Liquid rocket propellant

Main article: Liquid-propellant rocket

The highest specic impulse chemical rockets (liquidpropellant rockets) use liquid fuel propellants. Approximately 170 dierent liquid propellants have undergone
lab testing. This estimate excludes minor changes to a
specic propellant such as propellant additives, corrosion
inhibitors, or stabilizers. In the U.S. alone at least 25 different propellant combinations have been own.[1] However, there has not been a completely new propellant used
in ight for nearly 30 years.[2] Many factors go into choosing a propellant for a liquid propellant rocket engine.
The primary factors include ease of operation, cost, hazards/environment and performance. Bipropellants can
be either hypergolic propellant or nonhypergolic. A hypergolic combination of oxidizer and fuel will start to
burn upon contact. A nonhypergolic needs an ignition
source.[3]

1
1.1

History
Robert H. Goddard on March 16, 1926, holding the launching frame of his most notable invention the rst liquid-fueled
rocket.

Early development

On March 16, 1926, Robert H. Goddard used liquid oxygen (LOX) and gasoline as propellants for his rst partially
successful liquid rocket launch. Both are readily available, cheap and highly energetic. Oxygen is a moderate
cryogen air will not liquefy against a liquid oxygen
tank, so it is possible to store LOX briey in a rocket
without excessive insulation. Gasoline has since been replaced by dierent hydrocarbon fuels, for example RP-1
- a highly rened grade of kerosene. This combination
is quite practical for rockets that need not be stored, and
to this day, it is used in the rst stages of many orbital
launchers.

1.2

tact with the high density oxidizer. The German engine

was powered by hydrogen peroxide and a fuel mixture of
hydrazine hydrate and methyl alcohol. The U.S. engine
was powered by nitric acid oxidizer and aniline. Both engines were used to power aircraft, the Me-163B Komet
interceptor in the case of the German engine and RATO
units to assist take-o of aircraft in the case of the U.S.
engine.

1.3 1950s and 1960s

During the 1950s and 1960s there was a great burst of
activity by propellant chemists to nd high-energy liquid
and solid propellants better suited to the military. Large
strategic missiles need to sit in land-based or submarinebased silos for many years, able to launch at a moments
notice. Propellants requiring continuous refrigeration,
and which cause their rockets to grow ever-thicker blankets of ice, are not practical. As the military is willing
to handle and use hazardous materials, a great number
of dangerous chemicals were brewed up in large batches,
most of which wound up being deemed unsuitable for operational systems. In the case of nitric acid, the acid it-

Wartime

Germany had very active rocket development before and

during World War II, both for the strategic V-2 rocket
and other missiles. The V-2 used an alcohol/LOX liquid
propellant engine, with hydrogen peroxide to drive the
fuel pumps. The alcohol was mixed with water for engine
cooling. Both Germany and the United States developed
reusable liquid propellant rocket engines that used a storeable liquid oxidizer with much greater density than LOX
and a liquid fuel that would ignite spontaneously on con1

1 HISTORY

self (HNO3 ) is unstable, and corrodes most metals, making it dicult to store. The addition of a modest amount
of nitrogen tetroxide, N2 O4 , turns the mixture red and
keeps it from changing composition, but leaves the problem that nitric acid corrodes containers it is placed in,
releasing gases that can build up pressure in the process.
The breakthrough was the addition of a little hydrogen
uoride (HF), which forms a self-sealing metal uoride
on the interior of tank walls that Inhibited Red Fuming
Nitric Acid. This made IRFNA storeable. Propellant combinations based on IRFNA or pure N2 O4 as oxidizer and kerosene or hypergolic (self igniting) aniline,
hydrazine or unsymmetrical dimethylhydrazine (UDMH)
as fuel were then adopted in the United States and the Soviet Union for use in strategic and tactical missiles. The
self-igniting storeable liquid bi-propellants have somewhat lower specic impulse than LOX/kerosene but have
higher density so a greater mass of propellant can be
placed in the same sized tanks.

1.4

is buoyancy. Since hydrogen is a deep cryogen it boils

quickly and rises due to its very low density as a gas. Even
when hydrogen burns, the gaseous H2 O that is formed
has a molecular weight of only 18 u compared to 29.9
u for air, so it rises quickly as well. Kerosene on the
other hand falls to the ground and burns for hours when
spilled in large quantities, unavoidably causing extensive
heat damage that requires time consuming repairs and rebuilding. This is a lesson most frequently experienced by
test stand crews involved with rings of large, unproven
rocket engines. Hydrogen-fueled engines also have some
special design requirements such as running propellant
lines horizontally so traps do not form in the lines and
cause ruptures due to boiling in conned spaces. These
considerations, however, apply to all cryogens such as liquid oxygen and liquid natural gas as well. Use of liquid
hydrogen fuel has an excellent safety record and superb
performance that is well above that of all other practical
chemical rocket propellants. (See bipropellant rocket engine performance table below.)

