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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 91 records · Page 5
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

A prototype scintillator real‐time beam monitor for ultra‐high dose rate radiotherapy

Background: FLASH Radiotherapy (RT) is an emergent cancer RT modality where an entire therapeutic dose is delivered at more than 1000 times higher dose rate than conventional RT. For clinical trials to be conducted safely, a precise and fast beam monitor that can generate out-of-tolerance beam interrupts is required. This paper describes the overall concept and provides results from a prototype ultra-fast, scintillator-based beam monitor for both proton and electron beam FLASH applications. Purpose: A FLASH Beam Scintillator Monitor (FBSM) is being developed that employs a novel proprietary scintillator material. The FBSM has capabilities that conventional RT detector technologies are unable to simultaneously provide: (1) large area coverage; (2) a low mass profile; (3) a linear response over a broad dynamic range; (4) radiation hardness; (5) real-time analysis to provide an IEC-compliant fast beam-interrupt signal based on true two-dimensional beam imaging, radiation dosimetry and excellent spatial resolution. Methods: The FBSM uses a proprietary low mass, less than 0.5 mm water equivalent, non-hygroscopic, radiation tolerant scintillator material (designated HM: hybrid material) that is viewed by high frame rate CMOS cameras. Folded optics using mirrors enable a thin monitor profile of ∼10 cm. A field programmable gate array (FPGA) data acquisition system generates real-time analysis on a time scale appropriate to the FLASH RT beam modality: 100–1000 Hz for pulsed electrons and 10–20 kHz for quasi-continuous scanning proton pencil beams. An ion beam monitor served as the initial development platform for this work and was tested in low energy heavy-ion beams ( 86 Kr +26 and protons). A prototype FBSM was fabricated and then tested in various radiation beams that included FLASH level dose per pulse electron beams, and a hospital RT clinic with electron beams. Results: Results presented in this report include image quality, response linearity, radiation hardness, spatial resolution, and real-time data processing. Furthermore, the HM scintillator was found to be highly radiation damage resistant. It exhibited a small 0.025%/kGy signal decrease from a 216 kGy cumulative dose resulting from continuous exposure for 15 min at a FLASH compatible dose rate of 237 Gy/s. Measurements of the signal amplitude versus beam fluence demonstrate linear response of the FBSM at FLASH compatible dose rates of >40 Gy/s. Comparison with commercial Gafchromic film indicates that the FBSM produces a high resolution 2D beam image and can reproduce a nearly identical beam profile, including primary beam tails. The spatial resolution was measured at 35–40 µm. Tests of the firmware beta version show successful operation at 20 000 Hz frame rate or 50 µs/frame, where the real-time analysis of the beam parameters is achieved in less than 1 µs. Conclusions: The FBSM is designed to provide real-time beam profile monitoring over a large active area without significantly degrading the beam quality. A prototype device has been staged in particle beams at currents of single particles up to FLASH level dose rates, using both continuous ion beams and pulsed electron beams. Using a novel scintillator, beam profiling has been demonstrated for currents extending from single particles to 10 nA currents. Radiation damage is minimal and even under FLASH conditions would require ≥50 kGy of accumulated exposure in a single spot to result in a 1% decrease in signal output. Beam imaging is comparable to radiochromic films, and provides immediate images without hours of processing. Real-time data processing, taking less than 50 µs (combined data transfer and analysis times), has been implemented in firmware for 20 kHz frame rates for continuous proton beams.

2D beam imaging↗
DOE OSTI2026

Solid-State Syntheses, Crystallographic Spatial Disorders, Thermal Behaviors, and Bandgaps of Hybrid Organic-Inorganic Manganese Halides: A2Mn(Cl/Br)4 (A = NH4+, C(NH2)3+, & C3H4N2+)

