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All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

Pore-Scale Study on the Positive Feedback Between Stress and Porosity Caused by Pressure Solution in Porous Media

Pressure solution is an important process in the evolution of sedimentary rocks, which provide storage space for most of our petroleum resources. It directly influences the generation, migration, and storage of petroleum fluids in subsurface sedimentary rocks. Here, in this paper, we develop a pore-scale, mechanochemical model to demonstrate a possible positive feedback between the local porosity and pore surface stress, in which a higher local porosity causes a higher local pore surface stress, thus enhancing pressure solution and consequently further increasing the local porosity. Pore surface stress represents stress on a solid grain adjacent to a pore. Specifically, the pore-scale, mechanochemical model directly simulates the stress distribution over solid and pore surfaces using a finite element model. The dissolution of solids at the solid-pore interfaces under a far-from-equilibrium condition is simulated using a first-order kinetics model that accounts for the local stress distribution. The updated pore geometry, caused by pore surface dissolution, is then used in the stress simulation in the next numerical iteration. Two types of porous media, the Oriskany sandstone and an artificial porous medium with spherical pores, were tested in the mechanochemical simulation. The positive stress-porosity feedback during pressure solution was observed in both samples. In addition, the model quantitatively illustrated the distribution of local mineral dissolution rates on all pore surfaces, as well as its relation to the effective mineral dissolution rate of the entire sample. Based on the comparison between the two porous media, the local mineral dissolution was regulated by pore space distribution, geometry, and coalescence during pressure solution. This work is the first that uses direct, pore-scale numerical simulation to demonstrate the positive stress-porosity feedback during pressure solution, which has the potential to advance the understanding of the mechanical-chemical (MC) coupling in many geological processes that are relevant to subsurface energy systems, such as the recovery of petroleum hydrocarbons and geothermal energy.

CT scanning↗
DOE OSTI2020

Unraveling the dislocation–precipitate interactions in high-entropy alloys

The precipitates play a significant role in not only enhancing the strength, but also maintaining the high toughness in alloys. However, the interactions of the nanoscale precipitates with dislocations in the high entropy alloys (HEAs) are difficult to observe directly by in-situ TEM experiments due to the limits of the resolution and time. Here, using atomic simulations we report the synergistic strengthening of the coherent precipitate and atomic-scale lattice distortion in the HEAs at cryogenic/elevated temperatures. The effects of temperature, chemical disorder, precipitate spacing, precipitate size, elemental segregation, and dislocation-cutting number on the critical stress for the dislocation to overcome a row of precipitates are studied. A random stacking fault energy landscape along the slip plane, the lattice distortion at different temperatures, and the interface/surface energy at various crystallographic orientations are obtained. Compared with the traditional metals and alloys, HEAs have the severe atomic-scale lattice distortions to generate the local high tensile/compressive stress fields. This complex stress causes the dislocation line to bend, and thus improves the dislocation slip resistance, resulting in the strong solid-solution strengthening. The stacking fault strengthening induced by the obvious difference of the stacking fault energies between the HEA matrix and precipitate (within the inner of the HEA matrix), and the formation of the antiphase domain boundary contribute to the high strength. The precipitate embedded by the solute atoms produces the strong lattice distortion to enhance the dislocation slip resistance at high temperatures. Hence, the current results provide the mechanistic insight into the phenomenon that the coherent precipitate combined with the severe atomic-scale lattice distortion can enhance the strength at cryogenic/elevated temperatures to further broaden the scope of applications of advanced HEAs.

36 MATERIALS SCIENCE↗
DOE OSTI2024

A high-order, localized-artificial-diffusivity method for Eulerian simulation of multi-material elastic-plastic deformation with strain hardening

A high-order method for Eulerian simulation of material undergoing large elastic–plastic deformation is developed. Thermodynamically consistent hyperelastic constitutive relations are assumed, facilitating the treatment of solids, liquids, and gases in a unified manner. Here, the method enables the simulation of multi-material interactions using a diffuse interface approach. Numerical capturing of material interfaces, shock waves, contact surfaces, and elastic-plastic strain discontinuities using high-order compact-difference schemes is assisted by Localized Artificial Diffusivity (LAD). In the new setting involving elastic–plastic deformation, the previously established terms for the artificial properties are verified to effectively regularize normal shocks. Additional LAD terms are introduced to the elastic and plastic kinematic equations to regularize shear shocks and other strain discontinuities, improving solution stability. Other important features of the method that improve robustness include the numerical treatment of compatibility terms in the kinematic equations, and the treatment of rotation. Particular emphasis is focused toward new advancements of the methods for plastic-deformation integration and the associated strain hardening of the material, including rate-dependent plasticity. The method is demonstrated on a variety of test problems, including 1-D impacts, a variant of the Shu-Osher problem, a Taylor impact, and a Richtmyer-Meshkov instability between two elastic–plastic solids with strain hardening.

