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At least 577 records · Page 32
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Investigating microstructure evolution in block copolymer membranes

Block copolymer self-assembly in conjunction with nonsolvent-induced phase separation (SNIPS) has been increasingly leveraged to fabricate integral-asymmetric membranes. The large number of formulation and processing parameters associated with SNIPS, however, has prevented the reliable construction of high performance membranes. In this study, we apply dynamical self-consistent field theory to model the SNIPS process and investigate the effect of various parameters on the membrane morphology: solvent selectivity, nonsolvent selectivity, initial film composition, and glass transition composition. We examine how solvent selectivity and concentration of polymers in the film impact the structure of micelles that connect to form the membrane matrix. In particular, we find that preserving the order in the surface layer and forming a connection between the supporting and surface layer are nontrivial and sensitive to each parameter studied. Furthermore, the effect of each parameter is discussed, and suggestions are made for successfully fabricating viable block copolymer membranes.

36 MATERIALS SCIENCE↗
NASA NTRS1976

Influence of transverse shear on an axial crack in a cylindrical shell

An axial crack in a cylindrical shell is investigated by use of a 10th order shell theory, which accounts for transverse shear deformations as well as a special kind of orthotropy. The symmetric problem is formulated in terms of two coupled singular integral equations, which are solved numerically. The asymptotic membrane and bending stress fields ahead of the crack are found to be self similar. Stress intensity factors are given as a function of the shell parameter for various values of the ratio crack length to shell thickness. considerable differences from 8th order shell theory results are found for the bending stresses, while the membrane stresses of the 8th order theory seem to be a lower limit reached for very thin shells.

Krenk, S.↗
NASA NTRS1977

Influence of transverse shear on an axial crack in a cylindrical shell

An axial crack in a cylindrical shell is investigated by use of a 10th order shell theory, which accounts for transverse shear deformations as well as a special kind of orthotropy. The symmetric problem is formulated in terms of two coupled singular integral equations, which are solved numerically. The asymptotic membrane and bending stress fields ahead of the crack are found to be self similar. Stress intensity factors are given as a function of the shell parameter for various values of the ratio crack length to shell thickness. Considerable differences from 8th order shell theory results are found for the bending stresses, while the membrane stresses of the 8th order theory seems to be a lower limit reached for very thin shells.

Krenk, S.↗
NASA NTRS1978

Influence of transverse shear on an axial crack in a cylindrical shell

An axial crack in a cylindrical shell is investigated by use of a 10th order shell theory, which accounts for transverse shear deformations as well as a special kind of orthotropy. The symmetric problem is formulated in terms of two coupled singular integral equations, which are solved numerically. The asymptotic membrane and bending stress fields ahead of the crack are found to be self similar. Stress intensity factors are given as a function of the shell parameter for various values of the ratio shell radius to shell thickness. Considerable differences from 8th order shell theory results are found for the bending stresses, while the membrane stresses of the 8th order theory seems to be a lower limit reached for very thin shells.

Krenk, S.↗
DOE OSTI2021

Wafer-scale remote epitaxy of III-V semiconductors and applications

In conventional epitaxy of single-crystalline semiconductor materials, it is challenging to separate the grown layer with the substrate due to the strong bonding at the interface. Remote epitaxy is a recently discovered method to grow single-crystalline thin films on graphene, wherein the grown film can be exfoliated at the graphene interface to form freestanding membranes. Here, we present our recent development on remote epitaxy of III-V semiconductors. We show that directly growing 2D materials on III-V substrates as a remote epitaxy template is an ideal pathway that can eliminate transfer process-related defects and can realize wafer-scale process of remote epitaxy and substrate reuse. We present the strategies to grow 2D materials on the surface of III-V materials, which is much more challenging than thermally robust substrates such as SiO2/Si or sapphire. The nucleation of III-V on 2D material-coated III-V platforms via remote interaction is investigated both experimentally and theoretically. Lastly, we show advanced remote epitaxial platforms and optoelectronic applications enabled by remote epitaxy, and the capability to recycle the III-V substrates for repeated remote epitaxy and production of freestanding III-V thin films.

