Combustion, Explosion, and Shock Waves, Vol. 41, No. 2, pp.

121132, 2005

Hexanitrohexaazaisowurtzitane (CL-20) and CL-20-Based Formulations (Review)

U. R. Nair,1 R. Sivabalan,1 G. M. Gore,1 M. Geetha,1 S. N. Asthana,1 and H. Singh1
Translated from Fizika Goreniya i Vzryva, Vol. 41, No. 2, pp. 316, MarchApril, 2005. Original article submitted April 8, 2004.

UDC 536.46

This paper reviews the research and development work on CL-20, the most powerful high-energy material of today, as well as CL-20-based formulations. Methods of CL-20 synthesis and processes for obtaining a desired particle size are discussed. Particular attention is paid to optimization of conditions for obtaining the most stable high-density polymorph. The Fourier Transform Infrared spectroscopy and X-ray diraction appear to be eective means for distinguishing CL-20 polymorphs. The thermal decomposition pattern of CL-20 as well as the proposed decomposition and combustion mechanisms also form part of this manuscript. Investigations performed by various researchers show that its relatively high sensitivity needs special attention from the viewpoint of CL-20 preparation and processing of formulations based on this substance. Salient features of CL-20-based explosives and gun/rocket propellants studied are included into this review. CL-20 may be ranked as the most attractive compound for futuristic explosive and propellant formulations. The research activities performed by the authors on synthesis and characterization of CL-20 are briey described. Key words: HNIW, CL-20, formulations, rocket propellants, sensitivity, explosives.

INTRODUCTION 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaaza-tetracyclo[5,5,0, 03.11 ,05.9 ]dodecane or hexanitrohexaazaisowurtzitane (HNIW) is a high-energy material with a cage structure; Today it is considered as the most powerful explosive. In view of its superior performance, HNIW, popularly known as CL-20, can be regarded as a high-energy material of the next generation. Its attributes of great interest are high density ( > 2 g/cm3 ) and heat of formation (Hf 100 kcal/mole), which exceed the same parameters of cyclotetramethylenetetranitramine or HMX ( = 1.91 g/cm3 and Hf = 17 kcal/mole, respectively). The high performance of CL-20 is also reached owing to a strained cage structure carrying 6 NO2 substituents. The production technology breakthrough in the USA and France
1

(Thiokol Corporation and SNPE) [1] resulted in its emergence as a superior viable alternative to HMX [2]. SYNTHESIS The rst step in HNIW (CL-20) synthesis involves creation of the basic cage structure through condensation of glyoxal with benzylamine, leading to the formation of 2,4,6,8,10,12-hexabenzyl-2,4,6,12hexaazatetracyclo[5, 5, 0, 05.9 , 03.11 ]dodecane, commonly referred to as hexabenzylhexaazaisowurtzitane (HBIW) [3]. Ou et al. [4] found acetonitrile to be a reaction medium superior to ethanol for HBIW synthesis from the point of view of yield, quality, and reaction rate. Conversion of HBIW to CL-20 poses a major challenge. Direct nitration of HBIW to CL-20 by nitrolysis is unsuccessful because of competing nitration of phenyl rings [5] and thereby necessitates debenzylation by catalytic hydrogenation prior to nitration. 121

High Energy Materials Research Laboratory, Pune-411021, India; hemsociety@redimail.com.

0010-5082/05/4102-0121 c 2005 Springer Science + Business Media, Inc.

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Nair, Sivabalan, Gore, et al.

Hexaazaisowurtzitane itself being unstable, hydrogenation in the absence of the reactive acetylating agent leads to collapse of the cage structure:

Several attempts to develop the synthesis process led to the emergence of alternate routes of reductive debenzylation. Reductive debenzylation of HBIW under a wide variety of hydrogenation conditions in the presence of a palladium catalyst was investigated by Bellamy [6]. Hydrogenation in the presence of excess of acetic anhydride results in formation of the 4,10-dibenzyl-2,6,8,12-tetraacetyl2,4,6,8,10,12-hexaazaisowurtzitane (TADBIW) derivative, as was reported by Nielsen et al. [3, 7]. Further acetylation in acetic anhydride containing 1020% of acetic acid leads to formation of noticeable amounts of 4,10-diethyl-2,6,8,12-tetraacetyl2,4,6,8,10,12-hexaazaisowurtzitane, but there was no evidence of formation of hexaacetylhexaazaisowurtzitane.

