BNCP A Novel DDT Explosive and its Applications

By
Virendra Kumar*, A P Agrawal**, H Muthurajan*, and J P Agrawal**
* Armament Research and Development Establishment, Pune
** High Energy Material Research Laboratory, Pune
Abstract
Detonators / Igniters are the first element in an explosive train. They contain
a relatively small quantity of a sensitive explosive and a means for its initiation.
Detonators / Igniters used in India are sensitive to Electro-Static Discharge (ESD)
and Electro Magnetic Interference (EMI), hence indigenous development of new
detonators which are safe to handle has been the major thrust area. Lead azide and
lead styphnate are used in various explosive devices in India. Americans have
reported use of tetraaminebis(5-nitro-2H-tetrazolato-N2) tetraaminecobalt(III)
perchlorate (BNCP) as deflagration-to-detonation transition(DDT) explosive
because it is superior to lead azide in regard to safety/handling coupled with better
performance. The synthesis and characterization of BNCP has been done and
reported by us elsewhere[1]. The explosive properties of BNCP have been
evaluated by determining impact sensitivity, Spark sensitivity test, Friction
sensitivity and VOD. BNCP has been found superior and safer as compared to lead
azide for use in detonators. This paper presents the results of various tests and
comparison of BNCP with other initiatory explosives. The data suggests that BNCP
hold tremendous potential application in explosive devices in India. The paper also
presents the future plan of work for developing safe, environmental friendly
explosive devices using BNCP and Semiconductor Bridge.
Presented in Seminar on Propellants & Explosives at Ordinance Factory Bhandara
during 23-24 Jan 2002.

INTRODUCTION
The initiatory explosives are the starting point of a train of explosive events. The most
common primary explosive in use are mercury fulminate (Hg(OCN)2), lead azide (PbN6) and lead
styphnate (Pb(C6H3N3O9). But these initiatory compounds have their own limitations.
Liberman[2] studied the preparation and explosive properties of the inorganic explosive based on
coordination compound 2-5 cynotetrazolatopentaaminecobalt(III)perchlorate (C.P.) as one of
energetic primary explosive. But this explosive (CP) is no longer manufactured [3], as one of its
starting material cyanogen is not available due to environmental hazards associated with its use.
In view of above, detailed literature survey through international journals and internet
resources etc., have been carried out to indigenously synthesize and characterize the BNCP, with
combined efforts of HEMRL and ARDE. BNCP has been synthesized at HEMRL and
characterized using ESCA, IR, XRD and SEM. The explosive properties of BNCP have also been
studied. The thermal properties such as activation energy, enthalpy changes and thermal stability
have also been determined using Differential Scaning Calorimetry, DTA and DGA. The data thus
obtained have been compared with literature reported values of conventional initiatory explosive
like lead azide, Lead styphnate and Mercury fulminate.
LIMITATIONS OF CONVENTIONAL PRIMARY EXPLOSIVE
Heavy metal salt of certain weak acid like hydrozic acid, fulmiric acid, picric acid etc.,
have found extensive application in military as well as civil sectors. It is reported that these salts
burn ten to hundred times as fast as their original acids [4]. The thermo-explosive characteristics
of the metallic salts of these acids are of interest chiefly because of their ease of initiation and
capable of detonating when they are subjected to heat and shock. These types of inorganic
compounds are generally called primary explosives and were discovered in the early part of
sixteenth century. Following primary explosives are used extensively in explosive devices in
India.
MERCURY FULMINATE
First application of mercury fulminate in ignition caps is attributed during 1823 by the
chemist Liebig. Later on Nobel used the mercury fulminate as the first primary explosive in
detonators. Since mercury fulminate suffers from a number of serious drawbacks, which restrict
its use and therefore its application in detonators have been abandoned. The major drawbacks are
as follows.
i) Poor stability
ii) Property of being Dead pressed
iii) Very Sensitive to impact and friction
iv) High cost of mercury metal
v) Environmentally hazardous
The efforts were therefore made to replace the mercury fulminate with superior
substitutes such as lead azide and lead styphnate.
LEAD AZIDE
Lead azide was firstly prepared by Curtius during 1891 and developed to plant scale by
Dennis and Browne. Due to high hazards involved in manufacturing and handling of the pure
lead azide, the practical use of the lead azide was delayed for many decades. It also becomes
unstable in presence of moisture and carbon-di-oxide; giving out hydrazoic acid. Further it is not
compatible with copper and its alloys since the hydrazoic acid liberated forms dangerous copper
azide.
1

