What is Rocket Propellant?

Rocket propellant is the material used by a rocket engine to generate thrust.

The most common propellants consist of a fuel and an oxidizer that participate
in chemical reactions to produce extremely hot gases. These gases exert pressure that
propels the rocket forward while they are ejected in the form of a jet through the
rear. Propellant is the chemical mixture burned to produce thrust in rockets and
consists of a fuel and an oxidizer. A fuel is a substance which burns when
combined with oxygen producing gas for propulsion. An oxidizer is an agent that
releases oxygen for combination with a fuel.
The gauge for rating the efficiency of rocket propellants is specific impulse,
stated in seconds. It indicates how many pounds (or kilograms) of thrust are
obtained by the consumption of one pound (or kilogram) of propellant in one
second. Specific impulse is characteristic of the type of propellant. Its exact value
will vary to some extent with the operating conditions and design of the rocket
engine.

Rocket propulsion 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.
Principle of Operation of Rocket Propellants:
Rocket thrust is produced by pressures acting on the combustion chamber
and nozzle. In a chemically powered rocket, the engine creates thrust (forward
force) by combustion of the propellant materials to form very hot gases, which
expand in the combustion chamber and are ejected as a high-speed jet through a
nozzle in the rear. In a closed chamber, the gas pressure would be equal in each
direction and no acceleration would occur. By providing an opening at the bottom
of the chamber, there is no pressure acting on that side, but exhaust escapes from
that end. The remaining components of pressure produce a thrust on the side
opposite the opening. Using a nozzle increases the forces further, in fact multiplies
the thrust as a function of the area ratio of the nozzle, because the pressures also
act on the nozzle. The pressures act on the exhaust in the opposite direction and
accelerate it to very high speeds (in accordance with Newton's Third Law of
motion). This disequilibrium of pressures can be maintained for as long as
propellant is added to the combustion chamber.
 According to the conservation of momentum the speed of the exhaust of a
rocket determines how much momentum increase is created for a given amount of
propellant. The faster the net speed of the exhaust in one direction, the greater the
speed of the rocket in the opposite direction. As the propellant supply decreases,
the vehicle becomes lighter and acceleration increases until the rocket eventually
runs out of propellant. Much of the speed change occurs toward the end of the burn
when the vehicle is much lighter.

The first stage of a rocket usually uses high-density (low-volume) propellants to

reduce the area exposed to atmospheric drag and to obtain lighter tank age and
higher thrust/weight ratios. The Apollo Saturn V first stage used kerosene-liquid
oxygen rather than the liquid hydrogen-liquid oxygen used on the upper stages.
Hydrogen is highly energetic per kilogram, but not per cubic meter). The Space
Shuttle uses high-thrust, high-density solid rocket boosters (SRBs) for its lift-off,
with liquid hydrogen-liquid oxygen used partly for lift-off but primarily for orbital
insertion of the shuttle.

General features of rocket propellants:

Chemical propellants uses deliver specific impulse values ranging from

about 175 up to about 300 seconds. The most energetic chemical propellants are
capable of specific impulses up to about 400 seconds.

High values of specific impulse are obtained from high exhaust-gas

temperature, and from exhaust gas having very low (molecular) weight. To be
efficient, a propellant should have a large heat of combustion to yield high
temperatures, and should produce combustion products containing simple, light
molecules embodying such elements as hydrogen (the lightest), carbon, oxygen,
fluorine, and the lighter metals (aluminum, beryllium, lithium).

Most propellants are corrosive, flammable, or toxic, and are often all three.
One of the most tractable liquid propellants is gasoline. But gasoline is highly
flammable. Many propellants are highly toxic, to a greater degree even than most
war gases; some are so corrosive that only a few special substances can be used to
contain them; some may burn spontaneously upon contact with air, or upon
contacting any organic substance, or in certain cases upon contacting most
common metals.

Categories of rocket propellants:

  Solid propellant
 Liquid propellant
 Hybrid propellant
 Gaseous Propellants

Solid propellants:

Solid propellants (and almost all rocket propellants) consist of an oxidizer

and a fuel. In the case of gunpowder, the fuel is charcoal, the oxidizer is potassium
nitrate, and sulfur serves as a catalyst.

Solid-fueled rockets are much easier to store and handle than liquid fueled
rockets, which makes them ideal for military applications. The Space Shuttle and
many other orbital launch vehicles use solid fueled rockets in their first stages
(solid rocket boosters). 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 include fuel, oxidizer, 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.

Advantages:

 Much easier to store and handle.

 High propellant density makes for compact size.
 Simplicity and low cost make solid propellant rockets ideal for military and
space applications.
Disadvantges:

 Lower specific impulse than liquid fuel rockets.

