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Comparison Study of Conventional and Adaptive Mesh Refinement in Organic Material Decomposition Models
This study compares conventional mesh refinement techniques, specifically Uniform Mesh Refinement (UMR), with a new Adaptive Mesh Refinement (AMR) method, applied to Organic Material Decomposition (OMD) models. The proposed benefit of AMR is that only areas that require refinement, based on minimizing a specific field gradient, are refined thus decreasing model wall time compared to conventional UMR methods. This work specifically focuses on comparing UMR and AMR methods on decomposing (both No-Flow and Porous-Flow material models) Polymeric Methylene Diisocyanate (PMDI) polyurethane foam. Throughout the work, the geometry increased in complexity to assess the refinement methods performance at varying levels geometric intricacy. While AMR has been shown to work well in a variety of applications, the UMR approach proved to be computationally faster, for many of the geometries and foam decomposition models, than AMR. However, it was observed that at higher levels of refinement, greater than 3 UMR, AMR begins to be computationally better. Additionally, the settings used to perform AMR greatly impact its performance, and lessons learned, in terms of OMD models, are shared. Due to physics involved in material decomposition, specifically the evolution of state variables, these problems don’t fully benefit from the advantages of AMR.
Electrochemical Cell with Improved Water or Gas Management
An electrochemical cell having a water/gas porous separator prepared from a polymeric material and one or more conductive cell components that pass through, or are located in close proximity to, the water/gas porous separator, is provided. The inventive cell provides a high level of in-cell electrical conductivity.
Simple, Tough, and Effective Porous Coating for Anti-Corrosion Application
This presentation discusses how a change in polymeric binder, the material used for assembling hydrophobic nanoparticles into a porous structure, led to better mechanical toughness and a simpler fabrication process based on 100% commercially available components. Most importantly, the optimized porous coating can reduce the corrosion rate by two orders of magnitude (0.003 mm/year) due to higher diffusion barrier based on a more resistant tortuous diffusion path. The combination of simplicity, toughness, effectiveness, and scalability greatly enhanced the prospect of commercializing this technology as an internal anti-corrosion coating for natural gas pipelines.
A Review on Direct Air Capture of Carbon Dioxide: Sorbent Materials, Process Engineering, Industrial Scale-Up, and Future Perspectives
The relentless accumulation of anthropogenic greenhouse gases has driven atmospheric carbon dioxide concentrations to approximately 426 ppm, necessitating the aggressive deployment of negative-emission technologies to achieve net zero by 2050. Direct air capture (DAC) offers a scalable, location-independent approach to atmospheric carbon removal; however, it is fundamentally constrained by the significant thermodynamic barriers associated with capturing CO 2 from ultradilute ambient conditions, requiring minimum thermodynamic energy inputs substantially higher than those for postcombustion point sources. This comprehensive review critically examines the technological landscape of DAC, focusing on the interdependent triad of sorbent material design, contactor engineering, and regeneration thermodynamics. We evaluate the fundamental boundaries of adsorption, emphasizing that an optimal adsorption enthalpy and isosteric heat of adsorption must balance the high CO 2 uptake capacity with the energetic penalties of sorbent regeneration. A systematic, comparative analysis of state-of-the-art sorbents is presented, encompassing mesoporous silicas, zeolites, carbon-based materials (CBMs), metal−organic frameworks (MOFs), porous organic polymers (POPs), and polymeric membranes. Special attention is devoted to surface functionalization strategies, particularly amine grafting and impregnation, which transition capture mechanisms from physisorption to chemisorption to enhance selectivity under ambient moisture and low partial pressures. Furthermore, we assess the operational merits of various reactor configurations, including gas−solid, gas−liquid, and membrane contactors, alongside regeneration cycles such as temperature, vacuum, pressure, and moisture swing adsorption. Finally, the review bridges fundamental materials science with industrial application by chronicling the scale-up milestones of pioneering entities and providing a strategic roadmap for advancing DAC technology readiness levels toward global deployment.
