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NASA NTRS1992

Hydrazine monitoring in spacecraft

Hydrazine (HZ) and monomethyl hydrazine (MMH) are highly toxic compounds used as fuels in the Space Shuttle Orbiter Main Engines and in its maneuvering and reaction control system. Satellite refueling during a mission may also result in release of hydrazines. During extravehicular activities, the potential exists for hydrazines to contaminate the suit and to be brought into the internal atmosphere inadvertantly. Because of the high toxicity of hydrazines, a very sensitive, reliable, interference-free, and real-time method of measurement is required. A portable ion mobility spectrometer (IMS) has exhibited a low ppb detection limit for hydrazines suggesting a promising technology for the detection of hydrazines in spacecraft air. The Hydrazine Monitor is a modified airborne vapor monitor (AVM) with a custom-built datalogger. This off-the-shelf IMS was developed for the detection of chemical warfare agents on the battlefield. After early evaluations of the AVM for hydrazine measurements showed a serious interference from ammonia, the AVM was modified to measure HZ and MMH in the ppb concentration range without interference from ammonia in the low ppm range. A description of the Hydrazine Monitor and how it functions is presented.

Cross, J. H.↗
NASA NTRS1993

Active Hydrazine Vapor Sampler (AHVS)

The Active Hydrazine Vapor Sampler (AHVS) was developed to detect vapors of hydrazine (HZ) and monomethylhydrazine (MMH) in air at parts-per-billion (ppb) concentration levels. The sampler consists of a commercial personal pump that draws ambient air through paper tape treated with vanillin (4-hydroxy-3-methoxybenzaldehyde). The paper tape is sandwiched in a thin cardboard housing inserted in one of the two specially designed holders to facilitate sampling. Contaminated air reacts with vanillin to develop a yellow color. The density of the color is proportional to the concentration of HZ or MMH. The AHVS can detect 10 ppb in less than 5 minutes. The sampler is easy to use, low cost, and intrinsically safe and contains no toxic material. It is most beneficial for use in locations with no laboratory capabilities for instrumentation calibration. This paper reviews the development, laboratory test, and field test of the device.

Young, Rebecca C.↗
NASA NTRS1993

Near-infrared absorptions of monomethylhydrazine

The peak absorption coefficients for two near-infrared absorptions of monomethylhydrazine, CH3-N2H3, (MMH) were measured. Absorption bands located at 1.524 micrometers (6560/cm), 1.557 micrometers (6423/cm), and 1.583 micrometers (6316/cm) are assigned to the Delta upsilon = 2 overtones of the infared N-H stretching fundamentals at 3317, 3245 and 3177/cm. An absorption band located at 1.04 micrometers (9620 +/- 100/cm) is assigned to the Delta upsilon = 3 overtone of one of these fundamentals. The peak absorption coefficients (alpha(sub 10)) at 1.524 micrometers (6560 +/- 20/cm) and 1.04 micrometers (9620 +/- 100/cm) are 31 x 10(exp -3) and 0.97 x 10(exp -3)/(cm atm), respectively. Uncertainties in these coefficients were estimated to be less than +/- 20% due primarily to uncertainties in the partial vapor pressure of MMH.

Murray, Mark↗
NASA NTRS1999

Reactivities of Precision Cleaning Solvents with Hypergolic Propellants

The reactivities of several selected halogenated precision cleaning solvents with hypergolic propellants has been determined by analysis of the rates of formation of halide ion decomposition products. The solvents were Asahiklin AK 225, Asahiklin AK 225 AES, HFE 7100, HFE 7100 DE, Vertrel XF, Vertrel MCA, Vertrel MCA Plus, 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113), and trans-1,2-dichloroethylene (DCE). The propellants were hydrazine (HZ), monomethylhydrazine (MMH), and mixed oxides of nitrogen (MON-3). The Vertrel solvents showed significant reactivity with HZ. All of the solvents except DCE exhibited significant reactivity with MMH, particularly HFE 7100 DE and CFC-113. HFE 7100 DE, Vertrel MCA, and Vertrel MCA Plus also showed significant reactivity with MON-3 oxidizer.

