Notes on Chemical Propellants

For B.Tech I Semester

Propulsion

Propulsion is the act of changing the motion of a body. The mechanism of propulsion provide a
force that moves bodies that are at rest, changes a velocity or overcome s retarding forces when a
body is propelled through a medium. Jet propulsion is a means of locomotion whereby a reaction
force is imparted to a device by the momentum of the ejected mater.

Rocket propulsion is a kind of jet propulsion that produces thrust by ejecting stored mater, called
propellants. The different types of rocket propulsion and corresponding source of energy are
given in table 1

S.No. Type of propulsion Energy source

1 Chemical propulsion Combustion of propellants
2 Nuclear propulsion Energy from nuclear fission, radioactive
isotope decay and nuclear fusion reaction
are used to heat the stored gases like
hydrogen to generate thrust. The
technology is not fully developed.
3. Electric rocket propulsion The stored gas electrically heated to high
temperature by means of resistance heating
and the hot gas is thermodynamically
expanded and accelerated to supersonic
velocities through an exhaust nozzle.
4. Ionic propulsion The working fluid (Xenon) is ionized by
stripping electrons and the charged heavy
ions are accelerated to very high velocities
by means of electric fields. Subsequently
the ions are neutralized by combining with
the electrons to prevent the buildup of
space charge. ( Not fully developed)
5. Magneto plasma propulsion An electrical plasma is accelerated by
means of a magnetic field and ejected at
high velocity (Not fully developed)
6. Solar rocket propulsion Solar radiation is concentrated on high
temperature metals and the thermal energy
generated is exchanged to the working
fluid. The hot gas is then exhausted
through nozzles to generate thrust. Thrust
generated is low.

The rocket propulsion is not only useful for the deployment of satellite for communication,
remote sensing and global positioning but also for space missions and interplanetary missions. In
addition, the rocket propulsion technology is highly useful in the strategic defense systems such
as missiles.
Chemical Propellants

Chemical rocket propellants are high energy materials which on combustion or decomposition
generate large quantity of energy and large volume of gaseous products. The expulsion of these
high energy (high velocity) gaseous combustion/decomposition products through the nozzle of
the rocket produce thrust as per the Newton’s third law of motion. The chemical rocket
propellants are classified in to solid propellant, liquid propellant and cryogenic propellant.

Thrust: reaction force exerted by the ejection of combustion gases from the rocket nozzle is
called thrust. Thrust is expressed by the equation

F= m.Vc +Ac(Pc-Pa)

Where m= Mass flow rate through nozzle

Vc= Velocity of gas at the nozzle exit

Ac= Nozzle exit area

Pc = Nozzle exit pressure

Pa= Surrounding atmospheric pressure

The thrust of a rocket motor is measured using load cell

Specific Impulse (Isp): The total impulse is proportional to the total energy released by all the
propellants in the propulsion system. It is the thrust force integrated over the burning time
t
It = ∫0 F. dt

The specific impulse (Is) is the total impulse per unit weight of the propellant. It is an important
figure of merit of the performance of a rocket propulsion system. If the total mass flow rate of
propellant is m and standard acceleration due to gravity at sea level is go, the specific impulse Isp
can be calculated as
𝑡
∫0 𝐹. 𝑑𝑡
𝐼𝑠𝑝 =
𝑔𝑜 ∫ 𝑚. 𝑑𝑡
Where F is the thrust and m is total mass flow rate,

For constant thrust and propellant flow rate the equation can be written as

𝐼𝑡
𝐼𝑠 =
𝑚𝑝 . 𝑔𝑜
Where It is the total impulse and mp total effective propellant mass

Chamber Pressure: The force exerted by the combustion gases per unit area inside the rocket
motor is called chamber pressure (Pc). Rockets generally operate in the pressure range of 70 to
140 kg/cm2. For a given propellant configuration the ratio of surface area to throat area controls
the chamber pressure.

Characteristic Velocity: Characteristic velocity is defined as the product of the chamber

pressure and throat area to the mass flow rate

C* = Pc.At /m

It depends on the flame temperature, mean molecular mass of the combustion products and
propellant formulation. It is fundamental parameter which gives the energy available on
combustion. The characteristic velocity of propellants is in the range of 1200 to 1600 m/s.