Hydrogen

Many early rocket theorists believed that hydrogen would

be a marvelous propellant, since it gives the highest
specic impulse. It is also considered the cleanest when
used with a liquid oxygen oxidizer because the only byproduct is water. As hydrogen in any state is very bulky,
for lightweight vehicles it is typically stored as a deeply
cryogenic liquid. This storage technique was mastered in
the early 1950s as part of the hydrogen bomb development program at Los Alamos. It was then adopted for
hydrogen fueled stages such as Centaur and Saturn upper stages in the late 50s and early 1960s. Even as a
liquid, hydrogen has low density, requiring large tanks
and pumps, and the extreme cold requires tank insulation. This extra weight reduces the mass fraction of the
stage or requires extraordinary measures such as pressure
stabilization of the tanks to reduce weight. Pressure stabilized tanks support most of the loads with internal pressure rather than with solid structures. Most rockets that
use hydrogen fuel use it in upper stages only.

1.5 Lithium and uorine

The highest specic impulse chemistry ever test-red in

a rocket engine was lithium and uorine, with hydrogen
added to improve the exhaust thermodynamics (all propellants had to be kept in their own tanks, making this
a tripropellant). The combination delivered 542 s specic impulse in a vacuum, equivalent to an exhaust velocity of 5320 m/s. The impracticality of this chemistry
highlights why exotic propellants are not actually used:
to make all three components liquids, the hydrogen must
be kept below 252 C (just 21 K) and the lithium must
be kept above 180 C (453 K). Lithium and uorine are
both extremely corrosive, lithium ignites on contact with
air, uorine ignites on contact with most fuels, including
hydrogen. Fluorine and the hydrogen uoride (HF) in
the exhaust are very toxic, which makes working around
the launch pad dicult, damages the environment, and
makes getting a launch license that much more dicult.
Finally, both lithium and uorine are expensive compared
Gaseous hydrogen is commercially produced by the fuel- to most rocket propellants. This combination has thererich burning of natural gas. Carbon forms a stronger fore never own.
bond with oxygen so the gaseous hydrogen is left behind.
Liquid hydrogen is stored and transported without boilo because helium, which has a lower boiling point than
hydrogen, is the cooling refrigerant. Only when hydrogen 1.6 Methane
is loaded on a launch vehicle (where there is no refrigerIn November 2012, SpaceX CEO Elon Musk announced
ation) does it vent to the atmosphere.[4]
a new direction for the propulsion side of SpaceX: developing methane/LOX rocket engines.[5] SpaceX had
1.4.1 Comparison to kerosene
previously used only LOX/RP-1 for all of their primary
propulsion engines. As of March 2014, SpaceX is acLaunch pad res due to spilled kerosene are more damag- tively developing the Raptor methalox bipropellant rocket
ing than hydrogen res, primarily for two reasons. First, engine with over 1,000,000 lbf (4,400 kN) of thrust. The
kerosene burns about 20% hotter (absolute temperature) engine is slated to be used on a future super-heavy rocket,
than hydrogen. The second and more signicant reason the MCT launch vehicle.[6][7]

3
Firey Space Systems announced in July 2014 their plans performance largely osets the disadvantage of low dento use methane fuel for their small satellite launch vehicle, sity. Low density of a propellant leads to larger fuel tanks.
Firey Alpha, utilizing an aerospike engine design.[8]
However, a small increase in specic impulse in an upper
a signicant increase in payBlue Origin and United Launch Alliance announced in stage application can have
[2]
load
to
orbit
capability.
September 2014 the joint development of the BE-4
lox/methane engine. The BE-4 will provide 550,000 lbf
of thrust.[9]

1.7

3 Propellant table

Monopropellants

JANAF thermochemical data used throughout. Calculations performed by Rocketdyne, results appear in ModHydrogen peroxide decomposes to steam and oxyern Engineering for Design of Liquid-Propellant Rocket
gen
Engines, Huzel and Huang.[10] Some of the units have
Hydrazine decomposes energetically to nitrogen, been converted to metric, but pressures have not. These
hydrogen and ammonia (2N2 H4 -->N2 +H2 +2NH3 ) are best-possible specic impulse calculations.
and is the most widely used in space vehicles. (Am- Assumptions:
monia decomposition is endothermic and would decrease performance.)
adiabatic combustion
Nitrous oxide decomposes to nitrogen and oxygen
isentropic expansion
Steam when externally heated gives a reasonably
one-dimensional expansion
modest I of up to 190 seconds, depending on material corrosion and thermal limits
shifting equilibrium

