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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 1,063 records · Page 59
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Fe Oxidation and Species Distribution at the Rock–Fluid Interface of Marcellus Shale Reacted with Hydraulic Fracturing Fluid

Hydraulic fracturing of shale reservoirs resulted in significant opportunity for increased oil and gas production in the United States. Rock-fluid interactions can cause mineral dissolution and precipitation reactions that lead to permeability changes in the shale matrix, which ultimately may affect transport pathways and hydrocarbon production. Understanding the distribution of secondary precipitates, such as barite and Fe(III) (hydro)oxides, and cation leaching at the rock-fluid interface is an important step to further investigate how these geochemical processes can change permeability and transport pathways. In this study, thin sections of the fracture-matrix interface were made from reacted Marcellus shale cores. The thin sections were characterized using synchrotron X-ray fluorescence imaging and synchrotron X-ray absorption spectroscopy. Fe species with different oxidation states were identified in the maps, together with barite and Ca distribution. The results show that ferrihydrite, as newly formed Fe(III)-bearing precipitates, aligned well with the border of the Ca (e.g., calcite) leaching region in the reaction front. Some Fe-containing clay also dissolved, but the dissolution region for the clay was not as deep as the calcite. Further, the reaction front is about three times deeper in the direction parallel to the shale bedding than that perpendicular to the bedding. The Ca leaching region can be an index for reaction front detection for Marcellus shale. Reactive transport modeling was conducted and the predicted Ca leaching boarder align well with ferrihydrite precipitation, consistent with the experimental observation. The carbonate mineral dissolution can be crucial to promote fluid access into the shale matrix. Together with our previous study on the shale reactive surface, this follow-up study showed similar Ca leaching region and Fe(III) precipitates distribution in the reaction front regardless of barite precipitation on the surface, indicating that the barite coatings on the surface may not pose a significant impact on reactive transport at the shale-fluid interface.

04 OIL SHALES AND TAR SANDS↗
DOE OSTI2022

In Situ Visualization of Local Distortions in the High- T c Molecule-Intercalated Li x (C 5 H 5 N) y Fe 2– z Se 2 Superconductor

A time-resolved synchrotron X-ray total scattering study sheds light on the evolution of the different structural length scales involved during the intercalation of the layered iron–selenide host by organic molecular donors, aiming at the formation of the expanded-lattice Li x (C 5 H 5 N) y Fe 2– z Se 2 hybrid superconductor. The intercalates are found to crystallize in the tetragonal ThCr 2 Si 2 -type structure at the average level, however, with an enhanced interlayer iron–selenide spacing ( d = 16.2 Å) that accommodates the heterocyclic molecular spacers. Quantitative atomic pair distribution function (PDF) analysis at variable times suggests distorted FeSe 4 tetrahedral local environments that appear swollen with respect to those in the parent β-FeSe. Simultaneously acquired in situ synchrotron X-ray powder diffraction data disclose that secondary phases (α-Fe and Li 2 Se) grow significantly when a higher lithium concentration is used in the solvothermal reaction or when the solution is aged. These observations are in line with the strongly reducing character of the intercalation medium’s solvated electrons that mediate the defect chemistry of the expanded-lattice superconductor. In the latter, intralayer correlated local distortions indicate electron-donating aspects that reflect in somewhat enlarged Fe–Se bonds. Additionally, they also reveal a degree of relief of chemical pressure associated with a large distance between Fe and Se sheets (“taller” anion height) and a stretched Fe–Fe square planar topology. The elongation of the latter, derived from the in situ PDF study, speaks for a plausible increase in the Fe-site vacancy concentration. The evolution of the local structural parameters suggests an optimum reaction window where kinetically stabilized phases resemble the distortions of the edge-sharing Fe–Se tetrahedra, required for a high- T c in expanded-lattice iron-chalcogenides.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2025

Delta/Lambda Chirality: From Enantiomers to Diastereomers in Heterometallic Complexes with Chelating Ligands