Chemical propellant

Chemical propellants could be a combination of fuels consisting of carbon, hydrogen and

nitrogen and oxidizers. The specific impulse of a propellant is proportional to the square root of
the ratio of temperature to the average molecular mass of the combustion products. That is, a
propellant producing highest temperature and lowest molecular mass of the products up on
combustion will generates the highest specific impulse. In order to achieve lowest molecular
mass of the combustion products, propellants are made up of elements with low atomic masses
such as hydrogen, carbon, nitrogen boron, fluorine etc. In order to achieve high temperature of
the combustion products, the energy released during the combustion reaction has to be as large as
possible and the specific heat of the combustion products must be small. It is well known that the
specific heat of gases are in the order mono atomic gases<diatomic gases<polyatomic gases.
That is, the specific heat increases with increase in molecular mass and complexity of the
combustion products.

During the combustion, the chemical energy stored in the propellant is released. The energy
released is the difference in energy between the propellant and the combustion products. That is,
energy released depends on the nature of the propellant and combustion products. The same
propellant produces different energy if the products of combustion are different. For example,
combustion of carbon in limited supply of oxygen produces CO and 9208 kJ/kg of energy where
as the combustion of carbon in sufficient supply of oxygen produces CO2 and 32800kJ/kg of
energy. The above example clearly shows the oxidant to fuel ratio in a propellant is important.
The ratio of mass of oxidizer to the mass of fuel is called the mixture ratio. The stoichiometric
mixture ratio is the oxidizer to fuel mass ratio at which chemical reactions leading to the
complete oxidation of the fuel releases the maximum energy. The propellants with mixture ratio
less than and more than the stoichiometric ratio are called, fuel rich and oxidizer rich propellants.
Heat of formation of a compound is the energy released during the formation one mole of the
compound from the constituent elements at standard state. The heat of combustion is the
difference in heat of formation of the products to the reactants.

Heat of combustion = (sum of the heat of formation of combustion product-sum of the heat of
formation of propellant).

In order to achieve high negative value (heat release) of heat of combustion, the heat of
formation of the propellant must be either positive or very low negative value and the
combustion products must have high negative value of heat of formation. For example, fuels
such as hydrazine, HMX and RDX have positive value of heat of formation. The elements such
as hydrogen, oxygen and Al used as propellant have zero heat of formation.

Solid Rocket Propellant

Solid propellants are classified in to double base propellants and composite propellants

Double base Propellant

The double base propellant is a homogeneous mixture of nitrocellulose (a solid ingredient) and
nitroglycerin (liquid) and small amount of minor additives. The nitrocellulose and nitroglycerin
are explosive and functions as both fuel and oxidant. It is available in extruded and cast form.
The performance of double base propellant can be improved by adding crystalline nitramines
such as HMX and RDX. It is called modified double base propellant.

Composite propellant

Composite propellant is a heterogonous propellant in which the oxidizer crystals and a fuel
powder are held together in a matrix of synthetic rubber binder. The generally used oxidizer fuel
and binder are ammonium perchlorate (AP), aluminium powder and hydroxyl terminated
polybutadiene (HTPB), respectively.

Conventional composite propellant contain 60 to 72 % AP, nearly 22% Al powder 8 to 16 %

HTPB.

The density and performance of a composite propellant can be enhanced incorporating adding
energetic nitramines such as HMX and RDX and energetic plasticizer such a nitroglycerin
improve the performance. On the other hand, the lower energy composite propellant is obtained
by replacing AP with ammonium nitrate.
Ingredients in a Solid composite Propellant:
Inorganic Oxidizer

Major portion of composite propellant constitute inorganic oxidizer. Though a number of

inorganic oxidizers such as potassium nitrate, ammonium nitrate, potassium chlorate,
potassium perchlorate, ammonium perchlorate etc are available, the widely used oxidizer in
solid propellants is ammonium perchlorate (AP). The following characteristics of AP made it
an excellent oxidizer in solid propellant

1. High density
2. Non hygroscopic
3. Decompose before melting
4. High specific impulse ( 280 to 290 s)

Preparation of AP

AP is prepared in two steps. First step is the anodic oxidation of NaCl or NaClO3 solution to
produce NaClO4.

