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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 1,135 records · Page 63
All sourcesNASA NTRSDOE OSTI
DOE OSTI2019

Electrolyte Gated Oxides

Electrolyte gating has the potential to generate electric fields at the surface of materials in the 10 7 -10 8 V/cm range and induce charge carriers in these materials up to 10 14 -10 15 cm -2 , making this technique very attractive for studying complex and functional oxides. Several types of processes — notably including proton diffusion and intake — can occur during charging, which makes it crucially important to consider and understand exactly how a given material is interacting with an electrolyte. We report on several of these mechanisms and how to distinguish between them.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2019

Titanium Extraction from Spent Selective Catalytic Reduction Catalysts in a NaOH Molten-Salt System: Thermodynamic, Experimental, and Kinetic Studies

In this study, sodium hydroxide was used as an alkali reagent in roasting spent selective catalytic reduction (SCR) catalysts for titanium extraction. The thermodynamic analysis of the roasting process is discussed in terms of process design. The effects of various roasting parameters, such as the mass ratio of NaOH-to-SCR, temperature, and time, on the extraction efficiency of titanium were investigated; under the optimum parameters of 1.8:1, 550 °C, and 10 minutes, the titanium extraction yield reached 97.8 pct. The roasting kinetics of titanium extraction were also studied. The kinetics of titanium extraction follow the Avrami model, which is expressed as follows: −ln(1−x)=K{sub 0}C{sub m{sub N{sub a{sub O{sub H/m{sub S{sub C{sub R}{sup −2.012}}}}}}}}exp(−(4120/(8.314T)))t, and the overall roasting process is controlled by diffusion in the solid state, with an activation energy (E{sub a}) of 4.12 kJ/mol.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Examination of Dendritic Growth During Solidification of Ternary Alloys via a Novel Quantitative 3D Cellular Automaton Model

A three-dimensional (3D) quantitative cellular automaton (CA) model was developed to simulate dendritic growth during solidification processing of ternary alloys. A detailed method was proposed to solve solute diffusion and calculate the solid fraction for ternary alloys during solidification. The present model has been shown to accurately predict dendrite morphologies and solute distributions of both single equiaxed dendrite and columnar dendrites during solidification. The model was also used to study the influence of the concentration of a third component (Mg in the Al-Si-Mg system) on dendritic growth. With increasing Mg concentration, the steady-state dendrite tip growth velocity was shown to decrease, resulting in a shorter primary dendrite length. The 3D CA simulation results agree well with the prediction of the LGK theoretical model. Multi-columnar dendrite growth was simulated with different cooling rates. Primary and secondary dendrite morphology was shown to have little variation at low cooling rates (1.0 to 2.0 K/s) and a constant undercooling. The average secondary dendrite arm spacing was shown to decrease with the increase of cooling rate within this range. The 3D CA simulation results are in good agreement with the experimental directional solidification experiments of a commercial A356 (Al-7 wt pct Si-0.3 wt pct Mg).

36 MATERIALS SCIENCE↗
DOE OSTI2024

Achieving Metallurgical Bonding in Aluminum/Steel Bimetallic Castings

Abstract Aluminum castings are increasingly being used in automotive powertrain and structural applications for vehicle lightweighting. Cast aluminum parts often need to be machined and joined to steel components in multi-material systems. Bimetallic components produced by casting aluminum over steel substrate are advantageous due to the elimination of machining and traditional dissimilar material joining processes. However, forming a strong metallurgical bonding during overcasting process has been challenging. In this paper, the effects of processing conditions such as substrate surface preparation, pre-heating temperature, melt conditions as well as casting design were studied by investigating the bimetallic interfaces for aluminum A319 casting alloy and a high alloy steel substrate in a sand-casting process. Zn and Al-based substrate coatings were evaluated. The experimental results suggest a metallurgical bond between aluminum and steel can be formed during the sand-casting process via high temperature diffusion with or without coatings. Al-based substrate coating prior to overcasting results in the formation of a continuous layer of intermetallics at the bimetallic interface, with large Al–Si–Fe intermetallics penetrating the cast aluminum.