By systematically optimizing solid-state synthesis via the concerted use of differential scanning calorimetry and in-situ variable-temperature X-ray diffraction, we report the discovery of four new hybrid organic-inorganic manganese halides A2Mn(Cl/Br)4 (A = NH4+, C(NH2)3+, C3H4N2+), with emphasis on how the organic fragment geometry, polarity, and electron-donating properties influence crystallographic spatial disorders, thermal behaviors, and optical band gaps. With a nonpolar tetrahedral cation, as in (NH4)2MnCl4 (P21/c, mP30) or (NH4)2MnBr4 (C2/c, mC180), the direct optical bandgaps (4.36–4.28 eV) are wider than those with an organic nonpolar planar geometry, as in (C(NH2)3)2MnBr4 (P21/c, mP300, 4.07 eV), or an organic polar planar geometry, as in (C3H4N2+)2MnBr4 (I41/a, tI384, 4.05 eV). Furthermore, the organic components affect the spatial arrangement and dimensionality of the resulting inorganic frameworks comprised of Mn(Cl/Br)6 octahedra, with varying distortions, or spatially disordered MnBr4 tetrahedra. These resulting trends, coupled with the systematic investigation into synthesis, and the motivation behind elucidating the nuanced role of the organic cation, altogether expand upon the phase-space of hybrid materials beyond perovskites and demonstrate the potential for a rational design of hybrid materials with tailored optoelectronic functionalities for advanced energy applications.

Lee, Shannon J.↗
DOE OSTI2020

4D Printing of Stretchable Supercapacitors via Hybrid Composite Materials

Stretchable supercapacitors (SCs) have attracted significant attention in developing power-independent stretchable electronic systems due to their intrinsic energy storage function and unique mechanical properties. Most current SCs are generally limited by their low stretchability, complicated fabrication process, and insufficient performance and robustness. This study presents a facile method to fabricate arbitrary-shaped stretchable electrodes via 4D printing of conductive composite from reduced graphene oxide, carbon nanotube, and poly(3,4-ethylenedioxythiophene) polystyrene sulfonate. The electrode patterns of an arbitrary shape can be deposited onto prestretched substrates by aerosol-jet printing, then self-organized origami (ridge) patterns are generated after releasing the substrates from holding stretchers due to the mismatched strains. The stretchable electrodes demonstrate superior mechanical robustness and stretchability without sacrificing its outstanding electrochemical performance. The symmetric SC prototype possesses a gravimetric capacitance of ≈21.7 F g -1 at a current density of 0.5 A g -1 and a capacitance retention of ≈85.8% from 0.5 to 5 A g -1 . A SC array with arbitrary-shaped electrodes is also fabricated and connected in series to power light-emitting diode patterns for large-scale applications. Finally, the proposed method paves avenues for scalable manufacturing of future energy-storage devices with controlled extensibility and high electrochemical performance.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Interpreting inorganic compositional depth profiles to understand the rate-limiting step in vapor phase infiltration processes

Vapor phase infiltration (VPI) is a post-polymerization modification technique that infuses inorganics into polymers to create organic–inorganic hybrid materials with new properties. Much is yet to be understood about the chemical kinetics underlying the VPI process. The aim of this study is to create a greater understanding of the process kinetics that govern the infiltration of trimethyl aluminum (TMA) and TiCl 4 into PMMA to form inorganic-PMMA hybrid materials. To gain insight, this paper initially examines the predicted results for the spatiotemporal concentrations of inorganics computed from a recently posited reaction–diffusion model for VPI. This model provides insight on how the Damköhler number (reaction versus diffusion rates) and non-Fickian diffusional processes (hindering) that result from the material transforming from a polymer to a hybrid can affect the evolution of inorganic concentration depth profiles with time. Subsequently, experimental XPS depth profiles are collected for TMA and TiCl 4 infiltrated PMMA films at 90 °C and 135 °C. The functional behavior of these depth profiles at varying infiltration times are qualitatively compared to various computed predictions and conclusions are drawn about the mechanisms of each of these processes. TMA infiltration into PMMA appears to transition from a diffusion-limited process at low temperatures (90 °C) to a reaction-limited process at high temperatures (135 °C) for the film thicknesses investigated here (200 nm). While TMA appears to fully infiltrate these 200 nm PMMA films within a few hours, TiCl 4 infiltration into PMMA is considerably slower, with full saturation not occurring even after 2 days of precursor exposure. Infiltration at 90 °C is so slow that no clear conclusions about mechanism can be drawn; however, at 135 °C, the TiCl 4 infiltration into PMMA is clearly a reaction-limited process, with TiCl 4 permeating the entire thickness (at low concentrations) within only a few minutes, but inorganic loading continuously increasing in a uniform manner over a course of 2 days. Near-surface deviations from the uniform-loading expected for a reaction-limited process also suggest that diffusional hindering is high for TiCl 4 infiltration into PMMA. In conclusion, these results demonstrate a new, ex situ analysis approach for investigating the rate-limiting process mechanisms for vapor phase infiltration.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Self-assembled HfO 2 -Au nanocomposites with ultra-fine vertically aligned Au nanopillars

