Supercooled Conditions Research Articles

The shape of water – How cluster formation provides a unifying explanation of water’s anomalous properties

Water, essential to life on Earth, has many anomalous properties, that are not yet fully understood. We used density functional theory, the COSMO-RS implicit solvent model and statistical thermodynamics to calculate the dynamic equilibrium of formation of water clusters in water. Clusters of certain shape are predicted to be thermodynamically stable at ambient down to supercooled conditions and their presence almost quantitatively explains water’s anomalous properties as a function of temperature and pressure. The dodecahedron is the dominant cluster below ∼235 K and below ∼150 MPa and forms a miscibility gap with water below a critical point at ∼230 K. The hexagonal torus is the dominant cluster above ∼235 K and below ∼75 MPa. Both the dodecahedron and the torus are low-density clusters and their presence explains the density maximum of pure water at 277 K (+4 °C). The waters in these clusters are tetrahedrally coordinated, their structures are consistent with experimental data and their presence explains the observed tetrahedral fraction as a function of temperature. A significant part of the overall thermodynamic stability comes from the configurational entropy of the hydrogen bond network in the clusters, so dynamic cluster formation and reformation would be observed as fluctuations in the water structure, rather than stable clusters. At pressures above ∼100 MPa, many of water’s anomalous properties diminish or vanish, which is also the pressure above which high-density water clusters become more stable and prevalent. Our simple unifying 3-cluster theory reproduces water’s anomalous properties from supercooled to ambient temperatures and from ambient pressure up to at least 400 MPa, including density anomalies, two-liquid behavior, compressibility, and heat capacity.

Experimental study on visualization of TBAB hydrate formation in confined small channels

Hydrate crystals' microscopic characteristics and agglomerating morphologies play an important role in the hydrate reaction equipment's flow assurance and heat transfer. In order to study the formation process of hydrate, experimental quartz tubes with small diameters were selected, and a fully visualized flow loop system was established. The study investigated the effects of supercooling, solution concentration, tube diameter, and flow rate on hydrate blockage time and agglomeration morphology. The results show that under the same supercooling conditions, the density of single crystal hydrate formed in 10 wt%-20 wt% TBAB (Tetra-n-butylammonium bromide) hydrate solution is low, and the crystal front appears needle-like or sword-like, which is conducive to mass and heat transfer. High concentration TBAB solution(30 wt%-40 wt%) can form dense hydrate crystals, and the tip effect was significantly weakened. For low concentration TBAB solution, the increased flow rate can accelerate the formation of new nuclei and inhibit the growth of large crystals. Grout solutions with different particle sizes can be obtained by adjusting the flow rate. It was found that the initial morphology of TBAB hydrate crystals included spherical and cylindrical shapes, and the morphological evolution process of a single hydrate crystal was similar. Finally, a microscopic physical model of the TBAB hydrate growth and aggregation process was established.

Numerical Simulation of Ice Crystal Supercooled Droplet Mixed Phase Icing Based on the Improved Messinger Model

The ice crystal supercooled droplet mixed phase icing problem is an important research direction in aircraft icing and has received more attention in recent years. The thermodynamic process of the water film after the ice crystals impact on the surface determines the final ice shape, which is an important part of the accurate prediction of aircraft icing. In this paper, a thermodynamic model of ice crystal supercooled droplet mixed phase icing is proposed based on the extended Messinger model, according to the results of flow field and particle trajectory calculations. In this model, the mass and energy conservation equations of ice crystals, supercooled droplets, and liquid water are considered. The equations take the process of ice crystal adhesion and erosion into account, and the solution method of the equations is given. Ice shapes are calculated under various ice crystal supercooled droplet mixed phase conditions and compared with experimental results to demonstrate the validity of the numerical method. The effects of ice crystal erosion rate, melting ratio, and adhesion coefficient on the calculation results are analyzed by a numerical method. The results show that the ice crystal erosion rate has little effect on the ice shape, while a larger melting ratio and adhesion coefficient lead to more ice accretion.

