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Indicator Devices for Detection of Trace Gaseous Hydrazines

The relatively recent decrease in the acceptable time-weighted-average for hydrazines from 100 parts-per-billion (ppb) to 10 ppb rendered many trace hydrazine detectors either insensitive or inaccurate. Development of a rapid detection method for hydrazines at the new 10-ppb concentration was necessary so that test area personnel could reliably assess airborne hydrazines concentrations of a potentially contaminated area prior to entry. The reduction of Au(III) to Au(0) by hydrazines is a well characterized reaction and application of the corresponding yellow to purple color change was selected as a potentially useful means for detection of trace hydrazines in air. Tests with small quantities of KAuCl4 deposited on a variety of substrates were conducted using verified sources of 1,1-dimethylhydrazine, methylhydrazine, and hydrazine at approximately 10 ppb in air. Substrates tested were glass fiber filter paper, glass beads, anion exchange resin (AuCl4- form), and diatomaceous earth. The most successful of these substrates were glass fiber filter paper and diatomaceous earth. The KAuC14 impregnated glass fiber filter paper appeared to be somewhat light sensitive so further tests were conducted using the diatomaceous earth substrate. KAuCl4 concentration, substrate particle size, and sampler configuration were evaluated. Based on these tests, the device selected for further evaluation was a 5mm OD by 50mm glass tube containing 0.02-0.03g of 45/60 mesh diatomaceous earth coated with 2 percent KAuCl4. When connected to a sampling pump, response of the device to changes in relative humidity, ambient light, and high levels of other fluids, which might also be found in a propellant test area, was evaluated. False positive responses were not detected for exposures to relative humidity changes from 10 to 80 percent, sunlight for greater than 10 minutes, or percent levels of ammonia, isopropyl alcohol, nitrogen dioxide, and hydrogen. In addition, body emissions did not produce a false positive response in view of potential application for use inside protective clothing. The device was shown to reliably detect less than 10 ppb of the hydrazines tested using a 10 to 20L sample followed by a 2 to 5 minute color development time. Some field tests were conducted in parallel with conventional acidic firebrick sorbent tubes. There was generally very good agreement between the devices and firebrick sorbent tubes when greater than 10 ppb of a hydrazine was present.

Dee, Lou A.↗

Wipes, Coatings, and Patches for Detecting Hydrazines

Three color-indicating devices have been conceived as simple, rapid, inexpensive means of detecting hazardous liquid and gaseous substances in settings in which safety is of paramount concern and it would be too time-consuming or otherwise impractical to perform detection by use of such instruments as mass spectrometers. More specifically, these devices are designed for detecting hypergolic fuels (in particular, hydrazines) and hypergolic oxidizers in spacecraft settings, where occasional leakage of these substances in liquid or vapor form occurs and it is imperative to take early corrective action to minimize adverse health effects. With suitable redesign, including reformulation of their color indicator chemicals, these devices could be adapted to detection of other hazardous substances in terrestrial settings (e.g., industrial and military ones). One of the devices is a pad of a commercially available absorbent material doped with a color indicator. The absorbent material is made from 70 percent polyester and 30 percent nylon and can absorb about eight times its own weight of liquid. The color indicator is a mixture of conventional pH color indicator chemicals. Hydrazine and monomethyl hydrazine, which are basic, cause the color indicator to turn green. In the original intended application, the pad is wiped on a space suit that is suspected of having been exposed to leaking monomethyl hydrazine during a space walk, before the wearer returns to the interior of the spacecraft. If the wiped surface is contaminated with hydrazine, the pad turns green. In addition, the pad absorbs hydrazine from the wiped surface, thereby reducing or eliminating the hazard. Used pads, including ones that show contamination by hydrazine, can be stored in a sealed plastic bag for subsequent disposal. The second device, which has been proposed but not yet developed, would comprise a color indicator material in the form of either a coating on a space suit (or other protective garment) or a coating on a sheet that could be easily attached to and detached from the protective garment. The coating material would be a hydrogel doped with a suitable pH indicator. The hydrogel would also serve to maintain a level of moisture needed to support the chemical reaction mentioned in the next sentence. In addition to changing color to indicate the presence of any hypergolic fuel (which is basic) or hypergolic oxidizer (which is acidic) that might splash on the space suit, the pH indicator would also react with the hypergolic fuel or oxidizer and thereby bind it. The third device is a color dosimeter for detecting hydrazine liquid or vapor coming from microscopic leaks. This device is designed to satisfy several requirements specific to its original intended use in the auxiliary power unit of the space shuttle. These requirements include stability under vacuum, stability at moderate temperature, fast and irreversible change in color upon exposure to hydrazine, and visibility of the color change through polyimide tape.

