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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 1,171 records · Page 65

Numerical investigation of thermomechanical response of multiscale porous Ultra-High Temperature Ceramics

Recent advances in Ultra-High Temperature Ceramics (UHTC) manufacturing have permitted the development of multiscale porous UHTC microstructures. Within the target application of hypersonic vehicles, dense UHTCs are suitable for thermal protection on leading edges, whereas porous UHTCs may find a role in providing thermally insulated interfaces for temperature-sensitive interior components. Designing vehicles incorporating porous UHTCs requires a characterization of their thermomechanical properties across the full range of expected operating temperatures spanning –20 °C–2500 °C. This research represents a preliminary study in performing this characterization. Several numerical experiments are performed using a coupled thermomechanical implementation of the Material Point Method to determine the temperature dependence of effective material properties both with and without damage. Furthermore, complex time-dependent boundary conditions derived from known hypersonic flight profiles are simulated in order to probe the various couplings between deformation, damage and heat transfer. It is shown that the model reveals the importance of micro-buckling in determining effective material stiffness and thermal conductivity.

36 MATERIALS SCIENCE↗

Thermal conductivity of comets

The thermal conductivity of two comet models is calculated. Both models assume the comets to be heterogeneous in composition. One model considers the comet to have a nucleus of water-ice mixed with basaltic and meteoritic material in the form of dust and agglomerated particles surrounded by a layer of water-frost. The second model assumes the frost and water-ice layers have sublimated, leaving a porous structure to some depth composed of solid basaltic and meteoritic material with residual gases. K values are calculated as a function of depth, density, temperature and porosity.

Kumar, G. N.↗

Tailorable thermoplastic insulation foam composites enabled by porous-shell hollow glass spheres and expandable thermoplastic microspheres

Here we report a simple and commercially viable strategy to produce thermoplastic composite foams using synergistic foaming approaches – incorporating porous-shell hollow-interior glass spheres (PHGS) as a filler and utilizing expandable thermoplastic microspheres (EMS) as a physical blowing agent – for thermal insulation applications. The EMS in these composites ensure formation of highly porous, low-density foam while the PHGSs provide low thermal conductivity and lightweight mechanical reinforcement. Through systematic optimization of the PHGS and EMS loadings, a lightweight, and robust insulation with thermal resistivity greater than 27.7 m·K/W (R/in. > 4) is achieved. Notably, the fabricated foams also demonstrated comparable compressive strength than some commercial thermoplastic insulating materials. Through optimization of PHGS and EMS concentrations, results indicated similar thermal performance characteristics at varying foam densities, while higher loadings of both components lead to reduced insulation performance and weak mechanical stability of the foams. The results obtained, when coupled with the potential scalability and tailor ability of the overall process towards targeted insulation performance, not only endows competitiveness with current commercial thermoplastic insulating materials but also offers great promise for the development of unique thermoplastic composite foams for a variety of insulation systems.

36 MATERIALS SCIENCE↗

Porous carbon from lignocellulosic biomass with emphasis on corn plant waste residue for energy storage

The rising global demand for sustainable energy storage materials has driven the search for environmentally friendly and cost-effective electrode options. Hydrothermal conversion of lignocellulosic biomass has gained attention due to its low energy requirements and operation at relatively low temperatures, presenting a green alternative to traditional thermochemical methods. The resulting solid product, hydrochar, has been used as an adsorbent and soil amendment; however, chemical/thermal treatment significantly enhances its physical properties. These structural modifications transform hydrochar into an effective porous carbon electrode, offering abundant sites for electrolyte ion transport, critical for high-performance devices like supercapacitors and batteries. This review first discusses various waste biomass and sustainable feedstocks available globally. It compares two primary thermochemical conversion techniques, pyrolysis and hydrothermal carbonization/liquefaction, and examines their respective solid products, biochar and hydrochar, analyzing differences in their physical and chemical characteristics. The focus is placed on hydrochar, summarizing activation methods to produce porous carbon suitable for energy storage applications. Additionally, this review will include a dedicated section on the application of porous carbon derived from corn plant waste residue, considering that corn is one of the most abundant crops grown worldwide, which makes it an important and promising source for sustainable porous carbon production. The role of machine learning models in optimizing hydrothermal processes to produce high-quality hydrochar is also discussed, emphasizing how data-driven approaches can streamline process development. Finally, the review identifies the current challenges and prospects for lignocellulosic biomass-derived porous carbon as a sustainable electrode material in next-generation energy storage technologies.