Oxide-metal-based hybrid materials have gained great research interest in recent years owing to their potential for multifunctionality, property coupling, and tunability. Specifically, oxide-metal hybrid materials in a vertically aligned nanocomposite (VAN) form could produce pronounced anisotropic physical properties, e.g., hyperbolic optical properties. Herein, self-assembled HfO 2 -Au nanocomposites with ultra-fine vertically aligned Au nanopillars (as fine as 3 nm in diameter) embedded in a HfO 2 matrix were fabricated using a one-step self-assembly process. The film crystallinity and pillar uniformity can be obviously improved by adding an ultra-thin TiN-Au buffer layer during the growth. Here, the HfO 2 -Au hybrid VAN films show an obvious plasmonic resonance at 480 nm, which is much lower than the typical plasmonic resonance wavelength of Au nanostructures, and is attributed to the well-aligned ultra-fine Au nanopillars. Coupled with the broad hyperbolic dispersion ranging from 1050 nm to 1800 nm in wavelength, and unique dielectric HfO 2 , this nanoscale hybrid plasmonic metamaterial presents strong potential for the design of future integrated optical and electronic switching devices.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Design of tough adhesive from commodity thermoplastics through dynamic crosslinking

Tough adhesives provide resistance against high debonding forces, and these adhesives are difficult to design because of the simultaneous requirement of strength and ductility. Here, we report a design of tough reversible/recyclable adhesive materials enabled by incorporating dynamic covalent bonds of boronic ester into commodity triblock thermoplastic elastomers that reversibly bind with various fillers and substrates. The spectroscopic measurements and density functional theory calculations unveil versatile dynamic covalent binding of boronic ester with various hydroxy-terminated surfaces such as silica nanoparticles, aluminum, steel, and glass. The designed multiphase material exhibits exceptionally high adhesion strength and work of debonding with a rebonding capability, as well as outstanding mechanical, thermal, and chemical resistance properties. Bonding and debonding at the interfaces dictate hybrid material properties, and this revelation of tailored dynamic interactions with multiple interfaces will open up a new design of adhesives and hybrid materials.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Electron-induced chemical transformation of vapor-phase synthesized hybrid resist materials for EUV and beyond EUV lithography

Here, in this study, we utilize an in situ Fourier transform infrared (FTIR) spectroscopy chamber equipped with an electron flood gun to comprehensively investigate the electron-induced chemical transformations in advanced inorganic–organic hybrid resist thin films. The characteristics of the electron gun were assessed, showing a detectable current decrease with increasing Faraday cup bias voltage, confirming that the electron energies impacting the sample were within the expected range. This unique FTIR system was applied to study two hybrid resist thin-film systems, Al–HQ and Zn–HQ, both exhibiting saturation growth characteristics at 150 °C. Results revealed that Al–HQ demonstrated superior electron sensitivity compared to Zn–HQ at energies ≤ 100 eV. Chemical changes observed were consistent with previous findings, underscoring the potential of this methodology to elucidate exposure mechanisms. This research contributes to the fundamental understanding necessary for the development of advanced resist materials for the next-generation nanolithography applications.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Chemical crystallography by serial femtosecond X-ray diffraction

Abstract Inorganic–organic hybrid materials represent a large share of newly reported structures, owing to their simple synthetic routes and customizable properties 1 . This proliferation has led to a characterization bottleneck: many hybrid materials are obligate microcrystals with low symmetry and severe radiation sensitivity, interfering with the standard techniques of single-crystal X-ray diffraction 2,3 and electron microdiffraction 4–11 . Here we demonstrate small-molecule serial femtosecond X-ray crystallography (smSFX) for the determination of material crystal structures from microcrystals. We subjected microcrystalline suspensions to X-ray free-electron laser radiation 12,13 and obtained thousands of randomly oriented diffraction patterns. We determined unit cells by aggregating spot-finding results into high-resolution powder diffractograms. After indexing the sparse serial patterns by a graph theory approach 14 , the resulting datasets can be solved and refined using standard tools for single-crystal diffraction data 15–17 . We describe the ab initio structure solutions of mithrene (AgSePh) 18–20 , thiorene (AgSPh) and tethrene (AgTePh), of which the latter two were previously unknown structures. In thiorene, we identify a geometric change in the silver–silver bonding network that is linked to its divergent optoelectronic properties 20 . We demonstrate that smSFX can be applied as a general technique for structure determination of beam-sensitive microcrystalline materials at near-ambient temperature and pressure.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Confinement of 1D Chain and 2D Layered CuI Modules in K-INA-R Frameworks via Coordination Assembly: Structure Regulation and Semiconductivity Tuning

