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At least 1,351 records · Page 75

High Capacity Step-Shaped Hydrogen Adsorption in Robust, Pore-Gating Zeolitic Imidazolate Frameworks (Final Technical Report)

The use of porous adsorbents for the densification of H 2 under relatively mild pressures and temperatures has been long pursued through various avenues of synthetic organic frameworks, namely metal–organic frameworks. However, the overwhelming majority of these materials are macroscopically rigid, exhibiting adsorption–desorption profiles that require appreciable energetic input for their full payload capacity to be stored and subsequently delivered. This reduced “deliverable” capacity is a core inefficiency in the use of porous adsorbents for H 2 densification. Our core mission is to determine a material-based strategy that fundamentally alters the adsorption¬–desorption profile in a manner that obviates these deleterious energetic requirements. Towards this, we have focused on metal–organic frameworks that exhibit “cooperative flexibility”, wherein the material undergoes reversible macroscopic phase changes in response to changes to external temperature and/or adsorbate pressure (i.e., concentration). Where these reversible switches occur between states of disparate enough accessible porosity, cooperatively flexible frameworks can exhibit “step-shaped” adsorption–desorption profiles that enable use of the delivery gaseous payload without the aforementioned additional energy requirements. However, before our work, such the observation of this phenomenon with very weakly adsorbing H 2 had not been observed with the necessary profile and P/T conditions desired for H 2 storage and delivery. During this project we have leveraged a deep understanding of the phase change in family of cooperatively flexible metal–organic frameworks to systematically alter their adsorption–desorption profiles to achieve step-shaped adsorption and desorption of H 2 in a precise P/T regime that enables a high deliverable capacity. Specifically, the thermodynamics of the adsorption/desorption induced phase changes in the baseline framework CdIF-13 (sod–Cd(benzimidazolate) 2 ) were tuned using the mixed-linker, or multivariate, approach to framework derivatization. Follow this, we have pursued a similar approach to tuning the adsorption–desorption profile of a second framework family, MIL-53(Al), which contains only Al(III) and theoretically exhibits a much higher deliverable capacity. In total, our work demonstrates that by first understanding the structural consequences of phase changes in these materials, their behavior can be systematically altered through ligand substitutions, tuning the pressure and temperature conditions at which H 2 is adsorbed and desorbed. Thus, enabling high deliverable capacities of H 2 with minimized energetic requirements.

08 HYDROGEN↗

Porous Covalent Organic Polymers for efficient Fluorocarbon-based Adsorption Cooling

Adsorption-based cooling is an energy-efficient renewable-energy technology that can be driven using low-grade industrial waste heat and/or solar heat. Here, we report the first exploration of fluorocarbon adsorption using porous covalent organic polymers (COPs) for this cooling application. High fluorocarbon R134a equilibrium capacities and unique overall linear-shaped isotherms are revealed for the materials, namely COP-2 and COP-3. The key role of mesoporous defects on this unusual adsorption behavior was demonstrated by molecular simulations based on atomistic defect-containing models built for both porous COPs. Analysis of simulated R134a adsorption isotherms for various defect-containing atomistic models of the COPs shows a direct correlation between higher fluorocarbon adsorption capacities and increasing pore volumes induced by defects. Combined with their high porosities, excellent reversibility, fast kinetics, and large operating window, these defect-containing porous COPs are promising for adsorption-based cooling applications.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Ballistic Performance of Porous Ceramic Thermal Protection Systems at 9 km/s

Porous-ceramic, thermal-protection-systems are used heavily in current reentry vehicles like the Orbiter, and they are currently being proposed for the next generation of manned spacecraft, Orion. These materials insulate the structural components and sensitive electronic components of a spacecraft against the intense thermal environments of atmospheric reentry. Furthermore, these materials are also highly exposed to space environmental hazards like meteoroid and orbital debris impacts. This paper discusses recent impact testing up to 9 km/s on ceramic tiles similar to those used on the Orbiter. These tiles have a porous-batting of nominally 8 lb/cubic ft alumina-fiber-enhanced-thermal-barrier (AETB8) insulating material coated with a damage-resistant, toughened-unipiece-fibrous-insulation (TUFI) layer.

