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At least 91 records · Page 5
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Curing process and pore structure of metakaolin-based geopolymers: Liquid-state 1H NMR investigation

Geopolymers are emerging construction materials with lower carbon dioxide emissions compared to the conventional cementitious materials. The knowledge of the curing process and the related pore structures are important for optimizing the properties of these materials for different applications. The curing process and final pore structure are sensitive to the amount of used water, however the specifics are unclear. The curing process and pore structures of metakaolin-based geopolymers with a narrow water-to-solid (w/s) ratio (0.59–0.66) were monitored by nuclear magnetic resonance (NMR) relaxometry and cryoporometry. The 14-day curing process was investigated by monitoring the change of T{sub 2} and T{sub 1} relaxation times and water signal intensity. After the curing, the pore structures were characterized by 2D T{sub 1}-T{sub 2} correlation and T{sub 2}-T{sub 2} exchange measurements of absorbed water. The pore size distributions (PSDs) were measured with NMR cryoporometry and compared to nitrogen physisorption and mercury intrusion porosimetry (MIP) results. We found that the relaxation times decreased as the pore structure of the geopolymers matured during the curing while the dissolution and the condensation periods of the curing were distinguished by the changes in signal amplitude reflecting the proton density. After the curing, three distinct pore sizes and connectivity between pores were identified from T{sub 1}-T{sub 2} and T{sub 2}-T{sub 2} spectra. Their PSDs were measured, and they were found to correspond to two different pore sizes originating from the arrangement of clusters and defective pores. In the narrow w/s ratio (0.59–0.66), the curing times were the same for all samples when cured at 24 °C while the pore sizes were observed to increase as a function of the w/s ratio.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Deformation of pores in response to uniaxial and hydrostatic stress cycling in Marcellus Shale: Implications for gas recovery

One of the main challenges during gas production from shale reservoirs is low recovery rate. One contributing factor to this outcome is an insufficient understanding of pore systems, especially pore behaviour following changes in reservoir conditions or resulting from gas production practices. Because the pressure in the producing well can be controlled, understanding the effects of pressure variation on the pore size distribution and methane trapping is necessary to help design optimal conditions to improve the gas recovery rate. This work is the first systematic study of sub-millimeter pore deformation in shale caused by uniaxial and hydrostatic stress up to 100 MPa. Overmature samples from the Middle Devonian Marcellus Shale were analyzed using neutron scattering (SANS and USANS) techniques to interpret the response of nanopores to stress cycling of magnitude and duration compatible with the hydraulic fracturing treatments. Experiments reported here are performed at a series of uniaxial pressures up to 100 MPa and at hydrostatic pressures of deuterated methane 0 and 50 MPa. Since at the original depth of the shale samples’ burial of 2184 m the hydrostatic pressure is approximately 27 MPa and the lithostatic pressure is about 55 MPa, the experimental conditions reasonably well simulate the reservoir pressure regime. Our SANS and USANS results show that different pore sizes are affected by uniaxial stress in different ways. Specifically, in the pore size range from 1 nm to 800 nm, a decrease of pore density with pressure is observed, with the most depleted being mesopores of about 100 nm in diameter. The observed decrease is likely related to deformation of kerogen, followed by a loss of pore nano-volume, as well as methane trapped in the micropores. For pores larger than 5 μm, USANS data suggest that the negative trend is reversed at above 74 MPa, and the number density of large macropores may increase with increased stress even above the original value. The increased number of macropores at high pressure may create new interconnected conduits for gas migration, resulting in a better recovery rate. Another important finding of this study is an irreversible rearrangement of pore size distribution taking place after pressure cycling. Furthermore, this irreversible reorganization of pore size distribution should be taken into account during management of well production to maximize recovery rate.