Moodispaw, Michael P. (ORCID:0000000267635882)↗
DOE OSTI2016

Binding and leaching of trace elements in Portland cement pastes

Portland cement contains trace elements originating from the raw materials and the fuels used for cement production. The trace elements are bound to some extent during cement hydration. A small fraction remains dissolved in the pore solution. The dissolved fractions of antimony, barium, chromium, lead, molybdenum and vanadium were quantified in the course of hydration of four different Portland cements. The development of heavy metal concentrations signifies the relevant hydration products for the binding of heavy metals. For chromate and molybdate a substitution for sulfate in ettringite was found. Vanadium and antimony are most likely not bound in ettringite. Barium precipitates as barium sulfate. For lead no clear trends could be observed. Leaching experiments were carried out and the concentrations of the leachates were compared to pore solution concentrations to check if the solubility of the heavy metals is relevant or if the leaching process is controlled by diffusion.

36 MATERIALS SCIENCE↗
DOE OSTI2018

An effective numerical algorithm for intra-granular fission gas release during non-equilibrium trapping and resolution

Both fission gas release and gaseous swelling in nuclear fuel are driven by the transport of fission gas from within the fuel grains to grain boundaries (intra-granular fission gas release). The process involves gas atom diffusion in conjunction with trapping in and resolution from intra-granular bubbles, and is described mathematically by a system of two partial differential equations (PDE). Following Speight, under the assumption of equilibrium between trapping and resolution (quasi-stationary approximation) the system can be reduced to a single diffusion equation with an effective diffusion coefficient. Numerical solutions used in engineering fuel performance calculations invariably rely on this simplification. First, we investigate the validity of the quasi-stationary approximation compared to the solution of the general system of PDEs. Results demonstrate that the approximation is valid under most conditions of practical interest, but is inadequate to model intra-granular fission gas release during rapid transients to relatively high temperatures such as postulated reactivity initiated accidents (RIA). Then, we develop a novel numerical algorithm for the solution of the general problem in time-varying conditions. We verify the PolyPole-2 algorithm against a reference finite difference solution for a large number of randomly generated operation histories including prototypical RIA transients. Results demonstrate that PolyPole-2 captures the solution of the general PDE system with a high accuracy and a low computational cost. As a result, the PolyPole-2 algorithm overcomes the quasi-stationary approximation and the concept of an effective diffusion coefficient for the solution of the intra-granular fission gas release problem in nuclear fuel analysis.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2020

The Instability of Monolayer-Thick PbSe on VSe 2

Two-dimensional monolayers derived from 3D bulk structures remain a relatively unexplored class of materials because of the challenge of stabilizing non-epitaxial interfaces. Here, we report an unusual reconstruction during the deposition of precursors when targeting the synthesis of heterostructures with an odd number of PbSe monolayers. Multilayer elemental precursors of Pb|Se + V|Se were deposited to have correct number of atoms to form [(PbSe) 1+δ ] q (VSe 2 ) 1 where q is the number of PbSe monolayers in the heterostructure. Structural analysis of the self-assembled precursor via xray reflectivity, x-ray diffraction, and HAADF-STEM suggests three different behaviors upon deposition. Precursors with q 7 and even values of q have the targeted nanoarchitectures after deposition which are maintained as the products are selfassembled through a near diffusionless process. Significant lateral surface diffusion occurred during deposition of precursors with q = 1, 3, and 5 resulting in the precursor having a different nanoarchitecture than targeted. Additional perpendicular long range diffusion occurs during self-assembly of these precursors resulting in different final products than targeted. DFT calculations of PbSe blocks show that the odd numbered layers are less stable than even numbered layers, which suggests an energetic driving force for the observed rearrangement. This work highlights the importance of understanding the reaction mechanism when attempting to prepare 2D layers of constituents with bulk 3D structures.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Building Materials from Colloidal Nanocrystal Assemblies: Molecular Control of Solid/Solid Interfaces in Nanostructured Tetragonal ZrO 2

We describe in this paper a bottom-up approach to control the composition of solid/solid interfaces in nanostructured materials, and we test its effectiveness on tetragonal ZrO 2 , an inorganic phase of great technological significance. Colloidal nanocrystals capped with trioctylphosphine oxide (TOPO) or oleic acid (OA) are deposited, and the organic fraction of the ligands is selectively etched with O 2 plasma. The interfaces in the resulting all-inorganic colloidal nanocrystal assemblies are either nearly bare (for OA-capped nanocrystals) or terminated with phosphate groups (for TOPO-capped nanocrystals) resulting from the reaction of phosphine oxide groups with plasma species. The chemical modification of the interfaces has extensive effects on the thermodynamics and kinetics of the material. Different growth kinetics indicate different rate limiting processes of growth (surface diffusion for the phosphate-terminated surfaces and dissolution for the “bare” surfaces). Phosphate termination led to a higher activation energy of growth, and a 3-fold reduction in interfacial energy, and facilitated significantly the conversion of the tetragonal phase into the monoclinic phase. Finally, films devoid of residual ligands persisted in the tetragonal phase at temperatures as high as 900 °C for 24 h.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Heterolytic Scission of Hydrogen Within a Crystalline Frustrated Lewis Pair

