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ISO 15859 Propellant and Fluid Specifications: A Review and Comparison with Military and NASA Specifications

This work presents an overview of the International Organization for Standardization (ISO) 15859 International Standard for Space Systems Fluid Characteristics, Sampling and Test Methods Parts 1 through 13 issued in June 2004. These standards establish requirements for fluid characteristics, sampling, and test methods for 13 fluids of concern to the propellant community and propellant characterization laboratories: oxygen, hydrogen, nitrogen, helium, nitrogen tetroxide, monomethylhydrazine, hydrazine, kerosene, argon, water, ammonia, carbon dioxide, and breathing air. A comparison of the fluid characteristics, sampling, and test methods required by the ISO standards to the current military and NASA specifications, which are in use at NASA facilities and elsewhere, is presented. Many ISO standards composition limits and other content agree with those found in the applicable parts of NASA SE-S-0073, NASA SSP 30573, military performance standards and details, and Compressed Gas Association (CGA) commodity specifications. The status of a current project managed at NASA Johnson Space Center White Sands Test Facility (WSTF) to rewrite these documents is discussed.

Greene, Ben↗

Performance Increase Verification for a Bipropellant Rocket Engine

Component performance assessment testing for a, pressure-fed earth storable bipropellant rocket engine was successfully completed at Aerojet's Redmond test facility. The primary goal of the this development project is to increase the specific impulse of an apogee class bi-propellant engine to greater than 330 seconds with nitrogen tetroxide and monomethylhydrazine propellants and greater than 335 seconds with nitrogen tetroxide and hydrazine. The secondary goal of the project is to take greater advantage of the high temperature capabilities of iridium/rhenium chambers. In order to achieve these goals, the propellant feed pressures were increased to 400 psia, nominal, which in turn increased the chamber pressure and temperature, allowing for higher c*. The tests article used a 24-on-24 unlike doublet injector design coupled with a copper heat sink chamber to simulate a flight configuration combustion chamber. The injector is designed to produce a nominal 200 lbf of thrust with a specific impulse of 335 seconds (using hydrazine fuel). Effect of Chamber length on engine C* performance was evaluated with the use of modular, bolt-together test hardware and removable chamber inserts. Multiple short duration firings were performed to characterize injector performance across a range of thrust levels, 180 to 220 lbf, and mixture ratios, from 1.1 to 1.3. During firing, ignition transient, chamber pressure, and various temperatures were measured in order to evaluate the performance of the engine and characterize the thermal conditions. The tests successfully demonstrated the stable operation and performance potential of a full scale engine with a measured c* of XXXX ft/sec (XXXX m/s) under nominal operational conditions.

Alexander, Leslie↗

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.

Source record↗

Three Methods of Detection of Hydrazines

Three proposed methods for measuring trace quantities of hydrazines involve ionization and detection of hydrazine derivatives. These methods are intended to overcome the limitations of prior hydrazine- detection methods. Hydrazine (Hz), monomethylhydrazine (MMH), and unsymmetrical dimethylhydrazine (UDMH) are hypergolic fuels and are highly reactive, toxic, and corrosive. A capability to measure concentrations of hydrazines is desirable for detecting leaks and ensuring safety in aerospace settings and in some industrial settings in which these compounds are used. One of the properties (high reactivity) that make it desirable to detect trace amounts of hydrazines also makes it difficult to detect hydrazines and measure their concentrations accurately using prior methods: significant amounts are lost to thermal and catalytic decomposition prior to detection. Further complications arise from the sticky nature of hydrazines: Sample hydrazine molecules tend to become irreversibly adsorbed onto solid surfaces with which they come into contact during transport to detectors, giving rise to drift in detector responses. In each proposed method, the reactive, sticky nature of hydrazines would be turned to advantage by providing a suitably doped substrate surface with which the hydrazines would react. The resulting hydrazine derivatives would be sufficiently less sticky and sufficiently more stable so that fewer molecules would be lost to decomposition or adsorption during transport. Consequently, it would be possible to measure concentration with more sensitivity and less error than in prior techniques. The first proposed method calls for the use of a recently developed technique known as desorption electrospray ionization (DESI), in which a pneumatically assisted micro -electrospray at ambient pressure is directed at a surface of interest. In this case, the surface of interest would be that of a substrate described above.

