Explosives and Propellants

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introduction
 Propellants and explosives are chemical compounds or their
mixture that rapidly produce large volume of hot gases when
properly initiated.
or
 An explosive is chemical compound, either solid, liquid or gas in
an unstable state. when suitably initiated by shock, friction or
heat, they undergo a rapid chemical change from their original
compound into one or more stable compounds, usually gases.
 In the process of changing from an unstable to stable compound
they give out energy in the form of heat, light or sound, which as
a final result is violent explosion of gases.

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Introduction Conti…
 Propellants burns at relatively low rates measured in
centimetres per second, whereas explosives detonates at rates
of kilometres per second.
 Explosion is a process of internal burning.
 Instead of the O2 being supplied in the form the surrounding air,
it is supplied in the form of oxidizers or oxidants and is actually a
solid material that is in intimate contact with fuel.
 An activation energy of 125-250kJ/mol is usually required to
initiate the reaction, at which point the heat evolved is sufficient
to cause the reaction to continue and become self-sustaining.
 Ammonium nitrate, ammonium perchlorate or other inorganic
salts are used as a source of oxygen.

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uses

 Commercial explosives are essential to such industries as

mining, construction, geophysical exploration, and forming major
engineering jobs such as construction of tunnels, and Dams
would be impossibly expensive without explosives.

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Types of Explosives
 Explosives differ widely in their sensitivity and power

 Only those of comparatively insensitive nature, capable of being

controlled and having a high energy content are of importance
industrially or militarily.

 There are three fundamental types of explosives

 1) Mechanical
 2) Atomic
 3)Chemical

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Mechanical Explosive:

A mechanical explosive is one that depends on a physical action,

such as overloading a container with compressed air.

Atomic Explosives:

Atomic explosives or nuclear explosive is one in which a sustained

nuclear reaction can be made to take place with almost instant
rapidity, releasing large amounts energy.

Chemical Explosives:

 A chemical explosive is one that depends on a chemical

reaction.

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Chemical explosives
 Chemical explosives are divided into two categories in
accordance with their behaviour

1)Detonating or high explosives

a) Primary or initiating explosives (detonators)
b) booster and secondary explosives

2)Deflagrating or low explosives

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 Difference between Detonating &
Deflagrating
 There is a very great difference between the detonating and
deflagrating explosives.

 High explosives detonate at very high rates, from 2 to 9 x 103

m/s and the reaction front is a shock phenomenon moving
throughout the material

 Low explosives burn in layers to the surface at low rates around

10-2 m/s .

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Initiating or Primary Explosives
 Primary explosives are materials that are quite shock and heat
sensitive and that can be made to explode by the application of
the shock, flame, friction or heat source.
 They are very dangerous and are used in comparatively small
quantities to start the explosion of larger quantities of less
sensitive explosive.
 They are usually inorganic salts while the other conventional are
organic.
 Some primary explosives are mercury fulminate[Hg(ONC)2] ,
lead azide Pb(N3)2, basic lead styphnate ( tri nitro resorcinate),
diazodinitrophenol, and tetrazine ( a complex conjugated
nitrogen compound).

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 Most priming compositions consist of mixture of primary
explosive, fuel, and oxidant.
 An example is
 15% antimony sulfide, 20 % lead azide, 40% basic lead
styphnate, 20% barium nitrate and 5 % tetrazine.

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Booster High Explosives
 Booster high explosive are materials that are insensitive to
mechanical shock, and flame.

 But they explode with great violence when set off by an

explosive shock, such as obtained by detonating a small amount
of a primary explosive in contact with it.

 Thus they are energy amplifiers.

 Decomposition occurs, which is rapid rupturing of bonds
progressing directly through the mass of explosive.

 Detonating is thought to be a chain reaction and proceed at

rates around 6000m/s.
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 High rate of energy release makes the product explosive
rather than the total amount of energy release.

 As Nitro-glycerine has only one-eighth the energy of an

equivalent mass of gasoline.

