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At least 19 records

Emergent facilitation and glassy dynamics in supercooled liquids

In supercooled liquids, dynamical facilitation refers to a phenomenon where microscopic motion begets further motion nearby, resulting in spatially heterogeneous dynamics. This is central to the glassy relaxation dynamics of such liquids, which show super-Arrhenius growth of relaxation timescales with decreasing temperature. Despite the importance of dynamical facilitation, there is no theoretical understanding of how facilitation emerges and impacts relaxation dynamics. Here, we present a theory that explains the microscopic origins of dynamical facilitation. We show that dynamics proceeds by localized bond-exchange events, also known as excitations, resulting in the accumulation of elastic stresses with which new excitations can interact. At low temperatures, these elastic interactions dominate and facilitate the creation of new excitations near prior excitations. Using the theory of linear elasticity and Markov processes, we simulate a model, which reproduces multiple aspects of glassy dynamics observed in experiments and molecular simulations, including the stretched exponential decay of relaxation functions, the super-Arrhenius behavior of relaxation timescales as well as their two-dimensional finite-size effects. The model also predicts the subdiffusive behavior of the mean squared displacement (MSD) on short, intermediate timescales. Furthermore, we derive the phonon contributions to diffusion and relaxation, which when combined with the excitation contributions produce the two-step relaxation processes, and the ballistic–subdiffusive–diffusive crossover MSD behaviors commonly found in supercooled liquids.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Structural changes across thermodynamic maxima in supercooled liquid tellurium: a water-like scenario

Liquid polymorphism is an intriguing phenomenon which has been found in a few single-component systems, the most famous being water. By supercooling liquid Te to more than 130 K below its melting point and performing simultaneous small-angle and wide-angle X-ray scattering measurements, we observe clear maxima in its thermodynamic response functions around 615 K, suggesting the possible existence of liquid polymorphism. A close look at the underlying structural evolution shows the development of intermediate-range order upon cooling, most strongly around the thermodynamic maxima, which we attribute to bond-orientational ordering. The striking similarities between our results and those of water, despite the lack of hydrogen-bonding and tetrahedrality in tellurium, indicate that water-like anomalies may be a general phenomenon among liquid systems with competing bond- and density-ordering.

36 MATERIALS SCIENCE↗

Reversible structural transformations in supercooled liquid water from 135 to 245 K

Water has many anomalous properties compared to “simple” liquids, and these anomalies are typically enhanced in supercooled water.1-3 While numerous models have been proposed, including the liquid-liquid critical point,4,5 the singularity-free scenario,6 and the stability limit conjecture,1 a molecular-level understanding remains elusive. The main difficulty in determining which, if any, of these models is correct is the limited amount of data in the relevant temperature and pressure ranges. For water at ambient pressures, which is the focus of this work, data is largely missing from 160 – 232 K (“No Man’s Land”) due to rapid crystallization.2,3 Whether rapid crystallization is just an experimental obstacle, or a fundamental problem signaling the inability of water to thermally equilibrate prior to crystallization is also a major unanswered question.5,7 Here, we investigate the structural transformations of transiently-heated, supercooled water with nanosecond time resolution using infrared vibrational spectroscopy. The experiments demonstrate three key results. First, water’s structure relaxes from its initial configuration to a “steady-state” configuration prior to the onset of crystallization over a wide temperature range. Second, water’s steady-state structure can be reproduced by a linear combination of two, temperature-independent structures that correspond to a “high-temperature liquid” and a “low-temperature liquid.” Third, the observed structural changes are reversible over the full temperature range. Taken together, these results show that supercooled water can equilibrate prior to crystallization for temperatures from the homogeneous nucleation temperature, TH ~232 K,3 down to the glass transition temperature (Tg ~ 136 K). Second, the results provide support for the hypothesis that supercooled water can be described as a mixture of two, structurally-distinct, interconvertible liquids from 135 K to 245 K.5,8-18

