PROPELLANTS

Propellants
 The propellants are defined as the material which generates a
large volume of low molecular weight gaseous at high
temperature during combustion and which can self sustain
without the presence of ambient oxidizer.

 Propellants consists of both fuels and oxidizers.

 Based on the propellants usages the rocket engines are

classified as solid propellant motor, liquid rocket engines and
hybrid engine…
Types of Rocket Propulsion

• Solid
Fuel and oxidizer coexist in a solid matrix.
• Liquid
Fluid (liquid or gas) propellants stored separately.
Propellants routed to a combustion chamber to react.
• Hybrid
Combines elements of solid and liquid propulsion.
Fluid oxidizer injected into solid fuel grain.
Liquid Propellants
 Propellants are the materials that are combusted by the engine to produce
thrust.
 Bipropellant liquid rocket systems consist of a fuel and an oxidizer. They are
the most common due to their high performance, but are more complex.
 Several propellants can be used singularly as monopropellants (i.e. HTP
High-test peroxide or HTP is a high (85 to 98 percent)-concentration solution
of hydrogen peroxide , N2H4, UDMH), which release energy when they
decompose either when heated or catalyzed.
 The mission / requirements of the vehicle will directly effect the selection of
propellants and configuration (power cycle) of the propulsion system(s).
 The liquid propellants were classified as low energy propellants, medium
energy propellants and high energy propellants.
 The primary propellant types to be discussed are:
–Storable
–Space Storable
–Cryogenic
Desirable Physical Properties
• Low Freezing Point
• High Specific Gravity.
• Stability.
• Heat Transfer Properties.
• Ignition, Combustion, and Flame Properties.
• Temperature Variation.
Storable Propellants
 Storable propellants are liquid at sea level conditions of
temperature and pressure and can be stored indefinitely in
sealed tanks.
 One drawback of storable propellants is that, with the exception
of kerosene-based fuels (RP-1, RJ-1) they are invariably toxic,
reactive, corrosive, and difficult to handle.
 Most storable propellant combinations are hypergolic, meaning
that they ignite spontaneously when in contact with each other.
–Hypergolic propellant combinations are primarily used for
small thruster applications.
–Elimination of the ignition system reduces engine complexity
and enables thrust-on-demand capability.
 Space Storable Propellants
 Space storable propellants are liquid in the temperatures of space and generally
have a net boiling point greater than 230R.
 They can be stored for longer periods of time than cryogenic propellants when
in space and depending on the storage tank design, thermal environment, and
tank pressure.
 They are generally more energetic than most storable propellant combinations,
but are rarely used due to their extreme toxicity, reactivity and handling
difficulties.
 Actual application of space storable propellants in an operational propulsion
system is rare due to the toxicity hazards.
–Beginning in the late 1950’s, the USAF studied the use of space storable
propellants in upper stages. The findings indicated that the operational hazards
did not justify the performance gains.
–The XLR99-RM-1 rocket engine for the X-15 experimental hypersonic
aircraft used a LO2/NH3 propellant combination.
Cryogenic Propellants
o Cryogenic propellants are liquefied gases at extremely low temperatures (approx.
30R to 230R) and are typically the most energetic types of propellants.
o However, they are more difficult to store for any length of time (vaporization
losses) and require provisions for venting the propellant tank.
o LO2 and LH2 are the most commonly used liquid cryogenic propellants, and will be
used in the J-2X.
–LH2
•Advantages – High performance, excellent coolant
•Disadvantage – Low density (~4.5 lb/ft3 vs. 72 lb/ft3 for LO2, resulting in a
disproportionate size in propellant tanks)
–LO2
•Advantages – Non-toxic, high reactivity to fuel (high performance). Only fluorine
is a better oxidizer.
•Disadvantage – Not selective about what it uses as fuel. It prefers hydrogen or
hydrocarbons, but will consume almost anything with an oxidation potential.
Liquid Oxidizers
• Many different types of storable and cryogenic liquid oxidizer propellants
have been used, synthesized, or proposed.
• For high specific impulse this includes boron-oxygen-fluorine compounds,
oxygen-fluorine compounds, nitrogen fluorine formulations, and
fluorinated hydrocarbons; however, they all have some undesirable
characteristics and these synthetic oxidizers have not been proven to be
practical.
• Oxidizer liquids that have been used in experimental liquid rocket engines
include mixtures of liquid oxygen and liquid fluorine, oxygen di fluoride
(OF2) , chlorine tri fluoride (C1F3), or chlorine penta fluoride (C1F5).
• All of these are highly toxic and very corrosive. Several commonly used
oxidizers are listed below.
Liquid Oxygen (02)

• Liquid oxygen, often abbreviated as LOX, boils at 90 K at atmospheric

pressure; at these conditions it has a specific gravity of 1.14 and a heat of
vaporization of 213 kJ/kg.
• It is widely used as an oxidizer and burns with a bright white-yellow flame
with most hydrocarbon fuels.
• It has been used in combination with alcohols, jet fuels (kerosene-type),
gasoline, and hydrogen.
• The following missiles and space launch vehicles use oxygen:
• (1) with jet fuel--Atlas, Thor, Jupiter, Titan I, Saturn booster;
• (2) with hydrogen--Space Shuttle and Centaur upper stage;
• (3) with alcohol--V-2 and Redstone
Hydrogen Peroxide (H2O2)
 In rocket application, hydrogen peroxide has been used in a highly
concentrated form of 70 to 99%; the remainder is mostly water.
 Commercial peroxide is approximately 30% concentrated. Concentrated
hydrogen peroxide was used in gas generator and rocket applications between
1938 and 1965 (X-1 and X-15 research aircraft).
