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NASA State of Evaluation of High Purity Hydrazine (HPH) and Monomethylhydrazine (MMH)
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Mitigating Problems in Measuring Hypergolic Fuels
To monitor hydrazine concentrations accurately and safely, hydrazine is converted into a stable derivative that will be monitored and correlated to the actual hydrazine concentration. The hydrazine's reactivity is harnessed to produce a chemical reaction that will form a stable gas-phase derivative which will not react or decompose before it reaches the detector. Hydrazine, monomethylhydrazine, and unsymmetrical dimethylhydrazine belong to a class of compounds known as hypergolic fuels. These fuels self-ignite upon mixing with hypergolic oxidizer (dinitrogen tetroxide), without need of a spark or other ignition source. The resulting reaction produces thrust with exceptionally high energy, making these compounds particularly useful as rocket propellants. Hydrazines are also highly toxic and corrosive. The combined properties of reactivity, corrosivity, and toxicity present the potential for a leak, a disastrous situation in a hypergol-loaded system. Consequently, leak detection is of the utmost importance in protecting equipment and personnel. Hydrazine vapor quantification presents many challenges in addition to the safety concerns. The reactivity of these compounds causes thermal and catalytic decomposition, which results in significant losses. Further complications arise from the sticky nature of hydrazine. Molecules adsorb irreversibly to virtually any surface they make contact with before detection, which results in instrument drift. These properties make it difficult to accurately quantify hydrazines. Current analytical methods seek to minimize these interactions. After an extensive literature search to determine appropriate chemical reactions, a method was devised to quantify hydrazines, without the limitations of monitoring hydrazines.
STABILITY TESTS OF MONOPROPELLANTS EXPOSED TO FLAMES AND RIFLE FIRE
Tests of the stability of several monopropellants under the effects of impact and heat were conducted in order to assess the potential hazard in a propellant storage area from major fires and enemy attack. Hydrazine, hydrazine nitrate solution, n-propyl nitrate, and ethylene oxide were all tested in one-gallon aluminum containers (half of them filled to 25% and half to 95% capacity) by being subjected to oil bonfires and wood bonfires, and 20-mm incendiary, 20mm high explosive incendiary, and .30-caliber rifle fire. Aviation gasoline was tested in the same manner, for comparison. In the bonfire tests, all four monopropellants generally gave explosion intensities equivalent to one another regardless of the type of bonfire (oil or wood) or the amount of liquid in the test container. Occasionally, however, with hydrazine, hydrazine nitrate solution, and n-propyl nitrate, anomalous results occurred: there was either (a) no explosion or (b) an explosion of above average intensity. Ethylene oxide more nearly approximated the behavior of aviation gasoline than did the other monopropellants. In the rifle-fire tests, n-propyl nitrate appeared to be most shock- sensitive since it was exploded by all three types of ammunition. Hydrazine and hydrazine nitrate solution were exploded by the high-explosive ammunition, but not by the incendiary or .30-dber ammunition. Ethylene oxide was not exploded by any of the gunfire, but the liquid was ignited by both incendiary and high-explosive incendiary ammunition.
Study of monopropellants for electrothermal thrusters: Analytical task summary report
The feasibility of operating small thrust level electrothermal thrusters is determined with monopropellants other than MIL-grade hydrazine. The work scope includes analytical study, design and fabrication of demonstration thrusters, and an evaluation test program where monopropellants with freezing points lower than MIL-grade hydrazine are evaluated and characterized to determine their applicability to electrothermal thrusters for spacecraft attitude control. Results of propellant chemistry studies and performance analyses indicated that the most promising candidate monopropellants to be investigated are monomethylhydrazine, Aerozine-50, 77% hydrazine-23% hydrazine azide blend, and TRW formulated mixed hydrazine monopropellant (MHM) consisting of 35% hydrazine-50% monomethylhydrazine-15% ammonia.
