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 Primary explosives such as lead azide (LA) are essential to a huge range of military items, yet suffer from serious drawbacks related to their toxicity and lack of domestic production facilities. We have recently begun investigating a number of alternative, green replacement candidates, with a focus on application in stab detonators such as the M55. Candidates include small molecules such as high nitrogen compounds, as well as inorganic materials based on the newly emerging energetic field of nanoporous silicon composites. To date we have found 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 Navydeveloped 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

application in primers. These materials began to see widespread use in the early 20th century, when they replaced the even more toxic mercury fulminate (MF). The heavy metal, lead, is one of the only 17 substances listed on the EPA Toxic Chemical List. It is further regulated under the Clean Air Act as a Title II Hazardous Air Pollutant and classified as a toxic pollutant under the Clean Water Act. Lead is readily dispersed into the environment wherever military items are functioned, leading to a significant risk of exposure to military personnel and others who are in close proximity to practice ranges or the battlefield.

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

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

To help circumvent these critical issues, it is clear that less-toxic, more environmentally friendly primary

explosive materials are needed. Interest in this area has picked up considerably over the last decade as the LA stockpile has continued to be depleted; however, very few immediate solutions have presented themselves. In large part, this is due to the necessity for the compounds to 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), and numerous other compounds described elsewhere (Huynh et al., 2006a). Recently, the Navy (with contractor Pacific Scientific) has developed a copperbased complex, DBX-1, which has shown success in small scale tests. Although promising in terms of performance, many of these compounds have suffered from long-term stability issues, scale-up difficulty, low yields, and/or excessive sensitivity. Towards meeting the goal of discovering viable lead replacements, we endeavored to investigate compounds that met the following criteria during the course of our investigations: Sufficient sensitivity (e.g. impact, friction) to detonate relatively easily and reliably, yet can still be handled without excessive danger Thermally stable so as to not melt in the item, decompose in storage, or detonate prematurely due to thermal insult Avoids other toxic components or environmental hazards Can be synthesized from a straightforward, one or two step procedure using inexpensive reagents

friction, barium nitrate as an oxidizer, and tetrazene to impart extra sensitivity). The transfer charge is traditionally lead azide and is intended to initiate the output charge, a secondary explosive nitramine such as RDX.

Fig. 2: The M55 stab detonator

In attempting to meet the requirements described above and extend them to actual systems such as the M55, our efforts to date have focused on two general areas: the small-molecule, high-nitrogen organic approach, and the materials-based nanoporous silicon composite approach. 1.3 High Nitrogen Compounds A current focus in the field of new energetic discovery is the area of high-nitrogen molecules (Steinhauser, G. and Klaptke, T., 2008; Talawar, et al., 2009). Although not strictly defined, these compounds are generally considered to be molecules which contain 50% or more nitrogen content by atom. As a result, the major detonation product formed from energetic high nitrogen compounds is diatomic N2, which is both nontoxic and gaseous, meaning it is less likely to leave behind unwanted solid residues. Also of great importance, the high stability, low-energy state of the N2 product results in potentially large energy output during detonationhigh nitrogen compounds typically possess high heats of formation (Hf). Typically, high nitrogen 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 items, such as mortars and rockets, and its small size (Fig. 2) means that primary explosives which are successful in the M55 are also likely to be viable in larger detonators. The M55 (and most other stab detonators) consist of three charges (initiating, transfer, and output), the first two of which contain LS and/or LA. The initiating charge is intended to be highly sensitive so that it can be set off by the stabbing action of a firing pin, and is most often the stab mix formulation designated as NOL-130 (consists of LA and LS, in addition to antimony sulfide for increased

Fig. 3: Examples of high nitrogen frameworks

One high nitrogen compound we have investigated extensively is triazine triazide (TTA), also referred to as 2,4,6-azido-1,3,5-triazine or cyanuric triazide (CTA), depicted in Fig. 4. TTA is a known energetic material (Ott, 1921; Kessenich, et al, 1998) with high impact and friction sensitivity and energy performance comparable to lead azide. It is a heavy metal-free polyazide compound containing only carbon and nitrogen. It was preliminarily investigated at ARDEC in the mid-1900s, but was

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.

