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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.↗

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↗

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.↗

PAH in the laboratory and interstellar space

The theory that polycyclic aromatic hydrocarbons (PAHs) are a constituent of the interstellar medium, and a source of the IR emission bands at 3.3, 6.2, 7.7, 8.6, and 11.3 microns is being studied using PAH containing acid insoluble residue of the Orgueil CI meteorite and coal tar. FTIR spectra of Orgueil PAH material that has undergone thermal treatment, and a solvent insoluble fraction of coal tar that has been exposed to hydrogen plasma are presented. The UV excided luminescence spectrum of a solvent soluble coal tar film is also shown. Comparison of the lab measurements with observations appears to support the interstellar PAH theory, and shows the process of dehydrogenation expected to take place in the interstellar medium.

Wdowiak, Thomas J.↗

Development of CFC-Free Cleaning Processes at the NASA White Sands Test Facility

The NASA White Sands Test Facility (WSTF) is developing cleaning and verification processes to replace currently used chlorofluorocarbon-113- (CFC-113-) based processes. The processes being evaluated include both aqueous- and solvent-based techniques. The presentation will include the findings of investigations of aqueous cleaning and verification processes that are based on a draft of a proposed NASA Kennedy Space Center (KSC) cleaning procedure. Verification testing with known contaminants, such as hydraulic fluid and commonly used oils, established correlations between nonvolatile residue and CFC-113. Recoveries ranged from 35 to 60 percent of theoretical. WSTF is also investigating enhancements to aqueous sampling for organics and particulates. 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), tert-butylmethylether, and n-Hexane 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 autoignition and liquid oxygen mechanical impact testing.

Beeson, Harold↗

Photo-Induced Deuterium Enrichment in Residues Produced from the UV Irradiation of Pyrimidine in H2O and H2O+NH3 Ices

Organic compounds found in meteorites often show isotopic signatures of their interstellar/protosolar heritage as enrichments in D and 15N. Meteoritic organics found to be enriched in D include amino acids, hydroxy and dicarboxylic acids, as well as polycyclic aromatic hydrocarbons (PAHs). Processes that can produce isotopic enrichments in presolar/protosolar materials include gas-phase ion-molecule reactions, gas-grain surface reactions, and unimolecular photo-dissociation reactions involving PAHs. Because many molecules in interstellar clouds are enriched in D, the presence of D anomalies in meteorites is thought to originate from preserved or slightly altered interstellar/protostellar materials. However, the link between isotopic enrichments seen in space and those in meteoritic compounds and their relationship remain unclear. In this work, we present results of hydrogen isotopic fractionation for compounds in organic residues produced from the UV irradiation using an H2- discharge UV lamp of H2O:pyrimidine = 20:1 and H2O:NH3:pyrimidine = 20:2:1 ice mixtures at low temperature (is less than 20 K). After irradiation, the resulting residues are dissolved in H2O and analyzed with gas chromatography-mass spectrometry coupled with isotope ratio mass spectrometry (GC-MS/IRMS) [1], following a protocol similar to that used for previous analyses of comparable samples [2,3]. We used this technique to measure compound-specific D/H isotopic ratios for the initial pyrimidine and for two photo-products present in the residues, namely, 2,2'-bipyrimidine and an unidentified bipyrimidine isomer [2-4]. Measuring D enrichments in bipyrimidines has the advantage that the H atoms on these molecules are not easily exchangeable with other compounds, in particular the H2O and NH3 present in the ices or the solvents used to extract the samples for GC-MS/IRMS measurements. The δD value for the initial pyrimidine, measured with a high-temperature conversion elemental analyzer connected to the IRMS, was found to be -30% per mille. Preliminary measurements made on a residue produced from the UV irradiation of an H2O:NH3:pyrimidine = 20:2:1 ice mixture indicate δD values of +118% per mille for 2,2'- bipyrimidine and +92% per mille for the other bipyrimidine isomer, and therefore show a significant D enrichment during the photo-processing and warm-up that lead to their formation [5]. New measurements are currently being performed on a number of residues produced from simpler H2O:pyrimidine = 20:1 ice mixtures under different experimental conditions and will be presented here.

