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

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At least 559 records · Page 31
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Continuous polymer films deposited on top of porous substrates using plasma-enhanced atomic layer deposition and molecular layer deposition

Molecular layer deposition (MLD) is able to produce ultrathin polymer films with control over thickness, cross-linking, and chemical composition. With these capabilities, MLD should be useful in the fabrication of novel polymer membranes on porous supports. However, confining a continuous MLD film to the surface of porous substrates is difficult because of MLD film growth in the pores. The deposition in the pores lowers the conductance of the porous support. This paper presents a method to deposit continuous polymer films on top of porous substrates. In this method, Al2O3 plasma-enhanced atomic layer deposition (PE-ALD) using trimethylaluminum and oxygen plasma as the reactants was first used to cap the pores of the substrate. Subsequently, a polyamide MLD film was deposited on the Al2O3 PE-ALD capping layer using m-phenylenediamine and trimesoyl chloride as the reactants. The Al2O3 pore caps were then removed from the porous substrate by etching from the backside using a timed exposure to a dilute sodium hydroxide solution. This method was demonstrated using anodic aluminum oxide (AAO) and polyethersulfone (PES) porous substrates. Al2O3 PE-ALD film growth was limited to the top of the porous substrate, resulting in rapid surface recombination or high sticking coefficients for the reactive plasma species within the pores. Gas permeance measurements confirmed the pore capping of the AAO substrates. The reopening of the pores by dissolving the Al2O3 pore caps with a sodium hydroxide solution was monitored using gas permeance versus etch time. The removal of the Al2O3 pore caps from the PES substrates could also dissolve the Al2O3 layer underneath the MLD film. The loss of this Al2O3 layer led to the detachment of the MLD film from the PES substrate. However, the MLD film could be anchored to the PES support at fractures located in the Al2O3 film prior to the MLD. The Al2O3 film fracture allowed the MLD film to anchor firmly to the PES substrate by MLD in the pores of the PES porous substrate. The distance between the anchor points was a function of fracture density. This distance could be controlled by applying a tensile stress to the Al2O3 PE-ALD film to fracture the film through sample bending. This method produced firmly anchored polymer MLD films on top of the PES porous substrates.

Welch, Brian C. (ORCID:000000029747045X)↗
DOE OSTI2022

Non-equilibrium molecular dynamics simulation to evaluate the effect of confinement on fluid flow in silica nanopores

The flow of fluids in nano-confinement has applications in separations, water purification, medical systems and in the recovery of fluids in petroleum systems. It is believed that fluids do not obey continuum laws when flowing in nanopores (or in confinement). This paper attempts to shed light on various nano confinement effects such as fluid-wall interactions, pore size and molecular geometry, using molecular dynamic simulation. Here, water, hexane, and methanol flow behaviors were simulated for pore diameters ranging from 1 to 8 nm. In addition to the density analysis of the confined fluids, the fluid flows in saturated nanopores were simulated by the sectional flow method. Water and methanol molecules were completely stabilized in the 1 nm pore. Hexane molecules could not enter the 1 nm pore, due to geometric considerations. For the 2 – 8 nm pores, all fluids showed reduced flow rate compared to the Hagen–Poiseuille flow, due to an interfacial molecular layer stabilized at the pore surface. Flow reduction observed in these studies is contrary to significant flow enhancements observed for fluid flow in carbon nanotubes of similar dimensions. Water flow showed almost constant stick length for all the pore sizes. Methanol flow had the largest stick length. Hexane flow was reduced because of overcrowding of molecules at the pore surface. The effect of confinement diminished with an increase in pore diameter.

42 ENGINEERING↗
DOE OSTI2024

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↗
DOE OSTI2025

Shock compression of additively manufactured high solids loaded polymer composites with aligned porosity

