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At least 145 records · Page 8

Process of making carbon-carbon composites

A carbon composite structure, for example, an automotive engine piston, is made by preparing a matrix including of a mixture of non crystalline carbon particulate soluble in an organic solvent and a binder that has a liquid phase. The non crystalline particulate also contains residual carbon hydrogen bonding. An uncured structure is formed by combining the matrix mixture, for example, carbon fibers such as graphite dispersed in the mixture and/or graphite cloth imbedded in the mixture. The uncured structure is cured by pyrolyzing it in an inert atmosphere such as argon. Advantageously, the graphite reinforcement material is whiskered prior to combining it with the matrix mixture by a novel method involving passing a gaseous metal suboxide over the graphite surface.

Withers, James C.↗

Comparative Pore Structure and Dynamics for Bacterial Microcompartment Shell Protein Assemblies in Sheets or Shells

Bacterial microcompartments (BMCs) are protein-bound organelles found in some bacteria that encapsulate enzymes for enhanced catalytic activity. These compartments spatially sequester enzymes within semipermeable shell proteins, analogous to many membrane-bound organelles. The shell proteins assemble into multimeric tiles; hexamers, trimers, and pentamers, and these tiles self-assemble into larger assemblies with icosahedral symmetry. While icosahedral shells are the predominant form in vivo , the tiles can also form nanoscale cylinders or sheets. The individual multimeric tiles feature central pores that are key to regulating transport across the protein shell. Our primary interest is to quantify pore shape changes in response to alternative component morphologies at the nanoscale. We used molecular modeling tools to develop atomically detailed models for both planar sheets of tiles and curved structures representative of the complete shells found in vivo . Subsequently, these models were animated using classical molecular dynamics simulations. From the resulting trajectories, we analyzed the overall structural stability, water accessibility to individual residues, water residence time, and pore geometry for the hexameric and trimeric protein tiles from the Haliangium ochraceu m model BMC shell. These exhaustive analyses suggest no substantial variation in pore structure or solvent accessibility between the flat and curved shell geometries. We additionally compare our analysis to hydroxyl radical footprinting data to serve as a check against our simulation results, highlighting specific residues where water molecules are bound for a long time. Although with little variation in morphology or water interaction, we propose that the planar and capsular morphology can be used interchangeably when studying permeability through BMC pores.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Biomolecular budget of persistent, microbial-derived soil organic carbon: The importance of underexplored pools

The details of how soil microorganisms contribute to stable soil organic carbon pools are a pressing knowledge gap with direct implications for soil health and climate mitigation. It is now recognized that microbial necromass contributes substantially to the formation of stable soil carbon. However, the quantification of necromass in soils has largely been limited to model molecules such as aminosugar biomarkers. The abundance and chemical composition of other persistent microbial residues remain unresolved, particularly concerning how these pools may vary with microbial community structure, soil texture, and management practices. We use yearlong soil incubation experiments with an isotopic tracer to quantify the composition of persistent residues derived from microbial communities inhabiting sand or silt dominated soil with annual (corn) or perennial (switchgrass) monocultures. Persistent microbial residues were recovered in diverse soil biomolecular pools including metabolites, proteins, lipids, and mineral-associated organic matter (MAOM). The relative abundances of microbial contributions to necromass pools were consistent across cropping systems and soil textures. The greatest residue accumulation was not recovered in MAOM but in the light density fraction of soil debris that persisted after extraction by chemical fractionation using organic solvents. Necromass abundance was positively correlated with microbial biomass abundance and revealed a possible role of cell wall morphology in enhancing microbial carbon persistence; while gram-negative bacteria accounted for the greatest contribution to microbial-derived carbon by mass at one year, residues from gram-positive Actinobacteria and Firmicutes showed greater durability. Together these results offer a quantitative assessment of the relative importance of diverse molecular classes for generating durable soil carbon.

54 ENVIRONMENTAL SCIENCES↗

Tuning Phase Purity in Chiral 2D Perovskites

The introduction of chiral organic spacers in low-dimensional metal-halide perovskites triggers chiroptical activity, which is appealing for spintronic applications. However, a comprehensive understanding of structure formation and the ability to control phase purity in such materials have yet to be developed. Herein, the impact of processing conditions on the phase purity, microstructure, and chiroptical properties of chiral 2D perovskites is explored. The anisotropic emergence of a 1D perovskite inside the 2D matrix and its dependence on the organic cation chirality, solvent, and thermal annealing conditions are shown. By controlling these parameters, the in-plane conductivity of the films is nearly doubled. Furthermore, it is demonstrated, for the first time, that solvent choice and the spatial configuration of the organic cation can have an impact on the residual lattice strain and the energetic disorder of the system. The fundamentals presented here can help to improve the film deposition methods for low-dimensional chiral perovskites, offering strategies to control phase purity.