Young, Rebecca↗

Sensitized Liquid Hydrazine Detonation Studies

Vapor-phase hydrazine (N2H4) is known to be very sensitive to detonation while liquid hydrazine is very insensitive to detonation, theoretically requiring extremely high pressures to induce initiation. A review of literature on solid and liquid explosives shows that when pure explosive substances are infiltrated with gas cavities, voids, and/or different phase contaminants, the energy or shock pressure necessary to induce detonation can decrease by an order of magnitude. Tests were conducted with liquid hydrazine in a modified card-gap configuration. Sensitization was attempted by bubbling helium gas through and/or suspending ceramic microspheres in the liquid. The hydrazine was subjected to the shock pressure from a 2 lb (0.9 kg) Composition C-4 explosive charge. The hydrazine was contained in a 4 in. (10.2 cm) diameter stainless steel cylinder with a 122 in(sup 3) (2 L) volume and sealed with a polyethylene cap. Blast pressures from the events were recorded by 63 high speed pressure transducers located on three radial legs extending from 4 to 115 ft (1.2 to 35.1 in) from ground zero. Comparison of the neat hydrazine and water baseline tests with the "sensitized" hydrazine tests indicates the liquid hydrazine did not detonate under these conditions.

Rathgeber, K. A.↗

Catalytic Decomposition of Propellant Hydrazines, N-Nitrosodimethylamine, and N-Nitrodimethylamine

Remediation of propellant hydrazine spills, waste treatment, or cleanup of water contaminated with these propellants and/or their oxidation products is a subject of great concern for safety and the environment. Current remediation technologies typically employ oxidative methods, such as chlorination or ozonation. Methylated hydrazines, in particular 1,1-dimethythydrazine (UDMH) and to some degree monomethy1hydrazine (MMH), form N-Nitrosodimethylamine (NDMA) and N-Nitrodimethylamine (DMNM) during oxidation. These compounds are highly toxic and may persist if oxidative conditions are not sufficiently harsh. Since NDMA and DMNM may also be formed from exposure of MMH or UDMH to air, a need exists for a method that will remediate hydrazine, MMH, UDMH, NDMA, and DMNM. In this work, aqueous solutions of propellant hydrazines, NDMA, and DMNM were found to degrade by catalytic reduction with nickel-aluminum (Ni-Al) alloy under basic conditions. The reaction is based upon dissolution of At from Ni-Al alloy in aqueous media to form aluminum ion and hydrogen gas; and the resultant finely divided nickel catalyzes reduction of the hydrazine, nitrosoamine, or nitroamine by the hydrogen produced. Greater than 99 percent of hydrazine, MMH, UDMH, NDMA, and DMNM in aqueous solutions were degraded under laboratory conditions when reacted with Ni-Al alloy. UDMH was identified as an intermediate reduction product of NDMA and DNNM. NDMA and UDMH were identified as intermediate reduction products of DMNM. Control experiments without nickel showed no degradation of hydrazine, MMH or UDMH, while NDMA and DMNM were reduced to UDMH. Spill pillows containing Ni-Al alloy and solid sodium hydroxide were also found effective in absorption and degradation of UDMH. The application of chemical reduction as a means to propellant hydrazines, NDMA, and DMNM spill remediation, waste treatment, and water decontamination appears highly attractive.

