High-Performance Porous Organic Polymers for Environmental Remediation of Toxic Gases
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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
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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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Multiscale Porous High-temperature Heat Exchanger Using Ceramic Co-extrusion
In this project, our MIT, Purdue, and GE team aims to design, model, fabricate, and test a novel high temperature, compact, and durable ceramic heat exchanger to be operated under high temperature and pressure conditions for aerospace applications. Our approach is grounded in introducing multiscale porosity, i.e., centimeter-scale channels embedded with micrometer-scale channels, into the ceramic heat exchanger to significantly improve its heat transfer performance and mechanical strength while maintaining minimal pressure losses. We first developed high-fidelity thermal-fluid-mechanical model capable of precisely capturing the heat transfer rate, temperature profile, pressure drop, and mechanical stress throughout the entire heat exchanger design. Guided by our model, we identified the optimal design parameters for the SiC heat exchanger body and manifolds. Then, we established a completed fabrication procedure to create multiscale features in the ceramic heat exchanger, including co-extrusion, lamination, burnout, and sintering. We fabricated multiple heat exchanger bodies consisting of 6 × 6 and 3 × 3 centimeter-scale channels where each individual centimeter-scale channel comprises 625 crack-free microchannels with 90 μm × 90 μm opening. Owing to the multiscale features, our fabricated heat exchanger bodies exhibited desirable mechanical strength with 156 MPa flexural strength under 1300 Celsius degree. Despite the demonstrated highly tailorable microscopic features and superior mechanical strength, we identified delamination due to the complex interaction among ceramic, polymer, and gas species can be a critical challenge to create fully defect-free heat exchanger, which requires further fundamental investigations in future works. To test the heat exchanger performance, we constructed a high-temperature and high-pressure experimental apparatus that can be safely operated under 400 Celsius degree and 4 bar. With insights gained from mechanistic modeling, material development, and detailed characterization, a cost model was finally developed to understand the market potential of the developed technology, where a cost of $43,000 Celsius degree/kW was envisioned. This project developed a transformative approach to high-performance heat exchanger design. The thermal-fluid-mechanical design approach developed in this project can serve as a generic tool to guide the design of various heat-exchangers operated under high-temperature and high-pressure conditions. The material fabrication approach established in this project can be a useful guide for ceramic processing at extreme length scales.
42 ENGINEERING↗
A high performance porous flat-plate solar collector
A solar collector employing a porous matrix as a solar absorber and heat exchanger is presented and its application in solar air heaters is discussed. The collector is composed of a metallic matrix with a porous surface which acts as a large set of cavity radiators; cold air flows through the matrix plate and exchanges heat with the thermally stratified layers of the matrix. A steady-state thermal analysis of the collector is used to determine collector temperature distributions for the cases of an opaque surface matrix with total absorption of solar energy at the surface, and a diathermanous matrix with successive solar energy absorption at each depth. The theoretical performance of the porous flat plate collector is shown to exceed greatly that of a solid flat plate collector using air as the working medium for any given set of operational conditions. An experimental collector constructed using commercially available, low cost steel wool as the matrix has been found to have thermal efficiencies from 73 to 86%.
Lansing, F. L.↗
Strength and thermal shock resistance of porous reaction-bonded silicon nitride by direct nitriding of binder jet additively manufactured silicon
The direct nitridation of binder jet additively manufactured silicon to produce porous silicon nitride was explored. The Taguchi Design of Experiments method was used to systematically study the effect of time, temperature, and nitrogen flow rate on the direct nitriding of binder jet additively manufactured silicon to produce porous reaction-bonded silicon nitride (RBSN). Highly porous (61%) samples with high conversion (99%) to silicon nitride were achieved using a thermal profile that utilized two isothermal holds. Further, it was shown that these samples exhibited thermal shock resistance and a low coefficient of thermal expansion. These results indicate that RBSN is readily achievable through additive manufacturing.
Ceramics↗
Development of Ternary Transition Metal Oxide Catalysts for Oxygen Evolution Reaction
Electrochemical water splitting, a promising method for green hydrogen production, is currently hindered by the high cost of precious-group metal (PGM)-based catalysts for the oxygen evolution reaction (OER). This study addresses this challenge by advancing the development of catalysts for OER, focusing on the development of high-performance PGM-free catalysts using nickel-iron-cobalt (NiFeCo)-based aerogels. The catalysts were synthesized via a sol-gel method and critical point drying to achieve a highly porous structure with an exceptionally high surface area. The designed catalyst structure provides an ideal platform for maximizing catalytic active sites and enhancing mass transport kinetics. Co has been systematically incorporated into the current PGM-free state-of-the-art, NiFeOx catalyst, and the metal ratios have been optimized. In addition to the experimental studies, density functional theory calculations were performed to study the material’s properties of this ternary catalyst and the effect of Co addition on enhancing OER catalysis.