We report the heterolysis of molecular hydrogen under ambient conditions by the crystalline frustrated Lewis pair (FLP) 1-{2-[bis(pentafluorophenyl)boryl]phenyl}-2,2,6,6-tetramethylpiperidine (KCAT). The gas–solid reaction provides an approach to prepare the solvent-free, polycrystalline ion pair KCATH2 through a single crystal to single crystal transformation. The crystal lattice of KCATH2 increases in size relative to the parent KCAT by approximately 2%. Microscopy was used to follow the transformation of the highly colored red/orange KCAT to the colorless KCATH2 over a period of 2 h at 300 K under a flow of H2 gas. There is no evidence of crystal decrepitation during hydrogen uptake. Inelastic neutron scattering employed over a temperature range from 4–200 K did not provide evidence for the formation of polarized H2 in a precursor complex within the crystal at low temperatures and high pressures. However, at 300 K, the INS spectrum of KCAT transformed to the INS spectrum of KCATH2. Calculations suggest that the driving force is more favorable in the solid state compared to the solution or gas phase, but the addition of H2 into the KCAT crystal is unfavorable. Ab Initio methods were used to calculate the INS spectra of KCAT, KCATH2, and a possible precursor complex of H2 in the pocket between the B and N of crystalline KCAT. Ex-situ NMR showed that the transformation from KCAT to KCATH2 is quantitative and our results suggest that the hydrogen heterolysis process occurs via H2 diffusion into the FLP crystal with a rate-limiting movement of H2 from inactive positions to reactive sites.

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

Pinned Electrode/Electrolyte Interphase and Its Formation Origin for Sulfurized Polyacrylonitrile Cathode in Stable Lithium Batteries

Sulfurized polyacrylonitrile (SPAN) represents one of the most promising directions for high-energy-density lithium (Li)-sulfur batteries. However, the practical application of Li||SPAN is currently limited by the insufficient chemical/electrochemical stability of electrode/electrolyte interphase (EEI). Here, a pinned EEI layer is designed for stabilizing a SPAN cathode by regulating the EEI formation mechanism in an advanced LiFSI/ether/fluorinated-ether electrolyte. Computational simulations and experimental investigations reveal that, benefiting from the nonsolvating nature, the fluorinated-ether can not only act as a protective shield to prevent the Li polysulfides dissolution but also, more importantly, endow a diffusion-controlled EEI formation process. It promotes the formation of a uniform, protective, and conductive EEI layer pinning into SPAN surface region, enabling the high loading Li||SPAN batteries with superior cycling stability, wide temperature performance, and high-rate capability. Finally, this design strategy opens an avenue for exploring advanced electrolytes for Li||SPAN batteries and guides the interface design for broad types of battery systems.

25 ENERGY STORAGE↗
DOE OSTI2017

Porous Structured Ni–Fe–P Nanocubes Derived from a Prussian Blue Analogue as an Electrocatalyst for Efficient Overall Water Splitting

Exploring nonprecious metal electrocatalysts to replace the noble metal-based catalysts for full water electrocatalysis is still an ongoing challenge. In this work, porous structured ternary nickel–iron–phosphide (Ni–Fe–P) nanocubes were synthesized through one-step phosphidation of a Ni–Fe-based Prussian blue analogue. The Ni–Fe–P nanocubes exhibit a rough and loose porous structure on their surface under suitable phosphating temperature, which is favorable for the mass transfer and oxygen diffusion during the electrocatalysis process. As a result, Ni–Fe–P obtained at 350 °C with poorer crystallinity offers more unsaturated atoms as active sites to expedite the absorption of reactants. Additionally, the introduction of nickel improved the electronic structure and then reduced the charge-transfer resistance, which would result in a faster electron transport and an enhancement of the intrinsic electrocatalytic activities. Benefiting from the unique porous nanocubes and the chemical composition, the Ni–Fe–P nanocubes exhibit excellent hydrogen evolution reaction and oxygen evolution reaction activities in alkaline medium, with low overpotentials of 182 and 271 mV for delivering a current density of 10 mA cm–2, respectively. Moreover, the Ni–Fe–P nanocubes show outstanding stability for sustained water splitting in the two-electrode alkaline electrolyzer. Furthermore, this work not only provides a facile approach for designing bifunctional electrocatalysts but also further extends the application of metal–organic frameworks in overall water splitting.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Strain wave pathway to semiconductor-to-metal transition revealed by time-resolved X-ray powder diffraction

