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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 271 records · Page 15
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Discovery of charge density wave in a kagome lattice antiferromagnet

A hallmark of strongly correlated quantum materials is the rich phase diagram resulting from competing and intertwined phases with nearly degenerate ground state energies. A well-known example is the copper oxides, where a charge density wave (CDW) is ordered well above and strongly coupled to the magnetic order to form spin-charge separated stripes that compete with superconductivity. Recently, such rich phase diagrams have also been revealed in correlated topological materials. In two-dimensional kagome lattice metals consisting of corner-sharing triangles, the geometry of the lattice can produce flat bands with localized electrons, non-trivial topology, chiral magnetic order, superconductivity and CDW order. While CDW has been found in weakly electron correlated nonmagnetic AV 3 Sb 5 (A = K, Rb, Cs), it has not yet been observed in correlated magnetic ordered kagome lattice metals. Here we report the discovery of CDW within the antiferromagnetic (AFM) ordered phase of kagome lattice FeGe. The CDW in FeGe occurs at wavevectors identical to that of AV 3 Sb 5 , enhances the AFM ordered moment, and induces an emergent anomalous Hall effect. Furthermore, our findings suggest that CDW in FeGe arises from the combination of electron correlations-driven AFM order and van Hove singularities-driven instability possibly associated with a chiral flux phase, in stark contrast to strongly correlated copper oxides and nickelates, where the CDW precedes or accompanies the magnetic order.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Geochemical characterization of lithium deposition in fossil energy wastes

Lithium is a critical mineral used in rechargeable batteries for electric vehicles (EVs) and future modernization of electric grids with sensitive supply chains that are subject to volatility. Therefore, methods to recover lithium from domestic unconventional sources are actively being pursued in the United States. Herein, we report on the lithium recovery potential from four fossil energy waste feedstocks: oil and gas drill cuttings (sample number n = 16); oil and gas produced waters (n > 200) from Marcellus, Bakken and Permian basins; coal byproducts (n>20), such as coal ash; and acid mine drainage treatment solids (AMD solids). Select solid samples underwent sequential extraction to explore lithium hosting phases and simple organic and inorganic acid extraction to explore lithium recovery potential. Our preliminary results found lithium concentrations up to 440 mg/kg in select AMD treatment solids and up to 300 mg/L in Marcellus Shale produced waters, demonstrating these sources have lithium yield potentials comparable to conventionally mined lithium ores and brines. Sequential extractions revealed that lithium is mostly associated with clay and silicate phases in shale drill cuttings, whereas lithium resides in Fe,Mn-oxide reducible phases in AMD solids. Further, the lithium content in produced waters has a strong linear relationship with total dissolved solid (TDS) levels in three separate oil and gas basins. At the same TDS level, Marcellus Shale produced waters contain more lithium compared to Bakken Shale and Permian Basin waters, with higher percentages of Ca and Mg, major cations that might impact lithium recovery efficiencies. Our study demonstrates the heterogeneity of lithium hosts from different fossil energy wastes. Characterization results will inform future lithium recovery from these different feedstocks.

Stuckman, Mengling↗
DOE OSTI2022

Challenges and Opportunities of Fe-based Core-Shell Catalysts for Fischer-Tropsch Synthesis

Here, Fe-based catalysts are an active, selective, and low-cost option for tuning Fischer-Tropsch synthesis (FTS) selectivity toward desirable light olefins. By encapsulating Fe within ZSM-5, the resultant core-shell catalysts have the potential to control the product distribution via secondary reactions that occur over the acid sites of the zeolite shell. In this paper, Fe is encapsulated within ZSM-5 via the seed-directed growth technique and characterized with a suite of analytical techniques including Mössbauer spectroscopy and X-ray absorption fine structure (XAFS). Characterization of the core-shell catalysts indicates that some of the Fe-based active phase is destabilized during seed-directed growth, demonstrating the challenges associated with encapsulating an Fe-based active phase within zeolites. However, comparing FTS performance of the core-shell catalyst with the Fe-based control synthesized via incipient wetness impregnation demonstrates improved selectivity toward the desired C 2 -C 4 olefins and C 5+ hydrocarbons.