The Δ/Λ chirality observed in octahedral molecules with chelating ligands represents the major group of “chiral-at-metal” complexes. Upon shifting from mononuclear to polynuclear systems with multiple (≥2) chiral centers, not only enantiomers but also diastereomers should be considered. We present the first, to the best of our knowledge, diastereomeric pairs Δ,Δ,Δ/Λ,Λ,Λ (1) and Δ,Δ,Λ/ Λ,Λ,Δ (2) of the pentanuclear assembly [Mn II (ptac) 3 −Na- Co III (acac) 3 −Na-Mn II (ptac) 3 ] (ptac = 1,1,1-trifluoro-5,5-dimethyl- 2,4-hexanedionate; acac = acetylacetonate). Diastereomers 1 and 2 were isolated in pure form and found to exhibit distinctly different structural characteristics. Importantly, for compounds that are applied as single-source precursors for the quaternary oxide cathode material P2−Na 0.67 Mn 0.67 Co 0.33 O 2 , the diastereomers revealed different thermal behaviors in terms of volatility and thermal stability. Unambiguous assignment of the Mn and Co positions in both diastereomers has been confirmed by the synchrotron X-ray resonant diffraction technique. Oxidation states of metal ions have been verified by the synchrotron X-ray fluorescence spectroscopy. The diastereomerization between 1 and 2 is not taking place in the solid state (crystal-to-crystal), as well as in the gas phase. The transformation between two diastereomers was observed in the solutions of noncoordinating solvents and was related to the polarities of the solvents and diastereomeric molecules.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Effects of X-rays on Perovskite Solar Cells

Synchrotron micro- and nanoprobe beamlines have demonstrated great potential to advance photovoltaic devices. Most importantly, their small X-ray spot size has enabled the direct correlation of electrical performance with elemental composition at subgrain resolution for a variety of polycrystalline solar cells. Whereas the bulk of most inorganic semiconductors is stable under the high X-ray flux of focused X-ray beams, semiconductors with organic components are prone to a variety of degradation mechanisms. This is particularly critical to evaluate for the emerging organometal halide perovskite solar cells. In this study, we investigate the effects of hard X-rays on the nanoscale performance and elemental distribution of these solar cells. We show that their composition does not change during common operando and in situ measurements at synchrotron nanoprobes. However, we found a significant X-ray-induced electronic degradation of solar cells with methylammonium lead iodide absorbers. Time- and dose-dependent measurements unveiled two characteristic degradation time constants on the order of 12 and 200 s that are independent of the X-ray flux. On the basis of heat and dose simulations, we attribute the fast decay to the dose-driven creation of recombination centers, while the slow decay is compatible with the observation of compositional changes. Finally, we detail how degradation-induced measurement artifacts can be outrun and showcase the high correlation of the X-ray-beam-induced current with the iodine and lead distribution.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Structure, Bonding, and Vibrational Dynamics of a Triamine High Energy Density Material under Pressure

High energy density materials have complex intermolecular interactions which influence their stability and performance. We used a combination of synchrotron X-ray diffraction, synchrotron infrared spectroscopy, and Raman vibrational spectroscopy, supplemented by density functional theory calculations, to probe pressure-induced changes in structure and intermolecular interactions of 1H,4'H-[3,3'-bis(1,2,4-triazole)]-4',5,5'-triamine as a model high energy density material up to 40 GPa. We find that compression of the triamine is accompanied by increased intermolecular interactions that give rise to an interesting evolution of the structure and bonding with pressure. Analysis of the equation of state determined from the X-ray diffraction indicates a change in compression mechanism near 19 GPa consistent with changes in vibrational spectra that provide evidence for a structural rearrangement associated with changes in hydrogen bonding near that pressure. As a result, the overall compressional behavior calculated theoretically agrees with that observed experimentally though differences are found that indicate the need for improved treatment of the intermolecular interactions including hydrogen bonding under pressure.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Nanometer-Scale Correlations in Aqueous Salt Solutions

The intermediate-range (1–4 nm) correlation of cations, an- ions, and water in aqueous alkaline earth salt solutions is measured using synchrotron X-ray diffraction. We differentiate from the entire solution structure factor, S(Q), a separate region at low Q (<1 °A-1) containing local diffraction maxima (pre-peaks) that indicate nanometer-scale oscillatory behavior. These features are quantitatively reproduced with classical molecular dynamics simulations. At high concentrations, the pre-peaks emerge from correlations arising from existence of small quasi close-packed lattice- like structures comprised of cation hydration spheres. We also analyze the concentration dependence of the pre-peak and discuss the overall results in light of the rich literature dealing with intermediate-range correlations underlying universal phenomena in concentrated electrolytes. The authors were supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences. Pacific Northwest National Laboratory (PNNL) is operated by Battelle for the U.S. Department of Energy under Contract No. DE-AC05-76RL01830. Computing resources were generously allocated by PNNL's Institutional Computing program. DOE Contract No. DEAC02- 06CH11357 supports operation of the Advanced Photon Source at Argonne National Laboratory.