Current use

3.1 Denitions

Here are some common liquid fuel combinations in use 3.2 Bipropellants
today:
Denitions of some of the mixtures:
LOX and kerosene (RP-1). Used for the lower
stages of the Soyuz boosters, and the rst stage of the
IRFNA IIIa: 83.4% HNO3 , 14% NO2 , 2% H2 O,
U.S. Saturn V, Atlas, and Falcon 9 boosters. Very
0.6% HF
similar to Robert Goddards rst rocket.
IRFNA IV HDA: 54.3% HNO3 , 44% NO2 , 1%
H2 O, 0.7% HF
LOX and liquid hydrogen, used in the stages of
the Space Shuttle, Space Launch System, Ariane 5,
RP-1: see MIL-P-25576C, basically kerosene (apDelta IV, H-IIB, GSLV and Centaur.
proximately C10 H18 )
Nitrogen tetroxide (N2 O4 ) and UDMH or MMH.
MMH: CH3 NHNH2
Used in three rst stages of the Russian Proton
booster, Indian Vikas engine for PSLV and GSLV
rockets, most Chinese boosters, a number of mili- 3.3 Monopropellants
tary, orbital and deep space rockets, as this fuel combination is hypergolic and storable for long periods 4 References
at reasonable temperatures and pressures.
Hydrazine (N2 H4 ) and Aerozine-50 are also used in
deep space missions because they are storable and
hypergolic, and can be used as a monopropellant
with a catalyst.

2.1

Upper stage use

The liquid rocket engine propellant combination of liquid oxygen and hydrogen oers the highest specic impulse of currently used conventional rockets. This extra

[1] Sutton, G. P. (2003). History of liquid propellant rocket

engines in the united states. Journal of Propulsion and
Power. 19(6), 9781007.
[2] Sutton, E.P; Biblarz, O. (2010). Rocket Propulsion Elements. New York: Wiley.
[3] Larson, W.J.; Wertz, J. R. (1992). Space Mission Analysis
and Design. Boston: Kluver Academic Publishers.
[4] Richard Rhodes, Dark Sun: The Making of the Hydrogen
Bomb, 1995, pp. 483-504, Simon & Schuster, NY ISBN
978-0-684-82414-7

[5] Todd, David (2012-11-20). Musk goes for methaneburning reusable rockets as step to colonise Mars. FlightGlobal Hyperbola. Retrieved 2012-11-22. We are going
to do methane. Musk announced as he described his future
plans for reusable launch vehicles including those designed
to take astronauts to Mars within 15 years, The energy cost
of methane is the lowest and it has a slight Isp (Specic Impulse) advantage over Kerosene, said Musk adding, And
it does not have the pain in the ass factor that hydrogen
has.
[6] SpaceX propulsion chief elevates crowd in Santa Barbara. Pacic Business Times. 19 February 2014. Retrieved 22 February 2014.
[7] Belluscio, Alejandro G. (2014-03-07). SpaceX advances
drive for Mars rocket via Raptor power. NASAspaceight.com. Retrieved 2014-03-07.
[8] Firey - Firey Space Systems. Retrieved 5 October
2014.
[9] United Launch Alliance and Blue Origin Announce
Partnership to Develop New American Rocket Engine.
United Launch Alliance. Retrieved 5 October 2014.
[10] Huzel, D. K.; Huang, D. H. (1971), NASA SP-125,
Design of Liquid Propellant Rocket Engines (2nd ed.),
NASA
[11] SSC. sscspace.com. Retrieved 22 May 2015.
[12] Ano 1 23rd Annual AIAA/USU Conference on Small
Satellites SSC09-II-4 EXPANDING THE ADN-BASED
MONOPROPELLANT THRUSTER FAMILY K. Ano
[13] https://uppsagd.files.wordpress.com/2012/03/advanced_
monopropellants_combustion_chambers_and_
monolithic_catalyst_for_small_satellite_propulsion.pdf

External links
Cpropep-Web an online computer program to calculate propellant performance in rocket engines
Design Tool for Liquid Rocket Engine Thermodynamic Analysis is a computer program to predict the
performance of the liquid-propellant rocket engines.
Clark, John D. (1972). Ignition! An Informal History of Liquid Rocket Propellants (PDF). Rutgers
University Press. p. 214. ISBN 0-8135-0725-1.
for a history of liquid rocket propellants in the US
by a pioneering rocket fuel developer.

EXTERNAL LINKS

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6.1

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6.3

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