Greene, Ben↗

Hydrazine Conservation for the Dawn Spacecraft Operations at the Dwarf Planet Ceres

Dawn is a low-thrust interplanetary spacecraft currently orbiting the dwarf planet Ceres. After successfully completing its Vesta and Ceres prime missions, Dawn is now in its extended mission, continuously exploring Ceres. After losing the second reaction wheel assembly at the end of the Vesta mission, the feasibility of the Ceres mission was at risk due to the potentially significant increase in hydrazine consumption from using only the reaction control system thrusters. This paper summarizes the intense, collaborative efforts undertaken by the project to conserve hydrazine prior to Vesta departure, during cruise to Ceres, and throughout the Ceres mission. The project’s efforts in minimizing the number of turns are discussed. A special emphasis is given to describing various efforts taken by the Attitude Control Subsystem team in an attempt to reduce hydrazine consumption. These efforts include: changing default slew rates, control gain tuning, changing nadir pointing strategy with Ahead Cross Nadir pointing, hybrid control implementation using hydrazine based thrusters and two remaining reaction wheels, optimal science turn location analysis, and reaction wheel angular momentum management strategies for reducing the number of momentum unloadings. In addition to the Attitude Control Subsystem team’s efforts, the Mission Design and Navigation team’s efforts taken in designing hydrazine friendly orbit transfers are discussed. The trade study performed collaboratively by the Attitude Control Subsystem team and the Science Operations Support Team in choosing hydrazine friendly off-nadir targets is also discussed. Various simulation results are presented and compared against actual flight data obtained. Lastly, remaining hydrazine status at the end of the prime Ceres mission and the hydrazine management planning for the extended mission are discussed.

Salami, Mana↗

The X-Irradiation of Hydrazine and 1,1- Dimethylhydrazine

Hydrazine and 1,1-dimethylhydrazine were radiolyzed at room temperature by using about 1 gram of liquid or 1/2 to 2 liters of vapor at room-temperature vapor pressure. A tungsten-target X-ray source operating at 300 kilovolts and 6 to 8 milliamperes (0.1 to 1.0 A) was used at intensities of 1 times 10 (sup 2) to 1 times 10 (sup 3) roentgens per minute to give total doses of 4.1 rads to 2.3 times 10 (sup 6) rads. The amounts of decomposition were dependent on total dose and independent of dose rate. In the case of hydrazine vapor, the decomposition was also directly related to surface area. There was a lesser surface effect with liquid hydrazine, but this variable was not studied for 1,1-dimethylhydrazine. The order of decreasing sensitivity to X-radiation is as follows: hydrazine vapor, 1,1-dimethylhydrazine vapor, 1,1-dimethylhydrazine liquid, and hydrazine liquid. The decomposition products of hydrazine were nitrogen, hydrogen, ammonia, and unidentified products. The same products plus methylamine, dimethylamine, and hydrazine were found from the decomposition of 1,1-dimethylhydrazine. In addition, the 1,1-dimethylhydrazine underwent post-irradiation changes. Values for G (number of molecules of sample decomposed per 100 electronvolts of absorbed energy) of the order of 10 (sup 6) suggest that the vapor-phase decompositions are chain reactions.

X-RAY IRRADIATION↗

Insight the process of hydrazine gas adsorption on layered WS 2 : a first principle study

The process of hydrazine gas adsorption on layered WS 2 has been systematically studied from first principle calculations. Our results demonstrate that this adsorption process is exothermic, and hydrazine molecules are physically adsorbed. The layer-dependent adsorption energy and interlayer separation induced by van der Waals interaction exerted by hydrazine molecules lead to the difficulty in desorbing hydrazine molecules from layered WS 2 as the number of layers increases. The most interesting finding is the emergence of localized impurity states below the Fermi level upon the hydrazine adsorption, irrespective of the number of WS 2 layers, resulting in a significant effect on the band structures and subsequently changing its electrical conductivity. Furthermore, a layer-dependent small charge transfer occurs between hydrazine and layered WS 2 , leading to a charge redistribution and considerable polarization in the adsorbed systems. The existence of defects and the humidity, on the other hand, influences the sensitivity of layered WS 2 to the hydrazine adsorption. Here, obtained results show that a perfectly layered WS 2 might be a promising candidate as an efficient nanosensor to detect such toxic gas in dry environment.

