Supercooled Research Articles

Coupling structural, chemical composition and stress fluctuations with relaxation dynamics in metallic glasses

Understanding the atomistic mechanisms of relaxation dynamics in metallic glasses remains a longstanding challenge. Here, using microsecond time scale molecular dynamics simulations, three main relaxation stages in metallic glasses are identified. At about 0.6Tg, chemical composition plays a dominant role in the relaxation, manifested by stress accumulation and only minimal variations in structure. As Tg approaches, the confluence of structural heterogeneity and chemical composition leads to the decoupling of relaxation mechanisms. At this temperature, the relaxation results in a structure with a lower energy state and a lower level of stress. In the supercooled liquid regime, an extensive increase in the number of closed-packed icosahedral clusters is responsible for accelerated structural relaxation while their packing frustration leads to the accumulation of intrinsic residual stresses in the glass. The atomistic origin of these dynamic relaxation modes is discussed in terms of structural, chemical composition and stress variations.

Resistance Spot Welding of Stainless Steel and Titanium Plates with a Supercooled Liquid of Zr55Al10Ni5Cu30 Metallic Glass Ribbons

Resistance Spot Welding of Stainless Steel and Titanium Plates with a Supercooled Liquid of Zr55Al10Ni5Cu30 Metallic Glass Ribbons

Ising Paradigm in Isobaric Ensembles.

We review recent work on Ising-like models with "compressible cells" of fluctuating volume that, as such, are naturally treated in NpT and μpT ensembles. Besides volumetric phenomena, local entropic effects crucially underlie the models. We focus on "compressible cell gases" (CCG), namely, lattice gases with fluctuating cell volumes, and "compressible cell liquids" (CCL) with singly occupied cells and fluctuating cell volumes. CCGs contemplate singular diameters and "Yang-Yang features" predicted by the "complete scaling" formulation of asymmetric fluid criticality, with a specific version incorporating "ice-like" hydrogen bonding further describing the "singularity-free scenario" for the low-temperature unusual thermodynamics of supercooled water. In turn, suitable CCL variants constitute adequate prototypes of water-like liquid-liquid criticality and the freezing transition of a system of hard spheres. On incorporating vacant cells to such two-state CCL variants, one obtains three-state, BEG-like models providing a satisfactory description of water's "second-critical-point scenario" and the whole phase behavior of a simple substance like argon. Future challenges comprise water's crystal-fluid phase behavior and metastable states.

Assessment of HVAF thermally sprayed coatings: Unraveling microstructural, electrochemical, and tribological performance using glass former Fe-Cr-Mo-Nb-B feedstock powder

In this paper the microstructural features of the glass former Fe68Cr8Mo4Nb4B16 coatings are unveiled and related to their electrochemical and tribological responses. The coating was mostly glassy with some embedded borides (M3B2, M2B-tetragonal; M being the metallic elements of the alloy) and ferrite. The tribological behavior of the HVAF coated sample, characterized by a thickness of about 200 µm, ∼6% porosity and a Vickers hardness of 357 HV0.5, was assessed in a sphere-on-plate configuration, revealing a specific wear rate of approximately 5 ×10−4 mm3∙N−1m−1. The wear mechanism was dominated by delamination caused by fragile intersplats. The corrosion resistance of HVAF coatings was evaluated in 0.6 M NaCl solution and compared with the results obtained for the crystalline Fe68Cr8Mo4Nb4B16 ingot, produced by melting in an induction furnace, and for the AISI 1020 steel substrate. The HVAF coating showed satisfactory corrosion resistance compared to the carbon steel substrate and the crystalline ingot, with the highest corrosion potential, Ecorr, values (−533 mVSCE) and the lowest corrosion current density, icorr, (10−6 A∙cm−2) followed by a clear passivation window upon anodic polarization in 0.6 M NaCl solution. Evaluations of HVAF coating showed a higher glassy content compared to the gas-atomized feedstock powders. This suggests that during spraying, certain particles were molten and experienced cooling rates adequate to inhibit crystallization, resulting in the freezing of the supercooled liquid. This phenomenon contributes to the good corrosion resistance observed in the present work and offers an opportunity to enhance the electrochemical behavior of HVAF coatings.