03 NATURAL GAS↗
DOE OSTI2022

System and method for using ultramicroporous carbon for the selective removal of nitrate with capacitive deionization

The present disclosure relates to a flow through electrode, capacitive deionization (FTE-CDI) system which is able to adsorb nitrates from water being treated using the system. The system makes use of a pair of electrodes arranged generally parallel to one another, with a water permeable dielectric sandwiched between the electrodes. The electrodes receive a direct current voltage from an electrical circuit. At least one of the electrodes is formed from a carbon material having a hierarchical pore size distribution which includes a first plurality of pores having a width of no more than about 1 nm, and a second plurality of micro-sized pores. The micron-sized pores enable a flow of water to be pushed through the electrodes while the first plurality of pores form adsorption sites for nitrate molecules carried in the water flowing through the electrodes.

Campbell, Patrick↗
DOE OSTI2021

Maximizing selectivity: An analysis of isoporous membranes

Membranes are compelling candidates for many separation-based industrial processes. However, all synthetic membranes are subject to well-recognized permeability-selectivity trade-offs that hinder their use in advanced applications. Having uniform nanoscale pore size, isoporous nanofiltration and ultrafiltration membranes have attracted wide research interest. However, quantitative analysis of isoporous membrane performance is lacking - particularly at module and system-level scales. In this study, an analytical model is built to investigate how membrane pore-size distribution affects the solute separation efficiency (i.e., rejection and selectivity). The model accounts for convective hindrance as well as concentration polarization and explores effects on separation from the solute-to-pore-size ratio and percent recovery (i.e., fraction of feed flow that passes through the membrane). At the module level, our analysis suggests that a notably sharper rejection vs. solute size curve can be obtained as the pore-size distribution becomes narrower. Additionally, as the recovery increases, the rejection of a solute is maintained at a high level using isoporous membranes while the rejection drops rapidly for membranes that possess a disperse pore-size distribution. Furthermore, in the separation of mixed solutes, isoporous membranes achieve a large selectivity with a modest loss of permeability. Overall, this study elaborates the unique role that isoporous membranes play within the permeability-selectivity trade-off relations and identifies the most exciting opportunities for their future applications.

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

Nanopore Confinement of C-H-O Mixed-Volatile Fluids Relevant to Subsurface Energy Systems

The overarching goal of OU’s contribution to the project was to use novel computational approaches to quantify the effect of variable nanopore features (pore size, volume, topology, and chemistry) and the presence of water or salt solutions on the sorption and transport of carbon-bearing fluids. To achieve this goal OU collaborators tested test two related hypotheses: • The transport of water and aqueous electrolytes in nanopores is controlled by pore size, pore wall composition, and the type of salt – structure-maker (e.g., CaCl 2 ) versus structure-breaker (e.g., NaCl) that affect the hydrogen-bonding network. • The structure, solubility, and transport of carbon-bearing molecules in water or aqueous electrolyte-filled nanopores are controlled by the substrate type including degree of hydration, and pore features, and regulated by the hydration structure of the guest molecules.

58 GEOSCIENCES↗
DOE OSTI2021

Architected mesoporous crystalline magnesium silicates with ordered pore structures

Novel approaches to harness earth abundant silicates as building blocks for carbon dioxide removal, capture, utilization, and storage are gaining increasing attention in the context of sustainable and low carbon energy and resource recovery. Advancing a calibrated understanding of these fluid-silicate interactions is essential for developing scalable processes. One of the challenges in developing predictive controls over these interactions is the compositional and morphological heterogeneity of naturally occurring, heterogeneous magnesium silicate minerals. To address this challenge, the synthesis of architected mesoporous crystalline magnesium silicate (Mg 2 SiO 4 ) is proposed. While synthesis routes for producing amorphous mesoporous magnesium silicates have been developed via sol-gel methods, approaches to synthesize crystalline magnesium silicates with well-controlled pore size distributions have not been explored. The conventional approaches of converting matter that is amorphous to crystalline states at elevated temperatures results in a heterogeneous pore size distribution. To develop controls on pore size distribution, amorphous mesoporous magnesium silicates are coated with carbon. This approach preserves the pore size distributions during the amorphous to crystalline transformations of Mg-silicates at elevated temperatures. The carbon coating is removed on heating. Magnesium silicate particles produced using this approach have highly ordered pores around 2.58 nm and a specific surface area of 124.25 m 2 /g. In this study, we report the chemical compositions, morphologies, phase transitions, and pore structures of the intermediate materials produced during the synthesis of crystalline mesoporous magnesium silicates. The transitions, and pore structures of the intermediate materials produced during the synthesis of crystalline mesoporous magnesium silicates. Furthermore, the synthesis routes discussed in this study can be applied translationally to produce metal silicates with ordered mesoporous structures.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Role of pore dilation in molecular transport through the nuclear pore complex: Insights from polymer scaling theory

