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ARTICLE

DOI: 10.1002/zaac.201400053

Primary Explosives
Neha Mehta,*[a] Karl Oyler,[a] Gartung Cheng,[a] Akash Shah,[a] John Marin,[a] and
Kin Yee[a]

Keywords: Energetic materials; “Green” explosives; Primary explosives; DBX-1; Lead

Abstract. Primary explosives, unlike secondary explosives, show a
very rapid transition from combustion (or deflagration) to detonation
and are considerably sensitive to small stimuli, such as impact, friction,
electrostatic discharge, and heat. Primary explosives generate either a
large amount of heat or a shockwave, which makes the transfer of
the detonation to a less sensitive propellant or secondary explosive
possible.[1] Primary explosives are key components in detonators and
primers, which are the initiating elements to many military items such
as small, medium, and large caliber munitions, mortars, artillery, war-
heads, etc. The two most common military primary explosives are lead
azide and lead styphnate. Lead based compounds such as these have
well-established hazards to health and the environment. To overcome
these concerns, in common U.S. Army detonators and primers lead
azide was replaced with DBX-1 [copper(I) nitrotetrazolate], recently
developed by Pacific Scientific Energetic Materials Company and the
U.S. Naval Surface Warfare Center at Indian Head. Further, in order
to minimize the dangers to personnel and equipment associated with
synthesizing and handling primary explosives, a dedicated, remote-
operated facility for the synthesis and testing of primary explosives
has been developed.

1 Introduction
Primary explosives are very sensitive materials that can be
easily ignited by small stimuli of heat, impact, friction, and
electrostatic. Very small amount of energy is needed to initiate
such material; it is considered to be the materials that are more
sensitive than PETN.
Primary explosives are required to set off less sensitive ener-
getics such as secondary explosives (RDX, HMX, etc.) or pro-
pellants. Primary explosives are usually in milligram quantities
that are part of an energetic train that is required to set off
large quantity of secondary explosives.
Primary explosives are usually in milligram quantities that
are part of an energetic train that is required to set off large
quantity of secondary explosives. In large quantities they are
extremely dangerous to handle because of their sensitivity. Pri-
mary explosives are widely used in detonators, primers, blast-
ing caps, and initiators. The most commonly used primary ex-
plosives are lead azide, lead styphnate, and tetrazene (Fig-
ure 1).
Lead azide is the most powerful of all and is usually used
as a neat material in a transfer charge in detonators or in for-
mulations for stab initiation mix (e.g. NOL-130) or primer
mixes as it is easier to initiate. It is very sensitive to impact Figure 1. Ball drop impact test for primary explosives.
and friction; has a good shelf life in dry conditions, but is
unstable in the presence of oxidizing agents and ammonia.[2]
It cannot be dead pressed even at relatively low pressures. There are several types of lead azide but the most common are
RD-1333 and dextrinated lead azide. RD-1333 is 99 % pure
* N. Mehta
and relatively used in small detonators as transfer charge,
Fax: +1-973-724-5869 whereas dextrinated lead azide is approximately 93 % pure and
E-Mail: neha.mehta.civ@mail.mil usually used in larger detonators, blasting caps, and priming
[a] Explosives Development Branch
U.S.Army RDECOM-ARDEC compositions. Lead styphnate is used in formulations with lead
Picatinny Arsenal, NJ 07806–5000, USA azide for primer and initiation mixes and rarely found as a neat

