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Results for “solid solution mechanism”

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 289 records · Page 16
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Surface Protection and Catalytic CH Alumination

This dataset supports a publication, "Surface Protected Organozirconium Catalyzes C–H Alumination of Saturated Hydrocarbons", and describes the surface-organozirconium catalyzed exchange of ethyl group in AlEt3 for dodecyl or methyl from dodecane or methane. The research describes the benefits of capping remaining surface OH with SiMe3 for improving yields and turnovers. The dataset includes characterization of the precatalyst using solid-state nuclear magnetic resonance spectroscopy and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), as well as gas chromatography and solution NMR of reaction products.

Catalysis and mechanisms of reactions↗
DOE OSTI2026

Entropy-defect synergy for dual luminescence mechanism in spinel: Time-resolved anti-counterfeiting and fingerprint visualization

Multimodal luminescent materials, while promising for anti-counterfeiting, often lack dynamic time-dependent responses and controllable spatial distribution, limiting their encryption capabilities in the spatiotemporal dimension. Here, this work presents a coordinated control strategy based on entropy and defect engineering, and uses a backpropagation (BP) neural network for material screening to successfully prepare spinel Mg 0.8 (Fe 0.04 Co 0.04 Ni 0.04 Cu 0.04 Zn 0.04 )Cr 2 O 4 (MgA 5 CO) phosphors with time-dependent dynamic luminescence behavior. This phosphor simultaneously activated the d-d transition luminescence (∼618 nm) derived from Co 2+ /Cr 3+ and the defect luminescence (∼398 nm) related to zinc vacancies (V Zn ) in a single-phase solid solution. The phosphor exhibits a time-dependent color evolution from pink to purple under fixed-wavelength excitation, due to the different excited-state dynamics and decay lifetimes associated with the d-d transition and defect luminescence. Structural characterization and spectral analysis confirmed the existence of V Zn and its significant role in defect luminescence process. The fluorescent and dynamic luminescent properties of entropy-based spinel oxide enable its use in advanced anti-counterfeiting applications like fingerprint recognition and color-changing dedicated anti-counterfeiting mark, showing promise in high-end and time-dynamic anti-counterfeiting fields. This research not only developed a new type of fluorescent dynamic anti-counterfeiting material, but also provided a new idea for constructing advanced optical functional materials with multiple luminescence mechanisms.

Defect project↗
DOE OSTI2024

Manipulating the diffusion energy barrier at the lithium metal electrolyte interface for dendrite-free long-life batteries

Abstract Constructing an artificial solid electrolyte interphase (SEI) on lithium metal electrodes is a promising approach to address the rampant growth of dangerous lithium morphologies (dendritic and dead Li 0 ) and low Coulombic efficiency that plague development of lithium metal batteries, but how Li + transport behavior in the SEI is coupled with mechanical properties remains unknown. We demonstrate here a facile and scalable solution-processed approach to form a Li 3 N-rich SEI with a phase-pure crystalline structure that minimizes the diffusion energy barrier of Li + across the SEI. Compared with a polycrystalline Li 3 N SEI obtained from conventional practice, the phase-pure/single crystalline Li 3 N-rich SEI constitutes an interphase of high mechanical strength and low Li + diffusion barrier. We elucidate the correlation among Li + transference number, diffusion behavior, concentration gradient, and the stability of the lithium metal electrode by integrating phase field simulations with experiments. We demonstrate improved reversibility and charge/discharge cycling behaviors for both symmetric cells and full lithium-metal batteries constructed with this Li 3 N-rich SEI. These studies may cast new insight into the design and engineering of an ideal artificial SEI for stable and high-performance lithium metal batteries.