The effects of aligned porosity on the shock-compression response of additively manufactured (AM) composite structures with collinear and log-cabin geometries are investigated. The composites contain two inorganic and two organic particle populations and a UV-curable polymer binder. X-ray phase contrast imaging (X-PCI) is used as an in-material diagnostic in plate-impact experiments performed at the Dynamic Compression Sector of the Advanced Photon Source at the Argonne National Laboratory. Macroscale shock and particle velocities and microscale pore collapse velocities are measured from X-PCI images obtained from samples impacted in various orientations relative to the AM build directions. The linear shock and particle velocity relation for the structures with collinear build geometry shows directional differences, with the build direction exhibiting the highest slope and the filament print direction having the shallowest slope. Composites with log-cabin geometry, due to their slightly lower porosity and smaller sized pores, show higher shock velocities than the collinear structures at the same particle velocity. Microscale directionality effects are also observed, with the pore collapse velocity dependent on the pore configuration. Specifically, the pore collapse velocity is highest for pores elongated along the impact direction which is the case for the colinear structures impacted in the filament print direction, which is consistent with the directionality trend observed in the data for the shock and particle velocity equation of state. The pore collapse velocity approaches ∼80 % of the shock velocity and is several times the average bulk particle velocity, suggesting a highly hydrodynamic mechanism of pore collapse. Overall, both the macroscale response as measured by the shock and particle velocity relationship, and the microscale response as measured by the pore collapse velocity, are found to be anisotropic and dependent on the AM composite structure.

Wagner, K. B. [Georgia Institute of Technology, At↗
DOE OSTI2020

Melting of Magnesium Borohydride under High Hydrogen Pressure: Thermodynamic Stability and Effects of Nanoconfinement

The thermodynamic stability and melting point of magnesium borohydride were probed under hydrogen pressures up to 1000 bar (100 MPa) and temperatures up to 400 °C. At 400 °C, Mg(BH4)2 was found to be chemically stable between 700 and 1000 bar H2, whereas under 350 bar H2 or lower pressures, the bulk material partially decomposed into MgH2 and MgB12H12. The melting point of solvent-free Mg(BH4)2 was estimated to be 367-375 °C, which was above previously reported values by 40-90 °C. Our results indicated that a high hydrogen backpressure is needed to prevent the decomposition of Mg(BH4)2 before measuring the melting point and that molten Mg(BH4)2 can exist as a stable liquid phase between 367 and 400 °C under hydrogen overpressures of 700 bar or above. The occurrence of a pure molten Mg(BH4)2 phase enabled efficient melt-infiltration of Mg(BH4)2 into the pores of porous templated carbons (CMK-3 and CMK-8) and graphene aerogels. Both transmission electron microscopy and small-angle X-ray scattering confirmed efficient incorporation of the borohydride into the carbon pores. The Mg(BH4)2@carbon samples exhibited comparable hydrogen capacities to bulk Mg(BH4)2 upon desorption up to 390 °C based on the mass of the active component; the onset of hydrogen release was reduced by 15-25 °C compared to the bulk. Importantly, melt-infiltration under hydrogen pressure was shown to be an efficient way to introduce metal borohydrides into the pores of carbon-based materials, helping to prevent particle agglomeration and formation of stable closo-polyborate byproducts.

White, James L.↗
DOE OSTI2021

Effects of Strain Rate and Temperature on the Mechanical Properties of Simulated Silica Ionogels

Ionogels are hybrid materials formed by impregnating the pore space of a solid matrix with a conducting ionic liquid. By combining the properties of both component materials, ionogels can act as self-supporting electrolytes in Li batteries. In this study, molecular dynamics simulations are used to investigate the dependence of mechanical properties of silica ionogels on solid fraction, temperature, and pore width. Comparisons are made with corresponding aerogels. We find that the solid matrix fraction increases the moduli and strength of the ionogel. This varies nonlinearly with temperature and strain rate, according to the contribution of the viscous ionic liquid to resisting deformation. Additionally, owing to the temperature and strain sensitivity of the ionic liquid viscosity, the mechanical properties approach a linear mixing law at high temperature and low strain rates. The median pore width of the solid matrix plays a complex role, with its influence varying qualitatively with deformation mode. Narrower pores increase the relevant elastic modulus under shear and uniaxial compression but reduce the modulus obtained under uniaxial tension. Conversely, shear and tensile strength are increased by narrowing the pore width. All of these pore size effects become more pronounced as the silica fraction increases. Pore size effects, similar to the effects of temperature and strain rate, are linked to the ease of fluid redistribution within the pore space during deformation-induced changes in the geometry of the pores.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Molecular Structure of Adsorbed Water Phases in Silica Nanopores