Study of monopropellants for electrothermal thrusters: Design and fabrication task summary report
The feasibility of operating small thrust level electrothermal thrusters with monopropellants other than MIL-grade hydrazine was studied. Analytical study, design, and fabrication of demonstration thrusters was performed, and an evaluation test program was initiated to evaluate monopropellants with freezing points lower than MIL-grade hydrazine, and to determine their applicability to electrothermal thrusters for spacecraft attitude control. Five demonstration thrusters were fabricated to determine the feasibility of operation with monomethylhydrazine, Aerozine-50, 77 percent hydrazine-23 percent hydrazine azide, and a mixture of hydrazine monopropellants consisting of 35 percent hydrazine-50 percent monomethylhydrazine-15 percent ammonia. The present thruster is designed to produce a steady-state thrust level of 0.344 N at 1.724 x 1 million N/M sq feed pressure. Vacuum specific impulse goals were set at 1961 N-s/kg steady-state and 1716 N-s/kg pulsed-mode.
Green Applications for Space Power Project
Spacecraft propulsion and power for many decades has relied on Hydrazine monopropellant technology for auxiliary power units (APU), orbital circularization, orbit raising/lowering and attitude control. However, Hydrazine is toxic and therefore requires special ground handling procedures to ensure launch crew safety. The Swedish Company ECAPS has developed a technology based upon the propellant Ammonium Dinitramide (ADN) that offers higher performance, higher density and reduced ground handling support than Hydrazine. This blended propellant is called LMP-103S. Currently, the United States Air Force (USAF) is pursuing a technology based on Hydroxyl Ammonium Nitrate (HAN, otherwise known as AF-M315E) with industry partners Aerojet and Moog. Based on the advantages offered by these propellants, MSFC should explore powering APU's with these propellants. Due to the availability of space hardware, the principal investigator has found a collection of USAF hardware, that will act as a surrogate, which operates on a Hydrazine derivative. The F-16 fighter jet uses H-70 or 30% diluted Hydrazine for an Emergency Power Unit (EPU) which supplies power to the plane. The PI has acquired two EPU's from planes slated for destruction at the Davis Monthan AFB. This CIF will include a partnership with 2 other NASA Centers who are individually seeking seed funds from their respective organizations: Kennedy Space Center (KSC) and Dryden Flight Research Center (DFRC). KSC is preparing for future flights from their launch pads that will utilize green propellants and desire a low-cost testbed in which to test and calibrate new leak detection sensors. DFRC has access to F-16's which can be used by MSFC & KSC to perform a ground test that demonstrates emergency power supplied to the jet. Neither of the green propellant alternatives have been considered nor evaluated for an APU application. Work has already been accomplished to characterize and obtain the properties of these 2 propellants. However, the spacecraft are using existing leak detection sensors that are typically used for Hydrazine. Using these green propellants for the APU application requires decrementing their TRL down to 3. This task would aim to establish a TRL of 4 at conclusion by showing a proof of concept with a KSC-instrumented EPU asset at the MSFC Component Development Area (CDA). The task to accomplish this is called Green Application for Space Power or GRASP.
Study of monopropellants for electrothermal thrusters. Evaluation test program task summary report
An electrothermal thruster designed for operation with MIL-grade hydrazine is suitable for operation with propellants having lower freezing points. These propellants are 76% hydrazine - 24% hydrazine azide, Aerozine-50, 50% hydrazine - 50% monomethylydrazine, and a TRW-formulated mixture of 35% hydrazine - 50% monomethylhydrane - 15% ammonia. A steady-state specific impulse of 200 sec was exceeded by all propellants. A pulse-mode value of 175 sec specific impulse was exceeded by the azide blend for pulse widths greater than 50 ms and was met by the carbonaceous propellants for pulse widths greater than 100 ms. Longer residence times were required for the carbonaceous propellants; the original thruster design was modified by increasing the characteristic chamber length and density of screen packing. A substantial amount of thermal energy must be supplied to initiate decomposition of propellants containing unsymmetrical-dimethylhydrazine and monomethylhydrazine. The rate controlling factor appeared to be the endothermic removal of methyl radicals.
