role each phase-changing process plays in low-level Arctic clouds. Several months of cloud-resolving ICON simulations using a two-moment cloud microphysics scheme are evaluated. The microphysical-process rates are extracted using a diagnostic tool introduced here, which runs only the microphysical parameterization using previously simulated days. It was found that the processes impacting ice are more efficient during polar night than polar day. For the mixed-phase clouds (MPCs), it became clear that phase changes involving the vapour phase dominated in contrast to processes between liquid and ice. Computing the rate of the Wegener–Bergeron–Findeisen process further indicated that the MPCs frequently (42 % of the time) seemed to be glaciating. Additionally, the dependence of each process on the temperature, vertical wind, and saturation was evaluated. This showed that, in particular, the temperature influences the occurrence and interactions of different processes. This study helps to better understand how microphysical processes act in different regimes. It additionally shows which processes play an important role in contributing to the phase-partitioning in Arctic low-level mixed-phase clouds. Therefore, these processes could potentially be better targeted for improvements in the ICON model that aim to more accurately represent the phase-partitioning of Arctic low-level mixed-phase clouds. [ABSTRACT FROM AUTHOR]

High‐latitudinal mixed‐phase clouds significantly affect Earth's radiative balance. Observations of cloud and radiative properties from two field campaigns in the Southern Ocean and Antarctica were compared with two global climate model simulations. A cyclone compositing method was used to quantify "dynamics‐cloud‐radiation" relationships relative to the extratropical cyclone centers. Observations show larger asymmetry in cloud and radiative properties between western and eastern sectors at McMurdo compared with Macquarie Island. Most observed quantities at McMurdo are higher in the western (i.e., post‐frontal) than the eastern (frontal) sector, including cloud fraction, liquid water path (LWP), net surface shortwave and longwave radiation (SW and LW), except for ice water path (IWP) being higher in the eastern sector. The two models were found to overestimate cloud fraction and LWP at Macquarie Island but underestimate them at McMurdo Station. IWP is consistently underestimated at both locations, both sectors, and in all seasons. Biases of cloud fraction, LWP, and IWP are negatively correlated with SW biases and positively correlated with LW biases. The persistent negative IWP biases may have become one of the leading causes of radiative biases over the high southern latitudes, after correcting the underestimation of supercooled liquid water in the older model versions. By examining multi‐scale factors from cloud microphysics to synoptic dynamics, this work will help increase the fidelity of climate simulations in this remote region. Plain Language Summary: The efficacy of climate prediction is largely dependent on accurately estimating Earth's energy budget in global climate models (GCMs). The Southern Ocean region has a distinct history of showing large biases in energy budget within GCMs. This region also shows complex interactions between large‐scale dynamical conditions (e.g., low‐pressure systems) and microscale processes (e.g., cloud properties). This work used two field deployments at Macquarie Island, Southern Ocean and McMurdo Station, Antarctica to understand these interactions. Observations were obtained from year‐long measurements by ground‐based instruments, which were further compared with two GCMs. The two models were found to have errors representing cloud properties at Macquarie Island (e.g., too much liquid and too little ice) and McMurdo Station (e.g., too little ice and liquid), as well as errors representing net surface longwave (terrestrial) radiation and shortwave (solar) radiation. The combination of the insufficient amounts of cloud ice and liquid in the models at McMurdo, Antarctica may be the main cause of too much solar radiation absorbed by Earth's surface over that region, which also have implications for polar ice melting and ocean circulation in that remote region. Key Points: Extratropical cyclone compositing shows more asymmetric cloud properties in eastern and western sectors at McMurdo than Macquarie IslandSimulated ice water path is too low at both sectors and both sites; liquid water path is too high (low) at Macquarie (McMurdo)Model radiation biases are affected by both cloud properties and synoptic dynamics (e.g., extratropical cyclones) [ABSTRACT FROM AUTHOR]

