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At least 181 records · Page 10

Pentiptycene-based ladder polymers with configurational free volume for enhanced gas separation performance and physical aging resistance

Significance Gas separation membranes are an emerging energy-efficient alternative toward conventional, energy-intensive separation technologies such as cryogenic distillation. Ladder polymers with intrinsic microporosity show exceptional promise toward redefining state-of-the-art gas separation membranes due to their high permeability (throughput) and selectivity (separation efficiency). However, they are typically inhibited by major reductions in permeability over time due to collapsing membrane free volume (open space between polymer chains), forfeiting their greatest asset. This work explores a route toward enhanced aging resistance and overall separation performance by incorporating pentiptycene (an H-shaped scaffold containing five fused arene rings) into ladder-like polymers to incorporate natural, more permanent “micropores” that aren’t susceptible to densification of polymer chains that occurs over time in traditional microporous polymers.

36 MATERIALS SCIENCE↗

Evaluation of subsurface transport processes of delayed gas signatures applicable to underground nuclear explosions

Radioactive gas signatures from underground nuclear explosions (UNEs) result from gas-migration processes occurring in the subsurface. The processes considered in this study either drive or retard upward migration of gases from the detonation cavity. The relative importance of these processes is evaluated by simulating subsurface transport in a dual-permeability medium for the multi-tracer Noble Gas Migration Experiment (NGME) originally intended to study some aspects of transport from a UNE. For this experiment, relevant driving processes include weak two-phase convection driven by the geothermal gradient, over pressuring of the detonation cavity, and barometric pumping while gas sorption, dissolution, radioactive decay, and usually diffusion represent retarding processes. From deterministic simulations we found that over-pressuring of the post-detonation chimney coupled with barometric pumping produced a synergistic effect amplifying the tracer-gas reaching the surface. Bounding simulations indicated that the sorption and dissolution of gases, tending to retard transport, were much smaller than anticipated by earlier laboratory studies. The NGME observations themselves show that differences in gas diffusivity have a larger effect on influencing upward transport than do the combined effects of tracer-gas sorption and dissolution, which is consistent with a Sobol’ sensitivity analysis. Both deterministic simulations and those considering parametric uncertainties of transport-related properties predict that the excess in concentration of SF 6 compared to 127 Xe as might be captured in small volumetric samples should be much smaller than the order-of-magnitude contrast found in the large-volume gas samples taken at the site. While extraction of large-volume subsurface gas samples is shown to be capable of distorting in situ gas compositions, the highly variable injection rate of SF 6 into the detonation cavity relative to that of 127 Xe at the start of the field experiment is the most likely explanation for the large difference in observed concentrations.

58 GEOSCIENCES↗

Permeability scaling relationships of volcanic tuff from core to field scale measurements

A recent chemical explosive test in P-Tunnel at the Nevada National Security Site, Nevada, USA, was conducted to better understand how signals propagate from explosions in the subsurface. A primary signal of interest is the migration of gases that can be used to differentiate chemical from nuclear explosions. Gas migration is highly dependent on the rock permeability which is notoriously difficult to determine experimentally in the field due to a potentially large dependence on the scale over which measurements are made. Here, we present pre-explosion permeability estimates to characterize the geologic units surrounding the recent test. Permeability measurements were made at three scales of increasing size: core samples (≈2 cm), borehole packer system tests (≈1 m), and a pre-shot cavity pressurization test (> 10 m) across ten tuff units. Permeability estimates based on core measurements showed little difference from borehole packer tests. However, permeability in most rock units calibrated from cavity pressurization tests resulted in higher permeability estimates by up to two orders of magnitude. Here, we demonstrate that the scale of the measurement significantly impacts the characterization efforts of hydraulic properties in volcanic tuff, and that local-scale measurements (< 10 m scale) do not incorporate enough heterogeneity to accurately predict field-scale flow and mass transport.

