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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 1,315 records · Page 73
All sourcesNASA NTRSDOE OSTI
DOE OSTI2012

Structure and Transformation of Amorphous Calcium Carbonate: A Solid-State 43Ca NMR and Computational Molecular Dynamics Investigation

Amorphous calcium carbonate (ACC) is a metastable precursor to crystalline CaCO{sub 3} phases that precipitates by aggregation of ion pairs and prenucleation clusters. We use {sup 43}Ca solid-state NMR spectroscopy to probe the local structure and transformation of ACC synthesized from seawater-like solutions with and without Mg{sup 2+} and computational molecular dynamics (MD) simulations to provide more detailed molecular-scale understanding of the ACC structure. The {sup 43}Ca NMR spectra of ACC collected immediately after synthesis consist of broad, featureless resonances with Gaussian line shapes (FWHH = 27.6 {+-} 1 ppm) that do not depend on Mg{sup 2+} or H{sub 2}O content. A correlation between {sup 43}Ca isotropic chemical shifts and mean Ca-O bond distances for crystalline hydrous and anhydrous calcium carbonate phases indicates indistinguishable maximum mean Ca-O bond lengths of {approx}2.45 {angstrom} for all our samples. This value is near the upper end of the published Ca-O bond distance range for biogenic and synthetic ACCs obtained by Ca-X-ray absorption spectroscopy. It is slightly smaller than the values from the structural model of Mgfree ACC by Goodwin et al. obtained from reverse Monte Carlo (RMC) modeling of X-ray scattering data and our own computational molecular dynamics (MD) simulation based on this model. An MD simulation starting with the atomic positions of the Goodwin et al. RMC model using the force field of Raiteri and Gale shows significant structural reorganization during the simulation and that the interconnected carbonate/water-rich channels in the Goodwin et al. model shrink in size over the 2 ns simulation time. The distribution of polyhedrally averaged Ca-O bond distances from the MD simulation is in good agreement with the {sup 43}Ca NMR peak shape, suggesting that local structural disorder dominates the experimental line width of ACC.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Porous and Amorphous Mn x Mo 3 S 13 Chalcogel Electrode for High-Capacity Conversion-Based Lithium-Ion Batteries

While Li-ion batteries (LIBs) are a leading energy storage technology, their energy densities are limited by the low capacity of conventional intercalation cathodes, driving interest in high energy-density Li–S batteries that make use of conversion chemistry. Achieving high capacity, reversibility, and cycle stability, and controlling volume changes in conversion batteries during the charge–discharge process, however, remains challenging. Here, in this study, we present a porous, amorphous, sulfide-based Mn x Mo 3 S 13 chalcogel, which concurrently offers high capacity and cycle stability. The solution-processable room temperature synthesized Mn x Mo 3 S 13 (x = 0.25) chalcogel exhibits a local structure that resembles the Mo 3 S 13 cluster with Mn 2+ distributed across the Mo 3 S 13 matrix, as determined by synchrotron X-ray pair distribution function (PDF) and extended X-ray absorption fine structure (EXAFS). Ab initio molecular dynamics (AIMD) simulations reveal that Mn 2+ incorporation shortens the polysulfide chain in the gel matrix compared to the Mo 3 S 13 chalcogel, while forming a coordination environment with disulfide groups, analogous to the experimental findings. A Li/Mn 0.25 Mo 3 S 13 half-cell delivers 897 mAh g –1 capacity during the first discharge and retains 571 mAh g –1 capacity after 100 cycles at a C/3 rate. Distribution of relaxation time (DRT) unveils a stable solid–electrolyte interphase (SEI) formation upon cycling that enables charge–discharge reversibility. Here, the enhanced capacity retention and cycle stability compared to those of the Li/Mo 3 S 13 cell are attributed to the reduced dissolution of active mass into the electrolyte, facilitated by the formation of shorter polysulfide chains within the Mn 0.25 Mo 3 S 13 structure and the strong affinity of Lewis-acidic Mn 2+ for polysulfide anions generated during the charge–discharge process of the Li/Mn 0.25 Mo 3 S 13 cell. Thus, this work illustrates a design principle of material for high-capacity and cycle-stable Li-metal sulfide batteries.

