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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 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Cover Feature: Rational Design of a Uranyl Metal–Organic Framework for the Capture and Colorimetric Detection of Organic Dyes (Chem. Eur. J. 61/2020)

A new uranyl containing metal–organic framework was prepared and the diffraction data reveals the structure consists of interpenetrating 3D nets with a 4,3-connected tbo topology. Furthermore, each net contains large 22.8 Å pores and is constructed from monomeric, hexagonal bipyramidal uranyl nodes that are joined by 1,2,4,5-tetrakis(4-carboxyphenyl)benzene ligands. The crystalline material is stable in aqueous media and due to the large void space (constituting 76% of the unit cell by volume) can sequester organic dyes, the uptake of which induces a visible change to the color of the material.

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

Glassy embedded solid-state electrode assemblies, solid-state batteries and methods of making electrode assemblies and solid-state batteries

Batteries, component structures and manufacturing methods, in particular including a glassy embedded battery electrode assembly having a composite material structure composed of interpenetrating material components including a porous electroactive network including a solid electroactive material, and a continuous glassy medium including a Li ion conducting sulfide glass, can achieve enhanced power output, reduced charging time and/or improved cycle life.

Visco, Steven J.↗
DOE OSTI2022

Origin of the magnetic couplings for the weak ferromagnet Li + [TCNE] •- (TCNE = Tetracyanoethylene)

Based upon the 16-K crystal structure, the nearest-neighbor spin couplings (J; H = –2JS a •S b ) for the weak ferromagnet (=canted antiferromagnet) Li + [TCNE] •- (TCNE = tetracyanoethylene) (T c = 21 K), which possesses two interpenetrating diamondoid sublattices with two layers of parallel [TCNE] •- s canted with respect to each other by ~60°, are computed at the B3LYP/aug-cc-pV-TZ-level. Li[TCNE] has computed interlattice, through-space interactions that exceed the intralattice, through-bonding to Li + interactions, that are antiferromagnetic. The interlattice interactions dominate the spin coupling leading to the observed weak ferromagnetic behavior. Finally, the computed J's based upon the 50-K structure have the strongest ferromagnetic intralayer interlattice interactions increase by 2.9 ± 0.6% while the antiferromagnetic interlayer interlattice interaction increases by 23% with respect to the 16K results and are in accord with the observed initial increase and subsequent decrease in the temperature dependence of the canting angle that is a consequence of the these changing opposed interactions arising from the change in structure as a function of temperature.

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

Tailored Additive Design of Scaffold‐Free Porous Mg for Ultimate Hydrogen Storage

For hydrogen storage materials to become practically viable, comprehensive improvements in key properties—kinetics, thermodynamics, thermal transport, and durability—are crucial. Porous Mg structure has been proposed as a promising strategy due to its high storage capacity and ability to accommodate volume expansion. However, challenges such as sluggish kinetics and structural degradation resulting from instability due to vacant sites still remain. In this study, a tailored design of porous Mg structure with site-specific transition metal dual-doping and structure-reinforced carbon nanotube (CNT)-framework is presented for optimal hydrogen storage. Ti and Ni are strategically deposited on the surface to synergistically enhance hydrogen sorption kinetics by facilitating hydrogen dissociation and diffusion, while CNTs are interpenetrated into 3D Mg structure for improving thermal conductivity and maintaining the porous structure. The resulting composite demonstrates exceptional performance, achieving hydrogen absorption and desorption of 4.8 and 5.8 wt%, respectively, within 10 min with an impressively low activation energy for absorption of 46 kJ mol −1 H 2 . Even after 50 cycles, its capacity and porous structure are well preserved, showing excellent cyclability in comparison with previously reported materials. In conclusion, this delicate design strategy based on a comprehensive understanding of structural and chemical characteristics is key to maximizing the targeted performance.