Davis, Dennis D.↗
NASA NTRS2000

Impurities Formed in Artificially Aged Methylhydrazine

A sample of monomethylhydrazine (MMH) meeting MIL-PRF-27404C requirements was split into two portions. One portion was periodically exposed to atmospheric contaminants while stored in clear glass, and the other portion, held as a reference sample, was stored under nitrogen in amber glass. Impurities in both samples were periodically characterized by Gas Chromatograph-Mass Spectrometer (GC-MS) to determine what changes might occur in MMH when it is stored in less than ideal conditions. The qualitative and semi-quantitative results of this study are reported herein.

McClure, Mark B.↗
NASA NTRS1999

A Multiphase Equation of State for Hydrazine and Monomethylhydrazine

The objective of this work was to obtain a validated equation of state for hydrazine and monomethylhydrazine (MMH) and use this equation to calculate thermodynamic properties. The approach was based on using both reliable critical property values and a value of the acentric factor in the Soave Redlich Kwong and the Peng Robinson model equations of state. These equations were validated by comparing calculated molar volumes for phase equilibrium with published experimental values and comparing calculated vapor pressures with published experimental values over the temperature range appropriate for the corresponding state equations. The equation of state giving the best results was used to calculate enthalpy and entropy departure functions and fugacity values. Additional thermodynamic property calculations were performed to produce partial Mollier diagrams and thermodynamic properties containing internal energy, enthalpy, and entropy values for hydrazine and MMH. The analyses of systems in which either adiabatic or near-adiabatic compression of liquid or vapor hydrazine or low velocity detonations occur require a validated equation of state for representing occurring molar volumes and for energy calculations. Other calculations for thermodynamic properties of hydrazine are available, but the values are for a strict ideal gas state. This work characterized destructive events using hydrazine by calculating for isentropic compression temperatures. The final temperatures were calculated and compared using the ideal and real gas fluid equations of state.

Barragan, Michelle↗
NASA NTRS2001

Mars Flyer Rocket Propulsion Risk Assessment Kaiser Marquardt Testing

This report describes the investigation of a 10-N, bipropellant thruster, operating at -40 C, with monomethylhydrazine (MMH) and 25% nitric oxide in nitrogen tetroxide (MON-25). The thruster testing was conducted as part of a risk reduction activity for the Mars Flyer, a proposed mission to fly a miniature airplane in the Martian atmosphere. Testing was conducted using an existing thruster, designed for MMH and MON-3 propellants. The nitric oxide content of MON-3 was increased to 25%, to lower its freezing point to -55 C. The thruster was conditioned, along with the propellants, to temperature prior to hot firing. Thruster operating parameters included oxidizer-to-fuel mixture ratios of 1.6 to 2.7 and inlet pressure ranging from 689 to 2070 kPa. The test matrix consisted of many 10-second firings and several 60-, 300-, 600-, and 1200-second firings, as well as pulse testing. The thruster successfully accumulated nearly 10,000 seconds of operation without failure, at temperatures ranging from -40 C to 22 C. At nominal inlet pressures, the ignition delay was comparable to MMH/MON-3 operation. The optimal performance for the 8.9-N thruster was determined to be at a mixture ratio of 1.93 with an average specific impulse of 298 sec.

Marquardt, Kaiser↗
NASA NTRS2001

Electronic Nose: Evaluation of Kamina Prototype Unit

The Kamina, Sam and Cyranose electronic nose systems were evaluated and partially trained. Much work was performed on the Kamina as it has the ability to respond to low (less than 10 ppb) concentrations of hydrazine compounds. We were able to tell the difference between Hydrazine (Hz) and Monomethylhydrazine (MMH) in standard clean humid air. We were able to detect MMH in reduced pressure (1/3 atm) at about 250 ppb, however the training set was to far from the real situation to be useful now. Various engineering and usability aspects of both the noses was noted, especially the software. One serious physical engineering flaw was remedied in the Kamina system. A gas flow manifold was created for the Sam system. Different chips were evaluated for the Kamina system. It is still unclear if they can be exchanged without retraining the software.The Sam Detect commercial unit was evaluated for solvent detection and evaluation. It was able to successfully identify some solvents. The Cyranose, was observed and evaluated for two days. It has the ability to detect gasses in the 100 parts per million level but not the 10 parts per billion level. It is very sensitive to humidity changes; there is software to partially handle this.

