Rocket propellant

Rocket propellant is the reaction mass of a rocket. This reaction mass is ejected at the highest
achievable velocity 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.

A Delta IV Heavy during liftoff. The rocket is entirely

Overview

Rockets create thrust by expelling mass rear-ward, at high velocity. The thrust produced can be
calculated by multiplying the mass flow rate of the propellants by their exhaust velocity relative to
the rocket (specific impulse). A rocket can be thought of as being accelerated by the pressure of the
combusting gases against the combustion chamber and nozzle, not by "pushing" against the air
behind or below it. Rocket engines perform best in outer space because of the lack of air pressure
on the outside of the engine. In space it is also possible to fit a longer nozzle without suffering from
flow separation.

Most chemical propellants release energy through redox chemistry, more specifically combustion.
As such, both an oxidizing agent and a reducing agent (fuel) must be present in the mixture.
Decomposition, such as that of highly unstable peroxide bonds in monopropellant rockets, can also
be the source of energy.

In the case of bipropellant liquid rockets, a mixture of reducing fuel and oxidizing oxidizer is
introduced into a combustion chamber, typically using a turbopump to overcome the pressure. As
combustion takes place, the liquid propellant mass is converted into a huge volume of gas at high
temperature and pressure. This exhaust stream is ejected from the engine nozzle at high velocity,
creating an opposing force that propels the rocket forward in accordance with Newton's laws of
motion.

Chemical rockets can be grouped by phase. Solid rockets use propellant in the solid phase, liquid
fuel rockets use propellant in the liquid phase, gas fuel rockets use propellant in the gas phase, and
hybrid rockets use a combination of solid and liquid or gaseous propellants.

In the case of solid rocket motors, the fuel and oxidizer are combined when the motor is cast.
Propellant combustion occurs inside the motor casing, which must contain the pressures
developed. Solid rockets typically have higher thrust, less specific impulse, shorter burn times, and a
higher mass than liquid rockets, and additionally cannot be stopped once lit.

Rocket stages

In space, the maximum change in velocity that a rocket stage can impart on its payload is primarily
a function of its mass ratio and its exhaust velocity. This relationship is described by the rocket
equation. Exhaust velocity is dependent on the propellant and engine used and closely related to
specific impulse, the total energy delivered to the rocket vehicle per unit of propellant mass
consumed. Mass ratio can also be affected by the choice of a given propellant.

Rocket stages that fly through the atmosphere usually use lower performing, high molecular mass,
high-density propellants due to the smaller and lighter tankage required. Upper stages, which mostly
or only operate in the vacuum of space, tend to use the high energy, high performance, low density
liquid hydrogen fuel.

Solid chemical propellants

Solid propellants come in two main types. "Composites" are composed mostly of a mixture of
granules of solid oxidizer, such as ammonium nitrate, ammonium dinitramide, ammonium
perchlorate, or potassium nitrate in a polymer binding agent, with flakes or powders of energetic
fuel compounds (examples: RDX, HMX, aluminium, beryllium). Plasticizers, stabilizers, and/or burn
rate modifiers (iron oxide, copper oxide) can also be added.

Single-, double-, or triple-bases (depending on the number of primary ingredients) are homogeneous
mixtures of one to three primary ingredients. These primary ingredients must include fuel and
oxidizer and often also include binders and plasticizers. All components are macroscopically
indistinguishable and often blended as liquids and cured in a single batch. Ingredients can often
have multiple roles. For example, RDX is both a fuel and oxidizer while nitrocellulose is a fuel,
oxidizer, and structural polymer.

Further complicating categorization, there are many propellants that contain elements of double-
base and composite propellants, which often contain some amount of energetic additives
homogeneously mixed into the binder. In the case of gunpowder (a pressed composite without a
polymeric binder) the fuel is charcoal, the oxidizer is potassium nitrate, and sulphur serves as a
reaction catalyst while also being consumed to form a variety of reaction products such as
potassium sulfide.

