DEVELOPMENTS IN COMMERCIAL EXPLOSIVES OVER THE YEARS

By: Dr. Atul P Dwivedi

Explosives are an integral part of the mining services whether it is a mines, stone quarries,
infrastructure development works, tunnelling etc. In this paper a review has been done on
the past and the present developments in the field of explosives from the beginning. The
continuous development is the need for hour with the advancement in the techniques of
mining and blasting as more and more sophisticated instruments are used for the said
purpose the demand for more reliable and précised explosive material has grown very
rapidly. Due to the demands from the mining side there have been huge research done in
the field of explosives. The need of research also arisen because of the need for more safety
of the end user and also the environmental impacts of these materials. In this paper we have
discussed various types of commercial explosives used with their properties and advantages
over each other.

Rational large scale mining and excavation have forced the development of mining
equipment and consequently also explosive products including manufacturing, distribution
and handling. The safety and working environment has become most significant parameters
when the overall mining operation is evaluated. This has to a great extent influenced the
development towards less sensitive explosives.

In the simplest terms, an explosive is defined as a substance, which on initiation by friction,

impact, shock, spark, flame, heating, or any simple application of an energy pulse, undergoes
a rapid chemical reaction evolving a large amount of heat and so exerting a high pressure
on its surroundings. Explosives are used both commercially and for military applications.
Commercial uses of explosives include blasting (construction and road building), demolition,
fireworks, and metal forming, to name a few. Military uses of explosives may include
propellants (rockets and missiles), bursting charges (projectiles and bombs), and military
demolition and construction.
Oxygen balance (OB) is defined as the ratio of the oxygen content of a compound to the
total oxygen required for the complete oxidation of all carbon, hydrogen and other
oxidisable elements to CO2,H 2O, etc and is used to classify energetic materials as either
oxygen deficient or oxygen rich. Most energetic materials are oxygen deficient.

Generally, there are three categories of explosives, i.e., chemical, mechanical, and nuclear
explosives. Chemical explosives, the most commonly used explosives, are compounds or
mixtures of compounds that react to produce large volumes of rapidly expanding gases as
well as energy, heat, light, and shock waves that exert sudden pressures on the
surroundings. Mechanical explosives are those substances that tend to undergo a physical
change such as overloading a container with compressed air or steam. Nuclear explosives,
the most powerful explosives, produce sustained nuclear reactions while releasing a
tremendous amount of heat and energy.

The characteristics of chemical explosives influence the type of explosives that are used for
a specific application. Such characteristics include, but are not limited to: sensitivity,
stability, rate of detonation, and brisance.

 Sensitivity refers to the ease at which an explosive is ignited or detonated; it reveals

the amount and intensity of shock, friction, and heat that is required to initiate
detonation.
 Stability indicates the ability of an explosive to be stored without deterioration.
Deteriorating explosives may be more sensitive and more dangerous to handle. For
example, dynamite stored for a long time will allow nitroglycerin (NG) to seep out
and will become very unstable.
 Detonation rate refers to the speed at which a detonation wave travels through an
explosive and determines whether an explosive will exert a heaving effect or a
shattering effect.
 Brisance describes the shattering effect and is much greater when the rate of
detonation is high. Brisance is important in determining the effectiveness of an
explosive in fragmenting the likes of shells, bomb casings, and grenades.
VARIOUS IMPORTANT EXPLOSIVES PROPERTIES:
Velocity of Detonation (VOD)
It is the speed at which detonation wave travels through the media, it depends upon
Explosive type.
Weight Strength
Weight strength is the energy generated by an Explosive relative to that produced by an
equal weight of 94 AN 6 FO (94%) Fuel Oil.
Fume Characteristics
The explosives should liberate minimum harmful gases which used in proper ventilated
environment.
Thermal Stability
The formulation of explosives should be designed such that it should be stable in all normal
usage conditions.
Sensitivity
The explosives should remain insensitive to shock, friction and also to normal handling
conditions but it should be sufficiently sensitive to be satisfactorily detonated, and capable
of propagating satisfactorily, cartridge to cartridge, even over gaps which may occur in
practice.
Density
The density is important when selecting an Explosive for a particular use. With a high density
Explosive the energy of the shot is concentrated a desirable feature in tunnelling and mining
operations in hard ground. On the other hand when the output of lump coal from a mine is
important, it is advisable to use a low density Explosive, which distributes the energy along
the shot hole.
Water Resistance
When blasting is to be done under wet conditions, a water resistant Explosive is preferable.
BACKGROUND OF COMMERCIAL EXPLOSIVES:

The history of commercial explosives started in 1650 when it is recorded that the very old
Chinese Black Powder, used until then for military purposes, was adapted for mining in
Hungary and England. 100 years later the French chemist Berthollet experimented by mixing
Potassium Chlorate with Black Powder formulations, but the results were disastrous. In
1847, 2 Sobrero an Italian chemist, discovered a very powerful explosive, a "blasting oil”
called Nitroglycerine. Nitro Glycerine is an extremely powerful explosive which detonates at
the speed of more than 7000 metres per second, and which is extremely sensitive to any
shock. Its use was limited by many serious accidents and Alfred Nobel, with his genius for
invention, tried to find a way to de-sensitize the pure Nitro Glycerine to enable safer
handling. The first dynamite was obtained by the absorption of 75% of Nitro Glycerine into
25% of Kieselguhr. Dynamites were born and developed all over the world.

