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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 361 records · Page 20
All sourcesNASA NTRSDOE OSTI
DOE OSTI2018

Sharp and Tunable Crystal/Fano-Type Resonances Enabled by Out-of-Plane Dipolar Coupling in Plasmonic Nanopatch Arrays

Tuning resonance lineshapes of plasmonic structures is essential to create customized media with compelling optical properties for optimized light–matter interactions. The diversity of available metals and the variety of design architectures provide a rich portfolio for statically controlling the resonance lineshape. However, dynamic tuning of resonance attributes (e.g., the resonance wavelength and linewidth) are yet to be more expanded, especially when a narrow resonance linewidth is on demand. Here, using a plasmonic nanopatch array, sharp plasmonic crystal (PC) resonances are demonstrated across a wide spectral range of 230 nm, with full-width at half-maximum of only ≈6 nm. The combination of angle-resolved ellipsometry and full-wave simulations shows that diffractive coupling of out-of-plane electric dipoles is the principal contributor in the formation of such sharp PC resonances. In addition, the designed nanopatch PC supports a plasmonic Fabry–Pérot-like resonance that can be interfered with the PC resonance to generate complex Fano-type lineshapes. Finally, the coexistence of tunable resonance features renders the designed structures as a rich platform for applications seeking enhanced light–matter interactions and optical signal processing.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2025

A Route to Design Novel Functional Peptides by Applying a Denoising Diffusional Model to mRNA Display Libraries

In vitro directed evolution techniques, such as mRNA display, enable peptide ligand discovery and optimization. However, physical libraries that rely on a genetic code can only search a small fraction of sequence space due to inherent biases in the genetic code and experimental limitations. To address this challenge, denoising diffusion implicit models (DDIMs) are applied to generate novel peptide ligands against B‐cell lymphoma extra‐large (Bcl‐x L ), a key cancer target. Starting with high‐throughput sequencing data from previous selections, a DDIM is trained to produce novel sequences with high affinity binding. Experimental validation confirms that most generated sequences are functionally equivalent to the original library members for Bcl‐x L binding and demonstrated comparable binding kinetics and affinity relative to the wildtype and nearest original neighbors. Importantly, this approach generated rare sequences not easily accessible via mutation and directed evolution. These results indicate that DDIMs can complement and expand directed evolution data, efficiently exploring underrepresented regions of sequence space. This approach provides a broadly applicable framework for accelerating ligand discovery and optimizing molecular properties across diverse targets.

Qi, Pearl [Mork Family Department of Chemical Engi↗
DOE OSTI2017

Zeolite-Catalyzed Formaldehyde-Propylene Prins Condensation

Prins condensation of formaldehyde with propylene to form 3-buten-1-ol is investigated using microporous solid acid catalysts. Zn/H-beta shows high conversion but leads to a broad product distribution composed primarily of pyrans. Mechanistic studies revealed that 3-buten-1-ol reacts via Prins cyclization or dehydrate to 1,3-butadiene that further reacts with formaldehyde via a hetero-Diels–Alder reaction. These secondary reactions are suppressed over ZSM-5 catalysts: 3-buten-1-ol is the predominant product over H-ZSM-5 zeolite under all conditions investigated. 3-Buten-1-ol selectivity of up to 75 % is achieved. In a second step 3-buten-1-ol dehydrates at temperatures as low as 423 K, forming 1,3-butadiene. Although Brønsted acid sites are the primary catalytic sites, ion exchange of ZnII increases the overall rate and 3-buten-1-ol selectivity. H-ZSM-5 showed significant differences in reactivity and selectivity as a function of the Si/Al ratio; optimal catalytic properties were observed within Si/Al=40–140.

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

Self‐Consistent Convolutional Density Functional Approximations: Application to Adsorption at Metal Surfaces

The exchange-correlation (XC) functional in density functional theory is used to approximate multi-electron interactions. A plethora of different functionals are available, but nearly all are based on the hierarchy of inputs commonly referred to as “Jacob's ladder.” This paper introduces an approach to construct XC functionals with inputs from convolutions of arbitrary kernels with the electron density, providing a route to move beyond Jacob's ladder. We derive the variational derivative of these functionals, showing consistency with the generalized gradient approximation (GGA), and provide equations for variational derivatives based on multipole features from convolutional kernels. A proof-of-concept functional, PBEq, which generalizes the PBEα framework with mathematical equation being a spatially-resolved function of the monopole of the electron density, is presented and implemented. It allows a single functional to use different GGAs at different spatial points in a system, while obeying PBE constraints. Analysis of the results underlines the importance of error cancellation and the XC potential in data-driven functional design. After testing on small molecules, bulk metals, and surface catalysts, the results indicate that this approach is a promising route to simultaneously optimize multiple properties of interest.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2011