Kim, Hyunseok↗
DOE OSTI2021

Wafer-scale remote epitaxy of III-V semiconductors and applications

In conventional epitaxy of single-crystalline semiconductor materials, it is challenging to separate the grown layer with the substrate due to the strong bonding at the interface. Remote epitaxy is a recently discovered method to grow single-crystalline thin films on graphene, wherein the grown film can be exfoliated at the graphene interface to form freestanding membranes. Here, we present our recent development on remote epitaxy of III-V semiconductors. We show that directly growing 2D materials on III-V substrates as a remote epitaxy template is an ideal pathway that can eliminate transfer process-related defects and can realize wafer-scale process of remote epitaxy and substrate reuse. We present the strategies to grow 2D materials on the surface of III-V materials, which is much more challenging than thermally robust substrates such as SiO2/Si or sapphire. The nucleation of III-V on 2D material-coated III-V platforms via remote interaction is investigated both experimentally and theoretically. Lastly, we show advanced remote epitaxial platforms and optoelectronic applications enabled by remote epitaxy, and the capability to recycle the III-V substrates for repeated remote epitaxy and production of freestanding III-V thin films.

Kim, Hyunseok↗
DOE OSTI2020

Oxygen Reduction Reaction Activity of Nanocolumnar Platinum Thin Films by High Pressure Sputtering

Nanocolumnar platinum thin films (Pt-TFs) were produced by high pressure sputtering (HIPS) and investigated as oxygen reduction reaction electrocatalysts for polymer electrolyte membrane fuel cells. Conventional high-density Pt-TF prepared by low pressure sputtering was also studied for comparison. Pt-TFs were deposited on a microporous layer (MPL)-like surface composed of carbon particles to mimic catalyst-coated gas diffusion electrodes. Electron microscopy imaging revealed that HIPS Pt-TFs developed a cauliflower-like columnar microstructure, which originated from a shadowing effect during HIPS. This shadowing effect is enhanced on the rough surface of the MPL-like carbon that leads to the nano-cauliflower formation. With this approach, we also aimed to relate the catalyst performance obtained by benchtop tests directly to membrane electrode assembly test results. The electrochemically active surface area of Pt-TFs increased from 10 to 19 m 2 /g with increasing sputter pressure. Specific activity of conventional high-density and nanocolumnar films were similar at ~600 μA/cm 2 , which is likely due to their similar crystal grain sizes, >5 nm. On the other hand, mass-specific (MA) activity values increased from ~0.06 A/mgPt for conventional Pt-TF to ~0.13 A/mgPt for HIPS Pt-TFs, which is consistent with the columnar microstructure of HIPS films providing a better catalyst utilization compared to conventional Pt-TF.

08 HYDROGEN↗
DOE OSTI2023

Final Report on Development of Microwave Resonant Cavity Transducer for Fluid Flow Sensing: Development of Microwave Cavity Flow Meter for Advanced Reactor High Temperature Fluids

We are investigating a microwave resonant cavity transducer for flow sensing in the vessel of a high temperature fluid advanced reactor (AR), such as a molten salt cooled reactor (MSCR) or a sodium fast reactor (SFR). This transducer is a hollow metallic cylindrical cavity, with one of the flat walls of the cylinder flexible enough to undergo microscopic deflection due to dynamic fluid pressure. Membrane deflection leads to a shift in the microwave resonant frequency, which can be detected with a spectrum analyzer. We have developed a continuum electromechanics model of the microwave resonant cavity transducer performance. The deflection of the membrane is calculated using equations from the theory of plates and shells for deflection of radially constrained thin circular disk under uniform load. The microwave frequency shift is calculated using the equations from the microwave cavity perturbation theory. The transducer model was validated with proof-of-concept experimental data of water flow sensing with a Brass 360 right circular cylinder with 22.2mm diameter and 203µm thick wall. The cavity was excited through a subwavelength hole in TE 011 mode with resonant frequency f ≈ 17.8GHz. Subsequently, we have performed a preliminary proof-of-principle test of flow sensing in high temperature liquid sodium in environment. For this test, we have developed a cylindrical resonator with the same dimensions as for the Brass 360 cavity. The resonator for high temperature liquid sodium test was machined from stainless steel 316 and electroplated with silver on the interior surfaces. We have also developed and insertion probe consisting of a 50cm WR-42 brass waveguide enclosed in a protective SS316 tube. The cavity was excited through a subwavelength hole on the side of the wall of the cylinder in the TE 011 mode with resonant frequency f ≈ 17.8GHz. The liquid sodium setup consists of a cylindrical vessel with a center feed line, where a transducer inserted through the top cap of the vessel measures velocity of the impinging liquid jet. The sodium flow sensing study was performed in a liquid sodium vessel at 340°C temperature and ambient pressure. The flow rate was changed by varying sodium pump power, and a frequency shift of several hundred kHz was observed. The transducer was removed after 70 days of testing. No visual damage was observed, and the electromagnetic response remained the same. As a calibration experiment, we have assembled a water vessel with a center feed, and with dimensions similar to those of the liquid sodium setup. Water flow sensing was performed before and after liquid sodium test. The responses in both cases are similar and agree with COMSOL computer simulations. Because long-term (multi-year) experimental tests of transducer resilience to harsh environment are not practical, we have developed a probabilistic model of creep to estimate transducer resilience to the harsh environment. The probabilistic model considers diffusion creep under the condition of high temperature and low stress, where the stress and temperature are allowed to be random variables with Gaussian distributions. Using the probabilistic model, we estimate inelastic membrane deflections due to creep for several temperature ranges. We conclude that for temperatures less than 650°C, creep has negligible long-term effect on the transducer performance.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗
DOE OSTI2025