Space Shuttle Upgrades Advanced Hydraulic Power System
Three Auxiliary Power Units (APU) on the Space Shuttle Orbiter each provide 145 hp shaft power to a hydraulic pump which outputs 3000 psi hydraulic fluid to 41 hydraulic actuators. A hydrazine fuel powered APU utilized throughout the Shuttle program has undergone many improvements, but concerns remain with flight safety, operational cost, critical failure modes, and hydrazine related hazards. The advanced hydraulic power system (AHPS), also known as the electric APU, is being evaluated as an upgrade to replace the hydrazine APU. The AHPS replaces the high-speed turbine and hydrazine fuel supply system with a battery power supply and electric motor/pump that converts 300 volt electrical power to 3000 psi hydraulic power. AHPS upgrade benefits include elimination of toxic hydrazine propellant to improve flight safety, reduction in hazardous ground processing operations, and improved reliability. Development of this upgrade provides many interesting challenges and includes development of four hardware elements that comprise the AHPS system: Battery - The battery provides a high voltage supply of power using lithium ion cells. This is a large battery that must provide 28 kilowatt hours of energy over 99 minutes of operation at 300 volts with a peak power of 130 kilowatts for three seconds. High Voltage Power Distribution and Control (PD&C) - The PD&C distributes electric power from the battery to the EHDU. This 300 volt system includes wiring and components necessary to distribute power and provide fault current protection. Electro-Hydraulic Drive Unit (EHDU) - The EHDU converts electric input power to hydraulic output power. The EHDU must provide over 90 kilowatts of stable, output hydraulic power at 3000 psi with high efficiency and rapid response time. Cooling System - The cooling system provides thermal control of the Orbiter hydraulic fluid and EHDU electronic components. Symposium presentation will provide an overview of the AHPS upgrade, descriptions of the four hardware elements, and a summary of development results to date.
22 N HPGP Thruster Life Testing
In the ever-changing paradigm of efficient and capable spacecraft design, scientific missions continue pushing the envelope enabling spacecraft subsystems to deliver effective solutions to meet challenging new mission/spacecraft needs. From an in-space storable liquid chemical propulsion perspective, monopropellant hydrazine has been, and continues to be, a dependable propellant with considerable flight heritage, a variety of engine thrust classes available from multiple vendors, with repeatable and reliable performance. Additionally, the space propulsion industry has learned to successfully handle hydrazine, its regulations, the safety protocols, the personnel protective equipment, and the unique training standards–all requisite for loading spacecraft propulsion systems with toxic hypergolic hydrazine. The question now arises as to “what is next for in-space chemical propulsion?” Further, with the evolution and concrete advancements in innovative in-space green propellant technologies, capable of providing realizable benefits to scientific missions, concern over the reliability and availability of this higher performing and safer to handle class of propellants is waning. As science missions move forward with the potential flight in fusion of High Performance Green Propulsion (HPGP), NASA and its industry partners are working to address any gaps in system reliability, performance, or unique operational considerations. Propellant technology that offers both higher performance and significant reduction in personnel hazards compared to hydrazine presents an attractive propulsion subsystem design opportunity. Increased propulsion subsystem performance can result in lower spacecraft launch mass, larger scientific payloads, or extended on-orbit lifetimes. Mission trades using green propulsion technologies have been documented on multiple NASA Goddard Space Flight Center (GSFC) mission classes, examining various parameters and requirements to support mission architectures in Low Earth Orbit (LEO), High Earth Orbit (HEO), geostationary, lunar, planetary, and Quasi-halo orbit around Sun-Earth Lagrange point (L2). The results of these trade studies show promising, attainable benefits. The perceived programmatic risk of flying a newer propulsion technology has, unfortunately, not outweighed the benefits to date. To take advantage of the improved performance and mitigate programmatic risk, HPGP engines must demonstrate life testing at higher propellant throughputs than have currently been demonstrated. In an