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At least 289 records · Page 16

Far-Infrared Properties of Cyclic Olefin Copolymer

Cyclic olefin copolymer (COC) is an amorphous thermoplastic with desirable dielectric and mechanical characteristics for optical applications. In particular, its low refractive index, overall mechanical strength, and absence of strong absorption features make it a promising substrate material for far-infrared applications, which include frequency-selective surfaces, scattering filters, and windows. The dielectric properties of selected COC formulations are surveyed from ≈10−700 per.cm (1000−14µm), and representative usage as a thin film membrane structure in optical filters is presented.

Wollack, Edward J.↗

An Inflatable L-Band Microstrip SAR Array

Inflatable structures have been identified as one of the enabling technologies to achieve low mass, high packaging efficiency, and reliable deployment for future NASA spaceborne synthetic aperture radar (SAR) array antennas.

L-band↗

Durable High-Power Membrane Electrode Assemblies with Low Pt Loading

Recent progress in developing and implementing Pt-alloy cathode catalysts and thin (10-15 micron) low resistance membranes has enabled high performance state of art (SOA) membrane electrode assembly (MEA) with low Pt loading. However, these high performing MEAs do not meet durability requirements, especially at peak power, because of complex degradation mechanisms that are sensitive to the materials, MEA design, and fuel cell operating strategy. Specifically, power degradation of the cathode occurs via Pt and Co dissolution as well as deterioration of O 2 transport properties. Additionally, thin membranes are subject to failure due to manufacturing defects in the adjacent gas diffusion media and electrodes and the formation of membrane-attacking radical species caused by high gas crossover. In this project led by General Motors LLC (GM), the objective was to enhance the durability of SOA MEA through optimization of operating conditions, instead of new materials development. Along with our project partners, we have mapped the impact of operating conditions on the durability of SOA MEA. Output of the project include a low Pt loading SOA MEA that exceeds Department of Energy (DOE) 2020 target of >1 W/cm 2 at rated power and pathway to achieve >5000 h of durability. Durability studies in the project provide a detailed understanding of failure modes and operating condition sensitivity on cathode and membrane failure, critical for defining operating conditions and hybridization strategies that can guide system controls to maximize low-Pt MEA life. The project also generated and validated degradation models that will provide future research direction, critical for guiding future cycles of automotive MEA development.

08 HYDROGEN↗

Ultrathin-film composite (uTFC) membranes based on amorphous perfluoropolymers for liquid separations

Thin-film composite membranes based on ~100nm cross-linked polyamides (PAs) are state-of-the-art membranes for liquid separations such as desalination. However, the PA layer shows poor antifouling properties and instability in chlorine solutions. Herein, we show for the first time that glassy amorphous perfluoropolymers (PFPs, such as Teflon AF and Hyflon AD) can be fabricated into ultrathin film composite (uTFC) membranes with a selective layer of <20nm for desalination. Increasing the polymer concentration in the coating solutions from 0.05 mass% to 0.3 mass% increases the selective layer thickness from 9 to 25nm. When Teflon AF2400 was fabricated into 16-nm selective layers on various porous supports, the water permeance decreases from 0.37 LMH/bar for PES10k to 0.07 LMH/bar for PES1k, and the Na 2 SO 4 rejection increases from 86.6% to 95.2%. While the water permeance is lower than the commercial PA-based NF membranes, the rejection in these PFP-based membranes is comparable. Furthr, the effect of the porous support on the water permeance can be ascribed to the geometric restriction and satisfactorily described using an empirical model. Interestingly, the membranes also exhibit good Na + /Li + separation performance and stable performance for organic solvent nanofiltration, showcasing the versatility of the PFP-based uTFC membranes for various liquid separations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Reverse-osmosis membranes by plasma polymerization

Thin allyl amine polymer films were developed using plasma polymerization. Resulting dry composite membranes effectively reject sodium chloride during reverse osmosis. Films are 98% sodium chloride rejective, and 46% urea rejective.

Hollahan, J. R.↗

Tuning Exciton Emission via Ferroelectric Polarization at a Heterogeneous Interface between a Monolayer Transition Metal Dichalcogenide and a Perovskite Oxide Membrane

Here we demonstrate the integration of a thin BaTiO 3 (BTO) membrane with monolayer MoSe 2 in a dual gate device that enables in-situ manipulation of the BTO ferroelectric polarization with a voltage pulse. While two-dimensional (2D) transition metal dichalcogenides (TMDs) offer remarkable adaptability, their hybrid integration with other families of functional materials beyond the realm of 2D materials has been challenging. Released functional oxide membranes offer a solution for 2D/3D integration via stacking. 2D TMD excitons can serve as a local probe of the ferroelectric polarization in BTO at a heterogeneous interface. Using photoluminescence (PL) of MoSe 2 excitons to optically readout the doping level, we find that the relative population of charge carriers in MoSe 2 depends sensitively on the ferroelectric polarization. This finding points to a promising avenue for future-generations versatile sensing devices with high sensitivity, fast read-out, and diverse applicability for advanced signal processing.