Laboratory Astrochemistry↗

Prepsolv (TM): The optimum alternative to 1,1,1-trichloroethane and methyl ethyl ketone for hand-wipe cleaning of aerospace materials

Engineers at Hercules Aerospace, a rocket motor manufacturer in Utah, have worked closely with chemists at Glidco Organics to study the feasibility of using terpenes for zero-residue wipe cleaning. The result of this work is a technological breakthrough, in which the barrier to ultra-low non-volatile residue formation has been broken. After 2 years of development and testing, SCM Glidco Organics has announced the availability of Glidsafe(registered trademark) Prepsolv(TM): a state-of-the-art ultra-low residue terpene wipe cleaning agent that does not require rinsing. Prepsolv(TM) can successfully be used in simple hand-wipe cleaning processes without fear of leaving surface residues. Industry testing has confirmed that Prepsolv(TM) is not only highly effective, but can even be less expensive to use than traditional cleaning solvents like methyl chloroform. This paper addresses the features and benefits of Prepsolv(TM), and presents performance and material compatibility data that characterizes this unique cleaning agent. Since its commercialization, Hercules Aerospace has chosen Prepsolv(TM) as the optimum cleaning agent to replace ozone-depleting solvents in their weapons factory in Magna, UT. Likewise, Boeing has approved Prepsolv(TM) for cleaning components in the manufacture of commercial aircraft at their facilities in Seattle, WA and Wichita, KS. Additional approvals are forthcoming for this uniquely safe and effective solvent.

Gallagher, R. Scott↗

The Insoluble Carbonaceous Material of CM Chondrites as Possible Source of Discrete Organics During the Asteroidal Aqueous Phase

The larger portion of the organic carbon in carbonaceous chondrites (CC) is present as a complex and heterogeneous macromolecular material that is insoluble in acids and most solvents (IOM). So far, it has been analyzed only as a whole by microscopy (TEM) and spectroscopy (IR, NMR, EPR), which have offered and overview of its chemical nature, bonding, and functional group composition. Chemical or pyrolytic decomposition has also been used in combination with GC-MS to identify individual compounds released by these processes. Their value in the recognition of the original IOM structure resides in the ability to properly interpret the decomposition pathways for any given process. We report here a preliminary study of IOM from the Murray meteorite that combines both the analytical approaches described above, under conditions that would realistically model the IOM hydrothermal exposure in the meteorite parent body. The aim is to document the possible release of water and solvent soluble organics, determine possible changes in NMR spectral features, and ascertain, by extension, the effect of this loss on the frame of the IOM residue. Additional information is included in the original extended abstract.

Yabuta, H.↗

Solvent Replacement for Hydrochlorofluorocarbon-225 for Cleaning Oxygen System Components

This Technical Memorandum is the result of a 2-year project funded by the Defense Logistics Agency-Aviation, Hazardous Minimization and Green Products Branch, to identify and test two candidate solvents to replace hydrochlorofluorocarbon-225 (HCFC-225) for cleaning oxygen systems. The solvents were also compared to a second solvent composed predominantly of perfluorobutyl iodide (PFBI), which had received limited approval by the United States Air Force (USAF) for hand wipe cleaning of components for aviators’ breathing oxygen systems. The tests performed for this study were based on those reported in AFRL-ML-WP-TR-2003-4040, “The Wipe Solvent Program,” the test program used to qualify Ikon® Solvent P for USAF applications.The study was completed in August 2014, prior to the completion of a more extensive study funded by the NASA Rocket Propulsion Test (RPT) program. The results of the RPT project are reported in NASA/TP-2015-18207, “Replacement of Hydrochlorofluorocarbon–225 Solvent for Cleaning and Verification Sampling of NASA Propulsion Oxygen Systems Hardware, Ground Support Equipment, and Associated Test Systems.” The test methods used in this study for nonvolatile residue (NVR) background, materials compatibility, and cleaning effectiveness were different than those used for the RPT project; a smaller set of materials and contaminants were tested. The tests for this study were complementary to and provided supplementary information for the down-selection process during the course of the test program reported in NASA/TP-2015-218207.

Mitchell, M. A.↗

Chemical Aging of Environmentally Friendly Cleaners

Use of cleaners in the manufacturing area demands bottles that will hold a sufficient amount of material and allow for easy and controlled dispensing by the operator without contamination or material leaching from the bottle. The manufacturing storage conditions are also a factor that may affect cleaner chemical integrity and its potential to leave a residue on the part. A variety of squeeze bottles stored in mild (72 F, 10 % R.H., dark) and harsh (105 F, 50 % R.H., fluorescent lighting) conditions were evaluated to determine the effect of environment and bottle exposure on the chemical composition of TCA (1,1,1 trichloroethane) replacement solvents. Low Density Polyethylene (LDPE) bottles were found to be quite permeable to all the cleaners evaluated in this study indicating this bottle type should not be used in the manufacturing area. Fluorinated Polyethylene (FLPE) bottles showed little cleaner loss and change in cleaner chemical composition over time suggesting these bottles would be acceptable for use. Chemical analysis indicates limonene-containing cleaners show increased non-volatile residue (NVR) content with storage under harsh conditions. Some cleaners use BHT (butylated hydroxytoluene) as stabilizer and to protect against limonene oxidation. Under harsh conditions, BHT was quickly depleted resulting in higher NVR levels.

Evans, K.↗