The nuclear pore complex (NPC), a channel within the nuclear envelope filled with intrinsically disordered proteins, regulates the transport of macromolecules between the nucleus and the cytoplasm. Recent studies have highlighted the NPC’s ability to adjust its diameter in response to the membrane tension, underscoring the importance of exploring how variations in pore size influence molecular transport through the NPC. In this study, we investigated the relationship between pore size and transport rate and proposed a mathematical model describing this connection. We began by theoretically analyzing how the pore size scales with the characteristic dimensions of the mesh-like structure within the pore. By introducing key assumptions about how the meshwork structure influences molecular diffusion, we derived a mathematical expression for the transport rate based on the size of the pore and the transported molecules. To validate our model, we conducted Brownian dynamics simulations using a coarse-grained representation of the NPC. These simulations, performed across a range of pore sizes, demonstrated strong agreement with our model’s predictions, confirming its accuracy and applicability. Our model is specifically tailored for small-to-medium-sized molecules, approximately 5 nanometers in size, making it relevant to a wide range of transcription factors and signaling molecules. It also extends to molecules with weak and transient interactions with FG-Nups, such as importin-β. By presenting this model formula, our study offers a quantitative framework for analyzing the effects of pore dilation on nucleocytoplasmic transport.

Biochemistry & Molecular Biology↗
DOE OSTI2021

Engineering Graphene-Ceramic 3D Composite Foams by Freeze Drying

A 3D graphene foam produced by the chemical vapor deposition (CVD) technique is recognized as an effective nanofiller material, as it does not agglomerate in the matrix. Though CVD facilitates pristine graphene foam production, the method poses limitations in developing large-scale 3D graphene composite foams as advanced engineering materials. In this paper, a freeze-drying (FD) process is used to produce a composite 3D foam, which is a mixture of graphene nanoplatelet (GNP) and a low-temperature co-fired ceramic (LTCC). The freeze-dried GNP-LTCC reticulated 3D composite foam has an average pore size ranging from 70 to 100 μm. Pore size is varied by regulating the heat transfer rate during the freezing process using a thermally conductive aluminum (Al) mold and a thermally insulating acrylonitrile butadiene styrene (ABS) mold. Computational thermal modeling is used to visualize the heat transfer and its effect on foam pore size. Subsequently, a freeze-dried GNP-LTCC composite foam is embedded into the LTCC matrix to form a hierarchical assembly by a spark plasma technique without compromising the 3D structure of the FD foam. This study established that a simple, eco-friendly, and scalable processing methodology can produce advanced graphene-based 3D composite foams as the future tailorable nanofillers for designing multimatrix materials.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Quantitative microstructural investigation of 3D-printed and cast cement pastes using micro-computed tomography and image analysis