NaClO3 + H2O NaClO4 + H2

The sodium perchlorate on double decomposition with ammonium chloride to form ammonium
perchlorate

NaClO4 + NH4Cl NH4ClO4 + NaCl

The produced AP is re-crystallized from water (AP is sparingly soluble in water)

AP with a broad distribution of particle size is used in solid propellant. The AP powder used for
propellant contains a course particle fraction (400 to 600 m), medium particle fraction ( 50 to
200 m), fine particle fraction ( 5 to 15 m) and ultrafine particle fraction ( < 5 m). The broad
particle size distribution leads to better packing of AP particles in the composite propellant and
therefore higher loading of AP in the composite propellant is possible. The AP is obtained in
course particle range and grinded to lower particle sizes at the site for propellant processing
because transportation of fine AP may leads to explosion.

Fuels

The function of fuel is to generate large amount of energy due to combustions. The commonly
used fuel in composite rocket propellant is aluminium powder of particle size in the range of 5 to
60 m. This aluminium powder burns in presence of the oxidizer and produce large amount of
heat energy and aluminium oxide particle. The amount of aluminum oxide used is in the range of
14 to 20%. The ballistic properties of propellant depend on the amount of fuel.
Boron and Beryllium are two alternatives for aluminium as fuel in composite propellant.
However, use of Beryllium limited due to its poisonous nature. On the other hand, boron is used
in a limited way in some of the rocket engines. Aluminium hydride and Beryllium hydride are
two high energy fuels. However, they are difficult to manufacture and unstable.

Binder

The oxidizer and fuel particle in a composite propellant are held together in a propellant grain
using a polymeric binder. That is, the polymeric binder provides structural integrity and required
mechanical strength to the propellant. In addition, the polymeric binder acts as fuel as its
combustion produce large amount of heat and gas molecules. Polymers such as PVC, polyesters,
polyethers, polybutadiene etc. are used as binder in composite propellant.

The commonly used binder in composite propellant is hydroxyl terminated poly butadiene (
HTPB). It is available in the form of a low molecular weight pre-polymer. The HTPB is prepared
by either free radical polymerization of butadiene with hydrogen peroxide or by the anionic
polymerization of butadiene with dialkyl lithium. The mechanism of free radical polymerization
of butadiene with hydrogen peroxide is as below

The curing of HTPB is carried out by urethane chemistry using diisocyanate ( Toluene
diisocyanate).
 Curing reaction of HTPB

Energetic binder such as Glycidyl azide polymer (GAP) is also used in composite propellant.
These binders contain oxidizing groups which enhances the energy and causes moderate
improvement in the performance of the propellant.

Structure of GAP
Plasticizers

A plasticizer is a low viscosity organic liquid which is also a fuel. It is added to improve the
processing characteristics and also improve the elongation properties of the cured propellant.
Simple molecules such as Di-octyl phthalate, Di butyl phthalate etc are used as plasticizer.

Burning rate modifiers

These are catalyst used to increase or decrease the burn rate of composite propellants. Ferric
oxide and copper chromate are used to increase the burn rate of composite propellant. On the
other hand, lithium fluoride is used to decrease the burn rate.

Other Additives

Energetic additives are sometimes added to composite propellant to tailor their performance.
Commonly used energetic additives are organic oxidants ( Explosives ) such as RDX, HMX,
Nitrocellulose and nitroglycerin etc.

In addition minor additives such as flow modifiers, stabilizers, bonding agent, curing catalyst etc
are also used in propellant formulations.

Propellant Processing

The composite propellants are processed to suitable grain geometries by either extrusion or
casting. Casting is the most popular method for the preparation of composite propellant. In this
method, the ingredients such as HTPB, AP, Aluminium powder, flow modifiers, plasticizer,
burning rate modifier and curing agent are mixed in a suitable mixer to prepare propallent slurry
having suitable flow characteristics and pot life. The slurry is then degassed by applying
vacuums and cast in the rocket motor casing. Suitable mandrel is placed in the casing to create
cavity as per the desired grain configuration. The cast propellant is then allowed to cure by the
reaction between HTPB and curing agent (TDI). The mandrel removed after proper curing of the
propellant slurry.