 In the combustion chamber, the propellant decomposes according to the
following chemical reaction, forming superheated steam and gaseous oxygen:
 H202 -- H20 + 1/202 + heat
 This decomposition is brought about by the action of catalysts such as
various liquid permanganates, solid manganese dioxide, platinum, and iron
oxide. In fact, most impurities act as a catalyst.
 H202 is hypergolic with hydrazine and will burn well with kerosene. The
theoretical specific impulse of 90% hydrogen peroxide is 154 sec, when used
as a monopropellant with a solid catalyst bed.
Nitric Acid (HNO3)
 There are several types of nitric acid mixtures that have been used as oxidizers between
1940 and 1965.
 The most common type, red fuming nitric acid (RFNA), consists of concentrated nitric
acid (HNO3) that contains between 5 and 20% dissolved nitrogen dioxide. The
evaporating red-brown fumes are exceedingly annoying and poisonous.
 Compared to concentrated nitric acid (also called white fuming nitric acid), RFNA is
more energetic, more stable in storage, and less corrosive to many tank materials. 
 Nitric acid is highly corrosive. Only certain types of stainless steel, gold, and a few other
materials are satisfactory as storage containers or pipeline materials.
 A small addition of fluorine ion (less than 1% of HF) inhibits the nitric acid, causes a
fluoride layer to form on the wall, and greatly reduces the corrosion with many metals. It
is called inhibited red fuming nitric acid (IRFNA).
 Nitric acid has been used with gasoline, various amines, hydrazine, dimethyl hydrazine,
and alcohols.
 It ignites spontaneously with hydrazine, fur-furyl alcohol, aniline, and other amines. The
specific gravity of nitric acid varies from 1.5 to 1.6, depending on the percentages of
nitric oxide, water, and impurities.
 This high density permits compact vehicle construction.
Nitrogen Tetroxide (N2O4)
 This is a high-density yellow-brown liquid (specific gravity of 1.44).
 It is only mildly corrosive when pure, but forms strong acids when moist or allowed
to mix with water.
 It readily absorbs moisture from the air. It can be stored indefinitely in sealed
containers made of compatible material.
 It is hypergolic with many fuels and can cause spontaneous ignition with many
common materials, such as paper, leather, and wood.
 The fumes are reddish brown and are extremely toxic. Because of its high vapor
pressure it must be kept in relatively heavy tanks.
 The freezing point of N204 can be lowered (by adding a small amount of nitric oxide
or NO) but at the penalty of a higher vapor pressure. This mixture of NO and N 204 is
called mixed oxides of nitrogen (MON) and different grades have been 2 and 30%
NO content.
 Nitrogen tetroxide is a storable propellant oxidizer and is used in the Titan missile
together with a fuel mixture consisting of hydrazine and unsymmetrical dimethyl
hydrazine.
 It is also used with mono methyl hydrazine fuel in the Space Shuttle orbital
manoeuvre system and reaction control system and in many spacecraft propulsion
systems.
Liquid Fuels
• Only a few have been used in production rocket
engines. Liquid fuels other than those listed below
have been used in experimental rocket engines, in
older experimental designs, and in some older
production engines.
• These include aniline, furfuryl alcohcol, xylidine,
gasoline, hydrazine hydrate, boro hydrides,- methyl
and/or ethyl alcohol, ammonia, and mixtures of some
of these with one or more other fuels.
Hydrocarbon Fuels
• Petroleum derivatives encompass a large variety of different hydrocarbon chemicals, most of
which can be used as a rocket fuel.
• Most common are those types that are in use with other applications and engines, such as
gasoline, kerosene, diesel oil, and turbojet fuel.
• Their physical properties and chemical composition vary widely with the type of crude oil
from which they were refined, with the chemical process used in their production, and with
the accuracy of control exercised in their manufacture.
• In general, these petroleum fuels form yellow-white, brilliantly radiating flames and give
good preformance. They are relatively easy to handle, and there is an sample supply of these
fuels available at low cost.
• A specifically refined petroleum product particularly suitable as a rocket propellant has been
designated RP-1. It is basically a kerosene-like mixture of saturated and unsaturated
hydrocarbons with a somewhat narrow range of densities and vapor pressure.
• RP-1 has been used with liquid oxygen in the Atlas, Thor, Delta, Titan I, and Saturn rocket
engines.
• Methane (CH4) is a cryogenic hydrocarbon fuel. It is denser than liquid hydrogen and
relatively low in cost. Experimental oxygen-methane engines have been tested, but they have
not yet flown.
Liquid Hydrogen (H2)
• Liquid hydrogen, when burned with liquid fluorine or liquid oxygen, gives
a high performance.
• It also is an excellent regenerative coolant. With oxygen it burns with a
colorless flame; however, the shock waves in the plume may be visible.
• liquid hydrogen is the lightest and the coldest, having a specific gravity of
0.07 and a boiling point of about 20 K.
• The very low fuel density requires bulky fuel tanks, which necessitate very
large vehicle volumes. The extremely low temperature makes the problem
of choosing suitable tank and piping materials difficult, because many
metals become brittle at low temperatures.
• Hydrogen burning with oxygen forms a nontoxic exhaust gas. This
propellant combination has been applied successfully to space launch
vehicles because of its high specific impulse.
• Here the payload capability usually increases greatly for relatively small
increases in specific impulse. However, the low density of hydrogen makes
for a large vehicle and a relatively high drag.
Hydrazine (N2H4)
 Hydrazine (N2H4)which is used as a bipropellant fuel as well as a
monopropellant.
 Hydrazine and its related liquid organic compounds, monomethyl
hydrazine (MMH) and unsymmetrical dimethyl hydrazine
(UDMH), all have similar physical and thermo chemical properties.
