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All sources NASA NTRS DOE OSTI

NASA NTRS1993

Sensitive, Selective Test For Hydrazines

Derivatives of hydrazines formed, then subjected to gas chromatography and detected via chemiluminescence. In method of detecting and quantifying hydrazine vapors, vapors reacted with dinitro compound to enhance sensitivity and selectivity. Hydrazine (HZ), monomethyl hydrazine, (MMH), and unsymmetrical dimethylhydrazine (UDMH) analyzed quantitatively and qualitatively, either alone or in mixtures. Vapors collected and reacted with 2,4-dinitrobenzaldehyde, (DNB), making it possible to concentrate hydrazine in derivative form, thereby increasing sensitivity to low initial concentrations. Increases selectivity because only those constituents of sample reacting with DNB concentrated for analysis.

Roundbehler, David↗

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 NTRS2007

Electrochemical Disposal of Hydrazines in Water

An electrochemical method of disposal of hydrazines dissolved in water has been devised. The method is applicable to hydrazine (N2H4), to monomethyl hydrazine [also denoted by MMH or by its chemical formula, (CH3)HNNH2], and to unsymmetrical dimethyl hydrazine [also denoted UDMH or by its chemical formula, (CH3)2NNH2]. The method involves a room-temperature process that converts the hydrazine to the harmless products N2, H2O, and, in some cases, CO2

Kim, Jinseong↗

NASA NTRS1972

Survey of materials for hydrazine propulsion systems in multicycle extended life applications

An assessment is presented of materials compatibility data for hydrazine monopropellant propulsion systems applicable to the Space Shuttle vehicle missions. Materials were evaluated for application over a 10-yr/100-mission operational lifetime with minimum refurbishment. A general materials compatibility rating for a broad range of materials and several propellants based primarily on static liquid propellant immersion testing and an in-depth evaluation of hydrazine decomposition as a function of purity, temperature, material, surface conditions, etc., are presented. The most promising polymeric material candidates for propellant diaphragms and seals appear to have little effect on increasing hydrazine decomposition rates, but the materials themselves do undergo changes in physical properties which can affect their 10-yr performance in multicycle applications. The available data on these physical properties of elastomeric materials as affected by exposure to hydrazine or related environments are presented.

Coulbert, C. D.↗

NASA NTRS1973

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

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

Chirivella, J. E.↗

NASA NTRS1976

The effects of aniline impurities on monopropellant hydrazine thruster performance

Both a 0.45-N and a 0.9-N thruster representative of the designs being flown on 3-axis stabilized spacecraft were used in testing various grades of hydrazine for the phenomenon of monopropellant hydrazine thruster catalyst bed poisoning. Both designs employed Shell 405 ABSG spontaneous catalyst. It is found that pulse shape distortion can be minimized, if not eliminated, by using aniline-free hydrazine. The mechanisms for both steady-state and pulse-mode performance loss are associated with the formation of a catalyst coke similar to the polycyclic aromatic poisons encountered in the petroleum industry. These poisoning mechanisms are reversible, with high-temperature operation being required to drive off the aniline coke deposits. It is recommended that a purified-grade hydrazine be considered for any mission that imposes operational conditions on a thruster which can result in aniline-induced poisoning of the catalyst bed.

Holcomb, L.↗

NASA NTRS1978

Evaluation of the SSRCT engine with a hydrazine as a fuel, phase 1

The performance parameters for the space shuttle reaction control thruster (SSRCT) when the fuel is changed from monomethylhydrazine to hydrazine were predicted. Potential problems are higher chamber wall temperature during steady state operation and explosive events during pulse mode operation. Solutions to the problems are suggested. To conduct the analysis, a more realistic film cooling model was devised which considers that hydrazine based fuels are reactive when used as a film coolant on the walls of the combustion chamber. Hydrazine based fuels can decompose exothermally as a monopropellant and also enter into bipropellant reactions with any excess oxidizer in the combustion chamber. It is concluded that the conversion of the thruster from MMH to hydrazine fuel is feasible but that a number of changes would be required to achieve the same safety margins as the monomethylhydrazine-fueled thruster.

Minton, S. J.↗

NASA NTRS1981

Monomethylhydrazine versus hydrazine fuels - Test results using a 100 pound thrust bipropellant rocket engine

A test program was performed to evaluate hydrazine (N2H4) as a fuel for a 445 Newton (100 lbf) thrust bipropellant rocket engine. Results of testing with an identical thruster utilizing monomethylhydrazine (MMH) are included for comparison. Engine performance with hydrazine fuel was essentially identical to that experienced with monomethylhydrazine although higher combustor wall temperatures (approximately 400 F) were obtained with hydrazine. Results are presented which indicate that hydrazine as a fuel is compatible with Marquardt bipropellant rocket engines which use monomethylhydrazine as a baseline fuel.