LEAD STYPHNATE
Lead styphnate also suffers from serious drawbacks as follows
i) Initiation Power The lead styphnate produces much less initiating power than of
mercury fulminated and lead azide
ii) The lead styphnate is very sensitive to electrostatic charge
iii) This compound is sensitive to impact and friction, therefore handling/transportation is
not safe.
iv) Environmentally hazardous
All these conventional primary explosives although suffer from serious drawbacks, are
still being used by military and civil community. Therefore, there are on going research and
development programme in the field of initiatory explosive to achieve less sensitive, more
compatible, better thermal stable and capable of undergoing fast deflagration to detonation
transition (DDT). The research and development work in the field of primary explosives in recent
years may be grouped into two categories as follows
i) Modifications of the traditional initiatory explosives (or)
ii) Synthesis of new initiatory compounds
BNCP
The present paper deals with synthesis of new initiatory explosive by selecting the field of
energetic coordination compound. During the last two decades the research and development of
primary explosives have been concerned mainly with energetic coordination compounds. Efforts
were made to meet the essential requirements like chemical and physical reproducibility, stability,
compatibility, safety in processing and use, functional efficiency, production and loading needs.
Lieberman, studied the preparative and explosive properties of the inorganic explosives based on
coordinate compound; 2,5-cynotetrazoltopentaaminecobalt(III)perchlorate (CP) as one of the
energetic coordination compound in the field of primary explosive. But this material is no longer
being manufactured as one of its starting material cyanogen is not made available due to its
hazardness and Environmental Protection Act (EPA) restrictions. In view of the above points, the
detailed literature survey was carried out on energetic coordination compounds and the program
was under taken to indigenous synthesis and characterization of such energetic coordination
compounds.
SYNTHESIS OF BNCP
The synthesis of BNCP consist of four steps as follows
(i) Preparation of 5-Aminotetrazole mono hydrate (AT)
5-Aminotetrazole mono hydrate is prepared by treating dicyanamide with sodium azide in
acidic medium at 650C. The chemical reaction involved in this reaction is represented in step A of
BNCP synthesis. 5-Aninotetrazole mono hydrate is abbreviated as AT for our convenience.
Step I
HN
HCl
2
1
+
2
NaN
NH
3
8C
H2N C NH.CN
2
650C
N
NH
N .H2O
N
dicyanamide
Sodium azide
5-aminotetrazole mono hydrate

(ii) Preparation of Sodium 5-nitrotetrazole dihydrate

5-Nitrotetrazole is the most energetic of the tetrazoles[5,6]. The diazotization of 5aminotetrazole mono hydrate (AT) in presence of excess sodium nitrite and Copper sulphate
gives the complex cupric salt intermediate Cu(NT)2.HNT.4H2O, which was then converted to the
sodium salt NaNT.2H2O using reported methods [ 7,8,9].
Step II
N

N
NH2.H2O

N
N
5-Aminotetrazole mono hydrate

Cu2+

N
N

N
--

N
NO2

N
2

NaNO2/H+
CuSO4

Cu2+

N
-N
N

NaOH/H2O
NO .4H2O
2

NO2

.N
N

N
Na+ N N
N

NO2.H2O

.2H2O

NO2

(iii) Preparation of Carbonato tetra amine cobalt(III) Nitrate (CTCN)

The synthesis of CTCN was accomplished by method as reported by Schlessinger G.
procedure [10].
Step III
Co(NO3) + 3NH3 (aq) + (NH4)2Co3 + H2O2

[Co(NH3)4CO3] NO3 + NH4NO3 + H2O

CTCN
(iv) Preparation of BNCP
The preparation of BNCP was accomplished by conventional co-ordination chemistry
methods as shown in the following sequence
Step IV(a)
CTCN + HClO4

[Co(NH3)4.2H2O] ClO4 + CO2 + HNO3

H2O

Step IV(b)