25 ENERGY STORAGE↗
DOE OSTI2018

Resolution of Electronic and Structural Factors Underlying Oxygen-Evolving Performance in Amorphous Cobalt Oxide Catalysts

Non-noble-metal, thin-film oxides are widely investigated as promising materials for catalyzing oxygen evolution reactions (OER). Cobalt oxide thin-films that are electrochemically formed in the presence of borate (CoBi) and phosphate (CoPi) serve as important reference catalysts for assessing correlations between oxyhydroxide domain structures with corresponding electronic properties and OER performance. Here, we present a comparison of CoPi and CoBi thin-film catalysts by a combination of advanced X-ray electronic and vibrational spectroscopies of L-edge synchrotron X-ray absorption (XAS), resonant X-ray emission (RXES), resonant inelastic X-ray scattering (RIXS), resonant Raman (RR) scattering, and high-energy X-ray pair distribution function (PDF) analysis. A detailed spectral analysis is presented and identifies relationships between the OER performance and electronic and molecular-type domain structures. XAS shows that CoBi is composed essentially exclusively of cobalt in octahedral coordination, while CoPi contains approximately 17% tetrahedral Co(II), with the remainder in octahedral coordination. Oxygen-mediated 4 p -3 d hybridization through Co-O-Co bonding was detected by RXES and the inter-site dd excitation was observed by RIXS in CoBi, but not in CoPi. RR shows that CoBi resembles a disordered layered LiCoO 2 -like structure while Co- Pi is amorphous. Distinct domain models in the nanometer range for CoBi and CoPi have been proposed on the basis of the PDF analysis coupled to XAS data. In conclusion, the observed differences provide important implications for the enhancement factors in OEC performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Resolving the Amorphous Structure of Lithium Phosphorus Oxynitride (Lipon)

© 2018 American Chemical Society. Lithium phosphorus oxynitride, also known as Lipon, solid-state electrolytes are at the center of the search for solid-state Li metal batteries. Key to the performance of Lipon is a combination of high Li content, amorphous character, and the incorporation of N into the structure. Despite the material's importance, our work presents the first study to fully resolve the structure of Lipon using a combination of ab initio molecular dynamics, density functional theory, neutron scattering, and infrared spectroscopy. The modeled and experimental results have exceptional agreement in both neutron pair distribution function and infrared spectroscopy. Building on this synergy, the structural models show that N forms both bridges between two phosphate units and nonbridging apical N. We further show that as the Li content is increased the ratio of bridging to apical N shifts from being predominantly bridging at Li contents around 2.5:1 Li:P to only apical N at higher Li contents of 3.38:1 Li:P. This crossover from bridging to apical N appears to directly correlate with and explain both the increase in ionic conductivity with the incorporation of N and the ionic conductivity trends found in the literature.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

Structure, Morphology, and Optical Properties of Amorphous and Nanocrystalline Gallium Oxide Thin Films

Ga2O3 thin films were produced by sputter deposition by varying the substrate temperature (Ts) in a wide range (Ts=25-800 oC). The structural characteristics and optical properties of Ga2O3 films were evaluated using X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray spectrometry (EDS), Rutherford backscattering spectrometry (RBS) and spectrophotometric measurements. The effect of growth temperature is significant on the chemistry, crystal structure and morphology of Ga2O3 films. XRD and SEM analyses indicate that the Ga2O3 films grown at lower temperatures were amorphous while those grown at Ts≥500 oC were nanocrystalline. RBS measurements indicate the well-maintained stoichiometry of Ga2O3 films at Ts=300-700 oC. The spectral transmission of the films increased with increasing temperature. The band gap of the films varied from 4.96 eV to 5.17 eV for a variation in Ts in the range 25-800 oC. A relationship between microstructure and optical property is discussed.

