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GREEN EXPLOSIVES: POTENTIAL REPLACEMENTS FOR LEAD AZIDE AND OTHER

TOXIC DETONATOR AND PRIMER CONSTITUENTS

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 GREEN EXPLOSIVES: POTENTIAL REPLACEMENTS FOR LEAD AZIDE
AND OTHER TOXIC DETONATOR AND PRIMER CONSTITUENTS
K. D. Oyler,* G. Cheng, N. Mehta, P. Redner, D. Kapoor
U.S. Army RDECOM-ARDEC
The Picatinny Arsenal, Picatinny, NJ 07806-5000

S. Subramanian
Vesta Sciences, Inc.
7 Deerpark Dr. Suite J, Monmouth Junction, NJ 08852-1921

ABSTRACT application in primers. These materials began to see

widespread use in the early 20th century, when they
Primary explosives such as lead azide (LA) are replaced the even more toxic mercury fulminate (MF).
essential to a huge range of military items, yet suffer from The heavy metal, lead, is one of the only 17 substances
serious drawbacks related to their toxicity and lack of listed on the EPA Toxic Chemical List. It is further
domestic production facilities. We have recently begun regulated under the Clean Air Act as a Title II Hazardous
investigating a number of alternative, green replacement Air Pollutant and classified as a toxic pollutant under the
candidates, with a focus on application in stab detonators Clean Water Act. Lead is readily dispersed into the
such as the M55. Candidates include small molecules environment wherever military items are functioned,
such as high nitrogen compounds, as well as inorganic leading to a significant risk of exposure to military
materials based on the newly emerging energetic field of personnel and others who are in close proximity to
nanoporous silicon composites. To date we have found practice ranges or the battlefield.
promising results through the use of triazine triazide
(TTA) in NOL-130-based stab mixes and primer
formulations as lead azide and lead styphnate
replacements. We have also investigated a Navy-
developed lead azide replacement candidate, DBX-1, and
found it to be successful in the M55 detonator. For the
inorganic approach, nanoporous silicon (PSi) powders
were fully characterized, and composites with inorganic
oxidizers were synthesized and have been shown to
possess energetic sensitivity and performance comparable
to primary explosives.

1. INTRODUCTION

Primary explosives (see Fig. 1 for examples) are key
components in military items ranging from the primers
used in small caliber ammunition to detonators employed
in much larger high explosives. They are classified by
their ability to detonate easily through the introduction of
a weak stimulus, including flame, heat, impact, friction,
or electric spark. This detonation is intended to initiate a
secondary or booster explosive, which in turn triggers the
main charge explosive or propellant. Although required
in small quantities relative to main charge formulations
based on RDX and other nitramines, primary explosives
are typically based on lead (Pb), a well-established health
and environmental hazard.
1.1 Lead-based Explosives
Lead-based explosives are ubiquitous in U.S. military
items today. Lead azide is the most widely implemented,
with lead styphnate (LS) also finding extensive
Fig. 1: Examples of common primary explosives
The toxicity issues are further exacerbated by the
scarcity of qualified lead-based explosive production in
the U.S., particularly in the case of LA, which has not
been produced on a large scale domestically since the
Vietnam War era. Instead, the military has been relying
on the rapidly dwindling stockpile of LA; the
questionable quality of this material has led to estimates
that the supply may be exhausted in as little as 3-5 years.
The development of replacements for these lead
compounds is clearly required to reduce the exposure of
the warfighter to toxic substances as well as to circumvent
a major production problem.
1.2 Lead-based Explosive Replacement
To help circumvent these critical issues, it is clear
that less-toxic, more environmentally friendly primary

1
explosive materials are needed. Interest in this area has friction, barium nitrate as an oxidizer, and tetrazene to
picked up considerably over the last decade as the LA impart extra sensitivity). The transfer charge is
stockpile has continued to be depleted; however, very few traditionally lead azide and is intended to initiate the
immediate solutions have presented themselves. In large output charge, a secondary explosive nitramine such as
part, this is due to the necessity for the compounds to RDX.
simultaneously possess several properties (high
sensitivity, stability, low toxicity, and appropriate
performance) which can be a major challenge to find in
one molecule. A number of materials and compounds
have been proposed, and even implemented in
applications. Examples include organics like
diazodinitrophenol (DDNP) (Meyer, 2007) inorganic
fuel/oxidizer combinations such as metastable interstitial
composites (MICs) (Dreizin, 2009), metal coordination
complexes (Huynh et al., 2006a, Huynh et al., 2006b), Fig. 2: The M55 stab detonator
and numerous other compounds described elsewhere
(Huynh et al., 2006a). Recently, the Navy (with In attempting to meet the requirements described
contractor Pacific Scientific) has developed a copper- above and extend them to actual systems such as the M55,
based complex, DBX-1, which has shown success in our efforts to date have focused on two general areas: the
small scale tests. Although promising in terms of small-molecule, high-nitrogen organic approach, and the
performance, many of these compounds have suffered materials-based nanoporous silicon composite approach.
from long-term stability issues, scale-up difficulty, low
yields, and/or excessive sensitivity. 1.3 High Nitrogen Compounds