25 ENERGY STORAGE↗

Composite wall concept for high temperature turbine shrouds: Survey of low modulus strain isolator materials

Plasma sprayed yttria stabilized zirconium oxide turbine seal specimens, incorporating various low modulus porous metal strain isolator pads between the zirconium oxide and a dense metal substrate, were subjected to cyclic thermal shock testing. Specimens that had a low modulus pad composed of sintered FeNiCrAlY fibermetal survived 1000 thermal shock cycles without spalling of the ceramic. A figure of merit for the low modulus pad materials taking into consideration the elastic modulus, thermal conductivity, strength, and oxidation resistance of the pad was proposed, and showed reasonable agreement with the thermal shock results. A potential surface distress problem on the zirconium oxide, associated with nonuniform temperature distribution and rapid stress relaxation was identified. One approach to solving the surface distress problem through application of laser surface fusion of the zirconium oxide layer showed some promise, but improvements in the laser surface fusion process are necessary to prevent process associated damage to the ceramic.

Bill, R. C.↗

Identification and Study of Validation Level Test Cases for Computational Modeling of Non-Charring Ablators

Computational modeling of Thermal Protection System (TPS) materials, used for aerospace applications, provides numerous advantages in preliminary selection and design of a heatshield material and shape for atmospheric entry vehicles. However, to serve as a reliable tool for prediction of material thermal and ablative behavior, the modeling approach needs to be validated against real experimental and flight data, preferably at a range of applied conditions. The validation study is typically very complex as it requires reliable measured data not only for the material thermal response and surface recession, but also well characterized environmental conditions. The validation problem becomes even more complex when the material thermal response is dictated by multi-physics effects such as solid conduction, in-depth thermal decomposition, pyrolysis gas flow and chemical reactions. The multi-physics effects complicate not only the modeling effort, but also the experimental measurement for validation of various aspects of the highly coupled problem. In this study, an attempt is made to identify suitable experimental data that could serve as a source for validation of material thermal response modeling tools. To reduce the computational complexity, this study focuses only on non-charring ablators, where the material thermal response could be modeled with a single governing equation for solid conduction and the ablation is limited only to the surface of the material. With a well characterized and publicly available experimental data being sparse, the study is limited in presenting test cases for only three materials: camphor, graphite and FiberForm® in the sequence of increased modeling complexity. Graphite is a commonly used TPS material for aerospace applications, both for leading edges of high-speed vehicles and internal insulation of solid rocket motors. FiberForm® is a porous carbon pre-form used in preparation of the well known PICA material Tran et al. [1996]. Inclusion of camphor into the list is conditioned with the relative simplicity in modeling the material thermal and chemical response and the low-enthalpy flow environment. In addition, camphor has been used as a simple test material for study of flow transition behavior by Stock and Ginoux [1973] and assessment of a heatshield shape change at flight relevant conditions by Rotondi et al. [2022]. In this work, the identified experimental data was extracted from the public literature and test cases that yet have been published. As it was found from the review, not a single test case contains an exhaustive set of data that would validate every aspect of the material physics. However, in the data collected, various aspects of the material behavior can be still validated, such as surface and in-depth temperature, amount of recession and a shape change. The identified experimental data for each case is accompanied with a characterized flow environment and simulated boundary conditions predicted by a Data-Parallel Line Relaxation (DPLR) code Wright et al. [1998]. In addition, material thermal response numerical simulations in each test case are performed with Kentucky Aerothermodynamics and Thermal Response System (KATS-MR) Zibitsker et al. [2022] providing a comparative study and a sanity check for the proposed validation data. Sample results from the performed numerical study are shown below. Figure 1 shows distribution of surface heat flux and pressure values on a hemi-cylinder model made of FiberForm® and tested in HyMETS arc-jet facility. The results are shown for the high pressure condition among the two tests. Flow simulation was performed with DPLR code on a quarter of original geometry. In the figure, the quarter shape was mirrored across zx and xy planes to show the complete distribution. Figure 2 shows the material response results for the high pressure case (7500 Pa), simulated with KATS-MR and a comparison to the experimental data for the surface temperature and shape shape. The simulation was performed on a 2-D slice, extracted in the xy plane at the middle of the sample. Figure 3 shows the material response simulation for the low pressure case (3500 Pa) and a comparison to the experimental data for surface temperature and shape change.