Miller, Joshua E.↗

Rational Designed Mixed-Conductive Sulfur Cathodes for All-Solid-State Lithium Batteries

All-solid-state lithium–sulfur batteries (ASSLSBs) hold great promise for safe and high-energy-density energy storage. However, developing high-performance sulfur cathodes has been proven difficult due to low electronic and ionic conductivities and large volume change of sulfur during charge and discharge. Here, we reported an approach to synthesize sulfur cathodes with a mixed electronic and ionic conductivity by infiltrating a solution consisting of Li 3 PS 4 (LPS) solid electrolyte and S active material into a mesoporous carbon (CMK-3). This approach leads to a uniform dispersion of amorphous Li 3 PS 7 (L 3 PS) catholyte in an electronically conductive carbon matrix, enabling high and balanced electronic/ionic conductivities in the cathode composite. The inherent porous structure of CMK-3 also helps to accommodate the strain/stress generated during the expansion and shrinkage of the active material. In sulfide-based all-solid-state batteries with Li metal as the anode, this cathode composite delivered a high capacity of 1025 mAh g –1 after 50 cycles at 60 °C at 1/8C. This work highlights the important role of high and balanced electronic and ionic conductivities in developing high-performance sulfur cathodes for ASSLSBs.

25 ENERGY STORAGE↗

Porous Covalent Organic Polymers for Efficient Fluorocarbon‐Based Adsorption Cooling

Abstract Adsorption‐based cooling is an energy‐efficient renewable‐energy technology that can be driven using low‐grade industrial waste heat and/or solar heat. Here, we report the first exploration of fluorocarbon adsorption using porous covalent organic polymers (COPs) for this cooling application. High fluorocarbon R134a equilibrium capacities and unique overall linear‐shaped isotherms are revealed for the materials, namely COP‐2 and COP‐3. The key role of mesoporous defects on this unusual adsorption behavior was demonstrated by molecular simulations based on atomistic defect‐containing models built for both porous COPs. Analysis of simulated R134a adsorption isotherms for various defect‐containing atomistic models of the COPs shows a direct correlation between higher fluorocarbon adsorption capacities and increasing pore volumes induced by defects. Combined with their high porosities, excellent reversibility, fast kinetics, and large operating window, these defect‐containing porous COPs are promising for adsorption‐based cooling applications.

Zheng, Jian↗

Experimental observation of nonlinear relation between pressure and water flux is consistent with the solution-diffusion model

In several recent studies, it has been proposed that the fundamental understanding of penetrant transport in dense polymer membranes occurring via the solution-diffusion model, which has been the generally accepted theoretical framework for describing penetrant transport in such materials for the past several decades, is flawed. An alternate mechanistic framework based on the idea of two-phase flow in a porous medium (i.e., pore-flow) has been broadly advanced instead, with proponents of this approach claiming that the pore-flow theoretical framework provides the necessary mechanistic insight to design novel polymeric membrane materials for emerging applications. In this study, we show experimental results for hydraulic permeation of water that are entirely consistent with the solution-diffusion theory, without modification, for three dense polymeric membranes: crosslinked poly(ethylene glycol diacrylate) (XLPEGDA), Nafion 117 ionomer in the sodium counterion form (Nafion 117-Na), and cellulose acetate (CA). By measuring water flux at transmembrane pressures up to 240 bar, we observe a nonlinear relationship between the transmembrane pressure (TMP) and water flux, J w , for XLPEGDA and Nafion 117-Na, while this relationship is linear for CA. We demonstrate that the behavior of these three materials is described via the solution-diffusion model. According to the solution-diffusion model, flux is, to a good approximation, proportional to the transmembrane concentration difference induced by the pressure difference across the membrane, rather than to TMP itself. Water sorption isotherms are reported for all three materials. They further justify the nonlinear relationship between TMP and J w observed in XLPEGDA and Nafion 117-Na, emphasizing that the nonlinearity in the flux/TMP relationship stems from nonlinearities in the sorption isotherm with pressure. Additionally, the relationship between water flux and TMP can be predicted, a priori, with no adjustable parameters when a predictive model for the diffusion coefficient of water is employed in conjunction with the experimental water sorption isotherms in the solution-diffusion model. Furthermore, our results demonstrate the validity of the solution-diffusion model to describe transport of penetrants in dense polymer membranes, while highlighting the sensitivity of the solution-diffusion model to the many physical and mathematical simplifications commonly applied to the theory in literature.

