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At least 127 records · Page 7

Crystal nucleation rates in one-component Yukawa systems

Nucleation in the supercooled Yukawa system is relevant for addressing current challenges in understanding a range of crystallizing systems including white dwarf (WD) stars. We use both brute force and seeded molecular dynamics simulations to study homogeneous nucleation of crystals from supercooled Yukawa liquids. With our improved approach to seeded simulations, we obtain quantitative predictions of the crystal nucleation rate and cluster size distributions as a function of temperature and screening length. These quantitative results show trends towards fast nucleation with short-ranged potentials. They also indicate that for temperatures T > 0.9⁢T m , where T m is the melt temperature, classical homogeneous nucleation is too slow to initiate crystallization but transient clusters of ~100 particles should be common. As a result, we apply these general results to a typical WD model and obtain a delay of ~0.6 Gyr in the onset of crystallization that may be observable.

36 MATERIALS SCIENCE↗

An Improved Convection Parameterization with Detailed Aerosol–Cloud Microphysics for a Global Model

Abstract A new microphysical treatment that includes aerosol–cloud interactions and secondary ice production (SIP) mechanisms is implemented in the convection scheme of the Community Atmosphere Model, version 6 (CAM6). The approach is to embed a 1D Lagrangian parcel model in the bulk convective plume of the existing deep convection parameterization. Aerosol activation, growth processes including collision/coalescence, and three processes of SIP mechanisms, two of which are normally overlooked in atmospheric models, are represented in this embedded parcel model. These microphysical processes are treated with a hybrid bin/bulk scheme and a high spatial and temporal resolution for the integration of the embedded parcel in 1D, allowing vertical velocity to determine the microphysical evolution following the in-cloud motion during ascent. Simulations of an observed case (Midlatitude Continental Convective Clouds Experiment) of a mesoscale convective system in Oklahoma, United States, with a single-column model (SCAM) version of CAM, are compared with aircraft in situ and ground-based observations of microphysical properties from the convection and precipitation. Results from the validation show the new microphysical scheme has a good representation of the ice initiation in the bulk convective plume, including the known and empirically quantified pathways of primary and secondary initiation, with benefits for the accuracy of properties of its supercooled cloud liquid. The sensitivity simulations and use of tagging tracers for the validated simulation confirm that the newly included SIP mechanisms are of paramount importance for convective microphysics and can be successfully treated in the global model.

54 ENVIRONMENTAL SCIENCES↗

Tethered Balloon System (TBS) Instrument Handbook

The Tethered Balloon System (TBS) is an unmanned aerial system composed of a helium-filled balloon, tether, winch, and sensors. Individual components of the system may change with each flight based on the desired measurements, atmospheric conditions, and flight strategy. The TBS operates within the U.S. Department of Energy (DOE)’s R-2204 Restricted Airspace, which encompasses a two-nautical-mile radius centered on Oliktok Point, Alaska that is segmented by altitude into R-2204 Low (0-1,499’ MSL or 0-457 m MSL) and R-2204 High (1,500-6,999’ MSL or 457-2133 m MSL). The TBS may operate outside of R-2204 if allowed to do so under a Certificate of Authorization from the Federal Aviation Administration.

42 ENGINEERING↗

Energy Frontier Research Centers: Center for the Computational Design of Functional Layered Materials (CCDM) August 1, 2014 - July 31, 2018; Center for Complex Materials from First Principles (CCM) August 1, 2018 - July 31, 2021 (Final Report)