 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.
 Its vapors may form explosive mixtures with air. If hydrazine is
spilled on a surface or a cloth, a spontaneous ignition with air can
occur.
UnsymmetricalDimethyl hydrazine
[(CH3)2NNH2]
 A derivative of hydrazine, namely, unsymmetricaldimethyl hydrazine
(UDMH), is often used instead of or in mixtures with hydrazine because
it forms a more stable liquid, particularly at higher temperatures.
 Furthermore, it has a lower freezing point (215.9 K) and a higher
boiling point (336.5 K) than a hydrazine.
 When UDMH is burned with an oxidizer it gives only slightly lower
values of Is than pure hydrazine.
 UDMH is often used when mixed with 30 to 50% hydrazine. This fuel
is used in the Titan missile and launch vehicle and spacecraft engines in
50% mixtures and has been used in the lunar landing and take-off
engines.
 UDMH is used in Russian and Chinese rocket engines.
Monomethylhydrazine (CH3NHNH2)
 Monomethylhydrazine (MMH) has been used extensively as a fuel in spacecraft rocket
engines, particularly in small attitude control engines, usually with N 204 as the oxidizer.
 It has a better shock resistance to blast waves, better heat transfer properties, and a better
liquid temperature range than pure hydrazine.
 Like hydrazine, its vapors are easily ignited in air; the flammability limits are from 2.5 to
98% by volume at atmospheric sea level pressure and ambient temperature.
 The materials compatible with hydrazine are also compatible with MMH. The specific
impulse with storable oxidizers usually is 1 or 2% lower with MMH than with N 2H 4.
 Both MMH an UDMH are soluble in many hydrocarbons; hydrazine is not. All hydrazines
are toxic materials, but MMH is the most toxic when inhaled, and UDMH the least toxic.
 Atmospheric concentrations of all hydrazines should be kept below 0.1 ppm for long
periods of exposure.
 Monomethylhydrazine, when added in relatively small quantities of 3 to 15% to hydrazine,
has a substantial quenching effect on the explosive decomposition of hydrazine.
 Monomethylhydrazine decomposes at 491 K, whereas hydrazine explodes at 369 K when
subjected to pressure shocks of identical intensity.
Monopropellants
 Monopropellants are storable liquid propellants that can be induced to decompose to a gaseous state in the
presence of a catalyst (or contamination) and release heat that can be converted to thrust.
 The propellant-feed and control-system simplicity associated with a monopropellant makes this type of propellant
attractive for certain applications. Hydrazine is being used extensively as a monopropellant in small attitude and
trajectory control rockets for the control of satellites and other spacecraft and also as a hot gas generator.
 Other monopropellants (ethylene oxide or nitromethane) were tried experimentally, but are no longer used today.
Concentrated hydrogen peroxide was used for monopropellant gas generation in the USA, Russia, and Germany
in engines designed before 1955.
 Ignition of monopropellants can be produced thermally (electrical or flame heat) or by a catalytic material. A
monopropellant must be chemically and thermally stable to insure good liquid storage properties, and yet it must
be easily decomposed and reactive to give good combustion properties.
 Catalysts – Shell 405, silver/cobalt plated wire gauze, sodium or potassium permanganate, etc.
 Some monopropellants can be used in bipropellant systems as either a fuel (N2H4, UDMH) or an oxidizer (HTP),
which can enable more operational flexibility
 The performance (i.e., Isp) is lower than that of bipropellant systems, but the systems are more simple (higher
reliability).
 One drawback of monopropellant systems is that the reactive nature of the propellant requires high standards of
cleanliness to prevent uncontrolled decomposition from contaminants.
 Examples
 –Hydrogen Peroxide (H2O2, HTP) up to 90-98% concentration
 –Hydrazine (N2H4) most commonly used
 –UDMH (used in GG in RD-119)
 –HAN (hydroxyl ammonium nitrate )(experimental)
Hydrazine as a Monopropellant
• Hydrazine is not only an excellent storable fuel, but also an excellent monopropellant
when decomposed by a suitable solid or liquid catalyst; this catalyst often needs to be
preheated for fast startup.
• Iridium is an effective catalyst at room temperature. At elevated temperature (about 450
K) many materials decompose hydrazine, including iron, nickel, and cobalt.
• Different catalysts and different reaction volumes make the decomposition reaction go to
different products, resulting in gases varying in composition or temperature. As a
monopropellant, it is used in gas generators or in space engine attitude control rockets.
• The catalytic decomposition of hydrazine can be described ideally as a twostep process;
this ignores other steps and intermediate products. First, hydrazine (NzH4) decomposes
into gaseous ammonia (NH3) and nitrogen (N2); this reaction is highly exothermic, i.e., it
releases heat. Secondly, the ammonia decomposes further into nitrogen and hydrogen
gases, but this reaction is endothermic and absorbs heat. These simplified reactions can be
written as
3N2H 4 --+ 4(1 -x)NH3 + (1 + 2x)N2 + 6xH 2
Here x is the degree of ammonia dissociation; it is a function of the catalyst type, size, and
geometry, the chamber pressure, and the dwell time within the catalyst bed. Hydrazine is
manufactured in several grades of purity.
Liquid Propellants Applications

Space Military
• Booster (1st stage) •SSM
–ICBM
• Sustainer (2nd stage)
–IRBM
• USE (3rd+ stage)
–SRBM
• Descent / Ascent –SLBM
• Experimental Aircraft •SAM
• Orbit maintenance, •ASM
position control, station •AAM
keeping and spacecraft •Aircraft
attitude control
The selection of Liquid Rocket Propellants
When selecting a propellant or propellant combination for a specific application, it is well to realize that
most propellants, in addition to their advantages, may have certain disadvantages. Thus, propellant
selection usually includes some compromises. The more important and desirable propellant features are
listed below. Order of importance may vary as a function of application.