Mizrahi, Michal [Bar-Ilan University, Ramat Gan, I↗
Capture of Hypervelocity Particles with Low-Density Aerogel
Recent impact experiments conducted at Johnson Space Center supported a space-exposed flight instrument called the orbital debris collector (ODC) to see whether SiO2 acrogel performed adequately as a collector to capture cosmic dust particles and/or manmade debris, or whether additional development is needed. The first ODC was flown aboard the Mir for 18 months, while the second will be flown aboard a spacecraft (Stardust, to be launched in 1999) that will encounter the comet Wild 2 and return to Earth. Aerogels are highly porous materials that decelerate high-velocity particles without substantial melting or modifications to the particles' components; in other denser materials, these particles would melt or vaporize upon impact. The experimental data in this report must be considered somewhat qualitative because they are characterized by substantial, if not intolerable, scatter, possibly due to experimental difficulties in duplicating given sets of initial impact conditions. Therefore, this report is a chronological guide of the experimenters' attempts, difficulties, progress, and evaluations for future tests.
Hoerz, Friedrich↗
Polyimide Cellulose Nanocrystal Composite Aerogels
Polyimide (PI) aerogels are highly porous solids having low density, high porosity and low thermal conductivity with good mechanical properties. They are ideal for various applications including use in antenna and insulation such as inflatable decelerators used in entry, decent and landing operations. Recently, attention has been focused on stimuli responsive materials such as cellulose nano crystals (CNCs). CNCs are environmentally friendly, bio-renewable, commonly found in plants and the dermis of sea tunicates, and potentially low cost. This study is to examine the effects of CNC on the polyimide aerogels. The CNC used in this project are extracted from mantle of a sea creature called tunicates. A series of polyimide cellulose nanocrystal composite aerogels has been fabricated having 0-13 wt of CNC. Results will be discussed.
Aerogels↗
Recovery of MOF-5 from Extreme High-Pressure Conditions Facilitated by a Modern Pressure Transmitting Medium
Here mechanisms underlying the mechanically induced amorphization of metal-organic frameworks (MOFs) are of current interest, and both high-pressure experimentation and molecular dynamics simulations have been used to reveal the fundamentals of load bearing, deformation, and pressure-induced amorphization (PIA) in these highly porous materials. Unfortunately, MOFs are typically highly susceptibility to amorphization, which limits the conditions under which they can be processed and used. However, their flexible structures can be stabilized to high pressures by incorporating guest species into the framework matrix. In this study, a large molecule pressure transmitting medium (DAPHNE 7575 ) is used as a structure-fortifying guest species to stabilize the prototypical MOF -5 to ultra-high pressures ( >9 GPa) and enable the recovery of crystalline material upon decompression. Structural changes associated with the penetration of the pressure transmitting medium on compression are examined using a combination of high pressure synchrotron powder diffraction and molecular dynamics simulations. This work enhances the understanding of PIA in MOFs while showcasing a potential route for the stabilization of MOFs to surprisingly high-pressures.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Lithium vanadium oxide (Li 1.1 V 3 O 8 ) thick porous electrodes with high rate capacity: utilization and evolution upon extended cycling elucidated via operando energy dispersive X-ray diffraction and continuum simulation
The phase distribution of lithiated LVO in thick (~500 μm) porous electrodes (TPEs) designed to facilitate both ion and electron transport was determined using synchrotron-based operando energy dispersive X-ray diffraction (EDXRD). Probing 3 positions in the TPE while cycling at a 1C rate revealed a homogeneous phase transition across the thickness of the electrode at the 1st and 95th cycles. Additionally, continuum modelling indicated uniform lithiation across the TPE in agreement with the EDXRD results and ascribed decreasing accessible active material to be the cause of loss in delivered capacity between the 1st and 95th cycles. The model was supported by the observation of significant particle fracture by SEM consistent with loss of electrical contact. Overall, the combination of operando EDXRD, continuum modeling, and ex situ measurements enabled a deeper understanding of lithium vanadium oxide transport properties under high rate extended cycling within a thick highly porous electrode architecture.