Kringle, Loni M.↗

Polarized View of Supercooled Liquid Water Clouds

Supercooled liquid water (SLW) clouds, where liquid droplets exist at temperatures below 0 C present a well known aviation hazard through aircraft icing, in which SLW accretes on the airframe. SLW clouds are common over the Southern Ocean, and climate-induced changes in their occurrence is thought to constitute a strong cloud feedback on global climate. The two recent NASA field campaigns POlarimeter Definition EXperiment (PODEX, based in Palmdale, California, January-February 2013) and Studies of Emissions and Atmospheric Composition, Clouds and Climate Coupling by Regional Surveys (SEAC4RS, based in Houston, Texas in August- September 2013) provided a unique opportunity to observe SLW clouds from the high-altitude airborne platform of NASA's ER-2 aircraft. We present an analysis of measurements made by the Research Scanning Polarimeter (RSP) during these experiments accompanied by correlative retrievals from other sensors. The RSP measures both polarized and total reflectance in 9 spectral channels with wavelengths ranging from 410 to 2250 nm. It is a scanning sensor taking samples at 0.8deg intervals within 60deg from nadir in both forward and backward directions. This unique angular resolution allows for characterization of liquid water droplet size using the rainbow structure observed in the polarized reflectances in the scattering angle range between 135deg and 165deg. Simple parametric fitting algorithms applied to the polarized reflectance provide retrievals of the droplet effective radius and variance assuming a prescribed size distribution shape (gamma distribution). In addition to this, we use a non-parametric method, Rainbow Fourier Transform (RFT),which allows retrieval of the droplet size distribution without assuming a size distribution shape. We present an overview of the RSP campaign datasets available from the NASA GISS website, as well as two detailed examples of the retrievals. In these case studies we focus on cloud fields with spatial features varying between glaciated and liquid phases at altitudes as high as 10 km, which correspond to temperatures close to the homogeneous freezing temperature of pure water drops (about -35 C or colder). The multimodal droplet size distributions retrieved from RSP data in these cases are consistent with the multi-layer cloud structure observed by correlative Cloud Physics Lidar (CPL) measurements.

Clouds↗

Origin of short- and medium-range order in supercooled liquid Ge 3 Sb 2 Te 6 from ab initio molecular dynamics simulations

Phase-change materials such as Ge–Sb–Te compounds have attracted much attention due to their potential value in electrical data storage. In contrast to the amorphous and crystalline phases, supercooled liquids are far from being deeply understood despite their inevitable role in both amorphization and crystallization processes. To this end, we have studied the dynamics properties and structural characteristics of liquid and supercooled liquid Ge 3 Sb 2 Te 6 during the fast cooling process. As the temperature decreases, chemical bonds become more homogeneous, but coordination numbers of Ge, Sb and Te atoms change very little. Meanwhile, the structural order of short-range configuration is obviously enhanced. Further studies suggest that Ge-centered, Sb-centered and Te-centered configurations change to the more ordered defective octahedrons mainly by adjusting the bond-angle relationship and bond length, rather than just by changing the coordination environment. It is the more ordered octahedrons that promote the formation of medium-range order. Our findings provide a deep insight into the origin of local structural order in supercooled liquid Ge 3 Sb 2 Te 6 , which is of great importance for the comprehensive understanding of amorphization and crystallization processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Partition between supercooled liquid droplets and ice crystals in mixed-phase clouds based on airborne in situ observations

Abstract. 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.

54 ENVIRONMENTAL SCIENCES↗

Unravel unusual hardening behavior of a Pd–Ni–P metallic glass in its supercooled liquid region

Monolithic metallic glasses often exhibit work softening induced by high atom mobility in the supercooled liquid region in tension. In this work, we report an unusual viscous flow of the Pd 42.5 Ni 42.5 P 15 metallic glass in its supercooled liquid region, which is characterized by a remarkable hardening behavior with decent plasticity during tension. To unravel the causes of this unusual hardening, we conducted structural and thermodynamic analyses by employing several experiments, including dynamic mechanical analysis, differential scanning calorimetry, high-resolution transmission electron microscopy, and in situ heating synchrotron high-energy x-ray diffraction. It was found that the unusual hardening behavior was attributed to structural ordering during deformation, rather than nanocrystallization or structural relaxation observed, sometimes, in metallic glasses deformed in supercooled liquid region. We also incorporated an additional work hardening region in the modified deformation map for metallic glasses.