One of the main challenges in ultrafast material science is to trigger phase transitions with short pulses of light. Here we show how strain waves, launched by electronic and structural precursor phenomena, determine a coherent macroscopic transformation pathway for the semiconducting-to-metal transition in bistable Ti 3 O 5 nanocrystals. Employing femtosecond powder X-ray diffraction, we measure the lattice deformation in the phase transition as a function of time. We monitor the early intra-cell distortion around the light absorbing metal dimer and the long range deformations governed by acoustic waves propagating from the laser-exposed Ti 3 O 5 surface. We developed a simplified elastic model demonstrating that picosecond switching in nanocrystals happens concomitantly with the propagating acoustic wavefront, several decades faster than thermal processes governed by heat diffusion.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Entropic barriers in the kinetics of aqueous proton transfer

Aqueous proton transport is uniquely rapid among aqueous processes, mediated by fluctuating hydrogen bond reorganization in liquid water. In a process known as Grotthuss diffusion, the excess charge diffuses primarily by sequential proton transfers between water molecules rather than standard Brownian motion, which explains the anomalously high electrical conductivity of acidic solutions. Employing ultrafast IR spectroscopy, we use the orientational anisotropy decay of the bending vibrations of the hydrated proton complex to study herein the picosecond aqueous proton transfer kinetics as a function of temperature, concentration, and counterion. We find that the orientational anisotropy decay exhibits Arrhenius behavior, with an apparent activation energy of 2.4 kcal/mol in 1M and 2M HCl. Interestingly, acidic solutions at high concentration with longer proton transfer time scales display corresponding decreases in activation energy. We interpret this counterintuitive trend by considering the entropic and enthalpic contributions to the activation free energy for proton transfer. Halide counteranions at high concentrations impose entropic barriers to proton transfer in the form of constraints on the solution’s collective H-bond fluctuations and obstruction of potential proton transfer pathways. The corresponding proton transfer barrier decreases due to weaker water-halide H-bonds in close proximity to the excess proton, but the entropic effects dominate and

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

DISPERSAL OF G-BAND BRIGHT POINTS AT DIFFERENT LONGITUDINAL MAGNETIC FIELD STRENGTHS

G-band bright points (GBPs) are thought to be the foot-points of magnetic flux tubes. The aim of this paper is to investigate the relation between the diffusion regimes of GBPs and the associated longitudinal magnetic field strengths. Two high resolution observations of different magnetized environments were acquired with the Hinode/Solar Optical Telescope. Each observation was recorded simultaneously with G-band filtergrams and Narrow-band Filter Imager (NFI) Stokes I and V images. GBPs are identified and tracked automatically, and then categorized into several groups by their longitudinal magnetic field strengths, which are extracted from the calibrated NFI magnetograms using a point-by-point method. The Lagrangian approach and the distribution of diffusion indices approach are adopted separately to explore the diffusion regime of GBPs for each group. It is found that the values of diffusion index and diffusion coefficient both decrease exponentially with the increasing longitudinal magnetic field strengths whichever approach is used. The empirical formulas deduced from the fitting equations are proposed to describe these relations. Stronger elements tend to diffuse more slowly than weak elements, independently of the magnetic flux of the surrounding medium. This may be because the magnetic energy of stronger elements is not negligible compared with the kinetic energy of the gas, and therefore the flows cannot perturb them so easily.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2021

Photo-exfoliation of MoS 2 quantum dots from nanosheets: an in-situ transmission electron microscopy study

Fabrication of transition metal dichalcogenide (TMD) quantum dots (QDs) is complex and requires submerging of powders in binary solvents and the constant tuning of wavelength and pulsed frequency of light to achieve a desired reaction. Here,iInstead of liquid state photoexfoliation, we utilize infrared laser irradiation of free-standing MoS 2 flakes in transmission electron microscope (TEM) to achieve solid-state multi-level photoexfoliation of QDs. By investigating the steps involved in photochemical reaction between the surface of MoS 2 and the laser beam, we gain insight into each step of the photoexfoliation mechanism and observe high yield production of QDs, led by an inhomogeneous crystalline size distribution. Additionally, by using a laser with a lower energy than the indirect optical transition of bulk MoS 2 , we conclude that the underlying phenomena behind the photoexfoliation is from multi-photon absorption achieved at high optical outputs from the laser source. These findings provide an environmentally friendly synthesis method to fabricate QDs for potential applications in biomedicine, optoelectronics, and fluorescence sensing.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Atomistic Mechanism Underlying the Si ( 111 ) - ( 7 × 7 ) Surface Reconstruction Revealed by Artificial Neural-Network Potential