CNT embedding↗
DOE OSTI2020

Doubly Interpenetrated Metal-Organic Framework of pcu Topology for Selective Separation of Propylene from Propane

We report that adsorptive separation is an appealing alternative technology to reduce the high energy and capital cost of the distillation separation of propylene/propane; however, it is very challenging to realize. A new flexible metal-organic framework (MOF) material [Zn 2 (BDC-Cl) 2 (Py 2 TTz)] with a doubly interpenetrated pillared paddle wheel structure of pcu (primitive cubic) topology has been realized for this difficult separation for the first time. Through a judicious choice of linkers, the framework has small pore apertures that lead to much more propylene adsorption than propane. The selective adsorption relies on the sieving effect of the flexible framework. The column breakthrough experiment further demonstrated that efficient separation can be achieved under dynamic conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

The interpenetration polymer network in a cement paste–waterborne epoxy system

The formation of the interpenetrating polymer network (IPN) structure within the cement-polymer system has been revealed by experiments from 2 dimensional to 3-dimensional scales. However, the microstructure design and performance prediction of IPN as a function of specific C-S-H/polymer components or ingredients' parameters e.g. water to cement ratios (w/c), polymer to cement ratios (p/c), monomer components, degree of polymerization (DP), etc. is by far not available. Here we developed a mesoscale model for IPN visualization based on the Flory-Huggins interaction theory which was applied to cement science for the first time. All the ingredients in the micro-structure were considered as soluble beads with rational sizes based on their properties obtained by molecular dynamic methods. The interaction parameters of each bead were then determined based on their element ratios and chemical backbones. The model was validated with the waterborne epoxy-cement material (WECM) in which a novel waterborne epoxy resin (WEP) was prepared and impregnated. The verification results on the 2D-3D scale show that the developed model predicts the WECM's IPN structures by rule and line concerning DP, w/c, and p/c in the mixture. The C-S-H beads were progressively scaled in size which alters the C-S-H texture to have completely different dissolution characteristics. Beads of diameter ~6 Å are more unstable and soluble which enable them to form a continuous phase in water or a composite structure with WEP. In contrast, beads with diameters larger than 10 Å have different properties with stronger nucleation effects. The results also suggest the impregnation content of WEP in cement-based material should be limited to 10% vol. to prevent the polymer IPN from decomposing into discrete clusters. The application of Flory-Huggins theory in cement-based composites demonstrates great potential in performance prediction and microstructure design.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Pressure and temperature dependences of the canting angle and increase in the magnetic ordering temperature, T c ( P ), for the weak ferromagnet Li + [TCNE]˙ – (TCNE = tetracyanoethylene)

The hydrostatic pressure dependence of the magnetic ordering temperature, T c (P), for the interpenetrating, diamondoid lattice-structured, weak ferromagnet (= canted antiferromagnet) Li + [TCNE]˙ – (TCNE = tetracyanoethylene) reversibly increases from 20.9 to 23.4 K at 9.73 kbar, an increase of 12% with a rate of increase, dT c /dP, of 0.27 K kbar –1 . The 5 T magnetization increased by 672% from 186 emu Oe mol –1 at ambient pressure to an average of 1440 emuOe mol –1 upon application of pressure. The remanent magnetization initially increases 30% from 10.8 to 14.0 emuOe mol –1 from ambient to 0.06 kbar, and increases further by 6% to a maximum of 14.8 emuOe mol –1 at 0.56 kbar before declining by 22% to 11.5 emuOe mol –1 at 9.73 kbar. The pressure-dependent coercive field, H cr (P), initially decreases by 42% from 31.1 Oe at ambient pressure to 18 Oe at 0.06 kbar, then increases to 52 Oe at 9.73 kbar. The canting angle, α, increases by 28% from 0.52° to 0.66° at 0.06 kbar, then decreases by 23% to 0.51° at 9.73 kbar, as well as increases by 2% from 0.536° to 0.548° from 1.8 to 2.5 K, before decreasing by 79% to 0.117° at 19 K. The interlattice interactions are attributed to be the primary exchange mechanism. Furthermore, α(T) and α(P) have similar dependencies that are attributed to a competition between an increase and a decrease in the intra- and interlayer C … N interlattice separations as the temperature and pressure increases.