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ARTICLE
material in applications as it is a poor initiator for detonation.
It is very sensitive to static discharge and is very dangerous to
handle. There are two forms of lead styphnate – normal and
basic. Basic lead styphnate has lower nitrogen content than
normal; both are used as ingredients in priming compositions.
Tetrazene is added in the formulations as a sensitizer, espe-
cially in stab initiation and primer mixes. Tetrazene is hydro-
lytically not entirely stable and in long term studies decom-
poses at temperatures above 90 °C.[3]
Although lead azide has been heavily employed for decades,
it is a very poisonous material that reacts with copper, zinc, or
alloys containing such metals, forming other azides that can be
highly sensitive and dangerous to handle. Further, lead-based
materials are well established to cause environmental and
health related problems. Lead-based materials are cataloged on
the EPA Toxic Chemical List (EPA list of 17 toxic chemicals);
they are additionally regulated under the Clean Air Act as Title
II Hazardous Air Pollutants, as well as classified as toxic pol-
lutants under the Clean Water Act, and are on the Superfund
list of hazardous substances.[4] Recently, under the Clean Air
Act, USEPA (U.S. Environmental Protection Agency) revised
the National Ambient Air Quality Standard (NAAQS) to
0.15 μg·m–3, which is ten times more stringent than the pre-
vious standard.[5] Lead is both an acute and chronic toxin, and
the human body has difficulty in removing it once it has been
absorbed and dissolved in the blood. Consequently, a chief
concern is the absorption of lead by humans from exposure to
initiating mix constituents, as well as the combustion by-prod-
ucts of lead based compositions. The health effects of lead are
well documented; however, recent studies have shown that
there are no safe exposure levels for lead, in particular for
children. There is a direct correlation between lead exposure
and developmental impacts, including IQ loss (even at the re-
vised lead NAAQS, exposure levels are consistent with an IQ
loss of over 2 points), behavioral issues and even hearing
loss.[6] Their use during training and testing deposits heavy
metals on ranges and can impact sustainable use of these ran-
ges.
These initiator and transfer charge compositions also require
expensive handling procedures during production and disposal.
Manufacturing of any lead-based primary explosives, such as
lead azide or lead styphnate, results in the production of sig-
nificant quantities of highly toxic hazardous waste. Handling
and storage of these compounds is also a concern.
Due to its environmental and health impact, there is a need
to develop “green” primary explosives, to replace lead based
compounds. We are seeking to replace lead azide and lead
based formulations in commonly used detonators, specifically
M55 stab detonators and percussion primers, such as M115,
M39, M42, etc. When seeking replacements for the lead com-
pounds, one important strategy we are focused on is the use of
high nitrogen compounds. These are widely considered to be
viable environmental energetics as the predominant detonation
product is non-toxic nitrogen (N2) gas,[7,8] at the same time,
they possess high heats of formation (Hf), which lead to high
energy output, in developing/testing a viable lead replacement,
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N. Mehta et al.
the following criteria are considered when investigating new
compounds.
(i) Material must be safe to handle and possess a rapid defla-
gration to detonation transition.
(ii) Must be thermally stable to greater than 150 °C and must
have a melting point greater than 90 °C.
(iii) Also should possess high detonation performance and
sensitivity.
(iv) Should have long term chemical stability.
(v) Should not contain toxic heavy metals or other known
toxins.
(vi) Easy to synthesize and affordable.
Over the years, there have been numerous attempts to use a
variety of materials to serve as a lead azide replacement. These
materials range from high-nitrogen compounds such as DDNP,
TTA, NiTZ, and materials based on metallic nanothermites
such as metastable intermolecular composites (MIC). Unfortu-
nately, these approached have not served as an adequate to
lead azide for numerous reasons. Other high nitrogen materials
and MIC did not meet the performance requirement or the pro-
cess was too tedious in synthesizing the material or there was
an issue meeting the requirements as mentioned above. To
date, the only viable material that has shown promise as a
“green” “drop-in” replacement to lead azide is DBX-1, cop-
per(I) 5-nitrotetrazolate. This material was first developed by
Pacific Scientific Energetic Materials Company (PSEMC), un-
der contract from the U.S. Naval Surface Warfare Center, In-
dian Head (NSWC-IH). We are currently focused on investiga-
ting the applicability of this material in the U.S. Army detona-
tor, primers, blasting caps, etc.
In addition, we at ARDEC have optimized the synthesis of
sodium nitrotetrazolate, which is the precursor for the synthe-
sis of DBX-1.[9] We are also looking at the long term stability
and compatibility studies of DBX-1 in detonators and pri-
mers.[10]
At the same time as we are developing to optimize the com-
pound, we are looking into minimizing the dangers to person-
nel and equipment associated with synthesizing and handling
primary explosives. For this reason, a remote-operated facility
dedicated only to synthesizing, scale-up and testing primary
explosives was developed by us in collaboration with Franklin
Engineering.
Though preliminary concerned with developing and opti-
mizing DBX-1, scientists/engineers at ARDEC are also con-
cerned with the synthesis of new explosives, such as for exam-
ple the recently synthesized potassium dinitraminobistetrazol-
ate.[1]
2 Experimental Section
When investigating a primary explosive candidate, first the sensitivity
tests (ball drop impact, BAM friction and electrostatic discharge) were
conducted to understand the sensitivity of a material and how to handle
the material for safety.
2.1 Ball Drop Impact Test
Impact sensitivity for primary explosive was measured by an in-house
customized ball-drop apparatus,[11] shown in Figure 1, which subjected
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Primary Explosives