The onset of ice nucleation in mixed-phase clouds determines the lifetime and microphysical properties of ice clouds. In this work, we develop a novel method that differentiates between various phases of mixed-phase clouds, such as clouds dominated by pure liquid or pure ice segments, compared with those having ice crystals surrounded by supercooled liquid water droplets or vice versa. Using this method, we examine the relationship between the macrophysical and microphysical properties of Southern Ocean mixed-phase clouds at -40 to 0 °C (e.g. stratiform and cumuliform clouds) based on the in situ aircraft-based observations during the US National Science Foundation Southern Ocean Clouds, Radiation, Aerosol Transport Experimental Study (SOCRATES) flight campaign. The results show that the exchange between supercooled liquid water and ice crystals from a macrophysical perspective, represented by the increasing spatial ratio of regions containing ice crystals relative to the total in-cloud region (defined as ice spatial ratio), is positively correlated with the phase exchange from a microphysical perspective, represented by the increasing ice water content (IWC), decreasing liquid water content (LWC), increasing ice mass fraction, and increasing ice particle number fraction (IPNF). The mass exchange between liquid and ice becomes more significant during phase 3 when pure ice cloud regions (ICRs) start to appear. Occurrence frequencies of cloud thermodynamic phases show a significant phase change from liquid to ice at a similar temperature (i.e. -17.5 °C) among three types of definitions of mixed-phase clouds based on ice spatial ratio, ice mass fraction, or IPNF. Aerosol indirect effects are quantified for different phases using number concentrations of aerosols greater than 100 or 500 nm (N>100 and N>500 , respectively). N>500 shows stronger positive correlations with ice spatial ratios compared with N>100. This result indicates that larger aerosols potentially contain ice-nucleating particles (INPs), which facilitate the formation of ice crystals in mixed-phase clouds. The impact of N>500 is also more significant in phase 2 when ice crystals just start to appear in the mixed phase compared with phase 3 when pure ICRs have formed, possibly due to the competing aerosol indirect effects on primary and secondary ice production in phase 3. The thermodynamic and dynamic conditions are quantified for each phase. The results show stronger in-cloud turbulence and higher updraughts in phases 2 and 3 when liquid and ice coexist compared with pure liquid or ice (phases 1 and 4, respectively). The highest updraughts and turbulence are seen in phase 3 when supercooled liquid droplets are surrounded by ice crystals. These results indicate both updraughts and turbulence support the maintenance of supercooled liquid water amongst ice crystals. Overall, these results illustrate the varying effects of aerosols, thermodynamics, and dynamics through various stages of mixed-phase cloud evolution based on this new method that categorizes cloud phases. [ABSTRACT FROM AUTHOR]

Mechanical stress governs the dynamics of viscoelastic polymer systems and supercooled glass-forming fluids. It was recently established that liquids with long terminal relaxation times are characterized by transiently frozen stress fields, which, moreover, exhibit long-range correlations contributing to the dynamically heterogeneous nature of such systems. Recent studies show that stress correlations and relaxation elastic moduli are intimately related in isotropic viscoelastic systems. However, the origin of these relations (involving spatially resolved material relaxation functions) is non-trivial: some relations are based on the fluctuation-dissipation theorem (FDT), while others involve approximations. Generalizing our recent results on 2D systems, we here rigorously derive three exact FDT relations (already established in our recent investigations and, partially, in classical studies) between spatio-temporal stress correlations and generalized relaxation moduli, and a couple of new exact relations. We also derive several new approximate relations valid in the hydrodynamic regime, taking into account the effects of thermal conductivity and composition fluctuations for arbitrary space dimension. One approximate relation was heuristically obtained in our previous studies and verified using our extended simulation data on two-dimensional (2D) glass-forming systems. As a result, we provide the means to obtain, in any spatial dimension, all stress-correlation functions in terms of relaxation moduli and vice versa. The new approximate relations are tested using simulation data on 2D systems of polydisperse Lennard–Jones particles. [ABSTRACT FROM AUTHOR]

Stiffness‐changing polymers are critically needed for intelligent and adaptive applications in soft robotics and wearable electronics; however, they suffer from the requirement of persistent external stimulation. Herein, a stiffness‐changing polymer network impregnated with a supercooled ionic liquid is introduced, which undergoes touch‐induced crystallization from a soft ionogel to a stiff plastic. The network exhibits a remarkable tunability in stiffness change, with the highest value exceeding 190 000 times between the soft and stiff states (3.5 kPa vs 691.1 MPa). This tremendous transition is achieved through the first‐order liquid–solid phase transition of the supercooled ionic liquid, which is highly reversible and isochoric via a heating‐cooling process. Unlike traditional stimuli, only a single touch is needed without sustained stimulation to trigger the stiffening from soft to stiff states. Importantly, the touch‐responsive polymer network can be extended to various types of ionic liquids and monomers, indicating excellent strategic versatility. Moreover, this unique ionogel exhibits switchable adhesiveness and ionic conductivity, effectively demonstrating smart adhesives and ionic switches with enhancements of more than 66 and 5800 times, respectively. This work provides a facile and versatile strategy for designing stable stiffness‐changing polymers, unlocking significant potential applications for next‐generation smart devices. [ABSTRACT FROM AUTHOR]