25 ENERGY STORAGE↗
DOE OSTI2022

The Schwarz alternating method for transient solid dynamics

Abstract In our earlier work, we formulated the Schwarz alternating method as a means for concurrent multiscale coupling in finite deformation solid mechanics for quasi‐static problems. Herein, we advance this method for the study of transient dynamic multiscale solid mechanics problems where information is exchanged back and forth between small and large scales. The extension to dynamics relies on the notion of a global time stepper. Within each global time step, the subdomains are coupled by the standard Schwarz iterative process. Remarkably, each subdomain can use its own time step or even its own time integrator to advance its solution in time, provided that they synchronize at each global time step. We study the performance of the Schwarz method on several examples designed for this purpose. Our numerical experiments demonstrate that the method is capable of coupling regions with different mesh resolutions, different element types, and different time integration schemes (e.g., implicit and explicit), all without introducing any artifacts that afflict other coupling methods for transient dynamics. Finally, we apply the dynamic Schwarz alternating method to the simulation of a bolted joint subjected to dynamic loading, as a demonstration of the performance of the method in a realistic scenario.

Mota, Alejandro↗
DOE OSTI2020

Leaching Kinetics of Rare Earth Elements from Fire Clay Seam Coal

Recovery of rare earth elements (REEs) from coal samples collected from the Fire Clay coal seam using diluted mineral acid solutions was investigated. The initial processing step was coal recovery using conventional froth flotation which concentrated the REEs in tailing material resulting in an upgrade to values around 700 ppm on a dry whole mass basis. Leaching experiments were performed on the flotation tailings material using a 1.2 M sulfuric acid solution adjusted to a temperature of 75 °C to study the extractability of REEs from coal material. The effect of particle size, leaching time, leaching temperature, and solid concentration on REE leaching recovery were evaluated. The kinetic data obtained from leaching over a range of temperatures suggested that the leaching process follows the shrinking core model with possibly a mixed control mechanism that may be a result of several heterogenous materials leaching simultaneously. Leaching recovery increased rapidly at the beginning of the reaction then slowed as the system reached equilibrium. The apparent activation energy determined from test data obtained over a range of temperatures using 1 M sulfuric acid was 36 kJ/mol for the first 20 min of reaction time and 27 kJ/mol for the leaching period between 20 and 120 min. The leaching of light REEs during the initial stage was determined to be driven by a chemical reaction, followed by the formation of a product layer, which required lower activation energy in the later stage of leaching. In regards to the heavy REEs, the major mechanism for leaching is desorption and the product layer formation does not affect the heavy REEs significantly.

58 GEOSCIENCES↗
DOE OSTI2020

Modeling of surface mechanical behaviors of soft elastic solids: theory and examples

Surfaces of soft solids can have significant surface stress, extensional modulus and bending stiffness. Previous theoretical studies have usually examined cases in which both the surface stress and bending stiffness are constant, assuming small deformation. In this work we consider a general formulation in which the surface can support large deformation and carry both surface stresses and surface bending moments. We show that the large deformation theory can be reduced to the classical linear theory (Shuttleworth equation). We obtain exact solutions for problems of an inflated cylindrical shell and bending of a plate with a finite thickness. Our analysis illustrates the different manners in which surface stiffening and surface bending stabilize these structures. We discuss how the complex surface constitutive behaviors affect the stress field of the bulk. Our calculation provides insights into effects of strain-dependent surface stress and surface bending in the large deformation regime, and can be used as a model to implement surface finite elements to study large deformation of complex structures.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Improved creep performance of CoCrFeNi high entropy alloys by Mo addition

The CoCrFeNi family of high entropy alloys has good mechanical and corrosion properties, performing like stainless steels with low yield stresses. They could, however, benefit from hardening methods for structural and high temperature applications. Here, this work investigates the potential for the CoCrFeNi alloy to be hardened with the addition of Mo. A series of CoCrFeNiMo alloys and their CoCrFeNi counterparts were subsequently manufactured at NETL and then mechanically creep tested at 650°C. The alloys were designed to possess a range of stacking fault energies which influence the mechanical properties of the alloys via the motion of their dislocations under stress. Results show that Mo-containing variants have creep rupture lives ranging from 4000 to 8000 hours, i.e., about two orders of magnitude longer than those for Mo-free variants. The significantly improved creep performance of the Mo-containing alloys is due to a combination of solid solution strengthening and precipitation strengthening from µ-phase and carbides.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Localized high concentration electrolytes decomposition under electron-rich environments

