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Environmentally Sound Processing Technology: JANNAF Safety and Environmental Protection Subcommittee and Propellant Development and Characterization Subcommittee Joint Workshop

Topics covered include: Risk assessment of hazardous materials, Automated systems for pollution prevention and hazardous materials elimination, Study design for the toxicity evaluation of ammonium perchlorate, Plasma sprayed bondable stainless surface coatings, Development of CFC-free cleaning processes, New fluorinated solvent alternatives to ozone depleting solvents, Cleaning with highly fluorinated liquids, Biotreatment of propyleneglycol nitrate by anoxic denitrification, Treatment of hazardous waste with white rot fungus, Hydrothermal oxidation as an environmentally benign treatment technology, Treatment of solid propellant manufacturing wastes by base hydrolysis, Design considerations for cleaning using supercritical fluid technology, and Centrifugal shear carbon dioxide cleaning.

Pickett, Lorri A.

Plasma Cleaning

NASA's Kennedy Space Center has developed two solvent-free precision cleaning techniques: plasma cleaning and supercritical carbon dioxide (SCCO2), that has equal performance, cost parity, and no environmental liability, as compared to existing solvent cleaning methods.

supercritical fluid cleaning

Alternative Solvents and Technologies for Precision Cleaning of Aerospace Components

Precision cleaning solvents for aerospace components and oxygen fuel systems, including currently used Vertrel-MCA, have a negative environmental legacy, high global warming potential, and have polluted cleaning sites. Thus, alternative solvents and technologies are being investigated with the aim of achieving precision contamination levels of less than 1 mg/sq ft. The technologies being evaluated are ultrasonic bath cleaning, plasma cleaning and supercritical carbon dioxide cleaning.

Green solvents

Green Solvents for Precision Cleaning

Aerospace machinery used in liquid oxygen (LOX) fuel systems must be precision cleaned to achieve a very low level of non-volatile residue (< 1 mg0.1 m2), especially flammable residue. Traditionally chlorofluorocarbons (CFCs) have been used in the precision cleaning of LOX systems, specifically CFC 113 (C2Cl3F3). CFCs have been known to cause the depletion of ozone and in 1987, were banned by the Montreal Protocol due to health, safety and environmental concerns. This has now led to the development of new processes in the precision cleaning of aerospace components. An ideal solvent-replacement is non-flammable, environmentally benign, non-corrosive, inexpensive, effective and evaporates completely, leaving no residue. Highlighted is a green precision cleaning process, which is contaminant removal using supercritical carbon dioxide as the environmentally benign solvent. In this process, the contaminant is dissolved in carbon dioxide, and the parts are recovered at the end of the cleaning process completely dry and ready for use. Typical contaminants of aerospace components include hydrocarbon greases, hydraulic fluids, silicone fluids and greases, fluorocarbon fluids and greases and fingerprint oil. Metallic aerospace components range from small nuts and bolts to much larger parts, such as butterfly valves 18 in diameter. A fluorinated grease, Krytox, is investigated as a model contaminant in these preliminary studies, and aluminum coupons are employed as a model aerospace component. Preliminary studies are presented in which the experimental parameters are optimized for removal of Krytox from aluminum coupons in a stirred-batch process. The experimental conditions investigated are temperature, pressure, exposure time and impeller speed. Temperatures of 308 - 423 K, pressures in the range of 8.3 - 41.4 MPa, exposure times between 5 - 60 min and impeller speeds of 0 - 1000 rpm were investigated. Preliminary results showed up to 86 cleaning efficiency with the moderate processing conditions of 323 K, 13.8 MPa, 30 min and 750 rpm.

solvents

Hydrofluoroether (HFE) Cleaning Fluid Replacement and Qualification

This NASA Engineering and Safety Center (NESC) Technical Assessment Report addresses the urgent need to identify, test, and qualify replacement cleaning solvents and technologies following 3M’s decision to discontinue production of hydrofluoroether (HFE) products, including Novec HFE-7100, by the end of 2025. HFE-7100 is widely used across NASA for precision cleaning of ground and flight hardware, especially in oxygen system components, and as a heat transfer fluid in high-power-density thermal control systems. The assessment evaluates commercially available replacement solvents, alternative cleaning technologies, and their compatibility with NASA’s operational requirements. Key findings include the identification of viable solvent replacements, their performance in contaminant removal, materials compatibility, and oxygen system safety. The report also explores novel cleaning approaches, including aqueous, supercritical CO₂, cryogenic aerosol, plasma, UV-ozone, magnetically optimized fluids, and induced charge active filtration, highlighting their merits, limitations, and readiness for NASA adoption. The NESC provides recommendations for solvent selection, facility adaptation, and continued technology maturation to ensure mission continuity and regulatory compliance.