TADBIW is obtained with a 75% yield by reductive (H2 and Pd/C) acetylation of HBIW in ethylbenzene, employing an N-acetoxysuccinimide and acetic anhydride combination [8]. Further hydrogenation of TADBIW with palladium acetate and acetic acid results in formation of 2,6,8,12-tetraacetyl2,4,6,8,10,12-hexaazaisowurtzitane (TADAIW) with a 73% yield. Reductive debenzylation of HBIW (H2 , Pd/C, and acetic anhydride) in the presence of N,N-dimethylacetamide [9] leads to formation of TADAIW as a major product along with TADBIW and tetraacetylmonobenzylhexaazaisowurtzitane. HBIW hydrogenation [10] in formic acid as a solvent (with a Pd catalyst) yields 4,10-diformyl-2,6,8,12-tetraacetyl2,4,6,8,10,12-hexaazaisowurtzitane (TADFIW). Attempts are made to optimize the requirement of the Pd catalyst [1113] as an economy measure [see scheme (1)]. TADBIW conversion to tetraacetyldinitrosohexaazaisowurtzitane (TADNIW) by adding N2 O4 or NOBF4 followed by TADNIW nitration with NO2 BF4 to CL-20 with a 90% yield is reported in much detail [14, 15]. Both TADAIW and TADFIW can be directly nitrated with a mixture of nitric and sulphuric acids [16, 17]. One-pot synthesis reported by Wang et al. [18] is a modied approach of CL-20 preparation from TADBIW through TADNIW (yield up to 82% and purity up to 98%). Kawabe et al. [19] claimed that the mixed acid nitration of TADAIW at 60 C for 24 hours yields 98% of CL-20. Sanderson et al. [20] established CL-20 manufacturing by mixed acid nitration of TADAIW at 85 C (99% conversion within ten minutes is reached). TADFIW nitration with concentrated nitric acid (98%) at a higher temperature (125 C) is re-

Hexanitrohexaazaisowurtzitane (CL-20) and CL-20-Based Formulations (Review) ported to produce CL-20 with a 9097% yield [21]. Recently, Chung et al. [22] made an attempt to synthesize pentaacetylhexaazaisowurtzitane or pentaacetylformylhexaazaisowurtzitane as a precursor to HNIW. In High-Energy Materials Research Laboratory, CL-20 was synthesized by nitrating TADBIW (obtained by reductive debenzylationacetylation of HBIW) with a NOBF4 NO2 BF4 mixture as a nitrating agent [23, 24]. In view of the high cost of NOBF4 and NO2 BF4 , attempts were made to apply synthesis approaches [25] involving TADAIW nitration by 9599% nitric acid. The reaction parameters were optimized, which allowed a 85% yield of CL-20.

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PARTICLE SIZE AND CRYSTALLIZATION CL-20 is often obtained in the form of polycrystalline particles with sharp corners and microscopically visible defects. It is possible to control the particle size of CL-20 by optimizing the crystallization process. A single solvent oers particle sizes between 50 and 100 m, whereas particles of 10 to 150 m can be obtained by varying the rate of addition of a less ecient solvent to the solution of CL-20 in an ecient solvent, provided that both solvents are miscible. Evaporation of the solvent from the CL-20 solution yields coarse or ne particles, depending on the type of the seed and evaporation rate. Thome et al. [28] investigated various solvents (such as diisopropyl ether, methylisobutylketone, nitrobenzene, and water) for CL-20 crystallization and observed blocking of energetically favorable sites by solvent molecules, resulting in odd-looking morphology in some cases. Goler et al. [1] recommended acetone, esters, and aromatic solvents for obtaining polymorphs with particle sizes in the range of 10150 m. They claimed that the smallest particle size (10 m) of CL-20 might be obtained by grinding the modication of CL-20. Wardle et al. [32] discussed the results of alternate crystallization processes examined at Thiokol. Both ne (3550 m) and coarse (>200 m) fractions of -CL20 were obtained without polycrystalline features and microscopic defects. Variations in the grinding parameters aorded a material with an average particle size ranging from 2 to 15 m. We managed to obtain CL20 with a particle size of (30 10) m using a ethyl acetate/heptane solvent combination. Johnston and Eugene [29] found that temperature of crystallization inuences the purity of the product, probably due to the to transition. Sanderson et al. [20] observed that dierent particle sizes of the modication can be obtained by classical supersaturation methods by seeding with particles. Marioth et al. [33] developed screening (RESS) units to obtain CL-20 in a narrow range of a prescribed particle size, using CHF3 as a supercritical uid. A software-aided SEM was used to analyze individual particles and particle-size distribution [34].