42 ENGINEERING↗

Deviation from Debye-Waller behavior in single crystalline freestanding Ni⁢ O membranes studied via ultrafast electron diffraction

Here, we realize single-crystal freestanding Ni⁢O films on Si⁢N membranes, enabling thin-film scattering experiments with little or no substrate background signal. These membrane samples provide a critical platform for performing ultrafast electron diffraction (UED) to probe the response of the lattice to laser excitation. We show that epitaxial Ni⁢O films on a water-soluble Sr 2 ⁢Ca⁢Al 2⁢ O 6 buffer layer on Sr⁢Ti⁢O 3 substrates can be transferred as freestanding films to the Si⁢N membranes while maintaining the epitaxial character of the films. An above-gap photoexcitation (𝜆 =266 nm) incident on the sample stimulates an initial lattice response of the order of 1.1 ps, followed by the persistence of this state for more than 20 ps. We observe typical Debye-Waller behavior in peaks with 𝑞 above the (220) family, but a distinct deviation from this behavior is seen in low-𝑞 peaks. We relate this behavior to a dynamic decrease in sample mosaicity in response to the optical pump of the order of 3% that endures for approximately 4 ps. We suspect that this dynamic mosaicity is due to laser-induced strain propagation. This work demonstrates the viability of the thin-film transfer method for UED and paves the way for the study of the dynamic response of antiferromagnetic thin-film oxides.

Wisser, Jacob J. [Stanford Univ., CA (United State↗

Optical memory development. Volume 3: The membrane light value page composer

The feasibility of producing a page composer for optical memory systems using thin, deformable, membrane-mirror elements as light valves was investigated. The electromechanical and optical performances of such elements were determined both analytically and experimentally. It was found that fast switching (approximately 10 microseconds), high-contrast (10 or greater), fatigue-free operation over missions of cycles, and efficient utilization of input light could be obtained with membrane light valves. Several arrays of 64 elements were made on substrates with feedthroughs, allowing access to individual elements from the backside of the substrate. Single light valves on such arrays were successfully operated with the transistors designed and produced for selection and storage at each bit location. This simulated the operation of a prototype page composer with semiconductor chips beam-lead bonded to the back of the substrate.

Cosentino, L. S.↗

Method for making a dynamic pressure sensor and a pressure sensor made according to the method

A method for providing a perfectly flat top with a sharp edge on a dynamic pressure sensor using a cup-shaped stretched membrane as a sensing element is described. First, metal is deposited on the membrane and surrounding areas. Next, the side wall of the pressure sensor with the deposited metal is machined to a predetermined size. Finally, deposited metal is removed from the top of the membrane in small steps, by machining or lapping while the pressure sensor is mounted in a jig or the wall of a test object, until the true top surface of the membrane appears. A thin indicator layer having a color contrasting with the color of the membrane may be applied to the top of the membrane before metal is deposited to facilitate the determination of when to stop metal removal from the top surface of the membrane.

Zuckerwar, Allan J.↗

Scalable Polymeric Few-Nanometer Organosilica Membranes with Hydrothermal Stability for Selective Hydrogen Separation

Nanoporous silica membranes exhibit excellent H 2 /CO 2 separation properties for sustainable H 2 production and CO 2 capture but are prepared via complicated thermal processes above 400 °C, which prevent their scalable production at a low cost. Here, we demonstrate the rapid fabrication (within 2 min) of ultrathin silica-like membranes (~3 nm) via an oxygen plasma treatment of polydimethylsiloxane-based thin-film composite membranes at 20 °C. The resulting organosilica membranes unexpectedly exhibit H2 permeance of 280-930 GPU (1 GPU = 3.347 x 10 -10 mol m -2 s -1 Pa -1 ) and H2/CO2 selectivity of 93-32 at 200 °C, far surpassing state-of-the-art membranes and Robeson’s upper bound for H 2 /CO 2 separation. When challenged with a 3 d simulated syngas test containing water vapor at 200 °C and a 340 d stability test, the membrane shows durable separation performance and excellent hydrothermal stability. The robust H 2 /CO 2 separation properties coupled with excellent scalability demonstrate the great potential of these organosilica membranes for economic H 2 production with minimal carbon emissions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Size-Induced Ferroelectricity in Antiferroelectric Oxide Membranes (Adv. Mater. 17/2023)