The adsorption of water vapor in silica nanopores with different pore morphologies and surface hydrophilicities was studied to quantify the densities and thicknesses of the water sorption layers and deduce their molecular structures. Water adsorption to surface hydroxyls is described by a multilayer sorption model. At low pressure, the water adsorption isotherms are largely independent of pore size and the adsorbed amounts scale with the surface hydroxyl density. Adsorbed-phase densities corresponding to the adsorption of two water molecules per surface hydroxyl group are found in the first adsorbed water layer for a wide range of surface hydroxyl densities. The densities and layer thickness values found in narrow pores indicate that patchy adsorbed layers form if not enough water molecules exist for a full layer, which coexist with dry pore surface regions. This behavior indicates cooperative adsorption effects, i.e., a preference for the formation of hydrogen bonds between water molecules bound to surface hydroxyls. In narrow pores, pore condensation limits further growth of the sorption layer, and in larger pores and at the planar quartz surface, a second adsorbed water layer is formed, which can hold up to approximately 4 additional water molecules per surface hydroxyl group. The water molecules in these thicker adsorption layers arrange such that the sorption layer density is similar to the bulk water density. Pore confinement limitations on the sorption layers are observed in pores with radii of as large as 8 nm. Molecular dynamics modeling reveals two preferential orientations for water molecules adsorbing to surface hydroxyl groups and suggests an intralayer structuring in the adsorbed monolayer. Furthermore, adsorbed water molecules in the sorption layer are bonded to the surface hydroxyl group via the donation and acceptance of hydrogen bonds.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Selective ion transport through hydrated micropores in polymer membranes

Abstract Ion-conducting polymer membranes are essential in many separation processes and electrochemical devices, including electrodialysis 1 , redox flow batteries 2 , fuel cells 3 and electrolysers 4,5 . Controlling ion transport and selectivity in these membranes largely hinges on the manipulation of pore size. Although membrane pore structures can be designed in the dry state 6 , they are redefined upon hydration owing to swelling in electrolyte solutions. Strategies to control pore hydration and a deeper understanding of pore structure evolution are vital for accurate pore size tuning. Here we report polymer membranes containing pendant groups of varying hydrophobicity, strategically positioned near charged groups to regulate their hydration capacity and pore swelling. Modulation of the hydrated micropore size (less than two nanometres) enables direct control over water and ion transport across broad length scales, as quantified by spectroscopic and computational methods. Ion selectivity improves in hydration-restrained pores created by more hydrophobic pendant groups. These highly interconnected ion transport channels, with tuned pore gate sizes, show higher ionic conductivity and orders-of-magnitude lower permeation rates of redox-active species compared with conventional membranes, enabling stable cycling of energy-dense aqueous organic redox flow batteries. This pore size tailoring approach provides a promising avenue to membranes with precisely controlled ionic and molecular transport functions.

Science & Technology - Other Topics↗
DOE OSTI2023

Using small angle x-ray scattering to examine the aggregation mechanism in silica nanoparticle-based ambigels for improved optical clarity

Silica-based aerogels are a promising low-cost solution for improving the insulation efficiency of single-pane windows and reducing the energy consumption required for space heating and cooling. Two key material properties required are high porosity and small pore sizes, which lead to low thermal conductivity and high optical transparency, respectively. However, porosity and pore size are generally directly linked, where high porosity materials also have large pore sizes. This is unfavorable as large pores scatter light, resulting in reduced transmittance in the visible regime. In this work, we utilized preformed silica colloids to explore methods for reducing pore size while maintaining high porosity. Further, the use of preformed colloids allows us to isolate the effect of solution conditions on porous gel network formation by eliminating simultaneous nanoparticle growth and aggregation found when using typical sol–gel molecular-based silica precursors. Specifically, we used in situ synchrotron-based small-angle x-ray scattering during gel formation to better understand how pH, concentration, and colloid size affect particle aggregation and pore structure. Ex situ characterization of dried gels demonstrates that peak pore widths can be reduced from 15 to 13 nm, accompanied by a narrowing of the overall pore size distribution, while maintaining porosities of 70%–80%. Optical transparency is found to increase with decreasing pore sizes while low thermal conductivities ranging from 95 +/− 13 mW/m K are maintained. Mechanical performance was found to depend primarily on effective density and did not show a significant dependence on solution conditions. Overall, our results provide insights into methods to preserve high porosity in nanoparticle-based aerogels while improving optical transparency.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

An assessment of spall failure modes in laser powder bed fusion fabricated stainless steel 316L with low-volume intentional porosity

