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At least 73 records · Page 4

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.↗

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.↗

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↗

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↗

High Pressure X-ray Diffraction and Equation of State of Hydrazine

Synchrotron X-ray diffraction has been used to investigate the structure and equation of state (EOS) of hydrazine (N 2 H 4 ) up to 54.3 GPa at 298 K. The diffraction patterns could be fit to a monoclinic unit-cell structure and put strong constraints on previously reported phase transitions documented by vibrational spectroscopy over this pressure range. Pressure–volume ( P–V ) data were fit using a Vinet EOS, yielding parameters: V 0 = 45.2 Å 3 /molecule (fixed), K 0 = 11.8(7) GPa, and K 0 ′ = 6.5(2). Previously measured high-pressure vibrational frequency shifts were used to estimate the vibrational free energy and model P–V–T isotherms from 0 to 1200 K. The results of the P–V–T isotherms are compared to existing shock Hugoniot data on hydrazine and 298 K isotherms for assemblages of possible decomposition products. This comparison suggests dissociation at high density under shock loading. Good correspondence was found between the static lattice EOS as calculated by the model and the previously reported EOS as calculated by density functional theory. Finally, these results resolve existing uncertainties about the EOS and crystal symmetry of hydrazine at high pressure and provide valuable baseline information on this important energetic material.

diffraction↗

Reaction of Hydrazine with Solution- and Vacuum-Prepared Selectively Terminated Si(100) Surfaces: Pathways to the Formation of Direct Si–N Bonds

Here, the reactivity of liquid hydrazine (N 2 H 4 ) with respect to H-, Cl-, and Br-terminated Si(100) surfaces was investigated to uncover the principles of nitrogen incorporation into the interface. This process has important implications in a wide variety of applications, including semiconductor surface passivation and functionalization, nitride growth, and many others. The use of hydrazine as a precursor allows for reactions that exclude carbon and oxygen, the primary sources of contamination in processing. In this work, the reactivity of N 2 H 4 with H- and Cl-terminated surfaces prepared by traditional solvent-based methods and with a Br-terminated Si(100) prepared in ultrahigh vacuum was compared. The reactions were studied with X-ray photoelectron spectroscopy, atomic force microscopy, and scanning tunneling microscopy, and the observations were supported by computational investigations. The H-terminated surface led to the highest level of nitrogen incorporation; however, the process proceeds with increasing surface roughness, suggesting possible etching or replacement reactions. In the case of Cl-terminated (predominantly dichloride) and Br-terminated (monobromide) surfaces, the amount of nitrogen incorporation on both surfaces after the reaction with hydrazine was very similar despite the differences in preparation, initial structure, and chemical composition. Density functional theory was used to propose the possible surface structures and to analyze surface reactivity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electrochemical Strategy for Hydrazine Synthesis: Development and Overpotential Analysis of Methods for Oxidative N–N Coupling of an Ammonia Surrogate

Hydrazine is an important industrial chemical and fuel that has attracted considerable attention for use in liquid fuel cells. Ideally, hydrazine could be prepared via direct oxidative coupling of ammonia, but thermodynamic and kinetic factors limit the viability of this approach. Here, the present study evaluates three different electrochemical strategies for the oxidative homocoupling of benzophenone imine, a readily accessible ammonia surrogate. Hydrolysis of the resulting benzophenone azine affords hydrazine and benzophenone, with the latter amenable to recycling. The three different electrochemical N–N coupling methods are (1) a proton-coupled electron-transfer process promoted by a phosphate base, (2) an iodine-mediated reaction involving intermediate N–I bond formation, and (3) a copper-catalyzed N–N coupling process. Analysis of the thermodynamic efficiencies for these electrochemical imine-to-azine oxidation reactions reveals low overpotentials (η) for the copper- and iodine-mediated processes (390 and 470 mV, respectively), but a much higher value for the proton-coupled pathway (η ≈ 1.6 V). A similar approach is used to assess molecular electrocatalytic methods for electrochemical oxidation of ammonia to dinitrogen.

25 ENERGY STORAGE↗

THERMAL DECOMPOSITION OF HYDRAZINE

The Thermal Stability of Hydrazine has been studied in the temperature and pressure intervals of 175" to 250"C. and 300 to 430 p.s.i., Respectively. Previous studies of the decomposition of hydrazine indicated that several factors affect its stability (2, 5, 7). the rate of decomposition is increased by the presence of certain surfaces (especially metals and salts). pH, oxygen, and carbon dioxide. Further explosive decomposition Is attributable to the uncontrolled heterogeneous, gas-phase decomposition. These factors were considered in selecting the following experimental conditions: highly purified hydrazine was prepared in a nitrogen atmosphere, and this product was decomposed over triply distilled mercury in outgassed borosilicate glass tubes at ullages that were initially zero. This study also included the effects of added quantities of ammonia on the rate of decomposition and an investigation of the products of the decomposition.

Harold W. Lucien↗

Monopropellant hydrazine resistojet: Flight application design

The design, development, and testing of an engineering model nominal 20-millipound thrust monopropellant hydrazine resistojet program is directed toward the advanced development of an electrothermal hydrazine thruster (EHT). The EHT decomposes hydrazine thermally and expands the decomposition products through a nozzle to provide the impulse necessary to fulfill spacecraft propulsive requirements. The thruster is capable of operation at pulse widths from 0.050 second to steady state and delivers specific impulse values up to about 230 seconds depending on the duty cycle. The program is comprised of six tasks including analyses, the generation of specifications and other documentation, design, fabrication and test, data correlation, and recommendations for the design of flight units.