Localized high concentration electrolytes have been proposed as an effective route to construct stable solid–electrolyte interphase (SEI) layers near Li-metal anodes. However, there is still a limited understanding of decomposition mechanisms of electrolyte components during SEI formation. In this work, we investigate reactivities of lithium bis(fluorosulfonyl)imide (LiFSI, salt), 1,2-dimethoxyethane (DME, solvent) and tris(2,2,2-trifluoroethyl)orthoformate (TFEO, diluent) species in DME+TFEO mixed solvents and 1M LiFSI/DME/TFEO solutions. By supplying excess of electrons into the simulation cell, LiFSI is initially reduced via a 4-electron charge transferring reaction yielding F - and N(SO 2 ) 2 3- . The local solvation environment has little effect on the subsequent TFEO reaction, which typically requires 6 |e| to decompose into F - , HCOO - , CH2CF and - OCH 2 CF 3 . Besides, TFEO dehydrogenation reaction mechanism under the attack of anions is also identified. Unlike salt and diluent, DME shows good stability with any excess of electrons. Here, the energetics of most relevant reactions are characterized. Most reactions are thermodynamically favorable with low activation barriers.

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

Probing the pH Effect on Boehmite Particles in Water Using Vacuum Ultraviolet Single-Photon Ionization Mass Spectrometry

Boehmite has been widely used in theoretical research and industry, especially for hazardous material processing. For the liquid-phase treating process, the interfacial properties of boehmite are believed to be affected by pH conditions, which change its physicochemical behavior. However, molecular-level detection on cluster ions is challenging when using bulk approaches. Herein we employ in situ vacuum ultraviolet single-photon ionization mass spectrometry (VUV SPI-MS) coupled with a vacuum-compatible microreactor system for analysis at the liquid–vacuum interface (SALVI) to investigate the solute molecular composition of boehmite under different pH conditions for the first time. The mass spectral results show that more complex clustering of solute molecules exists at the solid–liquid (s–l) interface than conventionally perceived in a “simple” aqueous solution. Besides solute ions, such as boehmite molecules and fragments, the composition and appearance energies of these newly discovered solvated cluster ions are determined by VUV SPI-MS in different pH solutions. We offer new results for the pH-dependent effect of boehmite and provide insights into a more detailed solvation mechanism at the s–l interface. By comparing the key products under different pH conditions, fundamental understanding of boehmite dissolution is revealed to assist the engineering design of waste processing and storage solutions.

SALVI↗
DOE OSTI2022

Understanding Solid-Electrolyte Interphase Formation at the Lithium Metal Anode of Lithium-Sulfur Batteries

Lithium-sulfur (Li-S) batteries are one of the most promising chemistries for the next generation of energy storage devices. In a standard Li-S cell, the metallic lithium anode is an essential component of the battery due to its low density, extremely high theoretical specific capacity, and very low negative electrochemical potential. However, several challenges related to the use of Li metal have prevented this battery technology from becoming commercially available. For instance, Li-anodes are highly reactive, which results in the continuous decomposition of the electrolyte and the formation of the solid-electrolyte interphase (SEI) layer. This, combined with the non-uniform deposition of Liions during plating at the anode surface, can seriously affect the performance, cycling, and safety of the battery. In addition, it has been suggested that a controlled SEI formation at the metallic Li anode can yield enhanced battery performance. Hence, a comprehensive understanding of how the SEI layer is formed can help elucidate improvements in this battery technology. In this work, the formation of the SEI layer in Li-S batteries is investigated using density functional theory (DFT) and ab initio molecular dynamics (AIMD) simulations. The stability of liquid organic-based electrolyte components, salt concentration, electron-rich environments, and the use of inorganic solid-state electrolyte (SSE) materials are explored in order to provide molecular-level fundamental insights into how the nature and composition of the electrolyte can alter the initial stages of the SEI formation. The products of electrolyte decomposition and electro-/chemical reaction pathways of liquid electrolyte component such as solvent and salts are predicted from AIMD simulations of electrolyte-anode interfaces. Energetics of reactions from DFT ground-state optimizations are also presented to confirm the decomposition mechanisms. Some significant differences are then drawn regarding the use of low and high salt concentrations. Simulations under electron-rich environments show additional multielectron electrochemical reactions of solvent and salt decomposition taking place due to the excess of electrons and the presence of radical anions in the solution. Finally, the initial stages of formation, stability, and main constituents of interfaces between Li-metal and Sbased electrodes with sulfide-based SSEs are characterized in detail.