36 MATERIALS SCIENCE↗

Modulating Concentration Of Hydrazine Vapor To Aid Detection

Three techniques, flow modulation, filament modulation, and reactive-filter modulation developed to obtain selective response to hydrazine or to methyl hydrazines from photoionization detector. Implemented in portable selective hydrazine detectors, useful where continuous or rapid, repetitive quantitative measurements of concentrations of vapors of these toxic substances required. Measure concentration of gaseous hydrazines in presence of other gases like cyclohexane, chlorofluorocarbons, and ammonia. Produce modulated signal, amplitude and phase indicating amount of hydrazine, monomethyl hydrazine, or 1,1-dimethyl hydrazine present in mixture. Used with such other detectors as electrochemical cells.

Stetter, Joseph R.↗

Detailed Chemical Kinetic Modeling of Hydrazine Decomposition

The purpose of this research project is to develop and validate a detailed chemical kinetic mechanism for gas-phase hydrazine decomposition. Hydrazine is used extensively in aerospace propulsion, and although liquid hydrazine is not considered detonable, many fuel handling systems create multiphase mixtures of fuels and fuel vapors during their operation. Therefore, a thorough knowledge of the decomposition chemistry of hydrazine under a variety of conditions can be of value in assessing potential operational hazards in hydrazine fuel systems. To gain such knowledge, a reasonable starting point is the development and validation of a detailed chemical kinetic mechanism for gas-phase hydrazine decomposition. A reasonably complete mechanism was published in 1996, however, many of the elementary steps included had outdated rate expressions and a thorough investigation of the behavior of the mechanism under a variety of conditions was not presented. The current work has included substantial revision of the previously published mechanism, along with a more extensive examination of the decomposition behavior of hydrazine. An attempt to validate the mechanism against the limited experimental data available has been made and was moderately successful. Further computational and experimental research into the chemistry of this fuel needs to be completed.

Meagher, Nancy E.↗

Detection of hydrazine (H) and (MMH) using cyranose E-nose

The Cyranose electronic nose (e-nose) has been used for the first time to detect hydrazine (H) and monomethyl hydrazine (MMH). The concentrations of hydrazine chosen in this study were 52 ppm (parts per million), 18 ppm, and 1.1 ppm and the concentrations of MMH was 14 ppm and 1 ppm. The Cyranose E-nose has detected hydrazine of 52 ppm and 18 ppm with a good response. The response of the E-Nose for 1.1 ppm hydrazine was insignificant. The response of E-Nose for 14 ppm MMH was significant and 1 ppm MMH was reasonably identifiable. The Cyranose E-Nose may be used to detect hydrazine and MMH with concentrations of at least 18 ppm and 1 ppm, respectively.

cyranose↗

Explosive decomposition of hydrazine by rapid compression of a gas volume

In the present investigation of the initiation mechanism and the explosion mode of hydrazine decomposition, a 20 cm-long column of liquid hydrazine was accelerated into a column of gaseous nitrogen, from which it was separated by a thin Teflon diaphragm, in a close-ended cylindrical chamber. Video data obtained reveal the formation of a froth generated by the acceleration of hydrazine into nitrogen at the liquid hydrazine-gaseous nitrogen interface. The explosive hydrazine decomposition had as its initiation mechanism the formation of a froth at a critical temperature; the explosion mode of hydrazine is a confined thermal runaway reaction.