Environmental Molecular Sciences Laboratory↗
DOE OSTI2012

The Molecular Volcano Revisited: Determination of Crack Propagation and Distribution During the Crystallization of Nanoscale Amorphous Solid Water Films.

Temperature programmed desorption (TPD) is utilized to determine the length distribution of cracks formed through amorphous solid water (ASW) during crystallization. This distribution is determined by monitoring how the thickness of an ASW overlayer alters desorption of an underlayer of O2. As deposited the ASW overlayer prevents desorption of O2. During crystallization, cracks form through the ASW overlayer and open a path to vacuum which allows O2 to escape in a rapid episodic release known as the 'molecular volcano'. Sufficiently thick ASW overlayers further trap O2 resulting in a second O2 desorption peak commensurate with desorption of the last of the ASW overlayer. The evolution of this trapping peak with overlayer thickness is the basis for determining the distribution of crystallization induced cracks through the ASW. Reflection adsorption infrared spectroscopy (RAIRS) and TPD of multicomponent parfait structures of ASW, O2 and Kr indicate that a preponderance of these cracks propagate down from the outer surface of the ASW.

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

Gamma Radiation Effects in Amorphous and Crystalline Polyaryletherketones

This work investigates the effect of gamma radiation on chain scission and crosslinking in polyaryletherketone (PAEK) thermoplastic filaments, namely, polyetheretherketone (PEEK) and polyetherketoneketone (PEKK) that is either semicrystalline (PEKK-c) or highly amorphous (PEKK-a). The PAEK thermoplastic filaments were exposed to total ionizing doses (TID) of gamma radiation from 1 to 8 MGy in the Gamma Irradiation Facility at Sandia National Laboratories. A combination of thermal and FT-IR spectral analysis of the irradiated specimens was used to study the chain scission and crosslinking behavior between PEEK, PEKK-c, and PEKK-a. Crystallinity decreased with increased TID and melt enthalpy decreased. Despite clear indications of changes to melt and crystallization behavior, any change to the glass-transition temperature was minor until a post-irradiation thermal annealing occurred, which caused an increase in crystallinity. Gamma radiation impacted PEKK-a more due to the lower degree of initial crystallinity, where a reduction in melt enthalpy, crystallinity, and crystallization kinetics was observed. Despite these effects, the ability to achieve a higher degree of crystallization (X c < 20%) by annealing was not affected. The results presented here provide important insight into the performance of a class of commercialized PEKK thermoplastics exposed to a harsh radiation environment.

Crystallinity↗
DOE OSTI2017

Hidden amorphous phase and reentrant supercooled liquid in Pd-Ni-P metallic glasses

An anomaly in differential scanning calorimetry has been reported in a number of metallic glass materials in which a broad exothermal peak was observed between the glass and crystallization temperatures. The mystery surrounding this calorimetric anomaly is epitomized by four decades long studies of Pd-Ni-P metallic glasses, arguably the best glass-forming alloys. Here we show, using a suite of in-situ experimental techniques, that Pd-Ni-P alloys have a hidden amorphous phase in the supercooled liquid region. The anomalous exothermal peak is the consequence of a polyamorphous phase transition between two supercooled liquids, involving a change in the packing of atomic clusters over medium-range length scales as large as 18 Å. With further temperature increase, the alloy reenters the supercooled liquid phase which forms the room-temperature glass phase upon quenching. Finally, the outcome of this study raises a possibility to manipulate the structure and hence the stability of metallic glasses through heat-treatment.

