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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 415 records · Page 23
All sourcesNASA NTRSDOE OSTI
DOE OSTI2018

Impact of Helical Chain Shape in Sequence-Defined Polymers on Polypeptoid Block Copolymer Self-Assembly

Controlling the self-assembly of block copolymers with variable chain shape and stiffness is important for driving the self-assembly of functional materials containing nonideal chains as well as for developing materials with new mesostructures and unique thermodynamic interactions. The polymer helix is a particularly important functional motif. In the helical chain, the traditional scaling relationships between local chain stiffness and space-filling properties are not applicable; this in turn impacts the scaling relationships critical for governing self-assembly. Polypeptoids, a class of sequence-defined peptidomimetic polymers with controlled helical secondary structure, were used to systematically investigate the impact of helical chain shape on block copolymer self-assembly in a series of poly(n-butyl acrylate)-b-polypeptoid block copolymers. Small-angle X-ray scattering (SAXS) of the bulk materials shows that block copolymers form hexagonally packed cylinder domains. By leveraging sequence control, the polypeptoid block was controlled to form a helix only at the part either adjacent to or distant from the block junction. Differences in domain size from SAXS reveal that chain stretching of the helix near the block junction is disfavored, while helical segments at the center of cylindrical domains contribute to unfavorable packing interactions, increasing domain size. Finally, temperature-dependent SAXS shows that helix-containing diblock copolymers disorder at lower temperatures than the equivalent unstructured diblock copolymers; we attribute this to the smaller effective N of the helical structure resulting in a larger entropic gain upon disordering. These results emphasize how current descriptions of rod/coil interactions and conformational asymmetry for coil polymers do not adequately address the behavior of chain secondary structures, where the scalings of space-filling and stiff-elastic properties relative to chain stiffness deviate from those of typical coil, semiflexible, and rodlike polymers.

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

Blocky Selective Postpolymerization C–H Functionalization of Polyolefins

C–H functionalization of commodity polyolefins affords functional materials derived from a high-volume, low-cost resource. However, current postpolymerization modification strategies result in randomly distributed functionalization along the length of the polymer backbone, which has a negative impact on the crystallinity of the resultant polymers, and thus the thermomechanical properties. Here, we demonstrate an amidyl radical mediated C–H functionalization of polyolefins to access blocky microstructures, which exhibit a higher crystalline fraction, larger crystallite size, and improved mechanical properties compared to their randomly functionalized analogues. Taking inspiration from the site-selective C–H functionalization of small molecules, we leverage the steric protection provided by crystallites and target polymer functionalization to amorphous domains in a semicrystalline polyolefin gel. The beneficial outcomes of blocky functionalization are independent of the identity of the pendant functional group that is installed through functionalization. Here, the decoupling of functional group incorporation and crystallinity highlights the promise in accessing nonrandom microstructures through selective functionalization to circumvent traditional tradeoffs in postpolymerization modification, with potential impact in advanced materials and upcycling plastic waste.

Neidhart, Eliza K. [The University of North Caroli↗
DOE OSTI2019

High capacity vanadium oxide electrodes: effective recycling through thermal treatment

This study demonstrates that thermal regeneration is an effective approach to convert degraded phases to functioning electroactive materials, restore functional delivered capacity and recover material crystallinity while retaining the integrity of the parent electrode. V 2 O 5 nanowires were synthesized through a facile hydrothermal method and used to fabricate V 2 O 5 /carbon nanotube (CNT) binder free electrodes. Discharge of the V 2 O 5 –CNT electrodes coupled with operando energy dispersive X-ray diffraction shows no evidence of phase segregation throughout the 150 μm thick binder free electrodes indicating full utilization of a thick electrode. When V 2 O 5 is highly electrochemically lithiated (x > 2 in LixV 2 O 5 ), irreversible phase transformation to ω-LixV 2 O 5 was observed, accompanied by a capacity decrease of ~40% over 100 cycles. A simple thermal treatment of the entire electrode results in a delivered capacity equal to or higher than the original value. Both phase conversion and an increase in material crystallinity as a result of thermal treatment are observed where structural analysis indicates the formation of Li 1 V 3 O 8 . The electrode design approach with thick electrodes and functional thermal regeneration may provide a broader choice of electroactive materials through decreasing the environmental burden by extending the lifetime of energy storage systems.

