Hypergolic propellant

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The attendant wears a full hazmat suit due to the hazards of the hypergolic fuel hydrazine, here being loaded onto the MESSENGER space probe Hypergolic Fuel for MESSENGER.jpg
The attendant wears a full hazmat suit due to the hazards of the hypergolic fuel hydrazine, here being loaded onto the MESSENGER space probe

A hypergolic propellant is a rocket propellant combination used in a rocket engine, whose components spontaneously ignite when they come into contact with each other.

Contents

The two propellant components usually consist of a fuel and an oxidizer. The main advantages of hypergolic propellants are that they can be stored as liquids at room temperature and that engines which are powered by them are easy to ignite reliably and repeatedly. Common hypergolic propellants are difficult to handle due to their extreme toxicity or corrosiveness.

In contemporary usage, the terms "hypergol" and "hypergolic propellant" usually mean the most common such propellant combination: dinitrogen tetroxide plus hydrazine. [1]

History

The fact that turpentine may spontaneously combust when mixed with nitric acid was discovered as early as the late 17th century by Frederick Slare, [2] [3] however it remained a scientific curiosity for centuries until it was proposed to use it for rocket-assisted take off during WWII. [4]

In 1935, Hellmuth Walter discovered that hydrazine hydrate was hypergolic with high-test peroxide of 80–83%. He was probably the first to discover this phenomenon, and set to work developing a fuel. Prof. Otto Lutz assisted the Walter Company with the development of C-Stoff which contained 30% hydrazine hydrate, 57% methanol, and 13% water, and spontaneously ignited with high strength hydrogen peroxide. [5] : 13  BMW developed engines burning a hypergolic mix of nitric acid with various combinations of amines, xylidines and anilines. [6]

Hypergolic propellants were discovered independently, for the second time, in the U.S. by GALCIT and Navy Annapolis researchers in 1940. They developed engines powered by aniline and red fuming nitric acid (RFNA). [7] Robert Goddard, Reaction Motors, and Curtiss-Wright worked on aniline/nitric acid engines in the early 1940s, for small missiles and jet assisted take-off (JATO). The project resulted in the successful assisted take off of several Martin PBM and PBY bombers, but the project was disliked because of the toxic properties of both fuel and oxidizer, as well as the high freezing point of aniline. The second problem was eventually solved by the addition of small quantities of furfuryl alcohol to the aniline. [5] : 22–23 

An early hypergolic-propellant rocket engine, the Walter 109-509A of 1942-45. Walter Triebwerk HWK109-509 A Luftwaffenmuseum Berlin-Gatow Denis Apel.JPG
An early hypergolic-propellant rocket engine, the Walter 109-509A of 1942–45.

In Germany from the mid-1930s through World War II, rocket propellants were broadly classed as monergols, hypergols, non-hypergols and lithergols. The ending ergol is a combination of Greek ergon or work, and Latin oleum or oil, later influenced by the chemical suffix -ol from alcohol. [Note 1] Monergols were monopropellants, while non-hypergols were bipropellants which required external ignition, and lithergols were solid/liquid hybrids. Hypergolic propellants (or at least hypergolic ignition) were far less prone to hard starts than electric or pyrotechnic ignition. The "hypergole" terminology was coined by Dr. Wolfgang Nöggerath, at the Technical University of Brunswick, Germany. [8]

The only rocket-powered fighter ever deployed was the Messerschmitt Me 163B Komet. The Komet had a HWK 109-509, a rocket motor which consumed methanol/hydrazine as fuel and high test peroxide T-Stoff as oxidizer. The hypergolic rocket motor had the advantage of fast climb and quick-hitting tactics at the cost of being very volatile and capable of exploding with any degree of inattention. Other proposed combat rocket fighters like the Heinkel Julia and reconnaissance aircraft like the DFS 228 were meant to use the Walter 509 series of rocket motors, but besides the Me 163, only the Bachem Ba 349 Natter vertical launch expendable fighter was ever flight-tested with the Walter rocket propulsion system as its primary sustaining thrust system for military-purpose aircraft.

