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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 1,387 records · Page 77
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Correlated solvent coordinates accelerate multi-donor proton-coupled electron transfer

The rate of charge transfer within a discrete donor–acceptor (D/A) pair is well-described by semi-classical electron transfer theory, but the effects of multiple equivalent redox sites remain less understood. We report a series of ground-state intramolecular proton-coupled electron transfer (PCET) complexes designed to isolate the effects of donor number, N, while holding geometry, coupling, and driving forces constant. The [Ru(L) 3−N (OH) N ] 2+ complexes incorporate one, two, or three identical phenolic electron donors linked to Ru through rigid phenanthroline bridges (OH = 2,4-di-tert-butyl-6-(1-methyl-1H-imidazo[4,5-f][1,10]phenanthrolin-2-yl)phenol). Upon flash photolysis and oxidative quenching with methyl viologen (MV 2+ ), the transient Ru(III) oxidizes an appended phenol by PCET with the hydrogen-bonded imidazole nitrogen atom functioning as the base. The rate increased by 3.4-fold and 5.7-fold (1.7-fold and 1.9-fold after statistical correction) for two- and three-donor complexes compared to the single-donor system. The supra-statistical acceleration is attributed to a reduced effective outer sphere reorganization energy (λ m ) modeled by a partially shared solvent reaction coordinate, in which a subset of solvent dipoles is already oriented to stabilize charge from any donor. The final phenoxyl radical state is localized due to the transfer of a proton, and the recombination reaction with the viologen radical is not accelerated. These results demonstrate the effects of solvent dynamics on intramolecular PCET rates, offering a new strategy for the design of synthetic charge transfer systems.

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

Synthesis and Structural Investigation of Rigid Naphthyridine-Bis(carbene) for Trigonal Planar Coordination of Coinage Metals

Coinage metal complexes, particularly Cu(I) and Au(I), supported by N-heterocyclic carbenes are of broad interest in organometallic synthesis, catalysis, and luminescent materials. The d 10 coinage metals can adopt varied linear, trigonal planar, and tetrahedral geometries. However, two-coordinate, linear Cu(I) and Au(I) complexes supported by sterically demanding monodentate or chelating carbenes are generally observed. In most cases, chelating ligands generate multinuclear species with linear geometries at the corresponding Cu(I) centers rather than mononuclear complexes. In this report, we synthesized two bis(carbene) ligands anchored by a flexible bipyridine and a rigid naphthyridine backbone with tunable proximal and distal steric properties at the wingtips to examine the influence of backbone rigidity and directionality of carbene donors on the formation of trigonal planar coinage metal species. Here, the bipyridine-bis(carbene) (ImPy) 2 ligand exclusively stabilizes dinuclear chloride complexes of Cu(I) and Ag(I), whereas the naphthyridine-bis(carbene) (NBC) stabilizes mononuclear, trigonal planar chloride complexes of Cu(I) and Ag(I) and a dinuclear chloride Au(I) complex.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2000

Multi-Disciplinary Design Optimization Using WAVE

The current preliminary design tools lack the product performance, quality and cost prediction fidelity required to design Six Sigma products. They are also frequently incompatible with the tools used in detailed design, leading to a great deal of rework and lost or discarded data in the transition from preliminary to detailed design. Thus, enhanced preliminary design tools are needed in order to produce adequate financial returns to the business. To achieve this goal, GEAE has focused on building the preliminary design system around the same geometric 3D solid model that will be used in detailed design. With this approach, the preliminary designer will no longer convert a flowpath sketch into an engine cross section but rather, automatically create 3D solid geometry for structural integrity, life, weight, cost, complexity, producibility, and maintainability assessments. Likewise, both the preliminary design and the detailed design can benefit from the use of the same preliminary part sizing routines. The design analysis tools will also be integrated with the 3D solid model to eliminate manual transfer of data between programs. GEAE has aggressively pursued the computerized control of engineering knowledge for many years. Through its study and validation of 3D CAD programs and processes, GEAE concluded that total system control was not feasible at that time. Prior CAD tools focused exclusively on detail part geometry and Knowledge Based Engineering systems concentrated on rules input and data output. A system was needed to bridge the gap between the two to capture the total system. With the introduction of WAVE Engineering from UGS, the possibilities of an engineering system control device began to formulate. GEAE decided to investigate the new WAVE functionality to accomplish this task. NASA joined GEAE in funding this validation project through Task Order No. 1. With the validation project complete, the second phase under Task Order No. 2 was established to develop an associative control structure (framework) in the UG WAVE environment enabling multi-disciplinary design of turbine propulsion systems. The capabilities of WAVE were evaluated to assess its use as a rapid optimization and productivity tool. This project also identified future WAVE product enhancements that will make the tool still more beneficial for product development.