25 ENERGY STORAGE↗
DOE OSTI2023

Protection against Chemical Warfare Agents and Biological Threats Using Metal–Organic Frameworks as Active Layers

The SARS-CoV-2 pandemic outbreak and the unfortunate misuse of toxic chemical warfare agents (CWAs) highlight the importance of developing functional materials to protect against these chemical and pathogen threats. Metal–organic frameworks (MOFs), which comprise a tunable class of crystalline porous materials built from inorganic nodes and organic linkers, have emerged as a class of heterogeneous catalysts capable of rapid detoxification of multiple classes of these harmful chemical or biological hazards. In particular, zirconium-based MOFs (Zr-MOFs) feature Lewis acidic nodes that serve as active sites for a wide range of catalytic reactions, including the hydrolysis of organophosphorus nerve agents within seconds in basic aqueous solutions. In addition, postsynthetic modification of Zr-MOFs enables the release of active species capable of reacting with and deactivating harmful pathogens. Despite this impressive performance, utilizing Zr- MOFs in powder form is not practical for application in masks or protective uniforms. To address this challenge, our team sought to develop MOF/fiber composite systems that could be adapted for use under realistic operating conditions to protect civilians, military personnel, and first responders from harmful pathogens and chemical warfare agents. Over the last several years, our group has designed and fabricated reactive and biocidal MOF/fiber composites that effectively capture and deactivate these toxic species. In this Account, we describe the evolution of these porous and reactive MOF/fiber composites and focus on key design challenges and considerations. First, we devised a scalable method for the integration of Zr-MOFs onto textile substrates using aqueous precursor solutions and without using pretreated textiles, highlighting the potential scalability of this method. Moving beyond standard textiles, we also developed a microbial synthesis strategy to prepare hierarchically porous MOF/bacterial cellulose nanofiber composite sponges that can both capture and detoxify nerve agents when exposed to contaminated gas flows. The mass loading of the MOF in the nanofibrous composite sponge is up to 90%, affording higher work capacities compared to those of textile-fiber-based composites with relatively lower MOF loadings. Next, we demonstrated that heterogeneous polymeric bases are suitable replacements for volatile liquid bases typically used in solution-phase reactions, and we showed that these composite systems are capable of effectively hydrolyzing nerve agents in the solid state by using only water that is present as humidity. Moreover, incorporating a reactive dye precursor into the composite affords a dual function sensing and detoxifying material that changes color from white to orange upon reaction with the byproduct following nerve agent hydrolysis, demonstrating the versatility of this platform for use in decontamination applications. We then created chlorine-loaded MOF/fiber composites that act as biocidal and reactive textiles that are capable of not only detoxifying sulfur-mustard-based chemical warfare agents and simulants but also deactivating both bacteria and the SARS-CoV-2 virus within minutes of exposure. Lastly, we synthesized a mixed-metal Ti/Zr-MOF coating on cotton fibers to afford a photoactive biocidal cloth that shows fast and broad-spectrum biocidal performance against viruses and Gram-positive and Gram-negative bacteria under visible light irradiation. Given the tunable, multifunctional nature of these MOF/fiber composites, we believe that this Account will offer new insights for the rational design and preparation of functional MOF/fiber composites and pave the way toward the development of next-generation reactive and protective textiles.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Organic Synthetic Advanced Materials for Optoelectronic and Energy Applications (at National Taipei University of Technology)