Alternative Cleaning Technologies

Supercritical CO2 Cleaning System for Planetary Protection and Contamination Control Applications

Current spacecraft-compatible cleaning protocols involve a vapor degreaser, liquid sonication, and alcohol wiping. These methods are not very effective in removing live and dead microbes from spacecraft piece parts of slightly complicated geometry, such as tubing and loosely fitted nuts and bolts. Contamination control practices are traditionally focused on cleaning and monitoring of particulate and oily residual. Vapor degreaser and outgassing bakeout have not been proven to be effective in removing some less volatile, hydrophilic biomolecules of significant relevance to life detection. A precision cleaning technology was developed using supercritical CO2 (SCC). SCC is used as both solvent and carrier for removing organic and particulate contaminants. Supercritical fluid, like SCC, is characterized by physical and thermal properties that are between those of the pure liquid and gas phases. The fluid density is a function of the temperature and pressure. Its solvating power can be adjusted by changing the pressure or temperature, or adding a secondary solvent such as alcohol or water. Unlike a regular organic solvent, SCC has higher diffusivities, lower viscosity, and lower surface tension. It readily penetrates porous and fibrous solids and can reach hard-to-reach surfaces of the parts with complex geometry. Importantly, the CO2 solvent does not leave any residue. The results using this new cleaning device demonstrated that both supercritical CO2 with 5% water as a co-solvent can achieve cleanliness levels of 0.01 mg/cm2 or less for contaminants of a wide range of hydrophobicities. Experiments under the same conditions using compressed Martian air mix, which consists of 95% CO2, produced similar cleaning effectiveness on the hydrophobic compounds. The main components of the SCC cleaning system are a high-pressure cleaning vessel, a boil-off vessel located downstream from the cleaning vessel, a syringe-type high-pressure pump, a heat exchanger, and a back pressure regulator (BPR). After soaking the parts to be cleaned in the clean vessel for a period, the CO2 with contaminants is flushed out of the cleaning vessel using fresh CO2 in a first-in-first-out (FIFO) method. The contaminants are either precipitating out in the boil-off container or being trapped in a filter subsystem. The parts to be cleaned are secured in a basket inside and can be rotated up to 1,400 rpm by a magnetic drive. The fluid flows within the vessel generate tangential forces on the parts surfaces, enhancing the cleaning effectiveness and shortening the soaking time. During the FIFO flushing, the pump subsystem pushes fresh CO2 into the cleaning vessel at a constant flow rate between 0.01 and 200 mL/min, while the BPR regulates the pressure in the cleaning vessel to within 0.1 bar by controlling the needle position in an outlet valve. The fresh CO2 gas flows through the heat exchanger at a given temperature before entering the cleaning vessel. A platinum resistance thermometer (PRT) reads the cleaning vessel interior temperature that can be controlled to within 0.1 K. As a result, cleaning vessel temperature remains constant during the FIFO flushing. There is no change in solvent power during FIFO flushing since both temperature and pressure inside the cleaning vessel remain unchanged, thus minimizing contaminants left behind. During decompression, both temperature and pressure are strictly controlled to prevent bubbles from generating in the cleaning vessel that could stir up the contaminants that sank to the bottom by gravity.

Lin, Ying

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.

High Energy Cutting and Stripping Utilizing Liquid Nitrogen

The Aerospace Industry has endeavored for decades to develop hybrid materials that withstand the rigors of mechanized flight both within our atmosphere and beyond. The development of these high performance materials has led to the need for environmentally friendly technologies for material re-work and removal. The NitroJet(TM) is a fluid jet technology that represents an evolution of the widely used, large-scale water jet fluid jet technology. It involves the amalgamation of fluid jet technology and cryogenics technology to create a new capability that is applicable where water jet or abrasive jet (water jet plus entrained abrasive) are not suitable or acceptable because of technical constraints such as process or materials compatibility, environmental concerns and aesthetic or legal requirements. The NitroJet(TM) uses ultra high-pressure nitrogen to cut materials, strip numerous types of coatings such as paint or powder coating, clean surfaces and profile metals. Liquid nitrogen (LN2) is used as the feed stream and is pressurized in two stages. The first stage pressurizes sub cooled LN2 to an intermediate pressure of between 15,000 and 20,000 psi at which point the temperature of the LN2 is about -250 F. The discharge from this stage is then introduced as feed to a dual intensifier system, which boosts the pressure from 15,000 - 20,000 psi up to the maximum operating pressure of 55,000 psi. A temperature of about -220 F is achieved at which point the nitrogen is supercritical. In this condition the nitrogen cuts, strips and abrades much like ultra high-pressure water would but without any residual liquid to collect, remove or be contaminated. Once the nitrogen has performed its function it harmlessly flashes back into the atmosphere as pure nitrogen gas. The system uses heat exchangers to control and modify the temperature of the various intake and discharge nitrogen streams. Since the system is hydraulically operated, discharge pressures can be easily varied over a very wide range providing considerable flexibility for various operations. The NitroJet(TM) is an advance on the nitrogen fluid jet technology initially developed at the Idaho National Engineering Laboratory in Idaho Falls, Idaho. NitroCision(R) first introduced the NitroJet(TM) into a commercial setting in 2003 and there has been considerable interest from many diverse sectors of government and industry since then. While the current system is an industrial system with the size and mass normally associated with industrial applications, a smaller system that is much more compact is being contemplated for those applications that do not need the full capabilities of the larger system. The NitroJet(TM) can be deployed as a fixed or mobile system with multiple end effectors capable of cutting, stripping, cleaning, and surface profiling either in robotic or manual applications.