The mission of the DOE Energy Frontier Research Centers CCDM (2014-2018) and CCM (2018-2021) was to theoretically develop, computationally apply, and experimentally validate electronic structure methods for all materials, with a focus on the complex materials, especially layered and two-dimensional materials, strongly-correlated materials, and liquid water. This was achieved by over 200 published journal articles authored by about 17 senior investigators from physics and chemistry and from theory, computation, and experiment, plus their collaborators. In particular, the Centers confirmed the predictive power of the SCAN (strongly constrained and appropriately normed) density functional, which was constructed to satisfy 17 known exact constraints and several appropriate norms. Without being fitted to real bonded systems, and at a modest computational cost, SCAN correctly predicted covalent, ionic, metallic, hydrogen, and van der Waals bonds in many challenging materials. SCAN gave an improved description of defects in semiconductors, surface properties of metals, seven phases of ice, liquid water, liquid and supercooled silicon, subtle structural distortions in ferroelectrics, formation energies and structural predictions for solids, and critical pressures for structural phase transitions. Perhaps most remarkably, SCAN correctly described some strongly-correlated materials that were previously believed to be beyond the reach of density-functional approximations. SCAN is the only density functional that correctly predicts the band gap closing under chemical doping of the cuprate high-temperature superconducting materials. SCAN also predicts a landscape of competing stripe and magnetic phases in the cuprates. For some materials with some codes, SCAN has convergence problems that are greatly reduced by the CCM-developed r 2 SCAN, without loss of accuracy or rigor. SCAN and r 2 SCAN still make some self-interaction error, which is greatly reduced by the CCDM/ CCM-developed local orbital scaling correction (LOSC). These Centers further proved that the fundamental energy gaps of a solid from an orbital energy difference and from total energy differences are the same for a large class of generalized Kohn-Sham (GKS) functionals, including SCAN and standard hybrid functionals, and that symmetry breaking arises when a dynamic density fluctuation drops to zero frequency. The Centers identified new mechanisms for catalysis in layered materials with ions intercalated between the layers, investigated charge density waves both in model systems and in real layered materials, studied changes of band gap with the number of layers, and explored topological ultrathin films, bent nanoribbons, and defects.

08 HYDROGEN↗

X-ray and neutron scattering measurements of ordering in a Cu 46 Zr 54 liquid

The structural evolution of the equilibrium and supercooled Cu 46 Zr 54 liquids was investigated with a combination of elastic neutron scattering (with isotopic substitution) and synchrotron x-ray scattering studies. The partial pair correlation functions were determined over a wide temperature range (~270 °C). These show that the Cu–Cu and Zr–Zr ordering increases as the temperature decreases, while the Cu–Zr ordering decreases. We note this surprising result is in contradiction with the results from molecular dynamics studies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Neural Network Water Model Based on the MB-Pol Many-Body Potential

The MB-pol many-body potential accurately predicts many properties of water, including cluster, liquid phase, and vapor–liquid equilibrium properties, but its high computational cost can make applying it in large-scale simulations quite challenging. Here, in order to address this limitation, we developed a “deep potential” neural network (DPMD) model based on the MB-pol potential for water. We find that a DPMD model trained on mostly liquid configurations yields a good description of the bulk liquid phase but severely underpredicts vapor–liquid coexistence densities. By contrast, adding cluster configurations to the neural network training set leads to a good agreement for the vapor coexistence densities. Liquid phase densities under supercooled conditions are also represented well, even though they were not included in the training set. These results confirm that neural network models can combine accuracy and transferability if sufficient attention is given to the construction of a representative training set for the target system.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Self-consistent hopping theory of activated relaxation and diffusion of dilute penetrants in dense crosslinked polymer networks

We generalize a microscopic statistical mechanical theory of the activated dynamics of dilute spherical penetrants in glass-forming liquids to study the influence of crosslinking in polymer networks on the penetrant relaxation time and diffusivity over a wide range of temperature and crosslink fraction (f n ). Our calculations are relevant to recent experimental studies of a nm-sized molecule diffusing in poly-(n-butyl methacrylate) networks. The theory predicts the penetrant relaxation time increases exponentially with the glass transition temperature, T g (f n ), which grows roughly linearly with the square root of fn due to the coupling of local hopping to longer-range collective elasticity. Moreover, T g is also found to be proportional to a geometric confinement parameter defined as the ratio of the penetrant diameter to the mean network mesh size. The decoupling ratio of the penetrant and Kuhn segment alpha times displays a complex non-monotonic dependence on f n and temperature that is well collapsed based on the variable T g (f n )/T. A model for the penetrant diffusion constant that combines activated relaxation and entropic mesh confinement is proposed, which results in a significantly stronger suppression of mass transport with degree of effective supercooling than predicted for the penetrant alpha time. Furthermore, this behavior corresponds to a new network-based type of “decoupling” of diffusion and relaxation. In contrast to the diffusion of larger nanoparticles in high temperature rubbery networks, our analysis in the supercooled regime suggests that for the penetrants studied the mesh confinement effects are of secondary importance relative to the consequences of crosslink-induced slowing down of activated hopping of glassy physics origin.