(1) High energy release per unit of propellant mass, combined with low molecular weight of the combustion or
decomposition gases, for high specific impulse.
(2) Ease of ignition.
(3) Stable combustion.
(4) High density or high density impulse to minimize the size and weight of propellant tanks and feed system.
(5) Ability to serve as an effective coolant for the thrust chamber (optimum combination of high specific heat,
high thermal conductivity and high critical temperature).
(6) Reasonably low vapor pressure at 160 ° F (a frequent specification value) for low tank weight and low net
positive pump suction head requirement.
(7) Low freezing point (preferably less than -65 ° F') to facilitate engine operation at low temperature.
(8) Absence of corrosive effects; compatibility with engine construction materials.
(9) For storables: good storability as assisted by a high boiling point (preferably above 160 ° F), by the
resistance to deterioration during storage.
(10) Low viscosity (preferably less than 10 cp) to minimize pressure drops through feed system and injector.
(11) High thermal and shock stability to minimize explosion and fire hazard.
(12) Low toxicity of raw propellants, their fumes, and their combustion products.
(13) Low cost.
(14) Availability.
Performance data for liquid propellants
Performance data for liquid propellants
General Solid Propellant Characteristics
The desirable propellant characteristics are listed below
• High performance or high specific impulse; really this means high gas temperature
and/or low molecular mass.
• Predictable, reproducible, and initially adjustable burning rate to fit the need of the grain
design and the thrust-time requirement.
• For minimum variation in thrust or chamber pressure, the pressure or burning rate
exponent and the temperature coefficient should be small.
• High density.
• Good aging characteristics and long life.
• Low absorption of moisture, which often causes chemical deterioration.
• Simple, reproducible, safe, low-cost, controllable, and low-hazard manufacturing.
• Non-toxic exhaust gases.
• Not prone to combustion instability.
• Guaranteed availability of all raw materials and purchased components Over the
production and operating life of the propellant, and good control over undesirable
impurities.
• Predictable, reproducible ignition qualities.
Advantages and Applications of Solid Propellants
Advantages:
• High thrust to weight ratio.
• High density.
• Low molecular weight of products of combustion.
• They do not require feed system.
• Comparatively simple, ease to store and handling.
• Low cost.
Applications:
• Mostly in Rockets to launch low earth orbits satellites.
• Frequently used in military applications such as missiles.
• Ramjet engine.
• Gun propellants.
• Boosters for space shuttle launch vehicles etc.
• Gas generator applications etc.
Classification of Solid Propellants
o Homogeneous propellants. (mixed together at the
molecular level).
o Composite propellant or heterogeneous propellants.
(mixed at a macroscopic level)
o Composite modified double base propellants.
o Nitramine propellants. (RDX and HMX-
Cyclotrimethylene trinitramine and Cyclotetra
methylene tetranitramine )
Monopropellants
Homogeneous Propellants.
• Uniform in physical structure.
• Nitrocellulose – O – NO2 is the basic ingredient responsible for
the structural properties of homogeneous propellants.
• All practical homogenous propellants contain nitrocellulose in
small or large proportions.
• The homogeneous propellants thermoplastic in nature. They
soften increase in temperature.
• They are treated as smokeless propellants as the combustion
products only negligible amounts of solids, soot, coloured
gases, liquids or condensable gases.
• The combustion products are mostly water vapour, nitrogen and
oxides of carbon.
Single Base Propellant
• Propellant containing only nitrocellulose as its major ingredient is
known as Single base propellant.
• The nitrocellulose is not plasticised properly with the addition of
a significant amount of plasticiser.
• The propellant has a horny structure.
• These propellant powders are processed through solvent extrusion
process or ball powder process.
• Single base propellants are mainly used as gun propellants.
Nitrocellulose powders filled in the cartridge cases for pistols,
rifles, anti aircraft guns etc.
Double Base Propellant
• Double base propellants contain two energetic ingredients ie.
Nitrocellulose (fuel) and nitroglycerine (oxidizer) O – NO2 .
• nitroglycerine is used to plasticise the high molecular weight
nitrocellulose to yield a thermoplastic material.
• Nitrocellulose and nitroglycerine are high explosives each capable
of undergoing detonation with a detonation velocity of 6-7 km/s.
• The double base propellant has a density close to 1.6 g/cc and the
burning rate of commonly used double base propellants vary
between 5 to 20 mm/s under standard conditions and the heat of
combustion generally varies from 900 to 1200 calories per gram.
• Other complatible nitric esters like glycol dinitrate , diethylene
glycol dinitrate , metriol trinitrate etc.
Double Base Propellant
• Various process techniques such as solvent extrusion, solventless
extrusion, slurry casting and interstitial casting are used for
processing double base propellants depending on the requirements
of grain and geometry.
• Double base propellants are used as gun propellants. They can also
be case bonded to suit the thrust programme/mission requirements.
These two varieties are well suited for short range missiles,
sounding rockets.
• Double base propellants are also used for specialized applications
as in aircraft seat ejection cartridges, propellant assisted ship
engine starters, jet assisted aircraft take off systems etc.,
• Double-base (DB) propellants form a homogeneous propellant grain, usually a
nitrocellulose (NC*), a solid ingredient which absorbs liquid
• nitroglycerine (NG) plus minor percentages of additives. Both the major
ingredients are explosives and function as a combined fuel and oxidizer.
• Both extruded double-base (EDB) and cast double-base (CDB) propellant have
found extensive applications, mostly in small tactical missiles of older design.
