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At least 127 records · Page 7

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NASA NTRS1987

Thermal evolution of a differentiated Ganymede and implications for surface features

Thermodynamic models are developed for the processes which controlled the evolution of the surface Ganymede, an icy Jovian satellite assumed to have a rock-rich core surrounded by a water-ice mantle. Account is taken of a heat pulse which would have arisen from a Rayleigh-Taylor instability at a deep-seated liquid-solid water interface, rapid fracturing from global stresses imposed by warm ice diapiric upwelling, impacts by large meteorites, and resurfacing by ice flows (rather than core formation). Comparisons are made with existing models for the evolution of Callisto, and the difficulties in defining a mechanism which produced the groove terrain of Ganymede are discussed.

Kirk, R. L.↗

DOE OSTI2020

Energetic Tug-of-War between Pt and Leaky TiO 2 : Positive and Negative Effects on the Function of Molecularly-Modified p -Si(111)|TiO 2 |Pt Photocathodes

Photoelectrochemical solar energy conversion to chemical products is a promising avenue towards renewable fuels, and TiO 2 deposition on semiconductor photocathodes is a widespread surface protection strategy. However, the electronic, thermodynamic, and kinetic effects of protection layers on interfacial energetics remains poorly understood. Here, electrochemical data (photocurrent onset and flatband potentials) of p-Si(111)|TiO 2 |Pt is collected in contact with an outer-sphere redox couple. We find that onset potentials shift negatively as a function of increasing oxide thickness, but this effect is not reflected in the flatband potentials. This reveals the mechanism of these shifts is kinetic rather than thermodynamic,and suggests that hole leakage through the TiO 2 is responsible. When Pt nanoparticles are deposited onto the TiO 2 , positive shifts in both the onset and flatband potentials are observed, revealing Pt catalysts are beneficial for more than just increased catalytic rates. These results highlight the importance of understanding the effects of surface modifications on the energetics at the interface in both catalytic and simple electron transfer systems.

14 SOLAR ENERGY↗

NASA NTRS2015

Lattice Boltzmann Method for Spacecraft Propellant Slosh Simulation

A scalable computational approach to the simulation of propellant tank sloshing dynamics in microgravity is presented. In this work, we use the lattice Boltzmann equation (LBE) to approximate the behavior of two-phase, single-component isothermal flows at very low Bond numbers. Through the use of a non-ideal gas equation of state and a modified multiple relaxation time (MRT) collision operator, the proposed method can simulate thermodynamically consistent phase transitions at temperatures and density ratios consistent with typical spacecraft cryogenic propellants, for example, liquid oxygen. Determination of the tank forces and moments is based upon a novel approach that relies on the global momentum conservation of the closed fluid domain, and a parametric wall wetting model allows tuning of the free surface contact angle. Development of the interface is implicit and no interface tracking approach is required. A numerical example illustrates the method's application to prediction of bulk fluid behavior during a spacecraft ullage settling maneuver.

Orr, Jeb S.↗

DOE OSTI2021

Additive Destabilization of Porous Magnesium Borohydride Framework with Core--Shell Structure

Design of interfaces with thermodynamic and kinetic specificity is of great importance for hydrogen storage from both an applied and fundamental perspective. Here, in order to destabilize the metal hydride and protect the dehydrogenated products from oxidizing, a unique core-shell structure of porous Mg(BH4)2-based framework with a thin layer (no more than 5 nm) of MgCl2 additives on the surface, has been proposed and synthesized via a wet-chemical method. The local structure and electronic state of the present complex system are systematically investigated to understand the correlation between the distribution of additives and dehydrogenation property of Mg(BH4)2. A significant improvement is achieved for hydrogen desorption with chlorides: initial hydrogen release from MgCl2 decorated ..gamma..-phase Mg(BH4)2 particles commences at 100 °C and reaches a maximum of 9.4 wt% at 385 °C. Besides the decreased decomposition temperature, an activation barrier of about 76.4 kJ mol-1 lower than that of Mg(BH4)2 without MgCl2 is obtained. Moreover, MgCl2 decoration can also prevent the whole decomposed system (both Mg- and B- elements) from oxidizing, which is a necessary condition to reversibility.