ablation↗

Porous Media Approach for Modeling Closed Cell Foam

In order to minimize boil off of the liquid oxygen and liquid hydrogen and to prevent the formation of ice on its exterior surface, the Space Shuttle External Tank (ET) is insulated using various low-density, closed-cell polymeric foams. Improved analysis methods for these foam materials are needed to predict the foam structural response and to help identify the foam fracture behavior in order to help minimize foam shedding occurrences. This presentation describes a continuum based approach to modeling the foam thermo-mechanical behavior that accounts for the cellular nature of the material and explicitly addresses the effect of the internal cell gas pressure. A porous media approach is implemented in a finite element frame work to model the mechanical behavior of the closed cell foam. The ABAQUS general purpose finite element program is used to simulate the continuum behavior of the foam. The soil mechanics element is implemented to account for the cell internal pressure and its effect on the stress and strain fields. The pressure variation inside the closed cells is calculated using the ideal gas laws. The soil mechanics element is compatible with an orthotropic materials model to capture the different behavior between the rise and in-plane directions of the foam. The porous media approach is applied to model the foam thermal strain and calculate the foam effective coefficient of thermal expansion. The calculated foam coefficients of thermal expansion were able to simulate the measured thermal strain during heat up from cryogenic temperature to room temperature in vacuum. The porous media approach was applied to an insulated substrate with one inch foam and compared to a simple elastic solution without pore pressure. The porous media approach is also applied to model the foam mechanical behavior during subscale laboratory experiments. In this test, a foam layer sprayed on a metal substrate is subjected to a temperature variation while the metal substrate is stretched to simulate the structural response of the tank during operation. The thermal expansion mismatch between the foam and the metal substrate and the thermal gradient in the foam layer causes high tensile stresses near the metal/foam interface that can lead to delamination.

Ghosn, Louis J.↗

Wastepaper-derived porous carbon supported cobalt nanocomposites for all solid-state flexible supercapacitor

The conversion of wastepaper into high-value carbon materials has gained significant attention as a sustainable strategy for energy storage applications. Owing to its low cost, abundance, and intrinsic fibrous structure, wastepaper serves as an attractive precursor for carbon-based electrode materials. In this work, a novel electrode comprising cobalt nanoparticles and Co 3 O 4 embedded in wastepaper-derived porous carbon has been developed for use in a flexible all-solid-state asymmetric supercapacitor. The integration of cobalt nanoparticles and Co 3 O 4 introduces redox-active centres, which enhance the electrochemical activity of the carbon framework. Mean while, the interconnected porous and conductive carbon network enables rapid ion diffusion and efficient electron transport, synergistically improving the overall electrochemical performance. It delivers a high specific capacitance of 61.5 Fg -1 , a power density of 5143 W kg -1 , and an energy density of 9 Wh kg -1 at a current density of 2.5 A/ g. Furthermore, the device maintains outstanding cycling stability, retaining 82.86 % of its capacitance after 10,000 charge-discharge cycles. Practical applicability is confirmed through its ability to power

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Atomic layer deposition of nanofilms on porous polymer substrates: Strategies for success