Micromechanics of Spray-On Foam Insulation
Understanding the thermo-mechanical response of the Space Shuttle External Tank spray-on foam insulation (SOFI) material is critical, to NASA's Return to Flight effort. This closed-cell rigid polymeric foam is used to insulate the metallic Space Shuttle External Tank, which is at cryogenic temperatures immediately prior to and during lift off. The shedding of the SOFI during ascent led to the loss of the Columbia, and eliminating/minimizing foam lass from the tank has become a priority for NASA as it seeks to resume scheduled space shuttle missions. Determining the nature of the SOFI material behavior in response to both thermal and mechanical loading plays an important role as any structural modeling of the shedding phenomenon k predicated on knowledge of the constitutive behavior of the foam. In this paper, the SOFI material has been analyzed using the High-Fidelity Generalized Method of Cells (HFGMC) micromechanics model, which has recently been extended to admit a triply-periodic 3-D repeating unit cell (RUC). Additional theoretical extensions that mere made in order to enable modeling of the closed-cell-foam material include the ability to represent internal boundaries within the RUC (to simulated internal pores) and the ability to impose an internal pressure within the simulated pores. This latter extension is crucial as two sources contribute to significant internal pressure changes within the SOFI pores. First, gas trapped in the pores during the spray process will expand or contract due to temperature changes. Second, the pore pressure will increase due to outgassing of water and other species present in the foam skeleton polymer material. With HFGMC's new pore pressure modeling capabilities, a nonlinear pressure change within the simulated pore can be imposed that accounts for both of these sources, in addition to stmdar&-thermal and mechanical loading; The triply-periodic HFGMC micromechanics model described above was implemented within NASA GRC's MAC/GMC software package, giving the model access to a range of nonlinear constitutive models for the polymeric foam skeleton material. A repeating unit cell architecture was constructed that, while relatively simple, still accounts for the geometric anisotropy of the porous foam microstructure and its thin walls and thicker edges. With the lack of reliable polymeric foam skeleton materia1 properties, many simulations were executed aimed at backing out these material properties. Then, using these properties, predictions of the thermo-mechanical behavior of the foam, including calculated internal applied pressure profiles, were performed and compared with appropriate experimental data.
Tailored polyMOFs for ion transport in lithium-based battery electrolyte
Owing to their low flammability, solid-state and quasi-solid-state electrolytes are safer alternatives to liquid organic electrolytes for energy storage applications. Metal–organic frameworks (MOFs), with facile functional tunability, long-range order, and rich host–guest interactions, have been implemented as electrolyte materials in a wide range of energy storage applications. In this work, we investigate a class of MOFs called polyMOFs as quasi-solid-state electrolyte materials. Unlike MOF–polymer composites, which are physical mixtures of MOF particles and polymers, polyMOFs are composed of polymeric linkers and metal ion nodes that self-assembled into crystalline and porous framework materials. PolyMOFs thus marry the ionic transport properties of liquid electrolyte and polymers with the synthetic versatility and host–guest interactions of MOFs. We demonstrate that the functionality of the polymer backbone of the polyMOF linker can improve room-temperature ion transport in the material. The polyMOF based on poly(ethylene glycol) (PEG) exhibits greater ionic conductivity, lithium transference number, and lower activation energy than its polyethylene (PE) analog. Supported by solid-state 7 Li nuclear magnetic resonance spectroscopy, we propose these improvements are due to stronger coordination of Li + to oxide sites in PEG, allowing for dissociation of Li and its associated anion. DFT studies further reveal that the confined solvent molecule mediates Li + transport in PEG-functionalized UiO-66 via a metastable adsorption and hopping mechanism. This work lies at the interface of inorganic and polymer electrolytes, unveiling fundamental insights into the design of next-generation ion conductive materials for energy technologies.
Crosslinking Amine-Modified Silica Aerogels with Epoxies: Mechanically Strong Lightweight Porous Materials
The mesoporous surfaces of TMOS-derived silica aerogels have been modified with amines by co-polymerization of TMOS with APTES. The amine sites have become anchors for crosslinking the nanoparticles of the skeletal backbone of the aerogel by attachment of di-, tri and tetra-functional epoxies. The resulting conformal coatings increase the density of the native aerogels by a factor of 2-3 but the strength of the resulting materials may increase by more than two orders of magnitude. Processing variables such as amount of APTES used to make the gels, the epoxy type and concentration used for crosslinking, as well as the crosslinking temperature and time were varied according to a multivariable design-of-experiments (DOE) model. It was found that while elastic modulus follows a similar trend with density, maximum strength is attained neither at the maximum density nor at the highest concentration of -NH2 groups, suggesting surface saturation effects. Aerogels crosslinked with the tri-functional epoxide always show improved strength compared with aerogels crosslinked with the other two epoxides under identical conditions. Solid C-13 NMR studies show residual unreacted epoxides, which condense with ne another by heating crosslinked aerogels at 150 C.