• By adding crystalline nitramines (HMX or RDX)* the performance and density
can be improved; this is sometimes called cast-modified double-base propellant.
• A further improvement is to add an elastomeric binder (rubber-like, such as cross
linked polybutadiene), which improves the physical properties and allows more
nitramine and thus improves the performance slightly. The resulting propellant is
called elastomeric-modified cast double-base (EMCDB).
• These four classes of double base have nearly smokeless exhausts. Adding some
solid ammonium perchlorate (AP) and aluminum (A1) increases the density and
the specific impulse slightly, but the exhaust gas is smoky. The propellant is
called composite-modified double-base propellant or CMDB.
Triple base propellants
• A triple base propellant contains NC, NG and NQ
(Nitroguanidine).
• Nitroguanidine is an aliphatic nitramine with the characteristic N-
NO2 group.
• The triple base propellants formulation can be processed into
grains with reasonably good mechanical properties.
• They are also ballistically more stable and safe to use. These
propellants are smokeless in nature and are less erosive because
of their flame temperature.
• They are produced by solvent extrusion technique.
Ingredients for Homogenous Propellants
• Explosive plasticisers.
(NC, NG,NQ, and RDX)
• Inert plasticisers. Some solid plasticiser ( camphor, centralite, DNT) (TA,
DBP, DEP etc)
to reduce the sensitivity of NG.
to improve the mechanical properties of the propellant.
to adjust the energy level and burn rate.
to modify the processing characteristic of the propellant.
• Stabilisers.
During storage, the nitric esters under goes slow decomposition releasing
oxides of nitrogen. Once initiated further decomposition of nitrocellulose
is accelerated by the catalytic effect of the oxides. In order avoid this
stabilisers are added to retard the rate of decomposition of nitrocellose and
nitroglycerine . The commonly used stabilisers are diphenylamine,
orthonitro diphenyl amine, carbazole, centralite I and centralite II, aniline,
diphenyl benzamide etc..
Ingredients for Homogenous Propellants
• Burn rate modifiers. Fine carbon black, KP, Al etc..
• Darkening agents.
Darking agents such as carbon black in 0.1 to 0.5% are added to make the
propellants opaque.
• Platonising Agents: ballistic agent used to reduce the pressure index are known
as Platonising agents.
the n values of DBP are lies between 0.5 to 0.8. This can cause rapid increase
in chamber pressure and failure of the rocket motor. In order to lower values
of n the burning rate is less dependent on the pressure. Certain lead compounds
typically added to the propellants they are lead stearate, lead salicilate, lead
ethyl hexoate etc..
• Combustion instability suppressers.
Al,Zr etc…
• Flash and smoke suppressers.
Dinitrotoluene, potassium nitrate, potassium sulpahate and potassium cryolite
are used as flash suppressers.
Ingredients for Homogenous Propellants
Processing of Homogeneous Propellants
• Extrusion and Casting are two methods adopted for the
processing homogeneous propellants.
• Extrusion done by solvent or solventless process
depending on the use of a volatile solvent for achieving
the extrudable (plastic like) consistency for the
propellant mix.
• The casting done by either slurry casting process or
interstitial casting process.
Composite Propellants
• Heterogeneous solid propellants are basically made by physically mixing two
essential ingredients, oxidizer and fuel.
• Usually, the oxidizer is a solid, in particulate or powdery form; the fuel is
originally a highly viscous polymeric liquid referred to as a “pre-polymer”,
which after mixing with the solid oxidizer particles is solidified into a rubbery
solid by polymerisation a process known as curing.
• The polymeric fuel then acts as “binder” and it is popularly called so, in that it
binds all the oxidizer particles together in a composite solid form. For this
reason heterogeneous propellants is more commonly referred to as ‘Composite
Propellants”.
• The type and combination of ingredients used in the propellants for these
varied applications differ widely, depending upon the performance
requirements.
• Non – uniform physical structures.
Ingredients for Composite Propellants
o Oxidisers – AP, AN, KN and ADN etc.
o Fuels or Pre - Polymers – PVC, CTPB, HTPB etc.
o Plasticiser - DOA, DOP and DMP etc.
o Curing agent – TDI, IPDI, DDI and MDI etc.
o Metal fuel – Al, B, Be and Mg.
o Burn rate modifier – Fe2O3, Cu2Cr2O5 and LiF etc.
o Additives
Oxidizer
Ammonium Perchlorate:
• AP is a white crystalline solid, usually in powdery form. The crystals are
orthorhombic in structure at room temperature.
• AP is actually a monopropellant by itself, being oxidizer rich, and can
sustain self-deflagration above about 20 bar.
• In order to reduce the problem of clumping anti caking agents are used as a
coating on the AP particles. Typical anti-caking agents are tri-calcium
phosphate, preosil and fertflow.
• Propellants with fine AP burn faster in general than those with coarse AP.
• The AP based composite propellants usually produce white smoke on
combustion.
Ammonium Dinitramide:
• At present, there is good promise of ADN being used in propellants widely
in the future.
• ADN has a low melting point of around 90ºC and hygroscopic. High
temperature curing with AND propellants may be a significant problem.
• The propellant with coarse ADN burn faster than the fine AND. Very high
burning rate are achievable with the coarse AND.
Oxidizer
• Naturally crystallized AND appears in needle- shapes particle, which is not
convenient to propellant processing and performance. In order to overcome
this problems a method known as “Prilling” employed wherein, molten ADN
is atomized and crystallized into round particles.
Ammonium nitrate and Potassium perchlorate:
• AN is used in some application because of its low cost and smokeless and
relatively non toxic exhaust.