42 ENGINEERING↗
DOE OSTI2021

Resolving Chemical and Spatial Heterogeneities at Complex Electrochemical Interfaces in Li-Ion Batteries

The high specific capacities of Ni-rich transition metal oxides have garnered immense interest for improving the energy density of Li-ion batteries (LIBs). Despite the potential of these materials, Ni-rich cathodes suffer from interfacial instabilities that lead to crystallographic rearrangement of the active material surface as well as the formation of a cathode electrolyte interphase (CEI) layer on the composite during electrochemical cycling. While changes in crystallographic structure can be detected with diffraction-based methods, probing the chemistry of the disordered, heterogeneous CEI layer is challenging. In this work, we use a combination of ex situ solid-state nuclear magnetic resonance (SSNMR) spectroscopy and X-ray photoemission electron microscopy (XPEEM) to provide chemical and spatial information, on the nanometer length scale, on the CEI deposited on LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) composite cathode films. XPEEM elemental maps offer insight into the lateral arrangement of the electrolyte decomposition products that comprise the CEI and paramagnetic interactions (assessed with electron paramagnetic resonance (EPR) and relaxation measurements) in 13 C SSNMR provide information on the radial arrangement of the CEI from the NMC811 particles outward. Using this approach, here we find that LiF, Li 2 CO 3 , and carboxy-containing structures are directly appended to NMC811 active particles, whereas soluble species detected during in situ 1 H and 19 F solution NMR experiments (e.g., alkyl carbonates, HF, and vinyl compounds) are randomly deposited on the composite surface. We show that the combined approach of ex situ SSNMR and XPEEM, in conjunction with in situ solution NMR, allows spatially-resolved, molecular-level characterization of paramagnetic surfaces and new insights into electrolyte oxidation mechanisms in porous electrode films.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Soft-Switching Solid-State Transformer With Reduced Conduction Loss

Solid-state transformers (SSTs) are a promising solution photovoltaic (PV), wind, traction, data center, battery energy storage system (BESS), and fast charging electric vehicle (EV) applications. The traditional SSTs are typically three-stage, i.e., hard-switching cascaded multilevel rectifiers and inverters with dual active bridge (DAB) converters, which leads to bulky passives, low efficiency, and high electromagnetic interference (EMI). This article proposes a new soft-switching solid-state transformer (S4T). The S4T has full-range zero-voltage switching (ZVS), electrolytic capacitor-less dc link, and controlled dv/dt, which reduces EMI. The S4T comprises two reverse-blocking current-source inverter (CSI) bridges, auxiliary branches for ZVS, and transformer magnetizing inductor as a reduced dc link with 60% ripple. Compared with the prior S4T, an effective change on the leakage inductance diode is made to reduce the number of the devices on the main power path by 20% for significant conduction loss saving and retain the same functionality of damping the resonance between the leakage and resonant capacitors and recycling trapped leakage energy. The conduction loss saving is crucial, being the dominating loss mechanism in SSTs. Importantly, the proposed single-stage SST not only holds the potential for high power density and high efficiency but also has full functionality, e.g., multiport dc loads integration, voltage regulation, and reactive power compensation, unlike the traditional single-stage matrix SST. The S4T can achieve single-stage isolated bidirectional dc–dc, ac–dc, dc–ac, or ac–ac conversion. It can also be configured input-series output-parallel (ISOP) in a modular way for medium-voltage (MV) grids. Hence, the S4T is a promising candidate for the SST. The full functionality, e.g., voltage buck–boost, multiport, etc., and the universality of the S4T for the dc–dc, dc–ac, and ac–ac conversion are verified through the simulations and experiments of two-port and three-port MV prototypes based on 3.3 kV SiC MOSFETs in dc–dc, dc–ac, and ac–ac modes at 2 kV.

