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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 289 records · Page 16
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

The effect of pore structure in ethane-selective metal-organic frameworks for ethylene purification

Separation of ethylene from ethane is of great importance in petrochemical industry. Adsorptive separation making use of porous materials such as metal-organic frameworks (MOFs) is an energy efficient technology compared to the conventional cryogenic distillation. However, preferential adsorption of ethylene over ethane represents the major current challenge. Here we demonstrate how pore structure can significantly alter the adsorption selectivity in two isoreticular Zr-MOFs. A simple ligand functionalization in UiO-66 yields smaller/better matching pore for ethane, and weaker interaction with ethylene, greatly enhancing ethane/ethylene selectivity in MOF-801. Ab initio calculations combined with in situ infrared spectroscopic analysis unveil the nature of host-guest interactions and differences in the overall binding energies. Polymer-grade ethylene (99.9%) can be produced directly from ethane/ethylene mixture in a single step. Having well-balanced adsorption capacity and selectivity, low-cost synthesis and easy scalability MOF-801 stands out as a promising ethane-selective adsorbent for one-step ethylene purification under ambient conditions.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Modifying the pore size distribution in Fe-rich inorganic polymer mortars: An effective shrinkage mitigation strategy

Highlights: • Inorganic polymer mortar has mainly macropores and a drying shrinkage of 5.1 mm/m. • 2-methyl-2,4-pentanediol acts as air entrainer in inorganic polymer mortars. • Optimal dosage 2 wt% 2-methyl-2,4-pentanediol reduced drying shrinkage to 1.8 mm/m. • Heat curing inorganic polymer mortars reduced drying shrinkage more than 50%. • Blast Furnace slag addition increased drying shrinkage and reduced strength. Inorganic polymer (IP) binder is formed upon alkali-activation of Fe-rich (41 wt%) metallurgical slag leading to materials with mechanical properties comparable to ordinary Portland cement binders. Crack formation is reported in IPs, which can be related to volumetric stability, which is to date not thoroughly understood in IPs. This study determined the autogenous and drying shrinkage of IP mortars. Shrinkage mitigation strategies, such as the addition of 2-methyl-2,4-pentanediol (2MPL), blast furnace slag (GGBFS), and applying heat curing, were used separately or in combination. IP mortars exhibited autogenous expansion and high drying shrinkage. The addition of 2MPL led to a porosity increase, as air was entrained, decreasing the drying shrinkage with 64%. Additional heat curing had no effect on samples with 2MPL. Introducing GGBFS resulted in smaller pores, increasing drying shrinkage. Shrinkage in IP mortars is driven by its pore size distribution and higher shrinkage resulted in lower flexural strength.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Efficacy of SCMs to mitigate ASR in systems with higher alkali contents assessed by pore solution method

This study demonstrates the efficacy of supplementary cementitious materials (SCMs) to mitigate alkali-silica reaction (ASR) even when used in conjunction with cement of higher alkali contents (up to 1% Na{sub 2}O{sub eq}). The expansion of concrete prisms was studied immersed in simulated pore solution in order to address the limitations of conventional ASR testing methods, accelerated mortar bar test (AMBT) and concrete prism test (CPT). Expansion results demonstrate that 25% fly ash and 50% slag are both sufficient to mitigate ASR even with cements with alkali content up to 1% Na{sub 2}O{sub eq} and that the pore solution method is a viable alternative ASR testing method. Massive amounts of ASR products (~20 μm thickness) were observed in concretes without SCMs consistent with high degree of expansion and extensive cracking. Small amounts of ASR products (≤5 μm thickness) were also observed in concrete with SCMs despite absence of significant expansion.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Effects of anionic and nonionic surfactants on the dispersion and stability of nanoSiO2 in aqueous and cement pore solutions

It has been well recognized that the benefits and effectiveness of nanoparticles in cement-based materials could not be maximized if these are not well dispersed. To address this issue, in this study, different anionic (SDS and PCE) and nonionic surfactants (Tweens and Tritons) were used to disperse nanosilica (NS) in aqueous solution and cement pore solution. The results show that the dispersibility of NS in cement pore solution was improved, and the compressive strength of the cement-NS pastes increased linearly with critical micelle concentration (CMC) of nonionic surfactants. Among all surfactants studied, Triton X-405 led the paste to the highest increase in strength (33% at 1-day and 41% at 3-days) since it had the highest CMC. TEM and EDS analysis evidenced that this strength increase might be attributed to the nucleation of outer product CSH gel and its densification with calcite nanocrystals, attributed to Triton X-405 addition.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Characteristics of flow through randomly packed impermeable and permeable particles using pore resolved simulations