36 MATERIALS SCIENCE↗

Icing Physics Studies Using the 3D SIDRM Test Article: Aerodynamic and Supercooled Liquid Icing Analysis

In-flight icing is an important safety issue and is a factor that affects aircraft design and performance. Newer regulations are driving a need for improvements in airframe and engine icing simulation capability. Experimental data is required for development of icing physics models and simulation validation. To that end, this paper presents the analysis of the supercooled liquid icing data subset from tests conducted in 2022 at the NASA Icing Research Tunnel that studied both supercooled water and ice-crystal icing. The test article that was utilized replicated 3D geometrical features of an inter-compressor duct and strut region of a turbofan engine. The surfaces of the Simulated Inter-compressor Duct Research Model (SIDRM) can be heated to simulate the warm surfaces of the turbofan inter-compressor duct. The test article is instrumented with pressure taps, heaters, heat flux gauges, and thermocouples, while a 3D laser scanner, cameras, and a scale to measure ice mass were utilized to characterize the icing behavior. The aim of these tests was to generate ice accretions on the SIDRM test article under well-characterized supercooled liquid icing and ice crystal icing conditions. This paper discusses measurements related to aerodynamic testing and supercooled liquid icing tests that were conducted. Aerodynamic measurements were analyzed and compared to computational simulations and were found to be in good agreement for the range of airspeeds (50 to 230 knots) and angles of attack (0 to 4°) tested. Various parametric sweeps were conducted during the supercooled liquid icing portion of the test entry (cloud median volumetric diameter ranged from 15 to 90 µm, total air temperature from -3 to -17 °C, angle of attack from 0 to 4°, and accretion time from 5 to 20 min). These sweeps were performed to measure that parameter’s impact on ice accretion size, location (icing extent), characteristics (such as glaze/rime ice and shedding behavior), and test article surface temperature. Analysis of the test data showed that clouds composed of larger drops, colder air temperatures, smaller angles of attack, and longer spray times were the primary parameters that resulted in accretions with greater ice mass. Test article angle of attack and cloud droplet size influenced the location of ice accretion as these two parameters directly impact collection efficiency. With respect to icing characteristics, total air temperature dictated icing type, and smaller cloud drop size along with warmer air temperatures resulted in greater amounts of ice shedding. Surface temperature increased during ice accretion from the release of latent (fusion) heat, where total air temperature and cloud drop size impacted the amount of surface temperature change. The icing measurements collected during the SIDRM tests will be used to develop and validate 3D computational engine icing tools, such as GlennICE, that predictively assesses the onset and growth of ice. One of the goals of the sponsoring NASA project is to develop simulation models and tools that can assist in the design and certification of engines for flight in icing conditions in a cost effective way.

supercooled liquid icing↗

X-ray diffraction of metastable structures from supercooled liquid hydrogen

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.

36 MATERIALS SCIENCE↗

Supercooled Liquid Water Detection Capabilities from Ka-Band Doppler Profiling Radars: Moment-Based Algorithm Formulation and Assessment

The occurrence of supercooled liquid water in mixed-phase cloud (MPC) affects their cloud microphysical and radiative properties. The prevalence of MPCs in the mid- and high latitudes translates these effects to significant contributions to Earth’s radiative balance and hydrological cycle. The current study develops and assesses a radar-only, moment-based phase partition technique for the demarcation of supercooled liquid water volumes in arctic, MPC conditions. The study utilizes observations from the Ka band profiling radar, the collocated high spectral resolution lidar, and ambient temperature profiles from radio sounding deployments following a statistical analysis of 5.5 years of data (January 2014–May 2019) from the Atmospheric Radiation Measurement observatory at the North Slope of Alaska. The ice/liquid phase partition occurs via a per-pixel, neighborhood-dependent algorithm based on the premise that the partitioning can be deduced by examining the mean values of locally sampled probability distributions of radar-based observables and then compare those against the means of climatologically derived, per-phase probability distributions. Analyzed radar observables include linear depolarization ratio (LDR), spectral width, and vertical gradients of reflectivity factor and radial velocity corrected for vertical air motion. Results highlight that the optimal supercooled liquid water detection skill levels are realized for the radar variable combination of spectral width and reflectivity vertical gradient, suggesting that radar-based polarimetry, in the absence of full LDR spectra, is not as critical as Doppler capabilities. The cloud phase masking technique is proven particularly reliable when applied to cloud tops with an Equitable Threat Score (ETS) of 65%; the detection of embedded supercooled layers remains much more uncertain (ETS = 27%).