25 ENERGY STORAGE↗
DOE OSTI2022

Microscale THMC Modeling of Pressure Solution in Salt Rock: Impacts of Geometry and Temperature

Abstract Pressure solution, a mechanism that involves tight coupling between the geometry and thermal-hydro-mechanical-chemical (THMC) processes, plays an important role in diagenesis. In this study, we make the first attempt to conduct microscale THMC modeling to understand and quantify the impacts of geometry and temperature on pressure solution, taking natural salt rock as an example. This modeling capability is achieved by expanding a novel MC code that we developed previously (Hu et al. J Geophys Res: Solid Earth 126:e2021JB023112, 2021) to include temperature effects. We first conduct a simulation of an example that involves a single brine inclusion within a single halite grain and find that the temperature impact is limited for that case. We then extract geometry from an image of a natural salt rock and conduct simulations with different cases: (A) only temperature and no stress, (B) only stress and no temperature, and (C) with both stress and temperature. These different cases result in quite different phenomena. In case A, dissolution and precipitation occur across the entire system due to isolated pore space reaching a localized mass balance between dissolution, precipitation, and diffusion. In case B, intense geometric features (e.g., major asperities, inclusions) in one area undergo stress concentration, thus dominating pressure solution in that area. In case C, pressure solution is spread out at contacting highly stressed geometric features close to the hotter side. We conclude that geometric features dominate stress distribution, thus dominating pressure solution in a natural salt rock that may be affected by the temperature if a sufficient temperature gradient is applied.

58 GEOSCIENCES↗
DOE OSTI2021

The mechanism driving a solid–solid phase transition in a biomacromolecular crystal

A solid-solid phase transition (SSPT) occurs between distinguishable crystalline forms. Because of its importance in application and theory in material science and condensed matter physics, SSPT has been studied most extensively in metallic alloys, inorganic salt or small organic molecular crystals, but much less so in biomacromolecular crystals. In general, the mechanism of SSPT at atomic and molecular levels is not well understood. Here, we describe the ordered molecular rearrangements in biomacromolecular crystals of the adenine riboswitch (riboA) aptamer using real-time serial crystallography and solution atomic force microscopy (AFM). The large, ligand-induced conformational changes drive the initial phase transition from the apo unit cell (AUC) to the trans unit cell 1 (TUC1). During this transition, coaxial stacking of P1 duplexes becomes the dominant packing interface, whereas P2-P2 interactions are almost completely disrupted, resulting in “floating” layers of molecules. The coupling points in TUC1 and their local conformational flexibility allow the molecules to reorganize to achieve the more densely packed and energetically favorable bound unit cell (BUC). Our study thus reveals the interplay between the conformational changes and the crystal phases—the underlying mechanism that drives the phase transition. Using polarized video microscopy (PVM) to monitor the SSPT in small crystals at high ligand concentration, we have identified the time window during which the major conformational changes take place, and simulated the in crystallo kinetics. Together, these results provide the spatiotemporal information necessary for informing time-resolved crystallography (TRX) experiments. Moreover, this study illustrates a practical approach to characterize SSPT in transparent crystals.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Hydrolysis of methylphosphonic anhydride solid to methylphosphonic acid probed by Raman and infrared reflectance spectroscopies