Griffin, Timothy↗

Factors Contributing to Pilot Valve Fuel Seal Extrusion in Orbiter PRCS Thrusters

Extrusion of the polytetrafluoroethylene (PTFE) pilot seal used in the monomethylhydrazine (fuel) valve of the Orbiter Primary Reaction Control System (PRCS) thrusters has been implicated in numerous on-orbit thruster failures and on-ground valve failures. Two extrusion mechanisms have been proposed, one or both may be occurring. The first mechanism is attributed to thermal expansion mismatch between adjacent PTFE and metal parts used in the fuel valve, and is referred to as thermal extrusion. The second mechanism is attributed to nitrogen tetroxide (oxidizer) leakage from the adjacent oxidizer valve on the same thruster during ground turnaround, and is referred to as oxidizer-induced extrusion. Model calculations of PTFE pilot seal in an exact pilot valve configuration show that extrusion can be caused by differential thermal expansion, without the intervening influence of oxidizer. Experimental data on semitrapped PTFE and TFM (modified PTFE) specimens simulating a fuel pilot valve configuration show that thermal extrusion 1) is incremental and irreversible, 2) increases with the size of the thermal excursion, 3) decreases with successive thermal cycling, and 4) is accompanied by gap formation. Both PTFE and TFM exhibit a higher affinity for oxidizer than fuel. The property changes associated with oxidizer uptake may explain why oxidizer seals do not exhibit extrusion. Impression replicas of fuel pilot seals removed from the Orbiter fleet show two types of extrusion: extrusion of the entire seal (loaded extrusion), or extrusion of non-sealing surface (unloaded extrusion). Both extrusion types may arise from differences in service history, rather than in failure mechanism. The plausibility oxidizer-induced extrusion was evaluated. Preliminary calculations suggest that enough energy, heat, or gas may be liberated under certain operational scenarios to cause catastrophic extrusion. However, given the lack of supporting data, conclusions implicating oxidizer leakage as a factor in extrusion must be made with caution.

Waller, J.M.↗

Failure Investigation of an Intra-Manifold Explosion in a Horizontally-Mounted 870 lbf Reaction Control Thruster

In June 2010, an 870 lbf Space Shuttle Orbiter Reaction Control System Primary Thruster experienced an unintended shutdown during a test being performed at the NASA White Sands Test Facility. Subsequent removal and inspection of the thruster revealed permanent deformation and misalignment of the thruster valve mounting plate. Destructive evaluation determined that after three nominal firing sequences, the thruster had experienced an energetic event within the fuel (monomethylhydrazine) manifold at the start of the fourth firing sequence. The current understanding of the phenomenon of intra-manifold explosions in hypergolic bipropellant thrusters is documented in literature where it is colloquially referred to as a ZOT. The typical ZOT scenario involves operation of a thruster in a gravitational field with environmental pressures above the triple point pressure of the propellants. Post-firing, when the thruster valves are commanded closed, there remains a residual quantity of propellant in both the fuel and oxidizer (nitrogen tetroxide) injector manifolds known as the "dribble volume". In an ambient ground test configuration, these propellant volumes will drain from the injector manifolds but are impeded by the local atmospheric pressure. The evacuation of propellants from the thruster injector manifolds relies on the fluids vapor pressure to expel the liquid. The higher vapor pressure oxidizer will evacuate from the manifold before the lower vapor pressure fuel. The localized cooling resulting from the oxidizer boiling during manifold draining can result in fuel vapor migration and condensation in the oxidizer passage. The liquid fuel will then react with the oxidizer that enters the manifold during the next firing and may produce a localized high pressure reaction or explosion within the confines of the oxidizer injector manifold. The typical ZOT scenario was considered during this failure investigation, but was ultimately ruled out as a cause of the explosion. Converse to the typical ZOT failure mechanism, the failure of this particular thruster was determined to be the result of liquid oxidizer being present within the fuel manifold.

Durning, Joseph G., III↗

Historical Evolution of NASA Standard Materials Testing with Hypergolic Propellants and Ammonia (NASA Standard 6001 Test 15)

The NASA Johnson Space Center White Sands Test Facility (WSTF) has performed testing of hazardous and reactive aerospace fluids, including hypergolic propellants, with materials since the 1960s with the Apollo program. Amongst other test activities, Test 15 is a NASA standard test for evaluating the reactivity of materials with selected aerospace fluids, in particular hydrazine, monomethylhydrazine, uns-dimethylhydrazine, Aerozine 50, dinitrogen tetroxide oxidizers, and ammonia. This manuscript provides an overview of the history of Test 15 over a timeline ranging from prior to its development and first implementation as a NASA standard test in 1974 to its current refinement. Precursor documents to NASA standard tests, as they are currently known, are reviewed. A related supplementary test, international standardization, and enhancements to Test 15 are also discussed. Because WSTF was instrumental in the development and implementation of Test 15, WSTF experience and practices are referred to in this manuscript.

