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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 91 records · Page 5
All sourcesNASA NTRSDOE OSTI
NASA NTRS1983

Gravitational effects in dendritic growth

The theories of diffusion-controlled dendritic crystallization will be reviewed briefly, along with recently published critical experiments on the kinetics and morphology of dendritic growth in pure substances. The influence of the gravitational body force on dendrite growth kinetics will be shown to be highly dependent on the growth orientation with respect to the gravity vector and on the level of the thermal supercooling. In fact, an abrupt transition occurs at a critical supercooling, above which diffusional transport dominates the growth process and below which convective transport dominates. Our most recent work on binary mixtures shows that dilute solute additions influence the crystallization process indirectly, by altering the interfacial stability, rather than by directly affecting the transport mode. Directions for future studies in this field will also be discussed.

Glicksman, M. E.↗
NASA NTRS1991

Measurement and analysis of grain boundary grooving by volume diffusion

Experimental measurements of isothermal grain boundary grooving by volume diffusion are carried out for Sn bicrystals in the Sn-Pb system near the eutectic temperature. The dimensions of the groove increase with a temporal exponent of 1/3, and measurement of the associated rate constant allows the determination of the product of the liquid diffusion coefficient D and the capillarity length Gamma associated with the interfacial free energy of the crystal-melt interface. The small-slope theory of Mullins is generalized to the entire range of dihedral angles by using a boundary integral formulation of the associated free boundary problem, and excellent agreement with experimental groove shapes is obtained. By using the diffusivity measured by Jordon and Hunt, the present measured values of Gamma are found to agree to within 5 percent with the values obtained from experiments by Gunduz and Hunt on grain boundary grooving in a temperature gradient.

Hardy, S. C.↗
NASA NTRS2012

Multiscale Modeling of Grain Boundaries in ZrB2: Structure, Energetics, and Thermal Resistance

A combination of ab initio, atomistic and finite element methods (FEM) were used to investigate the structures, energetics and lattice thermal conductance of grain boundaries for the ultra high temperature ceramic ZrB2. Atomic models of idealized boundaries were relaxed using density functional theory. Information about bonding across the interfaces was determined from the electron localization function. The Kapitza conductance of larger scale versions of the boundary models were computed using non-equilibrium molecular dynamics. The interfacial thermal parameters together with single crystal thermal conductivities were used as parameters in microstructural computations. FEM meshes were constructed on top of microstructural images. From these computations, the effective thermal conductivity of the polycrystalline structure was determined.

Lawson, John W.↗
NASA NTRS1997

A Rationale for System-Dependent Advantages and Disadvantages of Solution Crystal Growth at Low Gravity

Protein crystallization experiments at reduced gravity have yielded crystals that, depending on the specific material, are either superior or inferior in their structural perfection compared to counterparts grown at normal gravity. A reduction of the crystals' quality due to their growth at low gravity cannot be understood from existing models. Our experimental investigations of the ground-based crystallization of the protein lysozyme have revealed pronounced unsteady growth layer dynamics and associated defect formation under steady external conditions. Through scaling analysis and numerical simulations we show that the observed fluctuations originate from the coupling of bulk transport with non-linear interface kinetics under mixed kinetics-transport control of the growth rate. The amplitude of the fluctuations is smallest when either transport or interfacial kinetics dominate the control of the crystallization process. Thus, depending on the specific system, crystal quality may be improved by either enhancing or suppressing the transport in the solution. These considerations provide, for the first time, a material-dependent rationale for the advantages, as well as the disadvantages, of reduced gravity for (protein) crystallization.

Rosenberger, Franz↗
NASA NTRS1985

Bulk Formation of Metallic Glasses and Amorphous Silicon from the Melt

By using metallic glass compositions with a high relative glass transition temperature, such as Pd40Ni40P20, homogeneous nucleation also becomes negligible. Large (5g) masses of this alloys were obtained using a molten B2O3 flux. Presently, bulk glass formation in iron based glasses is being investigated. It is expected that if an undercooling of about 250K can be achieved in a Ge or Si melt, formation of the amorphous semiconductor phase (rather than the crystal) may be kinetically favored. The volumetric behavior of undercooled liquid Ga droplet dispersion is investigated by dilatometry. A theoretical model (both analytical and numerical) was developed for transient nucleation in glass forming melts. The model, originally designed for isothermal conditions, was extended to continuous quenching. It is being applied to glass formation in various metallic and oxide systems. A further refinement will be the inclusion of diffusion controlled interfacial rearrangements governing the growth of the crystal embryos.