effort to proactively address the challenges with technology infusion into a risk-averse community, NASA and the Swedish National Space Agency (SNSA) outlined a collaborative Implementing Arrangement (IA) for the respective agencies to pursue increased HPGP technology maturation. This initial IA effort began in 2013, fresh off the heels of the successful PRISMA HPGP technology demonstration mission. The IA targeted objective is to reduce risk to potential future HPGP missions and fully characterize the LMP-103S propellant and associated engine performance. Over the past eight years, HPGP has flown in propulsion systems on twenty-five(25) spacecraft from seven(7) different Launch Ranges around the globe and on seven (7) different Launch Vehicles. Six(6) of these launches involved multiple loading operations for multiple spacecraft. For U.S. Range operations, nine (9) HPGP systems have been processed at Vandenberg Space Force Base(VSFB):six(6) in 2017, and three (3) in 2018. Six (6) more have been processed at Cape Canaveral Air Force Station (CCAFS)in May 2020, with three (3) systems launched in June 2020 and the remaining three (3) system were left loaded and ready until their launch in August of 2020. Three (3) more systems have been processed at Wallops Flight Facility(WFF)and launched in June 2021. In addition, these propulsion subsystems employed heritage propulsion subsystem component such as valves, filters, and pressure transducers, and have further demonstrated nominal functionality in both diaphragm and Propellant Management Device (PDM) propellant tanks. Based on these successes, HPGP technology continues to be considered for NASA Science Mission Directorate missions at GSFC. The work presented herein represents many years of development and collaborative efforts to successfully align higher performance, low toxicity hydrazine alternatives into scientific missions. NASA GSFC Propulsion Engineering, in collaboration with Bradford ECAPS, has developed mission specific thruster design and testing requirements to establish GSFC’s desired test conditions and firing sequences.In2017, the first flight-like 22N HPGP thruster Engineering Qualification Model (EQM-1)was designed and built by Bradford ECAPS to prove out the thruster design, materials, build process, and test campaign with respect to NASA GSFC critical component and mission requirements. This test program was developed to comprehensively test the thruster, the technology, and ultimately increase the 22N HPGP Technology Readiness Level(TRL). EQM-1was tested to environmental qualification levels prior to hot fire performance testing to represent the relevant end-to-end environment (launch to on-orbit operation)with required margin. This thruster demonstrated steady-state and pulse mode operational capability with propellant thruster throughput up to~53kg.At this throughput level, the EQM-1 engine began to present off-nominal performance and the test campaign was halted to allow for non-destructive testing and identify the root cause for the an omalous performance. Capitalizing on the successful elements of the EQM-1 campaign, an upgraded 22N HPGP EQM-2 has been manufactured by Bradford ECAPS to meet the complete GSFC requirements. The EQM-2 thruster’s test campaign has further demonstrated the robustness of the HPGP propulsion technology and increased the Technology Readiness Level (TRL) by undergoing a full acceptance test program, then proceeding into qualification, including environmental testing (vibration and shock to qualification levels),as well as hot-fire life testing, operating at steady-state and pulse modes with increased propellant thruster throughput to~150kg. The HPGP thruster performance testing enables effective HPGP thruster readiness evaluation to meet NASA candidate mission requirements in the future.
Trajectory correction propulsion for TOPS
A blowdown-pressurized hydrazine propulsion system was selected to provide trajectory correction impulse for outer planet flyby spacecraft as the result of cost/mass/reliability tradeoff analyses. Present hydrazine component and system technology and component designs were evaluated for application to the Thermoelectric Outer Planet Spacecraft (TOPS); while general hydrazine technology was adequate, component design changes were deemed necessary for TOPS-type missions. A prototype hydrazine propulsion system was fabricated and fired nine times for a total of 1600 s to demonstrate the operation and performance of the TOPS propulsion configuration. A flight-weight trajectory correction propulsion subsystem (TCPS) was designed for the TOPS based on actual and estimated advanced components.