Much is still unknown about the mechanisms and rates of environmental degradation of organophosphorous pesticides and agents. In this study we focus on the degradation of one organophosphorous compound, namely solid methyl phosphonic acid anhydride [CH3P(O)OHOP(O)OHCH3, MPAN] and its rate of conversion to methyl phosphonic acid (MPA) via heterogeneous hydrolysis. Pure MPAN was synthesized and loaded in open sample cups placed inside exposure chambers containing saturated salt solutions to control the relative humidity (RH). The reaction was monitored in the sample cup at various times using both infrared hemispherical reflectance (HRF) spectroscopy and Raman spectroscopy. Calibrated HRF and Raman spectra of both pure reagents as well as gravimetrically prepared mixtures were used to quantify the concentrations of MPAN and MPA throughout the reaction. Results show that both HRF and Raman spectroscopies are convenient non-invasive methods for detection of solid chemicals. The MPAN degradation rate displayed a very strong dependence on relative humidity: At room temperature the reaction showed 50% conversion of the MPAN in 761 ± 54 hours at 33% RH, 33 ± 4 hours at 43% RH, 17 ± 2 hours at 54% RH and just 7 ± 1 hours at 75% RH. Although MPAN hydrolysis is a second-order reaction, the 33 and 43% RH data, at early reaction times, could be fit with a zeroth order reaction, indicating water vapor and MPAN concentrations were not initially rate controlling. The 54 and 75% RH experiments showed significant deliquescence and decay data could only be fit assuming multiple reactions, implying chemical and/or physical processes partially controlled the hydrolysis rate, in contrast to a single process at low relative humidity.

methyl phosphonic acid, methyl phosphonic anhydrid↗
DOE OSTI2021

Unveiling enhanced oxidation resistance and mechanical integrity of multicomponent ultra–high temperature carbides

The development of a new class of multicomponent ultra-high temperature ceramics (MC-UHTCs), often referred to as high-entropy UHTCs, has gained increased interest due to the possibility of improved thermomechanical and oxidation properties. In this study, a systematic approach by gradual addition in the UHTC components ranging from a binary to a dense quaternary (Ta,Nb,Hf,Ti)C is synthesized using spark plasma sintering (SPS). The solid solutioning was the critical factor in homogenizing the composition in the multicomponent system. The segregation of NbC and HfC was seen in binary and ternary UHTC systems, while a single-phase homogeneity was observed in the quaternary UHTC improving its hardness up to 34.8 GPa. The presence of closely spaced slip lines in the MC-UHTCs enhances resistance to indentation damage up to 72% at an applied load of 200 N. The formation of complex mixed oxide phase of Hf6Ta2O17 ensued in the lower to negligible oxidation even up to 3 min of plasma exposure with temperature exceeding 2800°C. In sum, though the entropy remains medium (0.96R) for the selected system, the quaternary UHTC system undoubtedly has significantly better thermomechanical performance when compared to established baseline UHTCs. Furthermore, this raises the debate on the justification for calling a multicomponent system a “high entropy” to be seen in a new light. The developed MC-UHTCs elicits the paradigm of this new class of UHTCs expanding their potential in thermal protection systems for hypersonic applications.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Phase-field modeling of rate-dependent fluid-driven fracture initiation and propagation

The rate-dependent behavior associated with deformation and fracturing of materials, such as natural rocks, poses significant challenges for modeling. In addition to the complications of the viscoelastic response, the speed of fracture propagation reflects micromechanical mechanisms in the fracture process zone(FPZ). In order to represent these complicated behaviors, a thermodynamically consistent, rate-dependent fracture model is required. Based on rigorous thermodynamic principles, we derive a rate-dependent phase-field mechanical model coupled with single-phase fluid flow in both the matrix and the fracture. The model is guaranteed to satisfy energy conservation during fracture propagation. Here, the system of equations is solved using the introduced solution procedure and a novel preconditioner that accounts for the complex fluid-structure interaction. The proposed phase-field model is tested against several benchmark problems on solid-fluid coupling, fluid-driven fracture propagation and rate-dependent viscoelastic deformation. The model serves as a strong basis for investigating rate-dependent fracturing experiments and for making predictions of material behaviors under new conditions.