The 7×7 reconstruction of the Si(111) surface represents arguably the most fascinating surface reconstruction so far observed in nature. Yet, the atomistic mechanism underpinning its formation remains unclear after it was discovered sixty years ago. Experimentally, it is observed post priori so that analysis of its formation mechanism can only be carried out in analogy with archaeology. Theoretically, density-functional theory (DFT) correctly predicts the Si(111)-(7×7) ground state but is impractical to simulate its formation process; while empirical potentials failed to produce it as the ground state. Developing an artificial neural-network potential of DFT quality, we carried out accurate large-scale simulations to unravel the formation of the Si(111)-(7×7) surface. We reveal a possible step-mediated atom-pop rate-limiting process that triggers massive nonconserved atomic rearrangements, most remarkably, a critical process of collective vacancy diffusion that mediates a sequence of selective dimer, corner-hole, stacking-fault, and dimer-line pattern formation, to fulfill the 7×7 reconstruction. Our findings may not only solve the long-standing mystery of this famous surface reconstruction but they also illustrate the power of machine learning in studying complex structures.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Dissolved Organic Carbon 14C in Southern Nevada Groundwater and Implications for Groundwater Travel Times

Dissolved inorganic carbon (DIC) carbon-14 ( 14 C) ages must be corrected for complex chemical and physical reactions and processes that change the amount of 14 C in groundwater as it flows from recharge to downgradient areas. Because of these reactions, DIC 14 C can produce unrealistically old ages and long groundwater travel times that may, or may not, agree with travel times estimated by other methods. Dissolved organic carbon (DOC) 14 C ages are often younger than DIC 14 C ages because there are few chemical reactions or physical processes that change the amount of DOC 14 C in groundwater. However, there are several issues that create uncertainty in DOC 14 C groundwater ages including limited knowledge of the initial (A 0 ) DOC 14 C in groundwater recharge and potential changes in DOC composition as water moves through an aquifer. This study examines these issues by quantifying A 0 DOC 14 C in recharge areas of southern Nevada groundwater flow systems and by evaluating changes in DOC composition as water flows from recharge areas to downgradient areas. The effect of these processes on DOC 14 C groundwater ages is evaluated and DOC and DIC 14 C ages are then compared along several southern Nevada groundwater flow paths. Twenty-seven groundwater samples were collected from springs and wells in southern Nevada in upgradient, midgradient, and downgradient locations. DOC 14 C for upgradient samples ranged from 96 to 120 percent modern carbon (pmc) with an average of 106 pmc, verifying modern DOC 14 C ages in recharge areas, which decreases uncertainty in DOC 14 C A 0 values, groundwater ages, and travel times. The HPLC spectra of groundwater along a flow path in the Spring Mountains show the same general pattern indicating that the DOC compound composition does not change along this flow path. Although DOC concentration decreases from recharge-area to downgradient groundwater, the organic compounds are similar, indicating that DOC 14 C is unaffected by other processes such as microbial degradation. A small amount of organic carbon was leached from crushed volcanic and carbonate aquifer outcrop rock in rock-leaching experiments. The leached DOC was high in 14 C (75 pmc carbonate rocks, 91 pmc volcanic) suggesting that the leached DOC likely came from microbes in the rock samples. The small amount of DOC and high 14 C indicates that the amount of old organic carbon in these rocks is low so there should be minimal impact on groundwater DOC 14 C ages. Based on the results from this study, DOC 14 C ages do not require additional corrections. Several correction models were applied to DIC 14 C ages to correct for water-rock reactions along two carbonate and two volcanic flow paths and the corresponding travel times were compare to DOC 14 C travel times. The DOC 14 C travel times were hundreds to thousands of years shorter than uncorrected and corrected DIC 14 C travel times except for the upper section of one carbonate flow path. DOC 14 C travel times ranged from 400 to 5,400 years as compared to DIC 14 C that ranged from modern to 20,900 years. The DIC 14 C ages are greatly influenced by carbonate mineral and gas reactions and other processes such as matrix diffusion, isotope exchange, or adsorption, which are not always adequately accounted for in DIC 14 C groundwater age correction models.

54 ENVIRONMENTAL SCIENCES↗