Propellant material compatibility program and results
The effects of long-term (up to 10 years) contact of inert materials with earth-storable propellants were studied for the purpose of designing chemical propulsion system components that can be used for current as well as future planetary spacecraft. The primary experimental work, and results to date are reported. Investigations include the following propellants: hydrazine, hydrazine-hydrazine nitrate blends, monomethyl-hydrazine, and nitrogen tetroxide. Materials include: aluminum alloys, corrosion-resistant steels, and titanium alloys. More than 700 test specimen capsules were placed in long-term storage testing at 43 C in the special material compatibility facility. Material ratings relative to the 10-year requirement have been assigned.
Geostationary Operational Environmental Satellite (GOES) mission profile
The GOES mission profile used to achieve geostationary orbit following separation from the Delta launch vehicle is described. The mission profile was constrained by the solid-propellant apogee kick motor which was undersized relative to the spacecraft weight. The resulting deficiency in delivered delta-V had to be made up by the spacecraft hydrazine propulsion system. The mission profile which best utilizes the on-board hydrazine requires that the transfer orbit apogee height be biased 13,800 km above geosynchronous altitude. This maximizes the effectiveness of the apogee motor in performing the plane change necessary to achieve near-equatorial orbit. The highly eccentric drift orbit which results from the apogee motor firing has an average drift rate of 60 deg/day. Circularizing this orbit requires maneuvers designed to achieve geostationary position within a tightly constrained hydrazine allocation. The sequence takes advantage of the orbit changes resulting from attitude maneuvers and combined inplane/out-of-plane maneuvers to achieve hydrazine savings.
Sensing strategies for toxic vapor detection
This work was motivated by the recommendations of the American Conference of Governmental Industrial Hygienists (ACGIH) that threshold limits for hydrazine, H2N-NH2 in air be lowered from 100 to 10 parts-per-billion (ppb) concentration levels. Hydrazine is one of the high-energy propellants used in large volumes in Space Shuttle, Titan, payloads, and other aerospace operations. Since analytical methods presently available for hydrazine detection and/or determination do not satisfy such low levels of detection, the ultimate goal of this research is the development and characterization of a portable and compact chemical sensor ideally capable to detect (in real time) 1 ppb of hydrazine, continuously and reversibly. The laboratory prototype developed as part of this project is comprised of: (1) a reactor part in which H2N-NH2 reacts, generating chemiluminescence emission, with tris(2,2'-bipyridine)ruthenium(III), which is immobilized on an ion-exchange polymeric materials of a perfluorinated hydrocarbon containing sulfonate groups as exchange centers (Nafion); (2) an electrochemical three-electrode cell posed at a potential at which the immobilized ruthenium complex could be reoxidized to the 3-oxidation state (as to provide reversible and continuous detection); and (3) a low power consumption photomultiplier tube to collect and quantitatively integrate the emitted photons with the help of auxiliary electronics and readout device.
Inflight performance of the Ulysses reaction control system
The Ulysses spacecraft has been exploring the heliosphere since October 1990 in a six-year polar orbit. Despite varying operational demands, the pressure-fed monopropellant hydrazine reaction control system (RCS) has experienced few problems. The observed anomalies, having minimal operational impact, include plume impingement effects, electrical power overload effects and hydrazine gas generation effects. These anomalies are presented and discussed, with emphasis on the first observation of gas in the hydrazine propellant. The relatively low gas generation rate is attributed to: the use of high purity hydrazine; the configuration of the spin-stabilized spacecraft; the extensive use of titanium alloys; and the efficiency of the thermal control of the propellant tank which maintains a temperature of 21 C.