Highlights: • Processing alters the microstructure in 3D-printed lamellar cubic element. • A unique patterned and connected pore microstructure network exists. • Micro-channels are connected through micro-pores present at interfaces regions. • Three distinct pore volume domains exists in hardened microstructure. • Volume and frequency of pore, hydrated, and unhydrated clusters are dissimilar. Microstructural phases and mechanical properties of lamellar 3D-printed and cast hardened cement paste (hcp) elements were investigated using a lab-based X-ray microscope at two levels of magnification (0.4× and 4×). K-means clustering was used for quantitative image analysis. The entire volume of intact 3-days-old 3D-printed and cast hcp elements was characterized at 0.4× magnification. Three microstructural features (macro-pores, micro-channels, and interfacial micro-pores) were found to reside in three distinct pore size domains. The largest pores of the 3D-printed element were larger than the largest pores of the reference cast hcp element. Moreover, the smallest pore sizes of the 3D-printed element were found to be smaller than those present in the cast counterparts. Micro-channels were found to be connected to one another through the micro-pores present at interfacial regions, indicating the presence of a uniquely patterned and interconnected pore network. The role of locally weak and porous interfaces on mechanical response and fracture properties is discussed.

36 MATERIALS SCIENCE↗
DOE OSTI2024

DRIFT: Diffusivity Regulation of Isotopes by nanoconFinementT

Spontaneous isotope fractionation has been reported under nanoconfinement conditions in naturally occurring systems, but the origin of this phenomena is currently unknown. Two existing hypotheses have been proposed, one based on changes in the solvation environment of the isotopes that reduces the non-mass dependent hydrodynamics contribution to diffusion. The other is that isotopes have mass-dependent surface adsorption, varying their total diffusion through nanoconfined channels. To investigate these hypotheses, benchtop experiments, nuclear magnetic resonance (NMR) spectroscopy, and molecule scale modeling were applied. Classical molecular dynamics simulations identified that the Na + and Cl - hydration shells across the three different salt solutions ( 22 Na 35 Cl, 23 Na 35 Cl, 24 Na 35 Cl) did not vary as a function of the Na + isotope, but that there was a significant pore size effect, with larger hydration shells at larger pore sizes. Additionally, while total adsorption times did not vary as a function of the Na + isotope or pore size, the free ion concentration, or those adsorbed on the surface for <5% of the simulation time did exhibit isotope dependence. Experimentally, challenges occurred developing a repeatable experiment, but NMR characterization of water diffusion rates through ordered alumina membranes was able to identify the existence of two distinct water environments associated with water inside and outside the pore. Further NMR studies could be used to confirm variation in hydration shells and diffusion rates of dissolved ions in water. Ultimately, mass-dependence adsorption is a primary driver of variations in isotope diffusion rates, rather than variation in hydration shells that occur under nanoconfinement.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2022

Electrochemical Control of the Morphology and Functional Properties of Hierarchically Structured, Dendritic Cu Surfaces

Electrodeposited dendritic copper foams have been extensively studied as an electrocatalyst for CO 2 reduction reaction (CO 2 RR). Many parameters, such as dendrite size, porosity, pore size, and crystal faceting, define the hierarchical properties of these structures and their subsequent bubble evolution and CO 2 RR capabilities. Herein, the effects the electrodeposition conditions (potential, pH) have on the resulting crystallinity, microstructure, and macroporosity of the copper foam are studied. These morphological differences and the corresponding effects on electrocatalytic activity are characterized. It is shown that the composition of the electrodeposition bath can have significant effects on the mechanics of bubble formation and detachment at the surface during hydrogen evolution reaction in acidic solutions. Similarly, the electrodeposition conditions for the synthesis of the foam affect the product selectivity during CO 2 RR electrocatalysis. As a result, foams deposited in alkaline electrodeposition solutions show high faradaic efficiency and specificity toward C 2 H 6 , an uncommon product of CO 2 RR, at modest applied potentials (−0.8 V versus reversible hydrogen electrode.