POLYMORPHISM The focus of researchers investigating CL-20 polymorphs is on their relative stability and structural features [2629]. The modication (orthorhombic space groups Pb21 a) is found to be less stable with respect to polymorphic interconversion, whereas the modication (monoclinic space group P21 /c) is reported to be the most thermodynamically stable one under normal ambient conditions [30]. The and modications have the same molecular conformation as the modication but are packed dierently into the unit cell (orthorhombic Pbca and monoclinic P21 /c packings, respectively). The -type crystal lattice is stabilized by adding water to the unit cell; as a result, 1750% of crystal-lattice voids are lled by water molecules, as is evidenced by XRD patterns. The crystal of the modication of CL-20 corresponds to the monoclinic packing P21 /c with the parameters a = 8.848 (2) , A b = 12.567 (3) , c = 13.387 (3) , B = 106.90 (3) , A A A V = 1 424.2 (6) , and Dc = 2.044 cm1 . The transiA tion from the to the modication is observed at a temperature of 56.5 1.5 C. Shao-hua et al. [31] observed that the polymorph modication is determined by the dipole moment of nonsolvents in the case of crystallization in a solventnonsolvent system. Nonsolvents with a low dipole moment (petroleum ether, isooctane, cyclohexane, and trichloromethane) oer the modication of CL-20, whereas those with a high dipole moment (triethyleneglycol whose dipole moment is 5.0) give the polymorph. Nonsolvents having intermediate dipole moments (ethyl alcohol whose dipole moment is 1.68) yield a mixture of and polymorphs. A highpressure polymorph was observed by Russel et al. [26] during a reversible phase transition of the polymorph at a pressure of (0.7 0.05) GPa.

SPECTROSCOPY Extensive work on the spectral analysis (FTIR, 1 H, C, and 15 N NMR) of CL-20, including 2D experiments (using COSY, HETCOR, and NOESY) on its precursors, is reported in the literature [3545]. CL-20 samples synthesized by the authors at High-Energy Materi13

124 als Research Laboratory adopting nitration by both approaches (NOBF4 NO2 BF4 and HNO3 ) was also characterized by FTIR, 1 H NMR, and mass spectroscopic techniques. The observed spectral patterns were in close agreement with the reported ones [23]. Jacob et al. [44] established FTIR as a powerful tool for identication of dierent CL-20 polymorphs. Detailed measurements were performed in the frequency range of 1200 to 700 cm1 for dierent polymorphs. The polymorph displays distinct splitting of the absorption band in the range of 780 to 740 cm1 , in contrast to and polymorphs. It also shows a doublet in the range of 840 to 820 cm1 instead of a normal singlet obtained for other polymorphs. The 1 H NMR spectrum of CL-20 contains two signals: 8.4 ppm2 (corresponding to 4Ha ) and 8.2 ppm (corresponding to 2Hb ). The 15 N NMR spectrum shows a well-resolved resonance for two nonequivalent NO2 groups at 42.1 ppm (Nc ) and 45.1 ppm (Nd ) in the ratio of 2 : 1 [see scheme (2)]. A very broad resonance barely visible in the region around 190 ppm can be attributed to nitrogen atoms belonging to ring nitrogens (of nitramine groups).

Nair, Sivabalan, Gore, et al. trum; their shift values were found to be 4.08 and 4.03 ppm, respectively. The DEPT experiment also revealed two types of methane carbons at 76.9 and 80.6 ppm. The corresponding protons were identied at 4.15 and 3.57 ppm from the HETCOR spectrum. These ndings were validated by COSY and NOESY. The structure was again conrmed by 15 N NMR. The signal at 295.9 ppm was assigned to four nitrogen atoms in two ve-membered rings, and the signal at 316.1 ppm was attributed to two nitrogen atoms of the six-membered ring of the structure. The mass spectrum of CL-20 in the chemical ionization mode [14] exhibited molecular ion peaks at m/e = 467 (M + 29, 24%) and 439 (M + 1, 30%). Other signals were observed at m/e = 347 (26), 301 (28), 255 (14), and 209 (18).