Environmental sciences↗

Leveraging Free Volume Manipulation to Improve the Membrane Separation Performance of Amine‐Functionalized PIM‐1

Abstract Gas‐separation polymer membranes display a characteristic permeability–selectivity trade‐off that has limited their industrial use. The most comprehensive approach to improving performance is to devise strategies that simultaneously increase fractional free volume, narrow free volume distribution, and enhance sorption selectivity, but generalizable methods for such approaches are exceedingly rare. Here, we present an in situ crosslinking and solid‐state deprotection method to access previously inaccessible sorption and diffusion characteristics in amine‐functionalized polymers of intrinsic microporosity. Free volume element (FVE) size can be increased while preserving a narrow FVE distribution, enabling below‐upper bound polymers to surpass the H 2 /N 2 , H 2 /CH 4 , and O 2 /N 2 upper bounds and improving CO 2 ‐based selectivities by 200 %. This approach can transform polymers into chemical analogues with improved performance, thereby overcoming traditional permeability–selectivity trade‐offs.

Mizrahi Rodriguez, Katherine↗

Molecular design and fabrication of PIM-1/polyphosphazene blend membranes with high performance for CO 2 /N 2 separation

New polymeric blend membranes for CO 2 separation were synthesized based on insights from molecular dynamics simulation. A molecular-level structure-property relationship in polymers of intrinsic microporosity (PIM) based blend membranes, was investigated in detail computationally. Calculated local density profiles and energy of interaction of the blend membranes, composed of PIM-1 and various polyphosphazenes, showed that using the polyphosphazene with a higher concentration of ether side chains can improve the compatibility with PIM-1. Furthermore, based on the findings of computational studies, blend membranes were experimentally fabricated from PIM-1 and polyphosphazenes with various polyether side chain concentrations. Polyether concentration in polyphosphazenes was correlated with the film properties and gas transport performance of the blend membranes. Blend membranes showed very high CO 2 permeability (3100-5300 barrer) and improved CO 2 /N 2 selectivity (24-28), outperforming all other PIM-based blend membranes reported to date. Moreover, the CO 2 permeability performance of the blend membranes was tested 566 hours under real post-combustion flue gas from a coal-fired power plant, including CO 2 , N 2 , H 2 O, O 2 , SO x and NO x .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Large-Volume Stimulation of Rock for Greatly Enhanced Fluids Recovery using Targeted Seismic-Assisted Hydraulic Fracturing (Final Technical Report)

This project has developed and demonstrated a new technology for large-volume and targeted comminution of rock in low permeability formations to enhance recovery from unconventional oil and gas (UOG) resources. The technology is based on a strategically designed interaction of multiple induced seismic pulses that assist the hydraulic fracturing process to enhance shear and multi-planar crack formation. This greatly increased rock stimulation, through bulk comminution, is expected to cause significant increase in permeability leading to enhancement of recovery factors for sub- surface fluids. The proposed technology is especially applicable for enhanced recovery in emerging UOG plays, such as ductile shales that are resistant to opening-mode fracturing by conventional hydraulic fracturing processes. The project combines an integrated experimental and computation approach to develop and demonstrate a modular technology that can be easily implement in the field to augment current practices. The effort integrates a fundamental scientific understanding of dynamic material response under constraint and damage-induced permeability and porosity enhancements at multiple length scales, along with models of comminution due to the local release of kinetic energy associated with high shear strain rate of dynamic deformation. The results will be validated through small-scale experiments and then implemented in a lab-scale field test to demonstrate the developed technology. The project involves collaboration between a solid mechanician, a materials scientist, and a petroleum engineering geo-mechanician. It builds on a successful history of success and collaboration that includes both fundamental scientific exploration and technology development.

