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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 577 records · Page 32
All sourcesNASA NTRSDOE OSTI
NASA NTRS1977

Pressureless sintered beta prime-Si3N4 solid solution: Fabrication, microstructure, and strength

Si3N4, AlN, and Al2O3 were used as basic constituents in a study of the pressureless sintering of beta prime-Si3N4 solid solution as a function of temperature. Y2O3-SiO2 additions were used to promote liquid-phase sintering. The sintered specimens were characterized with respect to density, microstructure, strength, oxidation, and thermal shock resistance. Density greater than 98 percent of theoretical was achieved by pressureless sintering at 1750 C. The microstructure consisted essentially of fine-grained beta prime-Si3N4 solid solution as the major phase. Modulus of rupture strengths up to 483 MPa were achieved at moderate temperature (1000 C), but decreased to 228 MPa at 1380 C. This substantial strength loss was attributed to a glassy grain boundary phase formed during cooling from the sintering temperature. The best oxidation resistance was exhibited by a composition containing 3 mol % Y2O3-SiO2 additives. Water quench thermal shock resistance was equivalent to that of reaction sintered silicon nitride but lower than hot-pressed silicon nitride.

Dutta, S.↗
DOE OSTI2018

Phase transition lowering in dynamically compressed silicon

Silicon, being one of the most abundant elements in nature, attracts wide-ranging scientific and technological interest. Specifically, in its elemental form, crystals of remarkable purity can be produced. One may assume that this would lead to silicon being well understood, and indeed, this is the case for many ambient properties, as well as for higher-pressure behaviour under quasi-static loading. However, despite many decades of study, a detailed understanding of the response of silicon to rapid compression—such as that experienced under shock impact—remains elusive. Here, we combine a novel free-electron laser-based X-ray diffraction geometry with laser-driven compression to elucidate the importance of shear generated during shock compression on the occurrence of phase transitions. We observe lowering of the hydrostatic phase boundary in elemental silicon, an ideal model system for investigating high-strength materials, analogous to planetary constituents. Furthermore, we unambiguously determine the onset of melting above 14 GPa, previously ascribed to a solid–solid phase transition, undetectable in the now conventional shocked diffraction geometry; transitions to the liquid state are expected to be ubiquitous in all systems at sufficiently high pressures and temperatures.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Structural phase transition, narrow band gap, and room-temperature ferromagnetism in [KNbO{sub 3}]{sub 1−x}[BaNi{sub 1/2}Nb{sub 1/2}O{sub 3−δ}]{sub x} ferroelectrics

Structural phase transition, narrow band gap (E{sub g}), and room-temperature ferromagnetism (RTFM) have been observed in the [KNbO{sub 3}]{sub 1−x}[BaNi{sub 1/2}Nb{sub 1/2}O{sub 3−δ}]{sub x} (KBNNO) ceramics. All the samples have single phase perovskite structure, but exhibit a gradual transition behaviour from the orthorhombic to a cubic structure with the increase of x. Raman spectroscopy analysis not only corroborates this doping-induced change in normal structure but also shows the local crystal symmetry for x ≥ 0.1 compositions to deviate from the idealized cubic perovskite structure. A possible mechanism for the observed specific changes in lattice structure is discussed. Moreover, it is noted that KBNNO with compositions x = 0.1–0.3 have quite narrow E{sub g} of below 1.5 eV, much smaller than the 3.2 eV band gap of parent KNbO{sub 3} (KNO), which is due to the increasing Ni 3d electronic states within the gap of KNO. Furthermore, the KBNNO materials present RTFM near a tetragonal to cubic phase boundary. With increasing x from 0 to 0.3, the magnetism of the samples develops from diamagnetism to ferromagnetism and paramagnetism, originating from the ferromagnetic–antiferromagnetic competition. These results are helpful in the deeper understanding of phase transitions, band gap tunability, and magnetism variations in perovskite oxides and show the potential role, such materials can play, in perovskite solar cells and multiferroic applications.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2022