Atomic layer deposition (ALD) is a versatile technique for engineering the surfaces of porous polymers, imbuing the flexible, high-surface-area substrates with inorganic and hybrid material properties. Previously reported enhancements include fouling resistance, electrical conductance, thermal stability, photocatalytic activity, hydrophilicity, and oleophilicity. However, there are many poorly understood phenomena that introduce challenges in applying ALD to porous polymers. In this paper, we address five common challenges and ways to overcome them: (1) entrapped precursor, (2) embrittlement, (3) film fracture, (4) deformation, and (5) pore collapse. These challenges are often interrelated and can exacerbate one another. To investigate these phenomena, we applied various ALD chemistries to porous polymers including polyethersulfone, polysulfone, polyvinylidene fluoride, and polycarbonate track-etched membranes. Reaction-diffusion modeling revealed why certain precursors and processing conditions result in embrittling subsurface material growth, entrapment of unreacted precursors, and nongrowth. We quantify the limits of ALD processing temperatures that are dictated by thermal expansion mismatch and can lead to fractured ALD films. The results herein allow us to make recommendations to avoid, mitigate, or overcome the difficulties encountered when performing ALD and plasma-enhanced ALD on porous polymers. We intend this article to serve as a “lessons learned” guide informed by previous experience to provide a better understanding of the difficulties and limitations of ALD on porous polymers and knowledge-based guidelines for successful depositions. This knowledge can accelerate future research and help experimentalists navigate and troubleshoot as they expose porous polymers to reactive precursor vapors.

36 MATERIALS SCIENCE↗

Using block-copolymer nanolithography as a tool to sensitively evaluate variation in chemical dry etching rates of semiconductor materials with sub-5 nm resolution

Ion implantation is a robust and established method to customize the electronic properties of Si. However, fabricating doped, ultrafine semiconductor nanostructures can be challenging. Ion implantation has well-established effects on the dry etch rates of Si, which becomes increasingly consequential as the target dimension shrinks below a few tens of nanometers. While dry etching arrays of block copolymer-templated nanoscale holes (pitch = 37.5 nm, diameter ~25 nm) into p-type, n-type, and undoped Si, we observed that the lateral etch rate was notably larger for the n-type regions than p-type or undoped regions. By doing image analyses on high resolution electron micrographs of the nanostructured hole arrays, we were able to extract the porosity and average radii of the holes with subnanometer sensitivity and compare the relative etch rates between different doping conditions. We found that degenerately doped n-type silicon consistently etches between approximately 17% and 27% faster in the lateral direction than p-type Si, resulting in significantly larger porosity and, consequently, less mechanical stability. Here, we demonstrate that top-down dimensional analysis of a densely packed porous nanostructure is a robust method for assessing extremely small differences in the lateral, chemical etch rate of doped Si to a degree of sensitivity that was previously unachievable. The minute, dense-packed nature of block copolymer self-assembled nanostructures is shown to be ideal for this application. This proposed method could be useful for designing fabrication processes for heterogeneous nanostructures, as slight dry etch rate variations that may be within process tolerance at the micrometer-scale appear to have nontrivial consequences at the nanometer scale.

42 ENGINEERING↗

Nanoporous weakly coordinating anionic frameworks (Final Technical Report)