These slides cover Hung-Ju Yen's recent work in the synthesis and structural design of functional materials, which were further used for optoelectronic and energy applications, such as lithium ion battery, solar cell, LED, electrochromic, and fuel cells. This was for a job interview at National Taipei University of Technology. The following topics are detailed: current challenges for lithium-ion batteries; graphene, graphene oxide and nanographene; nanographenes with various functional groups; fine tune d-spacing through organic synthesis: varying functional group; schematic view of LIBs; nanographenes as LIB anode; rate performance (charging-discharging); electrochromic technology; electrochromic materials; advantages of triphenylamine; requirement of electrochromic materials for practical applications; low driving voltage and long cycle life; increasing the electroactive sites by multi-step synthetic procedures; synthetic route to starburst triarylamine-based polyamide; electrochromism ranging from visible to NIR region; transmissive to black electrochromism; RGB and CMY electrochromism.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Organic Synthetic Advanced Materials for Optoelectronic and Energy Applications (at Center for Condensed Matter Sciences)

These slides cover Hung-Ju Yen's recent work in the synthesis and structural design of functional materials, which were further used for optoelectronic and energy applications, such as lithium ion battery, solar cell, LED, electrochromic, and fuel cells. This was for a job interview at Center for Condensed Matter Sciences. The following topics are detailed: current challenges for lithium-ion batteries; graphene, graphene oxide and nanographene; nanographenes with various functional groups; fine tune d-spacing through organic synthesis: varying functional group; schematic view of LIBs; nanographenes as LIB anode; rate performance (charging-discharging); electrochromic technology; electrochromic materials; advantages of triphenylamine; requirement of electrochromic materials for practical applications; low driving voltage and long cycle life; increasing the electroactive sites by multi-step synthetic procedures; synthetic route to starburst triarylamine-based polyamide; electrochromism ranging from visible to NIR region; transmissive to black electrochromism; RGB and CMY electrochromism.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Surfactant-like peptide gels are based on cross-β amyloid fibrils

Surfactant-like peptides, in which hydrophilic and hydrophobic residues are encoded within different domains in the peptide sequence, undergo facile self-assembly in aqueous solution to form supramolecular hydrogels. These peptides have been explored extensively as substrates for the creation of functional materials since a wide variety of amphipathic sequences can be prepared from commonly available amino acid precursors. The self-assembly behavior of surfactant-like peptides has been compared to that observed for small molecule amphiphiles in which nanoscale phase separation of the hydrophobic domains drives the self-assembly of supramolecular structures. Here, we investigate the relationship between sequence and supramolecular structure for a pair of bola-amphiphilic peptides, Ac-KLIIIK-NH 2 (L2) and Ac-KIIILK-NH 2 (L5). Despite similar length, composition, and polar sequence pattern, L2 and L5 form morphologically distinct assemblies, nanosheets and nanotubes, respectively. Cryo-EM helical reconstruction was employed to determine the structure of the L5 nanotube at near-atomic resolution. Rather than displaying self-assembly behavior analogous to conventional amphiphiles, the packing arrangement of peptides in the L5 nanotube displayed steric zipper interfaces that resembled those observed in the structures of β-amyloid fibrils. Like amyloids, the supramolecular structures of the L2 and L5 assemblies were sensitive to conservative amino acid substitutions within an otherwise identical amphipathic sequence pattern. This study highlights the need to better understand the relationship between sequence and supramolecular structure to facilitate the development of functional peptide-based materials for biomaterials applications.

Das, Abhinaba [Emory University, Atlanta, GA (Unit↗
DOE OSTI2018

Characterization of Polycrystalline Fe{sub 2}B Compound with High Saturation Magnetization

The crystal structure, magnetic phase transition, high saturation magnetization, and chemical status of polycrystalline Fe{sub 2}B compound were investigated. The results show that a single phase with the CuAl{sub 2}-type tetragonal structure with space group of I4/mcm is clearly observed, and the Curie temperature is 1017 K. A maximum value of saturation magnetization (M) of 173 Am{sup 2}⋅kg{sup −1} was achieved when the saturated magnetic field was ∼5 kOe at 300 K. Moreover, XPS proved that the chemical status of Fe and B elements existed in the form of Fe{sub 2}B in this compound. The polycrystalline Fe{sub 2}B compound with large saturation magnetization is economical and non-toxic raw materials, which would be of considerable importance for exploring the potential applications in the magnetic functional material field.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2022

Reticular Chemistry for Highly Porous Metal–Organic Frameworks: The Chemistry and Applications

