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At least 181 records · Page 10

Double ChemFET for the In-Line Monitoring of Silver Dosing in Potable Water Systems

With NASA Advanced Exploration Systems (AES) Life Support Systems (LSS) baselining ionic silver (Ag+) as the biocide of choice, development in silver monitoring technologies becomes necessary to monitor and control Ag+ release. Ion-selctive field effect transistors (ISFETs) and chemically-sensitive field effect transistors (ChemFETs) are capable of selective detection of Ag+ with reversible and low detection limit responses. However, one major hurdle to ChemFET technologies is the requirement of a reference electrode, which can leak its fill solution into the potable water system and is prone to drift requiring frequent calibration. To circumvent this issue, we are developing a double chemically-sensitive field effect transistor (dChemFET). The dChemFET uses a second ChemFET to selectively monitor the counter ion and serves in place of the reference electrode. We report our work in developing the dChemFET, starting with the development of the Ag+ and NO3- ion selective memberanes (ISMs) to be used in the ChemFETs. The Ag+ ISM has a detection range of 50-105 ppb . The counter ion ISM, NO3- ISM, has shown a detection range of 400-105 ppb. NO3- ISMs are limited in detecting at lower ppb levels required for the dChemFET application on the potable water system. In response to this issue, we also report our studies in using the Ag+ ISM to measure deionized (DI) water as a reference measurement to be implemented in-line before the Ag+ is dosed.

Lance Dean Delzeit↗

Evaluation of Iodine and Silver as Biocides for Potable Water in Human Missions beyond Low Earth Orbit

Chemical biocides play an important role in potable water storage and distribution systems. They provide protection against microbial growth that can negatively impact efficient water transport and crew health. Molecular iodine and ionic silver have been used on the International Space Station for decades. Future orbiting and surface habitats will have potable water systems that will require reliable potable water storage and challenging transport schemes during daily operations with potentially lengthy and repeated periods of non-use. Based on a review of literature, experimental data, and flight data this paper categorizes the advantages and disadvantages of the two heritage biocides on ISS: iodine and silver. The history of biocide practices on ISS is compared to requirements of future human missions beyond low Earth Orbit. The upstream water quality supply and downstream water uses are defined with respect to the two biocides. The methods of injection and removal of the two biocides are compared for a range of downstream water uses including drinking water, hygiene water, technical water, oxygen generation water, and extravehicular activity water. The paper provides mission planners with a technical and engineering assessment of the two biocides and identifies gaps in knowledge and on-orbit experiences.

Dean Muirhead↗

Mitigation of Silver Ion Loss from Solution by Polymer Coating of Metal Surfaces, Part II

“Spacecraft potable water systems require a biocidal agent that effectively provides both immediate and residual disinfection over long periods of time. Ionic silver (Ag+) is a leading candidate for this application, but suffers from rapid concentration loss due to interactions with the metal storage containers and tubing. In order to maintain biocidal efficacy in systems with long periods of dormancy and to reduce the required rate of Ag+ injection, it is necessary to develop alternative materials and coatings for certified metal alloys that significantly reduce the Ag+loss.”1In this work, we continue our investigation of vapor-deposited parylene (AF4, and now C) polymers as conformal barrier coatings under long-term (ca. 1-year) immersion in ca. 400 ppb Ag+. The performanceof internal coatings in tubing/two-ferrule fitting systems is characterized. We report successful “aging” and high concentration Ag+pretreatment of parylene coatings for quantitative reduction of Ag+loss rates. In addition, we observe long-term blister-free adhesion of mechanically anchored parylene-AF4 on nano-structured Ti-6Al-4V alloy and chemically bonded parylene-C on 316L stainless steel. Finally, we report preliminary experiments with mechanical and chemical anchoring of laboratory-deposited parylene-C on 316L.

Silver↗

Considerations on Electrolytic Conductivity Measurement for Monitoring of Ionic Silver Biocide Dosing