36 MATERIALS SCIENCE↗
DOE OSTI2017

High-harmonic generation in amorphous solids

High-harmonic generation in isolated atoms and molecules has been widely utilized in extreme ultraviolet photonics and attosecond pulse metrology. Recently, high-harmonic generation has been observed in solids, which could lead to important applications such as all-optical methods to image valance charge density and reconstruct electronic band structures, as well as compact extreme ultraviolet light sources. So far these studies are confined to crystalline solids; therefore, decoupling the respective roles of long-range periodicity and high density has been challenging. Here we report the observation of high-harmonic generation from amorphous fused silica. We also decouple the role of long-range periodicity by comparing harmonics generated from fused silica and crystalline quartz, which contain the same atomic constituents but differ in long-range periodicity. These results advance current understanding of the strong-field processes leading to high-harmonic generation in solids with implications for the development of robust and compact extreme ultraviolet light sources.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Predicting orientation-dependent plastic susceptibility from static structure in amorphous solids via deep learning

It has been a long-standing materials science challenge to establish structure-property relations in amorphous solids. Here we introduce a rotationally non-invariant local structure representation that enables different predictions for different loading orientations, which is found essential for high-fidelity prediction of the propensity for stress-driven shear transformations. This novel structure representation, when combined with convolutional neural network (CNN), a powerful deep learning algorithm, leads to unprecedented accuracy for identifying atoms with high propensity for shear transformations (i.e., plastic susceptibility), solely from the static structure in both two- and three-dimensional model glasses. The data-driven models trained on samples at one composition and a given processing history are found transferrable to glass samples with different processing histories or at different compositions in the same alloy system. Our analysis of the new structure representation also provides valuable insight into key atomic packing features that influence the local mechanical response and its anisotropy in glasses.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Eliminating chemo-mechanical degradation of lithium solid-state battery cathodes during >4.5 V cycling using amorphous Nb2O5 coatings

Abstract Lithium solid-state batteries offer improved safety and energy density. However, the limited stability of solid electrolytes (SEs), as well as irreversible structural and chemical changes in the cathode active material, can result in inferior electrochemical performance, particularly during high-voltage cycling (>4.3 V vs Li/Li + ). Therefore, new materials and strategies are needed to stabilize the cathode/SE interface and preserve the cathode material structure during high-voltage cycling. Here, we introduce a thin (~5 nm) conformal coating of amorphous Nb 2 O 5 on single-crystal LiNi 0.5 Mn 0.3 Co 0.2 O 2 cathode particles using rotary-bed atomic layer deposition (ALD). Full cells with Li 4 Ti 5 O 12 anodes and Nb 2 O 5 -coated cathodes demonstrate a higher initial Coulombic efficiency of 91.6% ± 0.5% compared to 82.2% ± 0.3% for the uncoated samples, along with improved rate capability (10x higher accessible capacity at 2C rate) and remarkable capacity retention during extended cycling (99.4% after 500 cycles at 4.7 V vs Li/Li + ). These improvements are associated with reduced cell polarization and interfacial impedance for the coated samples. Post-cycling electron microscopy analysis reveals that the Nb 2 O 5 coating remains intact and prevents the formation of spinel and rock-salt phases, which eliminates intra-particle cracking of the single-crystal cathode material. These findings demonstrate a potential pathway towards stable and high-performance solid-state batteries during high-voltage operation.

Science & Technology - Other Topics↗
DOE OSTI2023

Amorphous nickel hydroxide shell tailors local chemical environment on platinum surface for alkaline hydrogen evolution reaction