Bunker, R. L.↗

Kaolinite-catalyzed air oxidation of hydrazine: Consideration of several compositional, structural and energetic factors in surface activation

Clay minerals have been shown to have numerous, curious, energetic properties by virtue of ultra-violet light release which can be triggered by gentle environmental changes such as wetting and dewetting by a variety of liquids, unique among them water and hydrazine. Since both water and hydrazine play multiple key roles in the air-oxidation of hydrazine on kaolinite surfaces, this reaction would seem to have prime potential for studying interrelationships of energy storage, release and chemical reactivity of clay surfaces, capacities basic to either the Bernal or Cairns-Smith roles of minerals in the origin of life. Establishment of the capacity for stored electronic energy to significantly alter surface chemistry is important, regardless of the reaction chosen to demonstrate it. Hydrazine air oxidation is overawingly complex, given the possibilities for step-wise control and monitoring of parameters. In the light of recently extended characterization of the kaolinite and model sheet catalysts we used to study hydrazine oxidation and gamma-irradiated silica, previous studies of hydrazine air-oxidation on aluminosilicate surfaces have been reevaluated. Our former conclusion remains intact that, whereas trace structural and surface contaminants do play some role in the catalysis of oxidation, they are not the only, nor even the dominant, catalytic centers. Initial intermediates in the oxidation can now be proposed which are consistent with production via O(-)-centers as well as ferric iron centers. The greater than square dependence of the initial reaction rate on the weight of the clay is discussed in the light of these various mechanistic possibilities.

Coyne, L. M.↗

Occupational safety considerations with hydrazine fuels

A simple pharmacokinetic model and a specially designed dermal vapor exposure chamber which provides respiratory protection were used to determine the rate of penetration of hydrazine and 1,1-dimethylhydrazine (UDMH) vapor through the skin of rats. Parameters for the pharmacokinetic model were determined from intravenous and inhalation exposure data. The model was then used to estimate the skin permeation coefficient for hydrazine or UDMH vapor from the dermal-vapor exposure data. This analysis indicates that UDMH vapor has a relatively high permeability through skin (0.7 cm/hr), a value somewhat higher than was obtained for hydrazine by the same procedure (0.09 cm/hr). Based on these skin permeability results, a skin-only vapor exposure limit giving protection equivalent to the inhalation Threshold Limit Value (TLV) could be calculated. The current TLV's for UDMH and hydrazine are 0.5 and 0.1 ppm, respectively. The corresponding skin-only TLV equivalents, for personnel wearing respiratory protection, are 32 ppm for UDMH and 48 ppm for hydrazine. Should the proposed lowering to the TLV's for these compounds to 0.01 ppm be adopted, the equivalent skin-only TLV's would become 0.64 ppm for UDMH and 4.8 for hydrazine.

Clewell, H. J.↗

Prototype development and test results of a continuous ambient air monitoring system for hydrazine at the 10 ppb level