The earliest ballistic missiles, such as the Soviet R-7 that launched Sputnik 1 and the U.S. Atlas and Titan-1, used kerosene and liquid oxygen. Although they are preferred in space launchers, the difficulties of storing a cryogen like liquid oxygen in a missile that had to be kept launch ready for months or years at a time led to a switch to hypergolic propellants in the U.S. Titan II and in most Soviet ICBMs such as the R-36. But the difficulties of such corrosive and toxic materials, including injury-causing leaks and the explosion of a Titan-II in its silo, [9] led to their near universal replacement with solid-fuel boosters, first in Western submarine-launched ballistic missiles and then in land-based U.S. and Soviet ICBMs. [5] : 47 

In the 1960s, late variants of French Véronique sounding rocket and the Vesta rocket, as well as the first stage of the first orbital SLV Diamant used [10] the combination of nitric acid and turpentine discovered by Slare. It may also be used in amateur rocketry. [11]

The Apollo Lunar Module, used in the Moon landings, employed hypergolic fuels in both the descent and ascent rocket engines. The Apollo spacecraft used the same combination for the Service Propulsion System. Those spacecraft and the Space Shuttle (among others) used hypergolic propellants for their reaction control systems.

The trend among Western space launch agencies is away from large hypergolic rocket engines and toward hydrogen/oxygen engines or methane/oxygen and RP-1/oxygen engines for various advantages and disadvantages. Ariane 1 through 4, with their hypergolic first and second stages (and optional hypergolic boosters on the Ariane 3 and 4) have been retired and replaced with the Ariane 5, which uses a first stage fueled by liquid hydrogen and liquid oxygen. The Titan II, III and IV, with their hypergolic first and second stages, have also been retired for the Atlas V (RP-1/oxygen) and Delta IV (hydrogen/oxygen). Hypergolic propellants are still used in upper stages, when multiple burn-coast periods are required, and in launch escape systems.

Characteristics

Hypergolic propellant tanks of the Orbital Maneuvering System of Space Shuttle Endeavour OMS Pod removal.png
Hypergolic propellant tanks of the Orbital Maneuvering System of Space Shuttle Endeavour

Advantages

Hypergolically-fueled rocket engines are usually simple and reliable because they need no ignition system. Although larger hypergolic engines in some launch vehicles use turbopumps, most hypergolic engines are pressure-fed. A gas, usually helium, is fed to the propellant tanks under pressure through a series of check and safety valves. The propellants in turn flow through control valves into the combustion chamber; there, their instant contact ignition prevents a mixture of unreacted propellants from accumulating and then igniting in a potentially catastrophic hard start.

As hypergolic rockets do not need an ignition system, they can fire any number of times by simply opening and closing the propellant valves until the propellants are exhausted and are therefore uniquely suited for spacecraft maneuvering and well suited, though not uniquely so, as upper stages of such space launchers as the Delta II and Ariane 5, which must perform more than one burn. Restartable non-hypergolic rocket engines nevertheless exist, notably the cryogenic (oxygen/hydrogen) RL-10 on the Centaur and the J-2 on the Saturn V. The RP-1/LOX Merlin on the Falcon 9 can also be restarted. [12]

The most common hypergolic fuels, hydrazine, monomethylhydrazine and unsymmetrical dimethylhydrazine, and oxidizer, nitrogen tetroxide, are all liquid at ordinary temperatures and pressures. They are therefore sometimes called storable liquid propellants. They are suitable for use in spacecraft missions lasting many years. The cryogenity of liquid hydrogen and liquid oxygen has so far limited their practical use to space launch vehicles where they need to be stored only briefly. [13] As the largest issue with the usage of cryogenic propellants in interplanetary space is boil-off, which is largely dependent on the scale of spacecraft, for larger craft such as Starship this is less of an issue.

Another advantage of hypergolic propellants is their high density compared to cryogenic propellants. LOX has a density of 1.14 g/ml, while on the other hand, hypergolic oxidizers such as nitric acid or nitrogen tetroxide have a density of 1.55 g/ml and 1.45 g/ml respectively. LH2 fuel offers extremely high performance, yet its density only warrants its usage in the largest of rocket stages, while mixtures of hydrazine and UDMH have a density at least ten times higher. [14] This is of great importance in space probes, as the higher propellant density allows the size of their propellant tank to be reduced significantly, which in turn allows the probe to fit within a smaller payload fairing.

Disadvantages

Relative to their mass, traditional hypergolic propellants possess a lower calorific value than cryogenic propellant combinations like LH2 / LOX or LCH4 / LOX. [15] A launch vehicle that uses hypergolic propellant must therefore carry a greater mass of fuel than one that uses these cryogenic fuels.

The corrosivity, toxicity, and carcinogenicity of traditional hypergolics necessitate expensive safety precautions. [16] [17] Failure to follow adequate safety procedures with an exceptionally dangerous UDMH-nitric acid propellant mixture nicknamed "Devil's Venom", for example, resulted in the deadliest rocketry accident in history, the Nedelin catastrophe. [18]

Hypergolic combinations

Common

Common hypergolic propellant combinations include: [19]

Less common or obsolete

Less-common or obsolete hypergolic propellants include:

Proposed, remain unflown

Pyrophoric substances, which ignite spontaneously in the presence of air, are also sometimes used as rocket fuels themselves or to ignite other fuels. For example a mixture of triethylborane and triethylaluminium (which are both separately and even more so together pyrophoric), was used for engine starts in the SR-71 Blackbird and in the F-1 engines on the Saturn V rocket and is used in the Merlin engines on the SpaceX Falcon 9 rockets.