Schattke, Nathan↗
NASA NTRS1999

High-Performance Bipropellant Engine

TRW, under contract to the NASA Lewis Research Center, has successfully completed over 10 000 sec of testing of a rhenium thrust chamber manufactured via a new-generation powder metallurgy. High performance was achieved for two different propellants, N2O4- N2H4 and N2O4 -MMH. TRW conducted 44 tests with N2O4-N2H4, accumulating 5230 sec of operating time with maximum burn times of 600 sec and a specific impulse Isp of 333 sec. Seventeen tests were conducted with N2O4-MMH for an additional 4789 sec and a maximum Isp of 324 sec, with a maximum firing duration of 700 sec. Together, the 61 tests totalled 10 019 sec of operating time, with the chamber remaining in excellent condition. Of these tests, 11 lasted 600 to 700 sec. The performance of radiation-cooled rocket engines is limited by their operating temperature. For the past two to three decades, the majority of radiation-cooled rockets were composed of a high-temperature niobium alloy (C103) with a disilicide oxide coating (R512) for oxidation resistance. The R512 coating practically limits the operating temperature to 1370 C. For the Earth-storable bipropellants commonly used in satellite and spacecraft propulsion systems, a significant amount of fuel film cooling is needed. The large film-cooling requirement extracts a large penalty in performance from incomplete mixing and combustion. A material system with a higher temperature capability has been matured to the point where engines are being readied for flight, particularly the 100-lb-thrust class engine. This system has powder rhenium (Re) as a substrate material with an iridium (Ir) oxidation-resistant coating. Again, the operating temperature is limited by the coating; however, Ir is capable of long-life operation at 2200 C. For Earth-storable bipropellants, this allows for the virtual elimination of fuel film cooling (some film cooling is used for thermal control of the head end). This has resulted in significant increases in specific impulse performance (15 to 20 sec). To determine the merits of a powder rhenium thrust chamber, Lewis On-Board Propulsion Branch directed TRW (under the Space Storable Rocket Technology Program and the High Pressure Earth Storable Rocket Technology Program) to design, fabricate, and test an engineering model to serve as a technology demonstrator.

Biaglow, James A.↗
NASA NTRS2015

Nontoxic Ionic Liquid Fuels for Exploration Applications

The toxicity of propellants used in conventional propulsion systems increases not only safety risks to personnel but also costs, due to special handling required during the entire lifetime of the propellants. Orbital Technologies Corporation (ORBITEC) has developed and tested novel nontoxic ionic liquid fuels for propulsion applications. In Phase I of the project, the company demonstrated the feasibility of several ionic liquid formulations that equaled the performance of conventional rocket propellant monomethylhydrazine (MMH) and also provided low volatility and low toxicity. In Phase II, ORBITEC refined the formulations, conducted material property tests, and investigated combustion behavior in droplet and microreactor experiments. The company also explored the effect of injector design on performance and demonstrated the fuels in a small-scale thruster. The ultimate goal is to replace propellants such as MMH with fuels that are simultaneously high-performance and nontoxic. The fuels will have uses in NASA's propulsion applications and also in a range of military and commercial functions.

Coil, Millicent↗
NASA NTRSDate not supplied

The Influence of Chemical Descriptors on the Reactivity of Potential Hypergolic Fuels With Hydrogen Peroxide

The state-of-the-art for storable hypergolic bipropellant systems is monomethylhydrazine (MMH) and mixed oxides of nitrogen (MON). While MMH and MON provide fast and highly reliable hypergolic ignition with excellent propulsive performance, they suffer from safety concerns impacting their production, cost, and supply to various test and launch facilities. In contrast, identifying and demonstrating low-toxicity fuels hypergolic with rocket grade hydrogen peroxide (H2O2) has been challenging with long ignition delay (IDT) and low propulsive performance affecting their deployment in flight systems. This work describes a preliminary observational study to assess the effects of molecular descriptors suspected to predict the reactivity and hypergolicity of compounds within the same chemical class (i.e., thioamide). The approach centered on evaluating functional groups, electrostatic potential, number of carbons, dipole moment, and adiabatic ionization energy. Thiourea is hypergolic with 89.2 wt.% H2O2 (minimum IDT of 21.9 ms) and was selected as a core fuel to study the reactivity of derived fuels with different functionalities. Additionally, the chemical properties were calculated with the Gaussian16 suite. The results showed that group substitution and generally increased number of carbons on thiourea increases IDT. It was observed that a more positively charged sulfur atom in the thioamide does not increase the reactivity towards H2O2. The dipole moment analysis revealed an overall trend of decreasing IDT due to increasing dipole moment. Finally, a lower adiabatic ionization energy related to increased IDTs for most cases. Additional chemical classes comprising a wider range of functionalities and electrophilic attributes are being investigated in on-going work.

