Sudipto Ganguly & Moupriya Das

EXPLOSIVES
➢INTRODUCTION: -

Any substance or device that can be made to produce a volume of rapidly expanding gas in an extremely
brief period is called explosive. An explosive (or explosive material) is a reactive substance that contains a
great amount of potential energy that can produce an explosion if released suddenly, usually accompanied
by the production of light, heat, sound and pressure. An explosive charge is a measured quantity of
explosive material, which may either be composed solely of one ingredient or be a mixture containing at
least two substances. The potential energy stored in an explosive material may, for example, be chemical
energy, such as nitroglycerin or grain dust pressurized gas, such as a gas cylinder, aerosol can or BLEVE
nuclear energy, such as in the fissile isotopes uranium-235 and plutonium-239.
Therefore, these are the three fundamental types: mechanical, nuclear and chemical. A mechanical
explosive is one that depends on a physical reaction, such as overloading a container with compressed air.
Such a device has some application in mining, where the release of gas from chemical explosives may be
undesirable, but otherwise is very little used. A nuclear explosive is one in which a sustained nuclear
reaction can be made to take place with almost instant rapidity, releasing large amounts of energy.

➢HISTORY OF CHEMICAL EXPLOSIVES: -

At its roots, the history of chemical explosives lies in the history of gunpowder. During the Tang Dynasty in
the 9th century, stumbled upon the explosive invention of gunpowder made from coal, saltpeter, and
sulfur in 1044. Gunpowder was the first form of chemical explosive and by 1161, the Chinese were using
explosives for the first time in warfare.
The first widely used explosive in warfare and mining was black powder, invented in 9th century. World
War I adopted TNT in artillery shells. World War I used new explosives. These have largely been replaced by
more powerful explosives such as C-4 and PETN. However, C-4 and PETN react with metal and catch fire
easily, yet unlike TNT, C-4 and PETN are waterproof and malleable.
This material was sensitive to water, and it produced copious amounts of dark smoke. The first useful
explosive stronger than black powder was nitroglycerin, developed in 1847. Since nitroglycerin is a liquid
and highly unstable, it was replaced by nitrocellulose, trinitrotoluene (TNT) in 1863, smokeless powder,
dynamite in 1867.

➢THEORY OF EXPLOSIVES: -

A general theory of explosives is that the detonation of the explosives charge causes a high velocity shock
wave and a tremendous release of gas. The shock wave cracks and crushes the rock near the explosives and
creates thousands of cracks in the rock. These cracks are then filled with the expanding gases. The gases
continue to fill and expand the cracks until the gas pressure is too weak to expand the cracks any further, or
are vented from the rock.
➢CHARACTERISTICS OF EXPLOSIVES: -

In general, an explosive has four basic characteristics:

(1) It is a chemical compound or mixture ignited by heat, shock, impact friction, or a combination of
these conditions;
(2) Upon ignition, it decomposes rapidly in a detonation;
(3) There is a rapid release of heat and large quantities of high-pressure gases that expand rapidly with
sufficient force to overcome confining forces; and
(4) The energy released by the detonation of explosives produces four basic effects; (a) rock
fragmentation; (b) rock displacement; (c) ground vibration; and (d) air blast.

➢INGREDIENTS USED IN MANUFACTURING OF EXPLOSIVES: –

The ingredients in manufacturing explosives are classified as:

a. Explosive bases -
An explosive base is a solid or a liquid which, upon application of heat or shock, breaks down very
rapidly into gaseous products, with an accompanying release of heat energy. Nitroglycerine is an
example.
b. Combustibles -
A combustible combines with excess oxygen in an explosive to achieve oxygen balance, to prevent the
formation of nitrous oxides (toxic fumes), and to lower the heat of the explosion.
c. Oxygen carriers -
Oxygen carriers assure complete oxidation of the carbon in the explosive mixture, which inhibits the
formation of carbon monoxide. The oxygen carriers assist in preventing a lowering of the exploding
temperature. A lower heat of explosion means a lower energy output and thereby less efficient
blasting.
d. Antacids -
Antacids are added to an explosive compound to increase its long term storage life, and to reduce the
acidic value of the explosive base, particularly nitroglycerin (NG).
e. Absorbents -
Absorbents are used in dynamite to hold the explosive base from exudation, seepage and settlement
to the bottom of the cartridge or container. Sawdust, rice hulls, nut shells, and wood meal are often
used as absorbents.
f. Antifreeze -
Antifreeze is used to lower the freezing point of the explosive.
➢PROPERTIES OF EXPLOSIVES: –
a. Air gap sensitivity –
Air gap sensitivity is a measure of an explosive's cartridge-to-cartridge sensitivity to detonation, under test
conditions, expressed as the distance through air at which a primed half-cartridge (donor) will reliably
detonate an unprimed half-cartridge (receptor).
b. Cap sensitivity –
Cap sensitivity is a measure of the minimum energy, pressure, or power required for initiation of a
detonation; i.e., "cannot be detonated by means of a No. 8 test blasting cap when unconfined."
c. Strength –
Two strength ratings are used for commercial dynamites. Weight strength compares products on an equal-
weight basis, and cartridge strength or bulk strength compares products on an equal-volume basis. Both
are expressed in percent, using straight nitroglycerin dynamite as a standard.
A number of factors are currently used to judge an explosive's ability to do the work desired, and today's
blaster must consider at least the following:
Detonation Pressure is a measure of the product's shock wave energy, influenced by the product's density
(latent energy) and detonation velocity (rate of energy release).
Pressure Magnitude or Gas Pressure is a measure of the potential expanding- gas energy, influenced by the
product's density (latent gas volume) and the heat and velocity of detonation (rate of gas production and
expansion).
When selecting explosives there are four basic categories:
1. Dynamites, including Granular Dynamite (Straight Dynamite, High-DensityExtra Dynamite and Low-
Density Extra Dynamite) and Gelatin Dynamite (Straight Gelatin Dynamite, Ammonia Gelatin Dynamite,
and Semigelatin Dynamite). Use of this is prohibited by policy unless a case specific waver is obtained
from the regional blasting officer.
2. Water Gels, Emulsions, and Slurries - consisting of Cartridges and Bulk products.
3. Dry Blasting Agents - consisting of Poured or Bulk ANFO, Aluminized ANFO, Densified ANFO, and
Packaged (waterproof) ANFO.
4. Binary Explosives - consisting of two-component products that are mixed in the field to form an
explosive.

➢TYPES OF CHEMICAL EXPLOSIVES: -

a. Detonating or High Explosives

b. Deflagrating or Low Explosives
Detonating explosives, such as TNT and dynamite, are characterized by extremely rapid decomposition and
development of high pressure, whereas deflagrating explosives, such as black and smokeless powders, involve
merely fast burning and produce relatively low pressures. Under certain conditions, such as the use of large
quantities and a high degree of confinement, some normally deflagrating explosives can be caused to detonate.
Detonating explosives are usually subdivided into two categories- primary and secondary. Primary explosives
detonate by ignition from some source such as flame, spark, impact, or other means that will produce heat of
sufficient magnitude. Secondary explosives require a detonator and, in some cases, a supplementary booster. A
few explosives can be both primary and secondary depending on the conditions of use.
Explosives may also be categorized by their sensitivity:
a. Primary explosives
b. Secondary or tertiary explosives
Sensitive materials that can be initiated by a relatively small amount of heat or pressure are primary explosives
and materials that are relatively insensitive are secondary or tertiary explosives.
1) NITROGLYCERIN -
Nitroglycerin, is a chemical explosive, discovered by an Italian chemist, Ascanio Sobrero, in 1846. Although
he first called it pyroglycerin, it soon came to be known generally as nitroglycerin or blasting oil.
Nitroglycerin (NG), also known as trinitroglycerin (TNG), nitro glyceryltrinitrate (GTN) or 1,2,3-
trinitroxypropane, is a dense, colorless, oily, explosive liquid most commonly produced by nitrating glycerol
with white fuming nitric acid under conditions appropriate to the formation of the nitric acid ester. Because
of the risks inherent in its manufacture and the lack of dependable means for its detonation, nitroglycerin
was largely a laboratory curiosity until Immanuel Nobel and his son Alfred made extensive studies of its
commercial potential in the years 1859-61. In 1862 they built a crude plant at Heleneborg. Sweden. Nobel
was granted a patent for the manufacture and use of nitroglycerin in the United States in 1866.
Even today most experts regard Nobel's invention of the blasting cap, a device for detonating explosives, in
1865, as the greatest advance in the science of explosives since the discovery of black powder. Since the
1880s, it has been used by the military as an active ingredient and gelatinizer for nitrocellulose in some solid
propellants such as cordite and ballistite. It is a major component in double-based smokeless propellants
used by reloaders. Combined with nitrocellulose, hundreds of powder combinations are used by rifle, pistol
and shotgun reloaders.

