CP620, Shock Compression of Condensed Matter - 2001 edited by M. D. Furnish, N. N. Thadhani, and Y. Horie © 2002 American Institute of Physics 0-7354-0068-7/02/$ 19.00 ALUMINISED EXPLOSIVE COMPOSITIONS BASED ON NQ AND BTNEN Michael F. Gogulya, Alexander Yu. Dolgoborodov, Michael A. Brazhnikov, Michael N. Makhov, and Vitaliy I. Arkhipov N. Semenov Institute of Chemical Physics RAS, Kosygin st. 4, Moscow, 117334, Russia Abstract. Aluminium containing explosive compositions based on nitroguanidine (NQ) or bistrinitroethylnitramine (BTNEN) were studied. The tested compositions contained Al (15% wt.) of different particles' size and particles' shape. There were measured the following explosive parameters: detonation velocity, pressure time histories and temperature time histories, velocity of accelerated metal plate, explosion heat. NQ pressure profile is of the shape predicted by ZND theory, thus C-J pressure was estimated. BTNEN detonation seems to be of more complicated nature. Effect of Al introduction into HE depends on the nature of HE and Al particles' size and shape as well. Al. Aluminium content in mixtures was 15% wt. NQ-crystals with low loose-packed density of 0.2 g/cm3 had needle-like shape and were about 5-10 fim of thick and about 50 j^m in length. BTNEN particles had needle-like shape with diameter of 1540 jLim and length up to 500 jum. Components of the mixtures merged in hexane were mixed in a rotating drum or manually. Then it was evaporated from the mixture at its boiling point (-70° C). Charges were pressed to density about 0.90-0.95 TMD. INTRODUCTION Aluminium is widely used as an additive enhancing detonation characteristics of HE. However, the mechanism of Al oxidation in and behind detonation wave is not well understood. This problem attracted new interest after ultra-fine Al (< 0.1 jum) became available [1]. For study, there were chosen two HE: BTNEN and NQ. The interest to BTNEN is due to its high density (1.96 g/cm3) and positive oxygen balance (OB = +16.5%). NQ, explosive with negative OB (-30.8%), is of particular interest as HE with high hydrogen content. EXPERIMENTAL TECHNIQUES Detonation velocity (D) was measured with the aid of a set of contact gauges (0.1 mm of thick) made of copper foil insulated with a plastic film. The time interval of detonation front travel was recorded by the frequency meter with an accuracy of 0.01 jus. Pressure histories and temperature ones were measured with the aid of dual-channel optical pyrometer (A,=420 and 627 nm) with time resolution about 10 ns. Indicator technique was used for pressure profile measurements [2]. Bromoform 20 mm- PREPARATION OF HE/A1 CHARGES Five Al batches were tested including spherical particles with size <0.1{0.9}; 7{0.98}; 15(0.99}; 150(0.99} M-m and flaked Al with size «lx20x20 jim {0.85}, containing 3.8% stearine,. Here figures in parentheses indicate content of active Al. The aforementioned Al batches are referred to below as Al(0.1), Al(7), Al(15), Al(150) and Al(fl) for flaked 962 thick layer was used as an indicator. Temperature measurements were performed by means of window technique [3]. LiF plate served as a window. When measuring D or temperature histories or pressure ones, HE samples were initiated with a plane wave generator made of RDX-wax composition. Charges 40 mm in diameter and -100 g in weight were tested. Plate acceleration technique [4] consists in measurements of the velocity of a 4-mm steel plate accelerated by detonation products (DP) in the direction of detonation wave propagation. NQ basic charge was 35-mm long. The length of BTNEN charge was 40 mm. The plate velocity was measured with an accuracy of ~1%. Explosion heats (EH) were measured in a bomb calorimeter made of steel vessel 5 litre in volume with an accuracy of -1%. It is placed in a