Catalytic Detonation of RDX/TNT Blend Explosives for the Assembly of Carbon Nanostructures Yeuh-Hui Lin* and Yi-Ming Su Chemical & Biochemical Engineering Department, Kao Yuan University, 821, Kaohsiung, Taiwan, ROC *Email: [email protected] Abstract 1. Introduction Nano-structured materials have been synthesized by a Due to their unique properties, carbon nanotubes self-heating detonation process using a RDX/TNT blend (CNTs) are an extremely attractive raw material for explosive (i.e. B explosive) for providing the need of high functional as well as structural applications. In recent years, temperatures, high shock waves, and parts of carbon dramatic advances have been accomplished, especially sources in the presence of metallic-containing catalysts. concerning the use of CNTs in nano-electronics. For this The products of carbon nanomaterials are characterized by field of application comparatively small amounts of highly SEM, EDX and TEM techniques. The systematic determined CNTs are sufficient to serve valuable functions, experiments that mixture of which makes relatively high prices tolerable. However, as RDX/metalcene with or without carbon source as a traditional CNT synthesis like arc-discharge, CVD or laser molecular precursor can be employed to produce transition ablation is energy- and setup-intensive, routes to cheap metals (Fe, Co and Ni) nanoparticles encapsulated in mass production of CNTs are highly demanded [1-3], concentric layers of graphitic carbon. Moreover, various especially for their utilization in structural materials, where pure carbon or metal nanostructures can be simply obtained large amounts are required. The novel structure of from the detonation of the desired molecular precursors. encapsulating second phase inside carbon shells can Therefore, catalytic detonation of carbon-rich explosives immunize the encapsulated species against environmental can be designed as a useful method and with the potential degradation effects while retaining their intrinsic properties, application for the production of nano-structured materials and can also offer an opportunity to investigate of dimensionally graphitic carried out indicate carbon-encapsulated nanoparticles and confined system. The synthesis of carbon-nanotubes. The experimental results show that the carbon-encapsulated metal nanoparticles has attracted metal compounds can be converted into metallic much attention for their wide promising applications, nanoparticles due to the fast decomposition with a especially in information technologies and biomedicines. reduction reaction after the detonation and this will play an There are many differences among these methods in important role for the growth of different size of carbon technique as well as in chemical and physical principles, capsules. The systematic of experiments indicate that it is the common base is that nanostructures always grow under possible for a cheaper process and can be as an alternative high temperature conditions. However, these processes are compared to these high energy and hardware intensive both high energy and hardware intensive, which lead to processes to assemble nano-sized carbon nanomaterials high cost of nanostructures and therefore constrains their under catalyzed-blast process. practical application [4-6]. Keywords: Detonation, Nanostructures, Explosives Explosive decomposition-experiments and shock wave synthesis of nanoscale materials have been described in literature. These include e.g. the preparation of binary nitrides such as c-BN, CNx-materials and GaN. Even the typical XRD result of the sample obtained from the commercial fabrication of diamond nanopowders is detonations of RDX-Fe mixture. XRD characterization is performed by shock wave methods [8-11]. In this way, performed to further validate the corresponding structure of uniform iron nanoparticles well encapsulated within the core and shell. No signals of iron carbide or iron oxide graphitic shells can be obtained, with crystalline structure are observed. Although it is difficult to completely rule out of parent ones. Therefore, a laboratory self-heating the presence of very small oxide and carbide particles from detonation process has been designed in-house and a more the XRD pattern because the particles possessing a effective synthesis of CNTs using nitro-amine CHNO scattering region smaller than 2 nm cannot be registered explosives as an energetic materials and the metal with the X-ray technique. TEM observation shows that the containing material as a catalyst. Here we report that size of the particles are larger than 5 nm, suggesting the individual carbon