42 ENGINEERING↗
DOE OSTI2025

Comparison of Nuclear Thermal Propulsion Reactor Cores Using Different Fuel Forms, Neutron Spectra, and Uranium Enrichments

A comparison of 300 MWt HEU and HALEU NTP cores using different fuel forms is presented to demonstrate trends and potentially inform fuel development. Compared to HEU, HALEU cores require additional in-core moderation. Beryllium was chosen as the reference in-core moderator material; metal hydrides may also be considered. Typical NTP fuel forms such as carbide and carbonitride solid solutions, carbide-graphite composites, CERMETs and CERCERs were considered together with less typical fuel forms such as UC and U metal. Be-moderated HALEU cores are heavier than HEU cores (1.9-2.7 and 0.9-2.0 metric tons, respectively). Furthermore, HALEU loading is very sensitive to the amount of in-core moderation which translates into tight fabrication tolerances. HALEU cores requires more reactivity control mechanisms than HEU cores to compensate for temperature feed-back. Using enrichments only slightly above HALEU (e.g., 25%) may provide a compromise between the administrative preference for using HALEU and the engineering preference for simplifying the reactor systems by, for example, not using in-core moderators.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2022

Pore-Scale Modeling of Mineral Growth and Nucleation in Reactive Flow

A fundamental understanding of mineral precipitation kinetics relies largely on microscopic observations of the dynamics of mineral surfaces exposed to supersaturated solutions. Deconvolution of tightly bound transport, surface reaction, and crystal nucleation phenomena still remains one of the main challenges. Particularly, the influence of these processes on texture and morphology of mineral precipitate remains unclear. This study presents a coupling of pore-scale reactive transport modeling with the Arbitrary Lagrangian-Eulerian approach for tracking evolution of explicit solid interface during mineral precipitation. It incorporates a heterogeneous nucleation mechanism according to Classical Nucleation Theory which can be turned “on” or “off.” This approach allows us to demonstrate the role of nucleation on precipitate texture with a focus at micrometer scale. In this work precipitate formation is modeled on a 10 micrometer radius particle in reactive flow. The evolution of explicit interface accounts for the surface curvature which is crucial at this scale in the regime of emerging instabilities. The results illustrate how the surface reaction and reactive fluid flow affect the shape of precipitate on a solid particle. It is shown that nucleation promotes the formation of irregularly shaped precipitate and diminishes the effect of the flow on the asymmetry of precipitation around the particle. The observed differences in precipitate structure are expected to be an important benchmark for reaction-driven precipitation in natural environments.

58 GEOSCIENCES↗
DOE OSTI2023

Synthesis and Structural Study of Substituted Ternary Nitrides for Ammonia Production

Over the past few decades, inorganic nitride materials have grown in importance in part due to their potential as catalysts for the synthesis of NH 3 , a key ingredient in fertilizer and precursor to industrial chemicals. Of particular interest are the ternary (ABN) or higher-order nitrides with high metal-to-nitrogen ratios that show promise in enhancing NH 3 synthesis reaction rates and yields via heterogeneous catalysis or chemical looping. Although metal nitrides are predicted to be numerous, the stability of nitrogen triple bonds found in N 2 , especially in comparison to the metal–nitrogen bonds, has considerably hindered synthetic efforts to produce complex nitride compounds. In this study, we present an exhaustive down-selection process to identify ternary nitrides for a promising chemical looping NH 3 production mechanism. We also report on a facile and efficient two-step synthesis method that can produce well-characterized η-carbide Co 3 Mo 3 N/Fe 3 Mo 3 N or filled β-manganese Ni 2 Mo 3 N ternaries, as well as their associated quaternary, (Co,Fe) 3 Mo 3 N, (Fe,Ni) 2 Mo 3 N, and (Co,Ni) 2 Mo 3 N, solid solutions. To further explore the quaternary space, syntheses of (Co,Ni) 3 Mo 3 N (Ni ≤ 10 mol %) and Co 3 (Mo,W) 3 N (W ≤ 10 mol %) were also investigated. The structures of the nitrides were characterized via X-ray powder diffraction. The morphology and compositions were characterized with scanning electron microscopy. In conclusion, the multitude of chemically unique, but structurally related, nitrides suggests that properties such as nitrogen activity may be tunable, making the materials of great interest for NH 3 synthesis schemes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