Towards meeting the goal of discovering viable lead A current focus in the field of new energetic
replacements, we endeavored to investigate compounds discovery is the area of high-nitrogen molecules
that met the following criteria during the course of our (Steinhauser, G. and Klapötke, T., 2008; Talawar, et al.,
investigations: 2009). Although not strictly defined, these compounds
are generally considered to be molecules which contain
 Sufficient sensitivity (e.g. impact, friction) to 50% or more nitrogen content by atom. As a result, the
detonate relatively easily and reliably, yet can still be major detonation product formed from energetic high
handled without excessive danger nitrogen compounds is diatomic N2, which is both non-
 Thermally stable so as to not melt in the item, toxic and gaseous, meaning it is less likely to leave
decompose in storage, or detonate prematurely due to behind unwanted solid residues. Also of great
thermal insult importance, the high stability, low-energy state of the N2
 Avoids other toxic components or environmental product results in potentially large energy output during
hazards detonation—high nitrogen compounds typically possess
 Can be synthesized from a straightforward, one or high heats of formation (Hf). Typically, high nitrogen
two step procedure using inexpensive reagents systems take the form of heterocyclic rings such as
substituted tetrazines or tetrazoles (Fig. 3).
Even when compounds are found which satisfy this
criteria, it is still far from a certainty that they will
perform well in actual items; factors such as critical
diameter and run-up distance can also play a crucial role.
For this reason, we also test our candidates in initiators
such as the M55 stab detonator. The M55 is an ideal
choice because employed by a large number of Army
Fig. 3: Examples of high nitrogen frameworks
items, such as mortars and rockets, and its small size (Fig.
2) means that primary explosives which are successful in
One high nitrogen compound we have investigated
the M55 are also likely to be viable in larger detonators.
extensively is triazine triazide (TTA), also referred to as
The M55 (and most other stab detonators) consist of three
2,4,6-azido-1,3,5-triazine or cyanuric triazide (CTA),
charges (initiating, transfer, and output), the first two of
depicted in Fig. 4. TTA is a known energetic material
which contain LS and/or LA. The initiating charge is
(Ott, 1921; Kessenich, et al, 1998) with high impact and
intended to be highly sensitive so that it can be set off by
friction sensitivity and energy performance comparable to
the stabbing action of a firing pin, and is most often the
lead azide. It is a heavy metal-free polyazide compound
stab mix formulation designated as NOL-130 (consists of
containing only carbon and nitrogen. It was preliminarily
LA and LS, in addition to antimony sulfide for increased
investigated at ARDEC in the mid-1900’s, but was
2
abandoned over concerns with its high sensitivity. Recent
recrystallization efforts at ARDEC have been successful
in producing the material in a safer to handle form and
allowed it to be synthesized at the 50 g level, opening the
door for its possibility as a lead-explosive replacement.
Fig. 4: Selection of investigated candidate compounds
An advantage of working with these high nitrogen
compounds is that they can frequently be tailored, through
the removal of acidic protons, into various metal or
organic salts. Salt formation tends to lead to increased
thermal stability, low volatility, greater density, and the
ability to tune important energetic properties like
sensitivity (Gao, 2007). As a result, we have also been
exploring several metal salts of tetrazole-based systems as
well, including copper 5-nitrotetrazole (DBX-1).
Molecules capable of being converted into salts have also
been studied, such as 5-nitriminotetrazole (NITz), 2-
methyl-5-nitraminotetrazole (MNATz), shown in Fig 4.
1.4 Nanoporous Silicon Composites
In addition to the high-nitrogen approach, inorganic
lead-replacements are also being explored, including the
use of high-surface area fuel/oxidizer composites such as
silicon-based nanomaterials. We have investigated
micron-sized silicon particles which contain sponge-like
nanoscale channels throughout, referred to as nanoporous
silicon (PSi). Nanoporous silicon is a material with a
wide range of potential applications beyond energetics,
including catalysis, photonics, electrochemical
applications such as batteries, and the recycling of silicon
found in photovoltaics. Within the last decade, porous