NO2
N

ATCP

+ 2 NaNT.2H2O

HClO4 / H2O
850C

ATCP = Aquotetraaminecobaltperchlorate

N
+

Cl O
N
N NH
3

H3N
Co
H3N
NH3

NO2

N N

BNCP

Steps I,II and III are well known and are described in a variety of literature sources. In
step IV(a), ATCP was prepared essentially by acidifying CTCN with aqueous perchloric acid
(3%) and a solution of sodium 5-nitrotetrazole dihydrate was added drop by drop into the

aqueous complex (ATCP) over 40 minutes. During addition, the mixture temperature was
strictly controlled in between 800C to 900C using water bath. When the addition is completed,
then the reaction mixture was digested with vigorous stirring for 3 hours at 800C. Slow cooling
of the reaction mixture to the room temperature (about 250C) will provide the precipitated
product. This can be achieved by keeping the reaction mixture for over night digestion. The
precipitated product is thus obtained, was filtered through watman filter paper No. 54, under slow
suction.
Recrystallization
The crude product thus obtained was recrystallized from slightly acidified distilled water with
perchloric acid (~1%). The yield of the BNCP thus obtained was ~75% and having the needle
shape crystal.
STRUCTURAL ELUCIDATION OF BNCP
ELEMENTAL ANALYSIS
The experimental results obtained in elemental analysis (6.31% C, 2.23% H, 41.45% N,
12.70% Co) are in agreement with the theoretically calculated values.
INFRARED SPECTROSCOPY
The IR spectrum of BNCP is shown as Figure 2. Presence of functional groups such as
NO2, NH3, ClO4, tetrazole ring, CN in BNCP is confirmed by IR Spectra.
SURFACE ELECTRON MICROSCOPY
To probe the grain orientation, surface emission microscopy (SEM) was used. SEM
micrograph as shown in Figure 3, shows the needle shape crystals of BNCP.
ELECTRON SPECTROSCOPY FOR CHEMICAL ANALYSIS
ESCA Spectrum of BNCP confirms the presence of Nitrogen in two different
environment (Nitrogen in NH3 ligand and Nitrogen in 5-aminotetrazole), Cobalt, Chlorine and
Oxygen. ESCA is also used to calculated the Binding energy of elements present in BNCP.
The structure of BNCP is presented as Figure 4.

mW

Figure 1. IR Spectrum of BNCP

Figure 2. Differential Scanning Calorimetry profile of BNCP

THERMAL ANALYSIS
DIFFERENTIAL SCANNING CALORIMETRY
1.600mg of BNCP was taken for DSC analysis. DSC experiment was carried out with an
inert atmosphere (N2 atmosphere 100ml/min). The DSC of BNCP was taken in the range of
20.00C to 300.00C with an increment of 100C per minute. The DSC profile of BNCP sample
scanned is presented in Figure 2.The DSC analysis shows that BNCP that we synthesized were
thermally stable over a wide range of temperature upto 1500C than the conventional primary
explosive. The enthalpy change of exothermic and endothermic reaction of BNCP was calculated
from the parameters obtained from the DSC profile of BNCP.
EXPLOSIVE CHARCTERISTICS
A number of empirical tests that are used to characterize the inpact sensitivity of
explosives. These tests are useful for safety considerations and design criteria. Many empirical
tests have been devised to assess the relative safety of handling and manipulating of explosives.
These tests attempt to duplicate parts of the complex accident environment to which explosive
materials may be exposed. The majority of these tests involve impact in one form or another.
There are also tests involving exposure to high-temperature sources and to electrical sparks. The
explosive characteristics of BNCP are tabulated in Table 1. The comparison of BNCP with other
primary explosives ( Pb(N3)2, PbC6H3N3O9 and Hg(CNO)2 ) as presented in Table 2 shows it is
superior than other explosives.
Table 1. Characteristic Properties on BNCP Compound
Sl
Properties
No
1

Crystal habit

2
3

Bulk density
Volatile matter
Impact Sensitivity 50%
Height of explosion
F of I (standard CE)
Friction Sensitivity
Figure of insensitiveness
Spark Sensitivity
Insensitive
Explosion Temperature
Velocity of detonation at
loading density 0.6 g/ml
Heat of explosion
Gas volume

4
5
6
7
8
9
10

Observations
Needle shape, Light
Orange colour
0.3 g/ml
0.02%
30 cm 34 cm
< 3.2 kg
Figure 3. Magnified surface view of BNCP using SEM

