Evaluation of Hydrazine Sensing, Material Compatibility and Testing Methods

Laura Barkett11 The Miltec Corporation and The University of Alabama in Huntsville, Huntsville, AL, 35899 In an effort to develop a hydrazine pressure sensor with superior response time, research has been done to investigate the possible methods for designing a new, more effective product. Hydrazine propellant leaks can cause toxic, damaging, or explosive environments for the spacecraft and can present safety concerns for the astronauts aboard. Higher time-to-criticality specifications for the sensors response can be beneficial for prevention of damage or loss of vehicle. Presently there are many types of hydrazine pressure and vapor sensing methods utilizing materials compatible with hydrazine. Research on currently used products reveals information that is valuable for implementation of a higher performing sensor that can be placed directly in line with the propellant tank. Quartz crystals, and piezoresistive approaches have been used in hydrazine pressure transducers, and calorimetric sensors, coulometric sensors, and evaporative cooling methods have been used for vapor detection. Several metals have been used throughout the years that have the ability to effectively withstand this harsh chemical over a long duration without showing significant erosion. However, finding durable materials has been challenging, and many used in the past have presented chemical compatibility problems. In recent years, materials such as elastomers, polymers, and diamond have been considered that may be more compatible to a hydrazine environment. It is necessary to evaluate these options in order to find construction materials for the prototyping and testing of a diamondbased solution that can harmlessly interface with the hydrazine and be directly submersed into the propellant.

I. Introduction

ANY organizations and ideas are investigated and their findings are being considered for present design process of an improved hydrazine sensor for use in propulsion systems to be implemented by Miltec Systems. Present sensing methods, compatible materials and testing procedures should be known and considered for the successful design a superior product. Several types of pressure sensing methods have been investigated and Appendix A contains a chart listing materials suitable for these applications. Hydrazine thrusters, are common among many aerospace programs, including satellites, space probes, launch vehicles, interplanetary landers, and missiles. Appendix B shows programs utilizing hydrazine propulsion systems. Information collected will supplement ideas for the diamond sensor and implementation and testing will be derived from this research. As a result of this new product, response time of hydrazine sensors will be improved.

II. Hydrazine Pressure Sensing Methods

Several different types of pressure sensing devices for hydrazine have already been used. Most hydrazine pressure transducers have been placed downstream from the tank, and not directly on or in the tank. A. Measuring the Pressurant Pressure of a hydrazine tank can be found by making measurements of the pressurant. One common technique for pressurizing employs a helium tank as shown in Fig. 1, set to remain at constant pressure. Pressure cannot be constant unless the system detects when to increase pressure to make up for propellant lost. This requires means of detecting pressure loss. When the helium and the hydrazine tanks are interconnected by a valve, as shown in Fig. 2,
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Launch Vehicle Co-Op Engineer, NASA Programs, 689 Discovery Dr. Huntsville AL, 25806, Student Member 1 American Institute of Aeronautics and Astronautics
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the pressures in the two tanks will be the same when the valve is opened. Therefore, the pressure transducer on the helium tank is efficient for revealing the pressure in the propellant tank1.

Figure 1. Helium Pressurant

Figure 2. Helium Gauging System

B. Pressure in the Pipes Another way is to put the transducer in a pipe attached to the tank, taking into consideration that the pressure in that pipe will be the same as the tank pressure as long as the system is closed. An example of such procedure has been used for temperature testing. During this experiment, rupture disks that burst at a given maximum pressure were replaced with pressure transducers.1 These rupture disks are placed at the beginning of a pipe adjacent to the top opening of the tanks. These were the stainless steel Schavitz Type P710 and the titanium Druck Type PDCR 110/D/W. The Druck type used a strain gauge on the inside of a titanium membrane to calculate pressure.2, 3 No further information was found for the Schavitz transducers.2 C. Bourdon Tube with Quartz Transducer Aeroquartz, Inc. manufactures a quartz crystal pressure transducer for hydrazine that uses a load-sensitive resonator. For this application, a curling Bourdon tube is used to apply loads caused from pressure in the tank onto a tuning fork, which has resonant vibrations maintained from an external, oscillator circuit. Compressional loading causes the resonator frequency to increase, indicating a higher pressure, while tension forces cause the resonator frequency to decrease indicating lower pressure. This gauging system relates pressure, temperature and tank volume to indicate the amount of propellant inside of the tank. D. Piezoresistive Method Bradford Engineering has utilized stainless steel and titanium fluid to interface with hydrazine. They developed a piezoresistive transducer with a stainless steel module that contains resistors buried beneath a silicone pad. The sensor diaphragm is filled with fluid that transfers pressure to the silicone, causing stress and a variation in resistivity.3 E. Transducer Complications Other hydrazine transducers have been known to present some problems. Pressure surges should be taken into account when considering the durability criteria for any new hydrazine pressure sensing designs. Previous pressure transducers used on hydrazine propulsion systems have produced incorrect readings due to the water hammer effect, which is basically a surge in pressure due to a sudden halt in fluid flow velocity. Water hammer testing reveals that these sudden surges may result in calibration error of digital piezoresistive pressure transducers. This problem has been corrected by simply replacing the transducers with analog transducers, which respond just as quickly.4 Also, studies show that any components of sensing systems to be integrated with the propellant tank must keep air, carbon dioxide and other such elements that promote corrosion from seeping in and allowing decomposition and pressure buildup of the hydrazine.5

