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At least 469 records · Page 26

All sources NASA NTRS DOE OSTI

DOE OSTI2020

Water-polyamide chemical interplay in desalination membranes explored by ambient pressure X-ray photoelectron spectroscopy

Reverse osmosis using aromatic polyamide membranes is currently the most important technology for seawater desalination. The performance of reverse osmosis membranes is highly dependent on the interplay of their surface chemical groups with water and water contaminants. In order to better understand the underlying mechanisms of these membranes, we study ultrathin polyamide films that chemically resemble reverse osmosis membranes, using ambient pressure X-ray photoelectron spectroscopy. This technique can identify the functional groups at the membrane–water interface and allows monitoring of small shifts in the electron binding energy that indicate interaction with water. We observe deprotonation of free acid groups and formation of a ‘water complex’ with nitrogen groups in the polymer upon exposure of the membrane to water vapour. The chemical changes are reversed when water is removed from the membrane. While the correlation between functional groups and water uptake is an established one, this experiment serves to understand the nature of their chemical interaction, and opens up possibilities for tailoring future materials to specific requirements.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Potential-induced wetting and dewetting in pH-responsive block copolymer membranes for mass transport control

Wetting and dewetting behavior in channel-confined hydrophobic volumes is used in biological membranes to effect selective ion/molecular transport. Artificial biomimetic hydrophobic nanopores have been devised utilizing wetting and dewetting, however, tunable mass transport control utilizing multiple transport modes is required for applications such as controllable release/transport, water separation/purification and energy conversion. Here, we investigate the potential-induced wetting and dewetting behavior in a pH-responsive membrane composed of a polystyrene-b-poly(4-vinylpyridine) (PS-b-P4VP) block copolymer (BCP) when fabricated as a hierarchically-organized sandwich structure on a nanopore electrode array (NEA), i.e. BCP@NEA. At pH < pK a (P4VP) (pK a ~ 4.8), the BCP acts as an anion-exchange membrane due to the hydrophilic, protonated P4VP cylindrical nanodomains, but at pH > pK a (P4VP), the P4VP domains exhibit charge-neutral, hydrophobic and collapsed structures, blocking mass transport via the hydrophobic membrane. However, when originally prepared in a dewetted condition, mass transport in the BCP membrane may be switched on if sufficiently negative potentials are applied to the BCP@NEA architecture. When the hydrophobic BCP membrane is introduced on top of 2-electrode-embedded nanopore arrays, electrolyte solution in the nanopores is introduced, then isolated, by exploiting the potential-induced wetting and dewetting transitions in the BCP membrane. The potential-induced wetting/dewetting transition and the effect on cyclic voltammetry in the BCP@NEA structures is characterized as a function of the potential, pH and ionic strength. Additionally chronoamperometry and redox cycling experiments are used to further characterize the potential response. The multi-modal mass transport system proposed in this work will be useful for ultrasensitive sensing and single-molecule studies, which require long-time monitoring to explore reaction dynamics as well as molecular heterogeneity in nanoconfined volumes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

Quantum water desalination: Water generation through separate pathways for protons and hydroxide ions in membranes

Much of the water desalination strategies has focused on designing pores and membranes that transport water and reject ions and other molecules at a high rate. In this paper, we discuss an approach where protons (H+) and hydroxide (OH−) ions are transported via different mechanisms through a porous membrane, and subsequently, once they have been transported through the membrane, they recombine to generate water. 2D materials such as graphene and MoS2 have generated significant interest for applications such as desalination. Here, we explore the applicability of one such 2D material—a cubic Ti2C MXene membrane—in desalination by creating a OH− ion selective pore, which significantly suppresses protons but allows OH− ions and water to go through. The catalytic properties of MXenes enable the dissociation of water on the surface, and the dissociated protons translocate through the membrane via quantum-dominated phenomena such as hopping from interstitial-to-interstitial. OH− ions translocate through a positively charged pore and recombine with protons on the other side of the membrane to form water. Our results indicate that water molecules generated via quantum processes can significantly enhance the overall transport of water across the membrane.