Hume, Howard

NASA Tech Briefs, April 2012

Topics include: Computational Ghost Imaging for Remote Sensing; Digital Architecture for a Trace Gas Sensor Platform; Dispersed Fringe Sensing Analysis - DFSA; Indium Tin Oxide Resistor-Based Nitric Oxide Microsensors; Gas Composition Sensing Using Carbon Nanotube Arrays; Sensor for Boundary Shear Stress in Fluid Flow; Model-Based Method for Sensor Validation; Qualification of Engineering Camera for Long-Duration Deep Space Missions; Remotely Powered Reconfigurable Receiver for Extreme Environment Sensing Platforms; Bump Bonding Using Metal-Coated Carbon Nanotubes; In Situ Mosaic Brightness Correction; Simplex GPS and InSAR Inversion Software; Virtual Machine Language 2.1; Multi-Scale Three-Dimensional Variational Data Assimilation System for Coastal Ocean Prediction; Pandora Operation and Analysis Software; Fabrication of a Cryogenic Bias Filter for Ultrasensitive Focal Plane; Processing of Nanosensors Using a Sacrificial Template Approach; High-Temperature Shape Memory Polymers; Modular Flooring System; Non-Toxic, Low-Freezing, Drop-In Replacement Heat Transfer Fluids; Materials That Enhance Efficiency and Radiation Resistance of Solar Cells; Low-Cost, Rugged High-Vacuum System; Static Gas-Charging Plug; Floating Oil-Spill Containment Device; Stemless Ball Valve; Improving Balance Function Using Low Levels of Electrical Stimulation of the Balance Organs; Oxygen-Methane Thruster; Lunar Navigation Determination System - LaNDS; Launch Method for Kites in Low-Wind or No-Wind Conditions; Supercritical CO2 Cleaning System for Planetary Protection and Contamination Control Applications; Design and Performance of a Wideband Radio Telescope; Finite Element Models for Electron Beam Freeform Fabrication Process Autonomous Information Unit for Fine-Grain Data Access Control and Information Protection in a Net-Centric System; Vehicle Detection for RCTA/ANS (Autonomous Navigation System); Image Mapping and Visual Attention on the Sensory Ego-Sphere; HyDE Framework for Stochastic and Hybrid Model-Based Diagnosis; and IMAGESEER - IMAGEs for Education and Research.

Source record

Experimental evidence of non-equilibrium phase separation in supercritical fluids

Supercritical fluids (SCFs), widely utilized in many industries, have long been regarded as homogeneous single-phase media. Recent simulation studies identified different phases (more gas-like or liquid-like) in SCFs at equilibrium, expanding the previous notion but still not addressing non-equilibrium properties of SCFs. Here we reveal the existence of long-lived liquid-like clusters in non-equilibrium SCFs by time-resolved small-angle neutron scattering measurements. Since SCFs in industrial applications frequently operate under dynamic, non-equilibrium conditions rather than strict thermodynamic equilibrium, our findings offer crucial information for improving the use of SCFs in industrial settings, like semiconductor cleaning and plant thermal-hydraulic engineering.

Lee, Juho [Pohang Univ. of Science and Technology

Removal of carbonaceous contaminants from silica aerogel

Capture of micrometeorite material from low Earth orbit or dust grains around active comets for return to terrestrial laboratories, capable of practicing the most up to date techniques of chemical isotopic and mineralogical analysis, will greatly enhance our knowledge of primitive material in the solar system. The next generation of space launched cosmic dust collectors will undoubtedly include extremely low density target materials such as silica aerogel as the decelerating and arresting medium. This material has been found to be clean from the point of view of inorganic elements and is thus acceptable for the purpose of harvesting grains to be studied by, for example PIXE, INAA, or SXRF. However, the process used in making aerogel leaves substantial carbon and hydrogen containing residues which would negate their suitability for collection and subsequent investigation of the very important CHON particles. Attempts to precondition aerogel by solvent extraction or heating at 500 C and 750 C in air for 24 hours or under a vacuum of 2(7)(exp -7) torr at 260 C were largely ineffective except that pyrolysis did reduce volatile species. In this investigation we have examined the use of supercritical fluids for the purpose of extracting organic residues. The logic of the new approach is that beyond the supercritical point a substance has the solvating properties of a liquid but the viscosity characteristics of a gas. For example carbon dioxide becomes supercritical at a pressure of 73 atmospheres and a temperature of 31 C; in consequence it can transform to a very powerful and ultraclean solvent. It can dissolve organic matter from low molecular weight up to molecules containing 90 carbon atoms. On release of pressure the fluid reverts to a gas which can easily be pumped away and removed from the substrate being extracted.

Huang, Hui-Ping