• AN changes its crystal structure at several phase transformation temperature,
which makes it somewhat thermally unstable.
• Its principal uses is with low burn rate, low performance rocket and gas
generator application.
• Main advantage using PSAN is its non-chlorinated nature.
• Propellants with KP have unacceptable levels high pressure exponent of
burning rate which cannot be easily controlled.
• But it is quite stable, offer acceptable performance.
Pre –Polymer or Binder
• The pre-polymer is usually a highly viscous liquid at standard conditions,
wherein giant molecules exert week Van der Waal’s forces on each other.
• The molecular weight of the pre-polymer runs into few thousands.
• The pre-polymer responsible for the mechanical integrity of the propellant
grains.
• Composite propellants for commercial rocket applications, the original choice of
binders was poly sulphide, poly urethane, poly styrene, poly vinyl chloride etc..
• Higher hydrocarbon based polymer were used to obtain the product gases with
low molecular weight and high specific impulse. With the emergence of the
poly-butadiene class of binders, like PBAA, PBAN,CTPB and HTPB.
• Now new energetic binders such as GAP are emerging which have the potential
of replacing HTPB.
• Lower viscosity of a pre-polymer enables easier propellant processing and
greater solid loading.
Plasticiser
• The plasticiser is a relatively low viscosity organic liquid added to the
propellant at about 2-3% level.
• The plasticiser is not considered to affect the ballistic performance of the
propellant and burning behavior.
• During the binder melt flow characteristics of the propellant cause the plateau
burning behavior, small change in the plasticiser concentration can somewhat
affect the plateau characteristics .
• Addition of a plasticiser has multiple effects:
– Lower viscosity of the propellant slurry for better mixing and casting.
– Improvement of the elongation characteristics of the binder, particularly at
low temperatures.
– Increase in the pot life of the propellants.
• Typical plasticisers materials are DOA,DOP,IDP, DMP,DOS etc..
Curing Agent
• Together with the pre-polymer, the curing agent dictates structural integrity of
the propellant grain.
• Curing agent will create a groups of cross-linked network.
• The choice of curing agent depends directly on the pre-polymer to be used in the
binder.
• The choice and amount of curing agent can influence a number of properties of
the propellant.
- the mixing process
- pot life
- aging characteristics
- binder melt flow, combustion and burning rate.
• Plateau burning rate and bi-plateau burning rate curves are possible under select
set of propellant formulation conditions by altering the curing agent alone.
• For PBAN,epoxy curing agents such as diepoxide/aziridyne are generally used.
• For CTPB,HTPB a rather wide class of di-isocyanate curing agent are used as
IPDI,TI,DI,MDI and HMDI etc…
Metal Fuels
• The main purpose of addition of metals in composite propellants is to increase
the temperature of the final combustion products that are exhausted out of the
rocket motor. The conversion of a correspondingly high thermal energy of the
product gases into kinetic energy in the nozzle results in increased specific
impulse of the propellant.
• Metals are also relatively dense .
• The choice of metals for use in propellants has been restricted mainly to Al,
Mg, B, and Be.
• Powdered spherical aluminum is the most common. It consists of small
spherical particles (5 to 60 lam diameter) and is used in a wide variety of
composite and composite-modified double-base propellant formulations,
usually constituting 14 to 20% of the propellant by weight.
• During rocket combustion this fuel is oxidized into aluminum oxide. These
oxide particles tend to agglomerate and form larger particles.
• The aluminum increases the heat of combustion, the propellant density, the
combustion temperature, and thus the specific impulse.
Metal Fuels
• Boron is a high-energy fuel that is lighter than aluminum and has a high
melting point (2304°C). It is difficult to burn with high efficiency in
combustion chambers of reasonable length.
• However, it can be oxidized at reasonable efficiency if the boron particle size
is very small.
• Boron is used advantageously as a propellant in combination rocket-air-
burning engines, where there is adequate combustion volume and oxygen from
the air.
• Beryllium burns much more easily than boron and improves the specific
impulse of a solid propellant motor, usually by about 15 sec, but it and its
oxide are highly toxic powders absorbed by animals and humans when
inhaled.
• The technology with composite propellants using powdered beryllium fuel has
been experimentally proven, but its severe toxicity makes its application
unlikely.
Burning rate (or) Ballistic modifier
• Burning rate and its pressure exponent are crucial parameters
directly involved in the design of a rocket motor.
• Propellant developers have to adjust the burning rate of the
propellant with a particular choice of formulation variables to the
levels that are required to meet mission specification.
• There are two kinds of burning rate modifiers: one that enhances the
burning rate is called Burning rate catalyst and those that depress it
is called Burning rate Depressant.
• Burning rate catalyst are ferric oxide, titanium dioxide, copper
chromite etc.Burning rate Depressant is lithium flouride etc.
• Burner rate modifier are also frequently referred as Ballistic
modifiers.
• To study effect of addition of several inorangic materials on burning
rate of composite rocket propellants known as Flexolite.
CMDBP
• The specific impulse of homogeneous propellants is remarkably low
compared to modern high energy composite propellants.
• In conventional DBP adjustment in energy level is made by varying
the percentage of nitrocellulose, nitroglycerine and inert components .
• The maximum specific impulse of practical DBP is of the order of
250 s with an NG content of 45%. NC is oxygen deficient by 30%
where as NG is oxygen surplus by 3.5%.
• The practical DBP is under oxidized from the point of view of
energetics. The energy level of the propellant can be increased by
supplementing oxygen.
• The propellants formed by adding AP or HMX to DBP are known as
CMDBP.
• They are used for missile propulsion and upper stage solid propellant
rockets.