74 ATOMIC AND MOLECULAR PHYSICS↗

NASA NTRS1995

Polarimetric signatures of sea ice. 1: Theoretical model

Physical, structral, and electromagnetic properties and interrelating processes in sea ice are used to develop a composite model for polarimetric backscattering signatures of sea ice. Physical properties of sea ice constituents such as ice, brine, air, and salt are presented in terms of their effects on electromagnetic wave interactions. Sea ice structure and geometry of scatterers are related to wave propagation, attenuation, and scattering. Temperature and salinity, which are determining factors for the thermodynamic phase distribution in sea ice, are consistently used to derive both effective permittivities and polarimetric scattering coefficients. Polarmetric signatures of sea ice depend on crystal sizes and brine volumes, which are affected by ice growth rates. Desalination by brine expulsion, drainage, or other mechanisms modifies wave penetration and scattering. Sea ice signatures are further complicated by surface conditions such as rough interfaces, hummocks, snow cover, brine skim, or slush layer. Based on the same set of geophysical parameters characterizing sea ice, a composite model is developed to calculate effective permittivities and backscattering covariance matrices at microwave frequencies to interpretation of sea ice polarimetric signatures.

Nghiem, S. V.↗

NASA NTRS1995

Polarimetric Signatures of Sea Ice: Theoretical Model - Part 1

Physical, structural, and electromagnetic properties and interrelating processes in sea ice are used to develop a composite model for polarimetric backscattering signatures of sea ice. Physical properties of sea ice constituents such as ice, brine, air, and salt are presented in terms of their effects on electromagnetic wave interactions. Sea ice structure and geometry of scatterers are related to wave propagation, attenuation, and scattering. Temperature and salinity, which are determining factors for the thermodynamic phase distribution in sea ice, are consistently used to derive both effective permittivities and polarimetric scattering coefficients. Polarimetric signatures of sea ice depend on crystal sizes and brine volumes, which are affected by ice growth rates. Desalination by brine expulsion, drainage, or other mechanisms modifies wave penetration and scattering. Sea ice signatures are further complicated by surface conditions such as rough interfaces, hummocks, snow cover, brine skim, or slush layer. Based on the same set of geophysical parameters characterizing sea ice, a composite model is developed to calculate effective permittivities and backscattering covariance matrices at microwave frequencies for interpretation of sea ice polarimetric signatures.

Nghiem, S. V.↗

DOE OSTI2025

Activation of propane on Ag–PdO(101) model surfaces

Oxidation of alkanes remains a central challenge in catalysis due to the high activation barriers of C–H bonds and the thermodynamic favorability of complete oxidation. Palladium oxide (PdO), particularly its (101) facet, is known for its high reactivity in alkane oxidation, which is attributed to its coordinatively unsaturated palladium (Pd) and O atoms. In this study, we investigate the effect of silver (Ag) incorporation on the oxidation behavior of propane over PdO(101) using temperature-programmed reaction spectroscopy (TPRS) under controlled conditions. While pristine PdO(101) exhibits complete oxidation of propane with CO₂ and H₂O desorption at high temperatures (approximately 475 K), Ag incorporation induces a new CO₂ desorption peak at significantly lower temperatures (approximately 330 K). This shift is attributed to the formation of new active sites at the Ag–PdO(101) interface. Quantitative analysis reveals that low-temperature activity correlates with Ag coverage, while overall CO₂ production decreases, suggesting a redistribution of reactivity rather than an increase in active surface area. Activation energy estimations using the Redhead method confirm that C–H bond activation becomes more facile at the interface, with a 46 kJ/mol reduction compared to pristine PdO(101). These findings demonstrate that incorporating a less reactive metal such as Ag into PdO surfaces not only modifies the reaction energetics but also enables the design of bimetallic catalysts with improved selectivity for partial oxidation reactions.

Chemistry↗

DOE OSTI2020

Affinity of small-molecule solutes to hydrophobic, hydrophilic, and chemically patterned interfaces in aqueous solution

Significance Increasing global population, urbanization, and climate change pose tremendous constraints on water availability. While membrane processes offer attractive, energy-efficient options, transformative advances in membrane technology are needed to enable reuse of poor-quality waters from diverse sources. This work brings fundamental understanding of solute–surface interactions to membrane phenomena, including selectivity and fouling. Molecular simulations reveal limitations of traditional predictive measures of solute–surface partitioning, suggesting alternative thermodynamic signatures for solute binding that highlight the contextual nature of hydrophobicity. An inverse design algorithm provides a tool to pattern membrane nanoscale chemistry to optimize solute affinity and selectivity. This work demonstrates how simulations can inform practical materials design for sustainable water treatment and, more broadly, many technologies involving water-mediated solute–surface interactions.