Unraveling the dynamic slowdown in supercooled water: The role of dynamic disorder in jump motions.

When a liquid is rapidly cooled below its melting point without inducing crystallization, its dynamics slow down significantly without noticeable structural changes. Elucidating the origin of this slowdown has been a long-standing challenge. Here, we report a theoretical investigation into the mechanism of the dynamic slowdown in supercooled water, a ubiquitous yet extraordinary substance characterized by various anomalous properties arising from local density fluctuations. Using molecular dynamics simulations, we found that the jump dynamics, which are elementary structural change processes, deviate from Poisson statistics with decreasing temperature. This deviation is attributed to slow variables competing with the jump motions, i.e., dynamic disorder. The present analysis of the dynamic disorder showed that the primary slow variable is the displacement of the fourth nearest oxygen atom of a jumping molecule, which occurs in an environment created by the fluctuations of molecules outside the first hydration shell. As the temperature decreases, the jump dynamics become slow and intermittent. These intermittent dynamics are attributed to the prolonged trapping of jumping molecules within extended and stable low-density domains. As the temperature continues to decrease, the number of slow variables increases due to the increased cooperative motions. Consequently, the jump dynamics proceed in a higher-dimensional space consisting of multiple slow variables, becoming slower and more intermittent. It is then conceivable that with further decreasing temperature, the slowing and intermittency of the jump dynamics intensify, eventually culminating in a glass transition.

Crystal Nucleation in Supercooled Atomic Liquids.

The liquid-to-solid phase transition is a complex process that is difficult to investigate experimentally with sufficient spatial and temporal resolution. A key aspect of the transition is the formation of a critical seed of the crystalline phase in a supercooled liquid, that is, a liquid in a metastable state below the melting temperature. This stochastic process is commonly described within the framework of classical nucleation theory, but accurate tests of the theory in atomic and molecular liquids are challenging. Here, we employ femtosecond x-ray diffraction from microscopic liquid jets to study crystal nucleation in supercooled liquids of the rare gases argon and krypton. Our results provide stringent limits to the validity of classical nucleation theory in atomic liquids, and offer the long-sought possibility of testing nonclassical extensions of the theory.

Improving Supercooled Water Forecast Through Real‐Time Aerosol Input: A Case Study

AbstractAccurately simulating and forecasting supercooled water has been crucial for addressing the threat of aircraft icing. This study utilized the Weather Research and Forecast model and Aerosol‐Aware Thompson‐Eidhammer microphysics (TE14) scheme to simulate supercooled water properties. Three high‐resolution experiments were conducted to explore the impact of increased model resolution and different aerosol initial conditions. The synoptic‐scale characteristics and cloud extent were well‐matched between observations and the model simulation, which established a background for supercooled water comparisons. Microphysical characteristics of supercooled droplets and the formation of supercooled large drops demonstrated the TE14 scheme's reasonable simulation of supercooled water microphysics under different aerosol loadings. In situ aircraft measurements were used to validate the simulated supercooled water properties. Results highlighted the sensitivity of supercooled water simulation to aerosol number concentration via droplet activation in the scheme. The choice for the aerosol initial condition could result in a significant underestimation or overestimation of supercooled water number concentration, consequently leading to biased estimations of droplet size. Incorporating real‐time forecast aerosol data improved the simulation by increasing cloud droplet number concentration and reducing droplet size. These findings underscored the importance of aerosols via droplet activation in accurately simulating cloud water properties and emphasized their role in forecasting aircraft icing hazards.

Dipolar Order Controls Dielectric Response of Glass-Forming Liquids.