25 ENERGY STORAGE↗
Manufacturing porous U-10Zr metallic fuels with controllable microstructure by volume control spark plasma sintering
In this paper, the volume control spark plasma sintering tool has been designed and applied to sinter porous U-10Zr metallic fuels, by which the sintered sample volume can be precisely controlled. Ethanol and NH 4 HCO 3 are used to control the powder compact or as pore formers to control the pore size and pore structure. Without pore formers, the fuel pellet displays an inhomogeneous microstructure consisting of highly porous and highly densified areas. Uneven powder stacking in the green body results in a non-uniform microstructure, and in the closed-packed area, Joule heating accelerates the neck formation and densification. The addition of ethanol reduces the friction between the powders, resulting in isolated pores formed by the stacking of powders during the sintering. By adding NH 4 HCO 3 , the pore size, and structure can be well controlled, and an interconnected pore structure can be obtained upon the decomposition of the NH 4 HCO 3 . Further, a uniform microstructure and pore distributions can be achieved through the U-10Zr fuel pellets by controlling current flow during the volume control SPS sintering. The microstructure and phase characterization of the sintered porous U-10Zr pellets show major phases of α-U and α-Zr for the sample with short dwelling. For the sample with long dwelling (30 min), the ω UZr 2 in the Zr-enriched area has been observed. The strategy of volume control SPS sintering with the assistance of pore formers could be used to fabricate porous U-10Zr metallic fuels to mimic the microstructure evolution of irradiated metallic fuels (including porosity) and could enable a possible solution for the design of new sodium-free metallic fuels for high burnup.
11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
Optimization of Delignified Wood Rods for Interfacial Solar Evaporation
Interfacial solar evaporation using three-dimensional evaporator materials has shown promise to achieve high evaporation rates exceeding the photothermal limit for water treatment and resource recovery processes. However, challenges remain in optimizing the material geometry to balance the vertical capillary uptake of water and the rate of evaporation to achieve both stable and high evaporation rates. Delignified wood can serve as a highly porous and hydrophilic substrate material to achieve high evaporation rates. In this work, we designed a suspended biochar-coated delignified wood rod evaporator and investigated the influence of its geometric parameters on its evaporation performance. The height of the evaporator exposed to air for evaporation was observed to be an important parameter in governing the evaporation rate, as shorter evaporators limited the available surface area for evaporation, but taller evaporators could not achieve sufficient rates of capillary uptake to maintain stable evaporation rates over 24 h under 1-sun illumination (1 kW m –2 ). In conclusion, the exposed height of the evaporator was optimized to achieve an average hourly evaporation rate of 3.05 ± 0.23 kg m –2 h –1 , which could be maintained in saline solutions containing up to 5 wt % NaCl.
Coating materials↗
The formation of filamentary sublimate residues (FSR) from mineral grains
The significant interparticle forces observed between solar system dust grains upon desorption or sublimation of excess volatiles in simulated Martian or cometary environments are presently investigated, in order to more precisely define these mechanisms and to simulate the types of deposits thereby formed. Some classes of phyllosilicate mineral grains are noted to bond together to form a highly porous filamentary sublimate residue (FSR) exhibiting an exceptionally high tensile strength for its density; this may be important in its control of erosion and sublimation in Martian and cometary environments. It is concluded that FSR formation from clean mineral grains in water ice may be important in the formation of the Martian polar layered terrain.
Storrs, A. D.↗
Sintered Fiber Electrodes
Method proposed to make improved porous electrodes for oxygen pumps, oxygen sensors, high-temperature solid-electrolyte fuel cells, and high-temperature solid-electrolyte electrolysis cells. Electrode made by sintering mat of conducting fibers. Many sintered bonds between intersecting fibers increase electrical conductivity and provide strength, yet allow mat to remain highly porous.
Schroeder, James E.↗
Porous reaction-bonded silicon nitride: Size effects for pressureless nitriding of binder jet additively manufactured silicon
The direct nitridation of binder jet additively manufactured silicon to produce porous reaction-bonded silicon nitride was explored to determine the maximum thickness of the sample that could be converted to >99% silicon nitride. The maximum thickness that could be nitrided was investigated by nitriding cubes of increasing physical size on the millimeter scale. Highly porous samples with high conversion ( > 99%) to silicon nitride were achieved in cubes with 35 mm edge length. It was shown that the silicon nitride phase content changes with increasing sample size.