36 MATERIALS SCIENCE↗

Replacement of ozone depleting and toxic chemicals in gravimetric analysis of non-volatile residue

The standard tests for determining nonvolatile residue accretion on spacecraft surfaces and in clean processing facilities rely on the use of halogenated solvents that are targeted for elimination because of their toxic or ozone-depleting natures. This paper presents a literature-based screening survey for candidate replacement solvents. Potential replacements were evaluated for their vapor pressure, toxicity, and solvent properties. Three likely candidates were identified: ethyl acetate, methyl acetate, and acetone. Laboratory tests are presented that evaluate the suitability of these candidate replacement solvents.

Arnold, G. S.↗

Ultrapure Water System at JSC for High Purity Cleaning of Flight Hardware, Astromaterial Handling Tools and Solar Wind Samples

Use of Ultrapure Water (UPW) for cleaning of astromaterial sample handling tools and containers was driven by the discontinuation of Freon 113 as a cleaning solvent, due to environmental concerns. Freon 113, recycled using distillation, was very effective at removing organic residues from sample handling hardware. The initial switch to high purity water for astromaterial tool cleaning was modeled after efforts at White Sands Test Facility (WSTF) and current semiconductor UPW production practices in the early 1990s. JSC curation’s first system was comprised of ion exchange polishing cylinders, 55 gallon PVDF-lined storage tank, a few tens of feet of PVDF piping, UV and particle filtration, and this system supported cleaning for lunar, meteorite and Cosmic Dust collectors lab operations. By 2000 a major expansion and upgrade was providing UPW of quality E-1 (ASTM D5127-90) or better at 10 gpm for cleaning of the Genesis solar wind payload for flight, in addition to sample handling tools for other astromaterials. This expansion included a 1000 gallon storage tank and several hundred feet of PVDF piping located in B. 31 and 31N. An extra reverse osmosis process unit was added to incoming water in 2005. Subsequently several major components were replaced, and in anticipation of adding new labs, an enlarged UPW system was designed in 2018 and completed in 2019. This system produces grade E1.1 UPW at 15 gpm in a continuous 1100 ft. loop with 5000 gal. storage tank, supplying 8 laboratories.

Ultrapure water↗

An overview of NASA testing requirements for alternate cleaning solvents used in liquid and gaseous oxygen environments

The elimination of CFC-containing cleaning solvents for oxygen systems has prompted the development of a number of alternative cleaning solvents that must now be evaluated not only for cleanability, but compatibility as well. NASA Handbook 8060.1(NHB 8060.1) establishes the requirements for evaluation, testing, and selection of materials for use in oxygen rich environments. Materials intended for use in space vehicles, specified test facilities, and ground support equipment must meet the requirements of this document. In addition to the requirements of NHB 8060.1 for oxygen service, alternative cleaning solvents must also be evaluated in other areas (such as corrosivity, non-metals compatibility, non-volatile residue contamination, etc.). This paper will discuss the testing requirements of NHB 8060.1 and present preliminary results from early screening tests performed at Marshall Space Flight Center's Materials Combustion Research Facility.

Strickland, John W.↗

Deep Eutectic Solvent Extraction of High-Purity Lignin from a Corn Stover Hydrolysate

Here, a lactic acid/chlorine chloride-based deep eutectic solvent (DES) was used for the extraction of high-purity lignin (up to 94.7%) in high yield (up to 75%) from the hydrolysis/fermentation residue corn stover hydrolysate (CSH), which was generated from a pilot-plant-scale biorefinery. A range of extraction conditions were investigated, which involved varying reaction temperature, time, and DES composition. The relationship between lignin yield, purity, and structural characteristics with DES treatment conditions was determined. The extraction of high-purity lignin from hydrolysis/fermentation residues presents a promising approach for enhancing the economic feasibility of a lignocellulose biorefinery. It was also determined that DES extraction can produce lignin with a controlled range of molecular weight and functional group content.