The newest nitramine solid propellants based on CL-20 (HNIW) can match the performance of
NTO/UDMH storable liquid propellants, but cannot be throttled or restarted.

Advantages

Solid propellant rockets are much easier to store and handle than liquid propellant rockets. High
propellant density makes for compact size as well. These features plus simplicity and low cost
make solid propellant rockets ideal for military and space applications.

Their simplicity also makes solid rockets a good choice whenever large amounts of thrust are
needed and the cost is an issue. The Space Shuttle and many other orbital launch vehicles use
solid-fueled rockets in their boost stages (solid rocket boosters) for this reason.

Disadvantages

Solid fuel rockets have lower specific impulse, a measure of propellant efficiency, than liquid fuel
rockets. As a result, the overall performance of solid upper stages is less than liquid stages even
though the solid mass ratios are usually in the .91 to .93 range, as good as or better than most liquid
propellant upper stages. The high mass ratios possible with these unsegmented solid upper stages
is a result of high propellant density and very high strength-to-weight ratio filament-wound motor
casings.

A drawback to solid rockets is that they cannot be throttled in real time, although a programmed
thrust schedule can be created by adjusting the interior propellant geometry. Solid rockets can be
vented to extinguish combustion or reverse thrust as a means of controlling range or
accommodating stage separation. Casting large amounts of propellant requires consistency and
repeatability to avoid cracks and voids in the completed motor. The blending and casting take place
under computer control in a vacuum, and the propellant blend is spread thin and scanned to assure
no large gas bubbles are introduced into the motor.

Solid fuel rockets are intolerant to cracks and voids and require post-processing such as X-ray
scans to identify faults. The combustion process is dependent on the surface area of the fuel. Voids
and cracks represent local increases in burning surface area, increasing the local temperature,
which increases the local rate of combustion. This positive feedback loop can easily lead to
catastrophic failure of the case or nozzle.

History

Solid rocket propellant was first developed during the 13th century under the Chinese Song dynasty.
The Song Chinese first used gunpowder in 1232 during the military siege of Kaifeng.[1][2][3][4][5]

During the 1950s and 60s, researchers in the United States developed ammonium perchlorate
composite propellant (APCP). This mixture is typically 69-70% finely ground ammonium perchlorate
(an oxidizer), combined with 16-20% fine aluminium powder (a fuel), held together in a base of 11-
14% polybutadiene acrylonitrile (PBAN) or Hydroxyl-terminated polybutadiene (polybutadiene rubber
fuel). The mixture is formed as a thickened liquid and then cast into the correct shape and cured
into a firm but flexible load-bearing solid. Historically, the tally of APCP solid propellants is relatively
small. The military, however, uses a wide variety of different types of solid propellants, some of
which exceed the performance of APCP. A comparison of the highest specific impulses achieved
with the various solid and liquid propellant combinations used in current launch vehicles is given in
the article on solid-fuel rockets.[6]

In the 1970s and 1980s, the U.S. switched entirely to solid-fueled ICBMs: the LGM-30 Minuteman
and LG-118A Peacekeeper (MX). In the 1980s and 1990s, the USSR/Russia also deployed solid-
fueled ICBMs (RT-23, RT-2PM, and RT-2UTTH), but retains two liquid-fueled ICBMs (R-36 and UR-
100N). All solid-fueled ICBMs on both sides had three initial solid stages, and those with multiple
independently targeted warheads had a precision maneuverable bus used to fine tune the trajectory
of the re-entry vehicles.

Liquid chemical propellants

The main types of liquid propellants are storable propellants, which tend to be cryogenic and
hypergolic propellants.

Advantages

Liquid-fueled rockets have higher specific impulse than solid rockets and are capable of being
throttled, shut down, and restarted. Only the combustion chamber of a liquid-fueled rocket needs to
withstand high combustion pressures and temperatures. Cooling can be done regeneratively with
the liquid propellant. On vehicles employing turbopumps, the propellant tanks are at a lower
pressure than the combustion chamber, decreasing tank mass. For these reasons, most orbital
launch vehicles use liquid propellants.