Through the application of cloud top temperature data and the extraction of supercooled cloud information in cloud-type data from the next-generation Himawari-8 geostationary satellite with high spatial–temporal resolution, a quantitative evaluation of the forecasting performance of the weather modification model named the Cloud and Precipitation Explicit Forecasting System (CPEFS) was conducted. The evaluation, based on selected forecast cases from 8 days in September and October 2018 initialized at 00 and 12 UTC every day, focused especially on the forecasting performance in supercooled clouds (vertical integrated supercooled liquid water, VISL > 0), including the comprehensive spatial distribution of cloud top temperature (CTT) and 3 h precipitation over 0.1 mm (R3 > 0.1). The results indicated that the forecasting performance for VISL > 0 was relatively good, with the Threat Score (TS) ranging from 0.46 to 0.67. The forecasts initialized at 12 UTC slightly outperformed the forecasts initialized at 00 UTC. Additionally, the corresponding spatial Anomaly Correlation Coefficient (ACC) of CTT between forecasts and observations was 0.23, and the TS for R3 > 0.1 reached as high as 0.87. For a mix of cold and warm cloud systems, there was a correlation between the forecasting performance of VISL > 0 and CTT. The trends in the TS for VISL > 0 and the ACC of CTT aligned with the forecast lead-time. [ABSTRACT FROM AUTHOR]

Zr-based metallic glass ribbons were interposed between stainless steel and titanium plates during dissimilar resistance spot welding. Upon welding, resistance heat caused the glass ribbons transition to a supercooled liquid state. By electrode force applied, the excess supercooled liquid was expelled from the nugget. The minimal supercooled liquid remaining in the nugget separated the two plates during welding, resulting in high reproducibility of mechanical properties in the dissimilar welding of stainless steel and titanium plates. [ABSTRACT FROM AUTHOR]

10.1063/5.0086517 53 J. Cui and K. A. Fichthorn, "OptiBoost: A method for choosing a safe and efficient boost for the bond-boost method in accelerated molecular dynamics simulations with hyperdynamics", J. Chem. Phys. 10.1063/5.0064866 17 R. Köster and M. Vogel, "Slow liquid dynamics near solid surfaces: Insights from site-resolved studies of ionic liquids in silica confinement", J. Chem. Phys. In the past few years, novel theoretical and experimental developments have significantly advanced our understanding of slow dynamics in viscous liquids, gels, glasses, and other dense, disordered materials. 10.1063/5.0078796 34 F. Alvarez, A. Arbe, and J. Colmenero, "Unraveling the coherent dynamic structure factor of liquid water at the mesoscale by molecular dynamics simulations", J. Chem. Phys. [Extracted from the article]

The physical aging of supercooled glycerol induced by upward temperature steps of amplitude reaching 45 K was studied by a new method consisting in heating a micrometer-thick liquid film at a rate of up to 60 000 K/s, holding it at a constant high temperature for a controlled duration before letting it quickly cool down to the initial temperature. By monitoring the final slow relaxation of the dielectric loss, we were able to obtain quantitative information on the liquid response to the initial upward step. The so-called TNM (Tool–Narayanaswamy–Moynihan) formalism provided a good description of our observations despite the large distance from equilibrium, provided that different values of the nonlinearity parameter were used for the cooling phase and for the (much further from equilibrium) heating phase. In this form, it allowed to precisely quantify how to design an ideal temperature step, i.e., where no relaxation occurs during the heating phase. It helped bringing a clear physical understanding of how the (kilosecond long) final relaxation is related to the (millisecond long) liquid response to the upward step. Finally, it made possible the reconstruction of the fictive temperature evolution immediately following a step, evidencing the highly non-linear character of the liquid response to such large amplitude temperature steps. This work illustrates both the strengths and limitations of the TNM approach. This new experimental device offers a promising tool to study far-from-equilibrium supercooled liquids through their dielectric response. [ABSTRACT FROM AUTHOR]