Propellant↗
NASA NTRS2024

NASA Engineering and Safety Center Technical Bulletin No. 24-01: Material Compatibility of Common Aerospace Metals in MMH/MON-3

The NESC evaluated material compatibility of some common aerospace metals in monomethylhydrazine (MMH) and nitrogen tetroxide (MON-3). Previous work had identified a lack of quantitative compatibility data for nickel alloy 718, 300 series stainless steel, and titanium Ti-6Al-4V in MMH and MON-3 to support the use of zero-failure-tolerant, thin-walled pressure barriers in these propellants. Static (i.e., not flowing) general corrosion and electrochemistry testing was conducted, evaluating varied processing forms and heat treatment of the metals, water content of propellant, and exposure duration. Corrosion-rate data for all tested product forms, fluids, and durations were on the order of 1 x 10 –6 inch per year rather than the previously documented “less than 1 x 10 –3 inch per year”. The majority of the corrosion products were seen in the first 20 days of exposure, with an overall corrosion rate decreasing with time due to the increased divisor (time). It is therefore recommended that corrosion testing be performed at multiple short-term durations to inform the need for longer-duration testing.

Heather K Hickman↗
NASA NTRS2025

Transit Habitat Government-Reference Conceptual Design Reaction Control System Propulsion Concept Design Data Book

The function of Transit Habitat (TH) Reaction Control System (RCS) propulsion is to provide free-flying spacecraft capabilities and to augment Gateway stack control when docked on Gateway. The requirements of multiple propellant replenishments and extensive life operation have significant impacts on selection of the propulsion system concept and components for the RCS. The intent of this document is to provide insight into the government-reference conceptual design of a propulsion system for TH element. A pressure-fed hypergolic bi-propellant system is the assumed propulsion approach for the RCS. Its architectural concept is being traded within the NASA Moon to Mars architecture. A pressure-regulated system is examined. The propellants under consideration are Monomethyl Hydrazine (MMH) and Mixed Oxides of Nitrogen with 3% Nitric Oxide (MON3). A peer review was conducted to assess the flow schematic design and propulsion component selection, compliant with a set of assumed requirements. Redundant components to satisfy one-fault tolerance for function and two-fault tolerance against catastrophic events are incorporated in the propulsion concept design. Instrumentation laid out on the schematic would be used to gather data to monitor the health of the propulsion system and to support quantity gauging of the propulsion system fluids. Venting propellant ullage gas overboard during the refilling operations poses a significant concern to the external surfaces of the TH. A liquid/gas separator would be required to eliminate, or at least reduce, the amount of liquid propellant expelled in the vent gas mixture. The technology readiness level of the phase separator for the TH must be advanced. Metal diaphragm and non-positive-expulsion PMD propellant tank systems were traded against each other, with the PMD architecture being selected. A blowdown concept is also considered for the TH RCS propulsion. Its fluid schematic is derived from the pressure-regulated schematic with removal of assemblies involving the helium pressurization and ullage venting. Its system wet mass is 10% heavier than the pressure-regulated due to thruster performance loss and larger propellant tanks. There is no firm constraint on the propulsion system mass at this phase of the design. The blowdown concept can offer reduction in component count and operation, that would lead to a more reliable propulsion system. The blowdown concept would also benefit avionics, thermal, power, and structures on the TH. Assessing these benefits will be carried as a future work. Drawbacks of thrust and minimum impulse bit (MIB) variations due to the blowdown operation would be acceptable to Guidance, Navigation, and Control (GNC). Although the blowdown concept has been selected as a current baseline, further evaluation of the concept will be the subject of future work to ensure that the blowdown propulsion operation is appropriate for the HT RCS propulsion. This document also highlights key trade studies and design decisions, including pros and cons of the selected concept. Other appropriate options for components are pointed out for future assessments. Additional background information and documents for further review are referenced in this report.