Irwin, Keith↗
NASA NTRS1993

Mechanically fastened composite laminates subjected to combined bearing-bypass and shear loading

Bolts and rivets provide a means of load transfer in the construction of aircraft. However, they give rise to stress concentrations and are often the source and location of static and fatigue failures. Furthermore, fastener holes are prone to cracks during take-off and landing. These cracks present the most common origin of structural failures in aircraft. Therefore, accurate determination of the contact stresses associated with such loaded holes in mechanically fastened joints is essential to reliable strength evaluation and failure prediction. As the laminate is subjected to loading, the contact region, whose extent is not known, develops between the fastener and the hole boundary through this contact region, which consists of slip and no-slip zones due to friction. The presence of the unknown contact stress distribution over the contact region between the pin and the composite laminate, material anisotropy, friction between the pin and the laminate, pin-hole clearance, combined bearing-bypass and shear loading, and finite geometry of the laminate result in a complex non-linear problem. In the case of bearing-bypass loading in compression, this non-linear problem is further complicated by the presence of dual contact regions. Previous research concerning the analysis of mechanical joints subjected to combined bearing-bypass and shear loading is non-existent. In the case of bearing-bypass loading only, except for the study conducted by Naik and Crews (1991), others employed the concept of superposition which is not valid for this non-linear problem. Naik and Crews applied a linear finite element analysis with conditions along the pin-hole contact region specified as displacement constraint equations. The major shortcoming of this method is that the variation of the contract region as a function of the applied load should be known a priori. Also, their analysis is limited to symmetric geometry and material systems, and frictionless boundary conditions. Since the contact stress distribution and the contact region are not known a priori, they did not directly impose the boundary conditions appropriate for modelling the contact and on-contact regions between the fastener and the hole. Furthermore, finite element analysis is not suitable for iterative design calculations for optimizing laminate construction in the presence of fasteners under complex loading conditions. In this study, the solution method developed by Madenci and Ileri (1992a,b) has been extended to determine the contact stresses in mechanical joints under combined bearing-bypass and shear loading, and bearing-bypass loading in compression resulting in dual contact regions.

Madenci, Erdogan↗
DOE OSTI2021

Generalising G 2 geometry: involutivity, moment maps and moduli

We analyse the geometry of generic Minkowski N = 1, D = 4 flux compactifications in string theory, the default backgrounds for string model building. In M-theory they are the natural string theoretic extensions of G2 holonomy manifolds. In type II theories, they extend the notion of Calabi-Yau geometry and include the class of flux backgrounds based on generalised complex structures first considered by Graña et al. (GMPT). Using E 7(7) × $\mathbb{R}$ + generalised geometry we show that these compactifications are characterised by an SU(7) ⊂ E 7(7) structure defining an involutive subbundle of the generalised tangent space, and with a vanishing moment map, corresponding to the action of the diffeomorphism and gauge symmetries of the theory. The Kähler potential on the space of structures defines a natural extension of Hitchin’s G 2 functional. Using this framework we are able to count, for the first time, the massless scalar moduli of GMPT solutions in terms of generalised geometry cohomology groups. It also provides an intriguing new perspective on the existence of G 2 manifolds, suggesting possible connections to Geometrical Invariant Theory and stability.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2025