a primary explosive to an impact of a free-falling steel ball. The stan- Initiation Level (TIL). Testing was usually begun at the minimum load
dard sample size was 30 mg for each trial. The steel ball normally used of the apparatus (0.1 N) for primary explosives or higher if experience
had a diameter of 1.9 cm and weighed 28.3 g. The steel ball was warranted it. If a reaction occurred in ten trials, the load was reduced
guided on a ball track which rose 81.28 cm vertically from a steel until no reactions were observed in ten trials.
base. The ball track might be moved up or down and locked in place.
A stainless-steel block was used as the sample holder. An iterative
procedure, varying the drop height in 2.54 cm increments, was used to
2.3 Electrostatic Sensitivity Test
determine the highest height at which no positive results were obtained
in 20 trials. This value was considered the Threshold of Initiation The ABL electrostatic test apparatus, shown in Figure 3, manufactured
Level (TIL). by Safety Management Services (SMS), performed the tests using the
“approaching needle” method.[12] The approaching needle simulated
an event of two objects coming together, one with a positive and one
2.2 BAM Friction with a negative charge, such that a discharge occurred at a finite sepa-
ration distance. The discharge of electrical energy occurred as a spark
The BAM Small Friction tester, shown in Figure 2, was used to deter-
at a single point. To accomplish this, the discharge needle was moved
mine the friction sensitivity of the sample. The Small BAM Friction
Test Method was described in STANAG 4487 “Explosives, Friction rapidly toward the test sample by an air-operated solenoid. As the
gap between the needle and ground closed, the electrical energy was
Sensitivity Tests”.[12] Approximately 30 mg of the sample was placed
discharged through the sample. The ABL ESD Test Apparatus gener-
on the porcelain plate. The porcelain pin was lowered onto the sample
and a weight was placed on the arm to produce the desired load. The ated voltages up to 10,000 VDC with energies as high as 37.5 J. All
tests were conducted using 5,000 VDC. At 5,000 VDC, the ABL ESD
tester was activated and the porcelain plate was reciprocated once to
Test Apparatus was capable of delivering energy from 0.0013 to 9.4 J.
and from. The results were observed as either a reaction (i.e. flash,
smoke, and/or audible report) or no reaction. An iterative procedure
was used to determine the highest load, at which no positive results
were obtained in 10 trials. This value was considered the Threshold of

Figure 2. BAM small friction test.

Figure 3. SMS ABL ESD test. Figure 4. (a) DSC. (b) Optical microscope. (c) SEM.

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ARTICLE N. Mehta et al.

Figure 4c) images and energy dispersive spectroscopy (EDS) spectra

were collected with an EVEX mini-SEM SX3000 instrument.

2.5 Performance Studies

Once the safety criteria were met, performance testing was done to
see how well the material behaved in an item. As mentioned earlier,
candidates were loaded into M55 detonators, using arbor hand presses
(Figure 5a) and tested for performance using stab detonator ball drop
test (Figure 5b).