Pore resolved simulations are performed to study the mean flow characteristics in porous media formed by random distribution of impermeable and permeable particles. Here, permeability of the medium and reactive surface areas are analyzed for a range of solid fractions, packing patterns and flow rates. The results are compared with models presented in the literature and with simulations of flow through ordered packings. Permeability of a randomly packed porous medium is found to depend on the heterogeneous distribution of porosity which results from particle agglomeration and is typically ignored by simpler models. The reactive surface area is dependent on the flow field at pore scale in addition to geometry. Moreover, the wake formed downstream of the particles at moderately high flow rates also affects the reactive surface area. Similar analysis is also performed by assuming particles to be permeable to account for dual scale porosity relevant for various engineering applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Pore-scale CFD simulations of clay mobilization in natural porous media due to fresh water injection

The present work investigates mechanisms of permeability impairment as a result of low-salinity fluid injection into brine-saturated porous media containing dispersible clays. Here, we present a computational fluid dynamics model at the pore-scale to simulate detachment, migration and straining of fine particles in porous media. The model uses an immersed boundary method to simulate the motion of clay fines in a fluid. In addition to the hydrodynamic forces, we model the Derjaguin-Landau-Verwey-Overbeek forces (DLVO) between clay fines and grains. Our simulations show the impact of the injected fluid's salinity and velocity on the concentration of clay fines retained on the grain surface. We see clay particles dislodging from the grain surface in clusters of up to 12 particles. Our simulation results also demonstrate clogging of narrow pore spaces by the detached particles from the grain surfaces.

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

Wellbore cement fracture permeability as a function of confining stress and pore pressure

Cemented annulus fractures are a major leakage path in a wellbore system, and their permeability plays an important role in the behavior of fluid flow through a leaky wellbore. The permeability of these fractures is affected by changing conditions including the external stresses acting on the fracture and the fluid pressure within the fracture. Laboratory gas flow experiments were conducted in a triaxial cell to evaluate the permeability of a wellbore cement fracture under a wide range of confining stress and pore pressure conditions. For the first time, an effective stress law that considers the simultaneous effect of confining stress and pore pressure was defined for the wellbore cement fracture permeability. Here the results showed that the effective stress coefficient (λ) for permeability increased linearly with the Terzaghi effective stress ( -p) with an average of λ = 1 in the range of applied pressures. The relationship between the effective stress and fracture permeability was examined using two physical-based models widely used for rock fractures. The results from the experimental work were incorporated into numerical simulations to estimate the impact of effective stress on the interpreted hydraulic aperture and leakage behavior through a fractured annular cement. Accounting for effective stress-dependent permeability through the wellbore length significantly increased the leakage rate at the wellhead compared with the assumption of a constant cemented annulus permeability.

58 GEOSCIENCES↗
DOE OSTI2025

Effect of pore fluid chemistry on the mechanical behavior of a divalent compacted bentonite, an experimental and constitutive study

Ongoing research in isolating high-level nuclear waste and spent fuel has highlighted compacted bentonite as a suitable material for engineered barrier systems in deep geological repositories due to its extraordinary swelling and retention properties. This research focuses on the chemo-mechanical behavior of compacted bentonite exposed to different pore fluids with different concentrations and loading conditions. The study involves swelling pressure and compressibility experiments along with mineralogy analysis employing X-ray diffraction (XRD) and Cation exchange. The tests were conducted on BCV (a Mg/Ca- bentonite) compacted at a dry density of 1.48 ± .02 Mg/m 3 . An advanced chemical-mechanical constitutive model for unsaturated highly expansive clays was adopted to simulate the material response and better understand its behavior. The model is able to account for the main phenomena at both macro and microstructural levels and the interactions between them. The model successfully replicated experimental observations. The XRD analyses support the macroscopic observation, indicating that salinity impacts crystalline swelling as demonstrated by the reduction of basal spacing from 19.27 Å to 15.68 Å when the osmotic suction increases from 0 MPa to 33 MPa. The results suggested that the osmotic pressure generated by the concentration in the pore fluids promotes a reduction in swelling pressures, swelling strains, and crystalline swelling of clay minerals. Also, it affects the pre-consolidation stress and the compressibility of the compacted samples. In conclusion, it was also observed that both solution type and solution concentration impact the clay swelling pressure.