We monitor the transformation of a liquid into an amorphous solid in simulations of a glass forming liquid by measuring the variation of a structural order parameter with either changing temperature or potential energy to establish the influence of the cooling rate on amorphous solidification. We show that the latter representation, unlike the former, exhibits no significant dependence on the cooling rate. This independence extends to the limit of instantaneous quenches, which we find can accurately reproduce the solidification observed during slow cooling. We conclude that amorphous solidification is an expression of the topography of the energy landscape and present the relevant topographic measures. [ABSTRACT FROM AUTHOR]

Water is vital for life, and without it, biomolecules and cells cannot maintain their structures and functions. The remarkable properties of water originate from its ability to form hydrogen-bonding networks and dynamics, which the connectivity constantly alters because of the orientation rotation of individual water molecules. Experimental investigation of the dynamics of water, however, has proven challenging due to the strong absorption of water at terahertz frequencies. In response, by employing a high-precision terahertz spectrometer, we have measured and characterized the terahertz dielectric response of water from supercooled liquid to near the boiling point to explore the motions. The response reveals dynamic relaxation processes corresponding to the collective orientation, single-molecule rotation, and structural rearrangements resulting from breaking and reforming hydrogen bonds in water. We have observed the direct relationship between the macroscopic and microscopic relaxation dynamics of water, and the results have provided evidence of two liquid forms in water with different transition temperatures and thermal activation energies. The results reported here thus provide an unprecedented opportunity to directly test microscopic computational models of water dynamics. [ABSTRACT FROM AUTHOR]

We explore the relationship between a machine-learned structural quantity (softness) and excess entropy in simulations of supercooled liquids. Excess entropy is known to scale well the dynamical properties of liquids, but this quasi-universal scaling is known to breakdown in supercooled and glassy regimes. Using numerical simulations, we test whether a local form of the excess entropy can lead to predictions similar to those made by softness, such as the strong correlation with particles' tendency to rearrange. In addition, we explore leveraging softness to compute excess entropy in the traditional fashion over softness groupings. Our results show that the excess entropy computed over softness-binned groupings is correlated with activation barriers to rearrangement. [ABSTRACT FROM AUTHOR]

FePBNbCr amorphous soft magnetic composites (SMCs) with high compaction density (ρ c) and commendable magnetic properties were successfully fabricated via low-pressure hot-compacting at 160 MPa. Due to the thermoplastic properties of amorphous powders in supercooled liquid region (Δ T x), the hot-compacting in the Δ T x is conducive to the increase of ρ c for the amorphous SMCs, thereby improving the corresponding soft magnetic properties via reducing the number of pinning sites. Compared with these of the cold-compacted amorphous SMCs at 600 MPa, the ρ c increases by 20.3 % to 6.04 g/cm3, the effective permeability increases by 5.26 times to 95.3, while the corresponding total core loss decreases 74.5 % to 154.4 kW/m3 (100 kHz, 0.05 T) for the amorphous SMCs hot-compacted at 495 °C with a pressure holding time of 6 min. These results indicate that the low-pressure hot compacting is an effective measure to further improve soft magnetic properties of the amorphous SMCs for rapidly adapting to the development needs of high-frequency and miniaturization of electronic devices. [ABSTRACT FROM AUTHOR]

A vast array of phenomena, ranging from chemical reactions to phase transformations, are analyzed in terms of a free energy surface defined with respect to a single or multiple order parameters. Enhanced sampling methods are typically used, especially in the presence of large free energy barriers, to estimate free energies using biasing protocols and sampling of transition paths. Kinetic reconstructions of free energy barriers of intermediate height have been performed, with respect to a single order parameter, employing the steady state properties of unconstrained simulation trajectories when barrier crossing is achievable with reasonable computational effort. Considering such cases, we describe a method to estimate free energy surfaces with respect to multiple order parameters from a steady state ensemble of trajectories. The approach applies to cases where the transition rates between pairs of order parameter values considered is not affected by the presence of an absorbing boundary, whereas the macroscopic fluxes and sampling probabilities are. We demonstrate the applicability of our prescription on different test cases of random walkers executing Brownian motion in order parameter space with an underlying (free) energy landscape and discuss strategies to improve numerical estimates of the fluxes and sampling. We next use this approach to reconstruct the free energy surface for supercooled liquid silicon with respect to the degree of crystallinity and density, from unconstrained molecular dynamics simulations, and obtain results quantitatively consistent with earlier results from umbrella sampling. [ABSTRACT FROM AUTHOR]