Restructuring of Benzimidazole-Based Copper Complexes during Electrochemical CO 2 Reduction

Copper-based molecular catalysts have been widely used for the electrochemical reduction of carbon dioxide (ERCO 2 ). However, establishing a correlation between structure and catalytic performance has been challenging due to the dynamic nature of these materials under ERCO 2 working conditions. Here, we report on the restructuring of the copper complexes [Cu(bzimpy)Cl 2 ] and [Cu(pyrben) 2 (NO 3 )]NO 3 during ERCO 2 in an acidic medium, evidencing its effects on the observed activity, selectivity, and stability. In situ X-ray absorption spectroscopy (XAS) suggested that, at sufficiently negative potentials, the Cu 2+ centers of both complexes are reduced to undercoordinated Cu 0 species. Pb underpotential deposition of post-ERCO 2 samples indicated that such Cu 0 species also present a dominant contribution of the (100) domain, which is in line with the high Faradaic efficiency toward C 2 products (∼45%) shown by both complexes at −1.24 V vs RHE. By combining online electrochemical mass spectrometry, in situ XAS, electron paramagnetic resonance (EPR), and quantitative product analysis, we found that [Cu(bzimpy)Cl 2 ] exhibits a partially reversible restructuring, regenerating the main complex moiety, [Cu(bzimpy)] 2+ , and its geometry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1994

Agglomeration multigrid for the three-dimensional Euler equations

A multigrid procedure that makes use of coarse grids generated by the agglomeration of control volumes is advocated as a practical approach for solving the three dimensional Euler equations on unstructured grids about complex configurations. It is shown that the agglomeration procedure can be tailored to achieve certain coarse grid properties such as the sizes of the coarse grids and aspect ratios of the coarse grid cells. The agglomeration is done as a preprocessing step and runs in linear time. The implications for multigrid of using arbitrary polyhedral coarse grids are discussed. The agglomeration multigrid technique compares very favorably with existing multigrid procedures both in terms of convergence rates and elapsed times. The main advantage of the present approach is the ease with which coarse grids of any desired degree of coarseness may be generated in three dimensions, without being constrained by considerations of geometry. Inviscid flows over a variety of complex configurations are computed using the agglomeration multigrid strategy.

Venkatakrishnan, V.↗
DOE OSTI2024

Medial axis and local thickness computation using the Fast Sweeping Method

This report describes an efficient and robust voxel-based methodology for computing the medial axis, local thickness, and distance-to-skeleton of arbitrary three-dimensional geometries. It is assumed that the object can be represented by an exact or approximate signed distance function on a discrete grid. The gradient of such function is used to formulate a hyperbolic partial differential equation (PDE) that models the collapse of the position vector in space. By exploiting the causality property of the PDE, the Fast Sweeping Method is able to obtain the solution in a finite number of sweeps independent of the mesh resolution. The intersection of characteristic lines leads to the formation of shocks and a discrete bisector function is used to identify the medial axis. The same PDE approach is used to compute the local thickness inside the object and obtain the distance-to-skeleton field. Multiple examples are given in two and three dimensions along with a resolution study. The methodology has optimal complexity and yields subsecond computational times for geometries with over a million zones on a single core. The methodology is also capable of parallelization across shared and distributed memory architectures.