Membrane Development for Vanadium Redox Flow Batteries

Large-scale energy storage has become a main bottleneck for increasing the percentage of renewable energy in our electricity grids. Redox flow batteries are considered to be among the best options for electricity storage in the megawatt range, and large demonstration systems have already been installed. Although the full technological potential of these systems has not been reached yet, currently the main problem hindering more widespread commercialization is the high cost of redox flow batteries. Nafion{reg_sign} as the preferred membrane material is responsible for {approx}11% of the overall cost of a 1 MW/8 MWh system. Therefore in recent years two main membrane-related research threads have emerged: (a) chemical and physical modification of Nafion membranes to optimize their properties with regard to vanadium redox flow battery (VRFB) application; and (b) replacement of the Nafion membranes with different, less expensive materials. This review summarizes the underlying basic science issues associated with membrane use in VRFBs and presents an overview of membrane-related research approaches aimed at improving the efficiency of VRFBs and making the technology cost-competitive. Promising research strategies and materials are identified and suggestions are provided on how materials issues could be overcome.

25 ENERGY STORAGE↗
DOE OSTI2019

Nitrogen-doped carbons derived from poly(ionic liquid)s with various backbones and cations

In this study, poly(ionic liquid)s (PILs) with various backbone/cation pairings (backbones - ethyl methacrylate, styrene; covalently attached cations - butylimidazolium, trimethylammonium, butylpyrrolidinium) were successfully synthesized as carbon precursors. Pyrolysis of PILs produced carbons with sheet-like structures with a metallic luster in contrast to the powder form of carbons produced from polyacrylonitrile. The results also show that cation type has a significant impact on surface area, graphitic content, graphitic nitrogen content, nitrogen retention, carbon yield and surface chemistry of the PIL-derived carbons. The design of nitrogen-doped carbons based on a diverse set of PILs with various cation and polymer backbone chemistries may be an effective strategy to optimize carbon properties for subsequent application in energy storage devices.

36 MATERIALS SCIENCE↗
DOE OSTI2025

The Triple Catalytic Action of Tertiary Nitrogen Catalysts in Recyclable Epoxy-Anhydride Thermosets

The thermosetting polymer matrix in fiber reinforced composites is an important component for energy related applications, such as the lightweighting of vehicles or their use in wind and waterpower turbine blades, due to their ability to provide superior adhesion, stiffness, and applicability to a wide range of manufacturing processes. Despite these benefits, today's thermosets are widely considered to be unrecyclable; thus, there is a large interest in redesigning these materials to be inherently recyclable so that energy intensive production of fibers and monomers can be circumvented, bolstering composite manufacture supply chains. Polyester covalent adaptable networks (PECANs) are one such promising alternative to the incumbent, nonrecyclable epoxy-amine thermosets. PECANs can be formed from the ring-opening co-polymerization (ROCOP) of epoxy-anhydride monomer mixtures and subsequent curing at mild temperatures to exhibit similar performance to conventional epoxies while also possessing unique dynamic chemistries along the ester-hydroxyl backbone that are capable of transesterification and thus reprocessability. While significant advancements have been made in formulating these materials for improved mechanical properties or optimizing solvolysis and reprocessing strategies, less attention has been placed on the impact of the residing amine catalyst used to generate the polyester network. In this work, we evaluated the triple-catalytic efficacy of 12 tertiary amines that act as a curing (bulk ROCOP), a transesterification (internal bond exchange), and a deconstruction (methanolysis) catalyst for PECAN thermosets. Specifically, we first distinguish between chain-growth and step-growth polymerization mechanisms for epoxy-amine and epoxy-anhydride mechanisms. We also utilized density functional theory (DFT) to estimate the basicity (pKb) of each catalyst. Of the tested catalysts, the ROCOP of the studied PECAN network can be completed between 95 and 247 min (at 80 degrees C), with variable gelation phenomena. Additionally, the stress relaxation (transesterification metric) efficiency of the tested PECAN networks with alternative embedded catalysts ranged from 95% to 15% reduction in stress after 5 h at 200 degrees C, and the depolymerization efficacy ranged from 2.5% to 9.8% deconstruction after 36 h at 130 degrees C. Overall, the nitrogen-based moieties were demonstrated to influence polymerization kinetics, catalyze the dynamic transesterification exchange mechanism, and aid in the solvolysis of the thermosets at end-of-life.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Cast-in-place, ambiently-dried, silica-based, high-temperature insulation