Recent Developments in Chemically Reactive Sensors for Propellants
Propellant system leaks can pose a significant hazard in aerospace operations. For example, a leak in the hydrazine supply system of the shuttle auxiliary power unit (APU) has resulted in hydrazine ignition and fire in the aft compartment of the shuttle. Sensors indicating the location of a leak could provide valuable information required for operational decisions. WSTF has developed a small, single-use sensor for detection of propellant leaks. The sensor is composed of a thermistor bead coated with a substance which is chemically reactive with the propellant. The reactive thermistor is one of a pair of closely located thermistors, the other being a reference. On exposure to the propellant, the reactive coating responds exothermically to it and increases the temperature of the coated-thermistor by several degrees. The temperature rise is sensed by a resistive bridge circuit, and an alarm is registered by data acquisition software. The concept is general and has been applied to sensors for hydrazine, monomethylhydrazine, unsym-dimethylhydrazine, ammonia, hydrogen peroxide, ethanol, and dinitrogen tetroxide. Responses of these sensors to humidity, propellant concentration, distance from the liquid leak, and ambient pressure levels arc presented. A multi-use sensor has also been developed for hydrazine based on its catalytic reactivity with noble metals.
Aerojet - AJ10-137 Apollo Service Module Engine
The general configuration of the SPS engine was 20,000 pounds of thrust, with a chamber pressure of 100 psi and specific impulse (Isp) of 314.5. The very large nozzle had an area ratio of 62.5:1 (exit area to throat area). The propellants were nitrogen tetroxide (also known as N2O4 and nitrous oxide) and A-50. A-50 was a hydrazine family fuel. Aerojet developed it for the Titan Missile Program when they went with Titan II, to store it in the launch silos. They wanted the highest performance they could get. N2H4 was just pure hydrazine, which doesn't take low temperature very well. In fact, it freezes about like water. We started adding unsymmetrical-dimethylhydrazine (UDMH) to the hydrazine until such time as it would meet the environmental specifications the Air Force needed for Titan II. It turned out it s roughly a fifty-fifty mix. We still had to be careful with that fuel because the two fluids didn't mix very well chemically. We had to spray the two fluids through some special nozzles to get them to emulsify with each other into a single fluid. If we ever got it too cold or froze it, the hydrazine separated back out. Then, if we tried to run the engine, things could go boom in the night. The inlet pressure was only 165 pounds per square inch absolute (psia), but we needed at least forty psi pressure drop across the injector just to get some kind of stable flow. It was a whole new game for some of us. We didn't have much supply pressure to work with. It had the aluminum injector to keep the weight down. That was a couple feet in diameter, and we didn't have a lot of propellant to cool it. In fact, we had to use both propellants to keep the injector cool. There were twenty-two ring channels in the injector. Specification required 750 seconds duration, or fifty engine restarts during a flight. There were several first flight things we accomplished with the engine. It was the first ablative thrust chamber of any size to fly. (See Slide 6, Appendix G) There were no liners in it. It was just straight ablative material. It took us a while to figure that out. It was a throat-gimbaled engine, and it was the first engine to fly with columbium (also known as niobium, used as an alloying element in steels and superalloys) in the nozzle.
Hydrocarbon-Seeded Ignition System for Small Spacecraft Thrusters Using Ionic Liquid Propellants
"Green" propellants based on Ionic-liquids (ILs) like Ammonium DiNitramide and Hydroxyl Ammonium Nitrate have recently been developed as reduced-hazard replacements for hydrazine. Compared to hydrazine, ILs offer up to a 50% improvement in available density-specific impulse. These materials present minimal vapor hazard at room temperature, and this property makes IL's potentially advantageous for "ride-share" launch opportunities where hazards introduced by hydrazine servicing are cost-prohibitive. Even though ILs present a reduced hazard compared to hydrazine, in crystalline form they are potentially explosive and are mixed in aqueous solutions to buffer against explosion. Unfortunately, the high water content makes IL-propellants difficult to ignite and currently a reliable "coldstart" capability does not exist. For reliable ignition, IL-propellants catalyst beds must be pre-heated to greater than 350 C before firing. The required preheat power source is substantial and presents a significant disadvantage for SmallSats where power budgets are extremely limited. Design and development of a "micro-hybrid" igniter designed to act as a "drop-in" replacement for existing IL catalyst beds is presented. The design requires significantly lower input energy and offers a smaller overall form factor. Unlike single-use "squib" pyrotechnic igniters, the system allows the gas generation cycle to be terminated and reinitiated on demand.