Notes

  1. ↑ "-ergol", Oxford English Dictionary

Related Research Articles

A monopropellant rocket is a rocket that uses a single chemical as its propellant. Monopropellant rockets are commonly used as small attitude and trajectory control rockets in satellites, rocket upper stages, manned spacecraft, and spaceplanes.

<span class="mw-page-title-main">Hydrazine</span> Colorless flammable liquid with an ammonia-like odor

Hydrazine is an inorganic compound with the chemical formula N2H4. It is a simple pnictogen hydride, and is a colourless flammable liquid with an ammonia-like odour. Hydrazine is highly hazardous unless handled in solution as, for example, hydrazine hydrate.

Unsymmetrical dimethylhydrazine (abbreviated as UDMH; also known as 1,1-dimethylhydrazine, heptyl or Geptil) is a chemical compound with the formula H2NN(CH3)2 that is primarily used as a rocket propellant. At room temperature, UDMH is a colorless liquid, with a sharp, fishy, ammonia-like smell typical of organic amines. Samples turn yellowish on exposure to air and absorb oxygen and carbon dioxide. It is miscible with water, ethanol, and kerosene. At concentrations between 2.5% and 95% in air, its vapors are flammable. It is not sensitive to shock.

<span class="mw-page-title-main">Dinitrogen tetroxide</span> Chemical compound

Dinitrogen tetroxide, commonly referred to as nitrogen tetroxide (NTO), and occasionally (usually among ex-USSR/Russian rocket engineers) as amyl, is the chemical compound N2O4. It is a useful reagent in chemical synthesis. It forms an equilibrium mixture with nitrogen dioxide. Its molar mass is 92.011 g/mol.

<span class="mw-page-title-main">Red fuming nitric acid</span> Chemical compound

Red fuming nitric acid (RFNA) is a storable oxidizer used as a rocket propellant. It consists of 84% nitric acid, 13% dinitrogen tetroxide and 1–2% water. The color of red fuming nitric acid is due to the dinitrogen tetroxide, which breaks down partially to form nitrogen dioxide. The nitrogen dioxide dissolves until the liquid is saturated, and produces toxic fumes with a suffocating odor. RFNA increases the flammability of combustible materials and is highly exothermic when reacting with water.

A propellant is a mass that is expelled or expanded in such a way as to create a thrust or another motive force in accordance with Newton's third law of motion, and "propel" a vehicle, projectile, or fluid payload. In vehicles, the engine that expels the propellant is called a reaction engine. Although technically a propellant is the reaction mass used to create thrust, the term "propellant" is often used to describe a substance which contains both the reaction mass and the fuel that holds the energy used to accelerate the reaction mass. For example, the term "propellant" is often used in chemical rocket design to describe a combined fuel/propellant, although the propellants should not be confused with the fuel that is used by an engine to produce the energy that expels the propellant. Even though the byproducts of substances used as fuel are also often used as a reaction mass to create the thrust, such as with a chemical rocket engine, propellant and fuel are two distinct concepts.

Monomethylhydrazine (MMH) is a highly toxic, volatile hydrazine derivative with the chemical formula CH6N2. It is used as a rocket propellant in bipropellant rocket engines because it is hypergolic with various oxidizers such as nitrogen tetroxide and nitric acid. As a propellant, it is described in specification MIL-PRF-27404.

T-Stoff (; 'substance T') was a stabilised high test peroxide used in Germany during World War II. T-Stoff was specified to contain 80% (occasionally 85%) hydrogen peroxide (H2O2), remainder water, with traces (<0.1%) of stabilisers. Stabilisers used included 0.0025% phosphoric acid, a mixture of phosphoric acid, sodium phosphate and 8-oxyquinoline, and sodium stannate.

<span class="mw-page-title-main">Liquid-propellant rocket</span> Rocket engine that uses liquid fuels and oxidizers

A liquid-propellant rocket or liquid rocket uses a rocket engine burning liquid propellants. (Alternate approaches use gaseous or solid propellants.) Liquids are desirable propellants because they have reasonably high density and their combustion products have high specific impulse (Isp). This allows the volume of the propellant tanks to be relatively low.