Nitramine Propellants
• High explosives such as HMX and RDX are added to fuel binder comprising
HTPB or GAP instead of AP and cured to form nitramine propellants.
• During combustion , the hydrocarbon gases from the polymer combine with the
fuel rich products of HMX and RDX to form low temperature products.
• Completed products of combustion such as CO2 and H2O will be absent.
Because both RDX and HMX are oxygen deficient by 21.6%.
• The polymeric binder acts as a coolant instead of burning the fuel rich products
of HMX and RDX.
• The infra-red radiation from the products is therefore reduced.
• The propellants formed by the addition of HMX and RDX to composite
propellants having small amounts of oxidiser AP.
Variation of combustion temperature, average molecular mass of the combustion
gases, and theoretical specific impulse (at frozen equilibrium) as a function
of oxidizer concentration for HTPB-based composite propellants. Data are for a
chamber pressure of 68 atm and nozzle exit pressure of 1.0 atm.
Selection of Composite Propellant Formulations
A propellant formulation is characterized by the following parameter
• Types of ingredients
• Total solid loading
• Metal content
• Oxidizer content
• Oxidizer particle size
• Relative fraction of fine and coarse particle
• Metal particle size
• Curing agent concentration
• Plasticizer concentration
Gelled Propellants
• Gelled propellants have additives that make them thixotropic materials.
They have the consistency of thick paint or jelly when at rest, but they
liquify and flow through pipes, valves, pumps, or injectors when an
adequate shear stress is applied.
• Inert solid particles can be suspended in oxidizer liquids. This increases
propellant density, density impulse, and thus reduces the size of tanks and
vehicles. Smaller vehicles have reduced drag and thus can allow an
increase in the range or speed of tactical missiles.
Advantages of Gelled Propellant
 There is no plugging of injector orifices or valve passages and good flow control
has been demonstrated.
 Individual gelled fuel propellants will be essentially nonflammable and will not
usually sustain an open fire.
 There is reduced susceptibility of leakage or spill, reduced sloshing of liquids in the
tanks, and the boil-off rate is reduced.
 Long-term storage without settling or separation is possible; more than 10 years has
been demonstrated.
 Explosions or detonations, which happen when a vehicle accident causes liquid
propellants to become inadvertently premixed, are much less likely with gelled
propellants, which are difficult to mix.
 Many spilled gelled propellants can be diluted with water and disposed of safely.
 Short-duration pulsing is possible.
 Most storable oxidizers, a few cryogenic propellants, and most liquid storable fuels
can be gelled.
 Explosions are much less likely when a propellant tank is penetrated by a bullet
Disadvantages of Gelled Propellants
• There is a small decrease in specific impulse due to dilution with a gelling agent, and less
efficient atomization or combustion. For example, the characteristic velocity c* of oxygen-
kerosene propellant is decreased by 4 to 6% when the kerosene is gelled and aluminum is
suspended in the fuel.
• When both the fuel and a nitric acid oxidizer are gelled, the performance loss (c*) can be as
high as 8%. Clever injector design and the selection of good gelling agents can reduce this
loss.
• Loading or unloading of propellants is somewhat more complex.
• Residual propellant quantity may be slightly higher, because the thixotropic fluid layer on
the walls of the tanks and pipes may be slightly thicker.
• Changes in ambient temperature will cause slight changes in propellant density and viscosity
and therefore also in mixture ratio;
• this can result in more leftover or residual propellant and thus in a slight reduction of
available total impulse. This can be minimized by careful selection of gelling agents so as to
match the rheological property changes of oxidizer and fuel over a particular temperature
range.
• Suspended metals can make the plume smoky and visible.
• Some gelling agents have resulted in unstable gelled propellants; that is, they separated or
underwent chemical reactions.
HYBRID ROCKET PROPELLANTS

• The classical hybrid containing an inert solid

fuel and liquid oxidizer has the largest
inventory of propellants, whereas the reverse
hybrid is more restricted. This is because
suitable solid oxidizers are limited in number,
are usually crystalline, and are difficult to cast
in moderate-to-large sizes because of
mechanical property limitations.
HYBRID ROCKET FUELS
• From the natural rubbers, the largest class of suitable fuels, based on performance and
mechanical properties, is the polymeric synthetic rubbers based on the polybutadiene
monomer, (PB with the formula C4H6). Typical polymers based on PB PB–
acrylonitrile (PBAN), PB–acrylic acid (PBAA), HTPB, and carbon-terminated PB
(CTPB). The most popular of this group, based on cost and commercial availability, is
HTPB. As with all of these polymers, they require curatives to polymerize, the favorite
ones being the diisocyanates (DI) such asTDI, DDI, and IPDI.
• A good working composition for the PBs is C4H6O0.1. Other hydrocarbons that have
been used, mostly in smaller motors to date, are the paraffin waxes, polyethylene (a
higher molecular weight version of paraffin), Plexiglas (Lucite), metatoluene
diamine/nylon, and, in earlier small-scale testing, the common fuels, coal and wood.
• The formulated fuels, PB polymers, and paraffin waxes, have the virtue of allowing
performance additives. A partial list of these additives include Al, AlH3, Li, LiH,
LiAlH4, Li3AlH6, B, B10H14, LiBH4, aromatic amines, anthracene, etc. These additives
can enhance either motor performance through Isp improvement or vehicle
performance through increased density and, hence, mass fraction.
• Another class of fuels is the cryogenic solids, including pentane, methane, CO, O2, and
H2.
HYBRID ROCKET OXDIZIERS
• The hybrid liquid oxidizers and those used in the liquid rocket
engines are essentially the same. These include O2, N2O, N2O4,
HNO3, inhibited red fuming nitric acid (IRFNA), FLOX( 2/3
F2 + 1/3 O2),H2O2, CTF (ClF3) and hydroxyl amine nitrate
(HAN). Of this group, the most energetic are O2 and FLOX.