High Entropy Oxide Relaxor Ferroelectrics

Relaxor ferroelectrics are important in technological applications due to strong electromechanical response, energy storage capacity, electrocaloric effect, and pyroelectric energy conversion properties. Current efforts to discover and design materials in this class generally rely on substitutional doping as slight changes to local compositional order can significantly affect the Curie temperature, morphotropic phase boundary, and electromechanical responses. In this work, we demonstrate that moving to the strong limit of compositional complexity in an ABO 3 perovskite allows stabilization of relaxor responses that do not rely on a single narrow phase transition region. Entropy-assisted synthesis approaches are utilized to synthesize single-crystal Ba(Ti 0.2 Sn 0.2 Zr 0.2 Hf 0.2 Nb 0.2 )O 3 [Ba(5B)O] films. The high levels of configurational disorder present in this system are found to influence dielectric relaxation, phase transitions, nanopolar domain formation, and Curie temperature. Temperature-dependent dielectric, Raman spectroscopy, and second-harmonic generation measurements reveal multiple phase transitions, a high Curie temperature of 570 K, and the relaxor ferroelectric nature of Ba(5B)O films. The first-principles theory calculations are used to predict possible combinations of cations to design relaxor ferroelectrics and quantify the relative feasibility of synthesizing these highly disordered single-phase perovskite systems. Further, the ability to stabilize single-phase perovskites with various cations on the B-sites offers possibilities for designing high-performance relaxor ferroelectric materials for piezoelectric, pyroelectric, and electrocaloric applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Active Fluids Form System-Spanning Filamentary Networks

Recent experimental realizations of liquid-liquid phase separation of active liquid crystals have offered an insight into the interaction between phase separation, ubiquitous in soft matter and biology, and chaotic active flows. Here, in this Letter, we use continuum theory to examine phase separation of an active liquid crystal and a passive fluid and report two new results. First, we provide an analytical derivation of the activity-induced suppression of the phase boundary of the coexistence region—a result first reported in simulations and experiments. We show that the shift in the critical point is a result of the balance between self-stirring active flows and phase-separating diffusive fluxes. Second, we show that this same balance is responsible for dramatically changing the morphology of the phase separated state, resulting in the emergence of a new mixed active phase consisting of a dynamical filamentous active network that invades the entire system area, trapping droplets of passive material. This structure exists even for very low volume fractions of active material. Our work provides an important step towards the goal of understanding how to use activity as a new handle for sculpting interfaces.

active nematics↗
DOE OSTI2017

Enhancing Anodic Catalytic Activity at High Fuel Utilization By Infiltration of Ni Nanoparticles

The performance of SOFCs degrades with increasing fuel utilization, since the fuel oxidation reaction faces increased competition for the triple-phase-boundary (TPB) sites in the anode from adsorbed water vapor species. Introduction of addition TPB sites by infiltration of Ni nanoparticles into the anode is an effective way to alleviate this problem. Both liquid and vapor phase infiltration of Ni nanoparticles into commercially available Ni/YSZ cermet anodes have been explored. The microstructure of the anode before infiltration has been examined by FIB/SEM 3-D reconstruction to quantify the TPB length. Infiltrated and un-infiltrated cells have been electrochemically characterized by I-V and electrochemical impedance spectroscopy (EIS) techniques in a temperature range of 600°C-800°C at varying water vapor partials pressures. The infiltrated Ni nanoparticles have been characterized by image analysis of SEM micrographs from fracture cross-sections, before and after electrochemical testing. The effects of the nanoparticles on cell electrochemical performance as a function of temperature and anode input water vapor content, the stability of the nanoparticles, as well as the thermodynamics of vapor phase infiltration of Ni are presented.