Under this award, we synthesized and characterized new weakly coordinating, anionic covalent organic frameworks. The motivation was to expand the class of covalent organic frameworks though the introduction of the first weakly coordinating anionic ones. The significance of the weakly coordinating anionic character of these frameworks is associated with the character of the counter (metal) cations in their pores. Those counter-cations, due to the inability to effectively coordinate to the pore walls, have a “naked”, and thus highly electrophilic, Lewis acidic character. Such properties are expected to translate to a number of interesting physical properties that can be potentially used for a range of energy-relevant applications. One of these applications is gas adsorption, separation, and storage. The electrophilic, Lewis acidic character of the counter-cations are expected to strongly bind to gas molecules entering the pores leading to higher gas sorption capacities. Other applications include heterogeneous catalysis, ion exchange, and solid state ion conduction. Within the project we explored a range of chemical blocks, and tested synthesis conditions to polymerize these building blocks to form the target materials. In particular, we focused on materials with group 15 elements like phosphorus in the oxidation state +5 and the coordination number 6, that have a formal -1 charge. The synthesis of such materials is challenging because its success depends on the absence of residual monomeric and oligomeric side-products in the pores, and the absence of significant framework interpenetration. Crystalline forms of these materials require sufficient reversibility of the polymerization reaction (which is difficult to achieve because group 15 elements like P tend to make strong covalent bonds with neighbored elements), as well as suitable polymerization rates that prevent the formation of kinetically controlled products. We had success with the preparation of anionic porous organic frameworks with anionic building blocks containing P(V)O6 octahedra synthesized through Yamamoto coupling reactions. These materials are non-crystalline because of the irreversible nature of the Yamamoto coupling reaction, but show porosity. The porosity and surface area can be significantly increased by co-reaction with electrostatically neutral co-reactants. Very high porosity and surface areas can be achieved when the materials are washed with hydrochloric acid. This method is commonly used to free products from Yamamoto coupling reactions from by-products. Indeed, this method removed by products from the pores of our materials, however it also led to the hydrolysis of the PO6 octahedra to form pending phosphonic acid groups (-PO3H)-groups in the frameworks (PA-POFs) which was actually not desired. Nonetheless, these materials showed high CO2 sorption capacities. In addition, they show extremely high (actually record) sorption capacities for the removal of a range of common micropollutants such as bisphenol A (BPA) and 4-nitrophenol in water. BPA is a wide-spread organic pollutant and a known endocrine disruptor. The maximum adsorption capacity of BPA at equilibrium is found to be as high as 3,366 mg g-1 by Langmuir adsorption model, which is more than 10 times greater than peer materials. The polymer also rapidly removes various other organic micropollutants with more than 90% removal efficiencies. In addition, the PA-POF material can be regenerated at least five times by mild washing using methanol without significant loss in removal efficiency. This is significant advantage over commonly used activated carbon materials (that are in Brita water faucet filters, for example). Comparison studies showed that only materials with the phosphonate groups show extreme sorption although the number of PA group is actually small according to solid state NMR and EDX data. More research would be needed to investigate why this is (a possibility is that the phosphonate groups have a multiplying effect in which a PA-induced initial adsorption leads to the adsorption of much more adsorbate). The extreme sorption capabilities can also be visually seen when colored adsorbates such as 4-nitrophenol are used, as the adsorption of the nitrobenzene leads to the decoloration of the solution. We have produced three short videos that illustrate the sorption capabilities compared to two peer materials (activated carbon from dismantled Brita water filters, and a electrostatically neutral, chemically related, porous organic polymer, respectively).

36 MATERIALS SCIENCE↗

Cathode degradation and erosion in high pressure arc discharges

The various processes which control cathode erosion and degradation were identified and evaluated. A direct current arc discharge was established between electrodes in a pressure-controlled gas flow environment. The cathode holder was designed for easy testing of various cathode materials. The anode was a water cooled copper collector electrode. The arc was powered by a dc power supply with current and voltage regulated cross-over control. Nitrogen and argon were used as propellants and the materials used were two percent thoriated tungsten, barium oxide impregnated porous tungsten, pure tungsten and lanthanum hexaboride. The configurations used were cylindrical solid rods, wire bundles supported by hollow molybdenum tubes, cylindrical hollow tubes, and hollow cathodes of the type used in ion thrusters. The results of the mass loss tests in nitrogen indicated that pure tungsten eroded at a rate more than 10 times faster than the rates of the impregnated tungsten materials. It was found that oxygen impurities of less than 0.5 percent in the nitrogen increased the mass loss rate by a factor of 4 over high purity nitrogen. At power levels less than 1 kW, cathode size and current level did not significantly affect the mass loss rate. The hollow cathode was found to be operable in argon and in nitrogen only at pressures below 400 and 200 torr, respectively.

Hardy, T. L.↗

Cathode degradation and erosion in high pressure arc discharges

The various processes which control cathode erosion and degradation were identified and evaluated. A direct current arc discharge was established between electrodes in a pressure-controlled gas flow environment. The cathode holder was designed for easy testing of various cathode materials. The anode was a water cooled copper collector electrode. The arc was powered by a dc power supply with current and voltage regulated cross-over control. Nitrogen and argon were used as propellants and the materials used were two percent thoriated tungsten, barium oxide impregnated porous tungsten, pure tungsten and lanthanum hexaboride. The configurations used were cylindrical solid rods, wire bundles supported by hollow molybdenum tubes, cylindrical hollow tubes, and hollow cathodes of the type used in ion thrusters. The results of the mass loss tests in nitrogen indicated that pure tungsten eroded at a rate more than 10 times faster than the rates of the impregnated tungsten materials. It was found that oxygen impurities of less than 0.5 percent in the nitrogen increased the mass loss rate by a factor of 4 over high purity nitrogen. At power levels less than 1 kW, cathode size and current level did not significantly affect the mass loss rate. The hollow cathode was found to be operable in argon and in nitrogen only at pressures below 400 and 200 torr, respectively.