In analogy to natural enzymes, an elaborated design of catalytic systems with a specifically tailored local chemical environment could substantially improve reaction kinetics, effectively combat catalyst poisoning effect and boost catalyst lifetime under unfavourable reaction conditions. Here we report a unique design of ‘Ni(OH) 2 -clothed Pt-tetrapods’ with an amorphous Ni(OH) 2 shell as a water dissociation catalyst and a proton conductive encapsulation layer to isolate the Pt core from bulk alkaline electrolyte while ensuring efficient proton supply to the active Pt sites. This design creates a favourable local chemical environment to result in acidic-like hydrogen evolution reaction kinetics with a lowest Tafel slope of 27 mV per decade and a record-high specific activity and mass activity in alkaline electrolyte. The proton conductive Ni(OH) 2 shell can also effectively reject impurity ions and retard the Oswald ripening, endowing a high tolerance to solution impurities and exceptional long-term durability that is difficult to achieve in the naked Pt catalysts. Furthermore, the markedly improved hydrogen evolution reaction activity and durability in an alkaline medium promise an attractive catalyst material for alkaline water electrolysers and renewable chemical fuel generation.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Revealing key structures for reversible sulfur redox in amorphous polymeric sulfur

Amorphous polymeric sulfur cathodes, such as sulfurized polyacrylonitrile (SPAN), enable high-energy lithium-sulfur batteries without cobalt or nickel, leveraging abundant sulfur. However, the limited in situ understanding of their synthesis and electrochemistry has impeded targeted optimization. Here, in this study, we integrate operando high-energy total scattering with sulfur K-edge X-ray absorption spectroscopy to monitor SPAN's formation and cycling in real time. Our results show that S-C bond formation halts further fusion of cyclized polyacrylonitrile, fostering π-π stacking and a transition from long-chain to short-chain sulfur-critical for reversible sulfur redox. These features synergistically minimize polysulfide dissolution and charge-transfer resistance, enabling optimized SPAN to achieve high capacity retention over 1,000 cycles. Operando X-ray absorption spectroscopy reveals that residual protons drive thiol-thione tautomerism, with lithium replacement during the first discharge causing ~20% irreversible capacity loss. To enhance performance, minimizing -NH groups and expanding pyridine networks are key. These findings transform SPAN optimization from empirical tuning to mechanism‑guided engineering and point the way towards sulfur loadings and energy densities competitive with state‑of‑the‑art Li‑ion cathodes.

25 ENERGY STORAGE↗
DOE OSTI2017

X-ray spectroscopic study of amorphous and polycrystalline PbO films, α-PbO, and β-PbO for direct conversion imaging

We investigated the electronic structure of Lead Oxide (PbO) – one of the most promising photoconductor materials for direct conversion x-ray imaging detectors, using soft x-ray emission and absorption spectroscopy. Two structural configurations of thin PbO layers, namely the polycrystalline and the amorphous phase, were studied, and compared to the properties of powdered α-PbO and β-PbO samples. In addition, we performed calculations within the framework of density functional theory and found an excellent agreement between the calculated and the measured absorption and emission spectra, which indicates high accuracy of our structural models. Our work provides strong evidence that the electronic structure of PbO layers, specifically the width of the band gap and the presence of additional interband and intraband states in both conduction and valence band, depend on the deposition conditions. We tested several model structures using DFT simulations to understand what the origin of these states is. The presence of O vacancies is the most plausible explanation for these additional electronic states. Several other plausible models were ruled out including interstitial O, dislocated O and the presence of significant lattice stress in PbO.

42 ENGINEERING↗
DOE OSTI2017

High-fraction brookite films from amorphous precursors

Structure-specific synthesis processes are of key importance to the growth of polymorphic functional compounds such as TiO 2 , where material properties strongly depend on structure as well as chemistry. The robust growth of the brookite polymorph of TiO 2 , a promising photocatalyst, has been difficult in both powder and thin-film forms due to the disparity of reported synthesis techniques, their highly specific nature, and lack of mechanistic understanding. In this work, we report the growth of high-fraction (~95%) brookite thin films prepared by annealing amorphous titania precursor films deposited by pulsed laser deposition. We characterize the crystallization process, eliminating the previously suggested roles of substrate templating and Na helper ions in driving brookite formation. Instead, we link phase selection directly to film thickness, offering a novel, generalizable route to brookite growth that does not rely on the presence of extraneous elements or particular lattice-matched substrates. In addition to providing a new synthesis route to brookite thin films, our results take a step towards resolving the problem of phase selection in TiO 2 growth, contributing to the further development of this promising functional material.