CHROMATOGRAPHY Jacob et al. [44] recommended high-pressure liquid chromatography (HPLC, C-18 column) as a preferred technique to establish CL-20 purity (within 0.5%). A mixture of acetonitrile, water, and phosphoric acid was found to be an eective eluent. CL-20 was also analyzed by HPLC by Tian [46, 47] using a Supelco LC-18 column. Liu et al. [48] determined the CL-20 content in explosive mixtures by applying HPLC on a Nova-Pak C18 column with a methanol-water mobile phase at a ow rate of 0.8 ml/min. Other components of the mixture (RDX, HMX, TNT, 2,4-DNT, benzotrifuroxan, tetryl, and 1,3,5-trinitrobenzene) did not interfere with determining the CL-20 content. Bellamy [49] established a method of purication of crude CL-20 in amounts up to 20 g by applying column chromatography. He found that passing of a CL-20 solution in heptane/ethyl acetate through a column of Darco activated carbon (type G-20, about 20 g of carbon per 1 g of CL20) allowed obtaining the nal product with purity of 99.95% with a 90% recovery.

(2) The 13 C NMR shows singlets at 75.0 and 72.1 ppm, respectively. Prabhakaran et al. [36] used distortionless enhancement by polarization transfer (DEPT) spectroscopy to dierentiate methyl, ethylene, and methane carbons in the HBIW molecule. Peaks at 256.9 and 56.2 ppm in the ratio of 2:1 were attributed to methylene carbons Cc and Cd [see scheme (3)].

THERMAL STUDIES Bouma et al. [34] reported the results of thermogravimetric analysis (TG), dierential thermal analysis (DTA), and dierential scanning calorimetry (DSC) of CL-20 at heating rates of 2 and 10 C/min in nitrogen and air environment. They observed an endotherm with the beginning of the temperature decrease between 107 and 113 with a minimum in the region of 116129 C, followed by an exotherm with the beginning of the temperature increase in the region of 202217 C with a

(3) The corresponding methylene protons Hc and Hd were identied by the 1 H heteronuclear correlation spec2

ppm stands for parts per million.

Hexanitrohexaazaisowurtzitane (CL-20) and CL-20-Based Formulations (Review) maximum in the range of 220239 C. They inferred that slow decomposition under isothermal conditions is dominated by N NO2 homolysis, and subsequently the backbone (cage) of the CL-20 molecule collapses. In a recent work, Korsounskii et al. [50] studied thermal decomposition of CL-20 under nonisothermal conditions (4 C/min) in air and argon with continuous evacuation (under dynamic vacuum). CL-20 was observed to ignite in air at a temperature of 243 C. In dynamic vacuum, ignition was not observed, probably, because the exothermic oxidative reaction was impossible owing to escape of NO2 . Ignition in argon occurred at a lower temperature (224 C), since argon is heavier than air and the eciency of NO2 escape is lower, which favors pronounced oxidative interaction. Nedelko et al. [51, 52] established that thermal decomposition of CL-20 is purely a solid-state process proceeding with self-acceleration and can be described by a rst-order kinetic law with autocatalysis. The kinetic parameters of noncatalytic and catalytic decomposition of CL-20 polymorphs, as reported by these researchers, are summarized in Table 1. The higher values of activation energy of the noncatalytic stage for the polymorph of CL-20 are indicative of its superior stability. Bohn [53] also observed autocatalytically accelerated thermal decomposition of CL-20 and inferred that decomposition is not accompanied by liquefaction. Brill and Patil [54] investigated the weight-loss patterns of CL-20 in the temperature range of 190204 C up to 50% transformations and obtained the activation energy Ea = 36.3 kcal/mole. Xingzhong et al. [55] reported a higher value Ea = 45.2 kcal/mole on the basis of accelerating rate calorimetry (ARC) experiments. We obtained Ea = 47 kcal/mole by DSC with Kissingers correlation [23]. Lobbecke et al. [56] found Ea = (41 6) kcal/mole for the noncatalytic process and Ea = (44 2) kcal/mole for the catalytic process in the temperature range of 160180 C. Thermal analysis results with respect to specic CL-20 polymorphs are also well reported. Simpson et al. [2] found by the DSC technique that -CL-20 exhibits two endotherms in the vicinity of 65 C and attributed them to and transitions. Nedelko et al. [52] inferred that the earlier stages of decomposition ( 1%) involve and phase transitions, and the decomposition process is governed by -CL-20 reactions. The rate of thermal decomposition appeared to increase in the order > > . In particular, ignition of -CL-20 at 216 C under linear heating rates of 24 C/min was observed. For comparison, the ignition temperatures for the and polymorphs was 226 and 230 C, respectively.

