Elucidating the mechanisms of Paraffin-Olefin separations using nanoporous adsorbents: An overview
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36 MATERIALS SCIENCE↗
SEARCH · Engineering Papers
Results for “Porous Materials”
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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Ionic-content-driven restructuring of spirobisindane ionene networks: implications for mechanics, self-healing, and gas transport
Polymers of intrinsic microporosity (PIMs) offer exceptional gas permeability but remain brittle and susceptible to physical aging, limiting their durability in separation applications. Here, we introduce a reconfigurable microporous polymer network that uniquely integrates permanent PIM microporosity with autonomous, intrinsic self-healing driven by imidazolium-based ionic motifs. Spirobisindane units generate the intrinsic free-volume architecture, while an imidazolium-containing polyamide ionene supplies dynamic ionic and hydrogen-bonding interactions that reorganize under mild activation. Incorporation of imidazolium-based ionic liquids further tunes cohesion, mobility, and densification, enabling the network to relax, re-associate, and retain microporosity without structural collapse. Through a comprehensive multiscale approach combining spectroscopy, scattering, thermal and mechanical characterization with all-atom molecular dynamics and density functional theory calculations, we elucidate how ionic content, as a single control parameter that reshapes free-volume distributions, modulates local coordination environments, and governs relaxation and healing kinetics. At intermediate ionic loadings, the networks achieve rapid, repeatable self-healing while maintaining CO$_2$ selectivity, demonstrating an optimal balance between segmental mobility and structural integrity. By establishing how hierarchical ionic interactions couple structure, dynamics, and transport in microporous ionene networks, this work provides generalizable design rules for adaptive soft-matter systems that require simultaneous mechanical resilience, reconfigurability, and selective gas transport.
36 MATERIALS SCIENCE↗
Effect of transport mechanism on the coarsening of bicontinuous structures: A comparison between bulk and surface diffusion
Here, coarsening of bicontinuous microstructures is observed in a variety of systems, such as nanoporous metals and mixtures that have undergone spinodal decomposition. To better understand the morphological evolution of these structures during coarsening, we compare the morphologies resulting from two different coarsening mechanisms, surface and bulk diffusion. We perform phase-field simulations of coarsening via each mechanism in a two-phase mixture at nominal volume fractions of 50%-50% and 36%-64%, and the simulated structures are characterized in terms of topology (genus density), the interfacial shape distribution, structure factor, and autocorrelations of phase and mean curvature. We observe self-similar evolution of morphology and topology and agreement with the expected power laws for dynamic scaling, in which the characteristic length scale increases over time proportionally to t 1/4 for surface diffusion and t 1/3 for bulk diffusion. While we observe the expected difference in the coarsening kinetics, we find that differences in self-similar morphology due to coarsening mechanism are relatively small, although typically they are larger at 36% volume fraction than at 50% volume fraction. In particular, we find that bicontinuous structures coarsened via surface diffusion have lower scaled genus densities than structures coarsened via bulk diffusion. We also compare the self-similar morphologies to those in literature and to two model bicontinuous structures, namely, constant-mean-curvature surfaces based on the Schoen G minimal surface and random leveled-wave structures. The average scaled mean curvatures of these model structures agree reasonably with those of the coarsened structures at both 36% and 50%, but we find substantial disagreements in the scaled genus densities and the standard deviations of mean curvature.
36 MATERIALS SCIENCE↗
Grain boundary effects in high-temperature liquid-metal dealloying: a multi-phase field study
Abstract A multi-phase field model is employed to study the microstructural evolution of an alloy undergoing liquid dealloying, specifically considering the role of grain boundaries. A semi-implicit time-stepping algorithm using spectral methods is implemented, which enables simulating large 2D and 3D domains over long time scales while still maintaining a realistic interfacial thickness. Simulations reveal a mechanism of coupled grain–boundary migration to maintain equilibrium contact angles with the topologically complex solid–liquid interface, which locally accelerates diffusion-coupled growth of a liquid channel into the precursor. This mechanism asymmetrically disrupts the ligament connectivity of the dealloyed structure in qualitative agreement with published experimental observations. The grain boundary migration-assisted corrosion channels form even for precursors with small amounts of the dissolving alloy species, below the parting limit . The activation of this grain boundary dealloying mechanism depends strongly on grain boundary mobility.