Effect of Polymer Electrode Morphology on Performance of a Lithium/Polypyrrole Battery
A variety of conducting polymer batteries were described in the recent literature. In this work, a Li/Polypyrrole secondary battery is described. The effect of controlling the morphology of the polymer on enhancement of counterion diffusion in the polymer phase is explored. A method of preparing conducting polymers was developed which yields high surface area per unit volume of electrode material. A porous membrane is used as a template in which to electrochemically polymerize pyrrole, then the membrane is dissolved, leaving the polymer in a fibrillar form. Conventionally, the polymer is electrochemically polymerized as a dense polymer film on a smooth Pt disk electrode. Previous work has shown that when the polymer is electrochemically polymerized in fribrillar form, charge transport rates are faster and charge capacities are greater than for dense, conventionally grown films containing the same amount of polymer. The purpose is to expand previous work by further investigating the possibilities of the optimization of transport rates in polypyrrole films by controlling the morphology of the films. The utility of fibrillar polypyrrole as a cathode material in a lithium/polymer secondary battery is then assessed. The performance of the fibrillar battery is compared to the performance of an analogous battery which employed a conventionally grown polypyrrole film. The study includes a comparison of cyclic voltammetry, shape of charge/discharge curves, discharge time and voltage, cycle life, coulombic efficiencies, charge capacities, energy densities, and energy efficiencies.
Advanced Aerogel Technology
The JPL Aerogel Laboratory has made aerogels for NASA flight missions, e.g., Stardust, 2003 Mars Exploration Rovers and the 2011 Mars Science Laboratory, as well as NASA research projects for the past 14 years. During that time it has produced aerogels of a range of shapes, sizes, densities and compositions. Research is ongoing in the development of aerogels for future sample capture and return missions and for thermal insulation for both spacecraft and scientific instruments. For the past several years, the JPL Aerogel Laboratory has been developing, producing and testing a new composite material for use as the high temperature thermal insulation in the Advanced Sterling Radioisotope Generator (ASRG) being developed by Lockheed Martin and NASA. The composite is made up of a glass fiber felt, silica aerogel, Titania powder, and silica powder. The oxide powders are included to reduce irradiative heat transport at elevated temperatures. These materials have thermal conductivity values that are the same as the best commercially produced high temperature insulation materials, and yet are 40% lighter. By greatly reducing the amount of oxide powder in the composite, the density, and therefore for the value of the thermal conductivity, would be reduced. The JPL Aerogel Laboratory has experimented with using glass fiber felt, expanded glass fiber felt and loose fibers to add structural integrity to silica aerogels. However, this work has been directed toward high temperature applications. By conducting a brief investigation of the optimal combination of fiber reinforcement and aerogel density, a durable, extremely efficient thermal insulation material for ambient temperature applications would be produced. If a transparent thermal insulation is desired, then aerogel is an excellent candidate material. At typical ambient temperatures, silica aerogel prevents the transport of heat via convection and conduction due to its highly porous nature. To prevent irradiative thermal transport, silica aerogel can be used in conjunction with a transparent polymeric material that blocks infrared radiation. The transparency of silica aerogel is typically greater than 90% for visible wavelengths from 500 nm to 900 nm for a 5 mm long path length.
Development of a Robust Reference Electrode in Aggressive Chemical and Radiation Environments in the Hanford Waste Tanks
The Hanford site stores more than 200 million liters of radioactive and chemically hazardous wastes from the production of weapons materials. The wastes are stored in 177 underground carbon-steel storage tanks, separated between 149 single shell tanks (SSTs) and 28 double shell tanks (DSTs). The DSTs provide critical retrieval and interim storage before the waste is vitrified in the Waste Treatment and Isolation Plant (WTP). The tanks will need to remain in-service far beyond the initial 40-year design life, and effective corrosion control practices must remain in force to extend the tanks’ lifespans. This effort includes direct measurements of corrosion rate (e.g., ultrasonic measurements and corrosion coupons) and electrochemical processes (e.g., linear polarization measurements and open circuit potential measurements). The Hanford site began monitoring the corrosion potential in select DSTs in 2008. Of the 45 reference electrodes that have been installed, 29 have failed and 6 others provided unreliable results. DOE-EM is supporting a 3-year program to develop a chemical and radiation resistant reference electrode for application in the Hanford tanks. The first year of the program focused on understanding the failure mechanism for the reference electrodes and identification of candidate construction materials that would mitigate degradation of the electrodes in the waste environment. During the second year of the program, the objectives were to: 1) test candidate materials under simulated waste conditions, 2) design components that will extend the service life of the electrode, 3) fabricate materials for prototype reference electrodes, and 4) assemble prototype reference electrodes for accelerated testing. The reference electrode is constructed of four principal parts: 1) junction, 2) casing, 3) inner chamber backfill materials, and 4) the sensing wire. Principally, improvements of the junction, casing, and inner chamber backfill materials are being pursued. The junction material at the interface between the waste and the inner chamber of the reference electrode was identified as a critical component in the failure of the reference electrodes. Nine candidate replacement junction materials were tested under simulated waste conditions to evaluate permeation rate. These materials included a variety of polymeric and ceramic materials, some of which were 3-D printed. Thus far, porous polyvinylidene fluoride materials have performed satisfactorily and are being considered for prototype development. The commercial electrode casing materials in general have performed well. Additionally, 3-D printing of chemically and mechanically stable materials is being investigated as a means for further improvement in fabrication consistency. SRNL has also investigated altering the reference electrode design to extend the service life. The new design of the interior of the reference electrode casing creates a longer, more tortuous path between the junction material and the electrode sensing wire. A finite element model was used to optimize the design without adversely impacting the circuit resistance of the electrode during the measurements, thus preserving the measurement accuracy while enhancing the service life. The inner chamber back fill materials are also critical to the performance of the reference electrode. Materials that are resistant to intruding tank waste and provide a conductive path to the sensing wire were investigated. Gel and powder materials that are interspersed with a conductive chloride bearing material were tested for their influence on diffusion and electrode resistance. All the investigated materials and components will be assembled, with collaboration from commercial vendors, to fabricate the initial prototypes. Accelerated testing of the prototypes will be initiated in Year 2 of the program and will be completed in Year 3. A recommendation on the materials of construction and the design of the new robust reference electrode will be presented to the Hanford tank farm facility.