125

Wardle et al. [32] reported the onset decomposition temperature of 220 C for the polymorph and 240 C for the polymorph of CL-20. The maximum decomposition rate temperatures recorded for , , and modications were 250, 240, and 253 C, respectively. Many researchers [50, 57, 58] reported that a residue amounting to 16% of the initial CL-20 sample was left after completion of exothermic decomposition. The residue remained stable up to 300 C, and subsequently decomposed to the extent of 60% at temperatures exceeding 610 C. FTIR investigations established the polymeric nature of the residue and suggested formation of the latter after elimination of ve nitrogroups. Exothermicity observed during DSC of CL-20 beyond 300 C may be caused by decomposition of the residue with the rupture of the N NO2 bond. Patil and Brill [57] reported the formation of a dark-colored residue at a temperature above 285 C, having an elemental composition averaging to about C4 H4 N4 O2 , during rapid thermal decomposition of -HNIW studied by T-jump Fourier-transform IR spectroscopy. Microscopic observations suggest that the initial cracking of crystals during the decomposition process is followed by disorientation of the fragments formed. The high preexponent of the CL-20 decomposition rate constant can be explained by lengthening of the bond in the transitional state, accompanied by the release of hindered rotation of NO2 in the N NO2 bond. HNCO, HCN, CO2 , and NO2 were reported [50] to be gaseous products of CL-20 decomposition. A newly developed [58] gem anvil cell technique (combination of high-pressure and thermal-shock conditions with lowtemperature matrix isolation) revealed the formation of H2 O, CO, and NO2 in addition to other gaseous decomposition products. A TG-MS analysis of CL-20 carried out by the authors exhibited evolution of gases, such as HCN, CO, CO2 , HNCO, and N2 O, identied by the peaks at m/e = 27, 28, 44, 43, and 44, respectively. Simpson et al. [2] obtained the heat of combustion of the modication of CL-20 equal to 3.649 106 J/mole, whereas the heat of combustion for the modication is 3.596 106 J/mole. The calorimetric heat of detonation obtained for the modication of CL-20 (12,200 J/cm3 ) was found to be greater than that for HMX (11,700 J/cm3 ). The time to explosion of CL-20 and RDX samples stored at a given temperature was fairly close to each other [2]. However, CL-20 was exposed to much more violent reactions, and its critical temperature (163 C) is lower than that of RDX and HMX (184 and 190 C), whereas in vacuum stability tests, CL-20 evolves a much smaller volume of the gas (0.02 cm3 ) than HMX.

126 TABLE 1

Nair, Sivabalan, Gore, et al.

Kinetic Parameters of Noncatalytic and Catalytic Thermal Decomposition of CL-20 [52] Kinetic parameters Polymorph Temperature,
C

E, kcal/mole noncatalytic stage 35.6 2.6 46.7 3.4 53.1 1.4 catalytic stage 55.4 1.9 49.4 1.7 45.3 2.6

A, sec1 noncatalytic stage 1011.91.3 1017.71.6 1020.30.7 catalytic stage 1023.00.9 1019.61.6 1017.61.2

166194 172194 192211

Note. The kinetic equation was adopted in the form d/dt = k1 (1 ) + k2 (1 ), ki = Ai exp(Ei /RT ), i = 1, 2.

TABLE 2
Density and Velocity of Detonation of Selected CL-20-Based PBXs Composition 96% CL-20; 1% Hy Temp; 3% DOA 96%HMX; 1% Hy Temp; 3% DOA RX-39-AA&AB: 95.595.8% CL-20; estane PBXC-19: 95% CL-20; EVA PATHX-1: 8895% CL-20; estane PATHX-2: 9295% CL-20; estane PATHX-3: 8594% CL-20; estane LX-19: 95% CL-20; estane LX-14: 95% HMX; estane PBXCLT-1:4970% CL-20; 4827% energetic material HNJ; 3% polymeric binder PVB PBXCL-1: 97% CL-20; 3% PVB 66.872.1% CL-20; HTPB 66.872.1% HMX; HTPB 32% CL-20; 48% TEX; 20% HTPB 32% HMX; 48% TEX; 20% HTPB 1.906 1.921 1.6481.710 1.5751.618 1.595 1.560 8.3849.102 9.102 8.3258.470 8.0308.107 [73] [1] [60] 1.942 0.001 1.896 0.002 1.8681.944 1.8691.923 1.8711.958 1.959 1.835 9.208 0.1 9.083 0.001 8.899.37 8.859.22 8.919.50 9.44 8.79 [2] [59] Density, g/cm3 1.901 1.792 Detonation velocity, mm/sec 9.018 8.748 Reference [60]