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 Clment et al. (Clment 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 surfaceto-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 hydrogenterminated (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. 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), 2methyl-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

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 surfacethis becomes a particular problem when dealing with small particle sizes, as a

significant portion of each particle will be oxide. In contrast, the PSi material produced by Vesta should remain almost completely un-oxidized, resulting in greater energy release. An additional advantage of nanoscale Si compared to nano-Al is its greater resistance to initiation by electrostatic discharge, a major current obstacle to the widespread use of Al-based nanothermites. When it comes to generating energetic composites with the PSi, our oxidizer incorporation methods are based on several general means: 1. Solution-based: oxidizer is dissolved in organic solvent, allowed to infiltrate into the Si, then solvent is removed Physical-mixing: oxidizer particles are blended with Si as dry powders Semiconductor techniques: oxidizers (e.g. metal oxides) are deposited through evaporation methods or solution-based sol-gels

3.1 High Nitrogen Compound Investigations Several high-nitrogen candidates have been or are currently under investigation, including TTA and DBX-1. These compounds were characterized and tested in M55 detonators as discussed in the Experimental section. Sensitivity and basic performance data for these compounds were measured and summarized in Table 1, along with data collected for lead azide and basic lead styphnate.
Table 1: Sensitivity and performance data for selected high nitrogen candidates compared to lead explosives Material LA LS TTA DBX-1 Impact (in) 7-11 5 3 4 Frict. (N) 0.1 0.1 0.1 0.1 ESD (mJ) 4.7 0.2 1.2 3.1 Dens. (g/cc) 4.80 3.00 1.54 2.58 DSC (C) 315 282 187 333 VOD (m/s) 5300 4900 6900 ~7000

2. 3.

To date, we have focused primarily on the first method (Fig. 5, right), beginning with oxidizers soluble in organic solvents (e.g. methanol, ethanol, etc.), as the hydrophobic Si surface will resist infiltration by aqueous solutions. 2. EXPERIMENTAL 2.1 Performance Evaluation After obtaining the green candidate materials (either through synthesis or outside sources), they were characterized for purity (NMR, DSC) and also by sensitivity tests (ball-drop impact, BAM friction, and 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 10,000 psi to complete the process. Detonators were then firedthrough ball-drop initiation with a firing pinonto steel or lead witness plates. The resulting plate dents where then measured for depth using laser profilometry and compared to the standard dents made by LA-based detonators. As specified in MIL-D-14978A, the dent requirement for an M55 should be at least 0.01 inches in a steel witness plate; this corresponds to roughly 0.08 inches in a lead plate. 3. RESULTS AND DISCUSSION

TTA was synthesized in a simple one-step procedure from cyanuric chloride and sodium azide, in acetone solution (Fig. 6). Isolation is obtained by simple crashprecipitation in water. This simplicity of production is what has allowed the material to be easily synthesized to at least 50 g. Its sensitivity and performance values are comparable to LA, although it suffers from a relatively low density (1.54 g/cc) and is not as thermally stable, although with a melting point of 94 C and decomposition point of 187 C it falls within desired parameters. Compatibility tests carried out by differential scanning calorimetry (DSC) show TTA to be compatible with aluminum and stainless steel, as well as energetic nitramines including RDX, HMX, and CL-20.

Fig. 6: TTA synthesis.

Despite appearing promising based on these initial tests, TTA did not perform as well when loaded into M55 detonators as replacement for LA in the transfer charge. As shown in Table 2, TTA did not yield a measurable dent on steel witness plates (and only ~0.04 in on lead plates). Further, when TTA was also used as the output charge as well as the transfer charge, the same result was observed. This finding strongly implies that the TTA is not sufficiently powerful in the M55 to achieve high-order detonation of the RDX output charge. This is likely a result of critical diameter or run-up distance issues; the

low density of TTA relative to LA is a major contributor as well.

