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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 145 records · Page 8

Alkaline Zinc Passivation Mechanism is Controlled by Hydroxide Concentration

We studied Zn passivation and oxide growth in Zincate (Zn(OH) 4 2− ) in 4 and 8 M KOH solutions using an electrochemical quartz crystal microbalance (EQCM), building on our initial work at 1 M KOH where passivation was kinetically controlled. A porous passivating oxide spontaneously forms on Zn electrodes when KOH is above 4 M and saturated with zincate. However, passivation does not occur when bulk zincate concentration is decreased, resulting in continual Zn dissolution. EQCM data suggests that the passivation mechanism is strongly affected by pOH. Mass transport and kinetic processes in the 4 M KOH electrolytes couple and govern Zn passivation. At 8 M, KOH concentration shifts passivation to mass transport control. We explain this by the increased solubility of Zn(OH) 3 − with increasing pOH. The variation in the mechanism of passivation implications for how passivation is handled in Zn-alkaline batteries. The importance of controlling the mass transport increases with increased pOH, suggesting that electrode design, additives, and potential flow should be optimized. At lower pOHs, kinetics and mass transport must be balanced to manage passivation effectively. Additionally, the changing nature of the native oxide layer on the surface has implications for the evenness of deposition and dissolution on the Zn electrode.

Wittman, Reed M. [Oak Ridge National Laboratory (O↗

Outgassing of casted and 3D printed silicones

Outgassing of 3D printed and casted silica-filled silicones was studied using a standard ASTM E-595 procedure and a modified Soreq’s method that allows very sensitive measurements of the outgassing kinetics even at low temperatures, 20 – 50 °C. We studied three different silica-filled silicones, non-porous cased M9787, and 3D printed LL50 and 40P materials. The present report shows that vacuum outgassing products of polysiloxane-based materials include multiple species. In addition to chemisorbed and physisorbed water outgassing, previously studied by TPD, polymer fragments of varying sizes evaporate as well. The chemical composition of the condensable volatile species collected on a Germanium substrate, was analyzed by FTIR. It was shown that all studied materials produce mostly PDMS-based outgassing products that form stable droplet-like structure on the Ge substrate. The highest amount of the condensable volatile species was measured for LL50. Isothermal TGA in nitrogen atmosphere of the LL50 material was compared to the standard vacuum outgassing. The results of TGA showed lower mass loss and higher water regain. The kinetics of the outgassing at relatively low temperatures of 20, 30 and 50 °C was studied using Thermoelectric Quartz Crystal Microbalance (TQCM). The TQCM surface was held at -10 °C to enhance condensation of the outgassed moisture. The analysis presented here, when combined with the extensive previous work on moisture outgassing, provides a better understanding of the aging mechanism of polysiloxane-based materials. In this work we show that outgassing techniques, usually applied for qualification of polymers for space-related applications, may be used as a complementary method to study thermal degradation and aging of silica-based silicones. Our results indicate that the long-term degradation mechanics and thermal degradation products depend primarily on the chemical composition of silicone-based material and only slightly affected by the manufacturing process. Surprisingly, the surface-to-volume ratio of the 3D printed vs. casted/molded materials showed only minor effect on the outgassing kinetic parameters.

36 MATERIALS SCIENCE↗

CRADA Number NFE-21-08827 with DayLyte, Inc. (CRADA Final Report)

DayLyte Batteries is developing an aqueous Sodium-Air battery made with abundant materials while being half to a third the weight of Li-ion to power electric aircraft, electric vehicles and provide renewable energy on demand. To make this battery practical, DayLyte is developing a thin film ceramic Nasicon solid electrolyte amenable to rapid scaleup as well as a protective coating that will protect the solid electrolyte from 50wt% NaOH during the battery’s end-of-discharge while still allowing Na-ions to pass back and forth. If the thin film solid electrolyte and stable coating can be developed it will open the world to step change in battery performance all while not sacrificing the environment on the way. The project was designed to first focus on making and characterizing the Nasicon membrane followed by measuring its electrochemical performance, then assembling a full cell, optimizing its NaOH stability and then optimize the overall prototype design. Over the past two years, we have significantly improved the Nasicon film uniformity, demonstrated protective ligands that are stable in 50wt% NaOH by measuring no mass change with a quartz crystal microbalance, tested different heating methods like tube furnace and rapid heating and developed glassy carbon coatings on the current collector to prevent Nasicon-current collector alloying. We have found that getting film uniformity as measured by electrochemical impedance spectroscopy (EIS) is difficult because of different factors like surface roughness, deposition uniformity and heat treatment time and uniformity. The glassy carbon coating should significantly reduce the surface roughness and by tuning the coating conditions the film deposition uniformity improves and using an automated heating method should lead to much improved film uniformity.