The primary specific impulse advantage of liquid propellants is due to the availability of high-
performance oxidizers. Several practical liquid oxidizers (liquid oxygen, dinitrogen tetroxide, and
hydrogen peroxide) are available which have better specific impulse than the ammonium
perchlorate used in most solid rockets when paired with suitable fuels.

Some gases, notably oxygen and nitrogen, may be able to be collected from the upper atmosphere,
and transferred up to low Earth orbit for use in propellant depots at substantially reduced cost.[7]

Disadvantages

The main difficulties with liquid propellants are also with the oxidizers. Storable oxidizers, such as
nitric acid and nitrogen tetroxide, tend to be extremely toxic and highly reactive, while cryogenic
propellants by definition must be stored at low temperature and can also have reactivity/toxicity
issues. Liquid oxygen (LOX) is the only flown cryogenic oxidizer. Others such as FLOX, a
fluorine/LOX mix, have never been flown due to instability, toxicity, and explosivity.[8] Several other
unstable, energetic, and toxic oxidizers have been proposed: liquid ozone (O3), ClF3, and ClF5.

Liquid-fueled rockets require potentially troublesome valves, seals, and turbopumps, which increase
the cost of the launch vehicle. Turbopumps are particularly troublesome due to high performance
requirements.
Current cryogenic types

Liquid oxygen (LOX) and highly refined kerosene (RP-1). Used for the first stages of the Atlas V,
Falcon 9, Falcon Heavy, Soyuz, Zenit, Angara and Long March 6, among others. This combination
is widely regarded as the most practical for boosters that lift off at ground level and therefore
must operate at full atmospheric pressure.

LOX and liquid hydrogen. Used on the Centaur upper stage, the Delta IV rocket, the H-IIA rocket,
most stages of the European Ariane 5, and the Space Launch System core and upper stages.

LOX and liquid methane (from liquefied natural gas). Used on Zhuque-2, Vulcan, and also planned
for use on several rockets in development, including New Glenn, Soyuz-7, SpaceX Starship, and
Rocket Lab Neutron.

Current storable types

Dinitrogen tetroxide (N2O4) and hydrazine (N2H4), MMH, or UDMH. Used in military, orbital, and
deep space rockets because both liquids are storable for long periods at reasonable
temperatures and pressures. N2O4/UDMH is the main fuel for the Proton rocket, older Long March
rockets (LM 1-4), PSLV, Fregat, and Briz-M upper stages. This combination is hypergolic, making
for attractively simple ignition sequences. The major inconvenience is that these propellants are
highly toxic and require careful handling.

Monopropellants such as hydrogen peroxide, hydrazine, and nitrous oxide are primarily used for
attitude control and spacecraft station-keeping where their long-term storability, simplicity of use,
and ability to provide the tiny impulses needed outweighs their lower specific impulse as
compared to bipropellants. Hydrogen peroxide is also used to drive the turbopumps on the first
stage of the Soyuz launch vehicle.

Mixture ratio

The theoretical exhaust velocity of a given propellant chemistry is proportional to the energy
released per unit of propellant mass (specific energy). In chemical rockets, unburned fuel or oxidizer
represents the loss of chemical potential energy, which reduces the specific energy. However, most
rockets run fuel-rich mixtures, which result in lower theoretical exhaust velocities.[9]

However, fuel-rich mixtures also have lower molecular weight exhaust species. The nozzle of the
rocket converts the thermal energy of the propellants into directed kinetic energy. This conversion
happens in the time it takes for the propellants to flow from the combustion chamber through the
engine throat and out the nozzle, usually on the order of one millisecond. Molecules store thermal
energy in rotation, vibration, and translation, of which only the latter can easily be used to add
energy to the rocket stage. Molecules with fewer atoms (like CO and H2) have fewer available
vibrational and rotational modes than molecules with more atoms (like CO2 and H2O). Consequently,
smaller molecules store less vibrational and rotational energy for a given amount of heat input,
resulting in more translation energy being available to be converted to kinetic energy. The resulting
improvement in nozzle efficiency is large enough that real rocket engines improve their actual
exhaust velocity by running rich mixtures with somewhat lower theoretical exhaust velocities.[9]

The effect of exhaust molecular weight on nozzle efficiency is most important for nozzles operating
near sea level. High expansion rockets operating in a vacuum see a much smaller effect, and so are
run less rich.