materials↗

Dual‐Ion Intercalation and High Volumetric Capacitance in a Two‐Dimensional Non‐Porous Coordination Polymer

Abstract Intercalation is a promising ion‐sorption mechanism for enhancing the energy density of electrochemical capacitors (ECs) because it offers enhanced access to the electrochemical surface area. It requires a rapid transport of ions in and out of a host material, and it must occur without phase transformations. Materials that fulfil these requirements are rare; those that do intercalate almost exclusively cations. Herein, we show that Ni 3 (benzenehexathiol) (Ni 3 BHT), a non‐porous two‐dimensional (2D) layered coordination polymer (CP), intercalates both cations and anions with a variety of charges. Whereas cation intercalation is pseudocapacitive, anions intercalate in a purely capacitive fashion. The excellent EC performance of Ni 3 BHT provides a general basis for investigating similar dual‐ion intercalation mechanisms in the large family of non‐porous 2D CPs.

Banda, Harish↗

Hydrogen generation through static-feed water electrolysis

A static-feed water electrolysis system (SFWES), developed under NASA sponsorship, is presented for potential applicability to terrestrial hydrogen production. The SFWES concept uses (1) an alkaline electrolyte to minimize power requirements and materials-compatibility problems, (2) a method where the electrolyte is retained in a thin porous matrix eliminating bulk electrolyte, and (3) a static water-feed mechanism to prevent electrode and electrolyte contamination and to promote system simplicity.

Jensen, F. C.↗

Observations of Methane and Ethylene Diffusion Flames Stabilized Around a Blowing Porous Sphere Under Microgravity Conditions

This paper presents the experimental and theoretical results for expanding methane and ethylene diffusion flames in microgravity. A small porous sphere made from a low-density and low-heat-capacity insulating material was used to uniformly supply fuel at a constant rate to the expanding diffusion flame. A theoretical model which includes soot and gas radiation is formulated but only the problem pertaining to the transient expansion of the flame is solved by assuming constant pressure infinitely fast one-step ideal gas reaction and unity Lewis number. This is a first step toward quantifying the effect of soot and gas radiation on these flames. The theoretically calculated expansion rate is in good agreement with the experimental results. Both experimental and theoretical results show that as the flame radius increases, the flame expansion process becomes diffusion controlled and the flame radius grows as gamma t. Theoretical calculations also show that for a constant fuel mass injection rate a quasi-steady state is developed in the region surrounded by the flame and the mass flow rate at any location inside this region equals the mass injection rate.

Atreya, Arvind↗

Cometary Silicates: Interstellar and Nebular Materials

Evidence for interstellar material in comets is deduced from IR spectra, insitu measurements of Halley, and chondritic porous interplanetary dust particles (CP IDPs). IR spectra of comets reveal the spectrally active minerals: amorphous carbon, amorphous silicates, and (in some comets) crystalline silicates. Evidence suggests amorphous silicates are of interstellar origin while crystalline silicates are of nebular origin. 10 microns spectra of comets and submicron amorphous silicate spherules in CP IDPs have shapes similar to lines-of-sight through the ISM. Thermal emission models of cometary IR spectra require Fe-bearing amorphous silicates. Fe-bearing amorphous silicates may be Fe-bearing crystalline silicates formed in AGB outflows that are amorphized through He+ ion bombardment in supernova shocks in the ISM. Crystalline silicates in comets, as revealed by IR spectra, and their apparent absence in the ISM, argues for their nebular origin. The high temperatures (less than l000 K) at which crystals form or are annealed occur in the inner nebula or in nebular shocks in the 5-10 AU region. Oxygen isotope studies of CP IDPs show by mass only 1 % of the silicate crystals are of AGB origin. Together this suggests crystalline silicates in comets are probably primitive grains from the early solar nebula.