25 ENERGY STORAGE↗

Mercury Detection Utilizing an Aquatic Animal as a Remote-Sensing Platform

Mercury species in open water, especially the accumulated methylmercury ion, pose a threat to fish and environment. Therefore, it is important to develop a small sensor package that can be integrated into a biotelemetry sensor carried by an aquatic animal, enhancing the ability to detect mercury contamination in large water areas. A quartz crystal microbalance (QCM) sensor using metal-organic framework (MOF) as sensing material was developed to detect mercury and methylmercury ions in real time based on acoustic wave perturbation. Thiol groups were introduced into the MOF UiO-66 through the organic linker to prepare the UiO-66-SH which was confirmed by infrared spectroscopy results. Batch adsorption experiments were conducted for the Hg 2+ , CH 3 Hg + , and Ca 2+ ions adsorption in the UiO-66-SH. The adsorption capacities of the mercury ions were more than an order of magnitude higher than those of the competing Ca 2+ ions at the same concentration. The frequency changes of the QCM sensor with the UiO-66-SH sensing film were an order of magnitude higher than those of the controlled baseline QCM sensor without a sensing film. Additionally, the frequency change can be tailored by adjusting the thickness of the MOF film and the adsorption properties of the sensing material. The sensor frequency change correlates well with ion adsorption capacities.

47 OTHER INSTRUMENTATION↗

Tuning gold-based surface functionalization for streptavidin detection: A combined simulative and experimental study

A rationally designed gold-functionalized surface capable of capturing a target protein is presented using the biotin–streptavidin pair as a proof-of-concept. We carried out multiscale simulations to shed light on the binding mechanism of streptavidin on four differently biotinylated surfaces. Brownian Dynamics simulations were used to reveal the preferred initial orientation of streptavidin over the surfaces, whereas classical molecular dynamics was used to refine the binding poses and to investigate the fundamental forces involved in binding, and the binding kinetics. We assessed the binding events and the stability of the streptavidin attachment through a quartz crystal microbalance with dissipation monitoring (QCM-D). The sensing element comprises of biotinylated polyethylene glycol chains grafted on the sensor’s gold surface via thiol-Au chemistry. Finally, we compared the results from experiments and simulations. We found that the confined biotin moieties can specifically capture streptavidin from the liquid phase and provide guidelines on how to exploit the microscopic parameters obtained from simulations to guide the design of further biosensors with enhanced sensitivity.

59 BASIC BIOLOGICAL SCIENCES↗

Atomic Force Microscopy to Characterize Antimicrobial Peptide-Induced Defects in Model Supported Lipid Bilayers