Current global crises related to clean energy and the environment entail the development of materials that are capable of addressing these challenges. Metal–organic frameworks (MOFs), a class of functional materials assembled from metal-containing nodes and organic ligands via coordination bonds, have been successfully developed for various applications, including catalysis, toxic chemical removal, and gas storage and separation, as a result of their highly tailorable nature and precisely engineered pore structures. In particular, the exceptionally high surface areas and porosities of MOFs are two of their most attractive characteristics and place them among the best porous materials for the storage of clean energy gases, such as hydrogen and methane. Reticular chemistry stands out as a prominent approach to the design of MOFs as this strategy allows for the rational top-down design of frameworks guided by topological nets to afford extended framework structures with precise architectural arrangements at the molecular level. Furthermore, bridging the gap between reticular chemistry design strategies and highly porous MOFs can facilitate the development of next-generation high-performance materials through state-of-the-art chemical design.

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

Predicting Oxygen Off-Stoichiometry and Hydrogen Incorporation in Complex Perovskite Oxides

Chemically and structurally complex solid compounds, including those with significant off-stoichiometry, are rapidly extending new material functionality across a variety of applications. Accelerated development of these compounds requires accurate predictions of material defect properties including effective defect formation energies and equilibrium defect concentrations. Traditional first-principles approaches typically examine dilute defect concentrations and relatively ordered atomic structures to identify the lowest energy defect sites. These approaches are rarely suitable for describing the disorder present in these systems and its influence on defect formation, which can lead to unphysically large predictions for defect concentrations. Here, we demonstrate a new method to accurately predict the temperature and pressure dependence of oxygen vacancy concentrations and proton interstitial concentrations in complex oxides. This method extends standard dilute defect calculations to incorporate atomic and magnetic disorder, employs the ensemble descriptions of defect sites resulting in improved predictions of defect formation energies, and accounts for effects beyond the dilute defect limit. To demonstrate our method, we show that the predicted defect concentrations in perovskites used as ceramic fuel cell cathodes, including Ba0.5Sr0.5Fe0.8Zn0.2O3-d, Ba0.5Sr0.5Co0.8Fe0.2O3-d, and BaCo1-x-y-zFexZryYzO3-d, are in good agreement with experimental values, thereby opening the door for predictive design of complex oxides by these applications.

DFT↗
DOE OSTI2022

High thermal conductivity in wafer-scale cubic silicon carbide crystals

High thermal conductivity electronic materials are critical components for high-performance electronic and photonic devices as both active functional materials and thermal management materials. We report an isotropic high thermal conductivity exceeding 500 W m –1 K –1 at room temperature in high-quality wafer-scale cubic silicon carbide (3C-SiC) crystals, which is the second highest among large crystals (only surpassed by diamond). Furthermore, the corresponding 3C-SiC thin films are found to have record-high in-plane and cross-plane thermal conductivity, even higher than diamond thin films with equivalent thicknesses. Our results resolve a long-standing puzzle that the literature values of thermal conductivity for 3C-SiC are lower than the structurally more complex 6H-SiC. We show that the observed high thermal conductivity in this work arises from the high purity and high crystal quality of 3C-SiC crystals which avoids the exceptionally strong defect-phonon scatterings. Moreover, 3C-SiC is a SiC polytype which can be epitaxially grown on Si. We show that the measured 3C-SiC-Si thermal boundary conductance is among the highest for semiconductor interfaces. These findings provide insights for fundamental phonon transport mechanisms, and suggest that 3C-SiC is an excellent wide-bandgap semiconductor for applications of next-generation power electronics as both active components and substrates.

