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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 73 records · Page 4

Isogeometric Bézier dual mortaring: The Kirchhoff–Love shell problem

Here in this paper we develop an isogeometric Bézier dual mortar method for coupling multi-patch Kirchhoff–Love shell structures. The proposed approach weakly enforces the continuity of the solution at patch interfaces through a dual mortar method and can be applied to both conforming and non-conforming discretizations. As the employed dual basis functions have local supports and satisfy the biorthogonality property, the resulting stiffness matrix is sparse. In addition, the coupling accuracy is optimal because the dual basis possesses the polynomial reproduction property. We also formulate the continuity constraints through the Rodrigues’ rotation operator which gives a unified framework for coupling patches that are intersected with G 1 continuity as well as patches that meet at a kink. Several linear and nonlinear examples demonstrated the performance and robustness of the proposed coupling techniques.

42 ENGINEERING↗

Proton-Coupled Group Transfer Enables Concerted Protonation Pathways Relevant to Small-Molecule Activation

The mechanistic identification of Nature's use of concerted reactions, in which all bond-breaking and bond-making occurs in a single step, has inspired rational designs for artificial synthetic transformations via pathways that bypass high energy intermediates that would otherwise be thermodynamically and kinetically inaccessible. Here, we electrochemically activate an organometallic Ruthenium(II) complex to show that, in acetonitrile solutions, the movement of protons from weak Brønsted acids, such as water and methanol, is coupled with the transfer of its negatively charged counterpart to carbon dioxide (CO 2 ) - a process termed proton-coupled group transfer - to stoichiometrically produce a metal-hydride complex and a carbonate species. These previously unidentified pathways have played key roles in CO 2 and proton reduction catalysis by enabling the generation of key intermediates such as hydrides and metallocarboxylic acids, while its applicability to carbon acids may provide alternative approaches in the electrosynthesis of chemical commodities via alkylation and carboxylation reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

N -Arylimide Molecular Balances: A Comprehensive Platform for Studying Aromatic Interactions in Solution

Noncovalent interactions of aromatic surfaces play a key role in many biological processes and in determining the properties and utility of synthetic materials, sensors, and catalysts. However, the study of aromatic interactions has been challenging because these interactions are usually very weak and their trends are modulated by many factors such as structural, electronic, steric, and solvent effects. Recently, N-arylimide molecular balances have emerged as highly versatile and effective platforms for studying aromatic interactions in solution. These molecular balances can accurately measure weak noncovalent interactions in solution via their influence on the folded–unfolded conformational equilibrium. The structure (i.e., size, shape, π-conjugation, and substitution) and nature (i.e., element, charge, and polarity) of the π-surfaces and interacting groups can be readily varied, enabling the study of a wide range of aromatic interactions. These include aromatic stacking, heterocyclic aromatic stacking, and alkyl–π, chalcogen–π, silver–π, halogen–π, substituent–π, and solvent–π interactions. The ability to measure a diverse array of aromatic interactions within a single model system provides a unique perspective and insights as the interaction energies, stability trends, and solvent effects for different types of interactions can be directly compared. Some broad conclusions that have emerged from this comprehensive analysis include: (1) The strongest aromatic interactions involve groups with positive charges such as pyridinium and metal ions which interact with the electrostatically negative π-face of the aromatic surface via cation–π or metal–π interactions. Attractive electrostatic interactions can also form between aromatic surfaces and groups with partial positive charges. (2) Electrostatic interactions involving aromatic surfaces can be switched from repulsive to attractive using electron-withdrawing substituents or heterocycles. These electrostatic trends appear to span many types of aromatic interactions involving a polar group interacting with a π-surface such as halogen–π, chalcogen–π, and carbonyl–π. (3) Nonpolar groups form weak but measurable stabilizing interactions with aromatic surfaces in organic solvents due to favorable dispersion and/or solvophobic effects. Furthermore, a good predictor of the interaction strength is provided by the change in solvent-accessible surface area. (4) Solvent effects modulate the aromatic interactions in the forms of solvophobic effects and competitive solvation, which can be modeled using solvent cohesion density and specific solvent–solute interactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Spectroscopic Properties of Americium(III) in Mineral Acid Media

We report the preparation and optical characterization of three solutions of Am(III) in common aqueous (aq.) mineral acids (HCl, HNO 3 and HBr), including absorption, emission, and Raman vibrational analyses. To our knowledge, this study provides the first detailed absorption spectra of Am(III) spanning the entire UV/Vis/NIR region in these mineral acids reported since the 1960s. Here, using this high-resolution absorption data, provided in an open access format for the broader field, we build on prior work by Carnall and others to provide detailed optical analysis including all transition assignments. This work also includes the first reported absorption spectrum of Am(III) in aq. HBr. Characteristic Am(III) luminescence could be detected from all three samples. These are the first reports of emission from Am(III) in these acid systems, which build on prior emission reports collected from aq. HClO 4 solutions. The acquired emission spectra display anion-dependent shifting of the visible-region transitions by up to 21 nm from their predicted positions, akin to the nephelauxetic effect. The shift magnitude trends linearly according to the acid p K a and more generally according to the transition metal spectrochemical series. These ligand field effects, coupled with luminescence lifetime experiments, indicate that weak Am-X interactions persist in solution.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