Chemical physics, nucleation, Madelung potential↗
DOE OSTI2021

New Insights into Secondary Organic Aerosol Formation at the Air–Liquid Interface

Air-liquid interfacial processing of volatile organic compound oxidation has been suggested as an important source of secondary organic aerosols. However, owing to the lack of techniques for in situ air-liquid interface analysis, the detailed interfacial mechanism remains speculative. To obviate this, the analysis of air-liquid interfacial reactions and the dynamics of glyoxal oxidation as a model volatile organic compound using in situ liquid synchrotron-based vacuum ultraviolet single photon ionization mass spectrometry enabled by the system for analysis at the liquid vacuum interface microreactor is reported. This approach allows for determination of reaction intermediates and oxidation products including polymers and oligomers at the air-liquid interface by mass spectral analysis and appearance energy measurements. Furthermore, an expanded reaction mechanism of photooxidation free radical induced reactions as a source of aqueous secondary organic aerosol formation is proposed based on these new results, suggesting that single photon ionization could be applied to provide unique insights into interfacial chemistry changing the earth atmospheric composition.

aqueous secondary organic aerosol, glyoxal, photoo↗
DOE OSTI2022

Role of Zeolite Structural Properties toward Iodine Capture: A Head-to-head Evaluation of Framework Type and Chemical Composition

This study evaluated zeolite-based sorbents for iodine gas [I2(g)] capture. Based on the framework structures and porosities, five zeolites, including two faujasite (FAU), one ZSM-5 (MFI), one mesoMFI, one ZSM-22 (TON), as well as two mesoporous materials, were evaluated for I2(g) capture at room temperature and 150 °C in an iodine-saturated environment. From these preliminary studies, the three best-performing zeolites were ion-exchanged with Ag+ and evaluated for I2(g) capture under similar conditions. Energy-dispersive X-ray spectroscopy data suggest that Ag-FAU frameworks were the materials with the highest capacity for I2(g) in this study, showing ~3× higher adsorption compared to Ag-mordenite (Ag-MOR) at room temperature, but X-ray diffraction measurements show that the faujasite structure collapsed during the adsorption studies because of dealumination. The Ag-MFI zeolites are decent sorbents in real-life applications, showing both good sorption capacities and higher stability. In-depth analyses and characterizations, including synchrotron X-ray absorption spectroscopy, revealed the influence of structural and chemical properties of zeolites on the performance for iodine adsorption from the gas phase.

aluminosilicate zeolites, iodine, porosity, acidit↗
DOE OSTI2020

3D Morphology of Bimodal Porous Copper with Nano-Sized and Micron-Sized Pores to Enhance Transport Properties for Functional Applications

Multiscale porous metals with multiscale porosity from nanometer to micrometer have a high specific surface area and high effective diffusivity for ion transport, thereby enhancing functionalities and extending the applications of porous metals. Herein, the Cu–Fe–Al ternary system was selected as the precursor alloy to construct multiscale, bimodal porous copper by the chemical dealloying method. The effect of the phase composition and initial microstructure of precursor alloys (Al x Fe 75– x Cu 25 , x = 10–60) on the three-dimensional (3D) morphology of multiscale porous metals was systematically investigated, with a goal to precisely control the multiscale porous structure. The four crystal structure phases (body-centered cubic (BCC), face-centered cubic (FCC), CsCl type (B2), and monoclinic) in precursor alloys were analyzed by synchrotron X-ray diffraction refinement. The 3D morphology, feature size distribution, and tortuosity of four representative porous Cu after dealloying Al x Fe 75– x Cu 25 ( x = 10, 30, 50, and 60) precursor alloys were directly visualized and quantified via advanced synchrotron X-ray nanotomography. The relationship between the phases/crystal structures of precursor alloys and their corresponding porous morphology was established: the micron-sized pores in bimodal porous Cu are formed by dissolving the CuFeAl phase with BCC and monoclinic crystal structures, and the nano-sized pores are formed by dealloying the CuFeAl phase with FCC and B2 crystal structures. The size of the nanoporous structure depends on the ratio between the more noble and more active components in the precursor alloy, while the size of the microporous structure depends on the corresponding phase size in the precursor alloy. The tortuosity results showed that the multiscale porous structure with both nanoporosity and microporosity exhibits lower tortuosity, which will enhance transport properties for functional applications.