42 ENGINEERING↗
DOE OSTI2020

Ion irradiation and modification: The role of coupled electronic and nuclear energy dissipation and subsequent nonequilibrium processes in materials

Understanding material responses to energy deposition from energetic charged particles is important for defect engineering, ion-beam processing, ion-beam analysis and modification, geologic aging, space exploration, and nuclear applications. As an incident ion penetrates a solid, its energy is transferred to electrons and to atomic nuclei of the solid. Much of this electronic energy deposition is subsequently transferred to the atomic structure via electron–phonon (e–ph) coupling, leading to local inelastic thermal spikes in which energy dissipation is influenced by the local environment. In addition, intense ionization can lead to high densities of localized electronic excitations in wide-bandgap materials and ceramics that can affect defect dynamics and atomic mobility. Specifically, energy exchange between electrons and atomic nuclei, along with localized electronic excitations, can lead to substantial competitive (ionization-induced annealing), additive (both electronic and nuclear energy depositions contributing to damage production), and synergistic (more damage than the sums of separate damage processes) effects. Although nonmonotonic effects of the e–ph coupling strength and athermal processes are demonstrated for pre-existing defects and residual damage during ion–solid interactions, there is limited understanding of when such electronic effects must be considered in atomic-scale models of damage production and evolution in a broad variety of materials. Complex ceramics and chemically disordered solid solution alloys with different constituent elements allow a systematic evaluation of defect dynamics and irradiation performance with increasing complexity. Current knowledge regarding tuning of bonding characteristics and chemical disorder to control atomic-level dynamics is reviewed. Although a lack of fundamental understanding obstructs the advancement of reliable predictions for ion beam material modification, it highlights challenges and opens research opportunities. Insights into the complex electronic and atomic correlations with extreme energy deposition will strengthen our ability to design materials and predict ion-irradiation-induced damage in a radiation environment, and they may pave the way to better control fundamental processes and design new material functionalities for advanced technologies.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Organic Synthetic Advanced Materials for Optoelectronic and Energy Applications (at National Sun Yat-sen University)

These slides cover Hung-Ju Yen's recent work in the synthesis and structural design of functional materials, which were further used for optoelectronic and energy applications, such as lithium ion battery, solar cell, LED, electrochromic, and fuel cells. This was for a job interview at National Sun Yat-sen University. The following topics are detailed: current challenges for lithium-ion batteries; graphene, graphene oxide and nanographene; nanographenes with various functional groups; fine tune d-spacing through organic synthesis: varying functional group; schematic view of LIBs; nanographenes as LIB anode; rate performance (charging-discharging); electrochromic technology; electrochromic materials; advantages of triphenylamine; requirement of electrochromic materials for practical applications; low driving voltage and long cycle life; increasing the electroactive sites by multi-step synthetic procedures; synthetic route to starburst triarylamine-based polyamide; electrochromism ranging from visible to NIR region; transmissive to black electrochromism; RGB and CMY electrochromism.

36 MATERIALS SCIENCE↗
DOE OSTI2025

High entropy powering green energy: hydrogen, batteries, electronics, and catalysis

A reformation in energy is underway to replace fossil fuels with renewable sources, driven by the development of new, robust, and multi-functional materials. High-entropy materials (HEMs) have emerged as promising candidates for various green energy applications, having unusual chemistries that give rise to remarkable functionalities. This review examines recent innovations in HEMs, focusing on hydrogen generation/storage, fuel cells, batteries, semiconductors/electronics, and catalysis—where HEMs have demonstrated the ability to outperform state-of-the-art materials. We present new master plots that illustrate the superior performance of HEMs compared to conventional systems for hydrogen generation/storage and heat-to-electricity conversion. We highlight the role of computational methods, such as density functional theory and machine learning, in accelerating the discovery and optimization of HEMs. The review also presents current challenges and proposes future directions for the field. We emphasize the need for continued integration of modeling, data, and experiments to investigate and leverage the underlying mechanisms of the HEMs that are powering progress in sustainable energy.

batteries↗
DOE OSTI2019

High-Throughput Screening for Advanced Thermoelectric Materials: Diamond-Like ABX 2 Compounds