Engineering surface charges of nanofiltration membranes to maximize Li + /Mg 2+ separation properties

Polyamide-based nanofiltration (NF) membranes are attractive for Li + /Mg 2+ separation for lithium recovery from salt brine (containing mainly Mg 2+ ). However, Li + and Mg 2+ have similar hydration radii, resulting in a low separation factor (SF Li/Mg ). Herein, we demonstrate that SF Li/Mg can be significantly enhanced by optimizing the membrane surface positive charges. This results in an unexpected maximum SF Li/Mg at a solution pH slightly below its isoelectric point (IEP). Specifically, NF270 membrane was surface-grafted with 2-(methacryloyloxy)ethyltrimethylammonium chloride (META) or polyethylenimine (PEI) using bio-adhesive dopamine, forming a thin, stable, charged layer (20–40 nm) on the surface. The effects of solution pH and surface modification on the surface zeta potential (ZP) and single- and mixed-salt Li + /Mg 2+ separation properties are thoroughly investigated. For example, the META grafting increases the ZP from 9.2 to 16 mV and SF Li/Mg by 130 % from 35 to 80 at pH 4, superior to the state-of-the-art commercial NF membranes. Furthermore, this surface modification occurs at ≈22 °C in aqueous solutions and can be utilized to enhance commercial modules for practical applications.

Li+/Mg2+ separation↗
DOE OSTI2020

Multi-functional anodes boost the transient power and durability of proton exchange membrane fuel cells

Abstract Proton exchange membrane fuel cells have been regarded as the most promising candidate for fuel cell vehicles and tools. Their broader adaption, however, has been impeded by cost and lifetime. By integrating a thin layer of tungsten oxide within the anode, which serves as a rapid-response hydrogen reservoir, oxygen scavenger, sensor for power demand, and regulator for hydrogen-disassociation reaction, we herein report proton exchange membrane fuel cells with significantly enhanced power performance for transient operation and low humidified conditions, as well as improved durability against adverse operating conditions. Meanwhile, the enhanced power performance minimizes the use of auxiliary energy-storage systems and reduces costs. Scale fabrication of such devices can be readily achieved based on the current fabrication techniques with negligible extra expense. This work provides proton exchange membrane fuel cells with enhanced power performance, improved durability, prolonged lifetime, and reduced cost for automotive and other applications.

24 POWER TRANSMISSION AND DISTRIBUTION↗
DOE OSTI2020

Halogenation-Dependent Effects of the Chlorosulfolipids of Ochromonas danica on Lipid Bilayers