97 MATHEMATICS AND COMPUTING↗
NASA NTRS1977

Ray trajectories in a torus: An application of MACSYMA to a complex numerical computation

The study of ray trajectories of plasma waves in a torodial geometry using MACSYMA is an example of how symbolic, numerical, and graphical facilities can be used in concert to accomplish a complex computational goal. Computational features of this study which are of particular significance include: the derivation of code (i.e. writing functions to generate program fragments), the use of array functions to simplify the specification of a numerical iteration scheme, and the graphical presentation of the results. Mathematically, this study originates in the solution of a linear inhomogeneous partial differential equation in 3 dimensions by the method of characteristics. While it is possible to describe this equation compactly by using vector notation, and by specifying the spatial variation of the coefficients in terms of intermediate parameters, the transformation of the equation into a form amenable to solution is very tedious. A MACSYMA program is presented for obtaining description of the rf field structure excited by a waveguide located at the edge of a toroidal plasma confinement device.

Kulp, J. L.↗
DOE OSTI2025

Closing the Loop between In Situ Stress Complexity and EGS Fracture Complexity

We present an agent-guided approach to CAD geometry decomposition that automates hex/hybrid meshing with graph neural networks (GNNs) to accelerate next-generation ModSim workflows. Our end-to-end pipeline (i) reduces 3D boundary-representation (B-Rep) models to a 2D chordal axis skeleton (CAT) and then to a 1D bipartite graph of surface and curve nodes, (ii) assigns per node labels as Cubit® WebCut actions, (iii) trains a multi-action GNN under supervised learning, and (iv) predicts five surface-node and three curve-node actions on out-of-distribution test geometries. Each graph node carries geometric, topological, and meshing attributes drawn from the B-Rep “skin” and CAT “skeleton,” with two-way mappings across 3D↔2D↔1D representations to maintain traceability back to 3D CAD. The supervised learning model exhibits stable convergence of the binary cross-entropy loss and achieves 98.7% accuracy on unseen lattice models. To operationalize decision-making, we rank predicted commands by geometric significance and prototyped the agent-guided workflow through the Cubit® Meshing PowerTool GUI. As a stretch goal, we explore reinforcement learning (RL) to reduce or remove label requirements and to learn policies for action sequences that maximize total reward (e.g., size of hex-meshable regions and resulting hex mesh quality). When all-hex meshing is not feasible, the agent assists in producing hybrid meshes—prioritizing hex in critical regions and transitioning to tetrahedral elements (tets) elsewhere—maintaining fidelity while ensuring robustness. The overarching objective is to replace manual, heuristics-based decomposition with data-driven, reproducible automation, cutting meshing turnaround time by orders of magnitude. We anticipate direct impact on simulation workflows through intelligent, scalable decomposition of complex CAD models into hex-meshable subdomains.

42 ENGINEERING↗
DOE OSTI2024

Investigation of CAD-based Geometry Workflows for Multiphysics Fusion Problems Using OpenMC and MOOSE

Fusion system designs are complex and require intricate and accurate meshes to be properly modeled. In this study, we investigate the use of CAD-based geometry workflows in fusion systems multiphysics problems. A simplified tokamak was introduced and modeled in CAD using a multiphysics coupling of OpenMC Monte Carlo transport and MOOSE heat conduction. The meshed geometry was prepared using direct accelerated geometry Monte Carlo (DAGMC) for particle transport, and a volumetric mesh was also prepared to be used in MOOSE and to tally OpenMC results. Cardinal was used to run OpenMC Monte Carlo particle transport within MOOSE framework. The heat source distribution and tritium production were calculated in OpenMC. The data transfer system was used to transfer heat source and temperature distribution between OpenMC and MOOSE. Two computational studies related to mesh refinement were performed: (1) refining the DAGMC and volumetric meshes used for tallying results and solving heat conduction and (2) only refining the DAGMC particle transport mesh. The refinement of the tally mesh has a much larger effect on the runtime compared to the refinement of the DAGMC particle transport surface mesh.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2023

X-ray Absorption Spectroscopy Studies of a Molecular CO 2 -Reduction Catalyst Deposited on Graphitic Carbon Nitride