silicon has begun to be investigated for energetic
applications as a result of observations of its high
reactivity. In 2001, Kovalev et al reported the
observation of explosive reactions even at cryogenic
temperatures when porous silicon was immersed in liquid
oxygen (Kovalev, et al., 2001). This discovery was
extended to more conventional composites in 2002 when
Mikulec et al incorporated gadolinium nitrate into porous
silicon, which was observed to explode when triggered by
friction or an electric spark (Mikulec, et al, 2002).
Additionally, porous silicon composites have also been
3
studied by researchers at the Army Research Laboratory
(ARL) as initiators for devices such as
microelectromechanical systems (MEMS) (Currano et al,
2007). Solution-based incorporation of various inorganic
oxidizers was carried out by Clément et al. (Clément et al,
2005). The sensitive energetic behavior of the material
has been attributed to the high surface area resulting from
the nanoporous nature of the silicon. The greater surface-
to-surface contact between the fuel (silicon) and the
oxidizer (e.g. metal oxide, nitrate, perchlorate, etc.) can
result in an extremely rapid reaction. This type of
behavior has been well studied for other energetic
systems, such as those involving aluminum powders
where nano-sized Al particles have been shown to be
much more reactive than micron-sized particles (Moore,
et al, 2007).
Traditionally prepared through electrochemical
means on Si wafers, the method established at Vesta
Sciences produces a much more practical, economical,
and highly stable material through chemical etching of
bulk Si powder. Electron microscopy images (Fig. 5, left)
depict the porosity and micron particle size of the Vesta
PSi. A key point is that this approach leads to the
formation of a surface that is nearly completely hydrogen-
terminated (Si-H bonds) without any additional
processing steps. Such a surface is highly stable up to 300
°C, thus protecting the material from premature oxidation
in air. Additionally, the material itself is comprised of
micron-sized particles, which themselves contain the
nanoporous channels. Thus, the Vesta PSi has the same
high-surface area advantage as nanoparticles, but without
their safety handling concerns.
Fig. 5: (Left) TEM tomography of a Vesta PSi particle
depicting porosity (acquired by D. Turner and E. Chadwick,
University of Limerick, Ireland), and SEM image (inset) of
bulk powder. (Right) Illustration of oxidizer/energetic
incorporation into pores of PSi.
A great advantage of the silicon framework is that it
provides large potential as a fuel in energetic systems.
The theoretical energy yield from the oxidation of Si is 14
kJ/g (compared to 9 kJ/g for carbon and 16 kJ/g for
aluminum). Although the yield from Al is slightly higher,
aluminum particles readily form a coating of energetically
useless Al2O3 at their surface—this becomes a particular
problem when dealing with small particle sizes, as a
significant portion of each particle will be oxide. In 3.1 High Nitrogen Compound Investigations
contrast, the PSi material produced by Vesta should
remain almost completely un-oxidized, resulting in Several high-nitrogen candidates have been or are
greater energy release. An additional advantage of currently under investigation, including TTA and DBX-1.
nanoscale Si compared to nano-Al is its greater resistance These compounds were characterized and tested in M55
to initiation by electrostatic discharge, a major current detonators as discussed in the Experimental section.
obstacle to the widespread use of Al-based nano- Sensitivity and basic performance data for these
thermites. compounds were measured and summarized in Table 1,
along with data collected for lead azide and basic lead
When it comes to generating energetic composites styphnate.
with the PSi, our oxidizer incorporation methods are
based on several general means: Table 1: Sensitivity and performance data for selected high
nitrogen candidates compared to lead explosives
1. Solution-based: oxidizer is dissolved in organic
solvent, allowed to infiltrate into the Si, then Impact Frict. ESD Dens. DSC VOD
Material
(in) (N) (mJ) (g/cc) (°C) (m/s)
solvent is removed
2. Physical-mixing: oxidizer particles are blended LA 7-11 0.1 4.7 4.80 315 5300
with Si as dry powders LS 5 0.1 0.2 3.00 282 4900
3. Semiconductor techniques: oxidizers (e.g. metal TTA 3 0.1 1.2 1.54 187 6900
oxides) are deposited through evaporation 2.58 333 ~7000
DBX-1 4 0.1 3.1
methods or solution-based sol-gels