5 Joules

NO2
N

2600C
5700 m/sec
1053 cal/g
739 cm2/gm

Cl O
N
N NH
3
+

H3N
Co
H3N
NH3

NO2

N N

Figure 4. Structure of BNCP explosive

IMPACT SENSITIVITY
Fall-hammer method was adopted to find impact sensitivity, in this a steel mass called
Falling-hammer of 2kg drops from a pre-determined height on to a striker resting on the top of
the test sample, which is placed on a steel anvil. This 2kg steel mass is held at desired height by
a holding mechanism, on release of which by a lever. The hammer drops on a lubricated vertical
track with practically no friction.
5

For the purpose of Comparison of sensitiveness to impact, the actual force of impact
required for an explosive is not essential, what is determined is the figure of insensitiveness (F of
I) of the explosive under test as compared with that of standard explosive sample; Tetryl
[composition exploding (CE)]. The particle size of CE all passing through 300 micrometer (15sieve), was the standard explosive sample selected and its figure of insensitivity is arbitrarily
taken as 70. F of I is proportional to the minimum height from which the hammer falls causing
the explosive to function. As this height is not always constant due to unreliability of the
explosive, the fifty percent (50%) point (F.P.P) also called Median height, was determined
from a set of reading. If the F.P.P of the explosive is X cm and that of CE is Y cm, the F of I of
the explosive under test can be calculated using the formula as given below.
X
F of I of the explosive under test =
x 70
Y
The test is carried out at 260C under RH of 60% using an dried sample. This is done by keeping
the BNCP sample over silica gel in desicator for 4 days to remove any trace of free water. The
height of 50% explosion for BNCP and CE (Tetryl) were taken for calculating the figure of
insensitiveness as follow.
50% Explosion height of BNCP
F of I for BNCP =
x 70
50% Explosion height of CE
Experimental Result
The impact sensitivity of 50% height of explosion of BNCP is found to be 30 34 cms
SENSITIVITY TO FRICTION
The sensitivity to friction was measured by Julius Peters Apparatus by rubbing a small
quantity of explosive in an unglazed porcelain mortar. The sample being tested was compared
against a standard specimen. An improved method developed by the Bandesansalt Fur Material
Prufung (BAM), German Federal Republic yields reproducible numerical values.
The friction plates 25 x 25 x 5 mm of porcelain material was rigidly attached to the
sliding carriage of the machine so that the lines of sponge had a direction transversal to that of
the movement of the carriage. The loading arm of the machine was tilted upwards, the clamping
device for the porcelain friction pin (pistil) was united by turning it and the friction pin was
clamped into the tongs. The friction pin or pistil is a cylindrical shaped 10mm in diameter and 15
mm in height with a rough spherical end surface on both sides (radius of curvature 10 mm). The
BNCP sample of 2 mg was put partly under and partly in front of the porcelain pin. In this
position the loading arm was carefully set on the sample and weight selected accordingly to the
index on machine was suspended in appropriate position or slot. The load on the pistol may
vary between 0.01 gm and 1000gm. After this preparation for the test, the machine was switched
on and the red lamp on the right side flashed up. Then the button for the motor to start working
was pressed from a distance. It moved the carriage to and fro once by means of the gear and after
wards the movement was stopped automatically. The stroke length is 10 mm each way. Every
pin can be used twice and every plate four times on either side. The magnitude reported is the
smallest load on the pin under which deflagration, cracking or explosion has been noted. At one
load five consecutive test were conducted
Experimental Result
The friction insensitivity data thus been obtained indicate that the BNCP is insensitive to
friction upto 3.2 Kg.