spacecraft propulsion↗
NASA NTRS1971

Toxic Hazards Research Unit

The activities of the Toxic Hazards Research Unit (THRU) for the period of June 1970 through May 1971 reviewed. Modification of the animal exposure facilities primarily for improved human safety but also for experimental integrity and continuity are discussed. Acute toxicity experiments were conducted on hydrogen fluoride (HF), hydrogen chloride (HCl), nitrogen dioxide (NO2), and hydrogen cyanide (HCN) both singly and in combination with carbon dioxide (CO). Additional acute toxicity experiments were conducted on oxygen difluoride (OF2) and chlorine pentafluoride (ClF5). Subacute toxicity studies were conducted on methylisobutylketone and dichloromethane (methylene dichloride). The interim results of further chronic toxicity experiments on monomethylhydrazine (MMH) are also described.

Macewen, J. D.↗
NASA NTRS1972

Investigation of critical burning of fuel droplets

Measurements were made on the burning of liquid hydrazine, MMH, and UDMH in a combustion gas environment. The experimental range of these tests involved gas temperatures of 1660-2530 K, oxygen concentrations of 0-42% by mass and droplet diameters (employing both droplets and porous spheres) of 0.11-1.91 cm. at atmospheric pressure. A simplified hybrid combustion theory was developed which was found to correlate the present results as well as the experimental measurements of other investigators. Measurements were also made of the monopropellant strand burning rates and liquid surface temperatures of a number of nitrate ester fuels and hydrazine at elevated pressures. The temperature measurements for the nitrate esters were found to be in good agreement with a theoretical model which allowed for gas solubility in the liquid phase at high pressures. Experimental results were also obtained on the burning rates and liquid surface temperatures of a number of paraffin and alcohol fuels burning in air pressures up to 72 atm. For these tests, the fuels were burned from porous spheres in a natural convection environment. Initial findings on a pressurized flat flame burner are also described as well as the design of an oscillatory combustion apparatus to test the response of burning liquid fuels.

Allison, C. B.↗
NASA NTRS1972

Toxic Hazards Research Unit annual technical report, 1972

The activities of the Toxic Hazards Research Unit (THRU) for the period of June 1971 through May 1972 are reviewed in this report. Acute inhalation toxicity experiments were conducted on hydrogen chloride (HCl) gas and aerosol, ethyl bromide (C2H5Br), hydrogen bromide (HBr), hydrogen sulfide (H2S), ammonia (NH3), chlorine (CL2), and silane (SiH4). Subacute toxicity studies were conducted on chlorine pentafluoride (ClF5), dichloromethane (CH2Cl2) and coal tar volatiles. Further toxicity studies of subacute and chronic responses to inhaled monomethylhydrazine (MMH) are also described.

Macewen, J. D.↗
NASA NTRS1973

Thermal control and structures approach for fluorinated propulsion.

FLOX and fluorine oxidizers require cryogenic storage at 86 K (-305 F) aboard a spacecraft, whereas their respective fuels MMH and hydrazine require room temperature storage. Propulsion configuration trade-off studies have been made for two potential classes of missions, an outer planet orbiter utilizing RTG's and an inner planet orbiter utilizing solar panels. The preliminary designs incorporate the fuel tank within the thermally controlled electronics compartment and expose the cryogenic tank to space. The cryogenic tank is isolated with foam, shadow shields and a titanium truss support. Its vernier temperature control is accomplished with electrical heaters.

Stimpson, L. D.↗
NASA NTRS1973

Development of the propulsion subsystem for the Viking 75 Orbiter

The development of the Viking 75 Orbiter propulsion subsystem has been completed and qualification is under way. This development required an extension of the Mariner Mars 1971 propulsion subsystem technology to meet the Viking 75 requirements of three times the burn time and five times the number of burns. Modifications have been incorporated into the rocket engine to increase the cooling margin for the 2700-second Mars orbit insertion burn. This capability has been demonstrated in both engine firings and subsystem tests. A new surface tension device has been developed to position the propellants (N2O4 and MMH) over the tank outlets during zero-g flight. Extensive scale model testing has been conducted to prove this propellant management concept. This subsystem will provide midcourse corrections, an orbit insertion burn and 20 orbit trims for the Viking 75 Spacecraft. The Viking Project is managed by the Langley Research Center, National Aeronautics and Space Administration.

Vote, F. C.↗