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III. Methods for Detecting Hydrazine Vapors

Vapor sensing methods have also been efficient for detecting hydrazine. Discussed methods include calorimetric sensors, coulometric sensors, fiber optics and thermistor applications. A. Calorimetric and Coulometric Sensors Other sensing methods have also been efficient in hydrazine leak detection. Calorimetric and coulometric sensors utilize chemical reactions for measurement of hydrazine vapors, which are also corrosive. Devices made from gold-doped tungsten oxide and titanium dioxide may be used to detect hydrazine gases at high temperatures. Fiber optic sensors analyzing chemical reactions with spectroscopy have been used for detection of hydrazine gases at lower temperatures.6 B. Evaporative Cooling Leak Detection on Space Shuttle Orbiter Because the commercial hydrazine transducers are too sensitive for hydrazine applications, some recent detection test utilizing evaporative cooling have been conducted. Evaporative cooling occurs when the fluid surface pressure experiences sudden decrease. As a result of this pressure loss, the fluid becomes superheated and goes through rapid vaporization. The conduction from this vaporization caused a decrease in temperature, which is detected by a RTD sensor or thermistor. These sensors are encapsulated in foam that traps the vapors. In order for such a temperature drop from a leak to be detected, the fluid must be exposed to a space vacuum. Potential leak locations (i.e. connecting devices, fittings), shown in Fig. 3, are predicted and the foam is placed accordingly.7 Figure 3. Locations for Potential Leaks C. Space Shuttle Orbital Leak Detection by Chemical Reactive Heat Another method considered for the Space Shuttle employed detection of heat given off by a chemical reaction caused by escaped hydrazine. This technique uses a thermistor surrounded by hydrazine-compatible material that serves as a catalyst, while 10% of the material is made up of a material that has sufficient reactivity to generate heat without presenting a fire hazard. Approximately 90% of the material was Shell 405, leaving the remaining 10% alumina as a reactant. Such configuration of materials allows for multiple uses of the sensor.7

IV. Hydrazine Material Compatibility

Several metals presently show compatibility with hydrazine, and there are many polymers compatible with hydrazine. However, some of them are not durable or resistant to corrosion for an extended period of time, making them unsuitable for many long-term space missions. A. Metals Used with Hydrazine One of the best known stainless steel alloys for hydrazine applications is 304L.5 Hastelloy B, a nickel-based alloy, has also been found acceptable, and many different aluminum types demonstrate excellent compatibility.8 Titanium is also widely used. PSI has manufactured a hydrazine tank made of 6AL-4V annealed Titanium, with inlet/exit ports made from 3AL-2.5V titanium and 304L stainless steel transition tubes.9 Tungsten-inert gas (TIG) welding is used for binding the tanks together.10 Fig. 4 shows an example of a titanium hydrazine tank. Platinum, rhenium, and tantalum have been used for hydrazine catalytic functions.8