36 MATERIALS SCIENCE↗

DOE OSTI2023

Machine-Guided Design of Oxidation-Resistant Superconductors for Quantum Information Applications

Decoherence in superconducting qubits has long been attributed to two-level systems arising from the surfaces and interfaces present in real devices. A recent significant step in reducing decoherence was the replacement of superconducting niobium by superconducting tantalum, resulting in a tripling of transmon qubit lifetimes (T1). The identity, thickness, and quality of the native surface oxide, is thought to play a major role, as tantalum only has one oxide whereas niobium has several. Here we report the development of a thermodynamic metric to rank materials based on their potential to form a well-defined, thin, surface oxide. We first computed this metric for known binary and ternary metal alloys using data available from the Materials Project and experimentally validated the strengths and limits of this metric through the preparation and controlled oxidation of eight known metal alloys. Then we trained a convolutional neural network to predict the value of this metric from atomic composition and atomic properties. This allowed us to compute the metric for materials that are not present in the Materials Project, including a large selection of known superconductors, and, when combined with Tc, allowed us to identify new candidate superconductors for quantum information science and engineering (QISE) applications. We tested the oxidation resistance of a pair of these predictions experimentally. Our results are expected to lay the foundation for the tailored and rapid selection of improved superconductors for QISE.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2026

Programmable Phase Selection between Altermagnetic and Noncentrosymmetric Polymorphs of MnTe on InP via Molecular Beam Epitaxy

Phase selecting nearly degenerate crystalline polymorphs during epitaxial growth can be challenging yet critical to targeting physical properties for specific applications. Here, we establish how phase selectivity of altermagnetic and noncentrosymmetric polymorphs of MnTe can be programmed by subtle changes to the surface of lattice-matched InP substrates in molecular beam epitaxy growth. Bulk altermagnetic MnTe is thermodynamically stable in the hexagonal NiAs-structure and is synthesized here on the polar (111)A surface (In-terminated) of InP, while the noncentrosymmetric, cubic ZnS-structure with wide band gap (>3 eV), which epitaxially matches III–V materials, is stabilized on the (111)B surface (P-terminated). Electron microscopy, X-ray photoemission spectroscopy, and reflection high-energy electron diffraction indicate that phase selection is triggered at the interface and proceeds along the growing surface. First-principles calculations suggest that interfacial termination and strain have a significant effect on the interfacial energy; stabilizing the NiAs polymorph on the In-terminated surface and the ZnS structure on the P-terminated surface. Here, selectively grown, high-quality, phase pure films of both MnTe polymorphs will enable our understanding of the novel properties of these materials, thereby facilitating their use in new applications ranging from spintronics to microelectronic devices.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2022

Thermodynamic modeling of adsorption at the liquid-solid interface

Adsorptive separation techniques are significantly energy efficient in comparison to conventional thermal separation techniques such as distillation. Despite extensive research and development activities undertaken for mixed-gas adsorption, the use of adsorption techniques for the separation of multicomponent liquid mixtures is still limited. A major barrier is the lack of accurate adsorption thermodynamic models, which form the scientific foundation of process simulation of such systems, making the translation to industrial scale challenging. In this work, we have rigorously computed the surface excess of adsorption for six binary liquid mixtures on silica gel at 303 K using the frameworks of the generalized Langmuir isotherm (gL) and the adsorbed solution theory (AST). The six binary liquid mixtures were formed by the pair-wise combinations of four components: benzene, 1,2-dichloroethane, cyclohexane, and n-heptane. We have based our calculations by considering simultaneous equilibria of three phases: saturated vapor phase, bulk liquid phase, and adsorbed phase. Further, the composition of the corresponding saturated vapor phase was estimated by the Nonrandom Two-Liquid activity coefficient model and experimental vapor-liquid equilibria data. The activity coefficients of the adsorbed phase, the central issue of multicomponent adsorption thermodynamics, were calculated using the adsorption Nonrandom Two-Liquid activity coefficient model. Devoid of simplifying assumptions, gL and AST provide rigorous thermodynamic frameworks for adsorption equilibria of multicomponent liquid mixtures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS1987

Mixing-induced fluid destratification and ullage condensation

In many applications, on-orbit storage and transfer of cryogens will require forced mixing to control tank pressure without direct venting to space. During a no-vent transfer or during operation of a thermodynamic vent system in a cryogen storage tank, pressure control is achieved by circulating cool liquid to the liquid-vapor interface to condense some of the ullage vapor. To measure the pressure and temperature response rates in mixing-induced condensation, an experiment has been developed using Freon 11 to simulate the two-phase behavior of a cryogen. A thin layer at the liquid surface is heated to raise the tank pressure, and then a jet mixer is turned on to circulate the liquid, cool the surface, and reduce the pressure. Many nozzle configurations and flow rates are used. Tank pressure and the temperature profiles in the ullage and the liquid are measured. Initial data from this ground test are shown correlated with normal-gravity and drop-tower dye-mixing data. Pressure collapse times are comparable to the dye-mixing times, whereas the times needed for complete thermal mixing are much longer than the dye-mixing times.