Inherent-state melting and the onset of glassy dynamics in two-dimensional supercooled liquids

Below the onset temperature To, the equilibrium relaxation time of most glass-forming liquids exhibits glassy dynamics characterized by a super-Arrhenius temperature dependence. In this supercooled regime, the relaxation dynamics also proceeds through localized elastic excitations corresponding to hopping events between inherent states, i.e., potential-energy-minimizing configurations of the liquid. Despite its importance in distinguishing the supercooled regime from the high-temperature regime, the microscopic origin of To is not yet known. Here, we construct a theory for the onset temperature in two dimensions and find that an inherent-state melting transition, described by the binding-unbinding transition of dipolar elastic excitations, delineates the supercooled regime from the high-temperature regime. The corresponding melting transition temperature is in good agreement with the onset temperature found in various two-dimensional (2D) atomistic models of glass formers and an experimental binary colloidal system confined to a water-air interface. Additionally, we find the predictions for the renormalized elastic moduli to agree with the experimentally observed values for the latter 2D colloidal system. We further discuss the predictions of our theory on the displacement and density correlations at supercooled conditions, which are consistent with observations of the Mermin-Wagner fluctuations in experiments and molecular simulations.

Relaxation time scales of interfacial water upon fluid to ripple to gel phase transitions of bilayers.

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 ∼16.26μs 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 SErelation 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.

Lagrangian and Eulerian algorithms for water droplets in in-flight ice accretion

A particle tracking framework for the computation of the collection efficiency for in-flight ice accretion is presented. Algorithms for the computation of the collection efficiency are presented for both Lagrangian and Eulerian descriptions of the droplets equations. Strengths and weaknesses of each method are analyzed and possible solutions are described and implemented. For the Lagrangian solver, a method for automatic resolution adaptation is introduced, and a strategy for exploiting parallelism is described. In the Eulerian frame a scheme is presented for the solution of the equations on unstructured 3D grids using a relaxation approach. An hybrid Lagrangian Eulerian approach for the computation of the collection efficiency is also introduced which is relevant for Super-cooled Large Droplet condition. All presented algorithms are thoroughly verified, and a comprehensive validation is performed.

3D printing of fully recyclable continuous fiber self-reinforced composites utilizing supercooled polymer melts

A 3D printing approach for fully recyclable continuous fiber self-reinforced composites (CFSRCs) utilizing supercooled polymer melts was proposed. Continuous autologous fibers were added to the supercooled melt zone below the polymer matrix melting temperature avoiding fiber melting which successfully enlarged the processing temperature window. Through controlled supercooled melt conditions and heat transfer simulation, the supercooled melting temperature gradient control strategy for 3D printing CFSRCs were established. The processing temperature window enlarged from 2℃ to 30℃. Then the intrinsic connection among the printing temperature, crystallization behavior and mechanical properties of 3D printed CFSRCs were analysed. Furthermore, the interlaminar shear strength and transverse tensile property of CFSRCs were excellent than carbon fiber reinforced composites. Lastly, confirmation of the full recyclability of self-reinforced composites by mechanical recycling without mechanical property loss compared with virgin matrix. Fully recyclable CFSRCs based on 3D printing potentially establish a closed-loop recycling strategy for space applications.

Quantifying dynamical heterogeneity length scales of interface water across model membrane phase transitions.

All-atom molecular dynamics simulations of 1,2-dimyristoyl-sn-glycero-3-phosphocholine lipid membranes reveal a drastic growth in the heterogeneity length scales of interface water (IW) across fluid to ripple to gel phase transitions. It acts as an alternate probe to capture the ripple size of the membrane and follows an activated dynamical scaling with the relaxation time scale solely within the gel phase. The results quantify the mostly unknown correlations between the spatiotemporal scales of the IW and membranes at various phases under physiological and supercooled conditions.

Effect of supercooling on storage ability of different beef cuts in comparison to traditional storage methods

The effect of supercooling on different beef cuts was evaluated compared with traditional storage methods. Beef striploins and topsides were stored under freezing, refrigeration, or supercooling conditions and their storage ability and quality were analyzed during 28 days of storage. The total aerobic bacteria, pH, and volatile basic nitrogen were higher in the supercooled beef than in the frozen beef, but lower than in the refrigerated one, regardless of the type of cut. In addition, the discoloration of frozen and supercooled beef was slower than that of refrigerated beef. The results in storage stability and color indicate that supercooling can prolong the shelf-life of beef compared to refrigeration due to its temperature characteristic. In addition, supercooling minimized the problems of freezing and refrigeration, including ice crystal formation and enzyme-based deterioration; therefore, the qualities of topside and striploin were less affected. Collectively, these results indicate that supercooling can be a beneficial storage method for extending the shelf-life of different beef cuts.

Freshness Analysis of Raw Laver (Pyropia yenzoensis) Conserved under Supercooling Conditions.