A novel sol-gel chemistry approach was developed to enable the simple integration of a cast-in-place, ambiently-dried insulation into high temperature applications. The insulation was silica based, synthesized using methyltrimethoxysilane (MTMS) as the precursor. MTMS created a unique silica microstructure that was mechanically robust, macroporous, and superhydrophobic. To allow for casting into and around small, orthogonal features, zirconia fibers were added to increase stiffness and minimize contraction that could otherwise cause cracking during drying. Radiative heat transport was reduced by adding titania powder as an opacifier. To assess relevance to high temperature thermoelectric generator technology, a comprehensive set of materials characterizations were conducted. The silica gel was thermally stable, retained superhydrophobicity with a water contact angle > 150° , and showed a high electrical resistance > 1 GΩ, regardless of heating temperature (up to 600 °C in Ar for 4 h). In addition, it exhibited a Young's modulus ~3.7 MPa in room temperature and a low thermal conductivity < 0.08 W/m.K before and after heat treatment. Thus, based on the simplicity of the manufacturing process and optimized material properties, we believe this technology can act as an effective cast-in-place thermal insulation (CTI) for thermoelectric generators and myriad other applications requiring improved thermal efficiency.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Improving the performance of PM6 donor polymer by random ternary copolymerization of BDD and DTBT segments

Developing high-performance wide bandgap polymer donors to match the rapidly growing non-fullerene small molecule acceptors (NF-SMAs) is of great importance to further improve the photovoltaic performances of organic solar cells (OSCs). PM6 and D18 are two leading wide bandgap donor polymers, but their performances are highly sensitive to the molecular weights, which have distinct impact on the morphology and thereby the charge generation and recombination processes. Here, in this work, we reported the random ternary copolymerization of PM6 and D18 segments to develop random terpolymers with finely tuned photoelectronic properties and optimized blend morphology for high-performance OSCs. The resulting random terpolymers (PMD-5, PMD-10, PMD-15 and PMD-20) exhibited finely tuned absorptions, energy levels and blend morphology. The optimal morphology of PMD-15:L8-BO contributed to the fast exciton diffusion and dissociation, efficient charge extraction with suppressed recombination. Thus, the power conversion efficiency was improved from 17.22% of the control PM6 devices and 17.47% of the control D18 devices to 18.12% of PMD-15 based devices, which is the top performance of random terpolymers. Moreover, the PMD-15 exhibited much higher batch-to-batch reproducibility at a broad molecular weight range than that of PM6 and D18, showing promising for practical applications.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Curing process and pore structure of metakaolin-based geopolymers: Liquid-state 1H NMR investigation

Geopolymers are emerging construction materials with lower carbon dioxide emissions compared to the conventional cementitious materials. The knowledge of the curing process and the related pore structures are important for optimizing the properties of these materials for different applications. The curing process and final pore structure are sensitive to the amount of used water, however the specifics are unclear. The curing process and pore structures of metakaolin-based geopolymers with a narrow water-to-solid (w/s) ratio (0.59–0.66) were monitored by nuclear magnetic resonance (NMR) relaxometry and cryoporometry. The 14-day curing process was investigated by monitoring the change of T{sub 2} and T{sub 1} relaxation times and water signal intensity. After the curing, the pore structures were characterized by 2D T{sub 1}-T{sub 2} correlation and T{sub 2}-T{sub 2} exchange measurements of absorbed water. The pore size distributions (PSDs) were measured with NMR cryoporometry and compared to nitrogen physisorption and mercury intrusion porosimetry (MIP) results. We found that the relaxation times decreased as the pore structure of the geopolymers matured during the curing while the dissolution and the condensation periods of the curing were distinguished by the changes in signal amplitude reflecting the proton density. After the curing, three distinct pore sizes and connectivity between pores were identified from T{sub 1}-T{sub 2} and T{sub 2}-T{sub 2} spectra. Their PSDs were measured, and they were found to correspond to two different pore sizes originating from the arrangement of clusters and defective pores. In the narrow w/s ratio (0.59–0.66), the curing times were the same for all samples when cured at 24 °C while the pore sizes were observed to increase as a function of the w/s ratio.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Compositional inhomogeneityand segregation in (K 0.5 Na 0.5 )NbO 3 ceramics

The effects of the calcination temperature of (K 0.5 Na 0.5 )NbO 3 (KNN) powder on the sintering and piezoelectric properties of KNN ceramics have been investigated in this report. KNN powders are synthesized via the solid-state approach. Scanning electron microscopy and X-ray diffraction characterizations indicate that the incomplete reaction at 700 °C and 750 °C calcination results in the compositional inhomogeneity of the K-rich and Na-rich phases while the orthorhombic single phase is obtained after calcination at 900 °C. During the sintering, the presence of the liquid K-rich phase due to the lower melting point has a significant impact on the densification, the abnormal grain growth and the deteriorated piezoelectric properties. From the standpoint of piezoelectric properties, the optimal calcination temperature obtained for KNN ceramics calcined at this temperature is determined to be 800 °C, with piezoelectric constant d 33 =128.3 pC/N, planar electromechanical coupling coefficient k p =32.2%, mechanical quality factor Q m =88, and dielectric loss tan δ=2.1%.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Graph neural networks predict energetic and mechanical properties for models of solid solution metal alloy phases