Polymeric heat pipe wick
A wick for use in a capillary loop pump heat pipe is described. The wick material is an essentially uniformly porous, permeable, open-cell, polyethylene thermoplastic foam having an ultrahigh average molecular weight of from approximately 1 to 5 million, and an average pore size of about 10 to 12 microns. A representative material having these characteristics is POREX UF, which has an average molecular weight of about 3 million. This material is fully compatible with the FREONs and anhydrous ammonia and allows for the use of these very efficient working fluids in capillary loops.
Polymeric materials for unusual service conditions; Proceedings of the Conference, Moffett Field, Calif., November 29-December 1, 1972
Polymers for aircraft and spacecraft structures are considered, giving attention to novel foams and porous structures, aircraft nacelle composite structure technology, properties and processing of polyimidazoquinazoline composites, and the processing of organic matrices into structural composites. Other subjects discussed are related to high temperature resins and composites, elastomers for high temperature applications, fire retardant materials, polymers for critical pollution control, and polymers for critical medical use. Individual items are announced in this issue.
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.
Holistic Microstructure Control Strategies in Photopolymerization‐Induced Phase Separation of Acrylate Systems
Open porous materials, known for their large surface area and interconnected structures, are essential in various applications, including batteries, ion exchange, catalysis, filtration, and electronic waste recycling. A critical aspect of the functionality of porous membranes is the precise control of pore size and morphology. Photopolymerization-induced phase separation (photo-PIPS) offers a convenient and versatile methods for creating porous structures. However, controlling the porous morphology remains challenging due to the complex interplay between thermodynamics, polymerization kinetics, and monomer structures, which makes it difficult to establish the relationship between processing conditions and resulting morphology in photo-PIPS. Herein, a physics-based phase-field model capable of generating and characterizing the microstructures of porous materials based on both average and localized features is developed. Using the phase-field simulations as test bed, the effects of polarity, light intensity, and curing temperature, as well as the previously unexplored roles of chain transfer agents and substrates, on the morphology of the resulting porous microstructure are investigated. Experiments are performed to verify the results predicted by the simulations. This work lays out a comprehensive guide for designing PIPS-derived porous microstructures and offers practical engineering strategies for tailoring microstructure-level topology and size of pores for application-specific needs.
Filling Porous Microspheres With Magnetic Material
New process produces magnetic microspheres with controllable sizes, compositions, and properties for use in medical diagnostic tests, biological research, and chemical processes. Paramagnetic microspheres also made with process. Porous plastic microspheres prepared by polymerization of monomer in diluent by cross-linking agent. When diluent removed, it leaves tiny pores throughout polymerized spheres. Size and distribution of pores determined by amount and type of diluent and cross-linking agent.
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.
Ultra-thick three-dimensional interpenetrating graphene electrode architectures for high volumetric density energy storage
For electrochemical energy storage, increasing the electrode thickness is an effective approach to achieving higher energy density from a given material. However, this often compromises ion transport, leading to diminished performance. Here, in this study, we present a novel platform for fabricating complex 3D interpenetrating electrode structures via photo-polymerization 3D printing, integrated with computational structural optimization for energy storage. The platform employs an acrylate resin system infused with graphene oxide (GO), enabling high-fidelity printing of optimized porous structures and facilitating efficient electron and ion transport in ultra-thick electrodes. The optimized 3D layouts substantially enhance energy and power densities compared to conventional configurations, ensuring superior material utilization and minimal ohmic losses. Supercapacitors fabricated using this approach achieved an exceptional energy density of 4.7 Wh L−1 at a power density of 1689.0 W L−1, surpassing traditional designs. This work underscores the transformative role of structural optimization in advancing electrochemical performance and establishes a versatile pathway for developing next-generation energy storage systems with exceptional efficiency and functionality.