  Casting large amounts of propellant requires consistency and repeatability to
avoid cracks and voids in the completed motor.
 Solid fuel rockets are intolerant to cracks and voids and require post-
processing such as X-ray scans to identify faults.

Old usage:

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. 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. 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.

Current Usage:

Small solids often power the final stage of a launch vehicle, or attach to
payloads to boost them to higher orbits. Medium solids such as the Payload Assist
Module (PAM) and the Inertial Upper Stage (IUS) provide the added boost to
place satellites into geosynchronous orbit or on planetary trajectories. The Titan,
Delta, and Space Shuttle launch vehicles use strap-on solid propellant rockets to
provide added thrust at liftoff. The Space Shuttle uses the largest solid rocket
motors ever built and flown. Each booster contains 1,100,000 pounds (499,000 kg)
of propellant and can produce up to 3,300,000 pounds (14,680,000 Newtons) of
thrust.
COMPOSITION OF SOME SOLID ROCKET PROPELLANTS:

Propellant Type Composition

Balistite Double Base Nitrocellulose (51.5%), Nitroglycerine (43.0%),
(USA) Homogeneous Plasticiser (1.0%), Other (4.5%)
Cordite Double Base Nitrocellulose (56.5%), Nitroglycerine (28.0%),
(Soviet) Homogeneous Plasticiser (4.5%), Other (11.0%)
Aluminum Powder (16%) as fuel, Ammonium
Perchlorate (69.93%) as oxidizer, Iron Oxidizer
SRB
Composite Powder (0.07%) as catalyst, Polybutadiene Acrylic
Propellant
Acid Acrylonitrile (12.04%) as rubber-based binder,
Epoxy Curing Agent (1.96%)

Liqiud Propellants:

Liquid-fueled rockets have better 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 combustion pressures and
temperatures. On vehicles employing turbopumps, the fuel tanks carry very much
less pressure and thus can be built far more lightly, permitting a larger mass ratio.
For these reasons, most orbital launch vehicles and all first- and second-generation
ICBMs use liquid fuels for most of their velocity gain.

Liquid oxidizers like liquid oxygen, nitrogen tetroxide, and hydrogen

peroxide are available which have much better specific impulse than ammonium
perchlorate when paired with comparable fuels.

Advantages:

 Higher specific impulse than solid rockets.

 Capable of being throttled, shut down, and restarted.
 Cooling can be done regeneratively with the liquid propellant.
 On vehicles employing turbo pumps, the propellant tanks are at a lower
pressure than the combustion chamber, decreasing tank mass. So most
orbital launch vehicles use liquid propellants.
 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.
 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.

Disadavntages:

 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. 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 rocket. Turbopumps are
particularly troublesome due to high performance requirements.

Old Usage:

The first liquid-fueled rocket, launched by Robert Goddard on March 16,

1926, used gasoline and liquid oxygen. Liquid hydrogen was first used by the
engines designed by Pratt and Whitney for the Lockheed CL-400 Suntan
reconnaissance aircraft in the mid-1950s. In the mid-1960s, the Centaur and Saturn
upper stages were both using liquid hydrogen and liquid oxygen.

The highest specific impulse chemistry ever test-fired in a rocket engine

was lithium and fluorine, with hydrogen added to improve the exhaust
thermodynamics (making this a tripropellant). The combination delivered 542
seconds (5.32 kN·s/kg, 5320 m/s) specific impulse in a vacuum.

Current Usage:

 Liquid oxygen (LOX) and highly refined kerosene (RP-1). Used for the first

stages of the Atlas V, Falcon 9, Falcon Heavy, Soyuz, Zenit and developmental
rockets like Angara and Long March 6.
 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) are planned for use on
several rockets in development, including Vulcan, New Glenn, and SpaceX
Starship.

 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. Monopropellants such as hydrogen
peroxide, hydrazine, and nitrous oxide are primarily used for attitude
control and spacecraft station-keeping.  Hydrogen peroxide is also used to drive
the turbopumps on the first stage of the Soyuz launch vehicle.