For M55 detonators, first the initiation mix (15 mg), which comprises
of lead based formulations (lead azide, lead styphnate, tetracene, bar-
ium nitrate, antimony sulfide) was pressed at 482.6 mPa. The transfer
charge – “green” candidate to replace lead azide – was pressed at
68.9 mPa followed by RDX (output charge – 19 mg) pressed at
103.4 mPa; finally, the detonator was crimped with the foil. The com-
pleted detonator was transferred to a holder containing a witness plate
and a firing pin was placed on top. A 7.09 g steel ball was dropped
onto the firing pin from 7.62 cm height to initiate it, and the resulting
dent on the witness plate was measured by laser profilometer (Fig-
ure 5c). As specified in MIL-D-14978A, the dent requirement for an
M55 should have been at least 0.0254 cm in a steel witness plate.

Electric Detonators or blasting caps were fired in mini chamber as

shown in Figure 6. Detonation velocity and detonation pressure were
also conducted in this chamber to find the values for new primary
explosives at small scale. For primer performance testing, primers
were sealed in air-tight test apparatus and initiated by dropping a
226.8 g or 453.6 g steel ball; pressure transducers measured the output
(Figure 7).

Figure 6. Small firing chamber.

Figure 5. (a) Arbor press. (b) Stab detonator ball drop. (c) Laser profi-
lometer.

2.4 Analytical Studies

DSC and NMR (Figure 4a) were conducted to analyze the purity of
the material and also for the stability and to understand the chemical/
physical properties. Additional details were determined by optical mi-
croscopy (Figure 4b), for which scanning electron microscopy (SEM- Figure 7. Primer performance test setup.

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Primary Explosives
Figure 8. Primary explosives automated remote lab synthesizer (PE-
ARLS).
2.6 Safety Measures
When handling primary energetic materials, one knows that being ex-
tra careful and following all the safety precaution is a must. Wearing
cotton clothes (including underclothes) conductive shoes, Kevlar
gloves, Kevlar wrist protector, leather coat, full face shield, etc. is a
basic safety measure to follow when working with or handling primary
explosives. One should also use a conductive spatula and conductive
containers to mix or store primary energetic materials. One can never
be too extra careful when handling primary energetics material. For
safety reasons, ARDEC worked with Franklin Engineering to develop
customized synthesis and scale-up systems to safely make primary ex-
plosives. Figure 8 and Figure 9 shows our automated systems, Primary
Explosives Automated Remote Lab Synthesizer (PEARLS) and Pri-
mary Explosives Automated Remote Scale-up System (PEARSS).
Acknowledgements
We would like to acknowledge RDECOM Environmental Quality
Technology Ordnance Environmental Program and PM-JS for their
funding support. We would also like to thank Franklin Engineering,
especially Charlie Sturdivant, for his patience in designing the auto-
mated systems. Also like to thank Thomas M. Klapötke and his team
and Jerry Salan of Nalas Engineering.
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Pages: 6
Figure 9. Primary explosives automated remote scale-up system (PE-
ARSS).
References
[1] T. M. Klapötke, N. Mehta, Propellants Explos. Pyrotech. 2014,
39, 7–8.
[2] J. Akhavan, Chemistry of Explosives, 3rd ed., The Royal Society
of Chemistry, Cambridge, UK, 2011, p 35.
[3] T. M. Klapötke, Chemistry of High Energy Materials, 2nd ed., De
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[4] Overall Evaluations of Carcinogenicity to Humans, Int. Agency
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[5] Technology Transfer Network, Environmental Protection Agency
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[6] National Ambient Air Quality Standards (NAAQS) Environmental
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[7] G. Steinhauser, T. M. Klapötke, Angew. Chem. Int. Ed. 2008, 47,
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[8] M. Talawar, R. Sivabalan, T. Mukundan, H. Muthurajan, A.
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[10] T. M. Klapötke, N. Mehta, D. Piercey, J. Sabatini, K. Oyler, Z.
Naturforsch. 2014, 69b, 125–127.
[11] T. Dolch, N. Mehta, Technical Report ARMET-TR-09045, 2009.
[12] AOP-7 (Edition 2) – Manual of Data Requirements and Tests for
the Qualification of Explosive Materials for Military Use.
Received: January 31, 2014
Published Online: 䊏
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ARTICLE N. Mehta et al.

N. Mehta,* K. Oyler, G. Cheng, A. Shah, J. Marin,

K. Yee ................................................................................ 1–6
Primary Explosives

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