To date, we have focused primarily on the first TTA was synthesized in a simple one-step procedure
method (Fig. 5, right), beginning with oxidizers soluble in from cyanuric chloride and sodium azide, in acetone
organic solvents (e.g. methanol, ethanol, etc.), as the solution (Fig. 6). Isolation is obtained by simple crash-
hydrophobic Si surface will resist infiltration by aqueous precipitation in water. This simplicity of production is
solutions. what has allowed the material to be easily synthesized to
at least 50 g. Its sensitivity and performance values are
2. EXPERIMENTAL comparable to LA, although it suffers from a relatively
low density (1.54 g/cc) and is not as thermally stable,
2.1 Performance Evaluation although with a melting point of 94 °C and decomposition
point of 187 °C it falls within desired parameters.
After obtaining the green candidate materials (either Compatibility tests carried out by differential scanning
through synthesis or outside sources), they were calorimetry (DSC) show TTA to be compatible with
characterized for purity (NMR, DSC) and also by aluminum and stainless steel, as well as energetic
sensitivity tests (ball-drop impact, BAM friction, and nitramines including RDX, HMX, and CL-20.
ESD. Subsequently, their energetic performance was
tested by loading them as transfer charges into M55
detonators. As discussed previously, stab detonators such
as the M55 are actually three separate charges. In a
typical performance study, standard NOL-130 stab mix
was pressed into an aluminum M55 detonator cup at
70,000 psi of pressure, followed by the green candidate
material pressed at approximately 15,000 psi on top of the
NOL-130. Finally, the RDX output charge was pressed at
Fig. 6: TTA synthesis.
10,000 psi to complete the process. Detonators were then
fired—through ball-drop initiation with a firing pin—onto
Despite appearing promising based on these initial
steel or lead witness plates. The resulting plate dents
tests, TTA did not perform as well when loaded into M55
where then measured for depth using laser profilometry
detonators as replacement for LA in the transfer charge.
and compared to the standard dents made by LA-based
As shown in Table 2, TTA did not yield a measurable
detonators. As specified in MIL-D-14978A, the dent
dent on steel witness plates (and only ~0.04 in on lead
requirement for an M55 should be at least 0.01 inches in a
plates). Further, when TTA was also used as the output
steel witness plate; this corresponds to roughly 0.08
charge as well as the transfer charge, the same result was
inches in a lead plate.
observed. This finding strongly implies that the TTA is
not sufficiently powerful in the M55 to achieve high-order
3. RESULTS AND DISCUSSION
detonation of the RDX output charge. This is likely a
result of critical diameter or run-up distance issues; the
4
low density of TTA relative to LA is a major contributor Table 1, the properties of DBX-1 are also similar to LA
as well. and TTA, but it does have the benefit of a substantially
greater density compared to TTA. Perhaps attributed at
Table 2: M55 detonator performance for selected high least partially to this reason, DBX-1 also performed better
nitrogen candidates (refer to Fig. 2 for diagram of M55) in the M55 detonator tests, leading to consistently fired
items which yielded acceptable dent depths (Table 2).
Initiating Transfer Output Steel dent These results help to confirm the promise of DBX-1 as an
Charge Charge Charge depth (in) eventual LA replacement. However, at the current time
NOL-130 Lead Azide RDX 0.0148 DBX-1 is still limited to relatively small batch sizes of
NOL-130G Lead Azide RDX 0.0140 approx. 5 g, and significant effort must be put into the
scale up of the compound before it can be qualified.
NOL-130 TTA RDX ~0*
Additionally, although considerably more non-toxic than
NOL-130 TTA TTA ~0* lead, copper can still be a health and environmental
NOL-130 TTA CL-20 ~0* hazard at high concentrations.
NOL-130 TTA PETN ~0*
Other high nitrogen compounds were also evaluated,
NOL-130 DBX-1 RDX 0.0153
such as NITz and MNATz. However, these compounds
NOL-130G DBX-1 RDX 0.0123 were found to be unsuitable due to low thermal stability
*detonators fired successfully, but were not powerful enough to and insufficient impact sensitivity, respectively. Current
dent the steel plate ongoing efforts are focused on metal salt derivatives of
these compounds, including complexes with copper,
Several attempts were made to improve this situation calcium, and similar metals.
in the M55. One strategy involved recrystallizations of
the TTA from acetone/water in order to exert control over 3.2 Nanoporous Silicon Investigations
the particle size and morphology, the goal being to
improve packing densities in the M55 and increase The PSi material used in these studies was produced
performance. Although a degree of crystal control was at the Vesta facility located in Monmouth Junction, NJ via
demonstrated (Fig. 7), no improvement was observed a chemical etching method (Fig. 8) involving the
upon functioning additional M55 detonators. Another treatment of bulk Si particles with an aqueous solution of
strategy involved the use of more sensitive (relative to hydrofluoric acid (HF) and nitric acid (HNO 3). The
RDX) output charges in the M55. This method proved process is capable of producing as much as 500 g of PSi
equally unsuccessful even through the use of CL-20 or per batch.
PETN.