Herein, we present a new series of CuI-based hybrid materials with tunable structures and semiconducting properties. Furthermore, the CuI inorganic modules can be tailored into a one-dimensional (1D) chain and two-dimensional (2D) layer and confined/stabilized in coordination frameworks of potassium isonicotinic acid (HINA) and its derivatives (HINA-R, R = OH, NO 2 , and COOH). The resulting CuI-based hybrid materials exhibit interesting semiconducting behaviors associated with the dimensionality of the inorganic module; for instance, the structures containing the 2D-CuI module demonstrate significantly enhanced photoconductivity with a maximum increase of five orders of magnitude compared to that of the structures containing the 1D-CuI module. They also represent the first CuI-bearing hybrid chemiresistive gas sensors for NO 2 with boosted sensing performance and sensitivity at multiple orders of magnitude over that of the pristine CuI. Particularly, the sensing ability of CuI-K-INA containing both 1D- and 2D-CuI modules is comparable to those of the best NO 2 chemiresistors reported thus far.

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

Internal Microstructure Dictates Interactions of Polymer-grafted Nanoparticles in Solution

Understanding the effects of polymer brush architecture on particle interactions in solution is requisite to enable the development of functional materials based on self-assembled polymer-grafted nanoparticles (GNPs). Static and dynamic light scattering of polystyrene-grafted silica particle solutions in toluene reveals that the pair interaction potential, inferred from the second virial coefficient, A 2 , is strongly affected by the grafting density, σ, and degree of polymerization, N, of tethered chains. In the limit of intermediate σ (~0.3 to 0.6 nm -2 ) and high N, A 2 is positive and increases with N. This confirms the good solvent conditions and can be qualitatively rationalized on the basis of a pair interaction potential derived for grafted (brush) particles. In contrast, for high σ > 0.6 nm -2 and low N, A 2 displays an unexpected reversal to negative values, thus indicating poor solvent conditions. These findings are rationalized by means of a simple analysis based on a coarse-grained brush potential, which balances the attractive core-core interactions and the excluded volume interactions imparted by the polymer grafts. The results suggest that the steric crowding of polymer ligands in dense GNP systems may fundamentally alter the interactions between brush particles in solution and highlight the crucial role of architecture (internal microstructure) on the behavior of hybrid materials. The effect of grafting density also illustrates the opportunity to tailor the physical properties of hybrid materials by altering geometry (or architecture) rather than a variation of the chemical composition.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Molecular catalyst coordinatively bonded to organic semiconductors for selective light-driven CO 2 reduction in water

The selective photoreduction of CO 2 in aqueous media based on earth-abundant elements only, is today a challenging topic. Here we present the anchoring of discrete molecular catalysts on organic polymeric semiconductors via covalent bonding, generating molecular hybrid materials with well-defined active sites for CO 2 photoreduction, exclusively to CO in purely aqueous media. The molecular catalysts are based on aryl substituted Co phthalocyanines that can be coordinated by dangling pyridyl attached to a polymeric covalent triazine framework that acts as a light absorber. This generates a molecular hybrid material that efficiently and selectively achieves the photoreduction of CO 2 to CO in KHCO 3 aqueous buffer, giving high yields in the range of 22 mmol g -1 (458 μmol g -1 h -1 ) and turnover numbers above 550 in 48 h, with no deactivation and no detectable H 2 . The electron transfer mechanism for the activation of the catalyst is proposed based on the combined results from time-resolved fluorescence spectroscopy, in situ spectroscopies and quantum chemical calculations.