Figure 4. Titanium Section of Hydrazine Tank

B. Polymers used with Hydrazine Before the 1990s, many polymers were used for hydrazine compatibility. Examples of these are butyl rubber, ethylene propylene, and EPT-10.10 Elastomers used in the past have contained carbon black, which causes degradation of hydrazine. After researchers discovered this, they decided that silica fillers made compounds that would prove more compliant with the propellant. This prompted the development of EPR AF-E-332, a new ethylene 3 American Institute of Aeronautics and Astronautics
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propylene terpolymer.11 For most recent designs, there have been a number of ethylene propylene diene modified (EPDM) polymers that have been developed to construct the tanks. Fig. 5 shows a polymer auxiliary propellant unit diaphragm. Examples of these are the AF-E-332 elastomer by Pressure Systems Inc., MIL-R-83412 and the D11 material made by Royal Ordnance. However, it has been observed that the diaphragms materials become problematic and contaminants are extracted from these elastomers over a period of time. This resulted in tremendous performance degradation, as the leaching of these particles by the hydrazine was causing congestion in the thrusters. Another disadvantage of using these elastomers is that DuPont Elastomers stopped producing Nordel 1635, which was the base rubber for these materials.10,11,12 A R&D project led by iab Consulting has resulted in the development of two newer elastomers called SIFA 35 and SIFA 32. SIFA 35, having mechanical properties comparable to AF-E-332, Figure 5. Elastomeric Tank was tested extensively. After submerging samples of the new elastomer into hydrazine over different periods of time, the hydrazine was then taken out and analyzed for contaminants by spectroscopy. Also, tests were done to measure the initial and final mass of the samples to determine swelling due to immersion. The material also underwent other test (i.e. fungi, thermal cycling, radiation, fire testing) and it is concluded that this material is acceptable for long missions.12 Duponts Kalrez has been used in aerospace applications for thirty years. To address the industries demand for a product that was able to withstand extreme thermal conditions, demonstrate efficient compression set resistance and excellent seal force retention, a newer product was developed. Currently, Duponts Kalrez Aeroseal is the state-of-the-art elastomer for these functions. There are many polymers compatible with hydrazine. However, some of them are not durable or resistant to corrosion for an extended period of time, making them unsuitable for many long-term space missions. Several materials that demonstrate excellent compatibility include epoxy, Teflon, and DuPonts Kalrez. There are materials that are not as suitable as the ones previously mentioned, but still have decent compatibility. Examples are silicone and DuPonts ChemRaz, while even less compatible substances are polypropylene and natural rubber. Swelling of some polymers, such as Teflon, make them appropriate for sealant and o-ring applications, but not for storage. C. Hydrazine and Glass Glass can also be used with hydrazine. Examples are soft and pyrex glass, which is used for laboratory test beakers. Previous test have shown that pyrex does not ignite hydrazine in air in environments of 330C and atmospheric pressure.13

V. Testing Procedures for Hydrazine Applications

There are two primary malfunctions that occur when insufficient materials are used for hydrazine applications the material degrades, or the propellant decomposes. For materials testing, types of data obtained include permeability, elongation, tensile strength, creep, modulus, fatigue, stress relaxation, compression set, and swelling. Decomposition of hydrazine has been attributed to the catalyzing of its own impurities. A. Simple Swelling Analysis Pressure Systems Inc. and iab Consulting have tested elastomeric samples in test vessels filled with hydrazine. The samples are weighed and cleaned before immersion. Once the samples are submersed for a given period of time they are tensile tested, and weighed again for indication of swelling. Percent elongation is also found.12 B. Inductively Coupled Plasma Analysis Decomposition of the propellant after sample submersion is tested by inductively coupled plasma (ICP) analysis. This method utilizes the creation of plasma around the fluid, and deviations are observed through optical

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emissions spectroscopy. Given surface area (elastomer) to volume of hydrazine ratios are used, and components are precision cleaned to ensure accuracy of the measurements.12 D. The Prediction Method and Pressure Increase The prediction method uses short term data to predict long term outcomes. Samples are tested and values for the rates of pressure and metal buildup are found, as well as the surface degradation. In the case of pressure increase, gas production is correlated to the decomposition of the hydrazine, and metal build up is found as a function of the material and propellant reactions, while surface degradation is correlated to metal buildup. To relate the amount of material degradation and propellant decomposition, kinetic rate expressions are found and the long term outcome of such discrepancies may be predicted by using the collected data.14 E. Neutron Activation Analysis This test method utilizes stable isotopes irradiated by neutrons to emanate radioactive nuclide. Using radiation detection devices, conclusions can be made as to the makeup of the sample and its original quantity. An analyzer records the gamma rays in a certain energy level, revealing the total mass of the product radioisotope.14 F. Atomic Absorption Spectroscopy Atomic absorption spectroscopy, or AAS, is used for finding element concentrations, and involves the excitation of atoms by ultraviolet light. It is known that elements absorb light in narrow energy bands specific to that element. Substances analyzed by this method are vaporized and intercepted by radiation beams from the excitation source. However, this involves reducing the components to their elemental state, which can prove to be challenging. ASS has been accomplished by heating the substance, in the form of a fine mist, over an appropriate flame until vaporization is accomplished. In the 1970s a graphite tube furnace sampler was developed for this purpose, increasing the stability of the process and creating a larger surface for the optical path for observation. A cathode lamp, containing the element in question, is used for creating electromagnetic radiation. Light spectrums are emitted from the cathode, and the sample is energized. Sample concentration can be related to the amount of electromagnetic energy absorbed. Fig. 6 shows a spectrometer used for this purpose.14