Chemo-mechanical constitutive model↗
DOE OSTI2020

Pore-scale simulation of gas flow in microscopic permeable media with complex geometries

Lattice Boltzmann method (LBM) is an efficient tool to perform direct numerical simulation of gas flow in micro-size pores. Despite great advances in LBM and its use in describing gas flow in micro-size channels in slip and transitional flow regimes, exploring formulations that are able to capture flow behavior in domains with complex boundary geometries remains a challenging task. As a result, the impact of complexities in pore structures on gas flow may not be fully explored using LBM. In this study, we propose to use the combined bounce-back and Maxwellian diffusive reflection scheme to capture the slip velocity with a new set of slip coefficients. Optimal values of slip coefficients are determined using a gradient based method, where the results from the linearized Boltzmann equation is used as the reference solution. The proposed formulation is further validated against predictions from molecular dynamics simulation in the presence of complex geometries by introducing obstacles of different shapes in straight channels. LBM with the proposed boundary treatment is then used to investigate gas flow in a synthetic microscopic permeable medium. Here, results indicate that gas exhibits different flow configurations as Knudsen number varies, and apparent gas permeability appears to have up to a second-order dependency on the reciprocal mean pressure in slip and transitional flow regimes.

03 NATURAL GAS↗
DOE OSTI2026

Uncertainty quantification for Joule heating processes in fibrous pore-resolved media

Joule heating (JH) is an energy-efficient and sustainable technique for heating materials. Its application for industrial heating, particularly, has been gaining attention due to its potential for increasing the yield of various chemical products. The process involves the use of heating elements (materials that are highly conductive electrically and thermally) to heat up other materials or substances. These conductors, however, can exhbit varying degrees of uncertainty due to non-linearities in their temperature-dependent properties, which could result in variable material behavior. In this work, we carry out uncertainty quantification (UQ) at the pore scale to describe the uncertainty of such materials. In so doing, we applied the non-intrusive polynomial chaos expansion (PCE) technique to quantify the uncertainty within the system. The steady state Joule heating equation was solved numerically at the pore scale mimicking conditions within a heating chamber for propane dehydrogenation, and various electro-thermal profiles were obtained. We also examined the effect of the number of sampling points (20 – 100) and order of the PCE coefficients (2 – 5) on the accuracy of the temperature evaluations. The results were then benchmarked with the standard Monte Carlo (MC) method. The average temperature of the 4th-order global PCE showed good agreement with the MC results (which were positively skewed). Orders greater than 4 gave an underestimation of the temperatures while predictions for the peak temperature improved as the number of sampling points increased.

Fagbemi, Samuel [ORNL] (ORCID:0000000236995025)↗
DOE OSTI2020

Probing the Core–Shell Organization of Nanoconfined Methane in Cylindrical Silica Pores Using In Situ Small-Angle Neutron Scattering and Molecular Dynamics Simulations

Determining the structure of nanoconfined fluids is essential for predicting the fate of these fluids in subsurface geologic formations with nanoporous features and for engineering novel nanoporous materials for storing compressed gases. In this study, we probe the structure of nanoconfined methane at pressures in the range of 15–100 bar using in situ small-angle neutron scattering (SANS) measurements and molecular dynamics (MD) simulations. The structure of methane is probed in MCM-41 and SBA-15 with cylindrical pores and diameters of 3.3 and 6.8 nm, respectively. In situ SANS measurements and MD simulations showed that the confined methane molecules are organized in a core–shell structure, with the shell arising from the adsorption of methane molecules on the silica surface. The shell thicknesses of the adsorbed deuterated methane (CD4) molecules in MCM-41 obtained by SANS measurements are 1.4 ± 0.5, 2.1 ± 0.1, 3.2 ± 0.8, 4.0 ± 0.3, and 6.0 ± 0.7 Å at equilibrated pressures of 15.6, 35.6, 55.5, 73.3, and 95.7 bar, respectively. The shell thicknesses of the adsorbed CD4 layer in SBA-15 pores are 2.7 ± 0.5, 4.3 ± 0.7, 6.6 ± 0.7, 10.2 ± 0.3, and 14.6 ± 0.8 Å at equilibrated pressures of 15.5, 32.7, 52.4, 70, and 99.5 bar, respectively. These experimental results are in close agreement with the results predicted from MD simulations. Adsorption of methane molecules on the silica surfaces is primarily driven by van der Waals interactions between the methane molecules and the hydroxyl groups on the silica surface, while electrostatic interactions play a minor role. In conclusion, the experimental and simulation approaches described in this study provide fundamental insights into the organization of confined gases using methane as a specific example in the context of compressed fluid storage in natural and engineered materials for adaptive energy use.