Metal-ligand complexes have been extensively explored as well-defined molecular catalysts in small molecule activation reactions such as carbon dioxide (CO 2 ) reduction. Many hybrid photocatalysts have been prepared by coupling such complexes with photoactive surfaces for use in solar CO 2 reduction. In this work, we employ X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectroscopies, density functional theory (DFT) and computational XANES modeling to interrogate the structure of a hybrid photocatalyst consisting of a macrocyclic cobalt complex deposited on graphitic carbon nitride (C 3 N 4 ). Results show that the cobalt complex binds on C 3 N 4 through surface OH or NH 2 groups. By refining the local geometry and binding sites of this well-defined molecular cobalt complex on C 3 N 4 , here we established an important benchmark for modeling a large class of molecular catalysts that can be adapted to in situ/operando studies and further enhanced by applying chemometrics-based approaches and machine learning methods of XANES data analysis.

36 MATERIALS SCIENCE↗
NASA NTRS2010

Analysis of a Channeled Centerbody Supersonic Inlet for F-15B Flight Research

The Propulsion Flight Test Fixture at the NASA Dryden Flight Research Center is a unique test platform available for use on the NASA F-15B airplane, tail number 836, as a modular host for a variety of aerodynamics and propulsion research. The first experiment that is to be flown on the test fixture is the Channeled Centerbody Inlet Experiment. The objectives of this project at Dryden are twofold: 1) flight evaluation of an innovative new approach to variable geometry for high-speed inlets, and 2) flight validation of channeled inlet performance prediction by complex computational fluid dynamics codes. The inlet itself is a fixed-geometry version of a mixed-compression, variable-geometry, supersonic in- let developed by TechLand Research, Inc. (North Olmsted, Ohio) to improve the efficiency of supersonic flight at off-nominal conditions. The concept utilizes variable channels in the centerbody section to vary the mass flow of the inlet, enabling efficient operation at a range of flight conditions. This study is particularly concerned with the starting characteristics of the inlet. Computational fluid dynamics studies were shown to align well with analytical predictions, showing the inlet to remain unstarted as designed at the primary test point of Mach 1.5 at an equivalent pressure altitude of 29,500 ft local conditions. Mass-flow-related concerns such as the inlet start problem, as well as inlet efficiency in terms of total pressure loss, are assessed using the flight test geometry.

Ratnayake, Nalin A.↗
DOE OSTI2025

Assessing the viability of a new subsize tensile specimen geometry for evaluation of structural nuclear and additively manufactured materials

The use of subsize specimens in nuclear materials testing has been a subject of ongoing interest due to radiation safety concerns and resource conservation needs. It is also of interest in additive manufacturing (AM), also known as 3D-printing, as subsize specimens can more accurately represent the behavior of the small, intricate geometries often produced using AM. A novel, extremely small geometry, called the Subsize Teeny (SST) was recently developed and is of interest for implementation. Given its extraordinarily small size and the complexities associated with subsize specimen testing, adequate vetting of this geometry is necessary to ensure data quality. Here, a variety of unirradiated nuclear structural materials were tested in the SST geometry and compared against the well-established SSJ3 geometry. In addition, two case studies implementing the SST as a screening geometry for AM materials were also conducted. The question of SST viability was found to be highly nuanced and will often be dependent on the context or application in question. It was determined, however, that the SST is a largely invalid geometry for exceptionally coarse-grained materials or in cases where the physical defect volume equals or exceeds 0.1 % or where the specimen machining parameters result in significant surface alterations. On the other hand, it was determined that the SST may be employed with confidence if the test material is nearly or totally free of physical defects, isotropic, demonstrates homogeneous plastic deformation, and possesses a fine-grained, nearly or totally homogeneous microstructure with at least twelve slip systems.