36 MATERIALS SCIENCE↗
Super-resolution imaging reveals resistance to mass transfer in functionalized stationary phases
Chemical separations are costly in terms of energy, time, and money. Separation methods are optimized with inefficient trial-and-error approaches that lack insight into the molecular dynamics that lead to the success or failure of a separation and, hence, ways to improve the process. We perform super-resolution imaging of fluorescent analytes in five different commercial liquid chromatography materials. Unexpectedly, we observe that chemical functionalization can block more than 50% of the material’s porous interior, rendering it inaccessible to small-molecule analytes. Only in situ imaging unveils the inaccessibility when compared to the industry-accepted ex situ characterization methods. Selectively removing some of the functionalization with solvent restores pore access without substantially altering the single-molecule kinetics that underlie the separation and agree with bulk chromatography measurements. Our molecular results determine that commercial “fully porous” stationary phases are over-functionalized and provide an alternative avenue to characterize and direct separation material design from the bottom-up.
Science & Technology - Other Topics↗
Carbonate-Catalyzed CO 2 Insertion into Hydrocarbon C-H Bonds (Final Technical Report)
The development of methods to utilize CO 2 as a feedstock for chemical and fuel synthesis is critical for creating renewable alternatives to fossil fuel-based products. This project investigated a class of catalyst materials known as "dispersed carbonates", which are composed of alkali carbonate salts (e.g. potassium carbonate) dispersed in porous support materials. These catalysts react with CO 2 and organic molecules to form chemicals known as carboxylates that have wide applications in the chemical industry. The project used a combination of spectroscopic and reactivity studies to provide fundamental insight into the structure and mechanism of dispersed carbonates in these reactions, leading to variants with greater reactivity. In addition, dispersed carbonates were investigated for CO 2 hydrogenation catalysis, which is critical for processes under development for making sustainable fuels. The dispersed carbonates proved to be highly active and selective catalysts for the reverse water gas shift reaction in which CO 2 is hydrogenated to CO. The dispersed carbonates provide a compelling alternative to conventional metal-based catalysts for reverse water gas shift that could enable new process designs with higher efficiency and lower complexity.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Effect of Nanoconfinement on Polymer Chain Dynamics
Here, we report on a study of the effects of nanoconfinement on polymer chain dynamics within the framework developed by Muthukumar [Muthukumar, M. (1991). Journal of Non-Crystalline Solids, 131, 654-666.], who suggests that there is an entropically controlled dynamical regime between the Rouse and the reptation regimes that affects the power law dependence on molecular weight of the transport properties.
36 MATERIALS SCIENCE↗
Architecture-Dependent Thin Film Self-Assembly of Star Polystyrene-poly(2-vinylpyridine) Block Copolymers
Controlling the orientation of nanostructured block copolymer (BCP) thin films is essential for their use in templating, transport, and pattern transfer. Conventional efforts mainly focus on adjusting enthalpic interactions between the blocks and interfaces, while entropic contributions are often overlooked. Here, we show that the morphology of BCP thin films can be precisely tuned by the architectural design of star BCPs. Specifically, we synthesized multiarm star BCPs with a polystyrene (PS) core and poly(2-vinylpyridine) (P2VP) corona, which exhibits a lamellar microdomain morphology. The entropic penalty associated with a parallel orientation of the microdomains to the substrate is controlled by varying the number of arms comprising the star BCPs, from 2-arms (triblock) to 3-arms and 4-arms. We systematically investigated the thin film morphology at different depths using grazing incidence small-angle X-ray and neutron scattering (GISAXS and GISANS), atomic force microscopy (AFM), water contact angle (WCA), and interference microscopy. The results show that 2-arm star BCPs show a parallel orientation, the 3-arm star BCPs form a uniform PS film at the air surface with a vertical orientation of the microdomains underneath, and the 4-arm star BCPs exhibit a parallel microdomain orientation at the air surface with mixed parallel and perpendicular microdomain orientation in the bulk. Additionally, we found that the inclination angle of microdomains at the edges of islands and holes, resulting from the incommensurability between film thickness and the characteristic period of the microdomain morphology, increases with a higher number of arms. This suggests a greater grain boundary tilt angle in the microdomains of star-shaped block copolymers (BCPs). When silicon substrates were modified with PS homopolymer, the selective interaction between substrate and core blocks promotes a parallel orientation for the 4-arm star BCPs. In conclusion, this work shows that control of arm number in star BCPs affords diverse BCP thin film morphologies, offering insights into the star BCP conformations in thin films across different depths.