04 OIL SHALES AND TAR SANDS↗

Surface effects on deuterium permeation through vanadium membranes

Dense vanadium-based membranes offer high permeability and perfect selectivity to hydrogen isotopes, maintain favorable neutronic properties, and are compatible with liquid metals such as PbLi. These properties make vanadium membranes a promising fusion fuel cycle technology for processes such as tritium extraction from PbLi and exhaust processing. Surface contamination has a deleterious effect on the gas-phase hydrogen permeation through vanadium, and the reported permeabilities range from 10 -14 to 10 -7 mol m -1 s -1 Pa -0.5 . Thin dense films of palladium applied to clean vanadium surfaces enable a consistently high hydrogen permeability. In this study, uncoated vanadium resulted in deuterium permeabilities ranging from 2.8 × 10 -11 to 6.4 × 10 -9 mol m -1 s -1 Pa -0.5 at 300 °C–700 °C, respectively. Post-test analysis revealed a VO x surface layer and VC x subsurface layer formed on the feed side, while the as-received surface oxide dissolved leaving a submonolayer oxide on the permeate surface. Furthermore, the Pd-coated V resulted in a maximum deuterium permeability of 2.1 × 10 -7 m -1 s -1 Pa -0.5 at 375 °C upon activation of the Pd surface by oxidation and reduction. The deuterium permeation declined upon heating to 500 °C due to intermetallic diffusion between the Pd and V. The Mo 2 C-coated V resulted in deuterium permeabilities ranging from 2.7 × 10 -10 to 1.8 × 10-9 at 500 °C–700 °C, respectively, and a post-test analysis found the carbon in the Mo 2 C layer had dissolved into the V near the interface.

13 HYDRO ENERGY↗

Leakoff assessment of nanoparticle-stabilized CO 2 foams for fracturing applications

The leakoff of multiphase systems through porous media is a complicated process. In this study, we have designed an experimental setup that is used to assess the leakoff of the liquid and gas phase under pressurized conditions. The novelty of this study is that while most previous studies utilized fluid/gas in the aqueous phase, nanoparticles are introduced in this study, which formed a solid/fluid/gas multiphase system to boost foam performance and reduce leakoff. In the parametric experimental analysis, the effects of foam quality, core permeability, surfactant concentration, and polymer concentration on the dynamic and static leakoff rates of liquid and gas are evaluated. It was found that core permeability affects the leakoff of foam the most with a leakoff coefficient of up to 1.37015 $ft/\sqrt{min}$ for gas and up to 0.1056 $ft/\sqrt{min}$ for liquid under the experiment settings herein. The leakoff rate of gas is generally several magnitudes higher than that of the liquid. When CO 2 gas is present in the foam, the leakoff coefficient falls in the range between 0 and 1.37015 $ft/\sqrt{min}$ for gas, and between 0.0005 and 0.1056 $ft/\sqrt{min}$ for liquid. Finally, the methodology and results of this study shed light on the mechanistic understanding of the leakoff properties of multiphase systems and could be used to assist the design of foam fracturing for reservoir stimulation.

03 NATURAL GAS↗

Shale gas: Geochemical and physical constraints on genesis, storage, and producibility

Our research project on shale gas included two tasks: (1) Testing of different shales’ ability to geocatalytically generate natural gas at low temperatures; verification of geocatalytic methanogenesis would potentially render shale gas a quasi-renewable resource, and (2) quantification and characterization of porosity and permeability in organic-rich rocks with implication for producibility. Adequate porosity is required for geological storage of shale gas. At the same time, pore connectivity is essential for gas producibility.