Spaepen, F.↗
NASA NTRS1993

Convection effects on radial segregation and crystal melt interface in vertical Bridgman growth

We analytically study the influence of convection caused by horizontal heat transfer through the sides of a vertical Bridgman apparatus. We consider the case when the heat transfer across the side walls is small so that the resulting interfacial deformation and fluid velocities are also small. This allows us to linearize the Navier-Stokes equations and express the interfacial conditions about a planar interface through a Taylor expansion. Using a no tangential stress conditions on the side walls, asymptotic expressions for both the interfacial slope, and radial segregation at the crystal-melt interface are obtained in closed form in the limit of large thermal Rayleigh number. It is suggested that these can be reduced by appropriately controlling a specific heat transfer property at the edge of the insulation zone in the solid side.

Tanveer, S.↗
DOE OSTI2026

Impact of solvent forces and broken symmetry on the assembly of designed proteins at a liquid-solid interface

The era of protein design has enabled the creation of hybrid protein-inorganic interfaces, leading to both surface-directed self-assembly of de novo protein architectures and protein-directed formation of inorganic materials. However, the resulting patterns of protein assembly are often unexpected, implying that essential interactions are not accounted for in current design platforms. Here, we use high-speed atomic force microscopy (AFM) analyzed through machine learning to follow the assembly of protein nanorods in aqueous electrolytes on two types of mica exhibiting disparate symmetry elements, which are imprinted on the overlying hydration structure. Using Monte Carlo simulations, we reproduce the observed phases and show that an observed smectic phase, previously thought to be unstable for non-interacting rods in two dimensions, emerges when crystal symmetry introduces a directional bias. The findings demonstrate the importance of incorporating solvent forces as modulated by the hydration structure inherent to interfacial systems when designing protein assemblies at liquid-crystal interfaces. Coupling physics-based simulations that can account for these factors to de novo protein design algorithms can lead to improved design platforms for bio-inspired, hybrid materials.

bioinspired materials↗
DOE OSTI2026

In situ transmission electron microscopy observations of CaCO 3 crystallization onto polysaccharide-coated nanoparticles

Polysaccharides and proteoglycans are widely associated with the organic matrix at sites of CaCO 3 biomineralization, and previous studies indicate that these macromolecules may confer greater roles in mineral nucleation than previously recognized. This investigation uses in situ liquid-phase transmission electron microscopy (LP-TEM) to observe CaCO 3 nucleation onto aminated silica (SiO 2 –NH 3 + ) nanoparticles treated with a layer of chitosan (near-neutral derivative of chitin) or heparin (a carboxylated and highly sulfated glycosaminoglycan). In the absence of polysaccharides, few CaCO 3 particles formed and exhibited mobility. However, the SiO 2 –NH 3 + nanoparticles were enveloped in a region of higher mass density relative to the bulk solution, suggesting the development of a local solute-rich environment that surrounds the charged NH 3 + groups. The heparin- or chitosan-coated silica particles also exhibited regions of higher mass density around the nanoparticles. In the presence of these polysaccharide coatings, we observed the nucleation of abundant CaCO 3 particles whereby the polyanionic heparin promoted more nucleation than the weakly cationic chitosan. Many crystallites appeared to form at the polysaccharide–TEM cell membrane–solution interface, further indicating interfacial and macromolecule-specific control on crystallization. The combined results demonstrate that chitosan and heparin have an appreciable effect on the timing, size, and location of CaCO 3 nucleation compared to the polysaccharide-free nanoparticles.

15 GEOTHERMAL ENERGY↗
DOE OSTI2024

Selective atomic sieving across metal/oxide interface for super-oxidation resistance

Abstract Surface passivation, a desirable natural consequence during initial oxidation of alloys, is the foundation for functioning of corrosion and oxidation resistant alloys ranging from industrial stainless steel to kitchen utensils. This initial oxidation has been long perceived to vary with crystal facet, however, the underlying mechanism remains elusive. Here, using in situ environmental transmission electron microscopy, we gain atomic details on crystal facet dependent initial oxidation behavior in a model Ni-5Cr alloy. We find the (001) surface shows higher initial oxidation resistance as compared to the (111) surface. We reveal the crystal facet dependent oxidation is related to an interfacial atomic sieving effect, wherein the oxide/metal interface selectively promotes diffusion of certain atomic species. Density functional theory calculations rationalize the oxygen diffusion across Ni(111)/NiO(111) interface, as contrasted with Ni(001)/NiO(111), is enhanced. We unveil that crystal facet with initial fast oxidation rate could conversely switch to a slow steady state oxidation.