Thin Films. In article number 2210562, Ruijuan Xu, Kevin J. Crust, Varun Harbola, and co-workers report intrinsic size-driven scaling in lead-free antiferroelectric thin films. They demonstrate an intriguing antiferroelectric-to-ferroelectric transition upon reducing the thickness of antiferroelectric NaNbO 3 membranes. Here, the image shows the coexistence of ferroelectric and antiferroelectric phases in freestanding NaNbO 3 membranes.

36 MATERIALS SCIENCE↗

Matrimid substrates with bicontinuous surface and macrovoids in the bulk: A nearly ideal substrate for composite membranes in CO 2 capture

Scalable fabrication of thin-film composite (TFC) membrane for post-combustion carbon capture is often limited by the availability of high-performance nanoporous substrate. Ideally, the substrate should allow for fast gas transport at the selective layer/substrate interface as well as in the bulk of the substrate. In this study, highly permeable Matrimid substrates were prepared via vapor- and nonsolvent-induced phase separations. The phase separation mechanism of the Matrimid®/N-methyl-2-pyrrolidone casting solution was modulated by the addition of LiCl to control the solution thermodynamic stability, and nanoporous Matrimid substrates were formed with a bicontinuous surface and macrovoids in the bulk. This hierarchically optimized structure resulted in a CO 2 permeance of 2.60 × 10 5 GPU (1 GPU = 1 × 10 –6 cm 3 (STP) cm –2 s –1 cmHg –1 = 3.349 × 10 –10 mol m –2 s –1 Pa –1 ), which was ca. 11 times more permeable than a benchmark polyethersulfone substrate with cellular pores. The benefit of using this new substrate was demonstrated by coating a 170-nm amine-containing polymer to form a TFC facilitated transport membrane. The membrane exhibited a CO 2 permeance of 932 GPU at 57°C, which was 72 GPU higher than the counterpart coated on the benchmark substrate. Meanwhile, the CO 2 /N 2 selectivity was remained at 158. This permeance improvement could be well explained by the resistance-in-series model, where the improved permeance was attributed to the reductions in substrate and lateral diffusion mass transfer resistances. The upper bound (UB) analysis indicates that the Matrimid substrate is nearly ideal for the state-of-the-art polymers for CO 2 /N 2 separation. Here, the substrate improvement could also reduce the parasitic energy associated with the membrane process due to the reduced membrane cost and flue gas compression requirement.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

New sterically hindered polyvinylamine-containing membranes for CO 2 capture from flue gas

Amine-containing facilitated transport membranes can have both high permeability and selectivity due to the reversible reaction between CO 2 and amino groups for effective carbon capture from flue gas. In this study, we have developed an improved method for the synthesis of high-molecular-weight sterically hindered polyvinylamine (PVAm) as the new fixed-site carrier in thin-film composite membranes for CO 2 capture. Commercially available PVAm was N-monomethylated into poly-N-methyl-N-vinylamine (PVAm-CH 3 ) using the stepwise reductive amination with a highly polar fluorinated alcohol as the solvent to enhance the equilibrium shift to the formation of the imine intermediate. The method prevented over-alkylation, resulting in the increased yield of the target product. PVAm-CH 3 exhibited excellent CO 2 facilitation with a CO 2 permeability of 445.7 Barrer (1 Barrer = 3.349 x 10 –16 mol m m –2 s –1 Pa –1 ) and a CO 2 /N 2 selectivity of 70.3, which are above the Robeson 2008 upper bound. The PVAm-CH 3 solution retained a sufficiently high viscosity after incorporating the aminoacid salt, 2-(1-piperazinyl)ethylamine sarcosinate (PZEA-Sar), as the mobile carrier for the membrane coating on nanoporous polyethersulfone (PES) substrates without any penetration issues. The resultant thin-film composite PVAm-CH3/PZEA-Sar membrane with a thickness of approximately 170 nm exhibited a superior CO 2 performance of 1071 GPU (1 GPU = 3.349 x 10 –10 mol m –2 s –1 Pa –1 ) and a CO 2 /N 2 selectivity of 183 at 57°C and a feed gas pressure of 111.64 kPa (1.5 psig). This PVAm-CH 3 /PZEA-Sar membrane surpassed the latest redefined 2019 CO 2 /N 2 upper bound and outperformed other polymer-based membranes. Density functional theory calculations also demonstrated that PVAm-CH 3 showed a stronger preference, relative to PVAm, toward the more efficient bicarbonate pathway. Thus, the steric hindrance effect of PVAm-CH 3 enhanced the solubility of CO 2 in the polymer matrix and resulted in the higher CO 2 permeance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effect of surfactants and temperature on the hyperfiltration performance of poly(ether/urea) membranes