Smith, J. A.↗

NASA NTRS1983

Test program to demonstrate the stability of hydrazine in propellant tanks

The suitability of stainless steels and Inconel for long-term hydrazine propellant-storage tanks is investigated. Rectangular coupon samples cut from propellent tanks were sealed with a measured amount of hydrazine in glass capsules, stored at 43 or 60 C, and removed after 6 to 24 months, when corrosion of the coupon and decomposition of the hydrazine was determined, and SEM and electron spectroscopy were performed on some coupons. Corrosion was found to be unmeasurably low for all the coupons, and hydrazine decomposition produced less than 1.0 cu cm of gas per sq cm of wetted surface per year, except in those few cases when catalysis or contamination were detected. Especially good stability was observed for type 304L stainless steel. The decomposition rates determined in the coupon tests are confirmed by preliminary results of actual tank storage trials.

Moran, C. M.↗

NASA NTRS1986

Hydrazine reduction of transition metal oxides - In situ characterization using X-ray photoelectron spectroscopy

The transition metal oxides (TMOs) V2O5, FeO3, Co3O4, NiO, CuO, and ZnO were exposed to hydrazine at various pressures. The metallic surfaces were surveyed by in situ X-ray photoelectron spectroscopy to determine the irrelative rate of reduction by hydrazine. The most easily reducible oxide, CuO, could be reduced to the metallic state at room temperature and 10 to the -6th torr. The reaction is first order with respect to CuO, with an activation energy of about 35 kJ/mol. Two types of adsorption were seen to occur at 295 K: (1) a reversible component in which the measured N:Cu ratio increased to 0.60 at hydrazine pressures up to 0.5 torr, and (2) an irreversible component, with a N:Cu ratio of 0.28, which could not be removed by extended vacuum pumping. The results of this study are useful for the identification of TMO's that can be used as solid neatallizers of hydrazine spills, and for the preparation of metal surfaces for electroplating and evaporative thin-film coating.

Littrell, D. M.↗

NASA NTRS1988

Hydrazine vapor detonations

The detonation velocity and cell widths for hydrazine decomposition were measured over a wide range of temperatures and pressures. The detonation velocity in pure hydrazine was within 5 percent of the calculated C-J velocity. The detonation cell width measurements were interpreted using the Zeldovich-Doering-von Neumann model with a detailed reaction mechanism for hydrazine decomposition. Excellent agreement with experimental data for pure hydrazine was obtained using the empirical relation that detonation cell width was equal to 29 times the kinetically calculated reaction zone length.

Pedley, M. D.↗

NASA NTRS1991

Long life monopropellant hydrazine thruster evaluation for Space Station Freedom application

In support of propulsion system thruster development activity for Space Station Freedom (SSF), NASA Johnson Space Center (JSC) is conducting a hydrazine thruster technology demonstration program. The goal of this program is to identify impulse life capability of state-of-the-art long life hydrazine thrusters nominally rated for 50 pounds thrust at 300 psia supply pressure. The SSF propulsion system requirement for impulse life of this thruster class is 1.5 million pound-seconds, corresponding to a throughput of approximately 6400 pounds of propellant, with a high performance (234 pound-seconds per propellant pound). Long life thrusters were procured from Hamilton Standard, The Marquardt Company, and Rocket Research Company. Testing has initiated on the thruster designs to identify life while simulating expected thruster firing duty cycles and durations for SSF using monopropellant grade hydrazine. This paper presents a review of the SSF propulsion system and requirements as applicable to hydrazine thrusters, the three long life thruster designs procured by JSC and the resultant acceptance test data for each thruster, and the JSC test plan and facility.

Popp, Christopher G.↗

NASA NTRS1992

Occupational safety considerations with hydrazine

Hydrazine is a reducing agent that is most commonly used as a propellant and as an oxygen scavenger in boilers. Hydrazine is extremely irritating and has been demonstrated to produce both acute and chronic toxicity. As a result, the established permissible inhalation exposure limits are very low, and respiration protection is required whenever vapors are present. Liquid hydrazine penetrates the skin and produces a chemical burn; therefore, some protective measures must also be taken to protect the skin from liquid contact. Often, however, a cumbersome, whole-body protective suit is worn to protect against skin contact with vapor as well. To what extent it is actually necessary to protect skin from vapor penetration had not previously been demonstrated. In an attempt to answer this question, we conducted a study with rats to compare the dermal penetration of hydrazine vapor with inhalation. Pharmacokinetic modeling was used to compare body burdens resulting from these different routes of exposure. The analysis concluded that the vapor concentration during a skin-only exposure would have to be at least 200 times higher than that during inhalation to achieve the same body burden. This type of estimation illustrates the use of predictive toxicology in occupational exposures.