New Laboratory and Astrophysical Probes of Physics Beyond the Standard Model (Final Technical Report)

The first of these directions centers on new ideas in dark matter detection. As experimental scrutiny narrows the window for new physics at the weak scale, it has become apparent that the solution to the dark matter mystery may not reside there. Theoretical developments such as the hidden sector/valley paradigm have, at the same time, shown that compelling theories of dark matter reside below the weak scale. Searching for dark matter at lower mass scales requires looking beyond the current paradigm of dark matter direct detection based on nuclear recoils. It is the goal of this project to provide new ideas to guide the experimental program looking for light dark matter. I am actively proposing ideas for detecting dark matter as light as a meV, well beyond the current focus of GeV-TeV scale dark matter. Some of the ideas I have proposed, such as superconducting, superfluid, and polar material targets, are actively being developed into experiments. My group will provide the relevant calculations to determine dark matter reach, providing crucial input to experiment on which targets should be developed. We will also provide an effective field theory framework to understand which types of experiments are most sensitive to each interaction type. The second of these directions is on probes of dark matter substructure as a mean to constrain, or observe, models of dark matter. The standard ΛCDM paradigm assumes that the dark matter density perturbations are adiabatic, scale invariant, and produced during inflation. However, many standard models of dark matter will produce modifications of this prediction, such as axion models with symmetry broken below the inflationary scale. Remarkably, we have limited direct measurements of the dark matter clumpiness at mass scales below dwarf galaxies. This allows for the possibility of observing modifications from vanilla ΛCDM due to particle dynamics. In many cases, simulations of dark matter structure in the presence of non-scale invariant fluctu- ations are understudied or completely lacking. I plan to develop both theoretical predictions for small scale structure in models with additional matter power on small scales, as well as observa- tional probes of small scale halos or clumps. One idea I have been recently focused on is pulsar timing, though my group will pursue a variety of lensing and astrometric probes. Lastly, the most risky direction involves spacetime fluctuations from quantum gravity. I showed that if one assumes that metric fluctuations in the Minkowski vacuum, at a surface separating a region in and out of causal contact (which we call a “horizon”), are determined by standard thermodynamic considerations at horizon, these metric fluctuations are large enough to observe in an interferometer with similar sensitivity to LIGO. In a follow-up paper we showed that these assumption holds for the vacuum in AdS/CFT. In future work, I plan to connect this work to recent soft graviton results, to frame this work in a concrete Randall-Sundrum model, and to work out concrete phenomenological predictions from the model. This work unquestionably takes a less trodden path, and works well as part of a well-rounded portfolio of less and more risky ideas. Particle physics is currently at a juncture which requires bold exploration of qualitatively new directions. This proposal outlines some of my plans over the coming years in these directions, leaving room also for surprises.

79 ASTRONOMY AND ASTROPHYSICS↗

Buffer-free process cycle for CO 2 sequestration and carbonate production from brine waste streams with high salinity

A method includes: (1) using a chelating agent, extracting divalent ions from a brine solution as complexes of the chelating agent and the divalent ions; (2) using a weak acid, regenerating the chelating agent and producing a divalent ion salt solution; and (3) introducing carbon dioxide to the divalent ion salt solution to induce precipitation of the divalent ions as a carbonate salt. Another method includes: (1) combining water with carbon dioxide to produce a carbon dioxide solution; (2) introducing an ion exchanger to the carbon dioxide solution to induce exchange of alkali metal cations included in the ion exchanger with protons included in the carbon dioxide solution and to produce a bicarbonate salt solution of the alkali metal cations; and (3) introducing a brine solution to the bicarbonate salt solution to induce precipitation of divalent ions from the brine solution as a carbonate salt.

Sant, Gaurav↗

Buffer-free process cycle for CO 2 sequestration and carbonate production from brine waste streams with high salinity

A method includes: (1) using a chelating agent, extracting divalent ions from a brine solution as complexes of the chelating agent and the divalent ions; (2) using a weak acid, regenerating the chelating agent and producing a divalent ion salt solution; and (3) introducing carbon dioxide to the divalent ion salt solution to induce precipitation of the divalent ions as a carbonate salt. Another method includes: (1) combining water with carbon dioxide to produce a carbon dioxide solution; (2) introducing an ion exchanger to the carbon dioxide solution to induce exchange of alkali metal cations included in the ion exchanger with protons included in the carbon dioxide solution and to produce a bicarbonate salt solution of the alkali metal cations; and (3) introducing a brine solution to the bicarbonate salt solution to induce precipitation of divalent ions from the brine solution as a carbonate salt.