Antimicrobial peptides (AMPs) interact with bacterial cell membranes through a variety of mechanisms, causing changes extending from nanopore formation to microscale membrane lysis, eventually leading to cell death. Several AMPs also disrupt mammalian cell membranes, despite their significantly different lipid composition and such collateral hemolytic damage hinders the potential therapeutic applicability of the AMP as an anti-microbial. Elucidating the mechanisms underlying the AMP–membrane interactions is challenging due to the variations in the chemical and structural features of the AMPs, the complex compositional variations of cell membranes and the inadequacy of any single experimental technique to comprehensively probe them. (1) Background: Atomic Force Microscopy (AFM) imaging can be used in combination with other techniques to help understand how AMPs alter the orientation and structural organization of the molecules within cell membranes exposed to AMPs. The structure, size, net charge, hydrophobicity and amphipathicity of the AMPs affect how they interact with cell membranes of differing lipid compositions. (2) Methods: Our study examined two different types of AMPs, a 20-amino acid, neutral, α-helical (amphipathic) peptide, alamethicin, and a 13-amino acid, non-α-helical cationic peptide, indolicidin (which intramolecularly folds, creating a hydrophobic core), for their interactions with supported lipid bilayers (SLBs). Robust SLB model membranes on quartz supports, incorporating predominantly anionic lipids representative of bacterial cells, are currently not available and remain to be developed. Therefore, the SLBs of zwitterionic egg phosphatidylcholine (PC), which represents the composition of a mammalian cell membrane, was utilized as the model membrane. This also allows for a comparison with the results obtained from the Quartz Crystal Microbalance with Dissipation (QCM-D) experiments conducted for these peptides interacting with the same zwitterionic SLBs. Further, in the case of alamethicin, because of its neutrality, the lipid charge may be less relevant for understanding its membrane interactions. (3) Results: Using AFM imaging and roughness analysis, we found that alamethicin produced large, unstable defects in the membrane at 5 µM concentrations, and completely removed the bilayer at 10 µM. Indolicidin produced smaller holes in the bilayer at 5 and 10 µM, although they were able to fill in over time. The root-mean-square (RMS) roughness values for the images showed that the surface roughness caused by visible defects peaked after peptide injection and gradually decreased over time. (4) Conclusions: AFM is useful for helping to uncover the dynamic interactions between different AMPs and cell membranes, which can facilitate the selection and design of more efficient AMPs for use in therapeutics and antimicrobial applications.

Swana, Kathleen W.↗

Self-Cleaning Highly Porous TiO 2 Coating Designed by Swelling-Assisted Sequential Infiltration Synthesis (SIS) of a Block Copolymer Template

Photocatalytic self-cleaning coatings with a high surface area are important for a wide range of applications, including optical coatings, solar panels, mirrors, etc. Here, we designed a highly porous TiO 2 coating with photoinduced self-cleaning characteristics and very high hydrophilicity. This was achieved using the swelling-assisted sequential infiltration synthesis (SIS) of a block copolymer (BCP) template, which was followed by polymer removal via oxidative thermal annealing. The quartz crystal microbalance (QCM) was employed to optimize the infiltration process by estimating the mass of material infiltrated into the polymer template as a function of the number of SIS cycles. This adopted swelling-assisted SIS approach resulted in a smooth uniform TiO 2 film with an interconnected network of pores. The synthesized film exhibited good crystallinity in the anatase phase. The resulting nanoporous TiO 2 coatings were tested for their functional characteristics. Exposure to UV irradiation for 1 h induced an improvement in the hydrophilicity of coatings with wetting angle reducing to unmeasurable values upon contact with water droplets. Furthermore, their self-cleaning characteristics were tested by measuring the photocatalytic degradation of methylene blue (MB). The synthesized porous TiO 2 nanostructures displayed promising photocatalytic activity, demonstrating the degradation of approximately 92% of MB after 180 min under ultraviolet (UV) light irradiation. Thus, the level of performance was comparable to the photoactivity of commercial anatase TiO 2 nanoparticles of the same quantity. Our results highlight a new robust approach for designing hydrophilic self-cleaning coatings with controlled porosity and composition.

36 MATERIALS SCIENCE↗

Nozzle exhaust plume backscatter experiment using the JPL Molsink facility

Qualitative tests were made by injecting water through a rocket nozzle wall, and the droplet trajectories were observed photographically. These tests were conducted for nozzles in which boundary layer flow is significant. The tests indicated that both gases and particulate matter will be found in the region outside of the plume boundaries, and can be calculated using current analytical techniques. A test program is being conducted to measure the distribution of exhaust gases from small nozzles using an electron beam/photomultiplier system and a matrix of quartz crystal microbalances. Calibration tests, using simulated hydrazine exhaust product gas mixtures, were also conducted. The test program and results of the pumping calibration tests with hydrazine (simulated hydrazine exhaust products) are reported.

Simon, W.↗

Determination of contamination character of materials in space technology testing

The contamination characters of selected materials used in space technology testing. Specific materials were subjected to a thermal vacuum environment, and the outgases were collected on a cold test mirror surface. Approximately one-half of the surface of the mirror was subjected to ultraviolet irradiation while the outgases were being deposited on the mirror. The purpose of these experiments was to determine the effect of ultraviolet irradiation on the contaminative character of outgases from selected materials. The degree of contamination was measured in terms of degradation of the optical properties of the test mirror and the amount of deposit per unit area on quartz crystal microbalances placed near the test mirror, and by means of quadrupole mass spectral measurements of outgases from the test samples.