14 SOLAR ENERGY↗
DOE OSTI2023

Optically Enhanced Solid-State 1 H NMR Spectroscopy

Low sensitivity is the primary limitation to extending nuclear magnetic resonance (NMR) techniques to more advanced chemical and structural studies. Photochemically induced dynamic nuclear polarization (photo-CIDNP) is an NMR hyperpolarization technique where light is used to excite a suitable donor–acceptor system, creating a spin-correlated radical pair whose evolution drives nuclear hyperpolarization. Systems that exhibit photo-CIDNP in solids are not common, and this effect has, up to now, only been observed for 13 C and 15 N nuclei. However, the low gyromagnetic ratio and natural abundance of these nuclei trap the local hyperpolarization in the vicinity of the chromophore and limit the utility for bulk hyperpolarization. Here, we report the first example of optically enhanced solid-state 1 H NMR spectroscopy in the high-field regime. This is achieved via photo-CIDNP of a donor–chromophore–acceptor molecule in a frozen solution at 0.3 T and 85 K, where spontaneous spin diffusion among the abundant strongly coupled 1 H nuclei relays polarization through the whole sample, yielding a 16-fold bulk 1 H signal enhancement under continuous laser irradiation at 450 nm. These findings enable a new strategy for hyperpolarized NMR beyond the current limits of conventional microwave-driven DNP.

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

Optimal gas cooling with minimal aero-opticaldistortion for next generation high-average-power lasers (Progress report, Year 2)

Next-generation lasers that combine high-peak-power ultrashort pulses with high repetition rates have the potential to efficiently deliver the high-average-power outputs required for inertial fusion energy generation, laser-based particle acceleration, and to generate compact secondary x- and 𝛾-ray radiation sources, among others. The combination of long gain length with high surface-to-volume ratio to remove residual heat makes gas-cooled multi-slab amplifier heads an inherently aperture- and average power scalable technology that enables this new class of solid-state lasers, and their thermal management becomes the most pressing technical challenge. As the index-of refraction depends on the gas density, heat removal from the slab surfaces unavoidably entails scattering of propagated light from regions of high temperature fluctuations. The requirement to maximize convective heat extraction from the gain medium under the constraint of minimum optical aberration of the beam renders amplifier slab cooling a technological challenge at the intersection of aero-optics, fluid-mechanics and heat transfer. The goal of this research is to leverage computational fluid dynamics and aero optics simulations of different levels of fidelity to devise a numerical modeling and optimization framework for gas-cooled multi-slab amplifiers. The project will be conducted in close collaboration with the Advanced Photon Technologies Group at Lawrence Livermore National Laboratory, where a gas-cooled test stand for laser materials and thermal management structures will be developed and installed. The final goal of the collaborative effort is to manufacture and benchmark a physical prototype of an numerically optimized amplifier head design. Measurement data on solid-state and thermo-optical distortions will be used for the validation of the numerical models. The key technical challenge in this multi-objective design problem is that of balancing optimal heat removal with minimal optical distortion. To facilitate computationally efficient design optimization and, at the same time, deepen our basic understanding of the interaction of light with turbulence, a complementary study that combines high and low-fidelity flow simulations and aero-optical models is proposed. Along the lines of these two objectives and solution strategies, the project is organized into two thrusts.

42 ENGINEERING↗
DOE OSTI2024

Hydrogen in energy and information sciences

Beyond its fascinating chemistry as the first element in the Periodic Table, hydrogen is of high societal importance in energy technologies and of growing importance in energy-efficient computing. In energy, hydrogen has reemerged as a potential solution to long-term energy storage and as a carbon-free input for materials manufacturing. Its utilization and production rely on the availability of proton-conducting electrolytes and mixed proton–electron conductors for the components in fuel cells and electrolyzers. In computing, proton mediation of electronic properties has garnered attention for electrochemically controlled energy-efficient neuromorphic computing. Incorporation of substitutional and interstitial hydride ions in oxides, though only recently established, enables tuning of electronic and magnetic properties, inviting a range of possible exotic applications. This article addresses common themes in the fundamental science of hydrogen incorporation and transport in oxides as relevant to pressing technological needs. The content covers (1) lattice (or bulk) mechanisms of hydrogen transport, primarily addressing proton transport, but also touching on hydride ion transport; (2) interfacial transport; (3) exploitation of extreme external drivers to achieve unusual response; and (4) advances in methods to probe the hydrogen environment and transport pathway. The snapshot of research activities in the field of hydrogen-laden materials described here underscores exciting recent breakthroughs, remaining open questions, and breathtaking experimental tools now available for unveiling the nature of hydrogen in solid-state matter.