Basu, Soumendra Nath↗
DOE OSTI2016

Boron-Based Hydrogen Storage: Ternary Borides and Beyond

DOE continues to seek reversible solid-state hydrogen materials with hydrogen densities of ≥11 wt% and ≥80 g/L that can deliver hydrogen and be recharged at moderate temperatures (≤100 °C) and pressures (≤100 bar) enabling incorporation into hydrogen storage systems suitable for transportation applications. Boron-based hydrogen storage materials have the potential to meet the density requirements given boron’s low atomic weight, high chemical valance, and versatile chemistry. However, the rates of hydrogen exchange in boron-based compounds are thus far much too slow for practical applications. Although contributing to the high hydrogen densities, the high valance of boron also leads to slow rates of hydrogen exchange due to extensive boron-boron atom rearrangements during hydrogen cycling. This rearrangement often leads to multiple solid phases occurring over hydrogen release and recharge cycles. These phases must nucleate and react with each other across solid-solid phase boundaries leading to energy barriers that slow the rates of hydrogen exchange. This project sought to overcome the slow rates of hydrogen exchange in boron-based hydrogen storage materials by minimizing the number of solid phases and the boron atom rearrangement over a hydrogen release and recharge cycle. Two novel approaches were explored: 1) developing matched pairs of ternary borides and mixed-metal borohydrides that could exchange hydrogen with only one hydrogenated phase (the mixed-metal borohydride) and only one dehydrogenated phase (the ternary boride); and 2) developing boranes that could release hydrogen by being lithiated using lithium hydride with no boron-boron atom rearrangement.

08 HYDROGEN↗
NASA NTRS1977

Pressureless sintered beta-prime-Si3N4 solid solution - Fabrication, microstructure, and strength

Pressureless sintering of beta-prime-Si3N4 solid solution was studied as a function of temperature using Si3N4, A1N, and Al2O3 as basic constituents. Y2O3-SiO2 additions were used to promote liquid-phase sintering. The sintered specimens were characterized with respect to density, microstructure, strength, oxidation, and thermal shock resistance. Density greater than 98 percent of theoretical was achieved by pressureless sintering at 1750 C. The microstructure consisted essentially of fine-grained beta-prime-Si3N4 solid solution as the major phase. Modulus of rupture strengths up to 483 M Pa were achieved at moderate temperature (1000 C), but decreased to 228 M Pa at 1380 C. This substantial strength loss was attributed to a 'glassy' grain boundary phase formed during cooling from the sintering temperature. The best oxidation resistance was exhibited by a composition containing 3 mol % Y2O3-SiO2 additives. Water quench thermal shock resistance was equivalent to that of reaction sintered silicon nitride but lower than hot-pressed silicon nitride.

Dutta, S.↗
DOE OSTI2026

Doping Metallic Grain Boundaries to Control Atomic Structure and Damage Tolerance

Grain boundaries often act as sites for crack and void nucleation during plastic deformation of metallic materials. While it is known that grain boundary character and structure can greatly influence this damage nucleation process, the current level of control over such details is limited. The objective of this project was to obtain a fundamental understanding of how metallic grain boundary structure can be controlled through intelligent doping, with the idea of inducing planned amorphous grain boundary phases or complexions. The effect of amorphous complexion structure on dislocation accommodation mechanisms was studied, to improve the field’s understanding of damage nucleation at a promising type of interface. Different microstructural descriptors were studied, as grain boundaries can have large variations and complexity of local structure, and influence the mechanical damage resistance of these features was tested. Nanocrystalline systems that contain amorphous grain boundary complexions were prioritized, as these have more extreme variations in interfacial structure and damage tolerance, with an emphasis on isolating the importance of complexion population (type, thickness, etc.), network topology, local structure, and local chemistry. This research used a combination of computational, experimental, and characterization techniques to isolate and understand the importance of nanoscale grain boundary structure and interfacial chemistry. Amorphous grain boundary complexions were found to clearly increase a material’s resistance to mechanical damage, with the local distribution of structural short-range order within the complexions found to be an important descriptor for damage and the proposed focus of future work in this area.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Extracted Water Induces Concentration Fluctuations in Model Ternary Liquid–Liquid Extraction System