compartment with a distilled water [5]. For EH measurements, NQ and NQ/A1 mixtures were pressed in charges of 30 mm in diameter and 50-60 g in weight and placed into the 10-mm thick stainless steel casing. BTNEN and BTNEN/A1 mixtures were pressed in charges of 20 mm in diameter and 40-45 g in weight and placed into 7-mm thick casing of the same metal. In all aforementioned tests except EH and metal plate acceleration measurements hi BTNEN mixtures, there was used an additional RDX pellet (p0 = 1.68 g/cm3) 10 mm of thick to reinforce the initiation impulse. energy release caused by Al oxidation. In addition, one should concern energy losses through additive compression and its heating up. Competition of them controls D value. TABLE 1. Detonation Velocity HE Po, g/cm3 Al BTNEN 0 Dex, g/cm3 km/s POHE? (n) D*, km/s - 1.635(0.918) 1.635 7.94 7.94 Al(15) 1.743 (0.929) 1.640 7.94 7.92 Al(fl) 1.720(0.916) 1.616 7.78 7.86 Al(O.l) 1.785(0.951) 1.684 8.13 7.93 1.870(0.954) - 8.50 1.909(0.974) - 8.66 8.62 Al(150) 1.965(0.961) 1.875 8.38 1.955(0.956) 1.864 8.30 8.44 1.955(0.956) 1.864 8.28 8.42 8.04 8.35 Al(15) Al(7) Al(O.l) 1.914(0.936) 1.820 TABLE 2. D(p) Relationship b, a, HE (km cm3)/g s km/s 8.48 POHE*> g/cm3 Ref. [7] NQ 1.44 4.015 1.635 BTNEN 1.24 3.885 1.900 [6f **Data of the present work are also included for D(POHE) relationship construction. EXPERIMENTAL RESULTS 8.6 Detonation velocity data are listed hi Table 1, where p0 and t| are the absolute and relative charge density, Dex is experimental D and POHE is the density of HE in mixture. Basing on the relationship Did = a + bpoHE for pure HE, one can recalculate D measured at different charge density to those (D*) would be measured at the same density of HE in the mixture (POHE*): D*= Dex - b(pOHE - POKE*)- The coefficients, a and b, and POHE* are given hi Table 2. D* values are listed in Table 1 and they are plotted in Fig. 1. For comparison, the data for HMX/A1 are also presented. The results on D are influenced by a number of factors. First one is the decreasing of the number of moles of gaseous DP caused both by the decreasing of HE amount in the mixture and by the Al reaction with carbon oxides. Second factor is the 8.4 1 ."*- 8-2 Q 8.0 7.8 0 20 40 60 80 100 120 140 FIGURE 1. Detonation velocity versus Al particles' size: o BTNEN/A1; A - NQ/A1 (A - NQ/Al(fl)); • - HMX/A1 hi Fig. 2, 3 there are given pressure histories in DP for tested mixtures. For NQ, Fig. 2 demonstrates that 963 the C-J pressure would fall in interval of (22.1-^21.6) GPa, with corresponding polytrope index of 3.66 -5-3.77 and the detonation reaction zone of (0.7-fl.O) mm. Opposite to NQ, BTNEN pressure profile is not a classical one. The peculiarities seen for BTNEN at the front during first 0.05 jus retain for BTNEN/A1 mixtures. They are possibly caused by the macroscopic kinetic of BTNEN decomposition. 4400 4000 in 3600 H 3200 £ 2800 W 2400 2000 -0.4 0.0 0.4 0.8 1.2 1.6 2.0 2.4 2.8 TIME, microsecond FIGURE 4. Brightness temperature time histories with LiF used as the window (A, = 627 nm). 1 - BTNEN; 2 - BTNEN/A1(15); 3 BTNEN/A1(0.1); 4 - NQ; 5 - NQ/Al(fl); 6 - NQ/A1(0.1). The instant of time pointed as zero corresponding to the detonation wave entrance DP/LiF interface. 0.0 0.2 0.4 0.6 For NQ and NQ/A1 charges, data on metal plate acceleration velocity (W) are presented in Fig. 5. For NQ, the tests were performed at two densities. 0.8 TIME, microsecond FIGURE 2. Pressure time histories in the DP for NQ and NQ/A1 mixtures. The arrow shows C-J point for NQ. 1.70 1.65 0.0 0.2 0.4 mm 20 30 40 FIGURE 5. Steel plate velocity vs. distance for NQ and NQ/A1. 