Chemistry↗

Phase separation in mullite-composition glass

Aluminosilicates (AS) are ubiquitous in ceramics, geology, and planetary science, and their glassy forms underpin vital technologies used in displays, waveguides, and lasers. In spite of this, the nonequilibrium behavior of the prototypical AS compound, mullite (40SiO 2 -60Al 2 O 3 , or AS60), is not well understood. By deeply supercooling mullite-composition liquid via aerodynamic levitation, we observe metastable liquid–liquid unmixing that yields a transparent two-phase glass, comprising a nanoscale mixture of AS7 and AS62. Extrapolations from X-ray scattering measurements show the AS7 phase is similar to vitreous SiO 2 with a few Al species substituted for Si. The AS62 phase is built from a highly polymerized network of 4-, 5-, and 6-coordinated AlO x polyhedra. Polymerization of the AS62 network and the composite morphology provide essential mechanisms for toughening the glass.

36 MATERIALS SCIENCE↗

Measuring the density, viscosity, and surface tension of molten titanates using electrostatic levitation in microgravity

Rare earth and barium titanates are useful as ferroelectric, dielectric, and optical materials. Measurements of their thermophysical properties in the liquid state can help guide melt processing technologies for their manufacture and advance understanding of fragile liquids' behavior and glass formation. Here, we report the density, thermal expansion, viscosity, and surface tension of molten BaTi 2 O 5 , BaTi 4 O 9 , and 83TiO 2 -17RE 2 O 3 (RE = La or Nd). Measurements were made using electrostatic levitation and droplet oscillation techniques in microgravity, which provide access to quiescent liquid droplets and deep supercooling of 510–815 K below the equilibrium melting points. Densities were measured over 900–2400 K. Viscosities were similar for all four compositions, increasing from ~10 mPa s near 2100 K to ~30 mPa s near 1750 K. Surface tensions were 450–490 dyn cm -1 for the rare earth titanates and 383–395 dyn cm -1 for the barium titanates; surface tensions of all compositions had small or negligible temperature dependence over 1700–2200 K. In conclusion, for solids recovered after melt quenching, x-ray microtomography revealed the fracture mechanics in crystalline products and minimal internal porosity in glass products, likely arising from entrapped gas bubbles. Internal microstructures were generally similar for products processed either in microgravity or in a terrestrial aerodynamic levitator.

42 ENGINEERING↗

Atomic-level mechanisms of short-circuit diffusion in materials

This paper reviews the recent progress in understanding the atomic mechanisms of short-circuit diffusion along materials interfaces, such as grain and interphase boundaries, as well as lattice and interfacial dislocations/disconnections. Recent atomistic computer simulations have shown that short-circuit diffusion is dominated by collective atomic rearrangements in the form of strings and rings of mobile atoms. The process is dynamically heterogeneous in space and time and has many features in common with atomic dynamics in supercooled glass-forming liquids. We discuss examples of grain boundary, interphase boundary, and dislocation diffusion in metals and alloys, including the solute effect on the diffusion rates and mechanisms. Interphase boundaries are exemplified by Al–Si interfaces with diverse orientation relationships and atomic structures. The hierarchy of short-circuit diffusion paths in materials is reviewed by comparing the rates of grain boundary, interphase boundary, and dislocation diffusion. Future directions in the field of short-circuit diffusion in defect core regions are discussed.

36 MATERIALS SCIENCE↗

Radically Engineered Modular Air Separation System with Tailored Oxygen Sorbents

The commercial energy sector relies heavily on fossil fuel conversion, and in the process releases a significant amount of CO 2 . A promising technology to utilize fossil fuels with relatively affordable CO 2 capture is gasification. However, it requires a pure oxygen stream. The current state of the art method to produce oxygen is cryogenic air separation, which supercools air to a liquid, and then using distillation columns to separate the components. While this method has been thoroughly studied, it only has a 25% efficiency from a second law standpoint and therefore requires a significant amount of energy (and associated emissions) for oxygen production. This, then, lowers the incentive for carbon capture within a plant, so alternative methods need to be investigated. One potential method, chemical looping air separation (CLAS), is a promising method to replace state of the art oxygen generation technologies. CLAS utilizes a cyclic redox scheme with an oxygen sorbent to create pure oxygen streams. This approach typically utilizes a dual reactor scheme where the oxygen deficient sorbent enters the first reactor and is subjected to high oxygen partial pressures to re-oxidize the sorbent. Then the sorbent is sent to the reducing reactor, where it is subjected to low oxygen partial pressure (steam or vacuum) to releases oxygen. The overarching objective of this project was to discover the principles for rational design and optimization of oxygen sorbents and process design to ensure the process is a viable replacement for cryogenic air separation, especially in the context of modular gasification systems. This was done through development, characterization, testing, and analyses of (a) high temperature mixed composite oxides; (b) low temperature doped perovskite oxides (A1 x A2 1-x B1 y B2 1-y O 3 ); (c) scale up synthesis and testing of the optimized sorbent particles; (d) process design and analyses of the CLAS system in the context of modular gasification applications.