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

Structural metamaterials with innate capacitive and resistive sensing

Interpenetrating lattices consist of two or more interwoven but physically separate sub-lattices with unique behaviors derived from their multi-body construction. If the sublattices are constructed or coated with an electrically conducting material, the close proximity and high surface area of the electrically isolated conductors allow the two lattices to interact electromagnetically either across the initial dielectric filled gap or through physical contact. Furthermore, changes in the size of the dielectric gap between the sub-lattices induced by deformation can be measured via capacitance or resistance, allowing a structurally competent lattice to operate as a force or deformation sensor. In addition to resistive and capacitive deformation sensing, this work explores capacitance as a fundamental metamaterial property and the environmental sensing behaviors of interpenetrating lattices.

Computational Solid Mechanics↗
DOE OSTI2023

Soft, malleable double diamond twin

A twin boundary (TB) is a common low energy planar defect in crystals including those with the atomic diamond structure (C, Si, Ge, etc.). We study twins in a self-assembled soft matter block copolymer (BCP) supramolecular crystal having the double diamond (DD) structure, consisting of two translationally shifted, interpenetrating diamond networks of the minority polydimethyl siloxane block embedded in a polystyrene block matrix. The coherent, low energy, mirror-symmetric double tubular network twin has one minority block network with its nodes offset from the (222) TB plane, while nodes of the second network lie in the plane of the boundary. The offset network, although at a scale about a factor of 10 3 larger, has precisely the same geometry and symmetry as a (111) twin in atomic single diamond where the tetrahedral units spanning the TB retain nearly the same strut (bond) lengths and strut (bond) angles as in the normal unit cell. In DD, the second network undergoes a dramatic restructuring—the tetrahedral nodes transform into two new types of mirror-symmetric nodes (pentahedral and trihedral) which alternate and link to form a hexagonal mesh in the plane of the TB. The collective reorganization of the supramolecular packing highlights the hierarchical structure of ordered BCP phases and emphasizes the remarkable malleability of soft matter.

36 MATERIALS SCIENCE↗
NASA NTRS1989

Interpenetrating polymer networks from acetylene terminated materials

As part of a program to develop high temperature/high performance structural resins for aerospace applications, the chemistry and properties of a novel class of interpenetrating polymer networks (IPNs) were investigated. These IPNs consist of a simple diacetylenic compound (aspartimide) blended with an acetylene terminated arylene ether oligomer. Various compositional blends were prepared and thermally cured to evaluate the effect of crosslink density on resin properties. The cured IPNs exhibited glass transition temperatures ranging from 197 to 254 C depending upon the composition and cure temperature. The solvent resistance, fracture toughness and coefficient of thermal expansion of the cured blends were related to the crosslink density. Isothermal aging of neat resin moldings, adhesive and composite specimens showed a postcure effect which resulted in improved elevated temperature properties. The chemistry, physical and mechanical properties of these materials will be discussed.

Connell, J. W.↗
DOE OSTI2022

All-Inorganic Open-Framework Chalcogenides, A 3 Ga 5 S 9 · x H 2 O ( A = Rb and Cs), Exhibiting Ultrafast Uranyl Remediation and Illustrating a Novel Post-Synthetic Preparation of Open-Framework Oxychalcogenides