The propellant grain may also be processed by extrusion and further assembled in the rocket
motor case.

Photograph of Star grain composite propellant

Ignition of propellant is achieved by transferring heat produced by burning of a pyrotechnic

composition. The important pyrotechnic composition is a mixture of potassium nitrate, carbon
and sulphur in the ratio 0.75:0.15: 0.1. Metal powders are also added to the ignition mixture to
enhance amount of heat produced and the effective transfer of the heat to the propellant. The
combustion of the ignition mixture is initiated electrically. A fine electrical resistance wire (
nichrome) coated with a readily ignitable material is used. It is known as squib.

Burn rate of a Solid Propellant

The branch of applied science describing the combustion characteristics of a propellant is called
internal ballistics. The internal ballistics of a propellant depends on burn rate, burning surface
and grain geometry.

The burning surface of a propellant grain recedes in a direction perpendicular to the surface.
The rate of regression is the burning rate. The burning rate is usually expressed as cm/s or mm/s
or inch/ second. The burning rate is a function of propellant composition. In addition to the
propellant composition, the burning rate mainly depends on combustion chamber pressure and
initial temperature of the propellant. The burning rate can be determined by using standard
strand burn rate test, small scale ballistic evaluation motors and full-scale motors with good
instrumentation.

A strand burner is a small pressure vessel in which a thin strand (bar) of propellant is ignited
from one end and burnt to the other end. The strand is inhibited with an external coating so that it
will burn from only one end. The chamber pressure is simulated by pressurizing the container
with an inert gas. The burning rate can be measured by either optical or acoustic emission
measurements. The burning rate measured using strand burner is usually 4 to 12 % lower than
the burn rate measured using actual motor. However, the strand burning rate is widely used
during development of a new propellant or modification of an existing propellant.

The burning rate of a propellant is related to the chamber pressure as below

r= a. Pn

Where r is the burning rate in cm/s, P is the chamber pressure in MPa, “a” is an empirical
constant influenced by the initial temperature of the propellant grain. The constant” a” is called
temperature coefficient. “n’ is called burning rate exponent or combustion index. A plot of log
of burning rate against log of pressure gives a straight line. The slope of the line gives the
burning rate exponent.

Most of the propellants which are in practical use are having burning rate exponent in the range
of 0.2 to 0.6. Higher burning rate exponent gives a rapid change of burning rate with pressure.
When the n value approaches 1, the burning rate and chamber pressure are very much sensitive
to one another and a disastrous rise in chamber pressure occurs in few milliseconds. When “n”
approaches zero the combustion become unstable and even extinguish by itself.

Propellant Characteristics

The desirable propellant characteristics are as below

 1. High specific impulse. This means high gas temperature and low molecular weight of the
product gases
2. Predictable, reproducible and initially adjustable burning rate
3. The pressure or burning rate exponent and temperature coefficient should be in an
adequate range
4. Adequate physical properties over the intended operating temperature
5. High density
6. Predictable and reproducible ignition temperature
7. Good aging characteristics and long life
8. Low moisture absorption
9. Simple, low cost, reproducible, safe, controllable and nonhazardous manufacture
10. Relatively insensitive to certain energy stimuli such as impact and friction
11. Non-toxic exhaust gases
12. Not prone to combustion instability

Liquid Propellants

Liquid propellants are used in rocket engine. A rocket engine essentially contains a combustion
chamber, propellant tank, propellant feed system and nozzle.

Rocket engine diagram

 Photograph of a rocket engine

The term liquid propellant embraces all the various liquids that are used in rocket engines. They
undergo either chemical decomposition or combustion and generate energy and large volume of
gases. They include

1. Oxidizer ( liquid oxygen, N2O4, nitric acid )

2. Fuel ( Kerosene, liquid hydrogen)
3. Chemical compound or mixture of fuel and oxidizer capable of self decomposition or
combustion
The liquid propellants are classified in to monopropellant, bipropellant and cryogenic
propellant

Monopropellant contains an oxidizing agent and combustible matter in a single substance. It

may be a mixture of compound or a homogeneous material such as hydrogen peroxide and
hydrazine. Monopropellants are stable at ordinary atmospheric conditions but decompose and
give hot combustion gases on hating or catalyzed.