Instead of focusing on transfer-charge replacement in

the M55, the replacement of the LA and LS found in the
initiation charge—the NOL-130 stab mix—was explored
with TTA. For this approach, TTA was blended through
a physical mixing process with antimony sulfide, barium
nitrate, and tetrazene to create a new formulation
designated NOL-130 Green (NOL-130G). As illustrated
in Table 2, replacing the standard NOL-130 with this
TTA-based mixture led to successfully functioning M55
detonators, which also met the required dent depths.
Figure 7: Various TTA particle sizes and morphologies
obtained through recrystallization
Fig. 8: Synthetic process for Vesta PSi.
The porosity of the material was observed through
TEM tomography (Fig. 5, left) and can also be verified by
the observance of photoluminescence when the material is
excited with ultraviolet light—this feature is indicative of
quantum confinement and also confirms the presence of
the nanostructures (Fig. 9). Surface areas and pore sizes
of the etched powders were determined by Brunauer-
Emmett-Teller (BET) analysis. Through the modification
of the etching parameters, surface area, particle size, and
porosity could effectively be tailored. Depending on
conditions, particle sizes were found to range between 4
and 11 microns, with surface areas between 41 and 143
m2/g. Typically, the pore size averaged about 5 nm, but
this value could be increased to 11 nm by post-treatment
of the samples with etching solution.

Another investigated compound was DBX-1,

prepared from copper chloride and nitrotetrazolate salt in
a one-step process in aqueous solution. As shown in
5