Meserole, Jere S.↗

DOE OSTI2022

Assessing entropy for catalytic processes at complex reactive interfaces

When chemical reactions are accelerated by a catalyst, entropy differences between reactants and their transient intermediates can be the driving force behind the promotion or inhibition of desired and parasitic chemical pathways. Understanding and controlling catalytic processes therefore requires both a fundamental and practicable understanding of entropy in addition to enthalpy. In unstructured media such as the vapor phase equilibrated with sparsely covered surfaces, entropy can be adequately accounted for by well-established approaches based on translational, rotational, and harmonic vibrational partition functions. However, these approximations become inadequate in more complex condensed phase environments, e.g., solid liquid interfaces of confined reaction spaces. In this chapter, we provide an overview of the state-of-art in the computational quantification of entropy and its known ramifications on catalysis. The fundamental roles of thermodynamics and kinetics in catalysis are covered in enough detail to appreciate and contextualize the computational methods employed to compute chemically accurate estimates of entropy. These methods are discussed in appropriate detail and range from the ubiquitous harmonic oscillator approximation where entropy unrelated to high frequency oscillations is typically underestimated, to enhanced free energy sampling with molecular dynamics where the desired accuracy must be weighed against the associated computational cost of obtaining it. The rising importance of machine learning and artificial intelligence in accelerating methodological progress in this field is touched upon, as well. Finally, applications, successes, and pitfalls of using these methods are provided to showcase past and present accomplishments while clarifying where improvements in both understanding and methodology are still needed.

Kollias, Loukas↗

DOE OSTI2021

The influence of LiH and TiH 2 on hydrogen storage in MgB 2 II. XPS study of surface and near-surface phenomena

We report that Mg(BH 4 ) 2 is a promising solid-state hydrogen storage material, releasing 14.9 wt% hydrogen upon conversion to MgB 2 . The rehydrogenation of MgB 2 is particularly challenging, requiring prolonged exposure to high pressures of hydrogen at high temperature. Here we report an XPS study probing the influence of LiH and TiH 2 on the hydrogen storage properties of MgB 2 in the surface and near-surface regions, as a complementary investigation to a preceding study of the bulk properties. Surface and near-surface properties are important considerations for nanoscale and bulk hydrogen storage materials. If there are reactions occurring at the surface that modify the chemical composition in the near-surface region, species diffusion can alter the chemical composition even deep into the bulk of the material. For LiH/MgB 2 , metastable LiH–B and LiH–Mg species are produced that are more reactive than Bulk MgB 2 . With prolonged glovebox storage, the LiH/MgB 2 material shows increased reactivity towards O and C and enriched levels of Li and B in the near-surface region. In addition, Li induces the growth of Li 2 CO 3 in the surface and near surface regions. Exposing LiH/MgB 2 to hydrogen at 700 bar and 280 °C for 24 h produces borohydride at a temperature 100 °C below the threshold for bulk MgB 2 hydrogenation. In a specifically surface process with macroscopic implications, the hydrogenation conditions also cause Li 2 CO 3 to react with boron hydroxide in the sample to form a Li-deficient glassy lithium borate melt at the interfaces of the particles, bonding them together. Subsequent heating to 380 °C dehydrogenates the borohydride and eliminates the Li-deficient glassy lithium borate. The LiH/MgB 2 material is not reversible because desorption does not lead back to LiH/MgB 2 , but rather to elemental B and Mg metal in the near-surface region. In contrast to LiH, TiH 2 does not react with MgB 2 , despite the favorable thermodynamics for destabilization via TiB 2 formation. Furthermore, high pressure hydrogenation yields only unreacted TiH 2 and MgB 2 in the surface and near-surface regions. Thus, added TiH 2 provides no benefit to MgB 2 hydrogenation, in agreement with the findings of the preceding bulk study.

08 HYDROGEN↗

NASA NTRS1985

Sea ice - Multiyear cycles and white ice

The multiyear thickness cycles represent one of the interesting features of the sea ice studies performed by Semtner (1976) and Washington et al. (1976) with simple thermodynamic models of sea ice. In the present article, a description is given of results which show that the insulating effect of snow on the surface of the sea ice is important in producing these multiyear cycles given the physics included in the model. However, when the formation of white ice is included, the cycles almost disappear. White ice is the ice which forms at the snow-ice interface when the snow layer becomes thick enough to depress the ice below the water level. Water infiltrates the snow by coming through the ice at leads and generally freezes there, forming white ice.