Greene, Benjamin↗

A Summary of NASA and USAF Hypergolic Propellant Related Spills And Fires

Hypergolic fluids are toxic liquids that react spontaneously and violently when they contact each other. These fluids are used in many different rocket and aircraft systems for propulsion and hydraulic power including, orbiting satellites, manned spacecraft, military aircraft, and deep space probes. Hypergolic fuels include hydrazine (N 2H4) and its derivatives including monomethylhydrazine (MMH), unsymmetrical di-methylhydrazine (UDMH), and Aerozine 50 (A-50), which is an equal mixture of N2H4 and UDMH. The oxidizer used with these fuels is usually nitrogen tetroxide (N2O4), also known as di-nitrogen tetroxide or NTO, and various blends of N2O4 with nitric oxide (NO). Several documented, unintentional hypergolic fluid spills and fires related to the Apollo Program, the Space Shuttle Program, and several other programs from approximately 1968 through the spring of 2009 have been studied for the primary purpose of extracting the lessons learned. Spill sites include KSC, JSC, WSTF, CCAFS, EAFB, McConnell AFB, and VAFB.

Nufer, B. M.↗

Characterization of Monomethyihydrazine (MMH) Non-Volatile Residue

The Space Shuttle program has a unique propellant purity requirement for determination of nonvolatile residue (NVR) in monomethylhydrazine (MMH). TIis requirement differs from the Military Specification procurement specification by requiring a NVR analysis with a limit of less than or equal to 10 milligrams per liter. In June 2008, a routine MMH replenishment delivery was transferred into a NASA KSC owned tanker for future delivery to the Space Shuffle pad MMH storage tank. Per Shuffle standard operating procedure, the receiving tanker was sampled and analyzed for purity and surprisingly it failed the Shuttle use NVR specification limit. Detailed examination of the NVR revealed that it was fundamentally different than the typical MMH NVR. This paper will examine various aspects of NVR determination in MMH and the analytical characterization processes used to identify the NVR.

Davis, Chuck↗

Nontoxic Ionic Liquid Fuels for Exploration Applications

The toxicity of propellants used in conventional propulsion systems increases not only safety risks to personnel but also costs, due to special handling required during the entire lifetime of the propellants. Orbital Technologies Corporation (ORBITEC) has developed and tested novel nontoxic ionic liquid fuels for propulsion applications. In Phase I of the project, the company demonstrated the feasibility of several ionic liquid formulations that equaled the performance of conventional rocket propellant monomethylhydrazine (MMH) and also provided low volatility and low toxicity. In Phase II, ORBITEC refined the formulations, conducted material property tests, and investigated combustion behavior in droplet and microreactor experiments. The company also explored the effect of injector design on performance and demonstrated the fuels in a small-scale thruster. The ultimate goal is to replace propellants such as MMH with fuels that are simultaneously high-performance and nontoxic. The fuels will have uses in NASA's propulsion applications and also in a range of military and commercial functions.

Coil, Millicent↗

Particle Streak Velocimetry of Supersonic Nozzle Flows

A novel velocimetry technique to probe the exhaust flow of a laboratory scale combustor is being developed. The technique combines the advantages of standard particle velocimetry techniques and the ultra-fast imaging capabilities of a streak camera to probe high speed flows near continuously with improved spatial and velocity resolution. This "Particle Streak Velocimetry" technique tracks laser illuminated seed particles at up to 236 picosecond temporal resolution allowing time-resolved measurement of one-dimensional flows exceeding 2000 m/s as are found in rocket nozzles and many other applications. Developmental tests with cold nitrogen have been performed to validate and troubleshoot the technique with supersonic flows of much lower velocity and without background noise due to combusting flow. Flow velocities on the order of 500 m/s have been probed with titanium dioxide particles and a continuous-wave laser diode. Single frame images containing multiple streaks are analyzed to find the average slope of all incident particles corresponding to the centerline axial flow velocity. Long term objectives for these tests are correlation of specific impulse to theoretical combustion predictions and direct comparisons between candidate green fuels and the industry standard, monomethylhydrazine, each tested under identical conditions.