Here, this paper reports on spall failure and damage modes in Laser Powder Bed Fusion fabricated Stainless Steel 316L (SS316L) with intentional levels of low-volume (1–5 vol. %) porosity and pore sizes of 200, 350, and 500 μm. The fabricated specimens were subjected to uniaxial-strain plate-impact loading at ~4.5 GPa, to initiate incipient spall failure. Analysis of velocimetry profiles measured using multi-probe photon-Doppler velocimetry coupled with post-mortem analysis of soft-recovered samples reveals local suppression of spall failure (termed as spall-dominated) as a function of porosity, as the failure mechanism transitions from spall-centered tensile stress dominated to a pore-centered microstructure-dominated damage mode involving void/crack nucleation and growth at pre-existing pores. The critical porosity level where the suppression of spall failure is first observed, as well as the spall location, is dependent on both the volume fraction and the size of the initially fabricated pores. In samples of 500 μm pore size, the suppression of spall failure is observed with as little as 1 vol. % porosity, while samples with smaller pores (200 μm) still experience spall-centered tensile stress dominated failure with higher levels (5 vol. %) of porosity. In the case of pore-centered microstructure-dominated failure, spall damage can occur but the spall plane is shifted toward the rear free surface, or more generally in areas further away from the region with pores. Highly heterogeneous deformation twinning, shear banding, grain rotation, and cracking are observed in the vicinity of pre-existing pores and expected spall failure sites.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Surface Interactions and Nanoconfinement of Methane and Methane plus CO2 Revealed by High-Pressure Magic Angle Spinning NMR Spectroscopy and Molecular Dynamics

This study explores the fundamental, molecular- to microscopic-level behavior of methane gas confined into nanoporous silica proxies with different pore diameters and surface-to-volume (S/V) ratios. Surfaces and pore walls of nanoporous silica matrices are decorated with hydroxyl (-OH) groups, resembling natural heterogeneity. High-pressure MAS NMR was utilized to characterize the interactions between methane and the engineered nanoporous silica proxies under various temperature and pressure regimes. There was a change in the chemical shift position of confined methane slightly in the mixtures with nanoporous silica up to 393 K, as shown by high-pressure 13C-NMR. The 13C-NMR chemical shift of methane was changed by pressure, explained by the densification of methane inside the nanoporous silica materials. The influence of pore diameter and S/V of the nanoporous silica materials on the behaviors and dynamics of methane were studied. The presence of CO2 in mixtures of silica and methane needs analysis with caution because CO2 in a supercritical state and gaseous CO2 change the original structure of nanoporous silica and change surface area and pore volume. According to simulation, the picosecond scale dynamics of methane confined in larger pores of amorphous silica is faster. In the 4 nm pore, the diffusivity obtained from MD simulations in the pore with a higher S/V ratio is slower due to the trapping of methane molecules in adsorbed layers close to the corrugated pore surface. In contrast, relaxation measured with NMR for smaller pores (higher S/V) exhibits larger T1, indicating slower relaxation.

03 NATURAL GAS↗
DOE OSTI2021

Shape-memory polymer foam device for treating aneurysms

A system for treating an aneurysm in a blood vessel or vein, wherein the aneurysm has a dome, an interior, and a neck. The system includes a shape memory polymer foam in the interior of the aneurysm between the dome and the neck. The shape memory polymer foam has pores that include a first multiplicity of pores having a first pore size and a second multiplicity of pores having a second pore size. The second pore size is larger than said first pore size. The first multiplicity of pores are located in the neck of the aneurysm. The second multiplicity of pores are located in the dome of the aneurysm.

Ortega, Jason M.↗
DOE OSTI2021

Are you using the right probe molecules for assessing the textural properties of metal–organic frameworks?

