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A Review: Developments In Commercial Explosives Over The Years

Conference Paper · September 2018

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 “A REVIEW: DEVELOPMENTS IN COMMERCIAL
EXPLOSIVES OVER THE YEARS”
Dr. S. N. Sharma1, Mr. Atul P. Dwivedi2 And Mr. S. Sai Viswanathan3
1
Sr. General Manager (Works & Development)
2
Dy. Manager (Technical & Safety)
3
Dy. Manager (Projects & Maintenance)
Keltech Energies Ltd.
Village Garamsur, Nagpur
Maharashtra, India
(Corresponding 2uthor: dwivedi@keltechenergies.com)

Abstract:
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.

KEYWORDS: Commercial explosives, Developments, Properties,

Advantages

INTRODUCTION:

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
resistantExplosive is preferable.[3]

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.[7]

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.[2]

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. [4, 5, 6, 9]
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. Aluminised slurry and MMAN based
slurry. They are categorised according to the method of sensitisations. These two
formulations have some merits and some demerits. The slurry systems performs
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
Aluminised 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[1,8]. 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.

CONCLUSION:

In this review the developments in commercial explosives in the chronological order

have been given. The recent developments in Emulsion explosives gives allows the
miners to chose their requirement of explosives. The recent developments in
emulsion explosives have increased the self life and stability of the explosives with
enhancing its performance. There have been work going on in the field of detonators
to make its manufacturing safer.

REFERENCES:

1. B. Hariharanath, K.S. Chandrabhanu, A.G. Rajendran, M. Ravindran, and

C.B. Kartha, (2006)“Detonator using Nickel Hydrazine Nitrate as Primary
Explosive”, Defence Science Journal, Vol. 56, No. 3,pp. 383-389.
2. Cook, M.A. (1958) ‘Water Compatible Explosives’ in: The Science of
Explosives Reinhold Publishing Corp. New York pp.316–32.

3. Dr. Alim A. Fatah1 Richard D. Arcilesi, Jr.,Dr. Joseph A. McClintock,

Charlotte H. Lattin, Michael Helinski, Martin Hutchings(2008), Guide for
the Selection of Explosives Detectio and Blast Mitigation Equipment for
Emergency First Responders Guide 105–07

4. Liqiong Wang and Jie Fang, “Rheological Properties and Water-in-Oil

Structural Stability of Emulsion Matrixes”. Central European Journal of
Energetic Materials,10(1), 87-102, ISSN 1733-7178.
5. R. Dambov, (2011) Methods of blasting, Book, University “Goce
Delcev”, FTNS, Institute of mining, Stip, R. Macedonia.
6. R. Dambov, S. Bosevski (2011) Blasting technique in special conditions,
Monograf, SRGIM, Skopje, R. Macedonia.
7. Robert Hopler, The First One Hundred Years,IME.
8. Shunguan, Zhu; Youchen, Wu; Wenyi, Zhang & Jingyan, Mu.
(1997)Evaluation of a new primary explosive: Nickel hydrazine nitrate
(NHN) complex. Propell. Explos. Pyrotech., 22, 317-2.
9. Wang X.G.(2008), “Emulsion explosives”, Metallurgical Industry Press,
Beijing.

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