A bipropellant rocket engine consists of two separate liquid propellants, an oxidizer and a
fuel. They are stored in spate tanks and not mixed outside the combustion chamber.

Eg. Liquid oxygen, N2O4, Kerosene, Liquid hydrogen

Cryogenic propellant is liquefied gas at low temperature such as liquid hydrogen and liquid
oxygen

Storable propellants are liquid at ambient temperature and can be stored for long periods in
sealed tanks.

Eg. Nitric acid, Kerosene

Desirable Characteristics of a Liquid Propellant

Availability in large quantity at a low cost

Very good performances in terms of specific impulse, effective exhaust velocity etc. For high
performance a high content of chemical energy per unit of propellant mixture is highly
desirable for achieving high chamber pressure. A low molecular mass of the product gases of
the propellant combination is also desirable. Very fine metallic fuel particles such a
aluminium is suspended in liquid fuels to increase the specific impulse.

The liquid propellant must be compatible with the materials used for the construction of
liquid engine such as fuel and oxidizer tank, combustion chamber, pumps, piping etc.

Low freezing point will enable operation of rockets in cold weather.

The propellant should have high specific gravity to accommodate relatively large mass of
propellant in a tank of lower volume. This permits a relatively low structural vehicle mass
and low aerodynamic drag.

A propellant should have good chemical stability. This means no decomposition of the liquid
propellant during operation or log term storage. No appreciable absorption of moisture and
no adverse effect of small amount of impurities are also desirable.

A low viscosity and vapour pressure are desirable for good pumping properties
There should not be large variations in physical properties with temperature

Ignition and combustion

Propellant combinations which are spontaneously ignitable are called hypergolic propellants.
That is, the burning is initiated when the fuel and oxidizer come in contact with each other.
In this case an additional ignition system can be eliminated. In general, readily ignitable fuel
oxidizer combinations are desirable as they reduce the ignition delay. Non-spontaneously
ignitable propellants need an igniter. An igniter is a device that accomplishes an initial slight
pressurization of the chamber and initial heating of the propellant mixture to the point where
steady flow combustion can be self sustained. Combustion stability is another desirable
characteristic of a propellant. Smoke formation is objectionable in many applications.
Brilliant exhaust flame is also not desirable in some of the military applications.

Liquid Oxidizers

The commonly used liquid oxidizers in propellant are liquid Oxygen (LOX), hydrogen
peroxide, nitric acid and di-nitrogen tetroxide

Liquid oxygen is a widely used oxidizer in liquid propellants as it burns with bright white-
yellow flame with most hydrocarbon fuels. It has a specific gravity of 1.14 and heat of
vaporization of 213 kJ/kg. Although it usually does not burn spontaneously with organic
materials at ambient pressure, combustion or explosion can occur when a confined mixture of
LOX and organic matter is suddenly pressurized.

Liquid oxygen is generally obtained by fractional distillation of liquid air. It is necessary to

insulate the all lines, tanks, and valves etc. that contain LOX to minimize the evaporation
loss.

LOX is used in combination with fuels such as liquid hydrogen (cryogenic system) and
Kerosene.

Hydrogen Peroxide

The commercial hydrogen peroxide is 30% concentrated. However, the hydrogen peroxide
used for propellant application is in the concentration range of 70 to 99. The hydrogen
peroxide decompose in the combustion chamber in presence of catalyst such as liquid
permanganates, manganese dioxide etc. to superheated steam and oxygen.

H2O2 H2O + ½ O2 + heat

The application of hydrogen peroxide as propellant is limited due to the lack of long term
storage stability as concentrated hydrogen peroxide slowly decomposes in presence of any
impurity.
Nitric acid

Among several types of nitric acid, red fuming nitric acid (RFNA) is used as oxidizer in
liquid propellant. The RFNA contain 5 to 20 % dissolved nitrogen dioxide. The RFNA is
more energetic, stable during storage and less corrosive. Addition of ~ 1% fluoride further
reduces the corrosive nature of RFNA by forming a fluoride layer on the metal surface.
RFNA is used along with fuels like gasoline, alcohol, hydrazine, di methyl hydrazine etc.