A Hydrazine Vapor Area Monitor (HVAM) system is currently being field tested as a detector for the presence of hydrazine in ambient air. The MDA/Polymetron Hydrazine Analyzer has been incorporated within the HVAM system as the core detector. This analyzer is a three-electrode liquid analyzer typically used in boiler feed water applications. The HVAM system incorporates a dual-phase sample collection/transport method which simultaneously pulls ambient air samples containing hydrazine and a very dilute sulfuric acid solution (0.0001 M) down a length of 1/4 inch outside diameter (OD) tubing from a remote site to the analyzer. The hydrazine-laden dilute acid stream is separated from the air and the pH is adjusted by addition of a dilute caustic solution to a pH greater than 10.2 prior to analysis. Both the dilute acid and caustic used by the HVAM are continuously generated during system operation on an "as needed" basis by mixing a metered amount of concentrated acid/base with dilution water. All of the waste water generated by the analyzer is purified for reuse by Barnstead ion-exchange cartridges so that the entire system minimizes the generation of waste materials. The pumping of all liquid streams and mixing of the caustic solution and dilution water with the incoming sample are done by a single pump motor fitted with the appropriate mix of peristaltic pump heads. The signal to noise (S/N) ratio of the analyzer has been enhanced by adding a stirrer in the MDA liquid cell to provide mixing normally generated by the high liquid flow rate designed by the manufacturer. An onboard microprocessor continuously monitors liquid levels, sample vacuum, and liquid leak sensors, as well as handles communications and other system functions (such as shut down should system malfunctions or errors occur). The overall system response of the HVAM can be automatically checked at regular intervals by measuring the analyzer response to a metered amount of calibration standard injected into the dilute acid stream. The HVAM system provides two measurement ranges (threshold limit value (TLV): 10 to 1000 parts per billion (ppb)/LEAK: 100 ppb to 10 parts per million (ppm)). The LEAK range is created by dilution of the sulfuric acid/hydrazine liquid sample with pure water. This dual range capability permits the analyzer to quantify ambient air samples whose hydrazine concentrations range from 10 ppb to as high as 10 ppm. The laboratory and field prototypes have demonstrated total system response times on the order of 10 to 12 minutes for samples ranging from 10 to 900 ppb in the lLV mode and is greater than 2 minutes for samples ranging from 100 to 1300 ppb in the LEAK mode. Service intervals of over 3 months have been demonstrated for continuous 24 hour/day, 7 day/week usage. The HVAM is made up of a purged cabinet that contains power supplies, RS422 signal transmission capabilities, a UPS, an on-site warning system, and a Line Replaceable Unit (LRU). The LRU includes all of the liquid flow system, the analyzer, the control/data system microprocessor and assorted flow and liquid-level sensors. The LRU is mounted on a track slide system so it can be serviced inplace or totally removed and quickly exchanged with another calibrated unit, thus minimizing analyzer downtime. Once an LRU is removed from an analyzer enclosure, it can be brought to a laboratory facility for complete calibration and periodic maintenance.

Meneghelli, Barry↗

A Hydrazine Leak Sensor Based on Chemically Reactive Thermistors

Leaks in the hydrazine supply system of the Shuttle APU can result in hydrazine ignition and fire in the aft compartment of the Shuttle. Indication of the location of a leak could provide valuable information required for operational decisions. WSTF has developed a small, single use sensor for detection of hydrazine leaks. The sensor is composed of a thermistor bead coated with copper(II) oxide (CuO) dispersed in a clay or alumina binder. The CuO-coated thermistor is one of a pair of closely located thermistors, the other being a reference. On exposure to hydrazine the CuO reacts exothermically with the hydrazine and increases the temperature of the coated-thermistor by several degrees. The temperature rise is sensed by a resistive bridge circuit and an alarm registered by data acquisition software. Responses of this sensor to humidity changes, hydrazine concentration, binder characteristics, distance from a liquid leak, and ambient pressure levels as well as application of this sensor concept to other fluids are presented.

Davis, Dennis D.↗

Mobility Spectrometer Studies on Hydrazine and Ammonia Detection

An airborne vapor analyzer for detecting sub- to low- parts-per-million (ppm) hydrazine in the presence of higher concentration levels of ammonia has been under development for the Orion program. The detector is based on ambient pressure ionization and ion mobility characterization. The detector encompasses: 1) a membrane inlet to exclude particulate and aerosols from the analyzer inlet; 2) a method to separate hydrazine from ammonia which would otherwise lead to loss of calibration and quantitative accuracy for the hydrazine determination; and 3) response and quantitative determinations for both hydrazine and ammonia. Laboratory studies were made to explore some of these features including mobility measurements mindful of power, size, and weight issues. The study recommended the use of a mobility spectrometer of traditional design with a reagent gas and equipped with an inlet transfer line of bonded phase fused silica tube. The inlet transfer line provided gas phase separation of neutrals of ammonia from hydrazine at 50 C simplifying significantly the ionization chemistry that underlies response in a mobility spectrometer. Performance of the analyzer was acceptable between ranges of 30 to 80 C for both the pre-fractionation column and the drift tube. An inlet comprised of a combined membrane with valve-less injector allowed high speed quantitative determination of ammonia and hydrazine without cross reactivity from common metabolites such as alcohols, esters, and aldehydes. Preliminary test results and some of the design features are discussed.