During about 100 years the dynamites were constantly improved and Kieseguhr was
replaced by other types of more efficient and reactive absorbent products such as wood
meal, or even by absorbent products with explosive properties such as Nitro Cellulose, and
with the addition of Salt Oxidants which modify the oxygen balance of the product, such as
Ammonium Nitrate, or combustible products such as BNT and TNT. In the 30s in order to
reduce the freezing point of Nitro Glycerine and allow a better resistance to cold weather
Nitro Glycol was substituted for Nitro Glycerine. With the development of dynamites, the
addition of Ammonium Nitrate was one of the major advances. Ammonium Nitrate, a
powerful oxidiser, has been considered as an inert substance, but it is well known after some
famous disasters, that although its sensitivity is very low when the product is pure, its
sensitivity increases greatly in the presence of combustible impurities, and can therefore be
detonated with an appropriate booster. Some European manufacturers tried at the
beginning of the 20th Century, to replace dynamite with so-called Ammonal explosive in
which the main raw material is Ammonium Nitrate, sensitised with TNT instead of Nitro
Glycerine.

Dynamites remained the most effective commercial explosives until the discovery in the
1950s of Ammonium Nitrates fuel oil and in the 1960s of Water Gels. The Ammonium
Nitrates fuel oil, so called Anfo, which entered the market on a large scale around 1955, was
the first commercial explosive to really capture an important part of the dynamite market.
It is a very simple product based on Ammonium Nitrate. Since the disaster at Oppau in 1921,
it has been discovered that Ammonium Nitrate contaminated with paper and paraffin can
detonate.

Around 1960’s Emulsions were born! The water-in-oil, or oil-in-water emulsion provides a
very stable product whose sensitivity is due to the presence of air bubbles. The density, and
therefore the sensitivity is provided by the introduction of hollow glass bubbles, or by
specific chemical gassing techniques. Like ANFO or the first generation of water gels,
emulsions are totally insensitive to shocks or impact; their density can be changed easily as
can their sensitivity to detonators. They are manufactured either in cartridge form or more
and more, directly at the site of usage, with pump-trucks which deliver the sensitised
products directly into the mine-holes.

RECENT DEVELOPMENTS IN COMMERCIAL EXPLOSIVES: WATER GEL/SLURRY

EXPLOSIVES:
In water gel or Slurry systems there have not been decent developments. The year old
technology and the formulations are still going on. The water gel of slurry explosives are
made by two methods i.e. Aluminized slurry and MMAN based slurry. They are categorized
according to the method of sensitizations. These two formulations have some merits and
some demerits. The slurry systems perform well in heavy watery holes and in cold conditions
were as the MMAN base formulation are excellent for relatively drier holes and the climatic
conditions were temperatures are higher than 10°C. In India all the manufactures are making
Aluminized slurry except one manufacturer which manufactures MMAN based slurry.

EMULSION EXPLOSIVES:

Since its development in 1960’s there have been lots of technological changes in the
manufacture of Emulsion explosives. The bath process has been replaced by PLC based
continuous process. The raw materials used have been changed drastically. In its inception
the Emulsion explosives were made by using Emulsifiers and paraffin oil only, now these
have been replaced by new types of emulsifiers and the paraffin oils have been replaced by
many other sources of Hydrocarbons. The manufactures have shifted from SMO to PIBSA
based technology for cartridges and bulk emulsion matrix. The recent development in the
chemistry of Emulsifiers have lead to the development of PIBLA based technology which is
cost efficient and also provides longer shelf life and stability in extreme conditions. It
performs well if stored for longer periods of time when compared with the PIBSA based
technology.

Structure of PIBSA Structure of PIBLA

Emulsion consists of small droplets of ammonium nitrate solution, tightly packed in a

mixture of oil and wax. Looked at through a microscope, its structure resembles that of a
honeycomb. The thickness of the oil and wax membranes separating the droplets is less than
one ten thousandth of a millimetre. This involves an extremely large contact area between
the fuel-oil and wax and the oxidizer-ammonium nitrate. As a result very rapid and complete
explosive combustion is obtained. The oil and wax membrane also protects every droplet of
ammonium nitrate and makes the explosive highly water resistant. By adding "hot spots" in
the form of small hollow glass spheres (microspheres) or air bubbles the sensitivity of the
emulsion can be varied. The hot spots, which are only one tenth of a millimetre m diameter,
act as density gradients in the explosive and effectively transfer shock wave energy to heat
and enhance the rapid explosive combustion of the emulsion.

However, due to the super-saturated aqueous phase and the instability of the W/O structure
itself of the emulsion matrix, it is easy for emulsion explosives to crystallize and to be
affected by their surroundings, such as temperature, vibration and shearing, leading to
misfires, semi-explosions or extinguishment. There are many factors affecting the W/O
structural stability of emulsion matrixes, such as emulsifying technique and temperature,
and type, functionality, components, molecular weight, the addition rate of the emulsifier
etc.

The development of emulsion Boosters as low cost substitute of Pentolite Booster is also
gaining market. The requirements for the emulsion booster are rapidly increasing. The
emulsions CPT is gaining good market in seismic blasting as it give high energy output when
compared with slurry/water gel explosives for getting more accurate results or plots of the
seismic waves generated after blasting.

BLASTING ACESSORIES:

In blasting accessories there have been lot of developments from safety fuses to detonators.
The safety fuses have been replaced by detonating cords. Electrical detonators have been
replaced by more sophisticated electronic detonators. The delay detonators and shock tubes
have also been developed for safe mining. In detonators recently the high sensitive
explosives like Lead Azide (LA) and Lead Styphnate (LS) have been in some of the industries
substituted with less sensitive explosive i.e. Nickel hydrazine Nitrate (NHN). The NHN is less
sensitive to friction and impact as compared to LA & LS mixture. It is also environment
chemical friendly as it does not contain lead compounds. DDNP (diazo dinitro phenol) are
also used as the primary charge to reduce the amount of lead emitted into the atmosphere
by mining and quarrying operations.