The effects of atomic mass in terms of its zero-point vibrational energy, on molar volume, glass transition temperature Tg, and viscosity are studied in glassy and supercooled B2O3 liquids using boron isotope substitutions. The molar volume decreases and Tg and isothermal viscosity increase on the substitution of lighter 10B isotopes with the heavier 11B isotopes. These effects are argued to be a manifestation of the higher zero-point vibrational energy of the lighter isotope, which along with the anharmonicity of the potential well, results in a longer equilibrium inter-atomic distance and larger mean-square displacement with respect to that for the heavier isotope. The isotope effect on viscosity is increasingly enhanced as the temperature approaches Tg, which is shown to be consistent with the prediction of the elastic models of viscous flow and shear relaxation. [ABSTRACT FROM AUTHOR]

The most accepted origin for the water anomalous behavior is the phase transition between two liquids (LLPT) in the supercooled regime connected to the glassy first order phase transition at lower temperatures. Two length scale potentials are an effective approach that has long been employed to understand the properties of fluids with waterlike anomalies and, more recently, the behavior of colloids and nanoparticles. These potentials can be parameterized to have distinct shapes, as a pure repulsive ramp, such as the model proposed by de Oliveira et al. [J. Chem. Phys. 124, 64901 (2006)]. This model has waterlike anomalies despite the absence of LLPT. To unravel how the waterlike anomalies are connected to the solid phases, we employ molecular dynamics simulations. We have analyzed the fluid–solid transition under cooling, with two solid crystalline phases, BCC and HCP, and two amorphous regions being observed. We show how the competition between the scales creates an amorphous cluster in the BCC crystal that leads to amorphization at low temperatures. A similar mechanism is found in the fluid phase, with the system changing from a BCC-like to an amorphous-like structure in the point where a maxima in kT is observed. With this, we can relate the competition between two fluid structures with the amorphous clusterization in the BCC phase. These findings help to understand the origins of waterlike behavior in systems without the liquid–liquid critical point. [ABSTRACT FROM AUTHOR]

The slow relaxation of interface water (IW) across three primary phases of membranes is relevant to understand the influence of IW on membrane functions at supercooled conditions. To this objective, a total of ∼ 16.26 μ s all-atom molecular dynamics simulations of 1,2-dimyristoyl-sn-glycerol-3-phosphocholine lipid membranes are carried out. A supercooling-driven drastic slow-down in heterogeneity time scales of the IW is found at the fluid to the ripple to the gel phase transitions of the membranes. At both fluid-to-ripple-to-gel phase transitions, the IW undergoes two dynamic crossovers in Arrhenius behavior with the highest activation energy at the gel phase due to the highest number of hydrogen bonds. Interestingly, the Stokes–Einstein (SE) relation is conserved for the IW near all three phases of the membranes for the time scales derived from the diffusion exponents and the non-Gaussian parameters. However, the SE relation breaks for the time scale obtained from the self-intermediate scattering functions. The behavioral difference in different time scales is universal and found to be an intrinsic property of glass. The first dynamical transition in the α relaxation time of the IW is associated with an increase in the Gibbs energy of activation of hydrogen bond breaking with locally distorted tetrahedral structures, unlike the bulk water. Thus, our analyses unveil the nature of the relaxation time scales of the IW across membrane phase transitions in comparison with the bulk water. The results will be useful to understand the activities and survival of complex biomembranes under supercooled conditions in the future. [ABSTRACT FROM AUTHOR]