NASA interest in ionic silver (Ag+) as a biocide for spacecraft potable water systems motivates the development of Ag+ concentration sensors to ensure nominal dosing. The electrolytic conductivity change of highly-purified potable water is linearly related to the concentration of chemically-dosed Ag+ and could serve as a useful proxy measurement, while the conductivity change during electrolytic dosing may be less so, depending on the influent water chemistry and electrolytic efficiency. Understanding and mitigating the potentially deleterious effects of Ag+ interaction with conductivity measurement systems requires investigation. Issues associated with traditional conductivity cells, which rely on wetted(typically metal or graphite) electrodes, and capacitively-coupled contactless conductivity detection (C4D) for this application are considered. Traditional conductivity cells may potentially be subject to significant excitation-induced or auto-galvanic reduction of Ag+. These may result in Ag+ depletion or electrode fouling and associated measurement error. Proper selection of electrode material, excitation parameters, and cell geometry may limit such effects. C4D uses electrodes placed outside an inert, insulating material, with dielectric polarization enabling the production of an electric field and resultant current across the analyte solution. This approach could potentially mitigate problems with Ag+ depletion and fouling by eliminating the possibility of auto-galvanic deposition and reducing the Faradaic current density. However, it is necessary to confirm C4D performance at very low conductivity levels and to determine if long-term operation produces conductive deposits, which could result in measurement error. A commercial C4D system with 1/16” (1.59 mm)outer diameter flow tubing and claimed performance in the conductivity range appropriate for this application was identified, and its sensitivity in the upper parts of this range was confirmed in a preliminary experiment. A concept for a C4D detector that could allow for full rate flow-through using planar electrodes and thin-film dielectric layers is discussed.

silver↗

Enhancing the Infrared Emission from Silver Chalcogenide Quantum Dots Through Microcavity Coupling

Nanocrystals (NCs) appear as a promising platform for cost effective infrared optoelectronics, while offering a simplified coupling to the CMOS platform. However, this perspective is slowed down by toxicity concerns, the most effective materials being based on Pb and Hg. There is currently a large effort to bring forth new platforms that are active in the infrared with a reduced heavy metal content. Here, in this study, the focus is on silver chalcogenides, which, thanks to a combination of inter‐ and intraband transitions, is suited to cover both short and mid wave infrared ranges. However, this material being less mature, the achieved photoluminescence (PL) appears quite broad, which is problematic for device integration. Here, it is demonstrated that a strong control over the PL spectrum can be obtained through integration into a dielectric cavity that magnifies the electric field by a factor 20 and narrows the PL full width at half maximum down to 15 nm for an emission at telecom wavelength. The PL is also highly directional to avoid most waveguiding effects which is of utmost interest for enhancing the efficiency of NC‐based light emitting diodes.

infrared luminescence↗

Silver(I) Supported Liquid Membranes for Selective Ethylene Recovery from Mixed-Gas Streams of Tandem CO 2 Electrolysis

Large-scale olefin separations from unreacted paraffins and other byproduct gases are primarily done by energy-intensive cryogenic distillation processes at refineries. Silver(I) supported liquid membranes (Ag SLMs) can be implemented at smaller production scales of ethylene (C 2 H 4 ), a critical industrial chemical, such as its electrocatalytic (EC) production from CO 2 . Challenges of EC C 2 H 4 production mainly stem from reducing gases like hydrogen (H 2 ), where the redox reactions pertinent to Ag(I) facilitators diminish olefin transport. Herein we report that aqueous Ag(I) solution in a composite Ag SLM can operate in mixed-gas conditions containing H 2 gas utilizing reduced titania compounds, such as titanium(III) oxide (Ti 2 O 3 ). Embedding Ti 2 O 3 in the polydimethylsiloxane layer of Ag SLM assisted in selectively separating C 2 H 4 from mixed-gas feed streams related to CO 2 electrolysis containing H 2 . The direct exposure of a mixed-gas stream containing C 2 H 4 , CO 2 , CO, N 2 , and CH 4 with as high as 50 vol % H 2 maintained excellent C 2 H 4 separations for 7 days of continuous operation. The Ag SLM provided effective separations of C 2 H 4 from CO (at detection limits), CH 4 (selectivity ratio (α) = 20–30), and H 2 (α = ∼20), but C 2 H 4 from CO 2 (α = 2–4) revealed a slightly lower separation. These data show that aqueous Ag(I) solution(s) used in the SLMs can separate C 2 H 4 for extended periods, even under highly reducing gas conditions. Also, we report C 2 H 4 recovery from the gas mixture produced in the EC CO 2 reduction process. In conclusion, the Ag SLM gave C 2 H 4 selective separation from a five-component complex mixed-gas stream, relevant to tandem CO 2 electrolysis.

37 - INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL C↗

In Crystallo Synthesis of a Triplet Silver Nitrene

Reactive silver nitrenes are proposed intermediates in Ag-catalyzed C–H amination and olefin aziridination reactions. Synthesis and characterization of reactive Ag nitrenes has proven elusive due to fleeting lifetimes and argentophilic aggregation of Ag(I) precursors in solution. Here, we report the templated in crystallo synthesis and characterization of a mononuclear Ag nitrene supported by a tris(pyrazolyl)borate ligand. Photolytic N 2 elimination from the corresponding aryl azide complex yields a structurally defined Ag nitrene with a triplet ground state, as confirmed by crystallography, magnetic measurements, and quantum chemical calculations. This species displays both stoichiometric and catalytic nitrene transfer reactivity, enabling carbazole and indole formation from organic azides. These results leverage in crystallo templating to isolate a mononuclear triplet nitrene of Ag and provide a platform to experimentally elucidate ligand-controlled selectivity in Ag-catalyzed nitrene transfer catalysis.