25 ENERGY STORAGE↗
DOE OSTI2022

Comparing the Purity of Rolled versus Evaporated Lithium Metal Films Using X-ray Microtomography

Here, we present a comparison of lithium metal films produced via rolling and thermal evaporation using synchrotron hard X-ray microtomography. In past studies of rolled lithium metal foils, a large number of C, O, and N impurities were found and identified as the key cause for failure in lithium metal cells. In this comparison, the X-ray tomography data show that the evaporated lithium metal films have an average impurity concentration of 19 particles/mm3 in comparison to 1350 particles/mm3 in the rolled lithium metal. An analysis of the inner substrate/lithium interface and outer lithium surface of the thermally evaporated film shows a much greater concentration of impurities at these interfaces, further emphasizing the importance of interface engineering in producing high-quality lithium metal batteries. Furthermore, we show that, if surface contamination can be avoided, it is possible to obtain lithium films with no impurities detectable by synchrotron hard X-ray tomography.

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

Stabilizing a Li–Mn–O Cathode by Blocking Lattice O Migration through a Nanoscale Phase Complex

Among all intercalation cathodes for Li-ion batteries, Li–Mn–O layered oxides offer the highest initial energy density at the lowest cost, due to the joint contribution from cationic and anionic redox chemistry. However, the poor cycling capability, resulting from the continuous lattice O loss at high potentials (>4.5 V), hinders practical applications. Herein, we employed phase complex engineering to obtain a new Li–Mn–O nanohybrid cathode featuring the uniform and coherent integration of layered nanodomains and spinel nanodomains. The combination of DFT calculations, synchrotron-based transmission X-ray microscopy, in situ differential electrochemical mass spectrometry, in situ synchrotron XRD, and electrochemical tests demonstrated that the O migration path in layered nanodomains was blocked by the neighboring spinel nanodomains with a higher oxygen vacancy migration energy, thus effectively suppressing the irreversible lattice O loss at high potentials and enhancing the cycling stability in both capacity and average voltage. Finally, the strategy is experimentally demonstrated to be effective and it leads to a new path for developing stable high-energy-density cathode materials.

25 ENERGY STORAGE↗
DOE OSTI2024

Mechanistically Guided Materials Chemistry: Synthesis of Ternary Nitrides, CaZrN 2 and CaHfN 2

Recent computational studies have predicted many new ternary nitrides, revealing synthetic opportunities in this underexplored phase space. However, synthesizing new ternary nitrides is difficult, in part because intermediate and product phases often have high cohesive energies that inhibit diffusion. Here, we report the synthesis of two new phases, calcium zirconium nitride (CaZrN 2 ) and calcium hafnium nitride (CaHfN 2 ), by solid state metathesis reactions between Ca 3 N2 and MCl 4 (M = Zr, Hf). Although the reaction nominally proceeds to the target phases in a 1:1 ratio of the precursors via Ca 3 N 2 + MCl4 → CaMN 2 + 2 CaCl 2 , reactions prepared this way result in Ca-poor materials (Ca x M 2–x N2, x < 1). A small excess of Ca 3 N 2 (ca. 20 mol %) is needed to yield stoichiometric CaMN 2 , as confirmed by high-resolution synchrotron powder X-ray diffraction. In situ synchrotron X-ray diffraction studies reveal that nominally stoichiometric reactions produce Zr 3+ intermediates early in the reaction pathway, and the excess Ca 3 N 2 is needed to reoxidize Zr 3+ intermediates back to the Zr 4+ oxidation state of CaZrN 2 . Analysis of computationally derived chemical potential diagrams rationalizes this synthetic approach and its contrast from the synthesis of MgZrN 2 . These findings additionally highlight the utility of in situ diffraction studies and computational thermochemistry to provide mechanistic guidance for synthesis.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Evolution and interplay of lithium metal interphase components revealed by experimental and theoretical studies

