Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “pore sizes”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 145 records · Page 8

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↗

The crystal orientation of THF clathrates in nano-confinement by in situ polarized Raman spectroscopy

Gas hydrates form at high pressure and low temperatures in marine sediments and permafrost regions of the earth. Despite forming in nanoporous structures, gas hydrates have been extensively studied only in bulk. Understanding nucleation and growth of gas hydrates in nonporous confinement can help create ways for storage and utilization as a future energy source. Herein, we introduce a new method for studying crystal orientation/tilt during tetrahydrofuran (THF) hydrate crystallization under the influence of nano-confinement using polarized Raman spectroscopy. Uniform cylindrical nanometer size pores of anodic aluminum oxide (AAO) are used as a model nano-confinement, and hydrate experiments are performed in a glass microsystem for control of the flash hydrate nucleation kinetics and analysis via in situ polarized Raman spectroscopy. The average THF hydrate crystal tilt of 56 ± 1° and 30.5 ± 0.5° were observed for the 20 nm and 40 nm diameter pores, respectively. Crystal tilt observed in 20 and 40-nanometer-size pores was proportional to the pore diameter, resulting in lower tilt relative to the axis of the confinement at larger diameter pores. Finally, the results indicate that the hydrates nucleation and growth mechanism can depend on the nanoconfinement size. A 1.6 ± 0.01 °C to 1.8 ± 0.01 °C depression in melting point compared to the bulk is predicted using the Gibbs–Thomson equation as a direct effect of nucleation in confinement on the hydrate properties.

25 ENERGY STORAGE↗

Impact of Porous Transport Layer Morphology on the Performance of Proton Exchange Membrane Water Electrolyzers with Ultra-Low Iridium Loadings

Reducing Ir loadings in proton exchange membrane water electrolyzer anodes is critical for lowering capital expenses. Loading reduction could be achieved by improving the Ir activity via doping/alloying and/or the development of advanced microstructures. However, the anode porous transport layer (PTL) is a comparatively simple component whose properties also impact Ir utilization. Therefore, well-designed PTLs may also enable reduced Ir loadings. In this work, we survey eight PTLs from various manufacturers to observe their impact on cell performance at low (0.4 mg Ir cm -2 ) and ultralow (0.1 mg Ir cm -2 ) Ir loadings. The PTLs were characterized by their microstructural properties, including porosity, particle size distribution, and pore size distribution. Electrochemical cell performance was correlated to PTL morphology, and it was found that PTLs with lower porosities and smaller particle and pore radii enabled good performance even at ultralow Ir loadings. 1000-h durability testing indicated that using lower porosity PTLs can significantly improve durability behavior. A runaway voltage phenomenon was observed during durability testing of cells with ultralow Ir loadings, which was caused by increases in both anode and cathode overpotentials. Furthermore, we observed that the beginning of test performance of 0.1 mg Ir cm -2 cells correlates to the 1000-h degradation rates of 0.4 mg Ir cm -2 cells, suggesting that for the Ir catalyst used in this work, short-term testing at ultralow loadings can be used as an indicator of long-term degradation at higher loadings.

08 HYDROGEN↗

Scalable Freeze-Tape-Casting Fabrication and Pore Structure Analysis of 3D LLZO Solid-State Electrolytes

Nonflammable solid-state electrolytes can potentially address the reliability and energy density limitations of lithium-ion batteries. Garnet-structured oxides such as Li 7 La 3 Zr 2 O 12 (LLZO) are some of the most promising candidates for solid-state devices. Here, three-dimensional (3D) solid-state LLZO frameworks with low tortuosity pore channels are proposed as scaffolds, into which active materials and other components can be infiltrated to make composite electrodes for solid-state batteries. To make the scaffolds, we employed aqueous freeze tape casting (FTC), a scalable and environmentally friendly method to produce porous LLZO structures. Using synchrotron radiation hard X-ray microcomputed tomography, we confirmed that LLZO films with porosities of up to 75% were successfully fabricated from slurries with a relatively wide concentration range. The acicular pore size and shape at different depths of scaffolds were quantified by fitting the pore shapes with ellipses, determining the long and short axes and their ratios, and investigating the equivalent diameter distribution. The results show that relatively homogeneous pore sizes and shapes were sustained over a long range along the thickness of the scaffold. Additionally, these pores had low tortuosity and the wall thickness distributions were found to be highly homogeneous. These are desirable characteristics for 3D solid electrolytes for composite electrodes, in terms of both the ease of active material infiltration and also minimization of Li diffusion distances in electrodes. The advantages of the FTC scaffolds are demonstrated by the improved conductivity of LLZO scaffolds infiltrated with poly(ethylene oxide)/lithium bis(trifluoromethanesulfonyl)imide (PEO/LITFSI) compared to those of PEO/LiTFSI films alone or composites containing LLZO particles.