09 BIOMASS FUELS↗

Replacement Technologies for Precision Cleaning of Aerospace Hardware for Propellant Service

The NASA White Sands Test Facility (WSTF) is developing cleaning and verification processes to replace currently used chlorofluorocarbon-l13- (CFC-113-) based processes. The processes being evaluated include both aqueous- and solvent-based techniques. Replacement technologies are being investigated for aerospace hardware and for gauges and instrumentation. This paper includes the findings of investigations of aqueous cleaning and verification of aerospace hardware using known contaminants, such as hydraulic fluid and commonly used oils. The results correlate nonvolatile residue with CFC 113. The studies also include enhancements to aqueous sampling for organic and particulate contamination. Although aqueous alternatives have been identified for several processes, a need still exists for nonaqueous solvent cleaning, such as the cleaning and cleanliness verification of gauges used for oxygen service. The cleaning effectiveness of tetrachloroethylene (PCE), trichloroethylene (TCE), ethanol, hydrochlorofluorocarbon 225 (HCFC 225), HCFC 141b, HFE 7100(R), and Vertrel MCA(R) was evaluated using aerospace gauges and precision instruments and then compared to the cleaning effectiveness of CFC 113. Solvents considered for use in oxygen systems were also tested for oxygen compatibility using high-pressure oxygen autogenous ignition and liquid oxygen mechanical impact testing.

Harold Beeson↗

Hot Oil Removes Wax

Mineral oil heated to temperature of 250 degrees F (121 degrees C) found effective in removing wax from workpieces after fabrication. Depending upon size and shape of part to be cleaned of wax, part immersed in tank of hot oil, and/or interior of part flushed with hot oil. Pump, fittings, and ancillary tooling built easily for this purpose. After cleaning, innocuous oil residue washed off part by alkaline aqueous degreasing process. Serves as relatively safe alternative to carcinogenic and environmentally hazardous solvent perchloroethylene.

Herzstock, James J.↗

Precision Cleaning Verification of Nonvolatile Residues by Using Water, Ultrasonics, and Turbidity Analyses

Chlorofluorocarbons (CFC's) in the atmosphere are believed to present a major environmental problem because they are able to interact with and deplete the ozone layer. NASA has been mandated to replace chlorinated solvents in precision cleaning, cleanliness verification, and degreasing of aerospace fluid systems hardware and ground support equipment. KSC has a CFC phase-out plan which provides for the elimination of over 90 percent of the CFC and halon use by 1995. The Materials Science Laboratory and KSC is evaluating four analytical methods for the determination of nonvolatile residues removal by water: (1) infrared analyses using an attenuated total reflectance; (2) surface tension analyses, (3) total organic content analyses, and (4) turbidity analyses. This research project examined the ultrasonic-turbidity responses for 22 hydrocarbons in an effect to determine: (1) if ultrasonics in heated water (70 C) will clean hydrocarbons (oils, greases, gels, and fluids) from aerospace hardware; (2) if the cleaning process by ultrasonics will simultaneously emulsify the removed hydrocarbons in the water; and (3) if a turbidimeter can be used successfully as an analytical instrument for quantifying the removal of hydrocarbons. Sixteen of the 22 hydrocarbons tested showed that ultrasonics would remove it at least 90 percent of the contaminated hydrocarbon from the hardware in 10 minutes or less giving a good ultrasonic-turbidity response. Six hydrocarbons had a lower percentage removal, a slower removal rate, and a marginal ultrasonic-turbidity response.

Skinner, S. Ballou↗

Surfactant/Supercritical Fluid Cleaning of Contaminated Substrates

CFC's and halogenated hydrocarbon solvents have been the solvents of choice to degrease and otherwise clean precision metal parts to allow proper function. Recent regulations have, however, rendered most of these solvents unacceptable for these purposes. New processes which are being used or which have been proposed to replace these solvents usually either fail to remove water soluble contaminants or produce significant aqueous wastes which must then be disposed of. In this work, a new method for cleaning surfaces will be investigated. Solubility of typical contaminants such as lubricating greases and phosphatizing bath residues will be studied in several surfactant/supercritical fluid solutions. The effect of temperature, pressure, and the composition of the cleaning mixture on the solubility of oily, polar, and ionic contaminants will be investigated. A reverse micellar solution in a supercritical light hydrocarbon solvent will be used to clean samples of industrial wastes. A reverse micellar solution is one where water is dissolved into a non-polar solvent with the aid of a surfactant. The solution will be capable of dissolving both water-soluble contaminants and oil soluble contaminants. Once the contaminants have been dissolved into the solution they will be separated from the light hydrocarbon and precipitated by a relatively small pressure drop and the supercritical solvent will be available for recycle for reuse. The process will be compared to the efficacy of supercritical CO2 cleaning by attempting to clean the same types of substrates and machining wastes with the same contaminants using supercritical CO2. It is anticipated that the supercritical CO2 process will not be capable of removing ionic residues.