Figure 6. Atomic Absorption Spectrometer

G. Radioactive Tracer Technique This technique uses the same theory as the neutron activation method. The difference is that only one or a few radioisotopes are used. Metal samples are placed inside a nuclear reactor, or other such source of neutrons, and are then placed in the propellant. Once the metal sample is taken out of the propellant, the propellant is analyzed with a radiation detection device, and the radiation is correlated to the amount of metal impurities. Unlike the neutron activation analysis, a more advanced analyzer is not necessary because the amount of energy on the metal is already established.14 H. Extrapolation of Data with Temperature Increase Experimental data found by Rocketdyne and Sanford Research Institute in the 1970s shows that the decomposition is sensitive to storage temperatures. Higher temperatures speed the process considerably. Experiments showed also, that decomposition rates can be tested without waiting the entire duration of the time in consideration, by simply elevating the temperatures and extrapolating the data to the known ones of lower temperatures. This prevents observers from having to wait years to obtain exact reaction rates. It should be noted that, when there is excessive metallic corrosion, sludge formation, or pitting, these discrepancies will always be preceded by pressure rises above acceptable limits.15

VI.

Conclusion

Sensing methods, compatibility, and testing procedures for hydrazine materials will be evaluated, and Miltecs design and methods of test will be decided accordingly. This research should reveal enough information to ensure that Miltecs new diamond sensor is prototyped efficiently. Because diamond is known as one of the hardest and 5 American Institute of Aeronautics and Astronautics
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most durable materials, Miltec will consider using it for hydrazine applications. No information was found to suggest previous testing of diamond material with hydrazine.

Appendix A. Material Compatibility Chart

Metal/Hydrazine Compatibility Aluminum 2S Aluminum 61ST Aluminum 2SO Aluminum 75ST Aluminum 2SH Rhenium Aluminum 3S Steel 304 Aluminum 3SH Steel 347 Aluminum 24ST Tantalum Aluminum 52ST Titanium Hastelloy B Zirconium Polymer/Hydrazine Compatibility Acetal (Deirin) Natural Rubber Aflas Neoprene Buna N (Nitrile) Polyetherether Ketone Butyl Polypropylene EPDM Rubber PTFE (Teflon) Epoxy PVDF (Kynar) Hypalon Silicone Hytrelr Styrene Butadiene Kalrez Glass/Hydrazine Compatibility Soft Glass Pyrex

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Appendix B. Hydrazine Propulsion Applications

Programs Utilizing Hydrazine Thrusters Spacecraft/Aircraft Atlas IIIB AEROS Cassini Centaur Clementine COBE Corporal Missile Delta III EURECA (MMB/ERNO) EXOSAT Galileo Gemini Genesis GEOSTAT HEAO IDCSP/A INDOSTAR INTELSAT III & IV Magellan Mariner Mars Pathfinder NATO NEAR Nova Orbital Express OTS Pioneer RADARSAT ROCSAT SEASAT Sergeant Missile SKYNET II SOHO TACSAT TerraSar-X TITAN III TOPEX Voyager Type of Program Launch Vehicle Satellite Orbiter Rocket Observer Satellite Missile Launch Vehicle Satellite Satellite Unmanned Observer Spacecraft Manned Spacecraft Sample Collecting Spacecraft Satellite Satellite Satellite Satellite Satellite Venus Observer Space Probe Mars Lander Satellite Unmanned Observer Spacecraft Satellite Satellite Maintenance Vehicle Orbital Test Satellite Family Space Probe Remote Sensing Satellite Satellite Satellite Missile Satellite Solar Heliospheric Observatory Satellite Satellite Rocket Ocean Topography Satellite Interstellar Observer

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References
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