Sant, Gaurav↗

Investigating solutions to the strong CP problem (Final Technical Report)

The weak interaction violates a symmetry between particles and anti-particles that is called a CP symmetry. This violation is expected to induce CP violation in the strong interaction by a large amount. However, observations show that the CP violation in the strong interaction is smaller than expected by more than ten orders of magnitude. This discrepancy is called the strong CP problem, and solving it has been one of the motivations for constructing a theory beyond the Standard Model (SM). In this research program, the PI investigated possible signals of solutions to the strong CP problem. The signals were predicted for a variety of experiments and observations. These predictions bridge different subfields of particle physics, cosmology, and astrophysics that are otherwise disconnected. As a byproduct, the PI also applied the techniques developed in this study to theories with axion-like particles to reveal signals of axion-like particles.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Transmission coefficient of super-Janus solution

We calculate the transmission coefficient of the super-Janus interface conformal field theory, both at weak and at strong coupling, where latter is described holographically as a domain-wall solution on AdS 2 × S 2 × M 4 × Σ. Surprisingly we find perfect agreement between the free and strong coupling answer, mirroring a similar unexpected equivalence previously found for the entanglement entropy.

AdS-CFT correspondence↗

Tipping points emerge from weak mutualism in metacommunities

The coexistence of obligate mutualists is often precariously close to tipping points where small environmental changes can drive catastrophic shifts in species composition. For example, microbial ecosystems can collapse by the decline of a strain that provides an essential resource on which other strains cross-feed. Here, we show that tipping points, ecosystem collapse, bistability and hysteresis arise even with very weak (non-obligate) mutualism provided the population is spatially structured. Based on numeric solutions of a metacommunity model and mean-field analyses, we demonstrate that weak mutualism lowers the minimal dispersal rate necessary to avoid stochastic extinction, while species need to overcome a mean threshold density to survive in this low dispersal rate regime. Our results allow us to make numerous predictions for mutualistic metacommunities regarding tipping points, hysteresis effects, and recovery from external perturbations, and let us draw general conclusions for ecosystems even with random, not necessarily mutualistic, interactions and systems with density-dependent dispersal rather than direct mutualistic interactions.

59 BASIC BIOLOGICAL SCIENCES↗

An experimental comparison of a space-time multigrid method with PFASST for a reaction-diffusion problem

We consider two parallel-in-time approaches applied to a (reaction) diffusion problem, possibly non-linear. In particular, we consider PFASST (Parallel Full Approximation Scheme in Space and Time) and space-time multigrid strategies. For both approaches, we start from an integral formulation of the continuous time dependent problem. Then, a collocation form for PFASST and a discontinuous Galerkin discretization in time for the space-time multi-grid are employed, resulting in the same discrete solution at the time nodes. Strong and weak scaling of both multilevel strategies are compared for varying orders of the temporal discretization. Moreover, we investigate the respective convergence behavior for non-linear problems and highlight quantitative differences in execution times

97 MATHEMATICS AND COMPUTING↗

Geometry-aware framework for deep energy method: An application to structural mechanics with hyperelastic materials

Here, in this work, we introduce a novel physics-informed framework named the Geometry-Aware Deep Energy Method (GADEM) for solving structural mechanics problems on different geometries. As the weak form of the physical system equation (or the energy-based approach) has demonstrated clear advantages compared to the strong form for solving solid mechanics problems, GADEM employs the weak form and aims to infer the solution on multiple shapes of geometries. Integrating a geometry-aware framework into an energy-based method results in an effective physics-informed deep learning model in terms of accuracy and computational cost. Different ways to represent the geometric information and to encode the geometric latent vectors are investigated in this work. We introduce a loss function of GADEM which is minimized based on the potential energy of all considered geometries. An adaptive learning method is also employed for the sampling of collocation points to enhance the performance of GADEM. We present some applications of GADEM to solve solid mechanics problems, including a loading simulation of a toy tire involving contact mechanics and large deformation hyperelasticity. The numerical results of this work demonstrate the remarkable capability of GADEM to infer the solution on various and new shapes of geometries using only one trained model.