14 SOLAR ENERGY↗
DOE OSTI2023

Precise Pore Engineering of fcu–Type Y–MOFs for One–Step C 2 H 4 Purification from Ternary C 2 H 6 /C 2 H 4 /C 2 H 2 Mixtures

The purification of C 2 H 4 from C 2 H 6 /C 2 H 4 /C 2 H 2 mixtures is of great significance in the chemical industry for C 2 H 4 production but remains a daunting task. Guided by powerful reticular chemistry principles, herein a systematic study is carried out to engineer pore dimensions and pore functionality of fcu-type Y-based metal–organic frameworks (Y-MOFs) through the construction of a series of eight new structures using linear dicarboxylate linkers with different length and functional groups. This study illustrates how delicate changes in pore size and pore surface chemistry can effectively influence the adsorption preference of C 2 H 6 , C 2 H 4 , and C 2 H 2 by the MOFs. Importantly, clear relations between pore size/pore surface polarity and C 2 adsorption selectivities of this series of MOFs are established. In particular, HIAM-326 built on a linker decorated with trifluoromethoxy group shows notably preferential adsorption of C 2 H 6 and C 2 H 2 over C 2 H 4 , with balanced C 2 H 2 /C 2 H 4 and C 2 H 6 /C 2 H 4 selectivities. Furthermore, this endows the compound with the capability of one-step purification of C 2 H 4 from C 2 H 6 /C 2 H 4 /C 2 H 2 ternary mixtures, which is validated by breakthrough measurements where high purity C 2 H 4 (99.9%+) can be obtained directly from the separation column. Its adsorption thermodynamics and underlying selective adsorption mechanisms are further revealed by ab initio calculations.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Mechanical analysis of heterogeneous materials with higher-order parameters

Abstract Even though heterogeneous porous materials are widely used in a variety of engineering and scientific fields, such as aerospace, energy-storage technology, and bio-engineering, the relationship between effective material properties of porous materials and their underlying morphology is still not fully understood. To contribute to this knowledge gap, this paper adopts a higher-order asymptotic homogenization method to numerically investigate the effect of complex micropore morphology on the effective mechanical properties of a porous system. Specifically, we use the second-order scheme that is an extension of the first-order computational homogenization framework, where a generalized continuum enables us to introduce length scale into the material constitutive law and capture both pore size and pore distribution. Through several numerical case studies with different combinations of porosity, pore shapes, and distributions, we systematically studied the relationship between the underlying morphology and effective mechanical properties. The results highlight the necessity of higher-order homogenization in understanding the mechanical properties and reveal that higher-order parameters are required to capture the role of realistic pore morphologies on effective mechanical properties. Furthermore, for specific pore shapes, higher-order parameters exhibit dominant influence over the first-order continuum.

42 ENGINEERING↗
DOE OSTI2021

Autogenous shrinkage and hydration property of alkali activated slag pastes containing superabsorbent polymer

In this paper, the superabsorbent polymer (SAP) was applied as internal curing agent to study its effect on the autogenous shrinkage and hydration property of alkali activated slag (AAS) pastes. Liquid absorption and release processes of SAP in AAS pastes were characterized by {sup 1}H nuclear magnetic resonance ({sup 1}H NMR). Moreover, the microstructure and mechanical strength of AAS pastes containing SAP were also revealed. The results showed that the autogenous shrinkage of AAS pastes containing SAP was reduced by about 80.6%, 72.1% and 72.6%, respectively as the silicate modulus (Ms) increased from 0.8 to 1.4. The addition of SAP delayed the second exothermic peak, but increased the cumulative heat of AAS pastes. In addition, internal curing by SAP could promote the generation of C-A-S-H gels and hydrotalcite-like phases and increase the reaction degree of slag, particularly for AAS pastes with higher Ms, being attributed to the continuous release of entrained water and alkali activator solutions in SAP with the increase of hydration time. Furthermore, the addition of SAP would increase capillary pore size and pore volume of AAS pastes, and thus lead to the decrease of compressive strength.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Confinement-mediated phase behavior of hydrocarbon fluids: Insights from Monte Carlo simulations