Aerozine 50 is a 50:50 mix by weight of hydrazine and unsymmetrical dimethylhydrazine (UDMH), developed in the late 1950s by Aerojet General Corporation as a storable, high-energy, hypergolic fuel for the Titan II ICBM rocket engines. Aerozine continues in wide use as a rocket fuel, typically with dinitrogen tetroxide as the oxidizer, with which it is hypergolic. Aerozine 50 is more stable than hydrazine alone, and has a higher density and boiling point than UDMH alone.

The highest specific impulse chemical rockets use liquid propellants. They can consist of a single chemical or a mix of two chemicals, called bipropellants. Bipropellants can further be divided into two categories; hypergolic propellants, which ignite when the fuel and oxidizer make contact, and non-hypergolic propellants which require an ignition source.

UH 25 is a fuel mixture for rockets. It was developed for the European Ariane 2–4 launch vehicles.

Devil's venom was a nickname coined by Soviet rocket scientists for a hypergolic liquid rocket fuel composed of a dangerous combination of red fuming nitric acid (RFNA) and unsymmetrical dimethylhydrazine (UDMH). Both propellants are extremely dangerous individually: nitric acid is highly corrosive and releases toxic nitrogen dioxide during reactions, or even simply while exposed to air in its highly concentrated "red fuming" form, typically used as rocket propellant. UDMH is both toxic and corrosive.

<span class="mw-page-title-main">AJ10</span> Hypergolic rocket engine manufactured by Aerojet

The AJ10 is a hypergolic rocket engine manufactured by Aerojet Rocketdyne. It has been used to propel the upper stages of several launch vehicles, including the Delta II and Titan III. Variants were and are used as the service propulsion engine for the Apollo command and service module, in the Space Shuttle Orbital Maneuvering System, and on the European Service Module – part of NASA's Orion spacecraft.

<span class="mw-page-title-main">Viking (rocket engine)</span> Engines used in EU rocket Ariane

The Viking rocket engines were members of a series of bipropellant engines for the first and second stages of the Ariane 1 through Ariane 4 commercial launch vehicles, using storable, hypergolic propellants: dinitrogen tetroxide and UH 25, a mixture of 75% UDMH and 25% hydrazine.

<span class="mw-page-title-main">Aerojet LR87</span> American rocket engine family used on Titan missile first stages

The LR87 was an American liquid-propellant rocket engine used on the first stages of Titan intercontinental ballistic missiles and launch vehicles. Composed of twin motors with separate combustion chambers and turbopump machinery, it is considered a single unit and was never flown as a single combustion chamber engine or designed for this. The LR87 first flew in 1959.

<span class="mw-page-title-main">Rocket propellant</span> Chemical or mixture used in a rocket engine

Rocket propellant is used as reaction mass ejected from a rocket engine to produce thrust. The energy required can either come from the propellants themselves, as with a chemical rocket, or from an external source, as with ion engines.

<span class="mw-page-title-main">Aestus</span> Rocket engine

Aestus is a hypergolic liquid rocket engine used on an upper stage of Ariane 5 family rockets for the orbital insertion. It features unique design of 132 coaxial injection elements causing swirl mixing of the MMH propellants with nitrogen tetroxide oxidizer. The pressure-fed engine allows for multiple re-ignitions.

<span class="mw-page-title-main">XLR81</span> American Agena rocket motor (1963–1984)

The Bell Aerosystems Company XLR81 was an American liquid-propellant rocket engine, which was used on the Agena upper stage. It burned UDMH and RFNA fed by a turbopump in a fuel rich gas generator cycle. The turbopump had a single turbine with a gearbox to transmit power to the oxidizer and fuel pumps. The thrust chamber was all-aluminum, and regeneratively cooled by oxidizer flowing through gun-drilled passages in the combustion chamber and throat walls. The nozzle was a titanium radiatively cooled extension. The engine was mounted on a hydraulic actuated gimbal which enabled thrust vectoring to control pitch and yaw. Engine thrust and mixture ratio were controlled by cavitating flow venturis on the gas generator flow circuit. Engine start was achieved by solid propellant start cartridge.