54 ENVIRONMENTAL SCIENCES↗

Icing Physics Studies Using the 3D SIDRM Test Article: Aerodynamic and Supercooled Liquid Icing Analysis

In-flight icing is an important safety issue and is a factor that affects aircraft design and performance. Newer regulations are driving a need for improvements in airframe and engine icing simulation capability. Experimental data is required for development of icing physics models and simulation validation. To that end, this paper discusses analyzed data from icing tests conducted with a 3D test article in 2022 at the NASA Icing Research Tunnel. The test article, whose geometry is representative of an inter-compressor duct and strut region of a turbofan engine, has been designed and constructed to study the physics of supercooled water icing and ice crystal icing. The surfaces of the Simulated Inter-compressor Duct Research Model (SIDRM) can be heated to simulate the warm surfaces of the turbofan inter-compressor duct. The test article is instrumented with pressure taps, heaters, heat flux gauges, and thermocouples, while a 3D laser scanner, cameras, and a scale to measure ice mass were utilized to characterize the icing behavior. The aim of these tests was to generate ice accretions on the SIDRM test article under well-characterized supercooled liquid icing and ice crystal icing conditions. This paper discusses measurements related to aerodynamic tests and supercooled liquid icing tests that were conducted. Aerodynamic measurements were analyzed and compared to computational simulations and were found to be in good agreement for the range of airspeeds (50 to 230 knots) and angles of attack (0 to 4°) tested. Various parametric sweeps were conducted during the supercooled liquid icing portion of the test entry (cloud median volumetric diameter ranged from 15 to 90 µm, total air temperature from -3 to -17 °C, angle of attack from 0 to 4°, and accretion time from 5 to 20 min). These sweeps were performed to measure that parameter’s impact on ice accretion size, location, characteristics (such as glaze/rime ice and shedding behavior), and test article surface temperature. Analysis of the test data showed that clouds composed of larger drops, colder air temperatures, smaller angles of attack, and longer spray times were the primary parameters that resulted in accretions with greater ice mass. Test article angle of attack and cloud droplet size influenced the location of ice accretion as these two parameters directly impact collection efficiency. With respect to icing characteristics, total air temperature dictated icing type, and smaller cloud drop size along with warmer air temperatures resulted in greater amounts of ice shedding. Surface temperature increased during ice accretion from the release of latent (fusion) heat, where total air temperature and cloud drop size impacted the amount of surface temperature change. The icing measurements collected during the SIDRM tests will be used to develop and validate 3D computational engine icing tools, such as GlennICE, that predictively assesses the onset and growth of ice. One of the goals of the sponsoring NASA project is to develop simulation models and tools that can assist in the design and certification of engines for flight in icing conditions in a cost‑effective way.

supercooled liquid icing↗

Profiling Supercooled Liquid Water Clouds with Multi-Frequency Radar

An optimal estimation scheme is employed to demonstrate the utility of using multi-band radar observations for estimating supercooled liquid profiles. Qualitative comparisons with microphysical probe images show that the retrievals are capable of producing supercooled liquid consistent with in situ data. Finally, a path forward for quantifying performance and extending the study to a more robust measurement suite is given.

supercooled liquid↗

Glasses denser than the supercooled liquid

When aged below the glass transition temperature, T g , the density of a glass cannot exceed that of the metastable supercooled liquid (SCL) state, unless crystals are nucleated. The only exception is when another polyamorphic SCL state exists, with a density higher than that of the ordinary SCL. Experimentally, such polyamorphic states and their corresponding liquid–liquid phase transitions have only been observed in network-forming systems or those with polymorphic crystalline states. In otherwise simple liquids, such phase transitions have not been observed, either in aged or vapor-deposited stable glasses, even near the Kauzmann temperature. Here, we report that the density of thin vapor-deposited films of N,N'-bis(3-methylphenyl)-N,N'-diphenylbenzidine (TPD) can exceed their corresponding SCL density by as much as 3.5% and can even exceed the crystal density under certain deposition conditions. We identify a previously unidentified high-density supercooled liquid (HD-SCL) phase with a liquid–liquid phase transition temperature (T LL ) ~35 K below the nominal glass transition temperature of the ordinary SCL. Additionally, the HD-SCL state is observed in glasses deposited in the thickness range of 25 to 55 nm, where thin films of the ordinary SCL have exceptionally enhanced surface mobility with large mobility gradients. The enhanced mobility enables vapor-deposited thin films to overcome kinetic barriers for relaxation and access the HD-SCL state. The HD-SCL state is only thermodynamically favored in thin films and transforms rapidly to the ordinary SCL when the vapor deposition is continued to form films with thicknesses more than 60 nm.