Textural properties—such as the surface area, pore size distribution, and pore volume—are at the forefront of characterization for porous materials. Therefore, it is essential to accurately and reproducibly report a material's textural properties as they could ultimately dictate its applicability. This work aims to provide insightful and comprehensive studies of textural properties for a set of metal–organic frameworks (MOFs), a class of porous materials, using various gases to equip researchers in the field with a helpful guide and reference. Here, we selected a series of nine MOFs with different surface areas, pore sizes, shapes, and chemical environments to represent a wide range of materials. We probed the textural properties of these MOFs using traditional and distinctive gases: N 2 , Kr and O 2 at 77 K, Ar at 87 K, and CO 2 at 195 and 273 K. With regard to surface area, we discuss the validity and challenges associated with the current BET method, the importance of utilizing the Rouquerol et al. consistency criteria to ensure accuracy and reproducibility, and the recommended gas probes for certain materials. For pore size distribution, we discuss the efficacy of each probe for determining the pore sizes within a porous material relative to the calculated distribution from its crystal structure, the limitations of current computational kernels used to calculate pore size distributions, and the need for advanced kernels to envelope the diversity of porous materials. Finally, for pore volume, we discuss the use of the Gurvich rule to obtain the total pore volume in comparison with calculated values from crystal structures and its consistency as a metric for porous materials. Ultimately, we hope that this article will aid researchers in characterizing the textural properties of porous materials and encourage the development of new kernels capable of encompassing the complexity of MOFs and other porous materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Stochastic generation of electrolyzer anode catalyst layers

Here, we introduce a stochastic methodology to reproduce the complex pore structure observed in commercial iridium catalyst layers. This method preserves the α pore (pores smaller than 250 nm) and β pore (pores greater than or equal to 250 nm) regions of the catalyst layer. The morphology of the generated materials was validated by comparing the pore size distributions of generated materials against those obtained from commercial materials imaged using x-ray nano computed tomography. We further demonstrate that the pore size distributions of the generated materials are statistically indistinguishable from the imaged catalyst layers, indicating that the stochastic methodology is capable of accurately reproducing catalyst layer morphology. Pore network modelling was conducted on the generated catalyst materials to simulate single-phase permeability, electrical conductivity, and ionic conductivity, and these properties were found to be within experimentally measured ranges for electrolyzer catalyst layers. Additionally, simulations were performed on the generated materials with varying ionomer and iridium catalyst loadings. As the ionomer loading is added, proton conductivity increases exponentially, which demonstrates the importance of optimizing ionomer loading, considering that these effects will be exacerbated in the hydration and temperature conditions of operating electrolyzers. The stochastic material generation method presented in this work is a powerful tool for the development of novel low loading catalyst layers, where the effect of various structural parameters on electrolyzer performance characteristics can be explored.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Nanoscale Interfacial Smoothing and Dissolution during Unconventional Reservoir Stimulation Implications for Hydrocarbon Mobilization and Transport

Hydraulic fracturing of low-permeability rocks significantly enhances hydrocarbon production from unconventional reservoirs. However, fluid transport through low-permeability rocks, and the influence of geochemical transformations on pore networks, are poorly constrained. Mineral reactivity during interactions with injected water may alter the physical nature of the rock, which may affect hydrocarbon mobility. To assess alteration to the rock, we previously conducted a hydrothermal experiment that reacted cubed rock samples (1 cm3) with synthetic hydraulic fracturing fluid to simulate physicochemical reactivity during hydraulic fracturing. We analyzed unreacted and reacted rocks by small-angle neutron scattering and high-pressure mercury intrusion to determine how nanoscale (~1-1400 nm) pore networks of unconventional reservoir rocks are influenced by reaction with hydraulic fracturing injectates. We show that fluid-rock interactions have a two-fold influence on hydrocarbon recovery, promoting both hydrocarbon mobilization and transport. Pore-matrix interfaces smooth via removal of clay mineral surface asperities, reducing available surface area for hydrocarbon adsorption by ca. 12-75%. Additionally, hydraulic fracturing fluid-induced dissolution creates new pores with diameters ranging in size from 800-1400 nm, increasing the permeability of the rocks by a factor of 5-10. These two consequences of mineral dissolution act in concert to release hydrocarbons from the host rock and facilitate transport through the rock during unconventional reservoir production.

Herz-Thyhsen, Ryan↗
DOE OSTI2024

Hierarchically porous electrospun carbon nanofiber for high-rate capacitive deionization electrodes

