Liquid Propellants

Rocket Propellants

1) Liquid Propellants

2) Solid Propellants

3) Hybrid Propellants


In a liquid propellant rocket, the fuel and oxidizer are stored in separate tanks, and are fed through a system of pipes, valves, and turbopumps to a combustion chamber where they are combined and burned to produce thrust. Liquid propellant engines are more complex than their solid propellant counterparts, however, they offer several advantages. By controlling the flow of propellant to the combustion chamber, the engine can be throttled, stopped, or restarted.

A good liquid propellant is one with a high specific impulse or, stated another way, one with a high speed of exhaust gas ejection. This implies a high combustion temperature and exhaust gases with small molecular weights. However, there is another important factor that must be taken into consideration: the density of the propellant. Using low-density propellants means that larger storage tanks will be required, thus increasing the mass of the launch vehicle. Storage temperature is also important. A propellant with a low storage temperature, i.e. a cryogenic, will require thermal insulation, thus further increasing the mass of the launcher. The toxicity of the propellant is likewise important. Safety hazards exist when handling, transporting, and storing highly toxic compounds. Also, some propellants are very corrosive; however, materials that are resistant to certain propellants have been identified for use in rocket construction. Liquid propellants used in rocketry can be classified into three types: petroleum, cryogens, and hypergols.

Petroleum fuels are those refined from crude oil and are a mixture of complex hydrocarbons, i.e. organic compounds containing only carbon and hydrogen. The petroleum used as rocket fuel is a type of highly refined kerosene, called RP-1 in the United States. Petroleum fuels are usually used in combination with liquid oxygen as the oxidizer. Kerosene delivers a specific impulse considerably less than cryogenic fuels, but it is generally better than hypergolic propellants.

Specifications for RP-1 where first issued in the United States in 1957 when the need for a clean burning petroleum rocket fuel was recognized. Prior experimentation with jet fuels produced tarry residue in the engine cooling passages and excessive soot, coke and other deposits in the gas generator. Even with the new specifications, kerosene-burning engines still produce enough residues that their operational lifetimes are limited. Liquid oxygen and RP-1 are used as the propellant in the first-stage boosters of the Atlas and Delta II launch vehicles. It also powered the first-stages of the Saturn 1B and Saturn V rockets.

Cryogenic propellants are liquefied gases stored at very low temperatures, most frequently liquid hydrogen (LH2) as the fuel and liquid oxygen (LO2 or LOX) as the oxidizer. Hydrogen remains liquid at temperatures of -253 oC (-423 oF) and oxygen remains in a liquid state at temperatures of -183 oC (-297 oF). Because of the low temperatures of cryogenic propellants, they are difficult to store over long periods of time. For this reason, they are less desirable for use in military rockets that must be kept launch ready for months at a time. Furthermore, liquid hydrogen has a very low density (0.071 g/ml) and, therefore, requires a storage volume many times greater than other fuels. Despite these drawbacks, the high efficiency of liquid oxygen/liquid hydrogen makes these problems worth coping with when reaction time and storability are not too critical. Liquid hydrogen delivers a specific impulse about 30%-40% higher than most other rocket fuels.

Liquid oxygen and liquid hydrogen are used as the propellant in the high efficiency main engines of the Space Shuttle. LOX/LH2 also powered the upper stages of the Saturn V and Saturn 1B rockets, as well as the Centaur upper stage, the United States’ first LOX/LH2 rocket (1962). Another cryogenic fuel with desirable properties for space propulsion systems is liquid methane (-162 oC). When burned with liquid oxygen, methane is higher performing than state-of-the-art storable propellants but without the volume increase common with LOX/LH2 systems, which results in an overall lower vehicle mass as compared to common hypergolic propellants. LOX/methane is also clean burning and non-toxic. Future missions to Mars will likely use methane fuel because it can be manufactured partly from Martian in-situ resources. LOX/methane has no flight history and very limited ground-test history. Liquid fluorine (-188 oC) burning engines have also been developed and fired successfully. Fluorine is not only extremely toxic; it is a super-oxidizer that reacts, usually violently, with almost everything except nitrogen, the lighter noble gases, and substances that have already been fluorinated. Despite these drawbacks, fluorine produces very impressive engine performance. It can also be mixed with liquid oxygen to improve the performance of LOX-burning engines; the resulting mixture is called FLOX. Because of fluorine’s high toxicity, it has been largely abandoned by most space-faring nations. Some fluorine containing compounds, such as chlorine pentafluoride, have also been considered for use as an ‘oxidizer’ in deep-space applications.