2) DYNAMITE -
The second most important of Nobel's inventions was dynamite, in 1867. He coined the name from the
Greek dynamis, "power." The basis for the invention was his discovery that kieselguhr, a porous siliceous
earth, would absorb large quantities of nitroglycerin, giving a prod. The dominant base-charge materials are
now pentaerythritol tetranitrate (PETN) and cyclotrimethylenetrinitramine (RDX). These are as strong as
nitroglycerin, quite safe to manufacture and handle and relatively inexpensive. In addition to low density
nitromannite, diazodinitrophenol, lead styphnate and lead azide are widely used as ignition-primer charges.

3) LEAD AZIDE -

Lead azide(Pb(N)) is an inorganic compound. It is used in detonators to initiate secondary explosives. In a

commercially usable form, it is a white to buff powder. Lead azide is highly sensitive and usually handled
and stored under water in insulated rubber containers.
❖ Preparation and Explosive Properties of Lead Azide:

• Production history -
Lead azide in its pure form was first prepared by Theodor Curtius in 1891. Due to sensitivity and
stability concerns, the dextrinated form of lead azide (MIL-L-3055) was developed in 1920s and 1930s
with large scale production by DuPont Co. beginning in 1932. Detonator development during World
War II resulted in the need for a form of lead azide with a more brisant output. RD-1333 lead aride
(MIL-DTL-46225), a version of lead azide with sodium carboxymethy! cellulose as a precipitating
agent, was developed to meet that need.

• Production -
Lead azide is prepared by the reaction of sodium azide and lead nitrate in aqueous solution. Lead
acetate can also be used.
Thickeners such as dextrin or polyvinyl alcohol are often added to the solution to stabilize the
precipitated product. In fact, it is normally shipped in a dextrinated solution that lowers its sensitivity.

• Explosive characteristics -
Lead azide is highly sensitive and usually handled and stored under water in insulated rubber
containers. It will explode after a fall of around 150 mm (6 inch) or in the presence of a static
discharge of 7 millijoules. Its detonation velocity is around 5,180 m/s (17,000 ft/s).
Ammonium acetate and sodium dichromate are used to destroy small quantities of lead azide.
Lead azide has immediate deflagration to detonation transition (DDT), meaning that even small
amounts undergo full detonation (after being hit by flame or static electricity). Lead azide reacts with
copper, zinc, cadmium, or alloys containing these metals to form other azides. For example, copper
azide is even more explosive and too sensitive to be used commercially.

4) PETN -

Pentaerythritol tetranitrate was first prepared and patented in 1894 by the explosives manufacturer
Rheinisch-Westfalische Sprengstoff A.G of Cologne, Germany, PETN wasted by the German Military in World
War 1.
PETN is practically insoluble in water, weakly soluble in common nonpolar solvents such as aliphatic
hydrocarbons or tetrachloromethane, but soluble in some other organic solvents, particularly in acetone and
dimethylformamide.
PETN is resistant to attack by many chemical reagents; it does not hydrolyze in water at room temperature or
in weaker alkaline aqueous solutions.
Neutron radiation degrades PETN, producing carbon dioxide and some pentaerythritol dinitrate and
trinitrate. Gamma radiation increases the thermal decomposition sensitivity of PETN, lowers melting point
by few degrees Celsius, and causes swelling of the samples.
In the environment, PETN undergoes biodegradation. Some bacteria denitrate PETN to trinitrate and then
dinitrate, which is then further degraded. PETN has low volatility and low solubility in water, and therefore
has low bioavailability for most organisms. Its toxicity is relatively low, and its transdermal absorption also
seems to be low. It poses a threat for aquatic organisms. It can be degraded to pentaerythritol by iron.
❖ Preparation and Explosive Properties of PETN:

• Production -
It is produced by the reaction of pentaerythritol with concentrated nitric acid to form a precipitate which can
be recrystallized from acetone to give processable crystals.
Variations of a method first published in US Patent 2,370,437 by Acken and Vyverberg (1945 to Du Pont) form
the basis of all current commercial production.
PETN is manufactured by numerous manufacturers as a powder, or together with nitrocellulose and
plasticizer as thin plasticized sheets (e.g., Primasheet 1000 or Detasheet). PETN residues are easily
detectable in hair of people handling it. The highest residue retention is on black hair; some residues remain
even after washing.