08 HYDROGEN↗
DOE OSTI2024

Design considerations of series type hybrid circuit breaker (S‐HCB)

Abstract The series‐type direct current (DC) hybrid circuit breaker (S‐HCB) concept was previously reported to offer better performance than solid‐state circuit breakers (SSCB) and hybrid circuit breakers (HCB). S‐HCB offers low conduction power loss like an HCB and ‐scale interruption time, which is even faster than an SSCB. It uses a pulse transformer to isolate the lower‐voltage high‐inductance power electronic circuit from the high‐voltage, low‐inductance main power loop. This paper provides analysis of the impact of the S‐HCB circuit components on the overall system performance and a scalable S‐HCB design guide for different DC system voltage and current ratings. In addition, system energy flow analysis is performed in the time domain to provide an understanding of how energy is delivered, dissipated, and released throughout the entire fault interruption process. The S‐HCB prototype was experimentally tested at 3 kV/30 A and 6 kV/150A with the results showing the interruption of the low fault current of 30 A and the high fault current of 150 A within 8 and maintaining the fault current at a near zero value for 300 to enable an arcless opening of a series mechanical switch. The key design challenges of S‐HCB at high voltage and high current ratings were discussed and possible solutions to mitigate those challenges were introduced.

Alashi, Mahmoud↗
DOE OSTI2020

Effect of Computational Schemes on Coupled Flow and Geo-Mechanical Modeling of CO 2 Leakage through a Compromised Well

Carbon capture, utilization, and storage (CCUS) describes a set of technically viable processes to separate carbon dioxide (CO 2 ) from industrial byproduct streams and inject it into deep geologic formations for long-term storage. Legacy wells located within the spatial domain of new injection and production activities represent potential pathways for fluids (i.e., CO 2 and aqueous phase) to leak through compromised components (e.g., through fractures or micro-annulus pathways). The finite element (FE) method is a well-established numerical approach to simulate the coupling between multi-phase fluid flow and solid phase deformation interactions that occur in a compromised well system. We assumed the spatial domain consists of a three-phases system: a solid, liquid, and gas phase. For flow in the two fluids phases, we considered two sets of primary variables: the first considering capillary pressure and gas pressure (PP) scheme, and the second considering liquid pressure and gas saturation (PS) scheme. Fluid phases were coupled with the solid phase using the full coupling (i.e., monolithic coupling) and iterative coupling (i.e., sequential coupling) approaches. The challenge of achieving numerical stability in the coupled formulation in heterogeneous media was addressed using the mass lumping and the upwinding techniques. Numerical results were compared with three benchmark problems to assess the performance of coupled FE solutions: 1D Terzaghi’s consolidation, Liakopoulos experiments, and the Kueper and Frind experiments. We found good agreement between our results and the three benchmark problems. For the Kueper and Frind test, the PP scheme successfully captured the observed experimental response of the non-aqueous phase infiltration, in contrast to the PS scheme. These exercises demonstrate the importance of fluid phase primary variable selection for heterogeneous porous media. We then applied the developed model to the hypothetical case of leakage along a compromised well representing a heterogeneous media. Considering the mass lumping and the upwinding techniques, both the monotonic and the sequential coupling provided identical results, but mass lumping was needed to avoid numerical instabilities in the sequential coupling. Additionally, in the monolithic coupling, the magnitude of primary variables in the coupled solution without mass lumping and the upwinding is higher, which is essential for the risk-based analyses.

deformation flow↗
DOE OSTI2021

Direct Uranium Isotopic Analysis of Swipe Surfaces by Microextraction-ICP-MS

The ability to directly measure uranium isotope ratios on environmental swipes has been achieved through a solution-based microextraction process and represents a significant advancement toward the development of a rapid method to analyze international nuclear safeguard samples. Here, a microextraction probe is lowered and sealed onto the swipe surface, and analytes within the sampling site (~8 mm2) are dissolved and extracted into a flowing solvent of 2% nitric acid (HNO 3 ). The mobilized species are subsequently directed into an inductively coupled plasma-mass spectrometer (ICP-MS) for accurate and precise isotope ratio determination. This work highlights the novelty of the sampling mechanism, particularly with the direct coupling of the microextraction probe to the ICP-MS and measurement of uranium isotope ratios. The preliminary method detection limit for the microextraction-ICP-MS method, utilizing a quadrupole-based MS, was determined to be ~50 pg of 238 U. Additionally, precise and accurate isotope ratio measurements were achieved on uranium reference materials for both the major ( 235 U/ 238 U) and minor ( 234 U/ 238 U and 236 U/ 238 U) ratios. While the present work is focused on directly measuring uranium isotopic systems on swipe surfaces for nuclear safeguards and verification applications, the benefits would extend across many applications in which direct solid sampling is sought for elemental and isotopic analysis.