36 MATERIALS SCIENCE↗

Molecular interactions in diffusion-controlled aldol condensation with mesoporous silica nanoparticles

The aldol reaction of p-nitrobenzaldehyde in amino-catalyzed mesoporous silica nanoparticles (MSN) has revealed varying catalytic activity with the size of the pores of MSN. The pore size dependence related to the reactivity indicates that the diffusion process is important. A detailed molecular-level analysis for understanding diffusion requires assessment of the noncovalent interactions of the molecular species involved in the aldol reaction with each other, with the solvent, and with key functional groups on the pore surface. Such an analysis is presented here based upon the effective fragment potential (EFP). The EFP method can calculate the intermolecular interactions, decomposed into Coulomb, polarization, dispersion, exchange-repulsion, and charge-transfer interactions. In this study, the potential energy surfaces corresponding to each intermolecular interaction are analyzed for homo- and hetero-dimers with various configurations. The monomers that compose dimers are five molecules such as p-nitrobenzaldehyde, acetone, n-hexane, propylamine, and silanol. The results illustrate that the dispersion interaction is crucial in most dimers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Microstructure, Transport, and Mechanics of Compacted Clay Simulated at the 0.1 μm Scale (1400 Smectite Clay Particles) Using a Coarse-Grained Model with Explicit Counterions

Clay-rich geomaterials play a critical role in many subsurface systems. The macroscale properties of these materials (low permeability, high ionic conductivity, high swelling pressure, etc.) are sensitive to molecular-level adsorption and hydration interactions at clay−water interfaces. Efforts to develop multiscale simulation approaches to predict these properties reveal a scale gap between atomistic simulations (typically limited to systems smaller than 10 nm) and continuum-scale models (which use computational grid elements with dimensions ≳ 10 μm). In this study, we present a coarse-grained (CG) framework that partly bridges this gap by simulating compacted smectite clay assemblages with dimensions of 0.1 μm containing 1,400 clay particles across a range of dry densities (1,050 to 1,850 kg·m −3 ) and Na/Ca counterion compositions (Na fraction ranging from 0.2 to 1). The simulated systems, along with their reconstructed binary three-dimensional pore networks, are used to evaluate the microstructure, pore size distribution, tortuosity, ion diffusivity, and swelling pressure of compacted smectite clay. Results show that our approach captures important features of the mesoscale heterogeneity of compacted clays, including tactoid formation, hierarchical porosity, and anisotropic pore networks. Results also reveal how compaction and counterion composition govern emergent behaviors, including dominant pore sizes, directional transport, and electrochemical response. This work highlights the potential of CG simulations to bridge molecular and continuum scales and to advance geotechnical and environmental applications involving clay-rich materials as well as related nanoporous media such as geopolymers and calcium-silicate-hydrate. However, the results also suggest that accurate prediction of certain microstructural and mechanical properties (e.g., swelling pressure) may require even larger-scale systems on the order of 1 μm.

02 PETROLEUM↗

Rational Design of High-Performing Electrodes in Energy Storage Devices

Our approach in this project is to control conductivities of different ions by modulating the pore sizes in MOFs as sulfur hosts in cathodes. To validate our hypothesis that controlling the pore size of MOFs can effectively prevent LiPSs shuttling while allowing sufficient Li ion transport, which will ensure electrochemical cycling performance, we performed molecular dynamics (MD) simulations using a series of UiO MOFs with different linker sizes including LiPSs and electrolyte components (1M LiTFSI in DME/DOL 1:1 volume) in pores. Specifically, UiO-66, UiO-67, and UiO-68 are Zr-based MOFs with a linker length of 5.67 Å, 10.07 Å, and 14.35 Å, respectively, leading to different pore diameters of 8.4 Å, 12.8 Å, and 17.8 Å. We calculated the mean-squared displacements of Li and LiPS from MD simulations at 300 K for 50 ns or over to assess their mobility in MOFs.