• Explosive use -
The most common use of PETN is as an explosive with high brisance. It is more difficult to detonate than
primary explosives, so dropping or igniting it will typically not cause an explosion (at atmospheric pressure it
is difficult to ignite and burns relatively slowly), but is more sensitive to shock and friction than other
secondary explosives such as TNT. Under certain conditions a deflagration to detonation transition can occur.
PETN is a secondary explosive and as such is not as sensitive as prima ray explosive such as lead azide. PETN
is the least stable of the common military explosives, but can be stored without significant deterioration for
longer period than nitroglycerin or nitrocellulose.

• Explosive characteristics –

▪ Explosion energy: 5810 kJ/kg (1390 kcal/kg), so 1 kg of PETN has the energy of 1.24 kg TNT.
▪ Detonation velocity: 8350 m/s (1.73 g/cm³), 7910 m/s (1.62 g/cm³), 7420 m/s (1.5 g/cm³), 8500 m/s
(pressed in a steel tube).
▪ Volume of gases produced: 790 dm³/kg (other value: 768 dm³/kg).
▪ Explosion temperature: 4230 °C.
▪ Oxygen balance: -6.31 atom-g/kg.
▪ Melting point: 141.3 °C (pure), 140-141 °C (technical).
▪ Critical diameter (minimal diameter of a rod that can sustain detonation propagation): 0.9 mm for PETN
at 1 g/cm³, smaller for higher densities (other value: 1.5 mm)
5) CYCLONITE (RDX) -

RDX is an organic compound with the formula (O2N2CH2)3. It is a white solid without smell or taste,
widely used as an explosive. Chemically, it is classified as a nitramide. A more energetic explosive than
TNT, it was used widely in World War II and remains common in military applications. RDX
(cyclotrimethylenetrinitramine) is second in strength to nitroglycerin among common explosives
substances. When compressed to a density of 1.70, it has a confined detonation velocity of 27,000 fps.
RDX is a primary ingredient in composition B. Plasticity and high detonation velocity make it ideal in
shaped charges for oil well perforators (jet perforators) and furnace papers jet tappers. RDX is sometimes
the base charge for detonators. Composition B is a mixture of RDX and TNT with one to four percent wax
added. When cast, it has a density of 1.65 and a detonation velocity of about 25,000 fps. Like pentolite,
composition B is used in the cast form as a primer and booster for blasting agents.

❖ Preparation and Explosive Properties of Cyclonite (RDX):

• Production -
RDX is classified by chemists as a hexahydro-1,3,5-triazine derivative. It is obtained by treating hexamine
with white fuming nitric acid.

This nitrolysis reaction also produces methylene dinitrate, ammonium nitrate, and water as byproducts.
The overall reaction is:

• Explosive Characteristics –
The velocity of detonation of RDX at a density of 1.76 g/cm³ is 8,750 meters per second.
It is a colourless solid, of maximum theoretical density 1.82 g/cm³.
It is a heterocycle and has the molecular shape of a ring. It starts to decompose at about 170 °C and
melts at 204 °C. Its structural formula is: hexahydro-1,3,5-trinitro-1,3,5-triazine or (CH-N-NO2).
At room temperature, it is very stable. It burns rather than explodes and detonates only with a
detonator, being unaffected even by small arms fire. It is less sensitive than pentaerythritol tetranitrate
(PETN). However, it is very sensitive when crystallized below -4 °C.
Under normal conditions, RDX has a figure of insensitivity of exactly 80 (as this is the reference point).
RDX sublimates in vacuum, which limits its use in pyrotechnic fasteners for spacecraft.
➢ INTRODUCTION TO ROCKET PROPELLANTS: –