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

Charge carrier coupling to the soft phonon mode in a ferroelectric semiconductor

Many crystalline solids possess strongly anharmonic “soft” phonon modes characterized by diminishing frequency as temperature approaches a critical point associated with a symmetry breaking phase transition. While electron–soft phonon coupling can introduce unique scattering channels for charge carriers in ferroelectrics, recent studies on the nonferroelectric lead halide perovskites have also suggested the central role of anharmonic phonons bearing resemblance to soft modes in charge carrier screening. Here we apply coherent phonon spectroscopy to directly study electron coupling to the soft transverse optical phonon mode in a ferroelectric semiconductor SbSI. Photogenerated charge carriers in SbSI are found to be exceptionally long lived and are associated with a transient electro-optical effect that can be explained by interactions between charge carriers and thermally stimulated soft phonon excitations. Furthermore, these results provide strong evidence for the role of electron–soft phonon coupling in the efficient screening of charge carriers and in reducing charge recombination rates, both desirable properties for optoelectronics.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Contrasting phase changes of precipitation annual cycle between land and ocean under global warming

The annual cycle of precipitation is a fundamental aspect of the water cycle with global ramification. Climate warming induces a robust phase delay1-5 in zonal mean tropical precipitation concomitant with an amplitude enhancement6-8. Here, we find a large land ocean contrast in the phase response of precipitation annual cycle, with a phase delay over land and a phase advance over ocean as climate warms. The phase delay over land is mainly attributed to the increase in the effective heat capacity of the atmosphere, while the phase advance over ocean is associated with a precipitation shift from land to ocean during the peak rainy season. Through the energetic constraint, this precipitation shift is closely related to the opposite changes in the amplitude of surface temperature annual cycle between land and ocean, both as consequences of basic climate feedback processes under global warming: weakening of the summer trade wind over the tropical ocean increases the surface temperature seasonal amplitude through evaporation, while an increase of the atmospheric effective heat capacity and surface cooling feedback induces opposite temperature amplitude changes over the tropical land. The opposite precipitation phase changes between land and ocean will have myriad implications for terrestrial/marine ecosystems and human activities.

Song, Fengfei↗
DOE OSTI2020

Absence of Y-pocket in 1-Fe Brillouin zone and reversed orbital occupation imbalance in FeSe

The FeSe nematic phase has been the focus of recent research on iron-based superconductors (IBSs) due to its unusual properties, which are distinct from those of the pnictides. A series of theoretical/experimental studies were performed to determine the origin of the nematic phase. However, they yielded conflicting results and caused additional controversies. Here, we report the results of angle-resolved photoemission and X-ray absorption spectroscopy studies on FeSe detwinned by a piezo stack. We fully resolved band dispersions with orbital characters near the Brillouin zone (BZ) corner, and revealed an absence of any Fermi pocket at the Y point in the 1-Fe BZ. In addition, the occupation imbalance between d xz and d yz orbitals was the opposite of that of iron pnictides, consistent with the identified band characters. These results resolve issues associated with the FeSe nematic phase and shed light on the origin of the nematic phase in IBSs.

36 MATERIALS SCIENCE↗
DOE OSTI2021

A constitutive model for glass–ceramic materials

Glass–ceramics have received recent attention for use in glass–ceramic to metal hermetic seals. Due to their heterogeneous microstructure, these materials exhibit a number of advantageous responses over conventional glass based seals. Key amongst them is the possibility of a controllable thermal strain response and apparent coefficient of thermal expansion which may be used to minimize thermally induced residual stresses for aforementioned seals. Furthermore, these behaviors result from an inorganic glass matrix and variety of crystalline ceramic phases including silica polymorph(s) that may undergo reversible solid-to-solid transformations with associated inelastic strain. Correspondingly, these materials exhibit complex thermomechanical responses associated with multiple inelastic mechanisms (viscoelasticity and phase transformation). While modeling these behaviors is essential for developing and analyzing the corresponding applications, no such model exists. Therefore, in this work a three-dimensional continuum constitutive model for glass–ceramic materials combining these various inelastic mechanisms is developed via an internal state variable approach. A corresponding fully implicit three dimensional numerical formulation is also proposed and implemented. The model is used to simulate existing experiments and validate the proposed formalism. As an example, the simple seal problem of a glass–ceramic seal inside a concentric metal shell is explored. Finally, the impact of the cooling rates, viscoelastic shift factors, and inelastic strain on final residual stress state are all investigated and the differing contributions highlighted.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Influence of fixed charge concentration and water uptake on ion sorption in AMPS/PEGDA membranes