03 NATURAL GAS↗
DOE OSTI2022

Characterization of Porosity and Pore Accessibility of Vitrinite-Rich Bituminous and Subbituminous Coals by Small-Angle Neutron Scattering, Mercury Intrusion Porosimetry, and Low-Pressure N 2 Adsorption

Three bituminous and one subbituminous vitrinite-rich coals were characterized using small-angle neutron scattering with contrast matching, mercury intrusion porosimetry, and low-pressure N 2 adsorption techniques to quantify their porosity and pore accessibility in an effort to assess their solvent extractabilities, as a first approximation, for manufacturing useful end-products. The techniques revealed consistent results while complimenting one another. The total porosity was found to follow the coal rank with the lowest rank having the highest porosity within the studied coals. The amount of inaccessible pores was found to increase with rank for the bituminous coals studied here. Finally, the increase in the ease of accessibility and total porosity with decreasing rank suggested easier penetration of chemical reagents for solvent extraction, for example.

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

Facile Metal Release from Pore-Lining Phases Enables Unique Carbonate Zonation in a Basalt Carbon Mineralization Demonstration

Carbon-negative strategies such as geologic carbon sequestration in continental flood basalts offers a promising route to the removal of greenhouse gases, such as CO 2 , via safe and permanent storage as stable carbonates. This potential has been successfully demonstrated at a field scale at the Wallula Basalt Carbon Storage Pilot Project where supercritical CO 2 was injected into the Columbia River Basalt Group (CRBG). Here, we analyze recovered post-injection sidewall core cross-sections containing carbonate nodules using μ-XRF chemical mapping techniques that revealed compositional zonation within the nodules. The unique nature of the subsurface anthropogenic carbonates is highlighted by the near absence of Mg in an ankerite-like composition. Furthermore, a comparison between pre- and post-injection sidewall cores along with an in-depth chemical mapping of basalt pore lining cements provides a better understanding into the source and fate of critical cationic species involved in the precipitation of carbon mineralization products. Collectively, these results provide crucial insights into carbonate growth mechanisms under a time-dependent pore fluid composition. Finally, as such, these findings will enable parameterization of predictive models for future CO 2 sequestration efforts in reactive reservoirs around the world.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2026

Enhanced Manganese Oxidation at the Biofilm–Fluid Interface Drives Pore-Scale Patterns in Mineral Precipitation

Microbial oxidation of manganese (Mn) from aqueous Mn(II) to solid-phase Mn(III, IV) minerals catalyzes Mn(II) removal in natural and engineered porous systems. However, little is known about the spatiotemporal evolution of Mn biomineralization in confined spaces that experience simultaneous Mn(II) delivery and Mn oxide precipitation. Here, we combine time-lapse microscopy, image analysis, and mass spectrometry to quantify the extent and rate of Mn biomineralization by Pseudomonas putida GB-1 in an optically transparent two-dimensional porous medium. We found that Mn(II) oxidation initially occurred within biofilms but shifted over time toward the edges of biofilms in contact with pore fluid. Minerals precipitated outside of the initial biofilm footprint likely due to surface-mediated oxidation of Mn(II) by nascent biogenic Mn oxides, reinforcing a gradient in mineral accumulation from the Mn(II) source near the reactor inlet to the outlet. The rate of mineral precipitation outside the biofilm footprint surpassed the rate of mineral accumulation inside biofilms within 6 h and accounted for two-thirds of the total Mn oxide mass in the pore space at the end of the experiment. This work advances a mechanistic understanding of coupled biotic and abiotic Mn oxidation in porous environments while providing a novel platform to quantify microbe-mineral-fluid interactions.

Biofilms↗
DOE OSTI2026

Pore-Selective Fullerene Loading in a Porphyrin-Based Metal–Organic Framework Controls Photoinduced Charge-Transfer Dynamics

Building porous donor−acceptor networks based on host−guest interactions in metal organic frameworks (MOFs) provides unique opportunities for tuning charge separation in highly tailorable materials. Here we focus on installing electron-rich porphyrins and electron-deficient fullerene derivatives in the PCN-222 MOF using a solvent assisted ligand insertion (SALI) method. The fullerene is primarily bound in the large pore, where it is subject to distinct dielectric environments through dimethylformamide (DMF) and 1,4-dioxane solvent exchange. Following photoexcitation, sub-picosecond charge transfer involving initial exciplex population is observed, with different charge recombination pathways and lifetimes depending on solvent polarity through modulation of charge-transfer state energies. While the 1,4-dioxane environment yields charge recombination within 1 ns via local fullerene and porphyrin triplet state population, DMF results in charge recombination directly to the ground state on much longer time scales, including some lifetime components in the microsecond range. Fullerene loading influences these kinetics, and the potential for charge delocalization due to fullerene aggregation within the pores is evaluated by using molecular dynamics simulations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Cation Selectivity in Capacitive Deionization: Elucidating the Role of Pore Size, Electrode Potential, and Ion Dehydration