A salient feature of supercooled liquids consists in the dramatic dynamical slowdown they undergo as temperature decreases while no significant structural change is evident. These systems also present dynamical heterogeneities (DH): certain molecules, spatially arranged in clusters, relax various orders of magnitude faster than the others. However, again, no static quantity (such as structural or energetic measures) shows strong direct correlations with such fast-moving molecules. In turn, the dynamic propensity approach, an indirect measure that quantifies the tendency of the molecules to move in a given structural configuration, has revealed that dynamical constraints, indeed, originate from the initial structure. Nevertheless, this approach is not able to elicit which structural quantity is, in fact, responsible for such a behavior. In an effort to remove dynamics from its definition in favor of a static quantity, an energy-based propensity has also been developed for supercooled water, but it could only find positive correlations between the lowest-energy and the least-mobile molecules, while no correlations could be found for those more relevant mobile molecules involved in the DH clusters responsible for the system's structural relaxation. Thus, in this work, we shall define a defect propensity measure based on a recently introduced structural index that accurately characterizes water structural defects. We shall show that this defect propensity measure provides positive correlations with dynamic propensity, being also able to account for the fast-moving molecules responsible for the structural relaxation. Moreover, time dependent correlations will show that defect propensity represents an appropriate early-time predictor of the long-time dynamical heterogeneity. [ABSTRACT FROM AUTHOR]

Liquid–liquid transitions are present in a variety of substances. However, investigating the liquid–liquid transitions occurring in a supercooled liquid is difficult because of the interference from rapid crystallization. Here, we report a strong-to-fragile transition in a Pd32Ni52P16 metallic glass-forming supercooled liquid associated with a liquid–liquid transition. Since the liquid–liquid transition takes place at temperatures smaller than the crystallization temperature, the liquid viscosity can be acquired by creep experiments conducted at temperatures close to the glass transition temperature without interference from crystallization. The strong-to-fragile transition results in a 37% increase of the fragility index and a 56% elongation after thermal-plastic processing. An investigation on the loss-modulus peaks by a dynamic mechanical analyzer implies that the enhanced thermal plasticity is contributed by both glass transition and strong-to-fragile transition. This work highlights how liquid–liquid transition affects liquid fragility and how it may aid the thermal-plastic processing of metallic glass. [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]

We investigate the properties of water along the liquid/vapor coexistence line in the supercooled regime down to the no-man's land. Extensive molecular dynamics simulations of the TIP4P/2005 liquid/vapor interface in the range 198–348 K allow us to locate the second surface tension inflection point with a high accuracy at 283 ± 5 K, close to the temperature of maximum density. This temperature also coincides with the appearance of a density anomaly at the interface known as the apophysis. We relate the emergence of the apophysis to the observation of high-density liquid (HDL) water adsorption in the proximity of the liquid/vapor interface. [ABSTRACT FROM AUTHOR]

Many phase change materials (PCMs) are found to crystallize without exhibiting a glass transition endotherm upon reheating. In this paper, we review experimental evidence revealing that these PCMs and likely other hyperquenched molecular and metallic systems can crystallize from the glassy state when reheated at a standard rate. Among these evidences, PCMs annealed below the glass transition temperature Tg exhibit slower crystallization kinetics despite an increase in the number of sub-critical nuclei that should promote the crystallization speed. Flash calorimetry uncovers the glass transition endotherm hidden by crystallization and reveals a distinct change in kinetics when crystallization switches from the glassy to the supercooled liquid state. The resulting Tg value also rationalizes the presence of the pre-Tg relaxation exotherm ubiquitous of hyperquenched systems. Finally, the shift in crystallization temperature during annealing exhibits a non-exponential decay that is characteristic of structural relaxation in the glass. Modeling using a modified Turnbull equation for nucleation rate supports the existence of sub-Tg fast crystallization and emphasizes the benefit of a fragile-to-strong transition for PCM applications due to a reduction in crystallization at low temperature (improved data retention) and increasing its speed at high temperature (faster computing). [ABSTRACT FROM AUTHOR]

We report time resolved observations of the crystallization from liquid hydrogen, supercooled to temperatures below the melting point, using 11.2 keV X-ray diffraction from the Linac Coherent Light Source (LCLS). Changes to the metastable solid and liquid structure factors have been dynamically measured. This allows for a direct determination of the lowest energy crystal polymorphs, the stacking probabilities, as well as the liquid and solid densities and temperatures. Such measurements provide experimental evidence of an Arrhenius-like growth kinetics along the stacking direction during supercooling. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]