25 ENERGY STORAGE↗

Trace Adsorptive Removal of PFAS from Water by Optimizing the UiO‐66 MOF Interface

Abstract The confluence of pervasiveness, bioaccumulation, and toxicity in freshwater contaminants presents an environmental threat second to none. Exemplifying this trifecta, per‐ and polyfluoroalkyl substances (PFAS) present an alarming hazard among the emerging contaminants. State‐of‐the‐art PFAS adsorbents used in drinking water treatment, namely, activated carbons and ion‐exchange resins, are handicapped by low adsorption capacity, competitive adsorption, and/or slow kinetics. To overcome these shortcomings, metal–organic frameworks (MOFs) with tailored pore size, surface, and pore chemistry are promising alternatives. Thanks to the compositional modularity of MOFs and polymer–MOF composites, herein we report on a series of water‐stable zirconium carboxylate MOFs and their low‐cost polymer‐grafted composites as C 8 –PFAS adsorbents with benchmark kinetics and “parts per billion” removal efficiencies. Bespoke insights into the structure–function relationships of PFAS adsorbents are obtained by leveraging interfacial design principles on solid sorbents, creating a synergy between the extrinsic particle surfaces and intrinsic molecular building blocks.

Ilić, Nebojša↗

Insight on electrolyte infiltration of lithium ion battery electrodes by means of a new three-dimensional-resolved lattice Boltzmann model

Electrolyte filling takes place between sealing and formation in Lithium Ion Battery (LIB) manufacturing process. This step is crucial as it is directly linked to LIB quality and affects the subsequent time consuming electrolyte wetting process. Although having fast, homogeneous and complete wetting is of paramount importance, this process has not been sufficiently examined and fully understood. For instance, experimentally available data is insufficient to fully capture the complex interplay upon filling between electrolyte and air inside the porous electrode. We report here for the first time a 3D-resolved Lattice Boltzmann Method (LBM) model able to simulate electrolyte filling upon applied pressure of LIB porous electrodes obtained both from experiments (micro X-ray tomography) and computations (stochastic generation, simulation of the manufacturing process using Coarse Grained Molecular Dynamics and Discrete Element Method). The model allows obtaining advanced insights about the impact of the electrode mesostructures on the speed of electrolyte impregnation and wetting, highlighting the importance of porosity, pore size distribution and pores interconnectivity on the filling dynamics. Furthermore, we identify scenarios where volumes with trapped air (dead zones) appear and evaluate the impact of those on the electrochemical behavior of the electrodes.

25 ENERGY STORAGE↗

Measurement of Helium and Xenon Knudsen permeability in graphite IG-11

Here, understanding the flow and diffusion (transport) of gases through nuclear graphite is of interest in both the prismatic and pebble bed high-temperature gas reactors (HTGRs), for normal operation and under accident conditions, for example, as related to graphite oxidation. Both the laminar and turbulent gaseous transport are of interest. It has also been noted that nuclear graphite can have pore sizes that can possibly lead to non-continuum transport, as the pore size can be comparable to the gaseous mean free path. We report measurements and analyzes of experiments performed with IG-11 graphite in the pressure range of 10 Pa to 14,700 Pa, 293 K, using Helium, and research grade xenon (99.999%), respectively. These values are in fair agreement with those reported for different graphites and gases by other investigators, but are also higher by six orders of magnitude than those reported for Kr permeability in a developmental very low permeability graphite-HXT-90. Our measured ratio of the Helium and Xenon permeabilities is about 4, different from $\sqrt{\frac{m_{Xe}}{m_{He}}}$ ≈ 5.72 that corresponds to diffuse reflection at the graphite surface for both gases. Simple analysis indicates that the two gases have slightly different accommodation coefficients (about 25%) with the graphite surface. However, there could also be other reasons, such as experimental uncertainties or the need for a more detailed analysis.

36 MATERIALS SCIENCE↗

Effect of laser scanning speed on the microstructure, phase transformation and mechanical property of NiTi alloys fabricated by $\mathrm{LPBF}$

This study investigated the effects of laser scanning speed on the microstructure, phase transformation and properties of NiTi alloys fabricated by laser powder bed fusion (LPBF). In this study, the contributions of metallurgical factors under different scanning speeds, such as Ni evaporation, Ni4Ti3 precipitation, dislocations and internal stress, to the transformation temperature and transformation latent heat were clarified through specially designed experiments. Ni evaporation is found to have the most profound effect, followed by precipitation. Increasing scanning speed is found to reduce Ni loss, thus cause less increase in the transformation temperature and transformation heat of the LPBF-NiTi alloys. Increasing scanning speed also increases the microstructure non-uniformity and thus widens the transformation temperature interval. The orientations of residual stress exhibit strong crystallographic stiffness dependence. The LPBF-NiTi alloys with different scanning speeds all exhibited high strains (>13.4%) and excellent shape memory effect. A LPBF-NiTi honeycomb structure exhibited 96% shape recovery rate after a 60% pre-compressive deformation. Besides, there is an optimum scanning speed for minimum porosity and smallest average pore size. However, the pore structure is found to have weak influence on the tensile behaviour of the LPBF-NiTi alloys, possibly due to the high defect tolerance of the martensitic transformation.