Although F2 is very energetic, it has not reached operational
status because of its toxicity and corrosivity. FLOX, on the
other hand, is much less corrosive, can be used with
conventional carbonaceous fuels, and is much less hazardous
to use.
Reversed Hybrid Rocket Propellants
• The reverse hybrids are low performing except for
nitronium perchlorate (NP), which, however, is
thermally sensitive and potentially explosive. The
combination that most closely resembles the JP-4 (or
kerosene).
Performance of the Hybrid Rocket Propellants
• The table shows performance of the hybrid rocket propellants.
Typical Criteria Used in the Selection of a
Particular Rocket Propulsion System
• Mission Definition
Purpose, function, and final objective of the mission of an overall system are well defined and
their implications well understood. There is an expressed need for the mission, and the
benefits are evident. The mission requirements are well defined. The payload, flight regime,
vehicle, launch environment, and operating conditions are established.
• Affordability (Cost)
Life cycle costs are low. They are the sum of R&D costs, production costs, facility costs,
operating costs, and decommissioning costs, from inception to the retirement of the system.
Benefits of achieving the mission should appear to justify costs. Investment in new facilities
should be low.
• System Performance
The propulsion system is designed to optimize vehicle and system performance, using the
most appropriate and proven technology. Inert mass is reduced to a practical minimum, using
improved materials and better understanding of loads and stresses. Residual (unused)
propellant is minimal. Propellants have the highest practical specific impulse without undue
hazards, without excessive inert propulsion system mass, and with simple loading, storing,
and handling. Thrust-time profiles and number of restarts must be selected to optimize the
vehicle mission.
Typical Criteria Used in the Selection of a
Particular Rocket Propulsion System
• Survivability (Safety)
All hazards are well understood and known in detail. If failure occurs, the risk of personnel
injury, damage to equipment, facilities, or the environment is minimal.
• Reliability
Statistical analyses of test results indicate a satisfactory high-reliability level. Technical risks,
manufacturing risks, and failure risks are very low, well understood, and the impact on the
overall system is known. There are few complex components. Adequate storage and operating
life of components (including propellants) have been demonstrated. Proven ability to check
out major part of propulsion system prior to use or launch.
•  Controllability
Thrust buildup and decay are within specified limits. Combustion process is stable. The time
responses to control or command signals are within acceptable tolerances. Thrust vector
control response must be satisfactory.
• Maintainability
Simple servicing, foolproof adjustments, easy parts replacement, and fast, reliable diagnosis of
internal failures or problems. Minimal hazard to service personnel. There must be easy access
to all components that need to be checked, inspected, or replaced. Trained maintenance
personnel are available. Good access to items which need maintenance
Typical Criteria Used in the Selection of a
Particular Rocket Propulsion System
• Geometric Constraints
Propulsion system fits into vehicle, can meet available volume, specified length, or
vehicle diameter. There is usually an advantage for the propulsion system that has the
smallest volume or the highest average density. If the travel of the center of gravity has
to be controlled, as is necessary in some missions, the propulsion system that can do
so with minimum weight and complexity will be preferred.
• Prior Related Experience
There is a favorable history and valid, available, relevant data of similar propulsion
systems supporting the practicality of the technologies, manufacturability, performance,
and reliability. Experience and data validating computer simulation programs are
available. Experienced,
skilled personnel are available.
• Operability
Simple to operate. Validated operating manuals exist. Procedures for loading
propellants, arming the power supply, launching, igniter checkout, and so on, must be
simple. If applicable, a reliable automatic status monitoring and check-out system should
be available.
Typical Criteria Used in the Selection of a
Particular Rocket Propulsion System
• Producibility
Easy to manufacture, inspect, and assemble. All key manufacturing processes are
well understood. All materials are well characterized, critical material properties
are well known, and the system can be readily inspected. Proven vendors for key
components have been qualified. Uses standard manufacturing machinery and
relatively simple tooling. Hardware quality and propellant properties must be
repeatable. Scrap should be minimal. Designs must make good use of standard
materials, parts, common fasteners, and off-the-shelf components.
• Schedule
The overall mission can be accomplished on a time schedule that allows the system
benefits to be realized. R&D, qualification, flight testing, and/or initial operating
capability are completed on a preplanned schedule. No unforeseen delays. Critical
materials and qualified suppliers must be readily available.
Typical Criteria Used in the Selection of
a Particular Rocket Propulsion System
• Environmental Acceptability
• No unacceptable damage to personnel, equipment, or the surrounding countryside. No toxic
species in the exhaust plume. No serious damage (e.g., corrosion) due to propellant spills or
escaping vapors. Noise in communities close to a test or launch site should remain within
• tolerable levels. Minimal risk of exposure to cancer-causing chemicals. Hazards must be
sufficiently low, so that issues on environmental impact statements are not contentious and
approvals by environmental authorities become routine.
• Reusability
• Some applications (e.g., Shuttle main engine, Shuttle solid rocket booster, or aircraft rocket
assisted altitude boost) require a reusable rocket engine. The number of flights, serviceability,
and the total cumulative firing time then become key requirements that will need to be
demonstrated. Fatigue failure and cumulative thermal stress cycles can be critical in some of
the system components. The critical components have been properly identified; methods,
instruments, and equipment exist for careful check-out and inspection after a flight or test
• (e.g., certain leak tests, inspections for cracks, bearing clearances, etc.). Replacement and/or
repair of unsatisfactory parts should be readily possible. Number of firings before disassembly
should be large, and time interval between overhauls should be long.
END