03 NATURAL GAS↗

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↗

Risk assessment of wellbore leakage during underground hydrogen storage

The expansion of renewable energy sources would require large-scale energy storage options to overcome the intermittent nature of these sources. Underground hydrogen storage (UHS) in depleted hydrocarbon reservoirs offers a scalable and practical energy storage solution. These reservoirs are chosen for their availability and large capacity, but the unique properties of hydrogen raise concerns about potential leakage pathways, particularly through wellbores. In this study, we develop and apply, for the first time, reduced-order models (ROMs) specifically designed for efficient leakage risk prediction in UHS systems operating in depleted hydrocarbon reservoirs. Using 3,000 high-fidelity simulation scenarios, we examine the influence of 11 key parameters, including reservoir and aquifer depths, wellbore permeability and porosity, initial saturations of water, oil and gas fractions (hydrogen, light, intermediate, and heavy hydrocarbons), reservoir pressure multiplier, and the aquifer-to-reservoir volume ratio, to simulate leakage behavior over a 1,000-year timescale. We train ROMs using a two-step classification-regression approach, achieving R 2 values exceeding 99 % across all targets. These ROMs effectively capture the leakage evolution and identify critical controls of leakage, guiding the design of mitigation strategies. Results indicate that gas leakage occurs in about 27 % of scenarios as early as five years post-operation, reaching volumes of up to 106 ft3. Oil leakage is less frequent (~17 %) and typically begins decades later. Our findings also show that hydrogen often migrates first, owing to its smaller molecular size and higher buoyancy, followed by heavier hydrocarbons. Over time, these heavier components contribute significantly to the total leaked volume, reinforcing the need for targeted monitoring and remediation strategies. Our analysis highlights that deeper storage reservoirs, shallower aquifers, and low-permeability wellbores significantly reduce leakage risks. In conclusion, this work offers a robust framework for risk-informed UHS deployment, supporting energy security through reliable large-scale hydrogen storage while safeguarding environmental integrity.

08 HYDROGEN↗

Improving Gas Selectivity in Membranes Using Polymer-Grafted Silica Nanoparticles

Herein, we demonstrate that tuning of structural parameters and material chemistry enables control of the permeability and selectivity of gases (CO 2 , He, and CH 4 ) in membranes based on poly(butyl methacrylate)-grafted nanoparticles (PGNs). Our data show that the presence of nanoparticles and the overall dense packing of grafted chains noticeable in PGNs with low grafting density have an adverse effect on the diffusivity of gases. This effect is compensated by an improvement in the solubility of CO 2 gas promoted by the silica nanoparticle surface, yielding a substantial improvement in the permeability of CO 2 versus CH 4 . Furthermore, in membranes with high grafting density, changes in the structural arrangements and alterations in the membrane porosity, evident from small-angle X-ray scattering and positron annihilation lifetime spectroscopy, positively influence the permeability of He and CO 2 gases. In contrast, CH 4 permeability in the same membranes is significantly suppressed, suggesting the formation of a unique, highly selective environment for gas separation. As a result, an improvement of up to 50% in selectivity for gas pairs containing large CH 4 molecules is observed. Our studies provide fundamental insights into the role that structural parameters play in gas transport through polymer membranes, laying a foundation for the rational design of membranes with improved permeability and selectivity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Carbon nanotube-based mixed-matrix membranes with supramolecularly engineered interface for enhanced gas separation performance

Here in this study, novel nanocomposite membranes were fabricated from single-walled carbon nanotubes (SWNTs) and a triptycene-containing polyimide. The desirable interfacial morphology and homogenous dispersion of SWNTs were achieved by strong π-π stacking and supramolecular shape-fitting interactions between the nanotube and the paddlewheel-shaped triptycene moieties in polymer matrix. Mixed-matrix membranes (MMMs) containing 2–15 wt% of as-purchased SWNTs (AP-SWNTs) were prepared and tested for their gas transport properties. While all MMMs showed greatly enhanced permeabilities with well-maintained selectivities, a non-linear dependence of permeability on filler content was observed. Another series of MMMs with purified SWNTs (P-SWNTs) and acid-treated SWNT (A-SWNTs) were also prepared. The functionalized A-SWNT MMM exhibited the best separation performance at 2 wt% filler content among all MMMs, which can be attributed to the improved interfacial affinity with carboxylic acid functionalized surface of A-SWNTs.