1 - Al(fl); 2 - Al(O.l); 3 - Al(15); Dash - pure NQ. 0.6 TIME, microsecond The increase of NQ-charge density by 0.1 g/cm3 results in W increase by ~90 m/s. The curves for NQ/A1 mixtures were recalculated from the experimental data to NQ porosity in the charge of ~ 8% basing on the W-p relation for NQ. Increase in metal plate velocity is of -3.1% for NQ/A1 over pure NQ at AL = 40 mm. The curves for BTNEN and BTNEN/A1 are given in Fig. 6. For BTNEN, the tests were performed at two densities. The increase of BTNEN density by 0.1 g/cm3 results in W FIGURE 3. Pressure time histories in the DP for BTNEN and BTNEN/A1 mixtures. Brightness temperature histories are shown in Fig. 4. For HE/A1, rapid temperature decrease at 1.2 - 1.6 ^s is caused by rarefaction entered to the observing area. NQ/Al(fl) temperature curve can be explained by peculiarities of component package in the charge. It is seen that free oxygen of BTNEN DP reacts with Al more actively. 964 increase by -80 m/s. Trajectories for BTNEN/Al were recalculated in the same manner to BTNEN porosity in the charge -3%. Al(7) activity (98% over -90%). EH data are given in Table 3. EH of BTNEN/A1(7) is the highest due to the relatively small particles and high pure Al content. On the condition of the complete Al oxidation in DP of BTNEN, one can estimate the EH as ~ 8600 kJ/kg at content of pure Al 15% and that for DP of NQ as -5600 kJ/kg. The estimation indicates that for BTNEN (positive OB) there is complete Al oxidation in DP expanding in calorimetric bomb only for Al(7) and Al(O.l). For any tested NQ/A1 mixtures, there is no complete Al oxidation by DP ofNQ. CONCLUSION Effect of Al introduction into HE depends on the nature of HE and Al particles' size and shape as well. Ultra-fine Al manifests itself as an active powder among the tested ones. The advantages of ultra-fine Al caused by lesser particles' sizes are restricted by lower content of pure Al in powder. Al starts react with DP in detonation zone or immediately behind it, but the most part of Al oxidises in expanding DP at larger times. 1.720 30 40 AL,mm FIGURE 6. Steel plate velocity vs. distance for BTNEN and BTNEN/Al: 1 - Al(7); 2 - Al(15); 3 - Al(O.l); 4 - Al(150); dash line corresponds to pure BTNEN. It is seen that BTNEN/A1(7) and BTNEN/A1(15) mixtures provide higher gain in metal plate velocity than do the mixtures with EH of negative OB, e.g. HMX [8]. In similar mixture with BTNEN, the plate velocity augments by nearly 6% at AL = 40 mm. REFERENCES 1. Gen M. Ya., and Miller A. V., Patents of USSR, No 814432 and No 967029. 2. Gogulya M. F., and Dolgoborodov A. Yu., Chem. Phys. Rep. 13(12), 2059-2069 (1995). 3. Gogulya M. F., and Brazhnikov M. A., "Radiation of Condensed Explosives and Its Interpretation (Temperature Measurements)," in Proceedings of the 10-th International Symposium on Detonation, Boston1993, Office of Naval Research, ONR 33395-12, 1995, pp. 542-548. 4. Arkhipov V. I., Makhov M. N., and Pepekin V. I., Sov. Jnl Chem. Phys. 12(12), 2395-2399 (1994). 5. Pepekin V. L, Makhov M. N., Lebedev Yu. A., Dokl. Akad Nauk, 232(4), 852-855 (1977), (in Russian). 6. Kamlet M. J., and Hurwitz H. J., Chem. Phys., 48(8), 3685-3692 (1968). 7. Price Donna and Clairmont A. R., "Explosive Behavior of Nitroguanidine," in Proc. Twelfth Symp. (Intern.) on Combustion, The Combustion Institute, Pittsburgh, Pennsylvania, 1969, pp. 761-770. 8. Arkhipov V. L, Makhov M. N., Pepekin V. L, etal., Khim. Fiz., 18(12), 53-57 (1999), (in Russian). TABLE 3. Explosion Heat HE BTNEN £ AI po, g/cm3 Q,kJ/kg - 1.635 3480 Al(15) 1.743 4820 Al(fl) Al(O.l) 1.720 4930 1.785 4960 - 1.889 5230 Al(150) 1.945 8250 Al(15) 1.955 8450 Al(7) 1.945 8580 Al(O.l) 1.914 8420 Though plate acceleration ability of BTNEN is lower than that of HMX, the acceleration ability of BTNEN/Al approaches that of pure HMX at the same porosity. The advantages of Al(7) over Al(O.l) in metal plate velocity can be explained by higher 965
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