(S)TEM, oxidizing metals↗
DOE OSTI2021

Dynamic Barriers to Crystallization of Calcium Barium Carbonates

Metastable carbonates play important roles in geochemistry, biomineralization and serve as model systems for nonclassical theories of nucleation and growth. Balcite (Ca 0.5 Ba 0.5 CO 3 ) is a remarkable carbonate phase that is isostructural with a high-temperature modification of calcite (CaCO 3 ), yet can be synthesized at ambient conditions. Here, we investigate crystallization pathways in the Ba-Ca-CO 3 -H 2 O system, with a focus on the transformation of amorphous calcium barium carbonate (ACBC) to balcite and subsequent decomposition into the equilibrium calcite (CaCO3) and witherite (BaCO 3 ) phases. Density functional theory calculations show that balcite is an unstable solid solution (Ca 1-x BaxCO 3 , R 3¯ m) in the range 0.17 < x < 0.5, but is accessible through the amorphous ACBC precursor for x ≲ 0.5, and predict its decomposition into calcite and witherite. We confirm this pathway experimentally but found demixing to proceed slowly and remain incomplete even after 9 months. Nucleation kinetics of balcite from ACBC was assessed using a microfluidic assay, where increasing barium content led to a surprising increase in the balcite nucleation rate, despite decreasing thermodynamic driving force. We attribute crystallization rates that dramatically accelerate with time to changes in interfacial structure and composition during coarsening of the amorphous precipitate. By carefully quantifying the thermodynamic and kinetic contributions in the multistep crystallization of a metastable carbonate, we produce insights that allow us to better interpret the formation and persistence of metastable minerals in natural and synthetic environments.

36 MATERIALS SCIENCE↗
DOE OSTI2025

A-Cation-Dependent Structure–Optical Property Relationships of Halide Perovskite Heterostructures with Complex Interfaces

Halide perovskite heterostructures offer promising interfacial interactions for energy conversion, yet challenges in synthesizing structurally well-defined systems limit detailed investigations into structure–property relationships. In this article, we report the synthesis of compositionally controlled 3D/3D and 3D/2D halide perovskite heterostructures using evaporation crystallization-polymer pen lithography (EC-PPL) and a single-particle analysis of their properties. By systematically varying A-site cation combinations and crystal dimensions, we show that heterointerfaces induce local lattice distortions that modulate vibrational dynamics and electron-phonon coupling. These interfacial effects result in significantly extended carrier lifetimes compared to compositionally similar pure phases. Raman spectroscopy, temperature-dependent photoluminescence, and power-dependent emission analysis reveal that localized structural modulations at the interface govern exciton-phonon interactions. These effects are magnified in smaller crystals due to increased interfacial contributions. Our findings highlight the critical role of interface-driven lattice control in tuning the optoelectronic properties of halide perovskites and provide design principles for engineering heterostructures in next-generation optoelectronic devices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Creating Functional Oxynitride–Silicon Interfaces and SrNbO 2 N Thin Films for Photoelectrochemical Applications

Photoelectrochemical performance dependence upon absorption length, carrier diffusion length, and surface area of an oxynitride photoabsorber is investigated. How best to fabricate optical-quality thin films of bandgap-tunable oxynitrides is also discussed. We targeted the stoichiometric compound SrNbO 2 N as an optimal wide-bandgap photoabsorber (1.9 eV) for use with silicon (1.1 eV) in a tandem structure photoelectrochemical cell. Preparation of perovskite oxynitrides at high-temperature as isolated powders is often straightforward, but it is difficult to integrate them as thin films in tandem junction devices with low-temperature materials. Here we develop the first method to prepare optical-quality SrNbO 2 N thin-films of tunable thickness and roughness on single-crystal silicon substrate. This achievement required an interfacial layer of ultra-thin TaN to be used as a barrier to reduce the inter-diffusion of silicon and oxygen during oxynitride syn-thesis. We produced a variety of SrNbO 2 N film thicknesses (20-440 nm) on n + -Si(100) surfaces. Roughness factor (0.14-21) scaled with thickness. The intrinsic photoelectrochemical activity of these devices was evaluated using a low-barrier sacrificial electron donor. Photocurrent density and photovoltage revealed a significant (and non-linear) dependence on film thickness and roughness. Furthermore, absorption length, carrier diffusion length, and surface area were each found to play key roles. Balancing these is required for optimally performing devices.

08 HYDROGEN↗
DOE OSTI2021

Self-Assembly and Phase Separation for Transport: A brief argument for the continued exploration of liquid crystal flows and electrodeposition in micro-gravity

Phase separation, interfacial tension gradients, and molecular self-assembly are all phenomena frequently observed when manipulating soft condensed matter systems on Earth. Depending on the system these processes can also be quite predictable. For instance, on Earth water droplets placed on hydrophobic surfaces will have contact angles > 90° with limited spread, contrary to their wetting behavior on hydrophilic surfaces. However, in an environment that is in a constant state of free-fall, where the gravitational field is reduced by 10%, such as on the International Space Station (ISS), buoyancy and its effect on fluid convection also become negligible. Fluid flow and phase behavior become less predictable. Thus, continuing the prior example, even if water droplets still remain in contact with a surface in microgravity (µg), the interface between the air and droplets will still remain significantly curved, appearing almost as if they were placed over completely nonwetting surfaces (Fig. 1a). Moreover, the negligible opposing buoyant force would also mean that if immiscible liquid droplets of a less dense character, or air bubbles even (Fig. 1b), were to be suspended within a larger water drop, these immiscible droplets or air bubbles would not migrate toward any one direction unless either artificially propelled by an external force or internal reaction inducing flow.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1990