01 COAL, LIGNITE, AND PEAT↗

Thermodynamics of Liquid Uranium from Atomistic and Ab Initio Modeling

We present thermodynamic properties for liquid uranium obtained from classical molecular dynamics (MD) simulations and the first-principles theory. The coexisting phases method incorporated within MD modeling defines the melting temperature of uranium in good agreement with the experiment. The calculated melting enthalpy is in agreement with the experimental range. Classical MD simulations show that ionic contribution to the total specific heat of uranium does not depend on temperature. The density of states at the Fermi level, which is a crucial parameter in the determination of the electronic contribution to the total specific heat of liquid uranium, is calculated by ab initio all electron density functional theory (DFT) formalism applied to the atomic configurations generated by classical MD. The calculated specific heat of liquid uranium is compared with the previously calculated specific heat of solid γ-uranium at high temperatures. The liquid uranium cannot be supercooled below T sc ≈ 800 K or approximately about 645 K below the calculated melting point, although, the self-diffusion coefficient approaches zero at T D ≈ 700 K. Uranium metal can be supercooled about 1.5 times more than it can be overheated. The features of the temperature hysteresis are discussed.

36 MATERIALS SCIENCE↗

Containerless Techniques for in-situ X-Ray Measurements on Materials in Extreme Conditions

This article reviews containerless methods in the context of measuring materials in-situ using x-ray techniques. Non-contact processing enables high chemical purity to be achieved even at temperatures above 2000 °C. The absence of extrinsic heterogenous nucleation allows supercooling and supersaturation of liquids and solutions. In many cases new types of glass can be made, particularly from fragile liquids. Current methods for containerless processing are briefly reviewed. The application of scattering, spectroscopic and emerging x-ray techniques is described. Examples including measurements on molten metal oxides, molten metallic alloys and organic molecules are presented. The work is discussed in the broader context of combining structure and property data to predict how to make new applied materials.

36 MATERIALS SCIENCE↗

Melting curves of ice polymorphs in the vicinity of the liquid–liquid critical point

The possible existence of a liquid–liquid critical point in deeply supercooled water has been a subject of debate due to the challenges associated with providing definitive experimental evidence. The pioneering work by Mishima and Stanley [Nature 392, 164–168 (1998)] sought to shed light on this problem by studying the melting curves of different ice polymorphs and their metastable continuation in the vicinity of the expected liquid–liquid transition and its associated critical point. Based on the continuous or discontinuous changes in the slope of the melting curves, Mishima [Phys. Rev. Lett. 85, 334 (2000)] suggested that the liquid–liquid critical point lies between the melting curves of ice III and ice V. Herein we explore this conjecture using molecular dynamics simulations with a machine learning model based on ab initio quantum-mechanical calculations. We study the melting curves of ices III, IV, V, VI, and XIII and find that all of them are supercritical and do not intersect the liquid–liquid transition locus. We also find a pronounced, yet continuous, change in the slope of the melting lines upon crossing of the liquid locus of maximum compressibility. Finally, we analyze the literature in light of our findings and conclude that the scenario in which the melting curves are supercritical is favored by the most recent computational and experimental evidence. Although the preponderance of evidence is consistent with the existence of a second critical point in water, the behavior of ice polymorph melting lines does not provide strong evidence in support of this viewpoint, according to our calculations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

INL_Intern_Poster_ColeBailey [Poster]

Understanding the thermophysical properties of molten salts is crucial for the advancement of nuclear fuels. This project presents the design of a custom differential thermal analyzer (DTA) that utilizes non-contact ultrasonic mixing to agitate samples and prevent supercooling. The supercooling effect occurs when a liquid is below its freezing point without solidifying. This can be observed when a liquid in a freezer instantly transitions to its solid phase upon disturbance. By avoiding this effect, accurate transition temperatures of molten salts can be gathered for future applications. Initial mixing results were promising, leading to further refinement of the waveguides using ABAQUS to maximize input energy into the fluid. Future work will focus on integrating both mixing and cooling in conjunctions to observe the avoided effect.