36 MATERIALS SCIENCE↗

In-situ High-energy X-ray Diffraction Study of the Local Structure of Supercooled Liquid Si

While changes in the coordination number for liquid silicon upon supercooling, signaling an underlying liquid-liquid phase transition, have been predicted, x-ray and neutron measurements have produced conflicting reports. In particular some studies have found an increase in the first shell coordination as temperature decreases in the supercooled regime, while others have reported increases in the coordination number with decreasing temperature. Employing the technique of electrostatic levitation coupled with high energy x-ray diffraction (125 keV), and rapid data acquisition (100ms collection times) using an area detector, we have obtained high quality structural data more deeply into the supercooled regime than has been possible before. No change in coordination number is observed in this temperature region, calling into question previous experimental claims of structural evidence for the existence of a liquid-liquid phase transition.

Lee, G. W.↗

Automated characterization of spatial and dynamical heterogeneity in supercooled liquids via implementation of machine learning

Abstract A computational approach by an implementation of the principle component analysis (PCA) with K -means and Gaussian mixture (GM) clustering methods from machine learning algorithms to identify structural and dynamical heterogeneities of supercooled liquids is developed. In this method, a collection of the average weighted coordination numbers ( W C N s ‾ ) of particles calculated from particles’ positions are used as an order parameter to build a low-dimensional representation of feature (structural) space for K -means clustering to sort the particles in the system into few meso-states using PCA. Nano-domains or aggregated clusters are also formed in configurational (real) space from a direct mapping using associated meso-states’ particle identities with some misclassified interfacial particles. These classification uncertainties can be improved by a co-learning strategy which utilizes the probabilistic GM clustering and the information transfer between the structural space and configurational space iteratively until convergence. A final classification of meso-states in structural space and domains in configurational space are stable over long times and measured to have dynamical heterogeneities. Armed with such a classification protocol, various studies over the thermodynamic and dynamical properties of these domains indicate that the observed heterogeneity is the result of liquid–liquid phase separation after quenching to a supercooled state.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Characterization of supercooled liquid water in cirrus clouds from FIRE ETO lidar observations

The various modes of occurrence of supercooled liquid water in cirrus clouds are discussed using the data from the FIRE extended time observations (ETO). Results from lidar observations show that cirrus cloud scenes viewed from satellites may contain mixtures of 'high' and 'middle' cloud varieties, which affect the assessment of the derived cirrus cloud properties.

Sassen, Kenneth↗

Ice-Crystal Fallstreaks from Supercooled Liquid Water Parent Clouds

On 31 December 2001, ice-crystal fallstreaks (e.g., cirrus uncinus, or colloquially "Mare's Tails") from supercooled liquid water parent clouds were observed by ground-based lidars pointed vertically from the Atmospheric Radiation Measurement Southern Great Plains (SGP) facility near Lamont, Oklahoma. The incidence of liquid phase cloud with apparent ice-phase precipitation is investigated. Scenarios for mixed-phase particle nucleation, and fallstreak formation and sustenance are discussed. The observations are unique in the context of the historical reverence given to the commonly observed c h s uncinus fallstreak (wholly ice) versus this seemingly contradictory coincidence of liquid water begetting ice-crystal streaks.

Campbell, James R.↗

Total Temperature Measurements Using a Rearward Facing Probe in Supercooled Liquid Droplet and Ice Crystal Clouds

Engine Icing Performance loss: rollback, surge, flameout, and even internal engine damagePartial melting and refreeze of ice inside engine core (Mason et al., 2006). Ingestion of ice crystals and aggregates, mixed-phase droplets, or supercooled liquid dropletsNeed to better understand the conditions and properties that lead to engine icing.Simulation and analysis (physical and computational, and modeling)Test facilities (PSL, NRC, ...). Thermal and computational models and analysisProbesMultiple probes (aerothermal probes and ice cloud characterization probes and techniques). Total temperatureTraditional total temperature probes (vented forward facing)Heated total temperature probes (Goodyear). Rearward facing (developmental). Total temperature relevance. Thermal interaction between the icing cloud and air flow impinging particles contribute to kinetic heating effect (Gent et al., 2000). Measurement considerations Temperature sensor accuracy. Incomplete recovery of total temperature. Thermal surfaces (sources and sinks). Flow effects (viscous losses). Debris contamination, including icing and ice ingestion.

Agui, Juan H.↗