Wooden, Diane H.↗

Noise reducing screen devices for in-flow pressure sensors

An acoustic sensor assembly is provided for sensing acoustic signals in a moving fluid such as high speed fluid stream. The assembly includes one or more acoustic sensors and a porous, acoustically transparent screen supported between the moving fluid stream and the sensor and having a major surface disposed so as to be tangent to the moving fluid. A layer of reduced velocity fluid separating the sensor from the porous screen. This reduced velocity fluid can comprise substantially still air. A foam filler material attenuates acoustic signals arriving at the assembly from other than a predetermined range of incident angles.

Schmitz, Fredric↗

Porous Ceramic Cures at Moderate Temperatures, Is Good Heat Insulator

The problem: To develop a foamed-in-place refractory material that would provide good thermal insulation, mechanical support, and vibration shielding for enclosed objects at temperatures up to 30000 F. The preparation of conventional foamed refractory materials required long curing times (as much as 48 hours) and high temperatures (at least 700 F), rendering such materials unusable for in-place potting of heat-sensitive components. The solution: A foamed ceramic material that has the requisite thermal insulation and strength, and also displays other properties that suggest a wide range of applications.

Eubanks, Alfred G.↗

PuMA and Multiscale Modeling

The Porous Microstructure Analysis (PuMA) software was initially developed to analyze tomographic reconstructions of fibrous materials, commonly used as insulators in NASA spacecrafts. Since then, the software grew in capabilities and it is now able to compute many different geometric and physical properties, which are often anisotropic at multiple scales. In addition, PuMA can generate its own artificial microstructures in order to study their performance. This talk will give an overview of the main functions and display its application to some of the widely used carbon ablators for heatshields, including the more challenging woven architectures.

Federico Semeraro↗

The Porous Microstructure Analysis (PuMA) software

The open-source Porous Microstructure Analysis (PuMA) software was implemented to offer an efficient framework for determining material characteristics from 3D microstructures. Its development was inspired by progress in X-ray microtomography, an imaging technology that captures the internal structure of materials in 3D, and even in a 4D temporal context. Over recent years, this method has transformed the domain of materials science due to its capability to non-destructively examine material microstructures while presenting digital data about their geometrical details. It has provided insights into materials relevant to several NASA missions, including heatshields, parachute fabrics, meteorites, and other advanced composites. PuMA, in its current version 3, delivers an array of features, spanning from basic geometric insights of a microstructure to intricate anisotropic thermo-elastic and chemical behavior. Specifically, the software evaluates morphological attributes (specific surface area, volume fractions, mean intercept lengths, orientation) and physical characteristics (conductivity, elasticity, permeability, and tortuosity). Additionally, it can model material degradation processes, such as oxidation and surface chemistry interactions. The software can generate synthetic microstructures, from straightforward geometrical designs to intricate woven and non-woven geometries. Coupling material generation and characterization enable parametric studies and sensitivity analysis to optimize the microstructural performance and inform design decisions and reliability assessment based on uncertainty quantification. A recent addition to PuMA includes the TomoSAM plugin, devised to incorporate the cutting-edge Segment Anything Model (SAM). SAM is a promptable deep learning model that can identify objects and create image masks in a zero-shot manner, based only on a few user clicks. The synergy between these tools aids in the segmentation of complex 3D datasets from tomography or other imaging techniques, which would otherwise require a laborious manual segmentation process.

Tomography↗

The Porous Microstructure Analysis (PuMA) software

The open-source Porous Microstructure Analysis (PuMA) software was created to offer an efficient framework for determining material properties from 3D microstructures. Its development was inspired by progress in X-ray microtomography, an imaging technology that captures the internal structure of materials in 3D, and even in a 4D temporal context. Over recent years, this method has transformed the domain of materials science due to its capability to non-destructively examine material microstructures while presenting digital data about their geometrical details. It has provided insights into materials relevant to several NASA missions, including heatshields, parachute fabrics, meteorites, and other advanced composites. PuMA, in its current version 3, delivers an array of features, spanning from basic geometric insights of a microstructure to intricate anisotropic thermo-elastic and chemical behavior. Specifically, the software evaluates morphological attributes (specific surface area, volume fractions, mean intercept lengths, orientation) and physical characteristics (conductivity, elasticity, permeability, and tortuosity). Additionally, it can model material degradation processes, such as oxidation and surface chemistry interactions. The software can generate synthetic microstructures, from straightforward geometrical designs to intricate woven and non-woven geometries. Coupling material generation and characterization enables parametric studies and sensitivity analysis to optimize the microstructural performance and inform design decisions and reliability assessment based on uncertainty quantification. A recent addition to PuMA includes the TomoSAM plugin, devised to incorporate the cutting-edge Segment Anything Model (SAM) into our image segmentation workflow. SAM is a promptable deep learning model that can identify objects and create image masks in a zero-shot manner, based only on a few user clicks. The synergy between these tools aids in the segmentation of complex 3D datasets from tomography and other imaging techniques, which would otherwise require a laborious manual segmentation process.