Propellant is the chemical mixture burned to produce thrust in rockets and consists of a fuel and an oxidizer.
A fuel is a substance which burns when combined with oxygen producing gas for propulsion. An oxidizer is
an agent that releases oxygen for combination with a fuel.
Propellants are classified according to their state- liquid, solid, or hybrid.
(A) Liquid Propellants -
In a liquid propellant rocket, the fuel and oxidizer are stored in separate tanks, and are fed through a
system of pipes, valves, and turbopumps to a combustion chamber where they are combined and
burned to produce thrust. Liquid propellant engines are more complex than their solid propellant
counterparts, however, they offer several advantages. By controlling the flow of propellant to the
combustion chamber, the engine can be throttled, stopped or restarted.
Liquid propellants used by NASA and in commercial launch vehicles can be classified into three types:
1. Petroleum fuels are those refined from crude oil and are a mixture of complex hydrocarbons. The
petroleum used as rocket fuel is kerosene, or a type of highly refined kerosene called RP-1 (refined
petroleum 1). It is used in combination with liquid oxygen as the oxidizer.
2. Cryogenic propellants are liquefied gases stored at very low temperatures, namely liquid hydrogen (LH)
as the fuel and liquid oxygen (LO₂) as the oxidizer. LH, remains liquid at temperatures of -423 degrees F
and LO₂ remains in a liquid state at temperatures of -298 degrees F. Liquid hydrogen and liquid oxygen
are used as the propellant in the high efficiency main engines of the space shuttle.
3. Hypergolic propellants are fuels and oxidizers which ignite spontaneously on contact with each other
and require no ignition source, The easy start and restart capability of hypergolics make them ideal for
spacecraft maneuvering systems. Also, since hypergolics remain liquid at normal temperatures, they do
not pose the storage problems of cryogenic propellants. Hypergolics are highly toxic and must be
handled with extreme care. Hypergolic fuels commonly include bydrazine, monomethyl hydrazine
(MMH) and unsymmetrical dimethyl hydrazine (UDMH). The oxidizer is typically nitrogen tetroxide
(N2O4) or nitric acid (HNO3).

(B) Solid Propellants -

Solid propellant motors are the simplest of all rocket designs. They consist of a casing, usually steel,
filled with a mixture of solid compounds (fuel and oxidizer) which burn at a rapid rate, expelling hot
gases from a nozzle to produce thrust. When ignited, a solid propellant burns from the centre out
towards the sides of the casing. The shape of the centre channel determines the rate and pattern of
the burn, thus providing a means to control thrust. Unlike liquid propellant engines, solid propellant
motors cannot be shut down. Once ignited, they will burn until all the propellant is exhausted.
There are two families of solids propellants: homogeneous and composite. Both types are dense,
stable at ordinary temperatures, and easily storable.
1. Homogeneous propellants are either simple base or double base. A simple base propellant consists of a
single compound, usually nitrocellulose, which has both an oxidation capacity and a reduction capacity.
Double base propellants usually consist of nitrocellulose and nitroglycerine, to which a plasticiser is
added. Homogeneous propellants do not usually have specific impulses greater than about 210 seconds
under normal conditions. Their main asset is that they do not produce traceable fumes and are,
therefore, commonly used in tactical weapons. They are also often used to perform subsidiary functions
such as jettisoning spent parts or separating one stage from another.
2. Modern composite propellants are heterogeneous powders (mixtures) which use a crystallized or finely
ground mineral salt as an oxidizer. often ammonium perchlorate, which constitutes between 60% and
90% of the n ass of the propellant. The fuel itself is aluminum. The propellant is held together by a
polymeric binder, usually polyurethane or polybutadienes. Additional compounds are sometimes
included, such as a catalyst to help increase the burning rate, or other agents to make the powder
easier to manufacture. The final product is rubber like substance with the consistency of a hard rubber
eraser.

(C) Hybrid Propellants-

Hybrid propellant engines represent an intermediate group between solid and liquid propellant
engines. One of the substances is solid, usually the fuel, while the other, usually the oxidizer, is liquid.
The liquid is injected into the solid, whose fuel reservoir also serves as the combustion chamber. The
main advantage of such engines is that they have high performance, similar to that of solid
propellants, but the combustion can be moderated, stopped, or even restarted. It is difficult to make
use of this concept for vary large thrusts, and thus, hybrid propellant engines are rarely built.