Water content and charge density strongly influence ion sorption in charged membranes. However, isolating the individual effect of each parameter on ion sorption can be difficult due to experimental challenges associated with independently controlling these two variables during membrane synthesis. This frustrates development and validation of fundamental models and structure/property relationships. In this study, three series of uncharged and negatively charged hydrogel membranes were prepared using poly(ethylene glycol) diacrylate (PEGDA) as a cross-linker and 2-acrylamido-2-methylpropanesulfonic acid (AMPS) as an ionic monomer. Here, water content and charge density were controlled by varying AMPS content and PEGDA chain length. Ion sorption in these materials was measured using aqueous NaCl solutions at concentrations ranging from 0.01 to 1.0 M. At constant charge density, salt sorption increased as water content increased. At fixed water content, salt sorption decreased as charge density increased. Salt sorption in membranes with the highest water content and charge density was predicted using the Donnan/Manning model, which accounts for solution and membrane phase thermodynamic non-idealities. However, this approach could not predict sorption in weakly charged and uncharged membranes, presumably due to additional membrane phase thermodynamic non-idealities associated with ion solvation and uncharged polymer segments.

36 MATERIALS SCIENCE↗
DOE OSTI2021

In Situ Probing Potassium-ion Intercalation-induced Amorphization in Crystalline Iron Phosphate Cathode Materials

Na-ion and K-ion batteries are promising alternatives for large-scale energy storage applications due to their abundance and low cost. Intercalation of these large ions could cause irreversible structural deformation and partial to complete amorphization in the crystalline electrodes. The designing of new amorphous electrodes is another route to develop electrodes to store these ions reversibly. Lack of understanding of dynamic changes in the amorphous nanostructures during battery operation is the bottleneck for further developments. Here, we report the utilization of in situ digital image correlation and in-operando X-ray diffraction (XRD) techniques to probe dynamic changes in the amorphous phase of iron phosphate during potassium intercalation. In-operando XRD demonstrates amorphization in the electrode’s nanostructure during the first charge/discharge cycle. Additionally, the ex-situ high-resolution transmission electron microscopy further confirms the amorphization after potassium insertion. In situ strain analysis detects the reversible deformation associated with redox reactions in the amorphous phases. Our approach offers new insights on the mechanisms of ion intercalation in the amorphous nanostructures which are highly potent for development of next-generation batteries.

Ozdogru, Bertan↗
DOE OSTI2020

Mirostructure Characterization of Friction Consolidated Copper-Nickel using a Machine Learning Approach: Developing Process to Microstructure Associations

Friction consolidation (FC) is a solid phase processing approach where discrete material forms such as powders, chips, nuggets, etc. are densified via shear deformation. The precursors are placed in a billet container and brought in contact with a rotating tool that applying the desirable amount of normal force. Under the combined action of the rotation and normal pressure, the discrete precursor is consolidated through porosity reduction and shear deformation. FC is increasingly being studied as an attractive approach to manufacturing fully dense parts from powder forms owing to its ability to mix, alloy and consolidate difficult-to-process precursors in minimal number of process steps. Material consolidation and deformation in shear consolidation processes have been studied extensively previously for different material combinations previously. However, despite the extensive research in this area, understanding of the mechanistic processes in pore consolidation, deformation-induced mixing and material solubility during FC is still evolving. Material development using solid phase processing approaches such as FC is often performed based on research experience/education, which can be biased. Conventional analysis and simulation tools in this area tend to be successful only when material thermodynamic pathways and microstructural evolution sequences resulting from processing are clearly defined or known. They are not as effective for emerging advanced manufacturing technologies where material evolution pathways are not well established. The ability to predict optimal process parameters based on material chemistry and bulk properties is essential to accelerate materials design and processing, as are an understanding of the relevant structure-processing-property relationships. These structure-processing-property-performance relationships are at the core of materials science research. Microstructure characterization provides the link to these four core areas, often through visualizing material microstructure using imaging techniques. However, linking microstructure image data (i.e., micrographs) to variables of interest (e.g., processing parameters, material chemistry) in a reproducible, generalizable, and quantitative manner is a significant challenge. Typically, quantitatively linking image data to processing history relies on significant domain knowledge and manual or subject matter expert (SME)-heuristic based image analysis. Such an approach to image analysis has the potential to be biased, inefficient, and difficult to replicate.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Structural Stabilization of P2-type Sodium Iron Manganese Oxides by Electrochemically Inactive Mg Substitution: Insights of Redox Behavior and Voltage Decay