Niu, William↗

Variable hydrazine coordination modes from reactions with dichlorotris(triphenylphosphine)ruthenium(II)

The reactivity of the prominent ruthenium(II) catalyst and precursor, RuCl 2 (PPh 3 ) 3 , was explored with hydrazine and its derivatives. The reactions produced 6-coordinate ruthenium(II) products that bond with the hydrazine moiety in bridging (NH 2 NH 2 or NH 2 NHMe), end-on (NH 2 NHMe, NH 2 NHPh, or NH 2 NMe 2 ), or side-on (NH 2 NMe 2 ) fashions. The products have been characterized by single crystal X-ray diffraction and 31 P NMR spectroscopy. With NH 2 NH 2 , the dimeric product, [RuCl 2 (PPh 3 ) 2 ] 2 ($μ$-N 2 H 4 ) 2 , was formed under all conditions used. For other hydrazines, the reaction stoichiometry governed product formation to yield either bimetallic or monomeric products. When the RuCl 2 (PPh 3 ) 3 to hydrazine derivative ratio was 1:1 or lower, bimetallic complexes were formed while a 1:2 ratio produced monomeric compounds. The exception to the latter occurs with the production of the monomeric compound, RuCl 2 (PPh 3 ) 2 ($η$ 2 -NH 2 NMe 2 ), that forms employing a 1:1 ratio. In addition to stoichiometry, steric factors and hydrogen bonding played a significant role in dictating the bonding mode of hydrazines. The bimetallic complexes were further reacted to yield the corresponding monomeric products, adopting the form RuCl 2 (PPh 3 ) 2 (L) 2 (L = NH 2 NHMe, NH 2 NHPh, or NH 2 NMe 2 ). Reactions utilizing less than a 1:2 ratio of RuCl 2 (PPh 3 ) 3 to NH 2 NMe 2 produced a mixture of products that appear to be in equilibrium. In conclusion, FT calculations were performed to gain insight into the reaction energetics and molecular stability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Crowd-Sourced Technology Challenge for Improving Visual Color Detection of Hydrazine and Monomethylhydrazine Vapors in Spacecraft Environments

NASA currently uses a visual colorimetric detection method for potential hydrazine, monomethylhydrazine (MMH), or unsymmetrical dimethylhydrazine (UDMH) contamination in the International Space Station. Astronauts exposed to propellants or their residues during extravehicular activities may transfer contaminants into the airlock. The colorimetric detection method employs the Contamination Detection Kit (CDK), which uses a potassium tetrachloroaurate redox reaction with the propellant hydrazine vapors and a color comparison card to determine airborne concentrations. Seeking ideas for improvement, the NASA Tournament Lab (NTL) crowdsourced a way to tackle the challenge of detecting hydrazine and MMH vapors using colorimetric detection methods. This Rid the Rocket competition drew over 200 participants and 20 submissions from around the world proposing innovative ways to develop a new chemical colorimetric detection method for hydrazine and MMH vapors on spacecraft. Using a phased approach to evaluate contestants, NASA eventually narrowed the field to five finalists from the United States, Romania, Taiwan, and India. Concept papers and hardware submissions were judged on feasibility, creativity, and ability to detect hydrazine and MMH vapors before being sent to the NASA White Sands Test Facility for laboratory evaluation. Finalists employed variations of sampling methods and color-detection chemistry using a variety of sampling pumps and indicator pads or solutions—including those employing potassium or hydrogen tetrachloroaurate, para -dimethylaminobenzaldehyde (PDAB), and modifiers including sodium metasilicate and cetyltrimethylammonium bromide—to enhance gold nanoparticle formation and surface plasmon resonance (SPR) resulting in visual blue to purple color development. This paper presents a summary of the crowdsourced submissions and results of laboratory testing.

Crowd-Sourced↗