ABSTRACT: Lithium metal batteries (LMB) have high energy densities and are crucial for clean energy solutions. The characterization of lithium metal interphase is fundamentally and practically important but technically challenging. Taking advantage of synchrotron x-ray which has the unique capability of analyzing crystalline/amorphous phases quantitative-ly with statistical significance, we study the composition and dynamics of LMB interphase for a newly developed im-portant LMB electrolyte that is based on fluorinated ether. Pair distribution function analysis revealed the sequential role of anion and solvent in interphase formation during cycling. The relative ratio between Li2O and LiF first increases and then decreases during cycling, suggesting suppressed Li2O formation in both initial and long extended cycles. Theoretical studies revealed that in initial cycles, this is due to the energy barrier in many-electron transfer. In long extended cycles, the anion decomposition product Li2O encourages solvent decomposition by facilitating solvent adsorption on Li2O which is followed by concurrent depletion of both. This work highlights the important role of Li2O in transitioning from anion-derived interphase to a solvent-derived one.

Tan, Sha↗
DOE OSTI2024

Simultaneous Development of Antiferromagnetism and Local Symmetry Breaking in a Kagome Magnet (Co 0.45 Fe 0.55 )Sn

CoSn and FeSn, two kagome-lattice metals, have recently attracted significant attention as hosts of electronic flat bands and emergent physical properties. However, current understandings of their physical properties are limited to knowledge of the average crystal structure. Here, we report the Fe-doping induced coemergence of the antiferromagentic (AFM) order and local symmetry breaking in (Co 0.45 Fe 0.55 )Sn. Rietveld analysis on the neutron and synchrotron X-ray diffraction data indicates A-type antiferromagnetic order with the moment pointing perpendicular to the kagome layers, associated with the anomaly in the MSn(1) 2 Sn(2) 4 (M = Co/Fe) octahedral distortion and the lattice constant c. Reverse Monte Carlo (RMC) modeling of the synchrotron X-ray total scattering results captured the subtle local orthorhombic distortion involving off-axis displacements of Sn(2). Our results indicate that the stable hexagonal lattice above T N becomes unstable once the A-type AFM order is formed below T N . Here we argue that the local symmetry breaking has a magnetic origin, since the spatially varied M–Sn(2) bond lengths arise from out-of-plane magnetic exchange coupling J c via the exchange pathway M–Sn(2)–M. Our study provides comprehensive information on the crystal structure in both long-range scale and local scale, unveiling unique coupling between AFM order, octahedral distortion, and hidden local symmetry breaking.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Pyrochlore NaYbO2: A Potential Quantum Spin Liquid Candidate

The search for quantum spin liquids (QSL) and chemical doping in such materials to explore superconductivity have continuously attracted intense interest. Here, we report the discovery of a potential QSL candidate, pyrochlore-lattice β-NaYbO2. Colorless and transparent NaYbO2 single crystals, layered α-NaYbO2 (∼250 μm on edge) and octahedral β-NaYbO2 (∼50 μm on edge), were grown for the first time. Synchrotron X-ray single-crystal diffraction unambiguously determined that the newfound β-NaYbO2 belongs to the three-dimensional pyrochlore structure characterized by the R3̅m space group, corroborated by synchrotron X-ray and neutron powder diffraction and pair distribution function. Magnetic measurements revealed no long-range magnetic order or spin glass behavior down to 0.4 K with a low boundary spin frustration factor of 17.5, suggesting a potential QSL ground state. Under high magnetic fields, the potential QSL state was broken and spins order. Our findings reveal that NaYbO2 is a fertile playground for studying novel quantum states.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Time‐And‐Space Averaging Applied to Intermittent Multiphase Flow Experiments

Abstract Various researchers have studied fluctuations in pore‐scale phase occupancy during multiphase flow in porous media using synchrotron‐based X‐ray microcomputed tomography (micro‐CT). However, the impact of these fluctuations on the concept of a representative volume is not yet fully understood. In this study, we performed spatial and temporal averaging of multiphase flow experiments visualized with synchrotron‐based micro‐CT, focusing on oil saturation as the key parameter to determine a representative time‐and‐space average. Our findings revealed that a saturation value representative of both time and space was achieved during fractional flow experiments in drainage mode with fractional flows of 0.8, 0.5, and 0.3. Furthermore, we computed a range of relative permeabilities on the basis of whether momentaneous saturation or time‐and‐space averaged saturation was utilized for direct simulation. Our results highlighted the importance of time‐and‐space averaging in determining a representative relative permeability and indicated that the temporal and spatial scales covered in a typical micro‐CT flow experiment were sufficient to obtain a representative saturation value for sandstone rock under intermittent flow conditions.

Environmental Sciences & Ecology↗