The dielectric response of liquids reflects both reorientation of single molecular dipoles and collective modes, i.e., dipolar cross-correlations. A recent theory predicts the latter to produce an additional slow peak in the dielectric loss spectrum. Following this idea we argue that in supercooled liquids the high-frequency power law exponent of the dielectric loss β should be correlated with the degree of dipolar order, i.e., the Kirkwood correlation factor g_{K}. This notion is confirmed for 25 supercooled liquids. While our findings support recent theoretical work the results are shown to violate the earlier Kivelson-Madden theory.

Isotope effect on the anomalies of water: A corresponding states analysis.

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 244K. 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.

Freezing of sessile water droplets on titanium alloy surfaces with various roughness: An in-situ experimental study

The threat of icing caused by supercooled water droplets on aircraft components such as wings and compressors is a serious concern for aviation safety, and the surface roughness of these components can experience alterations due to environmental corrosion or damage. However, the potential impact of surface roughness variation on their susceptibility to icing remains unclear. In this study, the freezing experiments of sessile water droplets on the surfaces of a typical aero-engine titanium alloy (ZTC4) with varying roughness were conducted using a laser confocal micro-Raman spectrometer with a heating/freezing stage. Three freezing stages were captured via an optical microscope, and the temperature changes of water droplet during the cooling process were explored through heat transfer simulation. In addition, the relationship between Raman peaks and temperatures of frozen droplets was quantified. The results of 200 repeated experiments demonstrated that the freezing temperatures of sessile water droplets exhibited a two-parameter Weibull distribution, and there was a nonlinear positive correlation between the mean freezing temperature and surface roughness, which implied that environmental corrosion or damage leading to an increase in surface roughness may significantly elevate the probability of component icing and safety issues.

Temperature effects on the structure of lead metasilicate glass, supercooled liquid, crystal, and liquid: Vibrational anharmonicity and configurational transformations analyzed by molecular dynamics and Raman scattering

Raman spectroscopy and Molecular Dynamics (MD) simulations were employed to explore in detail the effects of temperature on the four stages of the PbO∙SiO2 system: glass, supercooled liquid, crystalline phases, and liquid. The Qn distribution up to 1153 K and the wavenumber temperature coefficients derived from vibrational anharmonicity were determined from the Raman data, whereas the structural transformation reflected in changes in the Qn population distribution up to 2400 K was inferred from MD simulations. The results indicate that reversible configurational transformations occur only in the higher temperature ranges of the supercooled liquid and more notably in the liquid state. During these transformations, the increase in the Q0 and Q1 populations occurs at the expense of the Q3 and Q4 populations. On the other hand, only vibrational anharmonicity was observed in the glass and crystalline states.

Liquid–liquid transition and ice crystallization in a machine-learned coarse-grained water model

Mounting experimental evidence supports the existence of a liquid-liquid transition (LLT) in high-pressure supercooled water. However, fast crystallization of supercooled water has impeded identification of the LLT line TLL(p) in experiments. While the most accurate all-atom (AA) water models display a LLT, their computational cost limits investigations of its interplay with ice formation. Coarse-grained (CG) models provide over 100-fold computational efficiency gain over AA models, enabling the study of water crystallization, but have not yet shown to have a LLT. Here, we demonstrate that the CG machine-learned water model Machine-Learned Bond-Order Potential (ML-BOP) has a LLT that ends in a critical point at pc = 170 ± 10 MPa and Tc = 181 ± 3 K. The TLL(p) of ML-BOP is almost identical to the one of TIP4P/2005, adding to the similarity in the equation of state of liquid water in both models. Cooling simulations reveal that ice crystallization is fastest at the LLT and its supercritical continuation of maximum heat capacity, supporting a mechanistic relationship between the structural transformation of water to a low-density liquid (LDL) and ice formation. We find no signature of liquid-liquid criticality in the ice crystallization temperatures. ML-BOP replicates the competition between formation of LDL and ice observed in ultrafast experiments of decompression of the high-density liquid (HDL) into the region of stability of LDL. The simulations reveal that crystallization occurs prior to the coarsening of the HDL and LDL domains, obscuring the distinction between the highly metastable first-order LLT and pronounced structural fluctuations along its supercritical continuation.