36 MATERIALS SCIENCE↗
Exploitation of Pore Structure for Increased CO 2 Selectivity in Type 3 Porous Liquids
CO 2 capture requires materials with high adsorption selectivity and an industrial ease of implementation. To address these needs, a new class of porous materials was recently developed that combines the fluidity of solvents with the porosity of solids. Type 3 porous liquids (PLs) composed of solvents and metal–organic frameworks (MOFs) offer a promising alternative to current liquid carbon capture methods due to the inherent tunability of the nanoporous MOFs. However, the effects of MOF structural features and solvent properties on CO 2 –MOF interactions within PLs are not well understood. Herein experimental and computational data of CO 2 gas adsorption isotherms were used to elucidate both solvent and pore structure influences on ZIF-based PLs. The roles of the pore structure including solvent size exclusion, structural environment, and MOF porosity on PL CO 2 uptake were examined. A comparison of the pore structure and pore aperture was performed using ZIF-8, ZIF-L, and amorphous-ZIF-8. Adsorption experiments here have verified our previously proposed solvent size design principle for ZIF-based PLs (1.8× ZIF pore aperture). Furthermore, the CO 2 adsorption isotherms of the ZIF-based PLs indicated that judicious selection of the pore environment allows for an increase in CO 2 selectivity greater than expected from the individual PL components or their combination. This nonlinear increase in the CO 2 selectivity is an emergent behavior resulting from the complex mixture of components specific to the ZIF-L + 2'-hydroxyacetophenone-based PL.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Multi-Scale Modeling of Low-Density Carbon-Phenolic Ablators
Protecting a spacecraft during atmospheric entry is one of highest risk factors that needs to be mitigated during design of a space exploration mission. At entry speeds from space, air turns into high-temperature plasma, and spacecraft Thermal Protection Systems (TPS) are needed to protect the vehicle payload. Modern successful material architectures of spacecraft shields use a porous carbon fiber substrate impregnated with phenolic as an ablator material. In the lecture, efforts to build a Predictive Material Modeling framework for porous ablators from micro-scale to macro-scale will be presented. Several numerical methods and techniques will be summarized that use voxelized images to compute geometrical properties of the porous substrate. These computed properties include porosity, specific surface area and tortuosity that are otherwise indirectly measured through experimental techniques. Direct simulation Monte Carlo (DSMC), a particle-based method for approximating the Boltzmann equation, is used to compute the permeability coefficient of the porous substrate based on its digitized representation. The method computes the flow within the microstructure, where the size of the pores may approach the mean-free-path of the flow. Finally, a high-fidelity model implemented in PATO (Porous-material Analysis Toolbox) is discussed, and some examples of ablative material response are presented, including for the first time 3D simulations of the full tiled heat shield for the Mars Science Laboratory (MSL) capsule.
Ablators↗
Silica–Derived Nanostructured Electrode Materials for ORR, OER, HER, CO 2 RR Electrocatalysis, and Energy Storage Applications: A Review**
Silica-derived nanostructured catalysts (SDNCs) are a class of materials synthesized using nanocasting and templating techniques, which involve the sacrificial removal of a silica template to generate highly porous nanostructured materials. The surface of these nanostructures is functionalized with a variety of electrocatalytically active metal and non-metal atoms. SDNCs have attracted considerable attention due to their unique physicochemical properties, tunable electronic configuration, and microstructure. These properties make them highly efficient catalysts and promising electrode materials for next generation electrocatalysis, energy conversion, and energy storage technologies. The continued development of SDNCs is likely to lead to new and improved electrocatalysts and electrode materials. This review article provides a comprehensive overview of the recent advances in the development of SDNCs for electrocatalysis and energy storage applications. It analyzes 337,061 research articles published in the Web of Science (WoS) database up to December 2022 using the keywords “silica”, “electrocatalysts”, “ORR”, “OER”, “HER”, “HOR”, “CO 2 RR”, “batteries”, and “supercapacitors”. The review discusses the application of SDNCs for oxygen reduction reaction (ORR), oxygen evolution reaction (OER), hydrogen evolution reaction (HER), carbon dioxide reduction reaction (CO 2 RR), supercapacitors, lithium-ion batteries, and thermal energy storage applications. It concludes by discussing the advantages and limitations of SDNCs for energy applications.