PROPERTIES OF SOME LIQUID ROCKET PROPELLANTS

Chemical Molecular Melting Boiling

Compound Density
Formula Weight Point Point
Liquid Oxygen O2 32.00 1.141 g/ml -218.8oC -183.0oC
Nitrogen Tetroxide N2O4 92.01 1.45 g/ml -9.3oC 21.15oC
Nitric Acid HNO3 63.01 1.55 g/ml -41.6oC 83oC
Liquid Hydrogen H2 2.016 0.071 g/ml -259.3oC -252.9oC
Hydrazine N2H4 32.05 1.004 g/ml 1.4oC 113.5oC
Methyl Hydrazine CH3NHNH2 46.07 0.866 g/ml -52.4oC 87.5oC
Dimethyl Hydrazine (CH3)2NNH2 60.10 0.791 g/ml -58oC 63.9oC
Dodecane (Kerosene) C12H26 170.34 0.749 g/ml -9.6oC 216.3oC

Hybrid Propellants:

Hybrid propellants consist of solid fuel and a liquid oxidize. For example,
liquid N2O4 (liquid oxidize) and acrylic robber (solid fuel). Hybrid propellant
engines represent an intermediate group between solid and liquid propellant
engines. The liquid is injected into the solid, whose fuel reservoir also serves as the
combustion chamber. The fluid oxidizer can make it possible to throttle and restart
the motor just like a liquid-fueled rocket.

Advantages:

 High performance, similar to that of solid propellants, but the combustion

can be moderated, stopped, or even restarted
 Hybrid rockets can also be environmentally safer than solid rockets since
some high-performance solid-phase oxidizers contain chlorine (specifically
composites with ammonium perchlorate).
 As 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.
Disadvantages:
 The casing around the fuel grain must be built to withstand full combustion
pressure and extreme temperatures.
 The primary remaining difficulty with hybrids is with mixing the propellants
during the combustion process. 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, 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.

Developments in Hybrid Propellants:

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.
 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 manned 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:

Compressed gas:
For low performance applications, such as altitude control jets, compressed
gases such as nitrogen have been employed. Energy is stored in the pressure of the
inert gas. 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.
Ion thruster:
Ion thrusters ionize a neutral gas and create thrust by accelerating the ions
(or the plasma) by electric and/or magnetic fields.

In the various devices for ion propulsion, each molecule of propellant (an

alkali metal, notably cesium) is caused to have an electric charge i.e the propellant
is ionized. This might be accomplished by passing the propellant over heated metal
grids. It is then possible to accelerate the charged molecules, or ions, to very high
velocities through a nozzle by means of an electric field. The performance of such
an ion engine is very good with values of specific impulse estimated to be as high
as 20,000 seconds. But the amount of electric power required is very large, so
weight of the power-generating equipment becomes a major obstacle to an efficient
vehicle.

An ion rocket offering 20,000 seconds of specific impulse, using cesium for
the propellant, would require about 2,100 kilovolts of electric power to produce 1
pound of thrust, assuming good efficiency. Optimistic estimates of electric-power-
supply weight in dictate that the power unit would weigh about 8,500 pounds. The
weight of the ion accelerator itself is small in comparison. Therefore, an ion rocket
can accelerate itself only very slowly (about 1/10,000 of 1 g in this example ) .
Free Radical Propellants:
If certain molecules are torn apart, they will give up large amounts of energy
upon recombining. It has been proposed that such unstable fragments, called free
radicals, be used as rocket propellants. The difficulty is these species tend to
recombine as soon as they are formed; hence, a central problem in their use is
development of a method of stabilization. Atomic hydrogen is the most promising
of these substances. Use of atomic hydrogen might yield a specific impulse of
about 1,200 to 1,400 seconds.

Kerosene Based Propulsion Fuels:

These fuels are a mixture of chemical compounds consisting of a highly
effective combustible element, Hydrogen, and a less effective one, Carbon. Fuels
of this class are known as Hydrocarbons. The chemical combination of the two
elements above yield substances less powerful than elemental Hydrogen but
considerably more powerful than elemental Carbon. Their physico-chemical
properties defining the expediency of their utilization are incomparably higher than
those of Carbon and Hydrogen. All of the petroleum products used as rocket
propellant components are liquids with high boiling points and low temperatures of
solidification, having a fairly high stability against decomposition from heating.

Hydroxyl Ammonium Nitrate based Propulsion Fuels:

Hydroxylammonium Nitrate (HAN, [NH3OH] NO3) is a viscous and denser
monopropellant which creates significant challenges in its atomization and this
viscous nature makes it particularly difficult to accommodate when designing
micro thrusters which rely on small flow paths. Only at the cost of high feed
pressures with a large injector pressure drop can traditional propellant-injection
technology achieve atomization. Current engine designs using HAN based
propellants require a high catalyst bed pre-heat temperature of approximately
300°C to 350°C to initiate propellant ignition and minimize catalyst degradation.
To efficiently engage the catalyst, finely atomized propellant spray should be
utilised. Finer atomization of the monopropellant may promote a greater degree of
reaction with the catalyst by increasing the rate of heat transfer and thus
decomposition of the HAN-based propellant.