 Most explosives when unconfined and unshocked will merely

burn if ignited.
 Important booster are RDX ( cyclo-trimethylene-tri-nitramine),
PENT ( pentarythritol-tetranitrate) , tetryl( 2,4,6, trinitrophenyl
methyl nitramine) , HMX ( cyclo tetramethylene tetranitramine)

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Blasting Agents:
 blasting agents are power full explosive agents.
 They are less sensitive (safe to handle) but more energetic and
also used to detonate secondary explosive.
 It is a mixture of fuel and oxidizer
 An example is a mixture of NH4NO3 and carbonaceous
combustibles as fuel oil or coal.
 They can not be detonated by mean of blasting cap when
unconfined.
 Blasting Cap
 A blasting cap is a small sensitive primary explosive device
generally used to detonate a larger, more powerful and less
sensitive secondary explosive such as TNT, dynamite.
 Blasting caps come in a variety of types as electric caps and
fuse caps. 13
 The need for blasting caps arises from sensitivity issues of an
explosive compound. All explosive compounds require a certain
amount of energy to detonate. If an explosive is too sensitive, it
may go off unexpectedly, so most commercial explosives are
formulated to be stable and safe to handle and will not explode if
accidentally dropped, mishandled, or exposed to fire. However,
such explosives (called secondary explosives) are hard to
detonate intentionally as well. A blasting cap contains an easy-
to-ignite explosive that provides the initial activation energy to
start a detonation in a more stable explosive.
 The blasting cap is stored separately
and not inserted into the main
explosive charge until just before use,
keeping the main charge safe

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 Slurry explosive
 slurry explosive are ammonium nitrate mixtures which frequently
contain another oxidizer as well as fuel dispersed in a fluid
medium.

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Explosives characteristics
 Evaluation of the explosive characteristic of a material is mainly
based on the assessment of following factors.
1. Test for sensitivity to impact and heat.
2. Stability on storage
3. Shattering ability (measure of the rapidity with which an
explosive develops its maximum pressure)
4. Explosive strength per unit weight
5. Volatility
6. Solubility, density, hygroscopicity
7. Compatibility with other explosives
8. Additives and other possible metal used for inclosure
The above mentioned test must be run in standard
manner.
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 Explosives use in mines and coal mine be of such a
type that on explosion they evolve less amount of
toxic gases and produce a minimum of flame. This
requirement assures that the explosive is incapable
of igniting mixture of air and coal dust or methane.

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Industrial Explosives
 History
 Cost per unit of work done is almost as important as safety for
industrial explosives. Present agents are less expensive and far
safe than their predecessors.
 Initially mixture of KNO3 , S, and charcoal in 75:15:10ratio, also
known as black powder, was used as blasting agent.
 On combustion its flame have great ignition power which is
suitable for certain type of work, specially for propellant ignition.
 Blasting agents and Slurry Explosives
 These explosive have become the principal industrial explosives
because they may be handled simply without danger and also
their cost is very low.
 These are ammonium nitrate mixtures sensitized with non-
explosive fuels such as oil or wax. properly initiated such
mixtures produce energies surpassing that of dynamite.
 NH4NO3 is the world’s most widely used explosive substance. 18
Nitro-glycerine and Dynamite

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Propellant for Rocket and Missiles
 Propellant:
 Propellants are mixtures of chemical compound that produce
large volume of gas at controlled, predestined rates.
 Their chief application are in launching projectiles from guns,
rockets, and for missiles system.
 Propellant for Guns:
 Black powder is the oldest propellant known. but its today use is
trivial.
 It burns far too fast for propellants use,if the ingredients are left in
finely divided form. hence large grains are used for better results.
 Black powder remains the best igniter available.