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

Dual interfacial H-bonding-enhanced deep-blue hybrid copper–iodide LEDs

Solution-processed light-emitting diodes based on non-toxic copper–iodide hybrids are a compelling solution for efficient and stable deep-blue lighting, owing to their tunability, high photoluminescence efficiency and environmental sustainability. Here we present a hybrid copper–iodide that shows near-unity photoluminescence quantum yield (99.6%) with an emission wavelength of 449 nm and colour coordinates (0.147, 0.087), alongside its emission mechanism and charge transport characteristics. Here, we use the thin film of this hybrid as the sole active emissive layer to fabricate deep-blue light-emitting diodes and subsequently enhance the device performance through a dual interfacial hydrogen-bond passivation strategy. This synergetic surface modification approach, integrating a hydrogen-bond-acceptor self-assembled monolayer with an ultrathin polymethyl methacrylate capping layer, effectively passivates both heterojunctions of the copper–iodide hybrid emissive layer and optimizes charge injections. We achieve a maximum external quantum efficiency of 12.57%, a maximum luminance of 3,970.30 cd m −2 with colour coordinates (0.147, 0.091) and an excellent operational stability (half-lifetime) of 204 hours under ambient conditions. We further showcase a large-area device of 4 cm 2 that maintains high efficiency. Our findings reveal the potential of copper–iodide-based hybrid materials for applications in solid-state lighting and display technologies, offering a versatile strategy for enhancing device performances.

14 SOLAR ENERGY↗
DOE OSTI2026

Phase-field model of freeze casting

Directional solidification of water-based solutions has emerged as a versatile technique for templating hierarchical porous materials. However, the underlying mechanisms of pattern formation remain incompletely understood. In this work, we present a detailed derivation and analysis of a quantitative phase-field model for simulating this nonequilibrium process. The phase-field model extends the thin-interface formulation of dilute binary alloy solidification with antitrapping to incorporate the highly anisotropic energetic and kinetic properties of the partially faceted ice-water interface. This interface is faceted in the basal plane normal to the ⟨0001⟩ directions and atomically rough in other directions within the basal plane. On the basal plane, the model reproduces a linear or nonlinear relationship between the interface growth rate and the kinetic undercooling that can be linked to experimental measurements. In both cases, spontaneous parity breaking of the solidification front is observed when the preferred growth direction is aligned with the temperature gradient. This phenomenon leads to the formation of partially faceted ice lamellae that drift laterally in one of the ⟨0001⟩ directions. Here, we demonstrate that the drifting velocity of the ice lamellae is controlled by the kinetics on the basal plane and converges as the thickness of the diffuse solid-liquid interface decreases. Furthermore, we examine the effect of the form of the kinetic anisotropy, which is chosen here such that the inverse of the kinetic coefficient varies linearly from a finite value in the ⟨0001⟩ directions to zero in all other directions within the basal plane, consistent with the assumption that the interface grows in local thermodynamic equilibrium in this plane. Our results indicate that the drifting velocity of ice lamellae is not affected by the slope of this linear relation, and the radius and undercooling at the tip of an ice lamella converge at relatively small slope values. Consequently, the phase-field simulations remain quantitative with computationally tractable choices of both the interface thickness and the slope assumed in the form of the kinetic anisotropy.