Kurch, C. K.↗

Monopropellant hydrazine resistoject: Engineering model fabrication and test task

The monopropellant hydrazine resistojet, termed the electrothermal hydrazine thruster (EHT) by TRW systems, thermally decomposes anhydrous hydrazine propellant to produce a high-temperature, low-molecular-weight gas for expulsion through a propulsive nozzle. The EHT developed for this program required about 3-5 watts of electrical power and produced 0.020 to 0.070 pound of thrust over the inlet pressure range of 100 to 400 psia. The thruster was designed for both pulsed and steady state operation. A summary of the GSFC original requirements and GSFC modified requirements, and the performance of the engineering model EHT is given. The experimental program leading to the engineering model EHT design, modifications necessary to achieve the required thruster life capability, and the results of the life test prgram. Other facets of the program, including analyses, preliminary design, specifications, data correlation, and recommendations for a flight model are discussed.

Murch, C. K.↗

Evaluation of the SSRCS engine with hydrazine as a fuel, phase 2

Test firing of the Space Shuttle Reaction Control Thruster (SSRCT) was conducted to determine the characteristic velocity and chamber throat temperatures when the fuel is changed from monomethylhydrazine (MMH) to hydrazine. Thruster performance with hydrazine was essentially as predicted. Characteristic velocity at a mixture ratio of 1.4 (equal volumetric flow) for hydrazine was 5180 feet/second compared with 5110 feet/second at a mixture of 1.6 for MMH. Specific impulse with 22:1 nozzle is calculated to be 280 lbf-sec/lbm. Thermal performance, as measured by chamber throat temperature, was dramatically different (colder) than predicted. Throat temperatures of 2330 F were predicted from a cooling model which assumed a reactive liquid cooling film. Throat temperatures of 800 - 1000 F were measured. An attempt to reconcile the differences between film cooling predictions and the measurements, indicated that an evaporation (nonreactive fluid) model rather than a decomposition (reactive fluid) model best fits the test data at 0/F = 1.4. At higher mixture ratios, a transition to temperatures typical of the reactive fluid model were observed.

Minton, S. J.↗

The monopropellant hydrazine propulsion subsystem for the Pioneer Venus spacecraft

The Pioneer Venus Orbiter and the Multiprobe spacecraft propulsion subsystems and their performance are presented. Monopropellant hydrazine subsystems on each spacecraft provided the capability to spin up the spacecraft after separation and perform all spin rate, velocity, and attitude changes required by the control subsystem to satisfy mission objectives. The propulsion subsystem provides thrust on demand by supplying anhydrous hydrazine from the propellant tanks through manifolds, filters and valves to the thrust chamber assemblies where the hydrazine is catalytically decomposed and expanded in a conical nozzle. The subsystems consist of seven 1 lbf thrusters for the Orbiter and six 1 lbf thrusters for the multiprobe which are isolated by two latch valves from the two propellant tanks so that two redundant thruster clusters are provided to ensure mission completion in the event of a single point failure. The propellant feed system is of all-welded construction to minimize weight and leakage and titanium is used as the primary material of construction. The multiprobe burned up on entering the Venus atmosphere with enough propellant left for the mission and the Orbiter was inserted into Venus orbit with enough propellant remaining for more than 2 earth years of orbital operations.

Barker, F. C.↗

Hydrazine-Compatible Elastomer

Hydrazine hardly reacts with ethylene propylene diene monomer, even at high temperatures. According to report to tests, EPDM is most hydrazine-compatible material among elastomers. Has strong potential as valve-seat and O-ring seal with hydrazine, especially at high temperatures.

Markles, O., F.↗

Hydrazine gas generator performance on Space Shuttle

The design, functions, performance, and applications of the hydrazine gas generators (GG) on the STS are detailed. The GGs provide gas horse power for the APUs that drive the hydraulic pumps on the SRBs, which have two cross-linked systems. The Orbiter has three-cross-linked APU systems, used for gimballing the main engine and booster nozzles, actuating the main engine fuel valves and the ET umbilical disconnect, actuation of the control surfaces, and powering the landing gear, brakes, and nose wheel steering. The major design components of the Orbiter GGs are an injector, a catalyst bed, a decomposition chamber, an exhaust nozzle, and an interface structure, with the main structural material being Hasteloy B. Hydrazine injected and dispersed into the catalyst bed decomposes into gas and exits for expansion in an APU turbine. Twenty-six GGs have flown on missions STS-1 through STS-6 with over three tons of hydrazine having been expended over 44 hr of operations, as no refurbishment to that point was necessary.

Patterson, I. J.↗

Explosive decomposition of hydrazine due to rapid gas compression

Results from tests which attempt to determine conditions which cause explosive decomposition of hydrazine from rapid gas compression are described. Hydrazine was initiated by pressure in combination with shock waves from the pressurant gas. A new test method was developed at the White Sands Test Facility which subjects a gas bubble in contact with liquid hydrazine to pure adiabatic compression. Results from this new test method are compared to those from the U-tube method.

Briles, O.↗

Treatment for hydrazine-containing waste water solution

The treatment for waste solutions containing hydrazine is presented. The invention attempts oxidation and decomposition of hydrazine in waste water in a simple and effective processing. The method adds activated charcoal to waste solutions containing hydrazine while maintaining a pH value higher than 8, and adding iron salts if necessary. Then, the solution is aerated.

Yade, N.↗

The catalysis of hydrazines

Hydrazine sulfate in a hot aqueous solution can be catalyzed in the direction of 3 N2H4 = 4 NH3 + N2. Free hydrazine in a hot aqueous solution dissociates in the presence of platinum in the following direction: 2 N2H4 = 2 NH3 + N2 + H2. In the presence of sodium hydroxide, the catalytic dissociation of hydrazine takes a third direction: 3 N2H4 = 2 NH3 + 2 N3 + 3 H2.

Tanatar, S.↗