1.4
Intensity (arb. Units)
1.2
1
0.8
0.6
0.4
0.2
0
0.5
Fig. 9: Photoluminescence of PSi, confirming quantum
confinement provided by the nanoscale structure.
As expected, the hydrogen-terminated material was
found to be extremely stable over time at temperatures up
to 300 °C. As diffuse reflectance infrared transmission
spectroscopy (DRIFTS) indicates on a standard sample of
prepared PSi, at room temperature (Fig. 10, trace a) the
Si-H bonds are clearly observed at approximately 600,
900, and 2100 cm-1. These features are still observed
after annealing for 3 hours in air at 150 °C along with the
presence of back-bonded oxygen, creating a stable surface
(Fig. 10, trace b). Heating to 500 °C for 30 min leads to
the complete release of the bonded hydrogen, allowing
air-oxidation to readily take place (Fig. 10, trace c). X-
ray photoelectron spectroscopy (XPS) measurements
(data not shown) also showed no change in the material
over the period of one year, indicating its resistance to
oxidation over time.
Fig. 10: DRIFTS spectra of PSi sample at elevated
temperatures.
To confirm the inertness of the pure PSi material,
ERL impact, BAM friction, and ESD sensitivity tests
were carried out. The tests verified the nearly complete
insensitivity of the material, as no reaction was observed
at the maximum settings for each instrument (100 cm for
impact, 360 N for friction, and 0.25 J for ESD).
Most notably, we have begun to carry out
investigations of composites of the PSi with various
oxidizers. To date, we have mainly focused on solution-
based incorporation (Clément et al, 2005), as these
methods present the most straightforward and simple
approach to generating PSi/oxidizer combinations. For
our initial studies, we have focused on the use of
perchlorate metal salts (NaClO4, LiClO4, etc.) as the
oxidizing constituent. Although by no means considered
to be green materials, perchlorates are a useful class of
initial tests subjects, as they combine high solubility in
organic solvents (necessary for infiltration into the
hydrophobic PSi structure) with very high oxidizing
1 1.5 2 2.5 3
power. As a result, composites with perchlorates will
Energy (eV) help to give an indication of the upper limits of the
material in terms of reactivity and energetic output.
In a typical synthesis, a concentrated solution of
perchlorate salt was prepared in an organic solvent such
as methanol. Generally, a roughly stoichiometric amount
of perchlorate solution was added in stages to PSi powder
possessing roughly 120 m2/g of surface area. After
solvent removal, the powder was physically blended with
extreme caution to insure a consistent mixture. To date,
this procedure has been scaled up the 5 g level with
NaClO4 as the oxidizer. This material was thoroughly
tested for sensitivity by impact, friction and ESD. After
statistical analysis, the 50 % impact height (Bruceton)
value was measured at 12.8 cm, the friction threshold was
found to be 16 N, and no reaction by ESD was observed
for 20 trials at 0.12 J. For purposes of comparison, PETN
(generally considered to possess borderline sensitivity
between primary and secondary classification) has a 50 %
impact height of 13.9 cm, and friction of 64 N. As a
result, the PSi/NaClO4 composite can be classified as a
primary explosive in terms of sensitivity. Notably, the
material is not overly sensitive to electrostatic discharge
(IAW DA PAM does not recommend any special ESD
safety equipment for substances which are over 0.1 J in
sensitivity, meaning this material is considerably safer to
handle than traditional primary explosives. Also,
considering that Al-based MIC compounds such as
nanothermites possess ESD sensitivity of 0.001 J or less,
this feature shows the promise of PSi-based materials for
these applications as well. In terms of thermal stability,
no reaction was generally observed until approximately
300 °C. As this is the same temperature region observed
to remove the hydrogen surface layer, this observation
suggests the advantage of the H-termination in protecting
the Si surface.
Formal testing of the explosive performance of the
composites is ongoing. However, qualitative observations
of the material’s performance during functioning reveals
very high outputs of both light and sound, suggesting a
rapid, substantial amount of energy being released.
4. CONCLUSIONS
We have investigated a number of materials for
applicability as replacements for lead-based explosives
such as LA and LS and focusing on high nitrogen
molecules as well as inorganic nanoporous
silicon/oxidizer composites. TTA shows promise as a
lead-replacement in stab initiation mixtures such as NOL-
6
 130, whereas DBX-1 appears to effectively replace LA in
the transfer charge of M55 detonators. Early
investigations of the PSi/perchlorate composites prove
them to possess appropriate sensitivity and energetic
performance to be promising as primary explosive
materials. In particular, their relative insensitivity to ESD
helps set them apart from most other primary explosives
and nanothermites. Future efforts are being undertaken to
incorporate various other oxidizers and even explosive
molecules into the PSi structure. Potential applications to
be explored include detonator as well as primer
applications.
ACKNOWLEDGEMENTS
We gratefully acknowledge funding support from the
RDECOM Ordinance Environmental Program (OEP),
PEO Ammunition, and the Small Business Innovation
Research (SBIR) program. We also thank R. Duddu and
K. Yang of SAIC as well as R. Damavarapu from
ARDEC for assistance in the synthesis and analysis of the
high-nitrogen compounds. In addition, DSC data was
collected by H. Grau, ARDEC, and sensitivity data
determined by J. Rivera and J. Marin of ARDEC. TEM
tomography was performed by D. Tanner and E.
Chadwick of the University of Limerick, Ireland.
Interaction of Hydrogenated Porous Silicon with
Oxygen at Cryogenic Temperatures, Phys. Rev. Lett.,
87, 068301.
Meyer, R., 2007: Explosives, 6th Edition, Wiley-VCH.
Mikulec, F., Kirtland, J., Sailor, M., 2002: Explosive
Nanocrystalline Porous Silicon and its use in Atomic
Emission Spectroscopy, Adv. Mater., 14, 38-41.
Moore, K., Pantoya, M., Son, S., 2007: Combustion
Behaviors resulting from Bimodal Aluminum Size
Distributions in Thermites, J. of Propulsion and
Power, 23, 181-185.
Ott, K., 1921: Explosive and Process of Making Same,
US Patent 1,390,378, filed Sept. 13, 1921.
Steinhauser, G., Klapötke, T., 2008: “Green” Pyro-
technics: A Chemists’ Challenge, Angew. Chem. Int.
Ed., 47, 3330-3347.
Talawar, M., Sivabalan, R., Mukundan, T., Muthurajan,
H., Sikder, A., Gandhe, B., Rao, A., 2009:
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