nanostructures, both unfilled and containing metal nanocrystals in a string-by-string bead-like arrangement, can be obtained reproducibly by detonative decomposition of a RDX/TNT explosive. cores will be bcc-Fe. The diffraction peak at about 26.2° can be assigned to the (002) planes of hexagonal graphite structure with an interlayer spacing of 0.34 nm, corresponding to the encapsulating carbon shells. The peak is rather asymmetry, broader and lower than that of the well-crystallized graphite, indicating a relatively small 2. Experimental crystalline dimension. Amorphous carbon background in The chemical reagents used were RDX/TNT energetic materials (B explosive), transition metal catalysts (Co, Ni, and Fe containing compounds) and anthracene (C14H10). The use of this specially system to study the catalysis-ssisted detonation process, the relationship between the experimental conditions and product distribution and roles of the catalyst types. Before the detonation experiments, the starting materials were mixed in desired ratios. The detonation was performed in a sealed stainless steel vessel connected with vacuum and inert gas control system, and induced external heating to ignition temperature. After the detonation, the reactor was cooled in air to room temperature. The gaseous products were vented and the solid products were collected for further characterizations. The reactor and various units of the collection system were weighted before and after the runs to determine the mass balance. Scanning Electron Microscopy with detection ) SEM equipped with EDX and Transmission electron microscopy (TEM) were employed to investigate the as-synthesized solid products. the products contributes to the broad diffraction peak in proximate to the graphite peak. A typical TEM image of the resulted material showing that the Fe–C core–shell structures with the carbon shells show relatively defective structure observed can be effectively protect the iron cores against the environmental degradation (Fig. 2). The iron cores are crystal and have lattice fringe spacing of 0.20 nm), related to the (110) plane of the bcc-Fe crystal or the (121) plane of the Fe7C3 crystal. The identification of the phase can be realized in virtue of XRD measurements (Fig. 1). As shown in Fig. 3, it indicate that the mixture result in catalytic detonation reaction and produce nanostructures under the condition. The above data show that the detonation-induced Co pyrolysis is able to controllably produce well-constructed Co–C core–shell nanostructures. In this process, since the detonation of RDX is induced by temperature-programmed heating. The hot gases (N2, CO, CO2, H2O) generated from the detonation collide with the gaseous molecules and make latter quickly decompose into small carbon (Cn) and Co species, which subsequently condense into solid materials when cooling. The 3. Results and discussion simultaneous condensation of the Co clusters and the Cn An individual metal catalyst was mixed with explosives species leads to the likely formation of a (Co, C) alloy, (RDX) before the detonation experiments. The materials whose carbon content varies with the system temperature. used in this study can be formulated, including explosive, When the carbon dissolution in the Co nanoparticles carbon reaches saturation, a precipitation of pure carbon around source, and catalyst, from which carbon nanomaterials can be effectively synthesized. Fig. 1 is a the nanoparticles would start in the form of graphite. Fig. 4 shows typical TEM patterns of the show that it is possible for a cheaper process and can be as as-synthesized samples obtained from the detonations of an alternatives compared to these high energy and RDX/Nickelocene/C14H10 mixture. The presence of Ni hardware intensive processes to assemble nano-sized catalyst is necessary for the nanostructures growth in this carbon nanomaterials under catalyzed-blast process. system, at least under the experimental used in this study. TEM image of this sample presents the effect of C14H10 4. Conclusion addition on the formation of carbon nanotubes. Elemental The detonation of nitro amine-containing CHNO analyses by EDX show that the products mainly consist of explosive as common as a RDX/TNT composite can be carbon and catalyst with very little amount of detectable used to synthesized carbon nanomaterials in the presence oxygen and nitrogen. Both of the recipe RDX/ of a catalyst. The approach has the potential ability to Nickelocene/C14H10 and RDX/cobaltcene/C14H10 of the convert waste energetic explosives to form highly valuable TEM micrograph in Figs. 4 and especially in Fig. 5 show materials. This