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

Strong Electronic Coupling of Graphene Nanoribbons onto Basal Plane of a Glassy Carbon Electrode

The grafting of molecular motifs to the conductive carbon represents a promising approach toward improved hybrid materials for electrocatalytic applications. Here, we investigate the electrochemical behavior of graphene nanoribbons (GNR) deposited onto a glassy carbon electrode using pi - pi stacking interactions. Using the bipyrimidine moiety on the nanoribbon edges as a reporter of the proton-coupled electron transfer chemistry, we illustrate that the simple electrochemical treatment of as-deposited nanoribbon generates a hybrid material that is in strong electronic communication with the conductive support. Overall, this work shows a strategy for modifying the basal plane of carbon materials and provides a potential platform for the incorporation of catalytic metal sites via coordination through the N-functionalities of GNR.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1993

Intercalated hybrid graphite fiber composite

The invention is directed to a highly conductive lightweight hybrid material and methods of producing the same. The hybrid composite is obtained by weaving strands of a high strength carbon or graphite fiber into a fabric-like structure, depositing a layer of carbon onto the structure, heat treating the structure to graphitize the carbon layer, and intercalating the graphitic carbon layer structure. A laminate composite material useful for protection against lightning strikes comprises at least one layer of the hybrid material over at least one layer of high strength carbon or graphite fibers. The composite material of the present invention is compatible with matrix compounds, has a coefficient of thermal expansion which is the same as underlying fiber layers, and is resistant to galvanic corrosion in addition to being highly conductive. These materials are useful in the aerospace industry, in particular as lightning strike protection for airplanes.

Gaier, James R.↗
NASA NTRS2016

Aerogel Hybrid Composite Materials: Designs and Testing for Multifunctional Applications

This webinar will introduce the broad spectrum of aerogel composites and their diverse performance properties such as reduced heat transfer to energy storage, and expands specifically on the aerogel/fiber laminate systems and testing methodologies. The multi-functional laminate composite system, AeroFiber, and its construction is designed by varying the type of fiber (e.g. polyester, carbon, Kevlar®, Spectra® or Innegral(TradeMark) and combinations thereof), the aerogel panel type and thickness, and overall layup configuration. The combination and design of materials may be customized and tailored to achieve a range of desired properties in the resulting laminate system. Multi-functional properties include structural strength, impact resistance, reduction in heat transfer, increased fire resistance, mechanical energy absorption, and acoustic energy dampening. Applications include aerospace, aircraft, automotive, boating, building and construction, lightweight portable structures, liquefied natural gas, cryogenics, transportation and energy, sporting equipment, and military protective gear industries.

Hybrid↗
DOE OSTI2025

Accelerated Self-Healing and Property Recovery in Brush Particle Solids Featuring Brush Dispersity

Brush particles, hybrid materials consisting of polymer chains tethered to particle surfaces, offer tunable properties that make them promising candidates for advanced functional materials. This study investigated the role of chain dispersity in the viscoelastic self-healing of poly (methyl acrylate) (PMA)-based brush particle solids. Increasing the molecular weight dispersity of grafted chains significantly enhanced both strain-to-fracture and toughness of brush particle solids, while the elastic modulus and glass transition temperature were independent of chain dispersity. Cut-and-adhere testing revealed a significant acceleration of the rate of toughness recovery in high-dispersity systems as compared to low-dispersity analogs for which toughness recovery markedly lagged the recovery of Young’s modulus. The results suggest that structure and property recovery in brush particle solids are sensitive to the dynamical heterogeneity of brush canopies and highlight the role of molecular weight dispersity as a design parameter to enable hybrid materials with advanced self-healing ability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Fabrication Development for SPT-SLIM, a Superconducting Spectrometer for Line Intensity Mapping

Line Intensity Mapping (LIM) is a new observational technique that uses low-resolution observations of line emission to efficiently trace the large-scale structure of the Universe out to high redshift. Common mm/sub-mm emission lines are accessible from ground-based observatories, and the requirements on the detectors for LIM at mm-wavelengths are well matched to the capabilities of large-format arrays of superconducting sensors. We describe the development of an R = lambda/Delta lambda = 300 on-chip superconducting filter-bank spectrometer covering the 120-180 GHz band for future mm-LIM experiments, focusing on SPT-SLIM, a pathfinder LIM instrument for the South Pole Telescope. Radiation is coupled from the telescope optical system to the spectrometer chip via an array of feedhorn-coupled orthomode transducers. Superconducting microstrip transmission lines then carry the signal to an array of channelizing half-wavelength resonators, and the output of each spectral channel is sensed by a lumped element kinetic inductance detector (leKID). Key areas of development include incorporating new low-loss dielectrics to improve both the achievable spectral resolution and optical efficiency and development of a robust fabrication process to create a galvanic connection between ultra-pure superconducting thin-films to realize multi-material (hybrid) leKIDs. We provide an overview of the spectrometer design, fabrication process, and prototype devices.

microstrip resonators↗