97 MATHEMATICS AND COMPUTING↗

Electro-assisted regeneration of pH-sensitive ion exchangers for sustainable phosphate removal and recovery

Removal and recovery of phosphate from wastewater can minimize deleterious environmental impacts and supplement fertilizer supply. Hybrid anion exchangers (HAIX, with doped ferric oxide nanoparticles (FeOnp)) can remove phosphate from complex wastewaters and recover concentrated phosphate solutions. Here, we integrate HAIX with a weak acid cation exchanger (WAC) to enrich phosphate and calcium in mild regenerants and precipitate both elements for recovery. We demonstrated an electro-assisted regeneration approach to avoid strong acid and base input. Based on demonstrated pH sensitivities of both materials, electrochemically produced mild electrolytes (pH 3 and pH 11), which are 100–1000 times less concentrated than typical regenerants, preserved 80% WAC and 50% HAIX capacities over five batch adsorption-regeneration cycles. FeOnp in HAIX facilitated regeneration due to pH sensitivity and their likely distribution on the resin particle surface, which reduced intraparticle diffusion path length. In column tests, repeatable phosphate removal (> 95%) from synthetic wastewater (3 mg P/L) was achieved with 20 kWh/kg P specific energy consumption. After removal, a similar 50% HAIX regeneration efficiency as batch experiments was achieved. In spent regenerant, more than 95% phosphorus was recovered as hydroxyapatite. This novel approach enhances ion exchange by minimizing chemical inputs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A new magnesium sheet alloy with high tensile properties and room-temperature formability

Lightweight sheet alloys with superior mechanical performance such as high strength, ductility and formability at room temperature (RT) are desirable for high volume automotive applications. However, ductility or formability of metallic alloys at RT are generally inversely related to strength, thereby making it difficult to optimize all three simultaneously. Here we design a new magnesium sheet alloy-ZAXME11100 (Mg-1.0Zn-1.0Al-0.5Ca-0.4Mn-0.2Ce, wt. pct.) via CALPHAD (CALculation of PHAse Diagram) modeling and experimental validation. This new sheet alloy offers an excellent RT formability with a high Index Erichsen (I.E.) value of 7.8 mm in a solution-treated condition (T4), due to its weak and split basal texture and fine grain structure. The new ZAXME 11100 alloy also shows a rapid age-hardening response during post-forming artificial aging treatment at 210 °C for 1hour (T6), resulting in a significant increase of yield strength from 159 MPa (T4) to 270 MPa (T6). The excellent combination of T4 ductility (31%), T4 formability (7.8 mm) and T6 yield strength (270 MPa) in this new magnesium alloy is comparable to that of common 6xxx series aluminum sheet alloys. Thus, this new magnesium sheet alloy is highly attractive for sheet applications in automotive and other industries.

36 MATERIALS SCIENCE↗

Variational Quantum Algorithms for Semidefinite Programming

A semidefinite program (SDP) is a particular kind of convex optimization problem with applications in operations research, combinatorial optimization, quantum information science, and beyond. In this work, we propose variational quantum algorithms for approximately solving SDPs. For one class of SDPs, we provide a rigorous analysis of their convergence to approximate locally optimal solutions, under the assumption that they are weakly constrained (i.e., N " M, where N is the dimension of the input matrices and M is the number of constraints). We also provide algorithms for a more general class of SDPs that requires fewer assumptions. Finally, we numerically simulate our quantum algorithms for applications such as MaxCut, and the results of these simulations provide evidence that convergence still occurs in noisy settings.

97 MATHEMATICS AND COMPUTING↗

Variational Quantum Algorithms for Semidefinite Programming

A semidefinite program (SDP) is a particular kind of convex optimization problem with applications in operations research, combinatorial optimization, quantum information science, and beyond. In this work, we propose variational quantum algorithms for approximately solving SDPs. For one class of SDPs, we provide a rigorous analysis of their convergence to approximate locally optimal solutions, under the assumption that they are weakly constrained (i.e., N$\gg$M, where N is the dimension of the input matrices and M is the number of constraints). We also provide algorithms for a more general class of SDPs that requires fewer assumptions. Finally, we numerically simulate our quantum algorithms for applications such as MaxCut, and the results of these simulations provide evidence that convergence still occurs in noisy settings.

97 MATHEMATICS AND COMPUTING↗

Crystal growth and nucleation at metal-organic framework / solution interfaces

Metal-organic frameworks (MOFs) represent an incredibly diverse class of materials with equally diverse applications in catalysis, separations, and gas storage. Despite the prevalence of MOF structures in the literature, in many cases the synthesis of pure, crystalline MOF materials remains a significant challenge, with failed syntheses often yielding mixed crystalline or non-porous amorphous products. Our recent work aims to enable targeted MOF synthesis by developing a comprehensive and predictive model of the fundamental processes occurring at the MOF-solution interface under synthetically-relevant conditions. Our recent accomplishments include: (i) development and implementation of a graphics processor-accelerated approach to simulation the nucleation of weak electrolytes, and the extension of these methods to large/complex solutes such as MOFs; and (ii) studies of the structure of ZIF interfaces under conditions relevant to crystal growth; and (iii) addressing important open questions in the mechanism of MOF solvent-assisted linker exchange, and important synthetic pathway for MOFs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