Physics↗

DOE OSTI2025

Spatiotemporal dynamics of ionic reorganization near biological membrane interfaces

Electrical signals in excitable cells involve spatially localized ionic fluxes through ion channels and pumps on cellular lipid membranes. Common approaches to understand how these fluxes spread assume that the membrane and the surrounding electrolyte comprise an equivalent circuit of capacitors and resistors, which ignores the localized nature of transmembrane ion transport, the resulting ionic gradients and electric fields, and their spatiotemporal relaxation. Here, we consider a model of localized ion pumping across a lipid membrane, and use theory and simulation to investigate how the electrochemical signal propagates spatiotemporally in and out of plane along the membrane. The localized pumping generates long-ranged electric fields with three distinct scaling regimes along the membrane: a constant potential near-field region, an intermediate monopolar region, and a far-field dipolar region. Upon sustained pumping, the monopolar region expands radially in plane with a steady speed that is enhanced by the dielectric mismatch and the finite thickness of the lipid membrane. For unmyelinated lipid membranes in physiological settings, we find remarkably fast propagation speeds of ∼ 40 m / s , allowing faster ionic reorganization compared to bare diffusion. Together, our paper shows that transmembrane ionic fluxes induce transient long-ranged electric fields in electrolyte solutions, which may play hitherto unappreciated roles in biological signaling. Published by the American Physical Society 2025

Row, Hyeongjoo (ORCID:000000033623512X)↗

DOE OSTI2024

Fabrication of model ultrafiltration membranes with uniform, high aspect ratio pores

Here, in this manuscript, we report the facile fabrication of large-area model membranes with highly uniform and high aspect ratio pores with diameters <20 nm. These membranes are useful for fundamental investigations of separation by size exclusion in the ultrafiltration regime, where species to be separated from solution have dimensions of 1–100 nm. Such investigations require membranes with narrow pores and high aspect ratios such that the Hagen–Poiseuille equation is followed, enabling well-known models such as the hindered transport model to be evaluated and other affecting factors to be ignored. We demonstrate that the sub-20 nm pores in the membrane are of sufficiently high aspect ratio such that water flux through the membrane is consistent with the Hagen–Poiseuille equation. The fabrication relies on self-assembling block copolymers to form uniform, densely packed patterns with sub-20 nm resolution, sequential infiltration synthesis to convert the block copolymer in situ into a mask with adequate contrast to etch pores with an aspect ratio >5, and low-resolution photolithography to transfer the pattern over a large area into a silicon nitride membrane. Model membranes with narrow pore-size distribution fabricated in this way provide the means to investigate parameters that impact size-selective ultrafiltration separations such as the relationships between solute or particle size and pore size, their distributions, and rejection profiles, and, therefore, test the validity or limits of separation models.

Chen, Wen↗

DOE OSTI2025

Dynamic control of molecular transport MXene transistor membranes

Controlled spatial confinement and surface properties of lamellar 2D nanomaterial membranes could enhance many precision separation processes. Traditionally, researchers view channel dimensions, surface properties, and permeation rates of these membranes as intrinsic properties that cannot be modulated in operando. We report that gate voltage applied to the conducting laminar MXene membrane can modulate the permeation rate of ions and neutral solutes, as well as its effective size rejection. In operando wide-angle x-ray scattering measurements reveal that these changes are not driven by electrically induced variations in the d spacing of the MXene layers. Instead, experimental data and continuum electrokinetic modeling reveal that ion transport through the MXene channels is primarily affected by Donnan equilibrium at the membrane-solution interface. We also report a strong increase in the permeation rates through the membrane under a low-frequency ac voltage gating regime that we attribute to diffusioosmotic flow oscillations induced in the membrane. Overall, MXene “transistor” membranes provide a previously unidentified approach to dynamic control of molecular separations.