Willits, J. D.↗

In-Space Engine (ISE-100) Development - Design Verification Test

In the past decade, NASA has formulated science mission concepts with an anticipation of landing spacecraft on the lunar surface, meteoroids, and other planets. Advancing thruster technology for spacecraft propulsion systems has been considered for maximizing science payload. Starting in 2010, development of In-Space Engine (designated as ISE-100) has been carried out. ISE-100 thruster is designed based on heritage Missile Defense Agency (MDA) technology aimed for a lightweight and efficient system in terms volume and packaging. It runs with a hypergolic bi-propellant system: MON-25 (nitrogen tetroxide, N2O4, with 25% of nitric oxide, NO) and MMH (monomethylhydrazine, CH6N2) for NASA spacecraft applications. The utilization of this propellant system will provide a propulsion system capable of operating at wide range of temperatures, from 50 C (122 F) down to -30 C (-22 F) to drastically reduce heater power. The thruster is designed to deliver 100 lb(sub f) of thrust with the capability of a pulse mode operation for a wide range of mission duty cycles (MDCs). Two thrusters were fabricated. As part of the engine development, this test campaign is dedicated for the design verification of the thruster. This presentation will report the efforts of the design verification hot-fire test program of the ISE-100 thruster in collaboration between NASA Marshall Space Flight Center (MSFC) and Aerojet Rocketdyne (AR) test teams. The hot-fire tests were conducted at Advance Mobile Propulsion Test (AMPT) facility in Durango, Colorado, from May 13 to June 10, 2016. This presentation will also provide a summary of key points from the test results.

Trinh, Huu P.↗

Water Hammer Simulations of MMH Propellant - New Capability Demonstration of the Generalized Fluid Flow Simulation Program

Fluid Transient analysis is important for the design of spacecraft propulsion system to ensure structural stability of the system in the event of sudden closing or opening of the valve. Generalized Fluid System Simulation Program (GFSSP), a general purpose flow network code developed at NASA/MSFC is capable of simulating pressure surge due to sudden opening or closing of valve when thermodynamic properties of real fluid are available for the entire range of simulation. Specifically GFSSP needs an accurate representation of pressure-density relationship in order to predict pressure surge during a fluid transient. Unfortunately, the available thermodynamic property programs such as REFPROP, GASP or GASPAK does not provide the thermodynamic properties of Monomethylhydrazine (MMH). This paper will illustrate the process used for building a customized table of properties of state variables from available properties and speed of sound that is required by GFSSP for simulation. Good agreement was found between the simulations and measured data. This method can be adopted for modeling flow networks and systems with other fluids whose properties are not known in detail in order to obtain general technical insight. Rigorous code validation of this approach will be done and reported at a future date.

Burkhardt, Z.↗

Europa Propulsion Valve Seat Material Testing

The Europa mission and spacecraft design presented unique challenges for selection of valve seat materials that met the fluid compatibility requirements, and combined fluid compatibility and high radiation exposure level requirements. The Europa spacecraft pressurization system valves will be exposed to fully saturated propellant vapor for the duration of the mission. The effects of Nitrogen Tetroxide (NTO) and Monomethylhydrazine (MMH) propellant vapors on heritage valve seat materials, such as Vespel SP-1 and Polychlorotrifluoroethylene (PCTFE), were evaluated to determine if an alternate material is required. In liquid system applications, Teflon is the only available compatible valve seat material. Radiation exposure data for Teflon in an air or vacuum environment has been previously documented. Radiation exposure data for Teflon in an oxidizer environment such as NTO, was not available, and it was unknown whether the effects would be similar to those on air-exposed samples. Material testing was conducted by Marshall Space Flight Center (MSFC) and White Sands Test Facility (WSTF) to determine the effects of propellant vapor on heritage seat materials for pressurization valve applications, and the effects of combined radiation and NTO propellant exposure on Teflon. The results indicated that changes in heritage pressurization valve seat materials' properties rendered them unsuitable for the Europa application. The combined radiation and NTO exposure testing of Teflon produced results equivalent to combined radiation and air exposure results.