The phase behavior of hydrocarbon fluids confined in porous media has been discussed to deviate significantly from that in the bulk environment due to the existence of sub-10nm pores. Though experiments and simulations have measured the bubble/dew points and sorption isotherms of hydrocarbons confined in both natural and synthetic nanopores, the confinement effects in terms of the strength of fluid-pore interactions tuned by surface wettability and chemistry have received comparably less discussion. More significantly, the underlying physics of confinement-induced phenomena remain obfuscated. In this work, we studied the phase behavior and capillary condensation of n-hexane to understand the effects of confinement at the molecular level. To systematically investigate the pore effects, we constructed two types of wall confinements; one is a structureless virtual wall described by the Steele potential and the other one is an all-atom amorphous silica structure with surface modified by hydroxyl groups. Our numerical results demonstrated the importance of fluid-pore interaction, pore size, and pore morphology effects in mediating the pressure-volume-temperature (PVT) properties of hydrocarbons. The most remarkable finding of this work was that the saturation pressure predicted from the van der Waals-type adsorption isothermal loop could be elevated or suppressed relative to the bulk phase, as illustrated in the graphical abstract. As the surface energy (i.e., fluid-pore interaction) decreased, the isothermal vapor pressure increased, indicating a greater preference for the fluid to exist in the vapor state. Sufficient reduction of the fluid-pore interactions could even elevate the vapor pressure above that of the bulk fluid.

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

Tailoring Nanoporous Silica and Natural Straw Structural Insulation Composites

Nanoporous silica exhibits ultralow thermal conductivity as a result of its nanoscale pore size, high pore volume, and specific surface area. In this study, we report the self-assembled surfactant-templated synthesis of nanoporous silica, which is integrated with cellulose fibers derived from natural straw to manufacture high thermal insulation and mechanically robust nanocomposites. The nanocomposite shows a low thermal conductivity of 22.5 mW/(m·K), a compressive modulus of 0.93 MPa, and a hydrophobicity with a water contact angle of 125°. Moreover, we observed a marked reduction in water absorption capacity and a carbon footprint of 0.21 kg CO 2 equiv/kg. Here, this study provides a pathway toward the development of nanoporous structural insulation materials for energy-efficient building applications.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Separation of alkane and alkene mixtures by metal–organic frameworks

The separation of alkane/alkene gas mixtures represents an important yet challenging process in the petrochemical industry to produce valuable chemical feedstocks with sufficiently high purity. These molecules have similar physical properties, making their separation difficult and capital-intensive. The current separation and purification technology relies largely on heat-driven distillations with a huge unit composed of hundreds of trays. Adsorptive separation using porous solids is capable of accomplishing the purification under ambient conditions, offering potential energy and environmental benefits. In particular, metal–organic frameworks (MOFs) hold enormous promise for this separation process in light of their highly tunable pore shape, pore size, and pore surface functionality. In this review article, we provide a comprehensive account of metal–organic frameworks that have been investigated for the separation of alkanes and alkenes with a focus on C 2 –C 3 hydrocarbons. Here, the material design rationale, separation mechanisms, and structure–property relations are highlighted. Finally, the existing challenges and possible design strategies for desirable materials are also discussed.

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

Relative-Humidity Dependence of Electrochemically Active Surface Area in Porous Carbon Catalyst Layers

Polymer-electrolyte fuel cells (PEFCs) utilize porous catalyst layers (CLs) formed of carbon supports on which Pt particles are deposited and ionomer films are distributed. Carbon supports themselves have varying degrees of porosity, where high-surface-area carbon (HSC) supports possess nanometer-sized interior pores that are suitable for Pt nanoparticle deposition but prevent deleterious ionomer penetration. However, this requires protons to transport through water pathways inside the pores. To understand the generation of such pathways, we examine the various mechanisms of water uptake by PEFC CLs, and the subsequent impact of water uptake on Pt utilization through developing a multiphysics model of the water wetting phenomena as a function of relative humidity. The model details water uptake via ionomer absorption, capillary condensation in the hydrophilic pores, and surface adsorption using molecular potential that account for various water and surface dipole interactions. The results quantify how mesoporous carbons with highly hydrophilic pores increase Pt utilization through the development of wetted layers, which at the same time enable optimized gas-transport pathways. It also demonstrates the impact of pore-size distribution (PSD) and physical and chemical parameters on the water uptake phenomena, allowing for future CL particle and structure optimization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