Isocompositional liquid-liquid transition in dilute aqueous LiCl solutions

We here demonstrate that small amounts of LiCl dissolved in water extend the existence window of deeply supercooled liquid water. This shift allows us to observe the isocompositional, sharp liquid-liquid transition (LLT), while this is not possible in pure water. Upon heating at ambient pressure, the hyperquenched and densified glass first turns into the high-density liquid (HDL) and then experiences the LLT to the low-density liquid (LDL) at 137–141 K and ambient pressure. At the LLT the viscosity suddenly jumps up by an order of magnitude, from ∼4.3×109Pas in HDL to ∼3.7×1010Pas in LDL for the 3.1 mol % solution based on our calorimetric analysis. That is, the LLT takes place clearly in the ultraviscous liquid domain at ambient pressure. By contrast, the viscosity of the emerging LDL at the LLT is still in the domain of the soft glass for pure water and for solutions exceeding 5 mol % LiCl that were studied in the past. This is owing to our observation that, first, the LDL's glass transition is lowered by about 8 K to 126 K in the presence of small amounts LiCl, whereas the HDL's glass transition remains at 118 K. Second, the stability of HDL at ambient pressure is increased by high-pressure annealing, shifting the LLT to higher temperatures. Published by the American Physical Society 2024

Single Cationic Conduction Under Anion-Blocking Conditions in Sodium Ionic Liquids: Na[((FSO2)2N) x ((CF3SO2)(FSO2)N)1−x ]

There is a demand for low-melting-point molten-salt electrolytes with high thermal and electrochemical stability for the development of high-performance sodium-ion batteries. Mixing sodium bis(fluorosulfonyl)amide (NaFSA) and sodium (fluorosulfonyl)(trifluoromethylsulfonyl)amide (NaFTA) results in a large depression in their melting points. In this study, the phase behavior and Na+ transport properties of binary mixtures of NaFSA and NaFTA were investigated. The mixture of NaFSA and NaFTA with a molar ratio of 8:2 has a melting temperature (T m) of 363 K, successfully achieving an ionic liquid consisting of single cationic (Na+) salts. This mixture easily forms a super-cooled liquid. The ionic conductivity (σ) of Na[(FSA)0.8(FTA)0.2] continuously varied from above T m to below T m, obeying the Vogel–Tamman–Fulcher equation, which coincides with its super-cooling nature. The ionic conductivity and apparent Na+ transference number (t Na+) under anion-blocking conditions at T m approached 10−3 S cm−1 and 0.92, respectively.

Mean-field analysis of the glassy dynamics of an elastoplastic model of super-cooled liquids

We present a mean-field theory of a coarse-grained model of a super-cooled liquid in which relaxation occurs via local plastic rearrangements. Local relaxation can be induced by thermal fluctuations or by the long-range elastic consequences of other rearrangements. We extract the temperature dependence of both the relaxation time and the length scale of dynamical correlations. We find two dynamical regimes. First, a regime in which the characteristic time and length scales diverge as a power law at a critical temperature T c . This regime is found by an approximation that neglects activated relaxation channels, which can be interpreted as akin to the one found by the mode-coupling transition of glasses. In reality, only a crossover takes place at T c . The residual plastic activity leads to a second regime characterised by an Arrhenius law below T c . In this case, we show that the length scale governing dynamical correlations diverges as a power law as , and is logarithmically related to the relaxation time.