DEFLAGRATION TEMPERATURE

A substance is classed as deflagrating explosive when a small amount of it in an

unconfined condition suddenly ignites when subjected to a flame, spark, shock, friction or
high temperatures. On initiation of deflagrating explosives, local, finite hotspots are
developed either through friction between the solid particulates, but the compression of
voids or bubbles in the liquid component or by plastic flow of the material. This in turn
produces heat and volatile intermediates, which then undergo highly exothermic reaction
in the gaseous phase. This whole process creates more than enough energy and heat to
initiate the decomposition and volatilization of newly exposed surfaces. Concomitantly,
deflagration is a self-propagating process. The rate of deflagration will increase with
increasing degree of confinement. Deflagrating explosive burn faster and more violently
than ordinary combustible materials. They burn with a flame or sparks or a hissing or
crackling noise. The deflagration temperature of BNCP was determined by keeping 2 mg of the
dried sample in a narrow glass tube (3mm diameter and 50 mm long) and it was then plugged
into the woods metal bath heated at the rate of 50C/min.
Experimental Result
The deflagration (explosion) temperature of BNCP was determined by wood metal bath
method taking 2mg sample each time and is found to be 2600C.
VELOCITY OF DETONATION (VOD)
The Velocity of Detonation (VOD) refers to the speed at which a one dimensional
detonation wave representing a shock front, travels through a charge of explosives confined in a
borehole. The VOD of an explosive depends upon various other factors, such as the physical state
of the explosive, whether cast or powdered, density, the constituents, their particle size, the
diameter of the hole (or charge), strength of the material and the degree of confinement [11,12].
The detonation pressure is a measure of the pressure in the detonation wave front. It is a function
of the VOD and the density of an explosive, and is therefore a very important property.
Radiography methodology was used to determine the Velocity of Detonation (VOD) of
BNCP having 0.64 g/c pressing density.
Experimental Result
The Velocity of Detonation of BNCP is found to be 5700 m/s, which is better than lead
azide for which the Velocity of Detonation is 3800 m/s.
COMPARISION OF BNCP WITH CONVENTIONAL EXPLOSIVES
Measured properties of BNCP are compared with reported data of conventional
explosives i.e Lead azide, Lead styphnate and Mercury fulminate in Table 2. The data indicate
that BNCP is superior to conventional primary explosives in following four aspects.
(i) BNCP has greater explosive output
(ii) Undergoes DDT with less confinement, in shorter distance
(iii) Environmentally less hazardous
(iv) Safe in handling

INITIATING TECHNIQUE FOR BNCP

Detonators are used for initiating explosives where a shock wave is required. Detonators
can be initiated by igniters. Igniters used for initiating explosives whose nature is to produce a
flame or flash for their initiation and not a shock as produced by detonators. Explosives of this
kind are known as deflagrating explosives. Detonators / igniter can be initiated by any one of the
following method [13].
a) Electrical means
b) Friction
c) Flash from another igniferous element
d) Stabbing
e) Percussion.
Figure 5. Schematic diagram of an electric detonator
Electrical initiated explosive devices (EIEDs) use electrical energy for initiation. It can
be done by any one of the following methods
i)
ii)
iii)
iv)
v)
vi)

Hot wire initiator

Dipped electric matches
Exploding bridge wire (EBW)
Slapper initiator
Metal film bridge
Semi conductor bridge
Figure 6. Schematic diagram of SCB detonator

SEMI CONDUCTOR BRIDGE

Bick and Schwarz [14] reported in 1985 that Semiconductor Bridge could be used in
place of Wire Bridge for initiation of explosive. BNCP has been used successfully in SCB based
explosive devices [15]. SCB chip has been developed by SSPL, Delhi and SCB detonator for use
in electronic fuze is under development [16]. Work on development of SCB based igniter and
detonator using BNCP is under progress. The schematic diagram of SCB detonator is shown in
Figure 6.
CONCLUSION
From our study it can be stated that BNCP is safe and very low hygroscopic nature.
Comparison of explosive properties confirms that BNCP is superior to Lead azide, Lead
styphnate, and Mercury fulminate. The Explosive characteristics of BNCP analysed from impact,
spark, friction sensitivity, deflagration temperature, velocity of detonation data shows that BNCP
is safe in handling and transportation. In future it will be a possible replacement for the
conventional initiatory explosives. BNCP is compatible with Semiconductor Bridge and it will be
used as an DDT explosive for SCB based electro-explosive devices. The use of BNCP will help
in developing safer explosive devices.

88

ACKNOWLEGEMENT
Authors are highly grateful to Shri PU Deshpande, Director, Armament Research &
Development Establishment, Pashan, Pune and Dr.Haridwar Singh, Director, High Energy
Material Research Laboratory, Pune for constant encouragement, motivation and permission to
present this paper. We extend our sincere thanks to Shri K N Pandey, Associate Director,
Armament Research & Development Establishment, Pashan, Pune and Dr. JP Agrawal,
Associate Director, High Energy Material Research Laboratory, Pune for his constant
encouragement and valuable guidance during the course of this work. Authors expresses sincere
thanks to Shri S Jayraman, Jt. Director, HEMRL for useful discussions and guidance during the
course of this work.
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