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 Smokeless powder:
 Smokeless powder(nitrocellulose based) replaced black powder
for several reasons.
 Its smoke less
 Its superior power and better storage characteristics.
 Principally because it can be formed into stable grains whose
size and shape governs the burning characteristics.
 Smokeless powder colloidal cellulose nitrate, usually contains a
plasticizer(such as nitro-glycerine or nitroglycol).
 Plasticizers increase the fluidity or plasticity.
 Some times non-explosive plasticizers such as dibutyl phthalate
is added and usually about 1% of diphenylamine to improve its
storage life.
 When only nitrocellulose of over 13% nitrogen content ,it is
known as single base powder.
 When two or more explosive ingridients are used it is called
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double grain powder.
Nitrocellulose

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Propellants for Rockets
 Rocket propulsion systems derive their energy from chemical
source.
 Rocket propellants are low explosives, which consist of fuels,
containing its own oxidant or necessary reactants for reaction
to proceed.
 The thrust of the escaping hot gases push the rocket forward,
according to Newton’s 3rd Law of Motion.
 High performance systems under fine control are used for
launching the missiles and spacecrafts.

 Selection of the propellant ingredients is important to generate

high chamber temp. & pressure.

 Fuel should be one which provides greater amount of heat for

smallest amount of weight. 23
Types of Propellants
 There are two types of propellants
1) Liquid Propellants 2) Solid Propellants
Liquid Propellants:
 Are those added to the combustion chamber as liquid.
 Liquid fuels are, for the most part, used in bipropellant
systems(fuel and oxidizer stored in two fuel tanks and fed
separately too the combustion chamber)
 Monopropellant combine the fuel and oxidizer in one mixture.
 Liquid propulsion systems are the mean for achieving the
propulsive energy require for human space travel.
 High performance rocket now use LOX(liquid O2 ) and LH2(liquid
H2) propellants, because of their high thrust and low cost.
 Greater storage efficiency is achieved by catalytic conversion of
nearly all the H2 to para form.
 (see table 22.5 for better known liquid propellants)
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Para Hydrogen:
 Hydrogen gas ordinarily is a mixture of two molecular forms, ortho-
and para-hydrogen, which differ by the spins of their electrons and
nuclei.
 These two types of diatomic hydrogen have different energy states.
In "ortho" H2, which is the most common form at room temperature,
the nuclei have "anti-parallel" spins.
 In "para" H2 the nuclei have parallel spins.

 "Ortho" H2 is less stable than "para" at liquid hydrogen

temperatures. It spontaneously changes to the "para" form,
releasing energy, which vaporizes a portion of the liquid.

 By using a catalyst such as hydrous ferric oxide to convert most of

the hydrogen to the more stable form during the liquefaction
process, the liquid hydrogen product can be stored without
excessive vent loss.
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Solid Propellants:
Solid propellants rocket have advantages over liquid in that
1. They are simple in design
2. And more easily stored, handeled or serviced.
3. They cost less.
4. The ingredients are combined in a mold which serves to
confine the material and impart the desired grain configuration.
5. They can be launched easily (and efficiently) and predicted
burning rates can be achieved.
Solid propellants are classified into two groups
1) Homogeneous 2) Heterogeneous or composite propellants
Heterogeneous:
Are those in which oxidizer and reducer(fuel) present in two distinct
phase.

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Homogeneous:
Are those in which oxidizer and reducer in a single or colloidal
phase. Or they differ from composite propellants by having the
oxidizing and reducing function in a same molecule. e.g
nitrocellulose dissolved in nitro-glycerine give a rubbery gelled
structure.
Uses:
solid fuels have verity of applications like missiles, target drones, in
rockets used for separation of stages during flight.