Materials science↗
DOE OSTI2022

Effect of heavy ion irradiation dose rate and temperature on α' precipitation in high purity Fe-18%Cr alloy

Cr-rich alpha prime precipitates (CrRP) induce hardening and embrittlement of FeCr alloys, but the kinetics of CrRP formation due to particle irradiation are not well understood. In this study, Fe18wt.%Cr alloy in solid solution state and pre-aged to produce relatively coarse CrRP was irradiated with 8 MeV Fe ions. The irradiation conditions involved two midrange doses of 0.37 and 3.7 displacements per atom (dpa), a wide range of dose rates (10 -5 –10 -3 dpa/s) and temperatures (300–450 °C). The distributions of CrRP after irradiation were studied with atom probe tomography (APT). The critical irradiation conditions to suppress CrRP formation were identified as 300 °C and 10-3 dpa/s; CrRP formation occurred readily at lower dose rates or higher temperatures. From 0.37 to 3.7 dpa, CrRP were observed to slightly grow at 350 °C and strongly coarsen at 450 °C. Specimens with pre-existing CrRP evolved into a similar precipitate distribution as detected after ion irradiation on solution annealed specimens at 300–350 °C to 0.37 dpa, indicating that the precipitate microstructure approaches a quasi-equilibrium for doses <1 dpa. Limited shrinking of pre-existing CrRP was observed after irradiation at 450 °C to 0.37 dpa, indicating a higher recovery rate at this temperature. Additionally, the evolution of CrRP is quantitatively explained by employing corrections to the historic Nelson-Hudson-Mazey precipitate stability model, and a radiation modified precipitation mechanism is proposed to account for the competition between radiation enhanced diffusion and ballistic dissolution which results in the modifications on both size and solute concentration of CrRP.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Nanoprecipitates to Enhance Radiation Tolerance in High-Entropy Alloys

The growth of advanced energy technologies for power generation is enabled by the design, development, and integration of structural materials that can withstand extreme environments, such as high temperatures, radiation damage, and corrosion. High-entropy alloys (HEAs) are a class of structural materials in which suitable chemical elements in four or more numbers are mixed to typically produce single-phase concentrated solid solution alloys (CSAs). Many of these alloys exhibit good radiation tolerance like limited void swelling and hardening up to relatively medium radiation doses (tens of displacements per atom (dpa)); however, at higher radiation damage levels (>50 dpa), some HEAs suffer from considerable void swelling limiting their near-term acceptance for advanced nuclear reactor concepts. In this study, we developed a HEA containing a high density of Cu-rich nanoprecipitates distributed in the HEA matrix. The Cu-added HEA, NiCoFeCrCu 0.12 , shows excellent void swelling resistance and negligible radiation-induced hardening upon irradiation up to high radiation doses (i.e., higher than 100 dpa). The void swelling resistance of the alloy is measured to be significantly better than NiCoFeCr CSA and austenitic stainless steels. Density functional theory simulations predict lower vacancy and interstitial formation energies at the coherent interfaces between Cu-rich nanoprecipitates and the HEA matrix. The alloy maintained a high sink strength achieved via nanoprecipitates and the coherent interface with the matrix at a high radiation dose (~50 dpa). From our experiments and simulations, the effective recombination of radiation-produced vacancies and interstitials at the coherent interfaces of the nanoprecipitates is suggested to be the critical mechanism responsible for the radiation tolerance of the alloy. Furthermore, the materials design strategy based on incorporating a high density of interfaces can be applied to high-entropy alloy systems to improve their radiation tolerance.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Isolation of Inner-Sphere Aquo Complexes of Samarium(II)

The cis-anti-cis and cis-syn-cis isomers of [Sm(dicyclohexano-18-crown-6)(H 2 O) 2 ]I 2 exhibiting trans water molecules bound to the Sm 2+ ion have been isolated and characterized. Sm 2+ possesses an electrochemical potential sufficient for water reduction, and thus these complexes add to the recent body of evidence that the oxidation of Sm 2+ by water can operate by a mechanism that is not straightforward. These complexes are obtained by the direct addition of stoichiometric amounts of water to solutions of the respective Sm(dicyclohexano-18-crown-6)I 2 isomers under an inert atmosphere. The parent complex, Sm(dicyclohexano-18-crown-6)I 2 , lacking coordinating water molecules can be obtained through rigorous exclusion of water. It was determined that the bulky cyclohexano-substituents deter intramolecular interactions between [Sm(dicyclohexano-18-crown-6)(H 2 O) 2 ]I 2 complexes and slow the oxidization of the metal centers. The extent of the stability of these complexes to the presence of water has been further probed through cyclic voltammetry, where it was found that the redox potential of both isomers of [Sm(dicyclohexano-18-crown-6)(H 2 O) 2 ]I 2 maintains quasi-reversible behavior with a 50,000-fold excess of water to Sm 2+ in solution with the cis-syn-cis complex being quasi-reversible at even higher concentrations of water. Solution-phase spectroscopy of these complexes in acetonitrile shows a corresponding hypsochromic shift of the Sm 2+ 4f → 5d transition typically observed in the visible region from Sm 2+ complexes. Here, the crystalline compounds obtained in this study support solid-state spectroscopic trends observed from other Sm 2+ crown-ether complexes containing iodide counterions, wherein the proximity of the iodide ions to the metal center determines whether the complex can exhibit 4f → 4f photoluminescence.