LOX/hydrocarbon rockets are run slightly rich (O/F mass ratio of 3 rather than stoichiometric of 3.4
to 4) because the energy release per unit mass drops off quickly as the mixture ratio deviates from
stoichiometric. LOX/LH2 rockets are run very rich (O/F mass ratio of 4 rather than stoichiometric 8)
because hydrogen is so light that the energy release per unit mass of propellant drops very slowly
with extra hydrogen. In fact, LOX/LH2 rockets are generally limited in how rich they run by the
performance penalty of the mass of the extra hydrogen tankage instead of the underlying
chemistry.[9]

Another reason for running rich is that off-stoichiometric mixtures burn cooler than stoichiometric
mixtures, which makes engine cooling easier. Because fuel-rich combustion products are less
chemically reactive (corrosive) than oxidizer-rich combustion products, a vast majority of rocket
engines are designed to run fuel-rich. At least one exception exists: the Russian RD-180 preburner,
which burns LOX and RP-1 at a ratio of 2.72.

Additionally, mixture ratios can be dynamic during launch. This can be exploited with designs that
adjust the oxidizer to fuel ratio (along with overall thrust) throughout a flight to maximize overall
system performance. For instance, during lift-off thrust is more valuable than specific impulse, and
careful adjustment of the O/F ratio may allow higher thrust levels. Once the rocket is away from the
launchpad, the engine O/F ratio can be tuned for higher efficiency.

Propellant density

Although liquid hydrogen gives a high Isp, its low density is a disadvantage: hydrogen occupies
about 7 times more volume per kilogram than dense fuels such as kerosene. The fuel tankage,
plumbing, and pump must be correspondingly larger. This increases the vehicle's dry mass, reducing
performance. Liquid hydrogen is also relatively expensive to produce and store, and causes
difficulties with design, manufacture, and operation of the vehicle. However, liquid hydrogen is
extremely well suited to upper stage use where Isp is at a premium and thrust to weight ratios are
less relevant.

Dense propellant launch vehicles have a higher takeoff mass due to lower Isp, but can more easily
develop high takeoff thrusts due to the reduced volume of engine components. This means that
vehicles with dense-fueled booster stages reach orbit earlier, minimizing losses due to gravity drag
and reducing the effective delta-v requirement.

The proposed tripropellant rocket uses mainly dense fuel while at low altitude and switches across
to hydrogen at higher altitude. Studies in the 1960s proposed single-stage-to-orbit vehicles using
this technique.[10] The Space Shuttle approximated this by using dense solid rocket boosters for the
majority of the thrust during the first 120 seconds. The main engines burned a fuel-rich hydrogen
and oxygen mixture, operating continuously throughout the launch but providing the majority of
thrust at higher altitudes after SRB burnout.

Other chemical propellants

Hybrid propellants

Hybrid propellants: a storable oxidizer used with a solid fuel, which retains most virtues of both
liquids (high ISP) and solids (simplicity).

A hybrid-propellant rocket usually has a solid fuel and a liquid or NEMA oxidizer. The fluid oxidizer
can make it possible to throttle and restart the motor just like a liquid-fueled rocket. Hybrid rockets
can also be environmentally safer than solid rockets since some high-performance solid-phase
oxidizers contain chlorine (specifically composites with ammonium perchlorate), versus the more
benign liquid oxygen or nitrous oxide often used in hybrids. This is only true for specific hybrid
systems. There have been hybrids which have used chlorine or fluorine compounds as oxidizers and
hazardous materials such as beryllium compounds mixed into the solid fuel grain. Because just one
constituent is a fluid, hybrids can be simpler than liquid rockets depending motive force used to
transport the fluid into the combustion chamber. Fewer fluids typically mean fewer and smaller
piping systems, valves and pumps (if utilized).