36 MATERIALS SCIENCE↗

Plasma ammonia synthesis over mesoporous silica SBA-15

Herein we demonstrate the synthesis of ammonia via atmospheric DBD plasma discharge over silica. We evaluated the performance of three structural different silicas: non-porous silica, fumed-silica and mesoporous SBA-15 silica. The mesoporous SBA-15 sample resulted in an ammonia synthesis rate per gram of catalyst at least 3 times higher than that of the non-porous and fumed silica when employing a hydrogen rich gas feed. The hierarchical ordered pore size in the mesoporous range of SBA-15 allowed us to observe experimentally, the pore size effect in the plasma discharge. Specifically, the ammonia production is enhanced by the presence of mesopores that can effectively enable the discharge diffusion into the pore as predicted by theoretical calculations. The importance of the porous structure was confirmed by optical emission spectra which indicates a similarity on the relative intensity on the main plasma activated species in the gas phase such as N2+, NH and H_α for the three silicas employed in this work i.e., non-porous, fumed and mesoporous (SBA-15). Furthermore, the remarkable ammonia production when employing the SBA-15 shows that despite the similarities in the gas phase the main differences might be attributed to the diffusion of the plasma discharge into the pores.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

EXPERIMENTAL AND MODELING STUDY OF MOLECULAR TRANSPORT PHENOMENA IN COMPLEX LIQUID MIXTURES USING COVALENT ORGANIC FRAMEWORK MEMBRANES

Currently, 10-15% of the world’s energy is consumed by chemical separations, and more than 80% of that is used to purify organic liquids and recover rare earth elements and critical minerals. Membrane nanofiltration presents an energy-efficient, cost-effective, and eco-friendly alternative to current separation technologies. These complex liquid environments require high- performance, chemically-resistant membrane materials. Recently discovered Covalent Organic Frameworks (COFs) possess desirable properties as membrane materials for complex liquid separations. COFs are highly crystalline, chemically and thermally stable, with tunable size and charge. COFs, especially two-dimensional highly crystalline COFs, possess narrow pore-size distribution and controlled porous structures. Two-dimensional COFs are also resistant to swelling, another feature beneficial in complex liquid separations. Molecular interactions in complex liquid systems often dictate final membrane performance, resulting in a discrepancy between designed and apparent COF properties. Understanding and resolving this discrepancy is critical in utilizing COF membranes as a viable alternative to energy-intensive separations. The primary objective of this thesis was to use a commercially available COF TpPa-1 as a platform to investigate how mixed solvent environment affects COF membrane performance via experimental and molecular modeling studies. Specifically, the effects of solution pH, solvent- solvent-solute interactions in mixed solvents, and COF chemistry were carefully examined on apparent TpPa-1 pore size and permeability and targeted solute rejection of COF membranes for neat and mixed solvents. Experimental COF filtration performance was compared and corroborated with modeling predication. Findings from this study will provide guidance for future COF design, synthesis, and desired functional COF membrane performance.

Barnes, Anastasia↗

Mesoporous Crystalline Niobium Oxide with a High Surface Area: A Solid Acid Catalyst for Alkyne Hydration

A mesoporous crystalline niobium oxide with tunable pore sizes was synthesized via the sol–gel-based inverse micelle method. The material shows a surface area of 127 m 2 /g, which is the highest surface area reported so far for crystalline niobium oxide synthesized by soft template methods. The material also has a monomodal pore size distribution with an average pore diameter of 5.6 nm. A comprehensive characterization of niobium oxide was performed using powder X-ray diffraction, Brunauer–Emmett–Teller, thermogravimetric analysis, scanning electron microscopy, transmission electron microscopy, UV–vis, and X-ray photoelectron spectroscopy. The material acts as an environmentally friendly, solid acid catalyst toward hydration of alkynes under with excellent catalytic activity (99% conversion, 99% selectivity, and 4.39 h –1 TOF). Brønsted acid sites present in the catalyst were found to be responsible for the high catalytic activity. Lastly, the catalyst was reusable up to five cycles without a significant loss of the activity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Enhanced Menshutkin S N 2 Reactivity in Mesoporous Silica: The Influence of Surface Catalysis and Confinement