Pendse, Aaditya [Lawrence Livermore National Labor↗

DOE OSTI2026

Membrane Degradation in PEM Fuel Cells: Part I. Modeling Gas Crossover and the Pt Band

Understanding chemical degradation of the proton-exchange membrane in fuel cells is crucial for extending their lifetimes. Herein, various degradation reactions reported in literature are organized and analyzed, including direct radical generation and an indirect (Fenton) pathway. To understand the transport of dissolved H 2 and O 2 crossover gases as they relate to membrane degradation, an agglomerate-scale model is introduced, treating gas, ionomer, and catalyst as discrete phases. The model reveals a key phenomenon: at working potentials, dissolved gases are mostly consumed at the interface between the catalyst layer and the membrane, leaving little gas to cross the membrane. Under open-circuit conditions, dissolved gases are not consumed and can then cross the membrane. This explains high H 2 O 2 concentrations and degradation rates seen in experiments but not captured in previous models. Following mixed-potential theory, crossover gases supply the hydrogen-oxidation and oxygen-reduction reactions, which occur simultaneously on individual Pt particles comprising the Pt band in the membrane, forming reactive species (H 2 O 2 , OH·). Results show crossover gas almost entirely reacts on the Pt band, allowing little to reach the opposite electrode. Furthermore, the micro-scale geometry of the catalyst-layer/membrane interface impacts the gas crossover at working potentials, indicating that cell construction affects membrane durability.

Johnson, Evan F. [Lawrence Berkeley National Labor↗

DOE OSTI2021

Development of Membrane Platforms to Interrogate Host-Pathogen Interactions

Membrane fusion is a critical step in enveloped virus entry and infection; however, molecular understanding of enveloped virus entry and treatment options remain limited. In recent decades, advances in imaging have facilitated the development of methods to study single virus events and membrane organization providing insight towards entry mechanisms. Through these advances, membrane composition and organization have been shown to play a critical role in the entry process. This LDRD uses model membrane platforms and basic biophysics to investigate entry mechanisms of enveloped viruses and understand membrane-based delivery technologies. This team has established foundations for using membrane-based platforms and biophysical techniques at Sandia to characterize membrane fusion.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2024

Membrane Development for CO2 Capture from Steel Manufacturing

The U.S. government is targeting a net-zero carbon-emission economy by 2050, offering an exciting opportunity for membrane-based CO2 capture from various industrial point sources. Given that industrial flue gas has low CO2 partial pressures and high volumetric flow rates, high-permeance membranes are needed to make membrane technology economically viable for large-scale deployment. Thin film composite (TFC) membranes are necessary for this implementation because they can provide high permeance by forming a thin selective layer on top of a porous support. This presentation will report the rational design and fabrication of NETL’s highly permeable non-aging TFCs achieved by: synthesizing a high-performance rubbery selective material; developing a high-porosity membrane support; optimizing coating methods to assemble the two materials into scalable membranes; and scaling up membrane supports and TFCs via a roll-to-roll process. The novel rubbery selective material shows mixed-gas CO2 permeability of 930 Barrer and CO2/N2 selectivity of 44, exceeding the 2008 Robeson upper bound. The resulting TFCs yield remarkably high CO2 permeance of 4,500 GPU and CO2/N2 selectivity of 34 at 23ºC. Moreover, the TFCs exhibit not only excellent performance stability (or non-aging behavior) for 1,000 hours in the lab, but also maintain their separation properties in a 700-hour field test at the U.S. DOE’s National Carbon Capture Center using real humid flue gas.