Note. Hy Temp and PVB are trade marks for binders, DOA is dioctiladipate, estane is an aromatic polyester (polyurethaneEsterMDI), EVA is ethylene vinyl acetate, and TEX is the 4,10-dinitro-2,6,8,12-tetraoxa4,10-diazatetracyclo-[5,5,0, 05.9 , 03.11 ]dodecane explosive.

SENSITIVITY Simpson [2] reported that CL-20 exhibits impact (h50 = 14 cm for -CL-20 and h50 = 1221 cm for -CL-20) as well as friction sensitivity (insensitive up

to 6171 N) close to those for PETN (h50 = 1316 cm and insensitive up to 78 N), whereas it is more sensitive to these factors than HMX (32 cm and 114 N, respectively). Mezger et al. [59] also reported that CL20 is more sensitive to mechanical factors than HMX.

Hexanitrohexaazaisowurtzitane (CL-20) and CL-20-Based Formulations (Review) However, Dudek et al. [60] found that the impact sensitivity of CL-20 (h50 = 28 cm) is comparable to that of HMX (30 cm) and TNAZ (26 cm). Bouma et al. [34] established that CL-20 is friction-insensitive up to 84 N, whereas Mueller [61] reported its insensitivity up to 18 N. The sensitivity tests undertaken by the authors on the product obtained at High-Energy Materials Research Laboratory yielded h50 = 21 cm and friction insensitivity up to 120 N. The morphology of CL-20 plays an important role in this aspect [1]. Thus, rounded single crystals of CL-20 are reported to have a lower sensitivity to the impact: h50 = 36 cm, as compared to h50 = 19.4 cm for polycrystalline materials. Ultrasound-aided crystallization of CL-20 (frequency of 100 kHz and amplitudes of 0.41.0 m) decreases the sensitivity and improves stability [62]. Manning and Strauss [63] suggested a graphite coating (<2 wt.%) as an eective tool of sensitivity reduction.

127

FORMULATIONS CL-20 was evaluated in both propellant and explosive formulations. A large number of CL-20-based plastic bonded explosives (PBXs) are reported in the literature (Table 2). A comparison of their velocity of detonation (VOD) with that of the corresponding HMXbased formulations reveals a 1215% higher energy potential of CL-20 systems. CL-20 is also a superior alternative to RDX and HMX for applications in lowsignature rocket propellants. CL-20-incorporating propellants oer burning rates much higher (by 35110%) than those of HMX-based propellants (Table 3). The performance level of CL-20-based propellants in terms of Isp is found to be higher than that of RDX-based propellants. Goler et al. [1] reported CL-20glycidyl azide polymer (GAP) propellants to have Isp = 251 sec, in comparison to that of 242 sec for the corresponding RDX-based propellant. CL-20 is also a potential component of gun propellants having a superior impetus and high burning rates (Table 4). Hydroxyl-terminated polybutadiene (HTPB) and GAP nd application as binders of cast PBX, whereas thermoplastic elastomers (TPEs), such as estane/ethylene vinyl acetate (EVA), are a good choice for pressed PBX. Polyglycol adipate (PGA) as well as GAP are often incorporated as binders and bis-dinitropropyl formal/acetal (BDNPF/A) as well as trimethylol ethyl trinitrate (TMETN) systems are used as plasticizers. Bis-azido methyl oxetane (BAMO)-based TPEs have evinced interest in gun propellants.

Mezger et al. [59] formulated compositions with 8590% of CL-20 as an alternative to the todays most widely used HMX-based formulation LX-14.3 They also projected application of CL-20-based PBXs in explosively formed projectiles (EFP). Eiselle and Menke [64] reported the probability of application of CL-20-based compositions in rocket motors for highly accelerating guided tactical missiles (HVMs or HFKs). CL-20 propellants also have potential of application for high-velocity ballistic missiles. Harris et al. [65] recommended Hytrel (co-polymer of polybutylene terephthalate-polyether glycol) and BAMOAMMO (azido methyl methyl oxetane) co-polymerbased CL-20-containing propellants as a superior alternative to the M30 gun propellant. CL-20-containing propellant formulations based on NC plasticized with BDNPF/A or EPX are reported to be safe enough to be tested in a 40-caliber gun simulator [61]. Lewis et al. [66] studied a CL-20-based pyrotechnic gas-generating material that burns down to produce one or more reaction products that suppress re. Sato and Kodama [67, 68] studied HNIW as a base charge for detonators and as a lling of detonation cords.