A significant enhancement in the Menshutkin S N 2 reaction between 1-methylimidazole (MeIm) and methyl thiocyanate (MeSCN) is observed when the reaction is confined in the nanoscale silica pores of MCM41 and SBA15. The experiments in the silica pores are conducted without surrounding bulk reaction mixture. The influences of temperature, pore radius, and surface chemistry on the kinetics of the confined reaction are analyzed with time-dependent infrared spectroscopy, molecular dynamics simulations, and ab initio calculations. The rate constant of the pseudo-first order reaction increases with decreasing pore size, and the activation energy is found to decrease by 5.6 kJ/mol in the smallest pore studied (2.8 nm) relative to the bulk reaction. The rate constant dependence on pore size is accurately described by a two-state model in which molecules within the 4.6 Å interfacial layer experience a 2.4-fold rate constant increase relative to those reacting at the bulk rate further away from the interface. The removal of polar silanol groups from the silica surface via passivation with trimethylsilyl chloride results in bulk-like kinetics despite a reduction in the pore diameter, demonstrating the role of silanols as catalytic sites. Here, electronic structure calculations of the energy profile on a model silica surface confirm that silanol groups, particularly those of the vicinal type, can reduce the activation energy and reaction endothermicity through the donation of hydrogen bonds to the reactant, transition state, and product complexes.

36 MATERIALS SCIENCE↗

Designing Multiscale Porous Metal by Simple Dealloying with 3D Morphological Evolution Mechanism Revealed via X-ray Nano-tomography

Designing materials with multiscale, hierarchical structure is critical to drive the advancement of new technology. Specifically, porous metals with multiscale porosity from nanometer to micrometer sizes would lead to enhanced physical and chemical properties—the micron-sized pores can increase the effective diffusivity of ion transport within the porous media, and the nano-sized pores provide high specific surface area, enabling functionalities that are unique to nanoporous metals. A new ternary precursor alloy selection concept utilizing the different mixing enthalpies is demonstrated in this work for the design of multiscale, bimodal porous copper from a simple, one-step dealloying of Cu–Fe–Al ternary alloy. The nanoporosity in the bimodal porous structure is formed from dealloying of the Cu-rich phase, whereas the microporosity is controlled by dissolving the Fe-rich phase, determined by both the initial Fe particle size and sintering profile. In addition to advancing the materials design method, the multiscale pore formation during dealloying was directly visualized and quantified via an interrupted in situ synchrotron X-ray nano-tomography. The 3D morphological analysis on tortuosity showed that the presence of the microporosity can compensate the increase of the diffusion path length due to nanoporosity, which facilitates diffusion within the porous structure. Altogether the focus of the work is to introduce a new strategy to design multiscale porous metals with enhanced transport properties, and sheds light on the fundamental mechanisms on the 3D morphological evolution of the system using advanced synchrotron X-ray nano-tomography for future materials development and applications.

36 MATERIALS SCIENCE↗

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↗

The effect of inhomogeneities in coal-based mesophase pitch on filament formation and melt spinning for carbon fiber

Mesophase pitch-based carbon fibers excel as high specific strength and modulus materials, but challenges in stable, continuous melt spinning processing are a serious limiting factor. Inhomogeneities in the pitch may result in flow instabilities that can lead to filament breakage. This work aims to characterize and offer mitigation strategies for the negative effects that inhomogeneities such as isotropic binder, gels, and other inclusions impart on melt spinning of mesophase pitch. The effect of inhomogeneities on spinning stability are analyzed using capillary rheometry, borescope imaging of elongating filaments, and filtration. With no filter, immediate blockage of the spinning capillary occurred. Improvement in melt spinning duration was observed when a porous metal filter (20 μm nominal pore size) was utilized, but no significant further improvement in spinning duration was found upon decreasing the filter nominal pores size to 10, 5 and 2 μm. Moreover, flow instabilities that disrupted melt spinning stability were observed by capillary rheometry when the size of included isotropic pitch domains were larger than approximately 10 μm. Resultant carbon fiber properties and SEM imaging of fracture surfaces are reported.

01 COAL, LIGNITE, AND PEAT↗