Haynes, D. L.↗

Exhaust plume and contamination characteristics of a bipropellant (MMH/N2O4) RCS thruster

Results are presented for three recent tests in a series of thruster contamination experiments made in liquid helium-cooled environmental facility. The contaminating effects encountered on various materials, surfaces, and components, due to the exhaust products from a 5-pound thrust, bipropellant (MMH/N2O4) thruster are investigated. The angular distribution of plume effects around the periphery of the thruster established by transmittance changes of quartz samples over the wavelength range from 0.2 to 2.0 micrometer is studied, along with mass deposition rates at a specific location measured with a quartz crystal microbalance for three different experiments. Quadrupole mass spectrometer measurements of the exhaust products over the mass number range from 12 to 75; infrared transmittance measurements of contaminated samples for the wavelength range from 2.5 to 15 microns; and infrared transmittance measurements of residue from the thruster nozzle are also considered.

Spisz, E. W.↗

ATS-F radiant cooler contamination test in a hydrazine thruster exhaust

A test was conducted under simulated space conditions to determine the potential thermal degradation of the ATS-F radiant cooler from any contaminants generated by a 0.44-N(0.1-lbf) hydrazine thruster. The radiant cooler, a 0.44-N(0.1-lbf)hydrazine engine, and an aluminum plate simulating the satellite interface were assembled to simulate their flight configuration. The cooler was provided with platinum sensors for measuring temperature, and its surfaces were instrumented with six quartz crystal microbalance units (QCM) to measure contaminant mass deposits. The complete assembly was tested in the molecular sink vacuum facility (Molsink) at the Jet Propulsion Laboratory. This was the first time that a radiant cooler and a hydrazine engine were tested together in a very-high-vacuum space simulator, and this test was the first successful measurement of detectable deposits from hydrazine rocket engine plumes in a high vacuum. The engine was subjected to an accelerated duty cycle of 1 pulse/min, and after 2-hr of operation, the QCMs began to shift in frequency. The tests continued for several days and, although there was considerable activity in the QCMs, the cooler never experienced thermal degradation.

Chirivella, J. E.↗

Molecular flux measurements in the back flow region of a nozzle plume

A series of tests were conducted to measure the mass flux in the far field of a nozzle plume in a high vacuum with emphasis on the back flow region. The measurements presented provided fairly accurate data for off-axis angles as large as 140 deg (i.e., in the back flow region). This region, since it is well behind the exit plane, is of paticular interest to those concerned with instrument contamination. Usually sensitive spacecraft surfaces are located in the region affected by the back flow. Parameters such as expansion ratio, throat diameter, nozzle lip shape, and plenum (chamber) pressure were varied, carbon dioxide and nitrogen gases were flowed and mass flux measurements were taken using quartz crystal microbalances in as many as nine different locations relative to the tests nozzle. Several conclusions with respect to the effect of nozzle and gas parameters on the amount of back flow mass flux are offered, and it was demonstrated that gaseous mass fluxes, which are not predictable by present theories, are encountered in the region behind the nozzle exit plane. This knowledge is significant if materials incompatible with the gaseous exhaust products are used in this region.

Chirivella, J. E.↗

Mass flux measurements and correlations in the back flow region of a nozzle plume.

A series of tests were conducted to measure the mass flux in the far field of a nozzle plume in a high vacuum with emphasis on the back flow region. The measurements presented in this report provide fairly accurate data for off-axis angles as large as 140 deg (i.e., the back flow region). The tests utilized five different nozzles. Parameters such as expansion ratio, throat diameter, nozzle lip shape, and plenum (chamber) pressure were varied. Carbon dioxide and nitrogen gases were passed through, and mass flux measurements were taken using quartz crystal microbalances in as many as nine different locations relative to the test nozzle. The tests resulted in a large matrix of data that were correlated and compared to existing prediction theories. Several conclusions with respect to the effect of nozzle and gas parameters on the amount of back flow mass flux are offered, and it was demonstrated that gaseous mass fluxes, which are not predictable by present theories, are encountered in the region behind the nozzle exit plane.

Chirivella, J. E.↗