method represents a novel and low cost that the length of the tubes can reach more than a dozen process towards metal–carbon encapsulating structures, in microns and that they are segmented. The term which the needed high-temperature environment is self ‘‘bamboo-like nanotubes’’ has been introduced for this provided by the energy emitted from the RDX/TNT nanostructures morphology. Based on theoretical studies it detonation. sing this special system prticulate products are was supposed that nitrogen substitution of carbon in generated. Similar results were obtained when the reaction graphite develops buckled structures and enhances the was performed in a certain outward flow of gaseous compartmentization of nanostructures. However, a detailed reaction products and intermediate pressure decline rates, and possibly quantitative experimental investigation of the and in the presence of iron, nickel or cobalt, various influence of nitrogen incorporation on the morphology of nanostructures are formed. Uniform carbon-encapsulated carbon nanostructures remains to be conducted in the Fe nanoparticles are successfully synthesized through the future. The segment of long tube in Fig. 5 has diameters of detonation of RDX/TNT and metalcene mixture. For the about 50 to 100 nm (right). Similar to the left figure shown controlling formation of carbon-encapsulated metal that all produced materials the tube diameters vary between nanoparticles and carbon nanotubes, it is clear that C:metal 100 and 150 nm. All tubes prepared with Co transition ratio in the starting materials is considerable controled to metal and carbon sources (C14H10) were multi-walled with obtain tme majority of high yields of encapsulated metal the nanoparticles said dimensions. The morphology and the without the formation of carbon nanostructures yield varied depending on the metal. As can nanostructures. A further increase in caobon nanostructures be seen in Fig. 6, in the formation of the nanostructures of yield and tailoring of structure defects may be available in nanoparticles of nanoencapsule (right) and nano-sized relation to the optimization of reaction conditions. metal particles (Left), the explosive detonative plays an important role with the heat and the carbon species References produced from the detonation promote the decomposition [1] Iijima S. Helical microtubules of graphitic carbon[J]. and the reduction of catalyst particle and this lead to help the structure and mechanism control. The core area in HR-TEM image reveals the lattice fringe spacing of the core is about 0.20 nm with Fe–C core–shell structure can be formed selectively in the present approach via simply controlling the ratio of RDX/Ferrocene. The shells are uniform in thickness and usually consist of 5–18 layers. Nature, 1991,354(6348):56-58. [2] Bethune D S,Kiang C H,de Vries M S,Gorman G, Savoy R,Vazquez J. Nature, 1993;363 (6430): 605-607. [3] Thess A, Lee R,Nikolaev P, Dai H,Petit P,Robert J. Science, 1996; 273 (5274): 483-487. The spacing of the lattice fringes is about 0.34 nm, which is [4] Ebbesen T W,Ajayan P M. Large-scale synthesis of close to that of the graphite (002) planes. It is interesting to carbon nanotuebs J. Nature , 1992 , 358(6383) : note that these results experimentally used in this study 220-222. [5] N. S. Xu, R. V. Latham and Y. Tzng, Electro Lett., 29(1993)1596. [6] Z. Feng, I. G. Brown and J.W. Ager, J. Mater. Res., 10(1995) 1585. [7] R. T. K. Barker, P. S. Harris, R. B. Thomas and R. J. Waite, “Formation offilamentous carbon from iron , 100 nm Fig. 2. TEM image of the catalytic detonation of RDX/TNT over a Fe catalyst (1:1). cobalt, and chromium catalyzed decomposition of acetylene”, Journal of catalysis, 30, 86~95,1973. [8] M. Monthioux, “Filling single wall carbon nanotubes,” Carbon, 40, 1809~1823, (2004). [9] D. Globerg, F.F. Xu, Y. Bando, “Filling boron nitride nanotubes with metals,” Appl. Phys. A, 76, 479~485, (2003). [10] Subramoney S. Novel nanocarbons-structure, properties, and potential applications. Adv. Mater. 100 nm Fig. 3. TEM images of the catalytic detonation of RDX/TNT over a Co catalyst (1:1). 10(15):1157–71, (1998). [11] Saito Y. Nanoparticles and filled nanocapsules. Carbon 33(7):979–88 (1995). 100 nm 100 nm Fig. 4. TEM images for the catalyzed-blast of RDX/TNT a Ni catalyst (1:1). Fig. 5. TEM images for the catalyzed-blast of RDX/TNT /Cobalcene/C14H10 mixture. Fig. 1. XRD spectrum of catalytic detonation of RDX over Ni, Co and Fe catalysts. 10 nm 10 nm Fig. 6. HRTEM images of for the catalytic detonation of RDX/TNT explosive with Ni catalyst (10:1).
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