Additive manufacturing↗
DOE OSTI2020

2D Retrieval Frameworks for Hot Jupiter Phase Curves

Spectroscopic phase curves provide unique access to the three-dimensional properties of transiting exoplanet atmospheres. However, a modeling framework must be developed to deliver accurate inferences of atmospheric properties for these complex data sets. Here, we develop an approach to retrieve temperature structures and molecular abundances from phase curve spectra at any orbital phase. In the context of a representative hot Jupiter with a large day–night temperature contrast, we examine the biases in typical one-dimensional (1D) retrievals as a function of orbital phase/geometry, compared to two-dimensional (2D) models that appropriately capture the disk-integrated phase geometry. We guide our intuition by applying our new framework on a simulated Hubble Space Telescope (HST)+Spitzer phase curve data set in which the “truth” is known, followed by an application to the spectroscopic phase curve of the canonical hot Jupiter, WASP-43b. We also demonstrate the retrieval framework on simulated James Webb Space Telescope (JWST) phase curve observations. We apply our new geometric framework to a joint fit of all spectroscopic phases, assuming longitudinal molecular abundance homogeneity, resulting in an a factor of 2 improvement in abundances precision when compared to individual phase constraints. With a 1D retrieval model on simulated HST+Spitzer data, we find strongly biased molecular abundances for CH{sub 4} and CO{sub 2} at most orbital phases. With 2D, the day and night profiles retrieved from WASP-43b remain consistent throughout the orbit. JWST retrievals show that a 2D model is strongly favored at all orbital phases. Based on our new 2D retrieval implementation, we provide recommendations on when 1D models are appropriate and when more complex phase geometries involving multiple TP profiles are required to obtain an unbiased view of tidally locked planetary atmospheres.

79 ASTRONOMY AND ASTROPHYSICS↗
NASA NTRSDate not supplied

SIBatt-3D: In-Space/On-Surface 3D Printing of Sodium Ion Batteries from ISRU Materials

Constructed more than 20 years ago, the International Space Station’s primary power system originally used nickel-hydrogen batteries with a lifetime of 6.5 years, until NASA began the process of replacing them in 2016 with lithium-ion batteries with a lifetime of 10 years. The demanding and costly process was accomplished after four flights of the Japanese H-II Transfer Vehicle cargo spacecraft (with a cost of about $10,000 per pound of payload), and 13 different astronauts conducting 14 spacewalks. Besides utilization in the ISS, rechargeable batteries are present in many space applications: they are installed in exploration robots, life support systems and in portable communication devices, to mention some. In this context, this project is focused on the in-space manufacturing of shape-conformable batteries using in-situ resources, and aims to address the NASA’s gaps related to the development of next generation of energy storage devices (TX03), as well as in-space manufacturing and in-situ resource utilization (TX07). The proposed work also tackles the HEOMD’s objectives targeting the in-space additive manufacturing (AM) from Lunar/Martian materials (regolith as AM feedstock) to reinvigorate America’s Human Space Exploration Program (SPD-1). This project is in direct alignment with the STMD’s objectives to demonstrate in-space autonomous manufacturing and assembly of complete systems by 2030, and to enable humans to live and explore in space and on planetary surfaces by 2040 thanks to in-space habitation, infrastructure development and in-situ resource utilization (ST1 and ST5). Manufacturing of shape conformable batteries directly in-space and using in-situ resources would also contribute to reducing the payload weight and volume (TX12) for future missions, thus reducing risk for long term Mars missions where rapid resupply is logistically infeasible. Nowadays, commercial batteries consist of stacked two-dimensional (2D) sheets, which are only manufactured in restricted geometries (cylindrical and coin cell). Evolving from conventional 2D, complex 3D battery architectures have been proven to increase the electrochemical active surface area and ion diffusion path, leading to improved areal energy density and power performance. This tendency was illustrated in our recent in-depth modeling studies by simulating a classical Ragone plot exhibiting the energy-power relationship. Our team demonstrated through modeling that a complex gyroidal 3D printed battery architecture exhibits significantly improved power performances (>150% at the current density of 6C; full discharge in 10 minutes) in comparison to a traditional 3D printed planar geometry. Motivated by these results and as the fabrication of intricate 3D battery design is only possible experimentally thanks to the geometric freedom offered by additive manufacturing (AM), our team has already initiated leveraging thermoplastic material extrusion at the laboratory scale. While 3D printing of batteries is relatively recent (2013), it has witnessed a growing interest during the last recent years, as next-generation shape-conformable 3D batteries can be co-designed with the system. Consequently, dead-volume and mass brought from Earth are minimized, in addition to improved battery performance, in alignment with the aforementioned NASA’s objectives. Further, while this project is specifically dedicated to batteries, it lends itself towards the maturation of in-space manufacturing via 3D printing using in-situ resources, stated in HEOMD and STMD goals.