Tomography↗

Additive Manufacturing and Experimental Characterization of Nickel-Titanium Shape-Memory Alloy Wick Structures and Heat Pipes for Spacecraft Thermal Control

Shape memory alloys (SMA), such as those based on nickel-titanium (NiTi), are increasingly being applied as multifunctional spacecraft components. For thermal management applications, NiTi flow tubing hinges and self-deploying loop heat pipes have been demonstrated. Emerging additive manufacturing (AM) processes are enabling more complex SMA devices than can be formed from conventional plain wire, tubing, and sheet stock materials. This paper presents our progress toward applying powder bed fusion AM to producing porous NiTi wicks and NiTi-H2O heat pipes, which could be embedded in thermally deploying radiators for spacecraft thermal management. AM near-equiatomic NiTi (55.1 wt% Ni) porous wick specimens were produced with a range of deposition parameters. Transient acetone rate-of-rise experiments were performed to estimate wick permeability (K) and average pore radius (r_pore) values and identify parameter sets with high capillary performance. Surface treatments were evaluated to achieve hydrophilic wick structures. Evaluated treatments included chemical oxide growth with H2O2, oxide and sodium titanate growth with NaOH solution, and ultrasonic cleaning with specialty detergents that can remove hydrocarbon contaminants. The most durable hydrophilic surface conditions were obtained with the NaOH treatment. High performing wick deposition parameters were used to produce a full AM NiTi heat pipe, which was treated with NaOH solution to activate the wick. This heat pipe was operated on a test stand in the inverted configuration (upper evaporator and lower condenser), and demonstrated stable nearly isothermal operation for 150 hrs.

Thermal management↗

Additive Manufacturing and Experimental Characterization of Nickel-Titanium Shape-Memory Alloy Wick Structures and Heat Pipes for Spacecraft Thermal Control

Shape memory alloys (SMA), such as those based on nickel-titanium (NiTi), are increasingly being applied as multifunctional spacecraft components. For thermal management applications, NiTi flow tubing hinges and self-deploying loop heat pipes have been demonstrated. Emerging additive manufacturing (AM) processes are enabling more complex SMA devices than can be formed from conventional plain wire, tubing, and sheet stock materials. This paper presents our progress toward applying powder bed fusion AM to producing porous NiTi wicks and NiTi-H2O heat pipes, which could be embedded in thermally deploying radiators for spacecraft thermal management. AM near-equiatomic NiTi (55.1 wt% Ni) porous wick specimens were produced with a range of deposition parameters. Transient acetone rate-of-rise experiments were performed to estimate wick permeability (K) and average pore radius (r_pore) values and identify parameter sets with high capillary performance. Surface treatments were evaluated to achieve hydrophilic wick structures. Evaluated treatments included chemical oxide growth with H2O2, oxide and sodium titanate growth with NaOH solution, and ultrasonic cleaning with specialty detergents that can remove hydrocarbon contaminants. The most durable hydrophilic surface conditions were obtained with the NaOH treatment. High performing wick deposition parameters were used to produce a full AM NiTi heat pipe, which was treated with NaOH solution to activate the wick. This heat pipe was operated on a test stand in the inverted configuration (upper evaporator and lower condenser), and demonstrated stable nearly isothermal operation for 150 hrs.

Thermal management↗

Catalyst, structures, reactors, and methods of forming same

Structures, catalysts, and reactors suitable for use for a variety of applications, including gas-to-liquid and coal-to-liquid processes and methods of forming the structures, catalysts, and reactors are disclosed. The catalyst material can be deposited onto an inner wall of a microtubular reactor and/or onto porous support structures using atomic layer deposition techniques.

Moulton, Staci A.↗