Hybrid motors suffer two major drawbacks. The first, shared with solid rocket motors, is that the
casing around the fuel grain must be built to withstand full combustion pressure and often extreme
temperatures as well. However, modern composite structures handle this problem well, and when
used with nitrous oxide and a solid rubber propellant (HTPB), relatively small percentage of fuel is
needed anyway, so the combustion chamber is not especially large.
The primary remaining difficulty with hybrids is with mixing the propellants during the combustion
process. In solid propellants, the oxidizer and fuel are mixed in a factory in carefully controlled
conditions. Liquid propellants are generally mixed by the injector at the top of the combustion
chamber, which directs many small swift-moving streams of fuel and oxidizer into one another.
Liquid-fueled rocket injector design has been studied at great length and still resists reliable
performance prediction. In a hybrid motor, the mixing happens at the melting or evaporating surface
of the fuel. The mixing is not a well-controlled process and generally, quite a lot of propellant is left
unburned,[11] which limits the efficiency of the motor. The combustion rate of the fuel is largely
determined by the oxidizer flux and exposed fuel surface area. This combustion rate is not usually
sufficient for high power operations such as boost stages unless the surface area or oxidizer flux is
high. Too high of oxidizer flux can lead to flooding and loss of flame holding that locally
extinguishes the combustion. Surface area can be increased, typically by longer grains or multiple
ports, but this can increase combustion chamber size, reduce grain strength and/or reduce
volumetric loading. Additionally, as the burn continues, the hole down the center of the grain (the
'port') widens and the mixture ratio tends to become more oxidizer rich.

There has been much less development of hybrid motors than solid and liquid motors. For military
use, ease of handling and maintenance have driven the use of solid rockets. For orbital work, liquid
fuels are more efficient than hybrids and most development has concentrated there. There has
recently been an increase in hybrid motor development for nonmilitary suborbital work:

Several universities have recently experimented with hybrid rockets. Brigham Young University,
the University of Utah and Utah State University launched a student-designed rocket called Unity
IV in 1995 which burned the solid fuel hydroxy-terminated polybutadiene (HTPB) with an oxidizer
of gaseous oxygen, and in 2003 launched a larger version which burned HTPB with nitrous oxide.
Stanford University researches nitrous-oxide/paraffin wax hybrid motors. UCLA has launched
hybrid rockets through an undergraduate student group since 2009 using HTPB.[12]

The Rochester Institute of Technology was building an HTPB hybrid rocket to launch small
payloads into space and to several near-Earth objects. Its first launch was in the Summer of 2007.

Scaled Composites SpaceShipOne, the first private crewed spacecraft, was powered by a hybrid
rocket burning HTPB with nitrous oxide: RocketMotorOne. The hybrid rocket engine was
manufactured by SpaceDev. SpaceDev partially based its motors on experimental data collected
from the testing of AMROC's (American Rocket Company) motors at NASA's Stennis Space
Center's E1 test stand.
Gaseous propellants

GOX (gaseous oxygen) was used as the oxidizer for the Buran program's orbital maneuvering
system.

Inert propellants

Some rocket designs impart energy to their propellants with external energy sources. For example,
water rockets use a compressed gas, typically air, to force the water reaction mass out of the
rocket.

Ion thruster

Ion thrusters ionize a neutral gas and create thrust by accelerating the ions (or the plasma) by
electric and/or magnetic fields.