Crystals↗
DOE OSTI2021

Quantifying the chemical, electrochemical heterogeneity and spatial distribution of (poly) sulfide species using Operando SANS

In-situ and operando measurements are done to gain a better understanding of the precipitation mechanisms during charge and discharge in lithium sulfur batteries. A carbon felt networked with microfibers consisting of pores, 2 nm and smaller, is used as a freestanding sulfur host. Three different methods of sulfur infiltration are explored in order to determine the best one to fill most of the pores. It was identified to be a melt infiltration method in a vacuum oven, where the pores including the ultra-micropores, are successfully filled. In-situ electrochemical impedance spectroscopy measurements show a solid product formation occurring at the sulfur cathode, both during the high voltage plateau and at the end of discharge. In a 3-electrode EIS measurement, a similar solid product formation on the Li counter electrode due to its reaction with polysulfides is also observed. Operando small angle neutron scattering measurements show the solid product formation, in the carbon, both near the beginning and at the end of discharge, confirming the precipitation data via contrast changes as a function of charge and discharge. It is shown that Li 2 S precipitates in the pores at the beginning and the end of discharge, whereas S8 precipitates on the surface of the carbon felt. Finally, this lithium sulfur system shows both the quasi-solid-state and the solid-liquid-solid reactions in a typical ethereal electrolyte solution with a two-plateau discharge profile.

25 ENERGY STORAGE↗
DOE OSTI2023

A sharp interface Lagrangian-Eulerian method for flexible-body fluid-structure interaction

This paper introduces a sharp-interface approach to simulating fluid-structure interaction (FSI) involving flexible bodies described by general nonlinear material models and across a broad range of mass density ratios. This new flexible-body immersed Lagrangian-Eulerian (ILE) scheme extends our prior work on integrating partitioned and immersed approaches to rigid-body FSI. Our numerical approach incorporates the geometrical and domain solution flexibility of the immersed boundary (IB) method with an accuracy comparable to body-fitted approaches that sharply resolve flows and stresses up to the fluid-structure interface. Unlike many IB methods, our ILE formulation uses distinct momentum equations for the fluid and solid subregions with a Dirichlet-Neumann coupling strategy that connects fluid and solid subproblems through simple interface conditions. As in earlier work, we use approximate Lagrange multiplier forces to treat the kinematic interface conditions along the fluid-structure interface. This penalty approach simplifies the linear solvers needed by our formulation by introducing two representations of the fluid-structure interface, one that moves with the fluid and another that moves with the structure, that are connected by stiff springs. This approach also enables the use of multi-rate time stepping, which allows us to use different time step sizes for the fluid and structure subproblems. Our fluid solver relies on an immersed interface method (IIM) for discrete surfaces to impose stress jump conditions along complex interfaces while enabling the use of fast structured-grid solvers for the incompressible Navier-Stokes equations. The dynamics of the volumetric structural mesh are determined using a standard finite element approach to large-deformation nonlinear elasticity via a nearly incompressible solid mechanics formulation. This formulation also readily accommodates compressible structures with a constant total volume, and it can handle fully compressible solid structures for cases in which at least part of the solid boundary does not contact the incompressible fluid. Selected grid convergence studies demonstrate second-order convergence in volume conservation and in the pointwise discrepancies between corresponding positions of the two interface representations as well as between first and second-order convergence in the structural displacements. The time stepping scheme is also demonstrated to yield second-order convergence. To assess and validate the robustness and accuracy of the new algorithm, comparisons are made with computational and experimental FSI benchmarks. Test cases include both smooth and sharp geometries in various flow conditions. Furthermore, we also demonstrate the capabilities of this methodology by applying it to model the transport and capture of a geometrically realistic, deformable blood clot in an inferior vena cava filter.

97 MATHEMATICS AND COMPUTING↗