Table 2: M55 detonator performance for selected high nitrogen candidates (refer to Fig. 2 for diagram of M55) Initiating Charge NOL-130 NOL-130G NOL-130 NOL-130 NOL-130 NOL-130 NOL-130 Transfer Charge Lead Azide Lead Azide TTA TTA TTA TTA DBX-1 Output Charge RDX RDX RDX TTA CL-20 PETN RDX Steel dent depth (in) 0.0148 0.0140 ~0* ~0* ~0* ~0* 0.0153

Table 1, the properties of DBX-1 are also similar to LA and TTA, but it does have the benefit of a substantially greater density compared to TTA. Perhaps attributed at least partially to this reason, DBX-1 also performed better in the M55 detonator tests, leading to consistently fired items which yielded acceptable dent depths (Table 2). These results help to confirm the promise of DBX-1 as an eventual LA replacement. However, at the current time DBX-1 is still limited to relatively small batch sizes of approx. 5 g, and significant effort must be put into the scale up of the compound before it can be qualified. Additionally, although considerably more non-toxic than lead, copper can still be a health and environmental hazard at high concentrations. Other high nitrogen compounds were also evaluated, such as NITz and MNATz. However, these compounds were found to be unsuitable due to low thermal stability and insufficient impact sensitivity, respectively. Current ongoing efforts are focused on metal salt derivatives of these compounds, including complexes with copper, calcium, and similar metals. 3.2 Nanoporous Silicon Investigations The PSi material used in these studies was produced at the Vesta facility located in Monmouth Junction, NJ via a chemical etching method (Fig. 8) involving the treatment of bulk Si particles with an aqueous solution of hydrofluoric acid (HF) and nitric acid (HNO 3). The process is capable of producing as much as 500 g of PSi per batch.

NOL-130G DBX-1 RDX 0.0123 *detonators fired successfully, but were not powerful enough to dent the steel plate

Several attempts were made to improve this situation in the M55. One strategy involved recrystallizations of the TTA from acetone/water in order to exert control over the particle size and morphology, the goal being to improve packing densities in the M55 and increase performance. Although a degree of crystal control was demonstrated (Fig. 7), no improvement was observed upon functioning additional M55 detonators. Another strategy involved the use of more sensitive (relative to RDX) output charges in the M55. This method proved equally unsuccessful even through the use of CL-20 or PETN. Instead of focusing on transfer-charge replacement in the M55, the replacement of the LA and LS found in the initiation chargethe NOL-130 stab mixwas 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.

Fig. 8: Synthetic process for Vesta PSi.

Figure 7: Various TTA particle sizes and morphologies obtained through recrystallization

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 lightthis 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 BrunauerEmmett-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

1.4 1.2 1 0.8 0.6 0.4 0.2 0

0.5

1.5 2 Energy (eV)

2.5

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 power. As a result, composites with perchlorates will 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 materials 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-

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). Xray 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 solutionbased incorporation (Clment 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

Intensity (arb. Units)

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. REFERENCES Clment, D., Diener, J., Gross, E., Knzner, N., Timoshenko, V., Kovalev, D., 2005, Phys. Stat. Sol., 202, 1357-1364. Currano, L., Churaman, W., 2009: Energetic Nanoporous Silicon Devices, Journal of Microelectromechanical Systems, 18, 799-907. Dreizen, E., 2009: Metal-based Reactive Nanomaterials, Prog. in Energy and Comb. Sci., 35, 141-167. Gao, H., Ye, C., Gupta, O., Xiao, J.-C., Hiskey, M., Twanley, B., Shreeve, J., 2007: 2,4,5-Trinitroimidazole-based Energetic Salts, Chem. Eur. J., 13, 3853-3860. Huynh, M., Hiskey, M., Meyer, T., and Wetzler, M., 2006a: Green Primaries: Environmentally Friendly Energetic Complexes, Proc. Nat. Acad. Sci., 103, 5409-5412. Huynh, M., Coburn, M., Meyer, T., Wetzler, M., 2006b: Green Primary Explosives: 5-Nitrotetrazolato-N2ferrate Hierarchies, Proc. Nat. Acad. Sci., 103, 10322-10327. Kessenich, E., Klaptke, T., Knizek, J., Nth, H., Schulz, A., 1998: Characterization, Crystal Structure of 2,4Bis(triphenylphosphanimo)tetrazolo[5,1-a]-[1,3,5]triazine, and Improved Chemical Structure of 2,4,6Triazido-1,3,5-triazine, Eur. J. Inorg. Chem., 20132016. Kovalev, D., Yu, V., Timoshenko, N., Knzner, E., Gross, E., Koch, F., 2001: Strong Explosive

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., Klaptke, T., 2008: Green Pyrotechnics: 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: Environmentally Compatible Next Generation Green Energetic Materials (GEMs), J. Haz. Mat., 161, 589607.