Freezing raw laver is unsuitable for the laver industry due to process characteristics and economic problems. Therefore, this study attempted to investigate supercooled storage to extend the storage period without freezing, rather than refrigeration. To compare and analyze the storage ability of supercooling, the experiment was performed under refrigeration (5 °C), constant supercooling (CS, -2 °C), stepwise supercooling (SS, -2 °C), and freezing (-18 °C) conditions for 15 days, and the physicochemical changes according to the treatment and period were investigated. All SS samples, which were designed for stable supercooling, were kept in a supercooled state for 15 days. Two samples among the twelve total subjected to CS were frozen. At 9 days, the drip losses of the CS and SS samples were 6.32% and 6.48%, respectively, which was two times lower than that of refrigeration and three times lower than that of the frozen samples. The VBN of the refrigerated samples was 108.33 mg/100 g at 6 days, which exceeded the decomposition criterion. Simultaneously, the VBN of the other treatments was under the decomposition criterion of 30 mg/100 g. However, the VBN of both supercooling samples at 15 days increased to higher than the decomposition criterion. Regarding appearance, the refrigerated samples showed tissue destruction at 9 days, but tissue destruction of the CS and CC samples was observed at 15 days, and tissue destruction of the frozen samples was not observed until 15 days. Consequently, supercooling did not maintain quality for longer periods than freezing, but it did extend the shelf life more than refrigeration, and effectively preserved the quality for a short period.

Cooperative activated hopping dynamics in binary glass-forming liquids: effects of the size ratio, composition, and interparticle interactions.

Slow dynamics in supercooled and glassy liquids is an important research topic in soft matter physics. Compared to the traditionally focused one-component systems, glassy dynamics in mixture systems adds in a rich set of new complexities, which are fundamentally interesting and also relevant for many technological applications. In this paper, we apply the recently developed self-consistent cooperative hopping theory (SCCHT) to systematically investigate the effects of the size ratio, composition and interparticle interactions on the cooperative activated hopping dynamics of matrix (in larger size) and penetrant (in smaller size) particles in varied binary sphere mixture model systems, with a specific focus on ultrahigh mixture packing fractions that mimic the deeply supercooled glass transition conditions for molecular/polymeric mixture materials. Analysis shows that in these high activation barrier cases, the long-range elastic distortion associated with a matrix particle hopping over its cage confinement always generates an elastic barrier of a nonnegligible magnitude, although the ratio between the elastic barrier and local barrier contribution is sensitively dependent on all three mixture-specific system factors considered in this work. SCCHT predicts two general scenarios of penetrant-matrix cooperative activated hopping dynamics: matrix/penetrant co-hopping (regime 1) or the penetrant mean barrier hopping time shorter than that of the matrix (regime 2). Increasing the penetrant-to-matrix size ratio or the penetrant-matrix cross-attraction strength is found to universally enlarge the composition window of regime 1. Diverse dynamical properties characterising different aspects of the cooperative activated hopping process, including the penetrant and matrix transient localization lengths, penetrant and matrix hopping jump distances, different types of local and elastic activated barriers, and matrix long-time diffusivity, relaxation time and dynamic fragility are quantitatively studied against a wide range of variations over the three system factors. Of particular interest is the universal "anti-plasticization" phenomenon achievable for sufficiently strong cross-attractive interactions. The prospects this work opens for the exploration of a wide variety of polymer-based mixture materials are briefly discussed at the end.

Contrast Icing Wind Tunnel Tests between Normal Droplets and Supercooled Large Droplets

In order to compare and analyze the similarities and differences between normal droplet icing shapes and supercooled large droplet icing shapes, SADRI carried out normal droplet and supercooled large droplet icing wind tunnel tests in the NRC−AIWT icing wind tunnel. Taking the typical glaze ice in normal droplet icing conditions as the reference, the freezing drizzle and freezing rain icing tests under the supercooled large droplet conditions were carried out. The test results show that compared with normal droplets, the ice horn height of supercooled large droplets decreases with the increase in droplet particle size, and even the ice horn characteristics are not obvious when the icing condition is freezing rain. At the same time, the range and height of rough element ice shape after the main ice horn of supercooled large droplets are significantly larger and higher than those of the normal droplets, while the difference in the rough element in different supercooled large droplet icing conditions is small.

Supercooling Pretreatment Improves the Shelf-Life of Freeze-Dried Leuconostoc mesenteroides WiKim32.