Organic phase aggregation and phase splitting are two important (and connected) phenomena in liquid–liquid extraction of metal ions. Previously, we demonstrated how structure in binary mixtures of extractant and diluent originates from concentration fluctuations associated with the so-called “third-phase formation” liquid–liquid phase instability. For more complex systems, we sought to understand how extracted aqueous components affect these concentration fluctuations. Here, in this study, we use small-angle X-ray scattering and molecular dynamics simulations to investigate organic phase structural changes upon contact with water in a model ternary system of water/alkane/extractant. Critical exponents were determined from scattering with temperature variation and were consistent with mean field values. Then, by controlling the water content in the organic phase through direct dissolution of fixed quantities at constant temperature, we relate the observed increase in the fluctuation length scale to changes to the spinodal temperature of the third-phase formation phase boundary. We find a roughly linear relationship between water concentration and the spinodal temperature and a similar slope in that relationship for different linear alkane diluents. This suggests that the mechanism by which water extraction impacts the organic phase structure is to enhance concentration fluctuations through the introduction of additional polar extractant-water complexes, which increases the spinodal temperature and thereby decreases the reduced temperature, i.e., the distance to the instability. This explanation for how solutes induce aggregation in liquid–liquid extraction organic phases may extend to more complex systems, explaining the large increases in correlation lengths reported under high acid and metal loading.

Bonnett, Brittany L. [Argonne National Laboratory ↗
DOE OSTI2013

Diffuse phase transition in Li{sub 0.12}Na{sub 0.88}NbO{sub 3} piezoelectric ceramics

The morphotropic phase boundary composition viz. lithium sodium niobate, Li{sub 0.12}Na{sub 0.88}NbO{sub 3}, (LNN-12) was prepared by conventional solid state reaction and sintering route. The temperature dependent permittivity response near transition temperature showed a diffused phase transition (DPT). The degree of diffuseness, {gamma}, using the modified Curie-Weiss law, was found to be 1.92, indicative of almost-complete diffuse phase transition. The planar coupling constant k{sub p}, and mechanical quality factor Q{sub m}, measured by resonance-antiresonance method, were 0.17 and 413 respectively. These parameter values make LNN-12 ceramic an attractive candidate for transducers applications.

36 MATERIALS SCIENCE↗
DOE OSTI2013

Temperature dependences of the ferroelectric and dielectric properties of high curie temperature PbTiO{sub 3}–BiScO{sub 3}–Bi(Zn{sub 1/2}Zr{sub 1/2})O{sub 3}

Highlights: ► Ceramics exhibit enhanced ferroelectric properties with the increase of temperature. ► A strong second harmonic generation effect was observed. ► Transmission electron microscopy results confirm the existence of MPB. - Abstract: The piezoelectric ceramics (1 − x − y)PbTiO{sub 3}–xBiScO{sub 3}–yBi(Zn{sub 1/2}Zr{sub 1/2})O{sub 3} exhibit greatly enhanced ferroelectric properties above room temperature, between 100 and 200 °C. A strong second harmonic generation (SHG) effect was observed below 200 °C. The highest remanent polarization (∼40 μC/cm{sup 2}) and lowest coercive field (∼10 kV/cm) were obtained at 200 °C. X-ray diffraction (XRD) analysis was used to investigate the morphotropic phase boundary (MPB) structure of (1 − x − y)PbTiO{sub 3}–xBiScO{sub 3}–yBi(Zn{sub 1/2}Zr{sub 1/2})O{sub 3} ceramics. Transmission electron microscopy (TEM) results confirm the existence of MPB, where the rhombohedral and tetragonal phases coexist. The results of thermal expansion analysis show a low thermal expansion and stability of this material. The optimal high temperature piezoelectric ceramic is obtained by the composition of 0.05BZZ–0.34BS–0.61PT.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Thermodynamic and Magnetic Properties of the Two-Dimensional Anisotropic Ising Model with Competing Interactions

The two-dimensional anisotropic Ising model with competing interactions is studied on a square lattice by Monte Carlo methods using the Wang–Landau algorithm. The temperature dependences of the main thermodynamic and magnetic parameters are calculated. The distinctive features of temperature dependences of these parameters for different values of the competing interaction are shown. The dependences of the wave number of modulated structures on the ratio of exchange interaction parameters are plotted. The phase diagram of the model is built. The coordinates of the Lifshits point and the localization region of the phases with different wave vector values are calculated by interpolating phase boundaries of the d-iagram.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2018

Systematics of the Third Row Transition Metal Melting: The HCP Metals Rhenium and Osmium