46 - INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AN↗

The prevalence of precipitation from polar supercooled clouds

Abstract. Supercooled clouds substantially impact polar surface energy budgets, but large-scale models often underestimate their occurrence, which motivates accurately establishing metrics of basic processes. An analysis of long-term measurements at Utqiaġvik, Alaska, and McMurdo Station, Antarctica, combines lidar-validated use of soundings to identify supercooled cloud layers and colocated ground-based profiling radar measurements to quantify cloud base precipitation. We find that more than 85 % (75 %) of sampled supercooled layers are precipitating over the Arctic (Antarctic) site, with more than 75 % (50 %) precipitating continuously to the surface. Such high frequencies can be reconciled with substantially lesser spaceborne estimates by considering differences in radar hydrometeor detection sensitivity. While ice precipitation into supercooled clouds from aloft is common, we also find that the great majority of supercooled cloud layers without ice falling into them are themselves continuously generating precipitation. Such sustained primary ice formation is consistent with continuous activation of immersion-mode ice-nucleating particles (INPs), suggesting that supercooled cloud formation is a principal gateway to ice formation at temperatures greater than ∼-38 ∘C over polar regions. The prevalence of weak precipitation fluxes is also consistent with supercooled cloud longevity and with well-observed and widely simulated case studies. An analysis of colocated microwave radiometer retrievals suggests that weak precipitation fluxes can be nonetheless consequential to moisture budgets for supercooled clouds owing to small liquid water paths. The results here also demonstrate that the observed abundance of mixed-phase clouds can vary substantially with instrument sensitivity and methodology. Finally, we suggest that these ground-based precipitation rate statistics offer valuable guidance for improving the representation of polar cloud processes in large-scale models.

54 ENVIRONMENTAL SCIENCES↗

Dynamic Heterogeneity and Kovacs’ Memory Effects in Supercooled Water

Understanding the properties of supercooled water is important for developing a comprehensive theory for liquid water and amorphous ices. Because of rapid crystallization for deeply supercooled water, experiments on it are typically carried out under conditions in which the temperature and/or pressure are rapidly changing. As a result, information on the structural relaxation kinetics of supercooled water as it approaches (metastable) equilibrium is useful for interpreting results obtained in this experimentally challenging region of phase space. Here, we used infrared spectroscopy and the fast time resolution obtained by transiently heating nanoscale water films to investigate relaxation kinetics (aging) in supercooled water. When the structural relaxation of the water films was followed using a temperature jump protocol analogous to the classic experiments of Kovacs, similar memory effects were observed. In particular, after suitable aging at one temperature, water’s structure displayed an extremum versus the number of heat pulses upon changing to a second temperature before eventually relaxing to a steady-state structure characteristic of that temperature. A random double well model based on the idea of dynamic heterogeneity in supercooled water accounts for the observations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Anomalous temperature dependence of the experimental x-ray structure factor of supercooled water

The structural changes of water upon deep supercooling were studied through wide-angle x-ray scattering at SwissFEL. The experimental setup had a momentum transfer range of 4.5 Å-1, which covered the principal doublet of the x-ray structure factor of water. The oxygen–oxygen structure factor was obtained for temperatures down to 228.5 ± 0.6 K. Similar to previous studies, the second diffraction peak increased strongly in amplitude as the structural change accelerated toward a local tetrahedral structure upon deep supercooling. We also observed an anomalous trend for the second peak position of the oxygen–oxygen structure factor (q 2 ). We found that q 2 exhibits an unprecedented positive partial derivative with respect to temperature for temperatures below 236 K. Based on Fourier inversion of our experimental data combined with reference data, we propose that the anomalous q 2 shift originates from that a repeat spacing in the tetrahedral network, associated with all peaks in the oxygen–oxygen pair-correlation function, gives rise to a less dense local ordering that resembles that of low-density amorphous ice. The findings are consistent with that liquid water consists of a pentamer-based hydrogen-bonded network with low density upon deep supercooling.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