Fast and effective uranyl sequestration is of interest to the nuclear industry. Recently layered chalcogenide materials have demonstrated fast, selective, and efficient sorption properties towards uranyl cations and the development and investigation of new types of chalcogenide materials continues to be of interest and represents an intriguing option for uranyl remediation. Three new all-inorganic A 3 Ga 5 S 9 ·xH 2 O (A = Rb, Rb/Cs, and Cs) open-framework chalcogenides were obtained via an in-situ alkali carbonate to alkali sulfide conversion process achieved under mild hydrothermal conditions. The structures of the all-inorganic open framework chalcogenides consist of a 2-fold interpenetrated diamond-like 3D framework containing pseudo-T 3 [Ga 10 S 20 ] 10– supertetrahedra. 48% of the structural volume is occupied by A + cations and water species, as established by single-crystal X-ray diffraction (SCXRD), infrared (IR) and energy-dispersive (EDS) spectroscopies. The dynamic nature of the A + cations and water molecules within the pores was investigated via single crystal X-ray diffraction as well as by IR spectroscopy monitored H 2 O to D 2 O exchange experiments. Framework stability was probed with post-synthetic treatment of A 3 Ga 5 S 9 ·xH 2 O (A = Rb and Cs) samples in acidic solutions that resulted in the formation of the oxysulfide (A/H) 3 Ga 5 S 9–y O y ·xH 2 O (A = Rb and Cs; y = 0–1), as shown by SCXRD and IR. Ion-exchange studies on A 3 Ga 5 S 9 ·xH 2 O (A = Rb and Cs) samples were carried out utilizing a uranyl acetate solution. The presence of the UO 2 2+ species in the ion-exchanged product was supported by IR and EDS spectroscopies. Batch method ion-exchange experiments on Cs 3 Ga 5 S 9 ·xH 2 O powder demonstrated fast kinetics with 95% uranyl removal from the uranyl acetate solution during the first minute, a maximum uranyl uptake capacity of 15mg/g, and the subsequent elution of uranyl species with KCl solution. Furthermore, the porous and dynamic nature of the A 3 Ga 5 S 9 ·xH 2 O framework coupled with effective UO 2 2+ ···S 2– bonding interactions makes it a good potential sorbent for uranyl remediation from aqueous media.

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

Rational design of a uranyl metal-organic framework for the capture and colorimetric detection of organic dyes

A new uranyl containing metal-organic framework, RPL-1: [(UO2)2(C28H18O8)] · H2O (RPL for Radiochemical Processing Laboratory), was prepared, structurally characterized, and the solid-state photoluminescence properties explored. The single crystal X-ray diffraction data reveal the structure of RPL-1 consists of two crystallographically unique three dimensional, interpenetrating nets with a 4,3-connected tbo topology. Each net contains large pores with an average width of 22.8 Å and is formed from monomeric, hexagonal bipyramidal uranyl nodes that are linked via 1,2,4,5-tetrakis(4-carboxyphenyl)benzene (TCPB) linkers. The thermal and photophysical properties of RPL-1 were investigated using thermogravimetric analysis and absorbance, fluorescence, and lifetime spectroscopies. The material displays excellent thermal stability and temperature dependent uranyl and TCBP luminescence. The framework is stable in aqueous media and due to the large void space (constituting 76% of the unit cell by volume) can sequester organic dyes, the uptake of which induces a visible change to the color of the material.

Surbella, Robert G.↗
DOE OSTI2024

Viscoelastic relaxation and topological fluctuations in glass-forming liquids

In this study, a method for characterizing the topological fluctuations in liquids is proposed. This approach exploits the concept of the weighted gyration tensor of a collection of particles and permits the definition of a local configurational unit (LCU). The first principal axis of the gyration tensor serves as the director of the LCU, which can be tracked and analyzed by molecular dynamics simulations. Analysis of moderately supercooled Kob–Andersen mixtures suggests that orientational relaxation of the LCU closely follows viscoelastic relaxation and exhibits a two-stage behavior. The slow relaxing component of the LCU corresponds to the structural, Maxwellian mechanical relaxation. Additionally, it is found that the mean curvature of the LCUs is approximately zero at the Maxwell relaxation time with the Gaussian curvature being negative. This observation implies that structural relaxation occurs when the configurationally stable and destabilized regions interpenetrate each other in a bicontinuous manner. Finally, the mean and Gaussian curvatures of the LCUs can serve as reduced variables for the shear stress correlation, providing a compelling proof of the close connection between viscoelastic relaxation and topological fluctuations in glass-forming liquids.