Storage stability of freeze-dried lactic acid bacteria is a critical factor for their cost-effectiveness. Long-term storage of lactic acid bacteria enables microbial industry to reduce distribution costs. Herein, we investigated the effect of cold adaptation under supercooling conditions at -5°C on the viability of Leuconostoc mesenteroides WiKim32 during the freeze-drying process and subsequent storage. Cold adaptation increased the thickness of exopolysaccharides (EPS) and improved the viability of freeze-dried Leu. mesenteroides WiKim32. Compared to non-adapted cells, cold-adapted cells showed a 35.4% increase in EPS thickness under supercooling conditions. The viability of EPS-hydrolyzed cells was lower than that of untreated cells, implying that EPS plays a role in protection during the freeze-drying process. Cold adaptation increased the storage stability of freeze-dried Leu. mesenteroides WiKim32. Fifty-six days after storage, the highest viability (71.3%) was achieved with cold adaptation at -5°C. When EPS-containing broth was added prior to the freeze-drying process, the viability further increased to 82.7%. These results imply that cold adaptation by supercooling pretreatment would be a good strategy for the long-term storage of Leu. mesenteroides WiKim32.

Homogeneous ice nucleation rates for mW and TIP4P/ICE models through Lattice Mold calculations.

Freezing of water is the most common liquid-to-crystal phase transition on Earth; however, despite its critical implications on climate change and cryopreservation among other disciplines, its characterization through experimental and computational techniques remains elusive. In this work, we make use of computer simulations to measure the nucleation rate (J) of water at normal pressure under different supercooling conditions, ranging from 215 to 240K. We employ two different water models: mW, a coarse-grained potential for water, and TIP4P/ICE, an atomistic nonpolarizable water model that provides one of the most accurate representations of the different ice phases. To evaluate J, we apply the Lattice Mold technique, a computational method based on the use of molds to induce the nucleus formation from the metastable liquid under conditions at which observing spontaneous nucleation would be unfeasible. With this method, we obtain estimates of the nucleation rate for ice Ih and Ic and a stacking mixture of ice Ih/Ic, reaching consensus with most of the previously reported rates, although differing with some others. Furthermore, we confirm that the predicted nucleation rates obtained by the TIP4P/ICE model are in better agreement with experimental data than those obtained through the mW potential. Taken together, our study provides a reliable methodology to measure nucleation rates in a simple and computationally efficient manner that contributes to benchmarking the freezing behavior of two popular water models.

Liquid-liquid phase transition in deeply supercooled Stillinger-Weber silicon.

The existence of a phase transition between two distinct liquid phases in single-component network-forming liquids (e.g. water, silica, silicon) has elicited considerable scientific interest. The challenge, both for experiments and simulations, is that the liquid-liquid phase transition (LLPT) occurs under deeply supercooled conditions, where crystallization occurs very rapidly. Thus, early evidence from numerical equationof state studies was challenged with the argument that slow spontaneous crystallization had been misinterpreted as evidence of a second liquid state. Rigorous free-energy calculations have subsequently confirmed the existence of a LLPT in some models of water, and exciting new experimental evidence has since supported these computational results. Similar results have so far not been found for silicon. Here, we present results from free-energy calculations performed for silicon modeled with the classical, empirical Stillinger-Weber-potential. Through a careful study employing state-of-the-art constrained simulation protocols and numerous checks for thermodynamic consistency, we find that there are two distinct metastable liquid states and a phase transition. Our results resolve a long-standing debate concerning the existence of a liquid-liquid transition in supercooled liquid silicon and address key questions regarding the nature of the phase transition and the associated critical point.

Internal mixing air-assisted spray nozzle for large droplets: Experimental measurements and numerical simulations

In the present study, detailed experimental measurements of a large-droplet spray nozzle under a wide range of operating conditions have been conducted at China Aerodynamics Research and Development Center (CARDC) low-speed vertical wind tunnel facility. The droplet size distributions obtained from these measurements have been modeled using the Rosin-Rammler distribution. A multi-physics multi-phase numerical model for the simulation of the complex spray dynamics associated with the large-droplet spray nozzle has been developed in order to support the performance characterization of this device. More specifically, the primary breakup of liquid (water) in the atomizer-produced spray is modeled using a volume of fluid (VOF) to discrete phase model (DPM) transition representation. The numerical model is validated using the experimental measurements. The small relative error between the numerical predictions and experimental measurements for the droplet size distribution and for a number of characteristic droplet diameters suggest that the numerical model provides accurate high-fidelity predictions of the spray dynamics of the large-droplet spray nozzle. Moreover, it is shown that a simple modification of the spray nozzle (increasing the length of the mixing chamber by 50%) has a significant effect on the performance of the nozzle. In particular, the droplet median volumetric diameter and the spray angle are increased as the air pressure is decreased. Furthermore, an increase in the nozzle mixing chamber length results in a much broader droplet size distribution. The validated VOF-to-DPM transition model developed in this study can be used for a future redesign (involving modifications of some key geometric parameters) of the original large-droplet spray nozzle to generate reliably and robustly larger droplets required to simulate various supercooled large droplet conditions of practical relevance.