Capacitive deionization (CDI) is a promising technology that has gained interest for the desalination of brackish water. Hierarchically porous carbons are commonly used as electrodes for CDI due to their high surface areas and controlled pore size distributions that maximize ion adsorption capacity and rate. Electrospinning is an effective way of generating carbon nanofibers with high inter-fiber macroporosity that can be further modified to improve surface area, total pore volume, and pore size distribution. This work describes the use of sacrificial mesopore formers in tandem with a micropore etching technique to induce hierarchical porosity in electrospun fibers. Mesopores are formed via the dissolution of silica nanoparticles that are introduced into the fibers during the electrospinning step. After mesopore formation, micropores are etched into the resulting surface through KOH impregnation and thermal activation. This sequential technique creates a hierarchical network of pores from the inherent macroporosity of the fiber network, to the mesopores, and finally micropores to simultaneously maximize surface area and accessibility. Micropore formation is optimized to maximize specific surface area while maintaining physical integrity of the fibers. Further, the combination of mesopores and micropores enables fast ion adsorption rates and capacity. Carbon fiber electrodes fabricated in this method achieve specific surface areas exceeding 1400 m 2 g -1 , with pore volumes exceeding 1.0cc g -1 . The pore size distributions are highly controlled, with 80% of total pore volume coming from pores <20nm in radius. In 500 ppm constant voltage CDI tests, these fiber electrodes obtain a salt adsorption capacity of over 14 mg g -1 at a salt adsorption rate of ~4mg g -1 min -1 , showcasing the high capacity matched with high rate of these easily fabricated, inexpensive materials.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Impacts of Anisotropic Porosity on Heat Transfer and Off-Gassing during Biomass Pyrolysis

The pore structure of biogenic materials imbues the ability to deliver water and nutrients through a plant from root to leaf. This anisotropic pore granularity can also play a significant role in processes such as biomass pyrolysis that are used to convert these materials into useful products like heat, fuel, and chemicals. Evolutions in modeling of biomass pyrolysis as well as imaging of pore structures allow for further insights into the concerted physics of phase change-induced off-gassing, heat transfer, and chemical reactions. In this work, we report a biomass single particle model which incorporates these physics to explore the impact of implementing anisotropic permeability and diffusivity on the conversion time and yields predicted for pyrolysis of oak and pine particles. Simulation results showed that anisotropic permeability impacts predicted conversion time more than 2 times when the Biot number is above 0.1 and pyrolysis numbers (Py 1 , Py 2 ) are less than 20. Pore structure significantly impacts predicted pyrolytic conversion time (>8 times) when the Biot number is above 1 and the pyrolysis number is below 1, i.e., the “conduction controlled” regime. Therefore, these nondimensional numbers reflect that when internal heat conduction limits pyrolysis performance, internal pyrolysis off-gassing further retards effective heat transfer rates as a closely coupled phenomenon. Overall, this study highlights physically meaningful opportunities to improve particle-scale pyrolysis modeling and experimental validation relevant to a variety of feedstock identities and preparations, guiding the future design of pyrolyzers for efficient biomass conversion.

09 BIOMASS FUELS↗
DOE OSTI2023

Probing the Morphology and Mobility of Amines in Porous Silica CO 2 Sorbents by 1 H T 1 – T 2 Relaxation Correlation NMR

Molecular and oligomeric amines supported in porous oxide supports are a promising class of CO 2 sorbent materials studied for CO 2 removal from diverse streams such as flue gas and ambient air. Among the various amines investigated, low molecular weight, hyperbranched poly(ethyleneimine) (PEI), and tetraethylenepentamine (TEPA) are among the most extensively studied. While macroscopic structure–performance relationships relating the support structure, amine loading, and other factors affecting CO 2 sorption capacities and kinetics have been developed, structural and dynamic information about the organic amine phase in the porous support is less plentiful. The structure and mobility of amines impregnated in the pores of porous supports directly impact gas sorption, as the accessibility of amine sites in the pores directly relates to amine distribution in the pores and overall pore filling as well as the dynamics of the amine chains. Here, we prepare a family of mesoporous silica SBA-15 materials containing varying loadings of oligomeric (PEI) and molecular (TEPA) amines. 1 H T 1 –T 2 relaxation correlation solid-state NMR experiments are used to characterize the structural and dynamic properties of the confined amines. Both TEPA and PEI are shown to form multiple different domains in the pores, each with distinguishable dynamic properties. TEPA and PEI form more rigid layers around the silica support walls at lower organic loading fractions, characterized by lower mobilities, followed by the formation of more mobile domains less engaged in pore wall interactions at higher loadings. TEPA shows faster mobilities than PEI because of its lower molecular weight. TEPA also appears to more easily transfer between domains within the pores, leading to generally faster CO 2 uptake rates with higher sorption capacities, while PEI located closer to the pore walls remained much less mobile and is thus less engaged in CO 2 capture.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