Tran, Thien↗

DOE OSTI2024

Membrane-based Carbon Capture Process Optimization using CFD Modeling

Carbon capture is a promising option to mitigate CO2 emissions from existing coal-fired power plants, cement and steel industries, and petrochemical complexes. Among the available technologies, membrane-based carbon capture presents the lowest energy consumption, operating costs, and carbon footprint. In addition, membrane processes have important operational flexibility and response times. On the other hand, the major challenges to widespread application of this technology are related to reducing capital costs and improving membrane stability and durability. To upscale the technology into stacked flat sheet configurations, high fidelity computational fluid dynamics (CFD) that describes the separation process accurately are required. High fidelity simulations have been shown to be effective in studying the complex transport phenomena in membrane systems. In addition, obtaining high CO2 recovery percentages and product purity re-quires a multi-stage membrane process, where the optimal network configuration of the mem-brane modules must be studied in a systematic way. In order to address the design problem at process scale, we formulate a superstructure for the membrane-based carbon capture, including up to three separation stages. In the formulation of the optimization problem, we include reduced models, based on rigorous CFD simulations of the membrane modules.

Pedrozo, Hector A.↗

DOE OSTI2021

Recent Developments in High-Performance Membranes for CO 2 Separation

In this perspective article, we provide a detailed outlook on recent developments of high-performance membranes used in CO 2 separation applications. A wide range of membrane materials including polymers of intrinsic microporosity, thermally rearranged polymers, metal–organic framework membranes, poly ionic liquid membranes, and facilitated transport membranes were surveyed from the recent literature. In addition, mixed matrix and polymer blend membranes were covered. The CO 2 separation performance, as well as other membrane properties such as film flexibility, processibility, aging, and plasticization, were analyzed.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2023

Gas Separation Membrane Module Modeling: A Comprehensive Review

Membrane gas separation processes have been developed for diverse gas separation applications that include nitrogen production from air and CO2 capture from point sources. Membrane process design requires the development of stable and robust mathematical models that can accurately quantify the performance of the membrane modules used in the process. The literature related to modeling membrane gas separation modules and model use in membrane gas separation process simulators is reviewed in this paper. A membrane-module-modeling checklist is proposed to guide modeling efforts for the research and development of new gas separation membranes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS1983

Search for selective ion diffusion through membranes

The diffusion rates of several ions through some membranes developed as battery separators were measured. The ions investigated were Li(+), Rb(+), Cl(-), and So4. The members were crosslinked polyvinyl alcohol, crosslinked polyacrylic acid, a copolymer of the two, crosslinked calcium polyacrylate, cellulose, and several microporous polyphenylene oxide based films. No true specificity for diffusion of any of these ions was found for any of the membranes. But the calcium polyacrylate membrane was found to exhibit ion exchange with the diffusing ions giving rise to the leaching of the calcium ion and low reproducibility. These findings contrast earlier work where the calcium polyacrylate membrane did show specificity to the diffusion of the copper ion. In general, Fick's law appeared to be obeyed. Except for the microporous membranes, the coefficients for ion diffusion through the membranes were comparable with their values in water. For the microporous membranes, the values found for the coefficients were much less, due to the tortuosity of the micropores.

May, C. E.↗

NASA NTRS1985

The casting of semi-permeable membranes in a microgravity environment

The National Electric Company of Venezuela, C.A.D.A.F.E., is sponsoring the development of this experiment which represents Venezuela's first scientific experiment in space. The experience can be classified as an educational one which could add knowledge to the fundamental study of polymeric membranes. Presently, semi-permeable membranes are being manufactured from several different kind of polymers all over the world and specific applications have been identified in fluid separation processes such as reverse osmosis, ultrafiltration and electrodyalisis. Although, the ultrastructure of asymetric and composite membranes have been under intensive study, still there are many questions about the factors affecting this structure and their degree of correlation. Nevertheless, there is indication that the entire morphological structure of polymeric membranes could be affected by the differences in specific gravity between the cast solution and the coagulation liquid, normally used in the membranes preparation process. The casting of semi-permeable membranes in space might help to identify the effect of gravity upon the structure of these membranes. It is important to recognize that the casting process involves changes of states (liquid-gas, liquid-solid) and that in a micro gravity environment, there will be a reduction on buoyancy-driven natural convection and density gradients