High-throughput (HTP) calculations are a highly promising direction for the discovery of novel functional materials. Here we use an HTP framework to investigate the electronic structures and p-type thermoelectric properties of the ABX 2 compounds with diamond-like structures. We show application of HTP both to identify compounds and also to identify underlying trends. 65 entries out of 84,908 in Materials Informatics Platform are selected for this study. The electronic structures and chemical bonding analyses reveal that there exists a general conductive network consisted of the anion X sublattice, which dominates the electrical transport properties of the compounds. Electrical and thermal transport properties of the 41 pnictide and chalcogenide compounds with sufficient band gaps are studied. Pnictide compounds have relatively smaller Seebeck coefficients than the chalcogenide compounds. This is due to the smaller effective masses around the valence band maxima. The electrical conductivities and power factors, however, are better in pnictide compounds. This is because pnictide compounds have high electronic group velocities and electronic relaxation times. Combined with the predictions of lattice thermal conductivities based on the Slack model, 12 novel p-type and n-type ABX2 materials with high ZT values are predicted.

36 MATERIALS SCIENCE↗
DOE OSTI2019

A map of the inorganic ternary metal nitrides

Exploratory synthesis in new chemical spaces is the essence of solid-state chemistry. However, uncharted chemical spaces can be difficult to navigate, especially when materials synthesis is challenging. Nitrides represent one such space, where stringent synthesis constraints have limited the exploration of this important class of functional materials. Here, we employ a suite of computational materials discovery and informatics tools to construct a large stability map of the inorganic ternary metal nitrides. Our map clusters the ternary nitrides into chemical families with distinct stability and metastability, and highlights hundreds of promising new ternary nitride spaces for experimental investigation - from which we experimentally realized seven new Zn- and Mg-based ternary nitrides. As a result, by extracting the mixed metallicity, ionicity and covalency of solid-state bonding from the density functional theory (DFT)-computed electron density, we reveal the complex interplay between chemistry, composition and electronic structure in governing large-scale stability trends in ternary nitride materials.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Probing solid-state reaction through microstrain: A case study on synthesis of LiCoO 2

Solid-state reaction has been widely adopted as a low-cost and scalable approach to synthesize inorganic materials for industrial applications. However, a special caution must be paid to carefully control the synthesis condition in order to obtain final products with desired structure and physical/chemical properties. In this work, LiCoO 2 was investigated as a model material to illustrate the complexity of the solid-state reaction, as well as its condition control. Taking the advantage of the high flux and high penetration capability of synchrotron X-ray source, in-situ high-energy X-ray diffraction was deployed to investigate the structural evolution of materials during the solid-state reaction while ex-situ high-resolution X-ray diffraction was utilized to quantify the residual microstrains of LiCoO 2 . It is shown that the microstrain is a sensitive indicator to probe the completeness of the solid-state reactions, and that it also provides a more quantitative way to establish the structure-property relationship of materials. It can serve as a sensitive indicator for the rational design of synthesis process for functional materials.

25 ENERGY STORAGE↗
DOE OSTI2020

Tunable valleytronics with symmetry-retaining high polarization degree in SnS x Se 1–x model system

SnS has recently been shown to possess unique valleytronic capability with a large polarization degree, where non-degenerate valleys can be accessed using linearly polarized light, bestowed upon by the unique anisotropy and wavefunction symmetry. It is thus of utmost importance to demonstrate the extension of such effects for the IV–VI system in general, thereby elucidating the generality and tunability of such valleytronics. In this study, we show the highly tunable valleytronics via gradual compositional control of the tin(II) sulfo-selenide (SnS x Se 1–x ) alloy system with excellent retainment of symmetry-determined selection rules. We show the presence of both ΓY and ΓX valleys in all alloy compositions via selectivity in absorption and emission of linearly polarized light by optical reflection (R)/transmission (T) and photoluminescence measurements and tuned the bandgaps of the valleys within a range of 1.28 eV–1.05 eV and 1.48 eV–1.24 eV, respectively. This simultaneous tuning of non-degenerate valleys agrees well with theoretical calculations. We then fitted the bandgap values in compositional space, obtaining bowing parameters as a useful database. We further demonstrated the feasibility of using IV–VI valleytronics systems in general by elucidating the retainment of strong polarization degrees of as high as 91% across all compositions. The generalization of such purely symmetry-dependent valleytronics also opens up opportunities for the discovery of more multi-functional materials.

36 MATERIALS SCIENCE↗