White, Gary L.↗

Analysis of Nonvolatile Residue (NVR) from Spacecraft Systems

Organic contamination on critical spacecraft surfaces can cause electronic problems, serious attenuation of various optical signals, thermal control changes, and adhesion problems. Such contaminants can be detected early by the controlled use of witness mirrors, witness plates, wipe sampling, or direct solvent extraction. Each method requires careful control of variables of technique and materials to attain the ultimate sensitivities inherent to that procedure. Subsequent chemical analysis of the contaminant sample by infrared and mass spectrometry identifies the components, gives semiquantitative estimates of contaminant thickness, indicates possible sources of the nonvolatile residue (NVR), and provides guidance for effective cleanup procedures.

Colony, J. A.↗

Failure Analysis of Nonvolatile Residue (NVR) Analyzer Model SP-1000

National Aeronautics and Space Administration (NASA) subcontractor Wiltech contacted the NASA Electrical Lab (NE-L) and requested a failure analysis of a Solvent Purity Meter; model SP-IOOO produced by the VerTis Instrument Company. The meter, used to measure the contaminate in a solvent to determine the relative contamination on spacecraft flight hardware and ground servicing equipment, had been inoperable and in storage for an unknown amount of time. NE-L was asked to troubleshoot the unit and make a determination on what may be required to make the unit operational. Through the use of general troubleshooting processes and the review of a unit in service at the time of analysis, the unit was found to be repairable but would need the replacement of multiple components.

Potter, Joseph C.↗

Alternative Nonvolatile Residue Analysis with Contaminant Identification Project

Cleanliness verification is required in numerous industries including spaceflight ground support, electronics, medical and aerospace. Currently at KSC requirement for cleanliness verification use solvents that environmentally unfriendly. This goal of this project is to produce an alternative cleanliness verification technique that is both environmentally friendly and more cost effective.

Technology Portfolio System↗

Sulfonamide and Sulfonamido-phenol Ligands for Extraction of f-Elements from Alkaline High-Level Waste

Alkaline High Level Waste (HLW) has been accumulated at Hanford and Savannah River Sites as a result of reprocessing for nuclear weapons production during the cold war. A large volume (∼100 MGal) has been accumulated in carbon steel tanks at Savannah River (SRS) and Hanford. The tank waste contains three separate phases generated when NaOH was added to previously acidic Purex raffinates: 1-2 Supernatant liquid, salt-cake, and sludge. The sludge consists mainly of insoluble hydroxides of transition metals while the supernate and salt-cake contain caustic-soluble materials, including salts of highly radioactive fission products Cs(I) and Sr(II). Current treatment of alkaline HLW in SRS includes: i) The Actinide Removal Process (ARP), which is based on sorption of {sup 90}Sr and Actinides (An) on monosodium titanate (MST), also known as 'alpha-strike' process, followed by ii) Caustic Side Solvent Extraction (CSSX),4 which is used for the extraction of {sup 137}Cs by modified calixarenes in a hydrocarbon diluent. Residual actinides in some tanks are removed after CSSX by an additional ARP process commonly referred to as 'alpha-finishing'. Despite the success of ARP for Sr and An removal, as it is a sorption process, it represents the kinetic bottleneck of integrated salt waste processing. Hence potential introduction of additional organic ligands for actinide extraction (in a modified CSSX process) could simplify the overall integrated process, making it more efficient and economical, with less titanate needed and shorter sorption time, as some of the actinide component would be removed during CSSX. In this study tri-sulfonamide and o-sulfonamido-phenol (mono-sulfonamide) ligands have been studied as extractants for Sm(III), which is being used as an Am(III) surrogate. Our prior studies in the group using a tri-sulfonamide (iPr-tsa-B) showed favorable extraction for Sm(III) nitrate salts from alkaline solutions. Mono-sulfonamides possess similar orientation of binding sites to pyrocatechols, which have been found to be good ligands for Am(III) binding and extraction from alkaline media. Tri-sulfonamide of the type iPr-tsa-B6 (1 mM in CH{sub 2}Cl{sub 2} solution) was studied for Ln{sup 3+} extraction using Sm(NO{sub 3}){sub 3}.6H{sub 2}0 (10 and 25 μM) in alkaline solution of NaOH (0.05, 0.1, 0.2, 0.3 mM) / 0.1 M NaNO{sub 3}. Stripping of the organic phase was done using 0.1 M HNO{sub 3} and quantification of Sm{sup 3+} was done using ICP-OES at 359.3 nm. The need to improve stability of the complex led to synthesis of compounds with N-donor site closer to the central benzene ring to facilitate cation-π interactions. Synthesis of tri-sulfonamide type A: a) Chloromethyl methyl ether, SnCl{sub 4}, CH{sub 2}Cl{sub 2}, 0 deg. C, N{sub 2}, 4 h, 57%; b) NaN{sub 3}, reflux in H{sub 2}O/acetone for 22 h, 80%; c) PPh{sub 3}, THF/H{sub 2}O, 22 h, 79%; d) p-toluene sulfonyl chloride, Et{sub 3}N, 1,2-DCE, 22 h. Extraction: Sm(NO{sub 3}){sub 3}.6H{sub 2}O (2 mM) in 5 ml of aqueous NaOH (pH 10.5 - 14) + 6 ml of CH{sub 2}Cl{sub 2} solution of msa (20 mole equiv.) were rotated on a wheel (60 rpm; 20 h). Stripping: 5 ml of 0.1 M HNO{sub 3} + CH{sub 2}Cl{sub 2} solution of msa (after extraction, centrifugation and filtration) was rotated on the wheel (60 rpm; 20 h). Sm{sup 3+} was quantified using UV-Visible spectrophotometry.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