Ivan Vera↗

NASA NTRS1987

Electrochemical performance and transport properties of a Nafion membrane in a hydrogen-bromine cell environment

The overall energy conversion efficiency of a hydrogen-bromine energy storage system is highly dependent upon the characteristics and performance of the ion-exchange membrane utilized as a half-cell separator. The electrochemical performance and transport properties of a duPont Nafion membrane in an aqueous HBr-Br2 environment were investigated. Membrane conductivity data are presented as a function of HBr concentration and temperature for the determination of ohmic voltage losses across the membrane in an operational cell. Diffusion-controlled bromine permeation rates and permeabilities are presented as functions of solution composition and temperature. Relationships between the degree of membrane hydration and the membrane transport characteristics are discussed. The solution chemistry of an operational hydrogen-bromine cell undergoing charge from 45% HBr to 5% HBr is discussed, and, based upon the experimentally observed bromine permeation behavior, predicted cell coulombic losses due to bromine diffusion through the membrane are presented as a function of the cell state-of-charge.

Baldwin, Richard S.↗

NASA NTRS1990

Qualification of the RSRM case membrane case-to-insulation bondline inspection using the Thiokol Corporation ultrasonic RSRM bondline inspection system

Qualification testing of Combustion Engineering's AMDATA Intraspect/98 Data Acquisition and Imaging System that applies to the redesigned solid rocket motor (RSRM) case membrane case-to-insulation bondline inspection was performed. Testing was performed at M-67, the Thiokol Corp. RSRM Assembly Facility. The purpose of the inspection was to verify the integrity of the case membrane case-to-insulation bondline. The case membrane scanner was calibrated on the redesigned solid rocket motor case segment calibration standard, which had an intentional 1.0 by 1.0 in. case-to-insulation unbond. The case membrane scanner was then used to scan a 20 by 20 in. membrane area of the case segment. Calibration of the scanner was then rechecked on the calibration standard to ensure that the calibration settings did not change during the case membrane scan. This procedure was successfully performed five times to qualify the unbond detection capability of the case membrane scanner.

Cook, M.↗

NASA NTRS1992

Modeling of membrane processes for air revitalization and water recovery

Gas-separation and reverse-osmosis membrane models are being developed in conjunction with membrane testing at NASA JSC. The completed gas-separation membrane model extracts effective component permeabilities from multicomponent test data, and predicts the effects of flow configuration, operating conditions, and membrane dimensions on module performance. Variable feed- and permeate-side pressures are considered. The model has been applied to test data for hollow-fiber membrane modules with simulated cabin-air feeds. Results are presented for a membrane designed for air drying applications. Extracted permeabilities are used to predict the effect of operating conditions on water enrichment in the permeate. A first-order reverse-osmosis model has been applied to test data for spiral wound membrane modules with a simulated hygiene water feed. The model estimates an effective local component rejection coefficient under pseudosteady-state conditions. Results are used to define requirements for a detailed reverse-osmosis model.

Lange, Kevin E.↗

NASA NTRS1993

Permeable membrane experiment

The purpose of the Permeable Membrane Experiment is to gather flight data on three areas of membrane performance that are influenced by the presence of gravity. These areas are: (1) Liquid/gas phase separation, (2) gas bubble interference with diffusion through porous membranes and (3) wetting characteristics of hydrophilic membrane surfaces. These data are important in understaning the behavior of membrane/liquid/gas interfaces where surface tension forces predominate. The data will be compared with 1-g data already obtained and with predicted micrograviity behavior. The data will be used to develop designs for phase separation and plant nutrient delivery systems and will be available to the life support community for use in developing technologies which employ membranes. A conceptual design has been developed to conduct three membrane experiments, in sequence, aboard a single Complex Autonomous Payload (CAP) carrier to be carried in the Shuttle Orbiter payload bay. One experiment is conducted for each of the three membrane performance areas under study. These experiments are discussed in this paper.

Slavin, Thomas J.↗