Steady-state thermal-solutal convection and diffusion in a simulated float zone

Models describing the steady-state thermal diffusion in a pure system, the thermal-solutal diffusion in a binary system, and heat and momentum transverse in a pure system are presented. The geometry of the model is described by a 2D Cartesian coordinate system that is applicable for crystal sheets. The melting, solidifying, and melt/gas interfacial shapes as well as the thermal, flow, and solutal profiles are analytically evaluated as functions of the heat and ambient temperature profiles and material properties. The solution procedure involves a coupled asymptotic/numerical approach which reduces the coupled set of partial differential equations to ordinary type. The results should be applicable in situations where melt flows are not intense enough to change the thermal field in pure systems, or where the physical properties of the melt are such that the convective field is decoupled from the thermal field, the latter being established primarily by diffusion.

Young, G. W.↗
NASA NTRS2004

Dependence of Interfacial Excess on the Threshold Value of the Isoconcentration Surface

The proximity histogram (or proxigram for short) is used for analyzing data collected by a three-dimensional atom probe microscope. The interfacial excess of Re (2.41 +/- 0.68 atoms/sq nm) is calculated by employing a proxigram in a completely geometrically independent way for gamma/gamma' interfaces in Rene N6, a third-generation single-crystal Ni-based superalloy. A possible dependence of interfacial excess on the variation of the threshold value of an isoconcentration surface is investigated using the data collected for Rene N6 alloy. It is demonstrated that the dependence of the interfacial excess value on the threshold value of the isoconcentration surface is weak.

Yoon, Kevin E.↗
DOE OSTI2021

Metastable–solid phase diagrams derived from polymorphic solidification kinetics

Nonequilibrium processes during solidification can lead to kinetic stabilization of metastable crystal phases. A general framework for predicting the solidification conditions that lead to metastable-phase growth is developed and applied to a model face-centered cubic (fcc) metal that undergoes phase transitions to the body-centered cubic (bcc) as well as the hexagonal close-packed phases at high temperatures and pressures. Large-scale molecular dynamics simulations of ultrarapid freezing show that bcc nucleates and grows well outside of the region of its thermodynamic stability. An extensive study of crystal–liquid equilibria confirms that at any given pressure, there is a multitude of metastable solid phases that can coexist with the liquid phase. We define for every crystal phase, a solid cluster in liquid (SCL) basin, which contains all solid clusters of that phase coexisting with the liquid. Additionally, a rigorous methodology is developed that allows for practical calculations of nucleation rates into arbitrary SCL basins from the undercooled melt. It is demonstrated that at large undercoolings, phase selections made during the nucleation stage can be undone by kinetic instabilities amid the growth stage. On these bases, a solidification–kinetic phase diagram is drawn for the model fcc system that delimits the conditions for macroscopic grains of metastable bcc phase to grow from the melt. We conclude with a study of unconventional interfacial kinetics at special interfaces, which can bring about heterogeneous multiphase crystal growth. A first-order interfacial phase transformation accompanied by a growth-mode transition is examined.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2023

Gallium Oxide Heterojunction Diodes for 400 °C High‐Temperature Applications

β ‐Ga 2 O 3 ‐based semiconductor devices are expected to have significantly improved high‐power and high‐temperature performance due to its ultrawide bandgap of close to 5 eV. However, the high‐temperature operation of these ultrawide‐bandgap devices is usually limited by the relatively low 1–2 eV built‐in potential at the Schottky barrier with most high‐work‐function metals. Herein, heterojunction p ‐NiO/n‐ β ‐Ga 2 O 3 diodes fabrication and optimization for high‐temperature device applications are reported, demonstrating a current rectification ratio ( I ON / I OFF ) of more than 10 6 at 410 °C. The NiO heterojunction diode can achieve higher turn‐on ( V ON ) voltage and lower reverse leakage current compared to the Ni‐based Schottky diode fabricated on the same single‐crystal β ‐Ga 2 O 3 substrate, despite charge transport dominated by interfacial recombination. Electrical characterization and device modeling show that these advantages are due to a higher built‐in potential and additional band offset. These results suggest that heterojunction p–n diodes based on β ‐Ga 2 O 3 can significantly improve high‐temperature electronic device and sensor performance.

Sohel, Shahadat H.↗