The individual and combined effects of pasteurization temperature (347 K) and surfactants (anionic, cationic, and neutral) on a poly(ether/urea) thin-film hyperfiltration membrane were studied. Performance of this positively charged membrane was measured in terms of sodium chloride rejection and water flux. The observed effect was mostly on water flux and minimal on salt rejection. Pasteurization temperature caused an irreversible flux decline (flux decline slope of 0.09). The gradual flux reduction caused by neutral and cationic surfactants was reversible, whereas the flux reduction caused by anionic surfactant was irreversible and of similar magnitude to flux reduction caused by pasteurization temperature. The effects of anionic surfactant and pasteurization temperature were additive. Because of flux decline at elevated temperatures the poly(ether/urea) membrane is not very attractive for long-term spaceflight use.

Leban, M. I.↗

Ionic Liquid-Mediated Interfacial Polymerization for Fabrication of Reverse Osmosis Membranes

This study revealed the effects of incorporating ionic liquid (IL) molecules: 1-ethyl, 1-butyl, and 1-octyl-3-methyl-imidazolium chlorides with different alkyl chain lengths, in interfacial polymerization (IP) on the structure and property (i.e., permeate-flux and salt rejection ratio) relationships of resulting RO membranes. The IL additive was added in the aqueous meta-phenylene diamine (MPD; 0.1% w/v) phase, which was subsequently reacted with trimesoyl chloride (TMC; 0.004% w/v) in the hexane phase to produce polyamide (PA) barrier layer. The structure of resulting free-standing PA thin films was characterized by grazing incidence wide-angle X-rays scattering (GIWAXS), which results were correlated with the performance of thin-film composite RO membranes having PA barrier layers prepared under the same IP conditions. Additionally, the membrane surface properties were characterized by zeta potential and water contact angle measurements. It was found that the membrane prepared by the longer chain IL molecule generally showed lower salt rejection ratio and higher permeation flux, possibly due to the inclusion of IL molecules in the PA scaffold. This hypothesis was supported by the GIWAXS results, where a self-assembled surfactant-like structure formed by IL with the longest aliphatic chain length was detected.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Hydrophilic, light active coating for membranes

A porous membrane provides enhanced filtration of pollutants and particles by coating the membrane with conformal thin films of doped titanium dioxide via atomic layer deposition or, alternatively, sequential infiltration synthesis. The membrane can either be organic or inorganic, and the doping of the membrane, usually with nitrogen, is an important feature that shifts the optical absorption of the TiO2 from the UV range into the visible-light range. This enables the use of lower energy light, including sunlight, to activate the photocatalytic function of the film. The coating described in the present invention is compatible with virtually any porous membrane and allows for precise tuning of the pore size with molecular precision. The present invention presents a new coating process and chemical structure that provides catalytic activity, strongly enhanced by light, to both mitigate fouling and break down various organic pollutants in the process stream.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Bicontinuous substrates with reduced pore restriction for CO 2 -selective composite membranes

A substrate with bicontinuous structure is attractive for thin-film composite (TFC) membrane synthesis due to its high surface porosity and well-interconnected bulk morphology. In this study, the vapor-induced phase separation (VIPS) of the casting solution comprising water, 2-pyrrolidone, and polyethersulfone (PES) was studied. By tuning the water addition in the casting solution and water vapor exposure time, the optimized substrate exhibited a bicontinuous surface with a high porosity of 24.2% (or 216/µm 2 pore density), thereby mitigating pore restriction and showing a high CO 2 permeance of 2.94×10 5 GPU. Compared to the benchmark PES substrate with cellular surface pores and lower gas permeance, the use of the bicontinuous substrate led to a 12% increase in the CO 2 permeance of the TFC membrane. The mitigated pore restriction was further rationalized by a resistance-in-series model. The analysis of the lateral diffusion and substrate resistances indicates that an even higher surface pore density of the substrate is required to fully realize the potential of ultra-permeable, CO 2 -selective polymers in the TFC configuration. As a result, the scalability of the VIPS process was demonstrated by the roll-to-roll fabrication of the optimized bicontinuous substrate with a width of 21" and a length of >100'.

42 ENGINEERING↗