Water Diffusion Proceeds via a Hydrogen-Bond Jump Exchange Mechanism.

The self-diffusion of water molecules plays a key part in a broad range of essential processes in biochemistry, medical imaging, material science, and engineering. However, its molecular mechanism and the role played by the water hydrogen-bond network rearrangements are not known. Here we combine molecular dynamics simulations and analytic modeling to determine the molecular mechanism of water diffusion. We establish a quantitative connection between the water diffusion coefficient and hydrogen-bond jump exchanges, and identify the features that determine the underlying energetic barrier. We thus provide a unified framework to understand the coupling between translational, rotational, and hydrogen-bond dynamics in liquid water. It explains why these different dynamics do not necessarily exhibit identical temperature dependences although they all result from the same hydrogen-bond exchange events. The consequences for the understanding of water diffusion in supercooled conditions and for water transport in complex aqueous systems, including ionic, biological, and confined solutions, are discussed.

Low- and High-Density Unknown Waters at Ice-Water Interfaces.

Experimental confirmation of liquid polymorphs of water, high-density liquid (HDL) and low-density liquid (LDL), is desired for understanding not only the liquid state of matter but also the origin of the mysterious properties of water. However, this remains challenging because the liquid-liquid critical point of water lies in experimentally inaccessible supercooling conditions known as "no man's land". Here, we show by in situ optical microscopy that droplets and layers of low- and high-density unknown waters (LDUW and HDUW) appear macroscopically depending upon ice polymorphs at non-equilibrium interfaces between water and ices under experimentally accessible (de)pressurization conditions. These unknown waters were found to have characteristic velocities (about 20 and 100 m/s for LDUW and HDUW, respectively) different from water (about 40 m/s) and quasi-liquid layers (QLLs) (about 2 and 0.2 m/s for droplet and layer forms of QLLs, respectively). Our discoveries provide insight on liquid polymorphism of water.

Signatures of sluggish dynamics and local structural ordering during ice nucleation.

We investigate the microscopic pathway of spontaneous crystallization in the ST2 model of water under deeply supercooled conditions via unbiased classical molecular dynamics simulations. After quenching below the liquid-liquid critical point, the ST2 model spontaneously separates into low-density liquid (LDL) and high-density liquid phases, respectively. The LDL phase, which is characterized by lower molecular mobility and enhanced structural order, fosters the formation of a sub-critical ice nucleus that, after a stabilization time, develops into the critical nucleus and grows. Polymorphic selection coincides with the development of the sub-critical nucleus and favors the formation of cubic (Ic) over hexagonal (Ih) ice. We rationalize polymorphic selection in terms of geometric arguments based on differences in the symmetry of second neighbor shells of ice Ic and Ih, which are posited to favor formation of the former. The rapidly growing critical nucleus absorbs both Ic and Ih crystallites dispersed in the liquid phase, a crystal with stacking faults. Our results are consistent with, and expand upon, recent observations of non-classical nucleation pathways in several systems.

Isochoric supercooling cryomicroscopy

We introduce an isochoric (constant-volume) supercooling cryomicroscope (ISCM), enabling the ice-free study of biological systems and biochemical reactions at subzero temperatures at atmospheric pressure absent ice. This technology draws from thermodynamic findings on the behavior of water in isochoric systems at subfreezing temperatures. A description of the design of the ISCM and a demonstration of the stability of the supercooled solution in the ISCM is followed by an illustration of the possible use of the ISCM in the preservation of biological matter research. A comparison was made between the survival of HeLa cells in the University of Wisconsin (UW) solution in the ISCM at +4 °C under conventional atmospheric conditions and at −5 °C under isochoric supercooled conditions. Continuous real-time monitoring at cryopreservation temperature via fluorescence microscopy showed that after three days of isochoric supercooling storage, the percentage of compromised cells remained similar to fresh controls, while storage at +4 °C yielded approximately three times the mortality rate of cells preserved at −5 °C.