Hypergolic propellants are fuels and oxidizers that ignite spontaneously on contact with each other and require no ignition source. The easy start and restart capability of hypergols make them ideal for spacecraft maneuvering systems. Also, since hypergols remain liquid at normal temperatures, they do not pose the storage problems of cryogenic propellants. Hypergols are highly toxic and must be handled with extreme care.  Hypergolic fuels commonly include hydrazine, monomethyl hydrazine (MMH) and unsymmetrical dimethyl hydrazine (UDMH). Hydrazine gives the best performance as a rocket fuel, but it has a high freezing point and is too unstable for use as a coolant. MMH is more stable and gives the best performance when freezing point is an issue, such as spacecraft propulsion applications. UDMH has the lowest freezing point and has enough thermal stability to be used in large regeneratively cooled engines. Consequently, UDMH is often used in launch vehicle applications even though it is the least efficient of the hydrazine derivatives. Also commonly used are blended fuels, such as Aerozine 50 (or “50-50”), which is a mixture of 50% UDMH and 50% hydrazine. Aerozine 50 is almost as stable as UDMH and provides better performance. 

The oxidizer is usually nitrogen tetroxide (NTO) or nitric acid. In the United States, the nitric acid formulation most commonly used is type III-A, called inhibited red-fuming nitric acid (IRFNA), which consists of HNO3 + 14% N2O4 + 1.5-2.5% H2O + 0.6% HF (added as a corrosion inhibitor). Nitrogen tetroxide is less corrosive than nitric acid and provides better performance, but it has a higher freezing point. Consequently, nitrogen tetroxide is usually the oxidizer of choice when freezing point is not an issue, however, the freezing point can be lowered with the introduction nitric oxide. The resulting oxidizer is called mixed oxides of nitrogen (MON). The number included in the description, e.g. MON-3 or MON-25, indicates the percentage of nitric oxide by weight. While pure nitrogen tetroxide has a freezing point of about -9 oC, the freezing point of MON-3 is -15 oC and that of MON-25 is -55 oC.  USA military specifications for IRFNA were first published in 1954, followed in 1955 with UDMH specifications. 

The Titan family of launch vehicles and the second stage of the Delta II rocket use NTO/Aerozine 50 propellant. NTO/MMH is used in the orbital maneuvering system (OMS) and reaction control system (RCS) of the Space Shuttle orbiter. IRFNA/UDMH is often used in tactical missiles such as the US Army’s Lance (1972-91).  Hydrazine is also frequently used as a monopropellant in catalytic decomposition engines. In these engines, a liquid fuel decomposes into hot gas in the presence of a catalyst. The decomposition of hydrazine produces temperatures up to about 1,100 oC (2,000 oF) and a specific impulse of about 230 or 240 seconds. Hydrazine decomposes to either hydrogen and nitrogen, or ammonia and nitrogen.

Other propellants have also been used, a few of which deserve mentioning:  Alcohols were commonly used as fuels during the early years of rocketry. The German V-2 missile, as well as the USA Redstone, burned LOX and ethyl alcohol (ethanol), diluted with water to reduce combustion chamber temperature. However, as more efficient fuels where developed, alcohols fell into general disuse.  Hydrogen peroxide once attracted considerable attention as an oxidizer and was used in Britain’s Black Arrow rocket. In high concentrations, hydrogen peroxide is called high-test peroxide (HTP). The performance and density of HTP is close to that of nitric acid, and it is far less toxic and corrosive; however it has a poor freezing point and is unstable. Although HTP never made it as an oxidizer in large bi-propellant applications, it has found widespread use as a monopropellant. In the presence of a catalyst, HTP decomposes into oxygen and superheated steam and produces a specific impulse of about 150 s.  Nitrous oxide has been used as both an oxidizer and as a monopropellant. It is the oxidizer of choice for many hybrid rocket designs and has been used frequently in amateur high-powered rocketry. In the presence of a catalyst, nitrous oxide will decompose exothermically into nitrogen and oxygen and produce a specific impulse of about 170 s.

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