In-Space Manufacturing↗
DOE OSTI2021

Simulation of hardened cement degradation and estimation of uncertainty in predicted failure times with peridynamics

Modeling the degradation of cement-based infrastructure due to aqueous environmental conditions continues to be a challenge. In order to develop a capability to predict concrete infrastructure failure due to chemical degradation, here we created a chemomechanical model of the effects of long-term water exposure on cement paste. The model couples the mechanical static equilibrium balance with reactive–diffusive transport and incorporates fracture and failure via peridynamics (a meshless simulation method). The model includes fundamental aspects of degradation of ordinary Portland cement (OPC) paste, including the observed softening, reduced toughness, and shrinkage of the cement paste, and increased reactivity and transport with water induced degradation. This version of the model focuses on the first stage of cement paste decalcification, the dissolution of portlandite. Given unknowns in the cement paste degradation process and the cost of uncertainty quantification (UQ), we adopt a minimally complex model in two dimensions (2D) in order to perform sensitivity analysis and UQ. We calibrate the model to existing experimental data using simulations of common tests such as flexure, compression and diffusion. Then we calculate the global sensitivity and uncertainty of predicted failure times based on variation of eleven unique and fundamental material properties. We observed particularly strong sensitivities to the diffusion coefficient, the reaction rate, and the shrinkage with degradation. Also, the predicted time of first fracture is highly correlated with the time to total failure in compression, which implies fracture can indicate impending degradation induced failure; however, the distributions of the two events overlap so the lead time may be minimal. Extension of the model to include the multiple reactions that describe complete degradation, viscous relaxation, post-peak load mechanisms, and to three dimensions to explore the interactions of complex fracture patterns evoked by more realistic geometry is straightforward and ongoing.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Polarity-Tolerant Chloride Binding in Foldamer Capsules by Programmed Solvent-Exclusion

Persistent anion binding in a wide range of solution environments is a key challenge that continues to motivate and demand new strategies in synthetic receptor design. Though strong binding in low-polarity solvents has become routine, our ability to maintain high affinities in high-polarity solvents has not yet reached the standard set by nature. Anions are bound and transported regularly in aqueous environments by proteins that use secondary and tertiary structure to isolate anion binding sites from water. Inspired by this principle of solvent exclusion, we created a sequence-defined foldameric capsule whose global minimum conformation displays a helical folded state and is preorganized for 1:1 anion complexation. The high stability of the folded geometry and its ability to exclude solvent were supported by solid-state and solution phase studies. This capsule then withstood a 4-fold increase in solvent dielectric constant (εr) from dichloromethane (9) to acetonitrile (36) while maintaining a high and solvent-independent affinity of 10 5 M –1 ; ΔG ~ 28 kJ mol –1 . This behavior is unusual. More typical of solvent-dependent behavior, Cl – affinities were seen to plummet in control compounds, such as aryl-triazole macrocycles and pentads, with their solvent-exposed binding cavities susceptible to dielectric screening. Finally, dimethyl sulfoxide denatures the foldamer by putative solvent binding, which then lowers the foldamer’s Cl – affinity to normal levels. Furthermore, the design of this capsule demonstrates a new prototype for the development of potent receptors that can operate in polar solvents and has the potential to help manage hydrophilic anions present in the hydrosphere and biosphere.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