25 ENERGY STORAGE↗
Non-nebular Origin of Dark Mantles Around Chondrules and Inclusions in CM Chondrites
Our examination of nine CM chondrites that span the aqueous alteration sequence leads us to conclude that compact dark fine mantles surrounding chondrules and inclusions in CM chondrites are not discrete fine-grained rims acquired in the solar nebula as modeled by Metzler et al. [Accretionary dust mantles in CM chondrites: evidence for solar nebula processes. Geochim. Cosmochim. Acta 56, 1992, 2873-28971. Nebular processes that lead to agglomeration produce materials with porosities far higher than those in the dark mantles. We infer that the mantles were produced from porous nebular materials on the CM parent asteroid by impact-compaction (a process that produces the lowest porosity adjacent to chondrules and inclusions). Compaction was followed by aqueous alteration that formed tochilinite, serpentine, Ni-bearing sulfide, and other secondary products in voids in the interchondrule regions. Metzler et al. reported a correlation between mantle thickness and the radius of the enclosed object. In Yamato 791 198 we find no correlation when all sizes of central objects and dark lumps are included but a significant correlation (r(sup 2) = 0.44) if we limit consideration to central objects with radii >35 microns; a moderate correlation is also found in QUE 97990. We suggest that impact-induced shear of a plum-pudding-like precursor produced the observed "mantles"; these were shielded from comminution during impact events by the adjacent stronger chondrules and inclusions. Some mantles in CM chondrites with low degrees of alteration show distinct layers that may largely reflect differences in porosity. Typically, a gray, uniform inner layer is surrounded by an outer layer consisting of darker silicates with BSE-bright speckles. The CM-chondrite objects characterized as "primary accretionary rocks" by Metzler et al. did not form in the nebula, but rather on the parent body. The absence of solar-flare particle tracks and solar-wind-implanted rare gases in these clasts reflect their lithified nature and low surface/volume ratios during the period when they resided in the regolith and were subject to irradiation by solar particles. The clasts are analogous to the light-colored metamorphosed clasts in ordinary-chondrite regolith breccias (which also lack solar-flare particle tracks and solar-wind gas).
Trigo-Rodriquez, Josep M.↗
An experimental investigation of interfacial temperatures in blade-seal material rubbing of aircraft compressors
Results are presented for the rubbing of rotating (100 m/s) titanium blade specimens, with different plasma-sprayed tip coating, against an abradable porous seal material at two different incursion rates. In general, there was a good correspondence between the average transverse force of rubbing and the seal specimen surface temperature. Instantaneous seal surface temperature measurement showed a significant temperature jump before and after each rubbing with a high rate of cooling during each revolution and a high overall temperature level. Numerical predictions of both blade and seal temperature agreed well for the bare blade tip experiments but were consistently high for the coated blades. This suggests that the thermal properties of the coatings may significantly affect the temperatures and hence the wear characteristics of the system.