HYDROXYL TERMINATED POLY-BUTADIENE BASED

PROPULSION FUELS:
 Classical hybrid rockets store fuel in the form of a solid grain, as they
require only half the feed system hardware of liquid bipropellant engines,
providing a simpler, more flexible design with potentially improved reliability.
These engines can be throttled for thrust tailoring, performing motor shut down
and restart, and incorporate non-destructive mission abort modes. Hybrid rocket
fuels are benign, nontoxic, and non-hazardous to store and transport, unlike
Hydrogen which is a volatile liquid. HTPB depends on the mass flux of oxidizer as
the regression rate shows a decreasing trend from head end to nozzle end. The best
performance was shown by the mixture of 50% Paraffin Wax and 50% HTPB
among all test fuels available. The addition of 20% Alex powder into the HTPB
fuel was found to increase the mass burning rate by 70%. This demonstrates that a
very significant improvement of solid-fuel performance in hybrid motor operating
conditions can be achieved with ultra-fine aluminium powders. HTPB has high
mass burning rate increase of up to 63% was seen by 13% Nano-sized Alex
powder added, when compared to the baseline. HTPB is very safe, stable and it is
quite easy to cast it into different fuel geometries.

PARAFFIN WAX BASED PROPULSION FUELS:

Paraffin energizes offer at 3-4 times change over HTPB in regression rate,
which considers substantially higher thrust motors because of the expansion in the
mass flowing rate of the fuel. Various HTPB based fuel blends were examined yet
in the wake of testing and assembling preliminaries, the main center moved
towards blending HTPB and Paraffin. The mixture of Paraffin and HTPB produces
"clean"gasses compared to numerous different chemicals that can be utilized. They
are additionally both simple to acquire and simple to work with since they are non-
perilous. Moulding and detailing of HTPB is exceptionally well known in the
rocketry business. Paraffin is additionally simple to cast and pour since it can
basically be warmed past its melting point and can be filled in a shape.

HTPB is blended with small Paraffin circles consistently and cast into fuel
centers. The two fuels are not accepted to be molecularly reinforced in any
noteworthy method to each other aside from little thin territories around the surface
of the circles. The main inconvenience associated with making the wax centers was
the property of the wax that it contracted in volume while changing from fluid to
solid which occasionally caused splitting inside the fuel center. Paraffin Wax was
permitted to cool and resolidify gradually at room temperature to control this issue.
The blended fuel supposedly did better as far as regression rate than plain HTPB.
Not surprisingly, the higher concentration of Paraffin fuel regressed quicker than
the lower fixation blend. The regression rate of Paraffin was substantially higher
than that of alternate energizers. The high regression rate is offered by Paraffin
Wax due to its nature of forming droplets which readily escape from a liquid layer
on the surface of the fuel into the flame zone. This flame zone is comparatively
separated from the fuel surface. Greater simplicity is added due to the use of
Hydrogen peroxide and a catalyst bed as the oxidizer because they eliminate the
need for a complex and expensive igniter system.

Hydrogen Based Propulsion fuels:

The problems of injector and thrust chamber design are simplified in the
case of Hydrogen due to its high diffusivity and chemical reactivity and its high
cooling capacity’s. But Hydrogen lacks in a few places such as very low boiling
point and quite low density. Perhaps the most immediate application of liquid
Hydrogen is in top stages of existing boosters to improve the space payload
capability. While Hydrogen is a desirable fuel for the chemical property, it makes
an ideal working fluid in the nuclear rocket due to its physical characteristics. With
a specific impulse of well over twice that of any other expellant and specific
impulse of nuclear rockets using Hydrogen are expected to double that of the best
chemical systems. The performance results depend primarily upon the ratio of this
pressure to the exhaust pressure that is used and the combustion chamber pressure.
Hydrogen has the highest heating value. It also evolves a large amount of gas
during combustion. Their mixtures with some elements have physic-Chemical
properties fully suitable for propulsion purpose, but are less powerful. The main
drawback of liquid Hydrogen is its low boiling point which is -2540C, i.e., 7100
below that of liquid Oxygen. This causes difficulties in storing and transporting
large amounts of liquid Hydrogen.

Conclusion:
The knowledge that has been obtained through the research of rocket
technology has brought the promise of eventual commercialization of space even
closer. If more research and development is invested into solid-fuel and liquid-fuel
technology, the dream of commercializing the space industry can be realized.
Perhaps prior to that realization, whole new technologies for design and
construction of spacecraft and different fuels may be required. However, it is a
good bet that further research and development, cost effectiveness and overall
improvement with the current workhorses of space exploration will be around for
sometime.
Bibliography:
i) https://history.nasa.gov
ii) https://www.slideshare.com
iii) https://www.newworldencyclopedia.org
iv) https://www.scss.tcd.ie
v) https://www.researchgate.net