Layered P2-type Na 0.8 Mn 0.5 Fe 0.5 O 2 cathode material is a promising candidate for next-generation sodium-ion batteries due to the economical and environmentally benign characteristics of Mn and Fe. The poor cycling stability of the material, however, is still a problem that must be solved. To address the problem, here, electrochemically inactive Mg 2+ was introduced into the structure by substituting some of the Fe ions. It was shown that Mg substitution led to a smoother voltage profile with improved cycling performance and rate capability. These observations were attributed to the suppressed structural changes during electrochemical processes. Detailed redox mechanisms, associated local structural changes, and phase transitions were investigated by X-ray absorption spectroscopy and X-ray diffraction. From the detailed analysis of electrochemical behaviors, it was also identified how the redox reactions and structural disordering occurred in the high-and low-voltage regions and how Mg substitution stabilized the structure.

25 ENERGY STORAGE↗
DOE OSTI2023

In-situ Synthesis of PuCl 3 and Corresponding Raman and Density Functional Theory Vibrational Modes

The experimental and calculated Raman spectrum of PuCl 3 has been reported for the first time. PuCl 3 is a primary species found in plutonium metal refinement, specifically in pyrochemical salt processes including multicycle direct oxide reduction, metal chlorination, and electrorefining. As such, Raman signatures of PuCl 3 could serve as potential forensic indicators of material process history. A novel technique for synthesizing PuCl 3 from the in situ chlorination of plutonium metal with HCl was developed to establish these signatures. Cerium metal surrogates were utilized to ensure optimization of the plutonium experiments and to minimize personnel exposure, and all experiments were carried out in a Raman reaction chamber designed for air-tight, high vacuum environments. In situ Raman spectroscopy was employed in conjunction with density functional theory (DFT) to investigate the vibrational modes of PuCl 3 . Associated mixed oxy and hydroxyl phases are also reported. The combined Raman and DFT results have eliminated inconsistencies in Raman mode assignments for the MX 3 family of metal chlorides having P6 3 /m symmetry, and IR modes derived from the DFT calculations are additionally presented. The data observed in this study are of potential interest to nuclear forensic analyses, nuclear sample aging, nuclear energy, plutonium processing, and stockpile stewardship.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Reversible Electrochemical Lithium Cycling in a Vanadium(IV)- and Niobium(V)-Based Wadsley–Roth Phase

Fast charging remains one of the greatest safety challenges in Li-ion batteries due to Li-dendrite growth occurring on graphite anodes if they are lithiated too quickly. The search for high-rate anodes has highlighted materials in the Wadsley–Roth (WR) shear phase family. The relative abundance of V compared with traditional WR compositions of Nb and W makes V-based phases attractive. However, the high voltage and poor reversibility typically associated with V redox have made V-rich WR phases less studied than Nb- and W-rich phases. Here, we show that a new V-rich Wadsley–Roth phase, V 7 Nb 6 O 29 , achieves excellent rate capability and 80% capacity retention after 228 cycles with a relatively low average voltage of 1.76 V vs Li/Li + compared with other V-rich WR phases. Single-crystal X-ray diffraction reveals a P4/m space group with repeating 2 × 2 × ∞ and 3 × 3 × ∞ blocks of V 4+ and Nb 5+ octahedra. Finally, combined neutron pair distribution function analysis, X-ray absorption spectroscopy, and density functional theory calculations show that V redox is the primary source of capacity and that cycling stability is provided by the stable octahedral coordination adopted by V 4+ in the material.

25 ENERGY STORAGE↗
DOE OSTI2022

Potential Seismicity Along Basement Faults Induced by Geological Carbon Sequestration

Large-scale CO 2 sequestration into geological formations has been suggested to reduce CO 2 emissions from industrial activities. However, much like enhanced geothermal stimulation and wastewater injection, CO 2 sequestration has a potential to induce earthquake along weak faults, which can be considered a negative impact on safety and public opinion. This research shows the physical mechanisms of potential seismic hazards along basement faults driven by CO 2 sequestration under variation in geological and operational constraints. Specifically we compare the poroelastic behaviors between multiphase flow and single-phase flow cases, highlighting specific needs of evaluating induced seismicity associated with CO 2 sequestration. In contrast to single-phase injection scenario, slower migration of the CO 2 plume than pressure pulse may delay accumulation of pressure and stress along basement faults that may not be mitigated immediately by shut-in of injection. The impact of multiphase flow system, therefore, needs to be considered for proper monitoring and mitigation strategies.