Addona, Brad M.↗

Cryogenic Propulsion for the Titan Orbiter Polar Surveyor

Liquid hydrogen (LH2) and liquid oxygen (LO2) cryogenic propellants can dramatically enhance NASA sability to explore the solar system due to their superior specific impulse (Isp) capability. Although these cryogenic propellants can be challenging to manage and store, they allow significant mass advantages over traditional hypergolic propulsion systems and are therefore enabling for many planetary science missions. New cryogenic storage techniques such as sub-cooling and the use of advanced insulation and low thermal conductivity support structures will allow for the long term storage and use of cryogenic propellants for solar system exploration and hence allow NASA to deliver more payloads to targets of interest, launch on smaller and less expensive launch vehicles, or both. These new cryogenic storage technologies were implemented in a design study for the Titan Orbiter Polar Surveyor (TOPS) mission, with LH2 and LO2 as propellants, and the resulting spacecraft design was able to achieve a 43 launch mass reduction over a TOPS mission, that utilized a traditional hypergolic propulsion system with monomethylhydrazine (MMH) and nitrogen tetroxide (NTO) propellants. This paper describes the cryogenic propellant storage design for the TOPS mission and demonstrates how these cryogenic propellants are stored passively for a decade-long Titan mission that requires the cryogenics propellants to be stored for 8.5 years.

Cryogenic Propellant Storage↗

The Influence of Chemical Descriptors on the Reactivity of Potential Hypergolic Fuels With Hydrogen Peroxide

The state-of-the-art for storable hypergolic bipropellant systems is monomethylhydrazine (MMH) and mixed oxides of nitrogen (MON). While MMH and MON provide fast and highly reliable hypergolic ignition with excellent propulsive performance, they suffer from safety concerns impacting their production, cost, and supply to various test and launch facilities. In contrast, identifying and demonstrating low-toxicity fuels hypergolic with rocket grade hydrogen peroxide (H2O2) has been challenging with long ignition delay (IDT) and low propulsive performance affecting their deployment in flight systems. This work describes a preliminary observational study to assess the effects of molecular descriptors suspected to predict the reactivity and hypergolicity of compounds within the same chemical class (i.e., thioamide). The approach centered on evaluating functional groups, electrostatic potential, number of carbons, dipole moment, and adiabatic ionization energy. Thiourea is hypergolic with 89.2 wt.% H2O2 (minimum IDT of 21.9 ms) and was selected as a core fuel to study the reactivity of derived fuels with different functionalities. Additionally, the chemical properties were calculated with the Gaussian16 suite. The results showed that group substitution and generally increased number of carbons on thiourea increases IDT. It was observed that a more positively charged sulfur atom in the thioamide does not increase the reactivity towards H2O2. The dipole moment analysis revealed an overall trend of decreasing IDT due to increasing dipole moment. Finally, a lower adiabatic ionization energy related to increased IDTs for most cases. Additional chemical classes comprising a wider range of functionalities and electrophilic attributes are being investigated in on-going work.

Propellant↗

NASA Gateway Refueling Architecture and Concept of Operation

The Lunar Gateway is a deep space orbiting outpost being developed by NASA in partnership with ESA and other domestic and international partners. It is a critical component of NASA’s Artemis program supporting long-term human exploration of the moon and is designed to be refueled, requiring the on-orbit transfer of propellants. The first two modules of Gateway to be launched will be the Power and Propulsion Element (PPE) and the Habitation and Logistics Outpost (HALO). The PPE contains the bipropellant chemical and electrical propulsion systems that will provide attitude control and orbit raising capability for Gateway. The reaction control system (RCS) utilizes monomethylhydrazine (MMH) and mixed oxides of nitrogen-3 (MON-3) as the fuel and oxidizer, respectively. Helium is used as a pressurant. The Advanced Electric Propulsion Systems (AEPS) and Busek hall thrusters that comprise the solar electric propulsion (SEP) system use xenon as the propellent. The ESPRIT Refueling Module, provided by ESA, will supply the propellant refueling function to Gateway’s propulsion systems. On-orbit refueling is a complex, technically challenging operation that is key to enabling sustainable crewed Lunar and Martian exploration. Numerous systems may be involved in the refueling operation. Also numerous systems are required to enable the successful ability for Gateway to refuel such as, SEP, RCS, Structure & Mechanisms (S&M), Guidance, Navigation and Control (GNC), Thermal, Software, Vehicle System Manager (VSM), Flight Ops, Extra Vehicular Robotics (EVR), Communication and Tracking (C&T), Avionics, and more. This paper will detail the design architecture, concept of operations, and challenges associated with the Gateway refueling system. The methodologies used in Gateway will be compared to those implemented in OSAM-1 and the best practices documented by AIAA and CONFERS (Consortium For Execution Of Rendezvous And Servicing Operations).

Brandie L. Rhodes↗