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Matches
The manufacture of matches is an essential industry.
 They fall into two categories
1) Strike-anywhere matches 2) Safety matches
Strike-anywhere matches
The match head composition consist of Phosphorous sesquisulfide (P4S3) ,
an oxidizing agent such as Potassium or barium chlorate, ground glass
and glue.
They can be ignited by striking on any suitable surface.
Safety matches:
Safety matches are ignited by the generation of heat on the striking
surface of the box.
The striking surface on modern matchboxes is typically composed of 25%
powdered glass or other abrasive material, 50% red phosphorus, 5%
neutralizer(ZnO), 4% carbon black and 16% binder and the match head is
typically composed of 45–55% potassium chlorate, with a little sulfur and
starch, 20–40% of siliceous filler, diatomite and glue.
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Military Explosives
 Cost is less vital in the case of military explosives and accent is on
performance and good storage life.
 More organic materials are used, but ammonium nitrate remains the
major explosive substance.
 Some of the military explosives used for military are as under
TNT(tri-nitrotoulene):
TNT remains an important military explosive, particularly in mixture with
ammonium nitrate. Its low boiling point(80Co) permit loading into bombs
and shells into molten state.
TNT is made by multiple stage nitration of toulene with a mixture of
nitric and sulfuric acid.
The stages of nitration are, mono-, di-, and tri-nitrotoulene was formerly
used, but continuous flow stirrer tank reactors and tubular reactors are
also used that permit better yield, control and low cost.

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Tetryl:
Tetryl [ 2,4,6-trinitrophenylmethylnitramine], C6H2(NO2)3NCH3NO2]
is chiefly used as a base charge in blasting caps, as booster in
high explosives shells and as an ingredient of binary explosives.
It is generally prepared by the reaction of mixed sufuric and nitric
acid on dimethylaniline in a multi-stage nitration.

C6H5N(CH3)2 + 2HNO3  C6H3N(CH3)2.NO2.NO2 + 2H2O

+ 8HNO3  +6NO2 + CO2 + 6H2O

Tetryl is a powerful high explosive with intermediate sensitivity and

great shattering power.

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Picric Acid:
Picric acid( 2,4,6 trinitrophenol) is not made by the direct nitration of
phenol, because too many oxidative by products are formed.
It is manufactured by the nitration of mixed phenol sulphonates with
mixed acid.

Explosive-D:
explosive-D or ammonium picrate(NH 4OC 6H 2(NO 3) 3) is made ny
the neutralization of a hot aqueous solution of picric acid with
aquesous ammonia.
It is used in armor-piercing shell (is a type of ammunition designed
to penetrate armor ) as a bursting charge.

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PENT: (penta erythritol tetranitrate) ( C(CH2ONO2)4 )
PENT is one of the most sensitive of military high explosives.for use as a
booster explosive, a bursting charge. It is desensitized by mixing with TNT
or by Wax.
PENT may be made by the nitration of pentaerythritol with strong HNO3 at
about 50Co.
PENT is used in making detonating fuses and commercial blasting
caps and small medicinal use.
The reaction of decomposition probably
C(CH2ONO2)4  3CO2 + 2CO + 4H2O + 2N2
RDX: (Research & Development Explosive)
 ( cyclo-trimethylene-tri-nitramine )It is one of the most power ful
explosive known at the present time.
 RDX is used in a mixture with TNT and Aluminium, known as
tropex, for mines, depth charges and torpedo warheads.
 (torpedo is a self-propelled missile weapon with an explosive
warhead, launched above or below the water surface)
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Lead Azide: (Pb(N3)2)
Now Lead azide used as an initiating explosive for blasting caps
instead of mecu0ry fulminate. The felminates has less stability, has
to be manufactured in small batches and involve poisonous
mercury. Reverse is for lead azide.
Lead azide can be made in large batches by treatin sodium azide
with lead acetate or nitrate. Sodium azide can be made from
sodium amide and nitrous oxiode.

NaNH2 + N2O - NaN3 + H2O

2NaN3 + Pb( C2H3O2)2  Pb (N3)2 +2 Na(C2H3O2)

Lead Styphnate:
Styphnic acid is trinitroresorcinol and forms two salts on reaction
with lead acetate or nitrate, basic lead-
styphnate[C2H2(NO2)3OPbOH] and lead styphnate.the basic lead
styphnate used as primer ingredient.
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