Ledley, T. S.↗

DOE OSTI2020

Identifying crystal structures and chemical reactions at the interface of stanene on Bi 2 Te 3

Synthesizing monolayers and heterostructures is an enabling approach to extract new physical phenomena from bulk materials. Among the structures amenable to this approach is stanene, which is a monolayer of tin, similar to graphene, and has been predicted to host one-dimensional topological states at its edges. Stanene can be tuned by decorating with different adatoms, which makes it a promising platform on which to engineer topological devices. Here, we deposit Sn on Bi 2 Te 3 and characterize the growth using anomalous synchrotron x-ray scattering and x-ray photoelectron spectroscopy (XPS). X-ray diffraction data reveal the formation of epitaxial Sn-based structures, along with penetration of Sn into the Bi 2 Te 3 , with Sn intercalating between the upper 10 Bi 2 Te 3 quintuple layers. Additionally, XPS data show deposited Sn reacting to form SnTe and Bi at the Bi 2 Te 3 surface. The calculated heat of reaction for Sn and Bi2Te3 is consistent with an exothermic reaction to SnTe and Bi. Using thermodynamic calculations as a guide, we identify several candidate substrates that can stabilize the stanene phase.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

Tutorial review on structure – dendrite growth relations in metal battery anode supports

This tutorial review explains the emerging understanding of the surface and bulk chemistry – electrochemical performance relations in anode supports (aka secondary current collectors, substrates, templates, hosts) for lithium, sodium and potassium metal batteries (LMBs, SMBs or NMBs, and KMBs or PMBs). In relation to each section, the possible future research directions that may yield both new insight and improved cycling behavior are explored. Representative case studies from Li, Na and K metal anode literature are discussed. The tutorial starts with an overview of the solid electrolyte interphase (SEI), covering both the “classic” understanding of the SEI structure and the “modern” insights obtained by site-specific cryogenic stage TEM analysis. Next, the multiple roles of supports in promoting cycling stability are detailed. Without an optimized support architecture, the metal–electrolyte interface becomes geometrically unstable at a lower current density and cycle number. Taking into consideration the available literature on LMBs, SMBs and KMBs, it is concluded that effective architectures are geometrically complex and electrochemically lithiophilic, sodiophilic or potassiophilic, so as to promote conformal electrochemical wetting of the metal during plating/stripping. One way that philicity is achieved is through support oxygen surface chemistry, which yields a reversibly reactive metal–support interface. Examples of this include the well-known oxygen–carbon moieties in reduced graphene oxide (rGO), as well as classic ion battery reversible conversion reaction oxides such as SnO 2 . Unreactive surfaces lead to dewetted island growth of the metal, which is a precursor to dendrites, and possibly to non-uniform dissolution. Surveying the literature on various Li, Na and K metal supports, it is concluded that the key bulk thermodynamic property that will predict electrochemical wetting behavior is the enthalpy of infinite solution (Δ sol H ∞ ) of the metal (solute) into the support (solvent). Large and negative Δ sol H ∞ promotes uniform metal wetting on the support surface, corresponding to relatively low plating overpotential. Positive Δ sol H ∞ promotes dewetted islands and a relatively high overpotential. This simple rule explains a broad range of studies on Li, Na and K metal – support interactions, including the previously reported correlation between mutual solubility and wetting.

25 ENERGY STORAGE↗

DOE OSTI2025

The Role of Interfaces and Charge for Chemical Reactivity in Microdroplets

A wide variety of reactions are reported to be dramatically accelerated in aqueous microdroplets, making them a promising platform for environmentally clean chemical synthesis. However, to fully utilize the microdroplets for accelerating chemical reactions requires a fundamental understanding of how microdroplet chemistry differs from that of a homogeneous phase. Here, in this work, we provide our perspective on recent progress to this end, both experimentally and theoretically. We begin by reviewing the many ways in which microdroplets can be prepared, creating water/hydrophobic interfaces that have been frequently implicated in microdroplet reactivity due to preferential surface adsorption of solutes, persistent electric fields, and their acidity or basicity. These features of the interface interplay with specific mechanisms proposed for microdroplet reactivity, including partial solvation, possible gas phase channels, and the presence of highly reactive intermediates. We especially highlight the role of droplet charge and associated electric fields, which appears to be key to understanding how certain reactions, like the formation of hydrogen peroxide and reduced transition metal complexes, are thermodynamically possible in microdroplets. Lastly, we emphasize opportunities for theoretical advances and suggest experiments that would greatly enhance our understanding of this fascinating subject.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