Azides↗

Thermal Conductivity Measurement of Extrusion-Printed Silver Using Modulated Photothermal Radiometry

Flexible printed electronics is a rapidly growing field with applications in conformal and flexible devices. However, the physical properties of the films created by many state-of-the-art printing methods become highly dependent on printing parameters, resulting in varying thermal properties often differing significantly from their bulk ink components. To understand the influence of the printing process, we build upon our previous work, where a noncontact optical technique, known as modulated photothermal radiometry (MPTR), was used to measure the thermal conductivity of aerosol-jet-printed thin films. In this work, we use the method to study the thermal properties of extrusion-printed silver on glass and alumina substrates. A noise-resistant data analysis fitting technique is applied using a 2-D heat transfer model. Here, the thermal conductivity measurement is validated using the Weidemann-Franz (WF) relationship from measured electrical conductivity values.

42 ENGINEERING↗

Spray-Coated Silver as Backside Metal for III–V Photovoltaic Devices on GaAs and Ge Substrates

The accelerated increase in demand for III-V space photovoltaics on GaAs and Ge substrates, as well as growing interests in terrestrial applications, motivate the development of cost-effective, high-throughput processing routes of these materials. Here, in this study, we assess spray-coated silver (Ag) back contact metallization as a substitute for electron-beam-evaporated metals currently used in industry. We find that the spray-coated Ag films are dense and continuous. By means of quantum efficiency, dark current-voltage, and illuminated current-voltage characterizations, we show that spray-coated GaAs and Ge solar cells perform similarly to baseline devices with electroplated Au, including under high current densities. We estimate that the thresholds for specific contact resistance below which back contacts do not significantly contribute to resistive loss are 2.1 x 10 -1 Ω•cm 2 for GaAs and 4.7 x 10 -2 Ω•cm 2 for Ge. We experimentally confirm that our spray-coated samples meet these requirements. Peel tests show that the adhesion of plain spray-coated Ag films to the back of p-type Ge substrates used in III-V solar cells is currently insufficient, whereas adhesion to p-type GaAs substrates is outstanding and requires no further optimization.

14 SOLAR ENERGY↗

Synthesis and Characterization of Silver-Modified Nanoporous Silica Materials for Enhanced Iodine Removal

In aquatic environments, the presence of iodine species, including radioactive isotopes like 129 I and I 2 , poses significant environmental and health concerns. Iodine can enter water resources from various sources, including nuclear accidents, medical procedures, and natural occurrences. To address this issue, the use of natural occurring nanoporous minerals, such as zeolitic materials, for iodine removal will be explored. This study focuses on the adsorption of iodine by silver-modified zeolites (13X-Ag, 5A-Ag, Chabazite-Ag, and Clinoptilolite-Ag) and evaluates their performance under different conditions. All materials were characterized using scanning electron microscopey (SEM), energy-dispersive X-ray spectroscopy (EDS), powdered X-ray diffraction (P-XRD), Fourier-transform infrared spectrometry (FTIR), and nitrogen adsorption studies. The results indicate that Chabazite-Ag exhibited the highest iodine adsorption capacity, with an impressive 769 mg/g, making it a viable option for iodine removal applications. 13X-Ag and 5A-Ag also demonstrated substantial adsorption capacities of 714 mg/g and 556 mg/g, respectively, though their behavior varied according to different models. In contrast, Clinoptilolite-Ag exhibited strong pH-dependent behavior, rendering it less suitable for neutral to slightly acidic conditions. Furthermore, this study explored the impact of ionic strength on iodine adsorption, revealing that Chabazite-Ag is efficient in low-salinity environments with an iodine adsorption capacity of 51.80 mg/g but less effective in saline conditions. 5A-Ag proved to be a versatile option for various water treatments, maintaining its iodine adsorption capacity across different salinity levels. In contrast, Clinoptilolite-Ag exhibited high sensitivity to ionic competition, virtually losing its iodine adsorption ability at a NaCl concentration of 0.1 M. Kinetic studies indicated that the pseudo-second-order model best describes the adsorption process, suggesting chemisorption mechanisms dominate iodine removal. Chabazite-Ag exhibited the highest initial adsorption rate with a k 2 value of 0.002 mg g -1 h -1 , emphasizing its superior adsorption capabilities. Chabazite and Clinoptilolite, naturally occurring minerals, provide eco-friendly solutions for iodine adsorption. Chabazite superior iodine removal highlights its value in critical applications and its potential for addressing pressing environmental challenges.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