The chlorosulfolipids are amphiphilic natural products with stereochemically complex patterns of chlorination and sulfation. Despite their role in toxic shellfish poisoning, potential pharmacological activities, and unknown biological roles, they remain understudied due to the difficulties in purifying them from natural sources. The structure of these molecules, with a charged sulfate group in the middle of the hydrophobic chain, appears incompatible with the conventional lipid bilayer structure. Questions about chlorosulfolipids remain unanswered partly due to the unavailability of structural analogues with which to conduct structure–function studies. Here, we approach this problem by combining enantioselective total synthesis and membrane biophysics. Using a combination of Langmuir pressure–area isotherms of lipid monolayers, fluorescence imaging of vesicles, mass spectrometry imaging, natural product isolation, small-angle X-ray scattering, and cryogenic electron microscopy, we show that danicalipin A (1) likely inserts into lipid bilayers in the headgroup region and alters their structure and phase behavior. Specifically, danicalipin A (1) thins the bilayer and fluidizes it, allowing even saturated lipid to form fluid bilayers. Lipid monolayers show similar fluidizing upon insertion of danicalipin A (1). Furthermore, we show that the halogenation of the molecule is critical for its membrane activity, likely due to sterically controlled conformational changes. Synthetic unchlorinated and monochlorinated analogues do not thin and fluidize lipid bilayers to the same extent as the natural product. Overall, this study sheds light on how amphiphilic small molecules interact with lipid bilayers and the importance of stereochemistry and halogenation for this interaction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2003

Morphology of the Vestibular Utricule in Toadfish, Opsanus Tau

The uticle is an otolith organ in the vertebrate inner ear that provides gravitoinertial acceleration information into the vestibular reflex pathways. The aim of the present study was to provide an anatomical description of this structure in the adult oyster toadfish, and establish a morphological basis for interpretation of subsequent functional studies. Light, scanning electron and transmission electron microscopy were applied to visualize the sensory epithelium and its neural innervation. Electrophysiological techniques were used to identify utricular afferents by their response to translation stimuli. Similar to nerve afferents supplying the semicircular canals and lagena, utricular afferents commonly exhibit a short-latency increase of firing rate in response to electrical activation of the central efferent pathway. Afferents were labeled with biocytin either intraaxonally or with extracellular bulk deposits. Light microscope images of serial thick sections were used to make three-dimensional reconstructions of individual labeled afferents to identify the dendritic morphology with respect to epithelial location. Scanning electron microscopy was used to visualize the surface of the otolith mass facing the otolith membrane, and the hair cell polarization patterns of strioler and extrastriolar regions. Transmission electron micrographs of serial thin sections were compiled to create a three-dimensional reconstruction of the labeled afferent over a segment of its dendritic field and to examine the hair cell-afferent synaptic contacts.

Bass, L.↗
NASA NTRS2017

Molecular Based Temperature and Strain Rate Dependent Yield Criterion for Anisotropic Elastomeric Thin Films

A molecular formulation of the onset of plasticity is proposed to assess temperature and strain rate effects in anisotropic semi-crystalline rubbery films. The presented plane stress criterion is based on the strain rate-temperature superposition principle and the cooperative theory of yielding, where some parameters are assumed to be material constants, while others are considered to depend on specific modes of deformation. An orthotropic yield function is developed for a linear low density polyethylene thin film. Uniaxial and biaxial inflation experiments were carried out to determine the yield stress of the membrane via a strain recovery method. It is shown that the 3% offset method predicts the uniaxial elastoplastic transition with good accuracy. Both the tensile yield points along the two principal directions of the film and the biaxial yield stresses are found to obey the superposition principle. The proposed yield criterion is compared against experimental measurements, showing excellent agreement over a wide range of deformation rates and temperatures.

Bosi, F.↗
DOE OSTI2022

Porous condensers can double the efficiency of membrane distillation

Among membrane distillation (MD) configurations, air gap MD (AGMD) has superior energy efficiency at high salinity. However, flooding of the gap prevents optimal thin gap depths as water removal is a challenge. To address these challenges, this work provides the first analysis of efficiency enhancement via porous wicking conductive condensers in MD. To do so, we examined performance with experiments and comprehensive thermo-fluid numerical models; we find that the porous wick condenser significantly improves thermal efficiency, gain output ratio (GOR), and flux. MD experiments show that the porous copper foam improves the thermal efficiency of air gap membrane distillation up to 40 % and water flux up to 144 %. Numerical modeling shows the porous copper foam improves the GOR of membrane distillation in high salinity by 98.7 %, outperforming air gap MD, permeate gap MD, and conductive gap MD. Furthermore, the optimized thickness and permeability of porous condensers significantly help eliminate the risk of flooding in AGMD.