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

Three-dimensional hierarchically porous MoS 2 foam as high-rate and stable lithium-ion battery anode

Architected materials that actively respond to external stimuli hold tantalizing prospects for applications in energy storage, wearable electronics, and bioengineering. Molybdenum disulfide, an excellent two-dimensional building block, is a promising candidate for lithium-ion battery anode. However, the stacked and brittle two-dimensional layered structure limits its rate capability and electrochemical stability. Here we report the dewetting-induced manufacturing of two-dimensional molybdenum disulfide nanosheets into a three-dimensional foam with a structural hierarchy across seven orders of magnitude. Our molybdenum disulfide foam provides an interpenetrating network for efficient charge transport, rapid ion diffusion, and mechanically resilient and chemically stable support for electrochemical reactions. These features induce a pseudocapacitive energy storage mechanism involving molybdenum redox reactions, confirmed by in-situ X-ray absorption near edge structure. The extraordinary electrochemical performance of molybdenum disulfide foam outperforms most reported molybdenum disulfide-based Lithium-ion battery anodes and state-of-the-art materials. This work opens promising inroads for various applications where special properties arise from hierarchical architecture.

25 ENERGY STORAGE↗
DOE OSTI2026

Latent Catalysis as a Platform for Accessing Diverse Material Properties in Vat Photopolymerization 3D Printing

Vat photopolymerization (VP) 3D printing is an attractive strategy to manufacture customized polymer parts. The properties of printed materials are limited by the need to employ a low viscosity liquid resin and achieve rapid polymerization kinetics. To circumvent this limitation, dual‐cure methods have been developed using reagents embedded in the liquid resin formulation; however, the reagent‐based approach requires the discovery and optimization of new chemistry for each desired material. Here, in this work, we demonstrate a catalytic, dual‐cure platform that enables access to both Nylon‐6 and polyester interpenetrating networks through VP 3D printing under a universal approach. Structure–reactivity relationships of the latent NHC catalysts led to the identification of a magnesium chloride–NHC adduct as a latent catalyst that is orthogonal to radical polymerization and can be unmasked at elevated temperatures post‐printing to initiate ring‐opening polymerization of lactones and lactams. This strategy results in access to semicrystalline materials, which are a challenging morphology to access via VP 3D printing, that have attractive mechanical properties and can be printed at high resolution. This work represents the first photochemical‐based 3D printing of Nylon‐based materials and demonstrates the value of catalytic approaches to access new material properties in VP 3D printing.

Colliver, Cali N. [University of North Carolina, C↗
DOE OSTI2023

Structure and properties of bottlebrush polyelectrolyte complexes

Abstract Structural variation of polyelectrolytes has been shown to play an important role in altering polyelectrolyte complex (PEC) properties in recent years. However, molecular‐level details such as polyelectrolyte architecture remain underdeveloped. Here, we use a combination of ring‐opening metathesis polymerization (ROMP), atom‐transfer radical polymerization (ATRP), and postpolymerization reactions to create densely branched bottlebrushes of poly(dimethylamino ethyl methcacrylate) and poly(tert‐butyl methacrylate) with high molecular weights (MDa), which we then convert into fully charged and densely branched bottlebrushes of poly(trimethylaminoethyl methacrylate) (PTMAEMA) and poly(methacrylic acid) (PAA). We investigate the structure and properties of bottlebrush polyelectrolyte complexes (BPECs) using optical microscopy, rheology, cryogenic transmission electron microscopy (Cryo‐TEM), and small‐angle X‐ray scattering (SAXS). Bottlebrush polyelectrolyte complexes are white solids, which exhibit gel‐like mechanical properties, which we attribute to sidechain interpenetration. Using a combination of Cryo‐TEM and SAXS, we are able to outline the structural development of BPECs, detailing how the network topology, sidechain conformation, and interdigitation spacing changes as a function of salt. Our results provide a foundation for further exploration of branched architectures within polyelectrolyte complexation.

Polymer Science↗