Aguirre, Trevor [ORNL] (ORCID:0000000281469630)↗
Electrical conductivity in a non-covalent two-dimensional porous organic material with high crystallinity
Ultrathin porous films held together by non-covalent van der Waals interactions was obtained by a top-down approach, which is then utilized as channel material in a two-dimensional planar field-effect transistor device through easy stamp transfer.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
The Impact of Surficial Biochar Treatment on Acute H2S Emissions during Swine Manure Agitation before Pump-Out: Proof-of-the-Concept
Acute releases of hydrogen sulfide (H2S) are of serious concern in agriculture, especially when farmers agitate manure to empty storage pits before land application. Agitation can cause the release of dangerously high H2S concentrations, resulting in human and animal fatalities. To date, there is no proven technology to mitigate these short-term releases of toxic gas from manure. In our previous research, we have shown that biochar, a highly porous carbonaceous material, can float on manure and mitigate gaseous emissions over extended periods (days–weeks). In this research, we aim to test the hypothesis that biochar can mitigate H2S emissions over short periods (minutes–hours) during and shortly after manure agitation. The objective was to conduct proof-of-the-concept experiments simulating the treatment of agitated manure. Two biochars, highly alkaline and porous (HAP, pH 9.2) made from corn stover and red oak (RO, pH 7.5), were tested. Three scenarios (setups): Control (no biochar), 6 mm, and 12 mm thick layers of biochar were surficially-applied to the manure. Each setup experienced 3 min of manure agitation. Real-time concentrations of H2S were measured immediately before, during, and after agitation until the concentration returned to the initial state. The results were compared with those of the Control using the following three metrics: (1) the maximum (peak) flux, (2) total emission from the start of agitation until the concentration stabilized, and (3) the total emission during the 3 min of agitation. The Gompertz’s model for determination of the cumulative H2S emission kinetics was developed. Here, 12 mm HAP biochar treatment reduced the peak (1) by 42.5% (p = 0.125), reduced overall total emission (2) by 17.9% (p = 0.290), and significantly reduced the total emission during 3 min agitation (3) by 70.4%. Further, 6 mm HAP treatment reduced the peak (1) by 60.6%, and significantly reduced overall (2) and 3 min agitation’s (3) total emission by 64.4% and 66.6%, respectively. Moreover, 12 mm RO biochar treatment reduced the peak (1) by 23.6%, and significantly reduced overall (2) and 3 min total (3) emission by 39.3% and 62.4%, respectively. Finally, 6 mm RO treatment significantly reduced the peak (1) by 63%, overall total emission (2) by 84.7%, and total emission during 3 min agitation (3) by 67.4%. Biochar treatments have the potential to reduce the risk of inhalation exposure to H2S. Both 6 and 12 mm biochar treatments reduced the peak H2S concentrations below the General Industrial Peak Limit (OSHA PEL, 50 ppm). The 6 mm biochar treatments reduced the H2S concentrations below the General Industry Ceiling Limit (OSHA PEL, 20 ppm). Research scaling up to larger manure volumes and longer agitation is warranted.
Chen, Baitong (ORCID:0000000266071253)↗
Accretionary rims on inclusions in the Allende meteorite
The origin and composition of the rim sequence on the refractory inclusion in the Allende meteorite are studied. The different textures, mineralogy, and mineral-chemistry of the four layers of the rim are described. The layers are composed of: pyroxene, needles, olivine, hedenbergite, and andradite. Tables of the element and chemical compositions of the layers are presented. The data reveals that: (1) the layers are highly porous masses of euhedral crystals with no intergrowth; (2) layers contain highly disequilibrium mineral assemblages; and (3) the thickness of the layers varies with the underlying topography. These results support the theory that rim structures are accretionary aggregates formed from accretion of independently grown particles onto the surface of inclusions. The formation of the grains in the layers and matrix from nebular condensates is studied.
Macpherson, G. J.↗
Hot gas, regenerative, supported H.sub.2 S sorbents
Efficient, regenerable sorbents for removal of H.sub.2 S from moderately high temperature (usually 200.degree. C.-550.degree.C.) gas streams comprise a porous, high surface area aluminosilicate support, suitably a zeolite, and most preferably a sodium deficient zeolite containing 1 to 20 weight percent of binary metal oxides. The binary oxides are a mixture of a Group VB or VIB metal oxide with a Group IB, IIB or VIII metal oxide such as V-Zn-O, V-Cu-O, Cu-Mo-O, Zn-Mo-O or Fe-Mo-O contained in the support. The sorbent effectively removes H.sub.2 S from the host gas stream in high efficiency and can be repetitively regenerated at least 10 times without loss of activity.
Voecks, Gerald E.↗