The melting curves of rhenium and osmium to megabar pressures are obtained from an extensive suite of ab initio quantum molecular dynamics (QMD) simulations using the Z method. In addition, for Re, we combine QMD simulations with total free energy calculations to obtain its phase diagram. Our results indicate that Re, which generally assumes a hexagonal close-packed (hcp) structure, melts from a face-centered cubic (fcc) structure in the pressure range 20–240 GPa. We conclude that the recent DAC data on Re to 50 GPa in fact encompass both the true melting curve and the low-slope hcp-fcc phase boundary above a triple point at (20 GPa, 4240 K). A linear fit to the Re diamond anvil cell (DAC) data then results in a slope that is 2.3 times smaller than that of the actual melting curve. The phase diagram of Re is topologically equivalent to that of Pt calculated by us earlier on. Regularities in the melting curves of Re, Os, and five other 3rd-row transition metals (Ta, W, Ir, Pt, Au) form the 3rd-row transition metal melting systematics. We demonstrate how this systematics can be used to estimate the currently unknown melting curve of the eighth 3rd-row transition metal Hf.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Multiphase tin equation of state using density functional theory

In this work, we perform density functional theory (DFT) calculations of five solid phases and the liquid phase of tin. The calculations include cold curves of the five solid phases, phonon calculations in the quasiharmonic approximation over a range of volumes for each solid phase, and DFT-based molecular dynamics (DFT-MD) simulations of the liquid phase, including those of the melt curve using the Z method. Using the DFT results, we construct a tabular multiphase sesame equation of state for tin, referred to as sesame 2162. Comparisons to experimental data are made and show a high level of agreement in isobaric data, isothermal data, shock data, and phase boundary measurements, including measurements of the melt curve. The 2162 EOS will be useful for hydrodynamics simulations and has been designed with an eye toward hydrodynamics simulations that incorporate materials strength models and allow for modeling of the kinetics of phase transitions.

3-dimensional systems↗
DOE OSTI2025

Metastable Clusters and Competitive Solvation Tune Ion Pairing at Liquid Interfaces

The balance of hydrophobic and hydrophilic interactions underlies emergent phenomena in complex multicomponent chemical systems. Here, we show that a supposedly ‘non–interacting’ nonpolar phase can be used to competitively solvate amphiphilic molecules at an oil/aqueous interface. This solvation, as probed by surface specific nonlinear spectroscopy and simulations, results in a molecularly thin corrugated phase boundary featuring metastable assemblies that alter the hydrogen bonding networks of water and the apparent ‘hard/soft’ descriptors used to describe ionic interactions. We show that competitive solvation enhances amphiphile mobility, opening up otherwise energetically inaccessible complexes that transiently interact with aqueous phase ions. These transient species impact ensemble binding affinities and may represent the molecular agents responsible for aspects of ionic transport and function. In conclusion, the result of this work highlights how seemingly unrelated nonpolar interactions feedback onto aqueous phase chemical phenomena, providing a pathway to tune phase separation and self-assembly to access new reaction pathways using interfaces for a range of chemical and biological systems.

Anions↗
DOE OSTI2015

Piezoresponse and magnetic properties of multiferroic (1−x)Bi{sub 0.9}Dy{sub 0.1}FeO{sub 3}–xPbTiO{sub 3} solid solution

The multiferroic solid solution of (1−x)[0.9BiFeO{sub 3}–0.1DyFeO{sub 3}]–xPbTiO{sub 3} with compositions around the morphotropic phase boundary has been synthesized in the form of ceramics and characterized by Piezoresponse Force Microscope (PFM) and Superconducting Quantum Interference Device. Both the original local polar domain structure and the domain evolution after poling have been studied by PFM. The PFM phase imaging has revealed some interesting details of poling and domain switching process: The out-of-plane phase image shows a uniform direction of polarization along the applied electric field, while the in-plane phase image indicates two kinds of domains with antiparallel polarizations. This kind of poled domain structure is explained based on the orientations of the polarization as permitted by the rhombohedral crystal symmetry in grains of different crystallographic orientations. The magnetic properties measured within the temperature range from 1.8 K to 300 K reveal an interesting sequence of magnetic transitions from a weakly ferromagnetic order (WFM{sub 1}) to an antiferromagnetic state (AFM), and then to another weak ferromagnetic phase (WFM{sub 2}), upon cooling. A preliminary magnetic phase diagram is proposed for BDF-34PT.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