Here, we developed a PyTorch-based architecture called HydraGNN that implements graph convolutional neural networks (GCNNs) to predict the formation energy and the bulk modulus for models of solid solution alloys for various atomic crystal structures and relaxed volumes. We trained the GCNN surrogate model on a dataset for nickel–niobium (NiNb) generated by the embedded atom model (EAM) empirical interatomic potential for demonstration purposes. The dataset was generated by calculating the formation energy and the bulk modulus as a prototypical elastic property for optimized geometries starting from initial body-centered cubic (BCC), face-centered cubic (FCC), and hexagonal compact packed (HCP) crystal structures, with configurations spanning the possible compositional range for each of the three types of initial crystal structures. Numerical results show that the GCNN model effectively predicts both the formation energy and the bulk modulus as function of the optimized crystal structure, relaxed volume, and configurational entropy of the model structures for solid solution alloys.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Surviving nanoscale interfacial stability in extreme thermal expansion contrast Zn(CN) 2 -epoxy resin matrix composites

Here, we report the remarkable stability at the nanoscale matrix-filler interface in a series of overall low coefficient of thermal expansion (CTE) zinc cyanide (ZC)/epoxy resin composites. These interfaces demonstrate the stability of highly contrasting materials. These composites are designed to optimize the properties of both materials: epoxy resins are valued for their high strength, superb chemical resistance, low dielectric properties, and adhesive abilities. ZC, a model flexible framework, exhibits negative thermal expansion (NTE) behavior and compensates for the epoxy resin’s detrimentally large thermal expansion values. Filled resins minimize the native 65 ppm/°C CTE values to 19 ppm/° C over a wide temperature range while maintaining linearity, yielding composites compatible with typical metal and ceramic substrates’—commonly bonded to the resin— 0–20 ppm/° C CTE values. Additionally, with significant intrinsic differences in the materials, we use wide-angle X-ray diffraction and atomic force microscopy to elucidate thermal movement. The ZC/epoxy interface is surprisingly resilient over 1,000 cycles between -55° C and 75° C, extremes typical to aerospace applications. Further, we show that the resin viscosity remains less than 21 Pa*s at up to 30 vol% ZC, an important consideration for workability. We also discuss settling distribution, glass transition temperature, flexural strength, and longevity. All results point favorably towards practical implementation in low thermal expansion application needs: filling the gap in component design.

42 ENGINEERING↗
DOE OSTI2019

Measurement of mechanical and fracture properties of solid electrolyte interphase on lithium metal anodes in lithium ion batteries

Mechanical integrity of the solid electrolyte interphase (SEI) plays an essential role in determining the life and performance of lithium-ion batteries. Fracture and continued formation of the SEI contribute to consumption of lithium, drying of electrolyte, increase in impedance, and growth of dendrites resulting in capacity fade and premature failure. Electrolyte additives such as fluoroethylene carbonate (FEC) have been known to improve performance, but the underlying reasons have been elusive. Despite its importance, reliable methods for mechanical characterization of SEI have been lacking. In this paper, we present a new experimental technique that combines atomic force microscopy and membrane-bulge configuration to accurately measure the stress-strain behavior of SEI, including the onset of inelastic response and evolution of fracture. We characterize the SEI formed with two ethylene carbonate-based electrolytes, without and with fluoroethylene carbonate (FEC) additive. The measurements show a striking contrast; SEI with FEC additive has 80% higher elastic modulus and a vastly higher resistance to fracture. These findings offer a mechanical-behavior based rationale to understand how SEI controls battery performance. Moreover, the experimental technique offers a robust diagnostic tool to design electrolytes that can form SEI with the desired mechanical properties for optimal battery performance.

25 ENERGY STORAGE↗
DOE OSTI2023

The role of ionic liquids in resolving the interfacial chemistry for (quasi-) solid-state batteries

Interfacial issues impede the advancement of current solid state battery technology; thus, interface engineering approaches are necessary to enable solid-state configuration. The advantage of solid-state cells stems from their low flammability and high electrochemical stability. Ionic liquids are viscous and nonflammable compounds that possess the requisite physical properties while optimizing the interface between solid electrodes and solid electrolytes, accelerating interfacial ion transport and enabling the fabrication of engineered interphases via the supply of robust chemical building blocks. In conclusion, this review summarizes the roles of ionic liquids in solid-state batteries focusing on the interface, with insights into their functionality as well as highlighting their applicability in the next generation battery systems.

25 ENERGY STORAGE↗