Emery, A. F.↗
Large pores promote abnormal grain growth behavior in calcia doped alumina
Not Available
36 MATERIALS SCIENCE↗
The Steady Flow Resistance of Perforated Sheet Materials in High Speed Grazing Flows
A study was conducted to determine the effects of high speed grazing air flow on the acoustic resistance of perforated sheet materials used in the construction of acoustically absorptive liners placed in commercial aircraft engine nacelles. Since DC flow resistance of porous sheet materials is known to be a major component of the acoustic resistance of sound suppression liners, the DC flow resistance of a set of perforated face-sheets and linear 'wiremesh' face-sheets was measured in a flow duct apparatus (up to Mach 0.8). Samples were fabricated to cover typical variations in perforated face-sheet parameters, such as hole diameter, porosity and sheet thickness, as well as those due to different manufacturing processes. The DC flow resistance data from perforated sheets were found to correlate strongly with the grazing flow Mach number and the face-sheet porosity. The data also show correlation against the boundary layer displacement thickness to hole-diameter ratio. The increase in resistance with grazing flow for punched aluminum sheets is in good agreement with published results up to Mach 0.4, but is significantly larger than expected above Mach 0.4. Finally, the tests demonstrated that there is a significant increase in the resistance of linear 'wiremesh' type face-sheet materials.
Syed, Asif A.↗
Rational design of stable functional metal–organic frameworks
Functional porous metal–organic frameworks (MOFs) have been explored for a number of potential applications in catalysis, chemical sensing, water capture, gas storage, and separation. MOFs are among the most promising candidates to address challenges facing our society related to energy and environment, but the successful implementation of functional porous MOF materials are contingent on their stability; therefore, the rational design of stable MOFs plays an important role towards the development of functional porous MOFs. In this Focus article, we summarize progress in the rational design and synthesis of stable MOFs with controllable pores and functionalities. The implementation of reticular chemistry allows for the rational top-down design of stable porous MOFs with targeted topological networks and pore structures from the pre-selected building blocks. We highlight the reticular synthesis and applications of stable MOFs: (1) MOFs based on high valent metal ions (e.g., Al 3+ , Cr 3+ , Fe 3+ , Ti 4+ and Zr 4+ ) and carboxylate ligands; (2) MOFs based on low valent metal ions (e.g., Ni 2+ , Cu 2+ , and Zn 2+ ) and azolate linkers. We envision that the synthetic strategies, including modulated synthesis and post-synthetic modification, can potentially be extended to other more complex systems like metal-phosphonate framework materials.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
The Effect of Gravity on the Combustion Synthesis of Porous Biomaterials
Production of highly porous composite materials by traditional materials processing is limited by difficult processing techniques. This work investigates the use of self propagating high temperature (combustion) synthesis (SHS) to create porous tricalcium phosphate (Ca3(PO4)2), TiB-Ti, and NiTi in low and microgravity. Combustion synthesis provides the ability to use set processing parameters to engineer the required porous structure suitable for bone repair or replacement. The processing parameters include green density, particle size, gasifying agents, composition, and gravity. The advantage of the TiB-Ti system is the high level of porosity achieved together with a modulus that can be controlled by both composition (TiB-Ti) and porosity. At the same time, NiTi exhibits shape memory properties. SHS of biomaterials allows the engineering of required porosity coupled with resorbtion properties and specific mechanical properties into the composite materials to allow for a better biomaterial.
Castillo, M.↗
Optimizing hierarchical membrane/catalyst systems for oxidative coupling of methane using additive manufacturing
The advantage of a membrane/catalyst system in oxidative coupling of methane (OCM) compared to conventional reactive systems is that by introducing oxygen to the OCM catalytic sites through a membrane, parasitic gas phase reactions of O 2 (g), responsible for lowering product selectivity, can be avoided. The design and fabrication of membrane/catalyst systems has, however, been hampered by low volumetric chemical conversion rates, high capital cost, and difficulties in codesigning membrane and catalyst properties to optimize the performance. We solve these issues by developing a dual-layer additive manufacturing process, based on phase inversion, to design, fabricate and optimize a hollow fiber membrane/catalyst system for OCM. We demonstrate the approach though a case study using BaCe 0.8 Gd 0.2 O 3-δ (BCG) as the basis of both the catalyst and separation layers. We show that by using the manufacturing approach we can codesign the membrane thickness and catalyst surface area so that the flux of oxygen transport through the membrane and methane activation rates in the catalyst layer match each other. Here, we demonstrate that this “rate matching” is critical for maximizing the performance, with the membrane/catalyst system significantly overperforming conventional reactor designs under identical conditions.
36 MATERIALS SCIENCE↗