Study of long-term in-orbit pressure control of liquid krypton cryogenic storage tank

Due to its high specific impulse, low toxicity, contamination, safety, and cost, krypton has gradually replaced other propellants as the primary choice for electric thrusters on deep-space exploration and large-orbit transfer missions with long-range, long-duration, and large-thrust requirements. However, due to the cryogenic propellant itself having a low boiling point, controlling the pressure change of krypton cryogenic propellant during the process of long-term cryogenic storage has emerged as one of the most important issues that must be resolved and proven to achieve non-destructive storage of cryogenic propellant. This paper examines the necessity and viability of a cryogenic gas propellant liquefaction storage scheme and quantifies the effectiveness of tank pressure control of the supercooled liquid krypton injection mixing scheme to solve the problem at present. Its purpose is to offer scheme examples for the design of a krypton thruster propellant storage unit and the in-tank pressure control during the long-term application process.

Effect of Turbulence on the Collision Rate between Settling Ice Crystals and Droplets

Abstract In mixed-phase clouds, graupel forms by riming, a process whereby ice crystals and supercooled water droplets settling through a turbulent flow collide and aggregate. We consider here the early stage of the collision process of small ice crystals with water droplets and determine numerically the geometric collision kernel in turbulent flows (therefore neglecting all interactions between the particles and assuming a collision efficiency equal to unity), over a range of energy dissipation rate 1–250 cm2 s−3 relevant to cloud microphysics. We take into account the effect of small, but nonzero fluid inertia, which is essential since it favors a biased orientation of the crystals with their broad side down. Since water droplets and ice crystals have different masses and shapes, they generally settle with different velocities. Turbulence does not play any significant role on the collision kernel when the difference between the settling velocities of the two sets of particles is larger than a few millimeters per second. The situation is completely different when the settling speeds of droplets and crystals are comparable, in which case turbulence is the main cause of collisions. Our results are compatible with those of recent experiments according to which turbulence does not clearly increase the growth rate of tethered graupel in a flow transporting water droplets.

Fragility crossover mediated by covalent-like electronic interactions in metallic liquids

Abstract Fragility is one of the central concepts in glass and liquid sciences, as it characterizes the extent of deviation of viscosity from Arrhenius behavior and is linked to a range of glass properties. However, the intervention of crystallization often prevents the assessment of fragility in poor glass-formers, such as supercooled metallic liquids. Hence experimental data on their compositional dependence are scarce, let alone fundamentally understood. In this work, we use fast scanning calorimetry to overcome this obstacle and systematically study the fragility in a ternary La-Ni-Al system, over previously inaccessible composition space. We observe fragility dropped in a small range with the Al alloying, indicating an alloying-induced fragility crossover. We use x-ray photoelectron spectroscopy, resistance measurements, electronic structure calculations, and DFT-based deep-learning atomic simulations to investigate the cause of this fragility drop. These results show that the fragility crossover can be fundamentally ascribed to the electronic covalency associated with the unique Al-Al interactions. Our findings provide insight into the origin of fragility in metallic liquids from an electronic structure perspective and pave a new way for the design of metallic glasses.

Computer simulations of the glass transition and glassy materials

We provide an overview of the different types of computational techniques developed over the years to study supercooled liquids, glassy materials and the physics of the glass transition. We organise these numerical strategies into four broad families. For each of them, we describe the general ideas without discussing any technical details. We summarise the type of questions which can be addressed by any given approach and outline the main results which have been obtained. Finally we describe two important directions for future computational studies of glassy systems.

The RFOT Theory of Glasses: Recent Progress and Open Issues

The Random First Order Transition (RFOT) theory started with the pioneering work of Kirkpatrick, Thirumalai and Wolynes. It leverages methods and advances of the theory of disordered systems. It fares remarkably well at reproducing the salient experimental facts of super-cooled liquids. Yet, direct and indisputable experimental validations are missing. In this short survey, we will review recent investigations that broadly support all static aspects of RFOT, but also those for which the standard dynamical extension of the theory appears to be struggling, in particular in relation with facilitation effects. We discuss possible solutions and open issues.