The Development of Methodologies and Solvent Systems to Replace CFC-113 in the Validation of Large-Scale Spacecraft Hardware

Liquid oxygen is used as the oxidizer for the liquid fueled main engines during the launch of the space shuttle. Any hardware that comes into contact with pure oxygen either during servicing of the shuttle or in the operation of the shuttle must be validated as being free of nonvolatile residue (NVR). This is a safety requirement to prevent spontaneous combustion of carbonaceous NVR if it was to come into contact with pure oxygen. Previous NVR validation testing of space hardware used Freon (CFC-113) as the test solvent. Because CFC-113 no longer can be used, a program was conducted to develop a NVR test procedure that uses a safe environmentally friendly solvent. The solvent that has been used in the new NVR test procedure is water. Work that has been conducted over the past three years has served to demonstrate that when small parts are subjected to ultrasound in a water bath and NVR is present a sufficient quantity is dispersed into the water to analyze for its concentration by the TOC method. The work that is described in this report extends the water wash NVR validation test to large-scale parts; that is, parts too large to be subjected to ultrasound. The method consists of concentrating the NVR in the water wash onto a bed of silica gel. The total adsorbent bed is then analyzed for TOC content by using a solid sample probe. Work that has been completed thus far has demonstrated that hydrocarbon based NVR's can be detected at levels of less than 0.1 mg per square foot of part's surface area by using a simple water wash.

Clausen, Christian A., III↗

FTIR Study of Vapor Offgassing from Orbiter Tile Re-Waterproofing Materials

The work presented in this paper was performed to identify and quantify the offgassing behavior of alternative re-waterproofmg materials under investigation for application to Shuttle Orbiter Thermal Protection System (TPS) tile and blanket materials. The purpose was to determine whether the new materials would cause a problem with the operational analysis of residual vapors using the current portable vapor analyzer, a Miran 203. The materials investigated were limited to dimethylethoxysilane (DMES) and proposed solvent selected as suitable for use in re-waterproofing Orbiter TPS. The solvent was selected in another phase of the overall project. Obiter TPS tiles were injected with the re-waterproofing materials under constant conditions of temperature, relative humidity and air flow. The vapor concentrations of offgassing materials were monitored using Fourier Transform Infrared (FTIR) multi-component analysis, and with the Miran 203 instruments. The procedure was to record the time dependent concentrations of offgassing materials as analyzed by the FTIR, and the time response of the Miran 203 to the materials under consideration. The FTIR was calibrated for vapor phase DMES, tetramethyldisiloxane (TMDS), ethanol and the hydrocarbon solvents to be used to dilute the DMES for application to the TPS tile. The Miran 203 was calibrated for the operational measurement of DMES airborne vapors. The FTIR data, shows for the first time that the principal product which offgases from the tile after the first hour is not DMES, but TMDS and ethanol. The Miran 203 response to TMDS is the primary reading after the re-waterproofing operation is completed. The operational use of the Miran 203 to measure DMES vapors after re-waterproofmg operations has been responding to TMDS. The results of this study suggest that the historical complaints that have contributed to the low threshold limit value (TLV) for DMES concentrations, as read with the Miran 203, are actually based on instrumental responses to TMDS, for which no other toxicology information is available at this time. While there is some interference, the use of the tested hydrocarbon solvents does not adversely affect the response of the Miran 203.

Mattson, C. B.↗