Hardy, T. L.↗

Micro-cantilever beam experiments and modeling in porous polycrystalline UO 2

Understanding the impact of microstructure on the thermo-mechanical behavior of oxide nuclear fuels is vital to predicting their performance through multiscale models. Evaluating the mechanical properties at the sub-grain length scale is key to developing these multiscale models. In this work, 3D finite element (FE) models were constructed to simulate the micrometer-scale bending of micro-cantilever beams fabricated using porous polycrystalline uranium dioxide (UO 2 ) and tested at room temperature. Here, the results showed that the porosity and elastic anisotropy of individual grains can play a significant role in determining the effective mechanical properties of the material deduced from the tests. Specifically, the porosity had a non-negligible effect, given that the pore size was of the same order of magnitude as the dimensions of the micro-beams. Correlations between load-deflection data, pore location, and elastic properties (effective Young's modulus) were investigated using UO 2 micro-beam FE models, where pore clusters were included and placed at different locations along the length of the beam. Results indicated that the presence of pore clusters near the substrate, i.e., the clamp of the micro-cantilever beam, has the strongest effect on the load-deflection behavior, with the porosity leading to a reduction of stiffness that is the largest for any location of the pore clusters. Furthermore, it was also found that pore clusters located towards the middle of the span and close to the end of the beam have a comparatively small effect on the load-deflection behavior. Therefore, it is concluded that accurate estimates of Young's modulus can be obtained from micro-cantilever experiments after accounting for porosity on the one third of the beam length close to the clamp. This, in turn, provides an avenue to improve microscale experiments and their analysis in porous, anisotropic elastic materials.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Controlled 3D nanoparticle deposition by drying of colloidal suspension in designed thin micro-porous architectures

Nanoparticle deposition by drying of colloidal suspension in thin micro-porous architectures has attracted a lot of attention in scientific research as well as industrial applications. However, the underlying mechanisms of such three-dimensional (3D) deposition are not yet fully revealed due to the complexity of the co-occurring processes of two-phase fluid flows, phase change and mass transport. Consequently, the control of 3D nanoparticle deposition remains a challenge. We use a combined experimental and numerical approach to achieve controlled 3D nanoparticle deposition by drying of colloidal suspension in two pillar-based thin micro-porous architectures. By the design of pillar layout, rectangular-spiral and circular-spiral deposition configurations are obtained globally. By varying the surface wettability, vertically symmetric and sloped nanoparticle depositions can be achieved locally. While the numerical modeling reveals the mechanisms of liquid internal flow, as well as the impact of local drying rate on nanoparticle transport, accumulation and final deposition, the experimental results of deposition configurations validate the controlling strategies. This combined experimental and numerical work provides a framework to achieve desired 3D nanoparticle deposition in thin micro-porous architectures, with a thorough understanding of the underlying mechanisms of two-phase fluid flows, phase change and mass transport.

36 MATERIALS SCIENCE↗

3D-Printed Porous Supramolecular Sorbents for Cobalt Recycling

Electronic waste recycling is a recognized global challenge that requires new strategies to bind and release critical materials selectively, such as cobalt present in lithium-ion batteries. To address this challenge, hierarchical 3D-printed porous polymer scaffolds bearing supramolecular receptors were prepared using vat photopolymerization and their cobalt binding profiles were examined as a function of matrix polarity. By combining high-resolution digital light processing (DLP) with polymerization-induced phase separation (PIPS), functional acrylic copolymer networks with micrometer-level precision of geometry and nanometer-level pores were generated. Covalent integration of a methacrylate-functionalized bisdicyclohexyl acetamide (BDCA-MA) receptor enabled binding and release of cobalt(II) chloride (CoCl 2 ) via a solvent polarity switch mechanism involving a change in solvent from ethanol to water. The present structures proved reusable as shown by sustained high binding efficiency over five bind and release cycles. Finally, this platform represents a “green” and energy conscious method for future electronic waste recycling.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