Thermal rockets

Thermal rockets use inert propellants of low molecular weight that are chemically compatible with
the heating mechanism at high temperatures. Solar thermal rockets and nuclear thermal rockets
typically propose to use liquid hydrogen for a specific impulse of around 600–900 seconds, or in
some cases water that is exhausted as steam for a specific impulse of about 190 seconds. Nuclear
thermal rockets use the heat of nuclear fission to add energy to the propellant. Some designs
separate the nuclear fuel and working fluid, minimizing the potential for radioactive contamination,
but nuclear fuel loss was a persistent problem during real-world testing programs. Solar thermal
rockets use concentrated sunlight to heat a propellant, rather than using a nuclear reactor.

Compressed gas

For low performance applications, such as attitude control jets, compressed gases such as nitrogen
have been employed.[13] Energy is stored in the pressure of the inert gas. However, due to the low
density of all practical gases and high mass of the pressure vessel required to contain it,
compressed gases see little current use.
Nuclear plasma

In Project Orion and other nuclear pulse propulsion proposals, the propellant would be plasma
debris from a series of nuclear explosions.[14]

See also

ALICE (propellant)

Trinitramide

Timeline of hydrogen technologies

Category:Rocket fuels

Comparison: Aviation fuel

Nuclear propulsion

Ion thruster

Crawford burner

References

1. McGowen, Tom (2008). Space Race: The Mission, the Men, the Moon. Enslow Pub Inc. p. 7.
ISBN 978-0766029101.

2. Games, Alex (2007). Balderdash & Piffle (https://archive.org/details/balderdashpiffle0000gam

3. Gref, Lynn G. (2010). The Rise and Fall of American Technology. Algora. p. 95. ISBN 978-
0875867533.

4. Greatrix, David R. (2012). Powered Flight: The Engineering of Aerospace Propulsion (https://archi
ve.org/details/poweredflighteng00grea) . Springer. pp. 1 (https://archive.org/details/powered
flighteng00grea/page/n23) . ISBN 978-1447124849.

5. Mahaffey, James (2017). Atomic Adventures: Secret Islands, Forgotten N-Rays, and Isotopic
Murder - A Journey Through The Wild World of Nuclear Science. Pegasus Books. ISBN 978-
1681774213.
 6. M. D. Black, The Evolution of ROCKET TECHNOLOGY, 3rd Ed., 2012, payloadz.com ebook/History
pp. 109-112 and pp. 114-119

7. Jones, C., Masse, D., Glass, C., Wilhite, A., and Walker, M. (2010), "PHARO: Propellant harvesting
of atmospheric resources in orbit," IEEE Aerospace Conference.

8. "Toxic Propellant Hazards" (https://www.youtube.com/watch?v=Zha9DyS-PPA) on YouTube

9. Rocket Propulsion (http://www.braeunig.us/space/propuls.htm) , Robert A. Braeunig, Rocket

10. "Robert Salkeld'S" (http://www.pmview.com/spaceodysseytwo/spacelvs/sld039.htm) .

11. Ignition! An Informal History of Liquid Rocket Propellants, John D. Clark (Rutgers University
Press, 1972), Chapter 12

12. "Rocket Project at UCLA" (http://www.rocketprojectatucla.com) .

13. Steyn, Willem H; Hashida, Yoshi (1999). "An Attitude Control System for a Low-Cost Earth
Observation Satellite with Orbit Maintenance Capability" (http://digitalcommons.usu.edu/small
sat/1999/all1999/79/) . Small Satellite Conference. USU Small Satellite Conference Surrey
Space Centre. Retrieved 18 October 2016.

14. G.R. Schmidt; J.A. Bunornetti; P.J. Morton. Nuclear Pulse Propulsion – Orion and Beyond (http
s://ntrs.nasa.gov/archive/nasa/casi.ntrs.nasa.gov/20000096503_2000138021.pdf) (PDF).
36th AIAA / ASME / SAE / ASEE Joint Propulsion Conference & Exhibit, Huntsville, Alabama,
16–19 July 2000. AlAA 2000-3856.

External links

Rocket Propellants (http://www.braeunig.us/space/propel.htm) (from Rocket & Space