PROCESSING OF PROPELLANT CHARGES Prevailing casting, extrusion, and pressing techniques nd application in processing of CL-20-based formulations. Mueller [61] made an attempt to use a continuous twin-screw extrusion technology for propellant processing. Simpson et al. [2] reported injectionmoldable formulations containing approximately 80% of CL-20, 10% of bis-(2,2,2-uorodinitro)formal (FEFO), and 10% of mixed nitroformal FM-1. Simpson et al. [69] also used a sol-gel process for producing formulations based on CL-20. The processing steps involved polymerization of a reactive monomer with formation of a gel structure from a solution (e.g., an aerogel or a xerogel). Nano-composites are obtained by accommodating fuel and oxidizer moieties into the voids of the skeleton structure formed by sol-gel polymerization. Mezger et al. [59] established that there are no phase transitions of CL-20 during its processing at temperatures of 3090 C and pressures of 138345 MPa. However, Foltz et al. [27] found that production of CL-20- and estane-based propellants alters the phase state of CL20, thus, leading to a decrease in density of the formulation. A phase transition of the modication was observed at a temperature of 60 C, and long-time heating of CL-20-estane-based formulations at 100105 C
3

See Table 2 for the notation of various explosives.

128 TABLE 3
Burning Rates of CL-20-Incorporating Rocket Propellants Composition 60% CL-20; 40% PGA 60% HMX; 40% PGA 60% CL-20; 40% GAP 60% HMX; 40% GAP 60% CL-20; 40% GAP (catalyzed) 60% RDX; 40% GAP (catalyzed) 70% CL-20; 20% GAP; 10% BDNPF/A Burning rate, mm/sec 11.523 (715 MPa) 611 (715 MPa) 13.427.2 (715 MPa) 7.213.6 (715 MPa) 20.032.4 (720 MPa) 14.621.4 (720 MPa) 15 (7 MPa) n 0.92 0.89 0.94 0.91 0.48 (525 MPa) 0.37 (420 MPa) 0.57

Nair, Sivabalan, Gore, et al.

Reference [1] [1] [1]

[74]

Note. n is the exponent in the power law of the burning rate, PGA is polyglycol adipate, and GAP is a glycidyl azide polymer.

TABLE 4
Combustion Characteristics of CL-20-Incorporating Gun Propellants Composition 76% CL-20; BAMO/AMMO Impetus, J/g 1297 Flame temperature, K 3412 Burning rate, cm/sec 11.4829.97 (75.8179 MPa) 76% RDX; BAMO/AMMO 1182 2827 3.8610.97 (75.8179 MPa) CL-20; NC; BDNPF/A RDX; NC; BDNPF/A CL-20; 530% BAMO AMMO/BAMO NMMO/BEMO NMMO Note. NC is nitrocellulose, NMMO is nitrato methyl methyl oxetane, and BEMO is bis-ethoxy methyl oxetane. 1253 1220 12781349 3698 3390 20.3227.94 [61] [76] Reference [75]

led to and phase transition. This was attributed to the high solubility of CL-20 in estane owing to the high carbonyl content of the latter.

COMPATIBILITY OF COMPONENTS Wardle et al. [32] reported that HNIW is compatible with HTPB and polyethylene glycol (PEG) as well as with azido polymers and nitrate esters, while it is incompatible with polybutadiene acrylic acid acrylonitril terpolymer (PBAN). Vacuum stability tests re-

vealed relatively greater evolution of gases, in the case of estane-based formulations [PATHX-3 (96) and LX19] containing graphite, zinc stearate, metals (copper, molybdenum, aluminum, iron, and tantalum), and resins (RTV 3104, Ultem plastic, and loctite 12952) as additives than for CL-20 alone. However, the overall amount of gases evolved (0.10.3 cm3 ) at 100 C for 48 hours remained at an acceptable low level, except for loctite, where the volume of the evolved gas reached 1 cm3 , suggesting incompatibility of the latter with CL-20 [59]. A lower onset temperature of the exotherm for CL-20-based formulations containing