58 GEOSCIENCES↗
DOE OSTI2025

Cobalt–niobium co-doping of indium oxide: structural and adsorption/catalytic properties for CO 2 valorization

The co-doping of the indium oxide structure with cobalt and niobium is attempted using a microemulsion method to produce high-surface-area, mesoporous, functional materials. The co-doping leads to a major nanometric bixbyite oxide phase, with both cations occupying cation positions and affecting the size and shape of the oxide entities. For specific cobalt to niobium atomic ratios, the presence of a second surface phase is encountered. Such a surface phase corresponds to an ill-defined indium hydroxide-type phase. The coexistence of the two phases is a unique phenomenon associated with the presence of both cations, which play a decisive role in promoting the CO 2 adsorption capability of the solids, as well as the valorization of the molecule under dual heat–light excitation. The co-doping of indium oxide thus appears to be a unique way to intensify the analogous thermal (classical) catalytic process for the elimination/valorization of carbon dioxide.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Non-Richtmyer–Meshkov instability ejecta production based on shallow bubble collapse

The study of shock-driven ejecta production has focused on Richtmyer–Meshkov instability (RMI) growth from geometric features of the material surface. Extensive study of this mechanism under both single- and multiple-shock conditions has found that the ejected mass tends to be closely associated with the shocked surface phase, and its temperature is not dramatically greater than the hydrodynamic shock temperature of the bulk. In this work, we propose and demonstrate a new ejecta production mechanism that can occur under multiple-shock conditions based on the collapse of bubbles near the free surface of the material. This mechanism produces ejected mass that is much greater in quantity than observed in the RMI case. The particles are much hotter than predicted by the shock Hugoniot state, and the ejected mass does not appear to be strongly dependent upon initial surface finish. The ejecta source extends into the material with no clear remaining free surface. We name this mechanism Shallow Bubble Collapse (SBC) and discuss the conditions under which it activates. We demonstrate resolved modeling methods that enable the calculation, design, and study of SBC as a mechanism and perform a series of experiments to compare with the models. Under some multiple-shock conditions, SBC ejection produces ten times more ejected mass than RMI growth.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2022

Kinetic theory of particle-in-cell simulation plasma and the ensemble averaging technique

Abstract We derive the kinetic theory of fluctuations in physically and numerically stable particle-in-cell (PIC) simulations of electrostatic plasmas. The starting point is the single-time correlation at the start of the simulation between the statistical fluctuations of the weighted densities of macroparticle centers in the plasma particle phase-space. The fluctuations are associated with different initial conditions, typically due to the random initial conditions (in velocity space) of the macroparticles/simulation plasma, assigned according to their initial distribution of probability. The single-time correlations at all time steps and in each spatial grid cell are then determined from the Laplace–Fourier transforms of the discretized Klimontovich-like equation for the macroparticles and Maxwell’s equations for the fields, as computed by modern PIC codes. We recover the expressions for the electrostatic field and the plasma particle density fluctuation autocorrelation spectra as well as the kinetic equations describing the average evolution of PIC-simulated plasma particles, first derived by Langdon (1970b Proc. 4th Conf. Numerical Simulation of Plasmas ) using a test macroparticle approach perturbing a discretized Vlasovian plasma and then averaging the obtained physical quantity over the initial macroparticle velocity distribution. We generalize and extend these results to the modern algorithms in PIC codes using arbitrary macroparticle weights. Analytical estimates of statistical fluctuation amplitudes are derived as a function of the plasma simulation parameters, using the central limit theorem in the limit of a large number of macroparticles per cell. The theory is then used to analyze the ensemble averaging technique of PIC simulations where statistical averages are performed over ensembles of PIC simulations, modeling the same plasma physics problem but using different statistical realizations of the initial distribution functions of the macroparticles. This method is illustrated by linear Landau damping uncovering (from noise, which is usually considered numerical) the physical fluctuations driven by a single small amplitude electrostatic wave perturbing a PIC simulation plasma in equilibrium.

fluctuations correlations↗