Clewell, Harvey J., III↗

NASA NTRS1993

Dosimeter Badge Detects Hydrazines

Disposable dosimeter badge indicates approximate cumulative exposure to hydrazine or monomethyl hydrazine in air. Indication is change in colors of both paper tapes; one coated with para-N, N-dimethylaminobenzaldehyde. Colors of exposed tapes compared with colors on two preprinted color wheels to obtain estimate of exposure. Badges help minimize risks associated with exposure of personnel to hydrazine or monomethyl hydrazine, or suspected carcinogens. Also used as stationary monitors by taping them on walls or equipment at strategic locations.

Young, Rebecca C.↗

NASA NTRS1999

A Review of Hydrazine Sensors: The State of the Art

Several types of sensors have been developed over the past few years that quantify the vapor concentrations of the hydrazines. These sensors are able to detect concentrations as low as 10 parts per billion (ppb) up to several parts per million (ppm). The scope of this review will be focused on those sensors that are most current in the marketplace as either leak detectors or personnel monitors. Some technical information on the theory of operations of each hydrazine detector will also be included. The review will highlight current operations that utilize hydrazine sensors including the Kennedy Space Center (KSC), the United States Air Force (USAF) at Cape Canaveral Air Station (CCAS), USAF F-16 facilities. The orientation of the review will be towards giving users usable practical information on hydrazine sensors.

Meneghelli, B. J.↗

NASA NTRS2004

A Review of Hydrazine Sensors: The State of the Art

Several types of sensors have been developed over the past few years that quantify the vapor concentrations of the hydrazines. These sensor s are able to detect concentrations as low as 10 parts per billion (ppb) up to several parts per million (ppm). The scope of this review wi ll be focused on those sensors that are most current in the marketpla ce as either leak detectors or personnel monitors. Some technical information on the theory of operations of each hydrazine detector will a lso be included. The review will highlight current operations that utilize hydrazine sensors including the Kennedy Space Center (KSC), the United States Air Force (USAF) at Cape Canaveral Air Station (CCAS), USAF F-16 facilities. The orientation of the review will be towards giving users usable practical information on hydrazine sensors.

Meneghelli, B. J.↗

NASA NTRSDate not supplied

Material Compatibility Testing of Green Hydrazine

Green Hydrazine Propellant Blend (GHPB) is a new green propellant developed by Aerojet Rocketdyne and selected for continued testing at NASA’s Goddard Space Flight Center (GSFC). It primarily differs from previous "green” propellants by maintaining traditional hydrazine as the base constituent, along with additives that are intended to increase handling safety by lowering the concentration of hydrazine in the vapor. GSFC has performed material compatibility testing. The scope of this campaign included materials that are common in spacecraft or ground support equipment (GSE), and also included typical safety materials (e.g. permeation rates through gloves). The conclusion in a broad sense is that GHPB is less reactive than hydrazine, including the absorption of metals into the propellant, as examined by Inductively-Coupled Plasma (ICP) analysis of metals uptake.

Eric H Cardiff↗

DOE OSTI2026

Theoretical and kinetic modeling study of hydrazine oxidation

The present work constitutes the first theoretical and kinetic modeling study of hydrazine oxidation, which may be important for burnout in ammonia-fueled combustion. The kinetics of the oxidation of N 2 H 4 , N 2 H 3 and tHNNH by molecular oxygen were investigated via a quantum chemistry/canonical transition state theory approach. Geometries and anharmonic frequencies were obtained with density functional theory, and energies from coupled cluster calculations (CCSD(T)) extrapolated to the infinite basis set limit, with corrections for core-valence electron correlation, scalar relativistic effects, and higher level correlation up to lambda coupled cluster, CCSDT(Q) Λ . The key reactions occurred on the N 2 H 4 O 2 potential energy surface, where the results indicated a fast reaction of N 2 H 3 with HO 2 via singlet adducts to yield tHNNH + H 2 O 2 and HNN(H)O + H 2 O, while reaction on the triplet surface proceeds via a bound complex followed by a tight, submerged barrier to yield N 2 H 4 + O 2 . The results were incorporated in a detailed reaction mechanism, which was used to interpret the shock tube results from Michel and Wagner (1965) on the effect of O 2 on hydrazine conversion at 1100–1400 K. The kinetic model captured qualitatively the observed behavior, but underestimated the reaction rate under oxidizing conditions. The hydrazine pyrolysis chemistry dominated conversion at reducing conditions and/or high temperature. At oxidizing conditions and intermediate temperatures (≲ 1400 K), reactions of N 2 -amines with HO 2 and O 2 were important for the oxidation rate.

Ab initio calculations↗