Hexanitrohexaazaisowurtzitane (CL-20) and CL-20-Based Formulations (Review) loctite (199220 C) in comparison to those of other formulations is another indication of its incompatibility. Mueller [61] observed that CL-20-based propellants evolved 3 cm3 of the gas at 100 C in 48 hours. The best results in terms of gas evolution were obtained for the BDNPF/A binder. Heintz and Teipel [70] found that microencapsulation improves both stability and processibility. Tappan and Brill [71] observed that a mechanical mixture of CL-20 and NC decomposed as discrete units during DSC experiments, as was evidenced by two exotherms at 200 and 233 C. In CL-20/NC cryogels, however, a single exotherm was observed at 205 C, suggesting that NC decomposition aects CL-20 decomposition. T-jump/FTIR experiments also bring out the dominance of NC decomposition, except for cryogels with a low content of nitrocellulose: 90/10 CL-20/NC.

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0.19-cm connement, which implies its low vulnerability. PATHX-3 (94) was found to be comparable to LX14 in this regard. The burning rates of pressed pellets of CL-20-based formulations were substantially higher than that of LX-14 in closed vessel tests, indicating their more hazardous nature in terms of transportation and storage. The CL-20-based propellant developed by Mueller [61] exhibited much lower friction (160 N) and impact sensitivity (4 Nm) than CL-20 alone. As was reported by Eiselle and Menke [64], despite the safety classication of CL-20 propellants [CL-20/ AP/GAP/TMETN/BTTN (butanetrioltrinitrate)] being 1.1, their sensitivity to detonation is lower than that of pressed explosives as well as high-energy double-base and composite double-base propellants.

SENSITIVITY OF PROPELLANT FORMULATIONS Among pressed compositions, Mezger et al. [59] found that the impact and friction sensitivity of CL20-based LX-19 and PATHX-3(94) is almost comparable to that to HMX-incorporating LX-14, whereas compositions with a lower CL-20 content [PATHX-3(90)] were found to have a higher sensitivity. Card Gap test results reported by Wardle et al. [32] provided comparable safety characteristics of HNIW (93%)/binder and HMX (93%)/estane-based formulations (the card gap was 2.252.31 and 2.162.19 cm, respectively) in terms of shock susceptibility. This disagrees with the data of Dudek et al. [60], however, who found that HNIW/TEX/HTPB (32/48/20) formulations undergo detonation by a shock wave of 5.6 GPa in comparison with the value of 10.2 GPa for HMX/TEX/HTPB (32/48/20)-based formulations. Tarver et al. [72] also found a higher shock sensitivity of LX-19 by conducting the wedge and embedded manganin pressure gauge tests. Mezger et al. [59] applied a Variable Connement Cook-o Test (VCCT), to determine the response of CL-20-based formulations to slow the cook-o-type reaction. In this test, the sample 2.54 cm in diameter and 6.35 cm long was placed into a steel casing whose thickness ranged from 0.0381 to 0.19 cm. The wall thickness was considered as a means of connement. LX-19 underwent partial detonation with 0.076-cm connement in contrast to detonation of LX-14 with 0.19cm connement, further indicating a higher sensitivity of the former. On the other hand, PATHX-3 (90) with a lower CL-20 content underwent only deagration at

CONCLUSIONS Despite various routes available for CL-20 synthesis and production, the current cost of the material is high. New approaches are needed to achieve costeective mass production and, thus, to facilitate universal application of this high-potential material. The polymorphs of CL-20 are well characterized, and it is possible to tailor a method to obtain a desired morphology and particle size. Although CL-20 has been subjected to detailed thermal studies, the values of temperature and activation energy of the decomposition process reported by various researchers are considerably dierent, probably, because of the dierence in synthesis and manufacturing approaches and in morphology evaluation. These aspects need to be carefully reviewed, keeping all the parameters in perspective to pinpoint the mechanism of energy release by generating exhaustive comparative data on materials from dierent sources. Sensitivity aspects also need a detailed investigation in view of the disagreement in experimental ndings to ensure safe processing. It can be inferred from the reported results that CL-20-containing formulations are more sensitive to mechanical and shock factors than RDX- and HMX-based formulations. Exhaustive research and development programs are required to be undertaken to optimize the specic impulse and velocity of detonation of CL-20-based formulations without penalty on vulnerability in view of their emergence as an eective solution to future needs. An in-depth study on compatibility and stability aspects of CL-20-based formulations is also very important from the viewpoint of its application in various systems.

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