14 SOLAR ENERGY↗
DOE OSTI2018

Rapid and damage-free outgassing of implanted helium from amorphous silicon oxycarbide

Damage caused by implanted helium (He) is a major concern for material performance in future nuclear reactors. We use a combination of experiments and modeling to demonstrate that amorphous silicon oxycarbide (SiOC) is immune to He-induced damage. By contrast with other solids, where implanted He becomes immobilized in nanometer-scale precipitates, He in SiOC remains in solution and outgasses from the material via atomic-scale diffusion without damaging its free surfaces. However, the behavior of He in SiOC is not sensitive to the exact concentration of carbon and hydrogen in this material, indicating that the composition of SiOC may be tuned to optimize other properties without compromising resistance to implanted He.

42 ENGINEERING↗
DOE OSTI2018

Ultrathin amorphous carbon films synthesized by filtered cathodic vacuum arc used as protective overcoats of heat-assisted magnetic recording heads

Despite numerous investigations of amorphous carbon (a-C) films, a comprehensive study of the feasibility and optimization of sub-5-nm-thick a-C films deposited onto the write pole of heat-assisted magnetic recording (HAMR) heads is lacking. The main objective of this study was to identify the role of pulse substrate bias voltage and C+ ion incidence angle on the structure and thickness of 1–4-nm-thick a-C films deposited by a rather new thin-film deposition method, known as filtered cathodic vacuum arc (FCVA). The cross-sectional structure of a-C films synthesized under various FCVA conditions was examined by high-resolution transmission electron microscopy (HRTEM), scanning transmission electron microscopy (STEM), and electron energy loss spectroscopy (EELS). It was found that film growth under process conditions of low-to-intermediate substrate bias voltage (in the range of -25 to -100 V), low ion incidence angle (10°), very short deposition time (6 s), and fixed other deposition parameters (65% duty cycle of substrate pulse biasing and 1.48 × 10 19 ions/m 2 ·s ion flux) yields a-C films of thickness ≤4 nm characterized by a significant content (~50–60 at%) of tetrahedral ( sp 3 ) carbon atom hybridization. A threshold where sp 3 hybridization is greatly reduced due to limited film growth was determined from the HRTEM/STEM and EELS measurements. The results of this study demonstrate the viability of FCVA to produce extremely thin and uniform protective a-C films with relatively high sp 3 contents for HAMR heads.

Science & Technology - Other Topics↗
DOE OSTI2019

Mechanical Response of He-Implanted Amorphous SiOC/Crystalline Fe Nanolaminates

This study investigates the microstructural evolution and mechanical response of sputter-deposited amorphous silicon oxycarbide (SiOC)/crystalline Fe nanolaminates, a single layer SiOC film, and a single layer Fe film subjected to ion implantation at room temperature to obtain a maximum He concentration of 5 at. %. X-ray diffraction and transmission electron microscopy indicated no evidence of implantation-induced phase transformation or layer breakdown in the nanolaminates. Implantation resulted in the formation of He bubbles and an increase in the average size of the Fe grains in the individual Fe layers of the nanolaminates and the single layer Fe film, but the bubble density and grain size were found to be smaller in the former. By reducing the thicknesses of individual layers in the nanolaminates, bubble density and grain size were further decreased. No He bubbles were observed in the SiOC layers of the nanolaminates and the single layer SiOC film. Nanoindentation and scanning probe microscopy revealed an increase in the hardness of both single layer SiOC and Fe films after implantation. For the nanolaminates, changes in hardness were found to depend on the thicknesses of the individual layers, where reducing the layer thickness to 14 nm resulted in mitigation of implantation-induced hardening.

77 NANOSCIENCE AND NANOTECHNOLOGY↗