42 ENGINEERING↗

Brine Availability Test in Salt (BATS) FY21 Update

This report summarizes the 2021 fiscal year (FY21) status of ongoing borehole heater tests in salt funded by the disposal research and development (R&D) program of the Office of Spent Fuel & Waste Science and Technology (SFWST) of the US Department of Energy’s Office of Nuclear Energy’s (DOE-NE) Office of Spent Fuel and Waste Disposition (SFWD). This report satisfies SFWST milestone M2SF- 21SN010303052 by summarizing test activities and data collected during FY21. The Brine Availability Test in Salt (BATS) is fielded in a pair of similar arrays of horizontal boreholes in an experimental area at the Waste Isolation Pilot Plant (WIPP). One array is heated, the other unheated. Each array consists of 14 boreholes, including a central borehole with gas circulation to measure water production, a cement seal exposure test, thermocouples to measure temperature, electrodes to infer resistivity, a packer-isolated borehole to add tracers, fiber optics to measure temperature and strain, and piezoelectric transducers to measure acoustic emissions. The key new data collected during FY21 include a series of gas tracer tests (BATS phase 1b), a pair of liquid tracer tests (BATS phase 1c), and data collected under ambient conditions (including a period with limited access due to the ongoing pandemic) since BATS phase 1a in 2020. A comparison of heated and unheated gas tracer test results clearly shows a decrease in permeability of the salt upon heating (i.e., thermal expansion closes fractures, which reduces permeability).

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Theoretical Pathway toward Improved Reverse Osmosis Membrane Selectivity for Neutral Solutes: Inspiration from Gas Separations

We report highly rigid membrane materials with tailored structures have exhibited permeabilities and selectivities that exceed the polymer upper bound in gaseous and organic solvent separations for challenging mixtures containing species that are similar in size and shape. One potential question is whether such membrane materials can maintain meaningful guest diffusivities in situations where the microporous spaces are essentially full of guest molecules. Here, we use a simplified transition state theory approach to estimate the diffusivity of water and small organics within a microporous membrane. The transition state theory model is parameterized using experimental values from zeolites and carbon molecular sieve materials found in the literature. We demonstrate the differences in transport and Maxwell–Stefan diffusivities based on guest species loading with different isotherm behaviors. These calculations theorize a path forward for highly selective reverse osmosis membranes for aqueous phase separations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Diatom influence on the production characteristics of hydrate-bearing sediments: Examples from Ulleung Basin, offshore South Korea

The Ulleung Basin Gas Hydrate field expeditions in 2007 (UBGH1) and 2010 (UBGH2) sought to assess the Basin's gas hydrate resource potential. Coring operations in both expeditions recovered evidence of gas hydrate, primarily as fracture-filling (or vein type) morphologies in mainly silt-sized, fine-grained sediment, but also as pore-occupying hydrate in the coarser-grained layers of interbedded sand and fine-grained systems. A commonality across many of these occurrences is the presence of diatoms in the fine-grained sediment. Here we tested fine-grained sediment (median grain size <12.5 μm) associated with hydrate occurrences at four UBGH2 sites (UBGH2-2-2, UBGH2-3, UBGH2-6 and UBGH2-11) to investigate potential impacts of diatoms on efforts to extract methane from hydrate, or to tap hydrocarbon reservoirs beneath hydrate-bearing sediment. Two key considerations are: the extent to which diatoms control sediment mechanical properties, and the extent to which pore-water freshening, which occurs as gas hydrate breaks down during resource extraction, alters the diatom control on sediment mechanical properties. We conducted experiments to measure sediment index properties, sedimentation behavior and compressibility to address these considerations. We relied on scanning electron microscope (SEM) imagery and X-ray powder diffraction (XRD) to characterize the sediment mineralogy. Our high-level findings are that at the ~20–45% (by volume) diatom concentrations observed at these UBGH2 sites, sediment compressibility increases with diatom content, but diatoms only appear to increase porosity and permeability at the highest diatom concentration (~45%). Our measurements suggest in situ compression indices of 0.35–0.55 and permeabilities on the order of 0.01milliDarcies (1 × 10 -17 m 2 ) can be anticipated at these sites. Importantly, these properties are not expected to vary significantly upon pore water freshening that accompanies gas hydrate dissociation during production.

58 GEOSCIENCES↗