References

Citations
  1. ↑ Melof, Brian M.; Grubelich, Mark C. (2000-11-15). "Investigation of Hypergolic Fuels with Hydrogen Peroxide". 3rd International Hydrogen Peroxide Propulsion Conference. OSTI   767866.
  2. ↑ Slare, Frederick (1694). "An Account of Some Experiments Relating to the Production of Fire and Flame, Together with an Explosion; Made by the Mixture of Two Liquors Actually Cold. By Frederick Slare, M. D. Censor and Fellow of the Colledge of Physicians: and of the Royal Society". Philosophical Transactions (1683-1775). 18: 201–218. ISSN   0260-7085.
  3. ↑ Newman, William R. (2018-12-11). Newton the Alchemist: Science, Enigma, and the Quest for Nature's "Secret Fire". Princeton University Press. ISBN   978-0-691-17487-7.
  4. ↑ U.S. patent 2489051A
  5. 1 2 3 4 5 6 7 8 9 Clark, John D. (1972). Ignition! An Informal History of Liquid Rocket Propellants (PDF). Rutgers University Press. ISBN   978-0-8135-0725-5. Archived (PDF) from the original on 10 July 2022.
  6. ↑ Lutz, O. (1957). "BMW Developments". In Benecke, T. H.; Quick, A.W.; Schulz, W. (eds.). History of German Guided Missiles Development (Guided Missiles Seminar. 1956. Munich). Advisory Group for Aerospace Research and Development-AG-20. Appelhans. p. 420.
  7. ↑ Sutton, G. P. (2006). History of Liquid Propellant Rocket Engines. Library of flight. American Institute of Aeronautics and Astronautics. ISBN   978-1-56347-649-5.
  8. ↑ Botho, Stüwe (1998), Peenemünde West: Die Erprobungsstelle der Luftwaffe für geheime Fernlenkwaffen und deren Entwicklungsgeschichte[Peenemünde West: The Luftwaffe's test center for secret guided missiles and the history of their development] (in German), Peene Münde West: Weltbildverlag, p. 220, ISBN   9783828902947
  9. ↑ Schlosser, Eric (2013). Command and control: nuclear weapons, the Damascus Accident, and the illusion of safety. New York, NY: The Penguin Press. ISBN   978-1-59420-227-8.
  10. ↑ "Nitric acid/Turpentine". www.astronautix.com. Retrieved 2024-11-30.
  11. ↑ "Breaking Bad rocket style: Cooking fuel in a trailer lab | Pythom Space". www.pythomspace.com. Retrieved 2024-11-30.
  12. ↑ "SpaceX". SpaceX. Retrieved 2021-12-29.
  13. ↑ "Fuel Propellants - Storable, and Hypergolic vs. Ignitable by Mike Schooley". Archived from the original on 24 July 2021.
  14. ↑ "PROPERTIES OF ROCKET PROPELLANTS". braeunig.us. Archived from the original on 26 May 2022.
  15. ↑ Linstrom, Peter (2021). NIST Chemistry WebBook. NIST Standard Reference Database Number 69. NIST Office of Data and Informatics. doi:10.18434/T4D303.
  16. ↑ A Summary of NASA and USAF Hypergolic Propellant Related Spills and Fires at the Internet Archive
  17. ↑ "Toxic Propellant Hazards" on YouTube
  18. ↑ The Nedelin Catastrophe, Part 1, 28 October 2014, archived from the original on 15 November 2014
  19. ↑ "ROCKET PROPELLANTS". braeunig.us.
  20. ↑ Apollo 11 Mission Report - Performance of the Command and Service Module Reaction Control System (PDF). NASA - Lyndon B. Johnson Space Center. December 1971. pp. 4, 8. Archived from the original (PDF) on 12 July 2022.
  21. ↑ T.A., Heppenheimer (2002). Development of the Shuttle, 1972–1981 - Volume 2.. Smithsonian Institution Press. ISBN   1-58834-009-0.
  22. ↑ "Space Launch Report: Ariane 5 Data Sheet". Archived from the original on February 2, 2013.{{cite web}}: CS1 maint: unfit URL (link)
  23. ↑ "SpaceX Updates". SpaceX. 2007-12-10. Archived from the original on January 4, 2011. Retrieved 2010-02-03.
  24. ↑ "ISRO tests Vikas engine". The Hindu . 2014-03-23. Archived from the original on 2014-03-23. Retrieved 2019-07-29.
  25. ↑ "WAC Corporal Sounding Rocket". Archived from the original on 7 January 2022.
  26. ↑ "Project SPECTRA - Experimental evaluation of a Liquid storable propellant" (PDF). Archived from the original (PDF) on 4 November 2013.
  27. ↑ "Nitric acid/Hydrazine". Astronautix.com. Retrieved January 13, 2023.
  28. ↑ "High Test Peroxide" (pdf). Retrieved July 11, 2014.
  29. ↑ "European space-rocket liquid-propellant engines". Archived from the original on 23 July 2021.
  30. ↑ "P8E-9". Archived from the original on 12 May 2022.
  31. ↑ "Nitric Acid/UDMH". Archived from the original on 1 July 2022.
  32. ↑ Astronautix: RD-270 Archived 2009-04-30 at the Wayback Machine .
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