Nitrogen Tetroxide (N2O4)

Nitrogen tetroxide is the most important storable propellant oxidizer. This is a high density
(1.44 g/cc) yellow-brown liquid. It is hypergolic with many fuels. One of the problems
associated with nitrogen tetroxide is that it has a narrow liquid range. That is, it easily
evaporates as well as freeze. The freezing point of N2O4 can be lowered by adding a small
amount of NO. However, incorporation of NO increases the vapour pressure. N2O4 is
widely used in combination with fuels such as hydrazine, methyl hydrazine, unsymmetrical
dimethyl hydrazine etc.

Liquid Fuels

Liquid hydrocarbons

Petroleum derived hydrocarbons are used as fuels in propellant. The widely used one is RP-1.
RP-1 is a mixture of saturated and unsaturated hydrocarbons with a narrow range of densities
and vapour pressure. Its composition is similar to kerosene. The equivalent fuel developed
and used in ISRO is ISROSENE. The RP-1 is low in aromatics and olefin so as to avoid
carbon deposits in fuel cooling passages. RP-1-LOX combination is widely used in rockets.

Liquid hydrogen

Liquid hydrogen burns with liquid oxygen with a colorless flame. Of all the fuels liquid
hydrogen is the lightest and coldest one. It has a specific gravity of 0.07 and boiling point of
20 K. The very low fuel density necessitate bulky fuel tank. The extremely low temperature
makes the problem of choosing suitable tank and piping materials difficult because many
metals become brittle at these temperatures.

Because of the low temperature the liquid hydrogen tanks and piping need to be well
insulated to minimize its evaporation and condensation of moisture or air outside the tank. In
general, a vacuum jacket is also provided in addition to the thermal insulation. All common
liquids and solids solidify in liquid hydrogen and these solid particles plug the valves and
orifice. Therefore, the air and moisture from tanks and piping need to removed before
introducing the liquid hydrogen propellant. This is done either flushing with He gas or
applying vacuum.

Hydrazine

Hydrazine is a toxic colorless liquid with a high freezing point (274.3 K). Hydrazine has a
short ignition delay and is spontaneously ignitable with nitric acid and nitrogen tetroxide.
Pure anhydrous hydrazine is a stable liquid and can be stored in tanks for years. With
impurities or at high temperature it decomposes and release energy. Under pressure shock it
decomposes at temperature as low as 367 K. Materials such as stainless steel, nickel and
aluminium alloys are combatable with hydrazine.

Hydrazine is not only an excellent storable fuel, but also an excellent monopropellant when
decomposed by suitable solid catalyst. Iridium is an effective catalyst for decomposition of
hydrazine at room temperature. Many others such as iron, cobalt, nickel etc. act as effective
catalyst at elevated temperatures. The catalytic decomposition of hydrazine takes place in
two stages. In the first stage, hydrazine undergoes exothermic decomposition to ammonia
and nitrogen. In the second step, ammonia undergoes endothermic decomposition to nitrogen
and hydrogen. The overall decomposition can be represented as below

3 N2H4 4 (1-x) NH3 + (1+2x) N2 +6x H2

Where x is the degree of dissociation of ammonia.

Unsymmetrical Dimethylhydrazine (UDMH)

Unsymmetrical dimethylhydrazine has lower freezing point and higher boiling point than
hydrazine. UDMH and a combination of UDMH and hydrazine are used as liquid fuel in
rockets. It has a slightly lower Isp than pure hydrazine.

Monomethylhydrazine (MMH)

Monomethylhydrazene has a better shock resistance to blast waves, better heat transfer
properties and a better liquid temperature range than pure hydrazine. It has specific impulse 1
to 2 % lower than pure hydrazine. Addition of 3 to 15 % of MMH to pure hydrazine
substantially quenches the explosive decomposition of hydrazine.

References

1. George P Sutton and Oscar Biblarz, Rocket Propulsion Elements, John Wiley and Son
Inc. New Jersey, 2010.
2. Thomas A Ward, Aerospace Propulsion Systems, John Wiley and Son Inc., Singapore
2010.