42 ENGINEERING↗
DOE OSTI2021

Hydrogen permeability and stability of palladium films in a high pressure reactor

Palladium (Pd) thin films were fabricated by colloidal spray deposition (CSD) on substrates of porous yttrium stabilized zirconium oxide (YSZ). The films were sintered at 1140–1160 °C for 2–3 h in argon and had thickness of 5–11 μm. The hydrogen (H 2 ) permeation flux for the Pd film was measured with simulated feed gases (90% H 2 /He, syn-gas/steam, or syn-gas/steam with H 2 S) flowing on the film side and sweep gas (Ar) flowing on the substrate side. Here, the hydrogen flux with the Pd film was obtained by adjusting the flow rate and pressure of the gas. Hydrogen flux values of 121–173 cm 3 min -1 cm -2 were measured at 388–596 °C (feed: 90% H 2 /He at 200 mL min -1 ; sweep: Ar at 1400 mL min -1 ; and ΔP = ~170 psi), and the permeability was calculated and compared with literature values. Because Pd is known to be sensitive to some gases, the stability of Pd films was evaluated by examining the microstructures of samples after their exposure to gas mixtures containing CO, CO 2 , H 2 O, and H 2 S. From the results of stability tests in H 2 S-containing atmospheres, the Pd/Pd 4 S phase boundary was determined, and this measured boundary was compared to the Pd/Pd 4 S boundary calculated from the thermodynamic data in the literature.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Antimony nanobelt asymmetric membranes for sodium ion battery

In this study, composite asymmetric membranes containing antimony (Sb) nanobelts are prepared via a straightforward phase inversion method in combination with post-pyrolysis treatment. Sb nanobelt asymmetric membranes demonstrate improved cyclability and specific capacity as the alloy anode of sodium ion battery compared to Sb nanobelt thin films without asymmetric porous structure. The unique structure can effectively accommodate the large volume expansion of Sb-based alloy anodes, prohibit the loss of fractured active materials, and aid in the formation of stable artificial solid electrolyte interphases as evidenced by an outstanding capacity retention of ~98% in 130 cycles at 60 mA g -1 . A specific capacity of ~600 mAh g -1 is obtained at 15 mA g -1 (1/40C). When the current density is increased to 240 mA g -1 , ~80% capacity can be maintained (~480 mAh g -1 ). The relations among phase inversion conditions, structures, compositions, and resultant electrochemical properties are revealed through comprehensive characterization.

25 ENERGY STORAGE↗
DOE OSTI2020

Acid Exfoliation of Imine‐linked Covalent Organic Frameworks Enables Solution Processing into Crystalline Thin Films

Abstract Covalent organic frameworks (COFs) are highly modular porous crystalline polymers that are of interest for applications such as charge‐storage devices, nanofiltration membranes, and optoelectronic devices. COFs are typically synthesized as microcrystalline powders, which limits their performance in these applications, and their limited solubility precludes large‐scale processing into more useful morphologies and devices. We report a general, scalable method to exfoliate two‐dimensional imine‐linked COF powders by temporarily protonating their linkages. The resulting suspensions were cast into continuous crystalline COF films up to 10 cm in diameter, with thicknesses ranging from 50 nm to 20 μm depending on the suspension composition, concentration, and casting protocol. Furthermore, we demonstrate that the film fabrication process proceeds through a partial depolymerization/repolymerization mechanism, providing mechanically robust films that can be easily separated from their substrates.

Burke, David W.↗
NASA NTRS1997

An Experimental Study of Fatigue Crack Growth in Aluminum Sheet Subjected to Combined Bending and Membrane Stresses

An experimental study was conducted to determine the effects of combined bending and membrane cyclic stresses on the fatigue crack growth behavior of aluminum sheet material. The materials used in the tests were 0.040-in.- thick 2024-T3 alclad and 0.090-in.-thick 2024-T3 bare sheet. In the tests, the membrane stresses were applied as a constant amplitude loading at a stress ratio (minimum to maximum stress) of 0.02, and the bending stresses were applied as a constant amplitude deflection in phase with the membrane stresses. Tests were conducted at ratios of bending to membrane stresses (B/M) of 0, 0.75, and 1.50. The general trends of the results were for larger effects of bending for the higher B/M ratios, the lower membrane stresses, and the thicker material. The addition of cyclic bending stresses to a test with cyclic membrane stresses had only a small effect on the growth rates of through-thickness cracks in the thin material, but had a significant effect on the crack growth rates of through-thickness cracks in the thick material. Adding bending stresses to a test had the most effect on the initiation and early growth of cracks and had less effect on the growth of long through-thickness cracks.

Phillips, Edward P.↗