Capacitive deionization (CDI) is a promising water desalination technology that is applicable to the treatment of low-salinity brackish waters and the selective removal of ionic contaminants. In this work, we show that by making a small change in the synthetic procedure of hierarchical carbon aerogel monolith (HCAM) electrodes, we can adjust the pore-size distribution and tailor the selectivity, effectively switching between selective adsorption of calcium or sodium ions. Ion selectivity was measured for a mixture of 5 mM NaCl and 2.5 mM CaCl 2 . For the low activated flow-through CDI (fteCDI) cell, we observed extremely high sodium selectivity over calcium (S Na/Ca $\gg$ 10, no Ca 2+ adsorbed) at all of the applied potentials, while for the highly activated fteCDI cell, we observed a selectivity value of 6.6 ± 0.8 at 0.6 V for calcium over sodium that decreased to 2.2 ± 0.03 at 1.2 V. Molecular dynamics simulations indicated that the loss in Ca 2+ selectivity over Na+ at high applied voltages could be due to a competition between ion-pore electrostatic interactions and volume exclusion (“crowding”) effects. Interestingly, we also find with these simulations that the relative sizes of the ions change due to changes in hydration at a higher voltage.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Swelling-Assisted Sequential Infiltration Synthesis of Nanoporous ZnO Films with Highly Accessible Pores and Their Sensing Potential for Ethanol

Here, we report a swelling-assisted sequential infiltration synthesis (SIS) approach for the design of highly porous zinc oxide (ZnO) films by infiltration of block copolymer templates such as polystyrene-block- polyvinyl pyridine with inorganic precursors followed by UV ozone-assisted removal of the polymer template. We show that porous ZnO coatings with the thickness in the range between 140 and 420 nm can be obtained using only five cycles of SIS. The pores in ZnO fabricated via swelling-assisted SIS are highly accessible, and up to 98% of pores are available for solvent penetration. The XPS data indicate that the surface of nanoporous ZnO films is terminated with -OH groups. Density functional theory calculations show a lower energy barrier for ethanol-induced release of the oxygen restricted depletion layer in the case of the presence of -OH groups at the ZnO surface, and hence, it can lead to higher sensitivity in sensing of ethanol. We monitored the response of ZnO porous coatings with different thicknesses and porosities to ethanol vapors using combined mass-based and chemiresistive approaches at room temperature and 90 °C. The porous ZnO conformal coatings reveal a promising sensitivity toward detection of ethanol at low temperatures. In conclusion our results suggest the excellent potential of the SIS approach for the design of conformal ZnO coatings with controlled porosity, thickness, and composition that can be adapted for sensing applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

3D Morphology of Bimodal Porous Copper with Nano-Sized and Micron-Sized Pores to Enhance Transport Properties for Functional Applications

Multiscale porous metals with multiscale porosity from nanometer to micrometer have a high specific surface area and high effective diffusivity for ion transport, thereby enhancing functionalities and extending the applications of porous metals. Herein, the Cu–Fe–Al ternary system was selected as the precursor alloy to construct multiscale, bimodal porous copper by the chemical dealloying method. The effect of the phase composition and initial microstructure of precursor alloys (Al x Fe 75– x Cu 25 , x = 10–60) on the three-dimensional (3D) morphology of multiscale porous metals was systematically investigated, with a goal to precisely control the multiscale porous structure. The four crystal structure phases (body-centered cubic (BCC), face-centered cubic (FCC), CsCl type (B2), and monoclinic) in precursor alloys were analyzed by synchrotron X-ray diffraction refinement. The 3D morphology, feature size distribution, and tortuosity of four representative porous Cu after dealloying Al x Fe 75– x Cu 25 ( x = 10, 30, 50, and 60) precursor alloys were directly visualized and quantified via advanced synchrotron X-ray nanotomography. The relationship between the phases/crystal structures of precursor alloys and their corresponding porous morphology was established: the micron-sized pores in bimodal porous Cu are formed by dissolving the CuFeAl phase with BCC and monoclinic crystal structures, and the nano-sized pores are formed by dealloying the CuFeAl phase with FCC and B2 crystal structures. The size of the nanoporous structure depends on the ratio between the more noble and more active components in the precursor alloy, while the size of the microporous structure depends on the corresponding phase size in the precursor alloy. The tortuosity results showed that the multiscale porous structure with both nanoporosity and microporosity exhibits lower tortuosity, which will enhance transport properties for functional applications.

25 ENERGY STORAGE↗