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Uilimm● ● ● B : : :0 :00 0 I Informalreport Issued: Septemk 1978 UNCLASSIFIED I 42.3 1

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Uilimm● ● ● B : : :0 :00 0 I Informalreport Issued: Septemk 1978 UNCLASSIFIED I 42.3 1 - m m 6:~-El . 9 .5-___. Emmmmmml APPROVED@oo FOR -PUBLIC RELEASE I LA-7398-MS ● 0 ● . special Distribution UiliMM● ● ● b : : :0 :00 0 I InformalReport Issued: Septemk 1978 UNCLASSIFIED I 42.3 1 . I I Castable Ideal Composite Explosives I COPY Containing Ammonium Nitrate (U) r M. S. Fowler PUBLICLY RELEaLE T. M. Benziger i%~, FSS- 16 Date: &@T H. H. Cady CIC- 14 Date” M. D. Coburn .* B. W. Harris R. N. Ro@rs M. J. Urizar I CLdM51FIWS10Nciirmwu To BY AUTNC)RITYOF ~!!l/,./h I . I -i. I I Univefaity of California . LOS ALAMOS SCIENTIFIC LABORATORY I Post Office Box 1863 Los Alamos, New Mexico 87545 Classified by Phillip M. Lang ● * ● ** ● *. ● m ISD-6 Classification Analyst :: I i ‘w I ------ APPROVEDA4S”;A:”A= FOR PUBLIC RELEASE APPROVED● 0 FOR PUBLIC● ● ● ** RELEASE9. 9 .*99*.. TMswork wassupportedby the US Departmentof the Navy,NavalSeaSystemsCommand(SEA 0332). TM, ?SVOFI wu srepmd u all =COUO: of wOrk mnwsd * by tbe United Slates GOvet’nm.mL N.11ber4ba Unitd slat.c am tkn unwedsaw mwmnmlt of Cluray, norallyofIb* .mvlomh nor anY of tb.lt ee.twkon. dxrmmet.ma or tkmlr emvl.y.es, mmkes w wumnty. ●xsmw or Implkod. or ames any Ieul U.blllty .? mwondbllllv to? kbe wcwaw. .0mDl*tae9. or udulneu of my lnfonmklom. mwmntus, Prc.duet, oz Pmcem dkloaed, c.. raptatnis that lti U- would not hfrln.. PtiV.k!Y owned ckdILL UNITED STATCS . ..- DRPARTMCNT OF CNRR=V CONTRACT W-7409-SN9. X . .00 ● m iiuNCusslFIED .“ APPROVED .09FOR PUBLIC RELEASE ● * . ..8** ● ☛ ● *e ● 8* APPROVED● ** FOR● *OPUBLIC: 90, RELEASE ● * ● 9* ● ** ,** ● *O 9 ● ● :00000 ● : ● * ● ●: : .;. i.. i.: lJN~~ASSiFi~~ CASTABLE IDEAL COMPOSITE EXPLOSIVES CONTAINING AMMONIUM NITRATE by M. S. Fowler, T. M. Benziger, H. H. Cady, M. D. Coburn B. W. Harris, R. N. Rogers, and M. J. Urizar ABSTRACT Several ammonium salts of nitroheterocycles were prepared and charac- terized with respect to their physical properties and eutectic formation with ammonium nitrate (AN). The eutectic mixture of AN and the ammonium salt of 3,5-dinitro- 1,2,4-triazole (ADNT) was found to have a melting point low enough to be castable, a sensitivity similar to Composition B, and ideal detonation performance. We also found that other explosives can be slurried into the melt to improve physical characteristics or change the explosive performance. ;. ‘I%e phase diagram of AN and ADfi was determined, and availability and probable cost of materials was estimated. The ammonium salt of trinitroimidazale is an energetic and stable ex- plosive, and the problems associated with its synthesis have been studied for several years. A carbon-13 nuclear magnetic resonance (CMR) study has been used to elucidate its preparation from triiodoimidazole, and we have decided that it cannot be produced at ,an acceptable cost now. I 1 I. INTRODUCTION of nonideal explosives are usually slower than those of ideal explosives, and a significant amodnt of Ideal explosives are those that have reaction rates chemical reaction occurs behind the steady-state high enough to be nearly instantaneous or time in- detonation zone. Thus, experimentally determined dependent. Parameters such as detonation pressure detonation pressures and velocities of nonideal ex- and velocity can be calculated quite accurately on plosives are lower than those calculated assuming that assumption,’ although reaction zone thickness “instantaneous” reaction. For example, calculations * may be signitlcant.a predicted that an ideal mixture of HMX and Nonideal explosives are usually composite ex- lithium perchlorate would give 110% of the perfor- 8if plosives; that is, explosives that are mixtures of par- mance of pure HMX; however, a cylinder test of the ticulate oxidizera and fuels. However, nonideal ex- mixture showed that ita performance was signifi- plosives may contain an ideal explosive as an in- cantly less than that of HMX.8 Comparisons of gredient. Ammonium nitrate/fuel oil (ANFO), measured detonation velocities with BKWi calcula- ANnNT (Amatol), and AN/TNT/RDX (Amatex) tions for Amatex formulations with different are examples of nonideal explosives. Req@on~mte~ qm$~n~ of AN suggested that about 50% of the AN ● :: ..:: ::. ● ● * 99 :e. 1 APPROVED FOR PUBLIC RELEASE APPROVED● 9 FOR ●PUBLIC● ** ● 9 RELEASE ● .*- :a*9. a ulQC~SSIFIED reacts on a short enough time scale to ~e~t &&& iIfi. &’MP0SIT10Nf3 OF AN AND AM- tion velocity.’ Because of these and other similar MONIUM SALTS OF NITROHETEROCYCLES results, research on methods to make nonideal ex- plosives (especially those containing AN) behave The ammonium salts of 3-nitro-l,2,4-triazole ideally was given high priority by the Advanced [(1)],” 3,5-dinitro-l,2,4-triazole (ADNT) [(lI)],” Research Projects Agency? 3,5-dinitropyrazole [(111)],16 4,5-dinitroimidazole The performance of nonideal explosives can be [(IV) ],” 2,4-dinitroimidazole [(V)],” 4-nitro-l,2,3- improved by more intimate incorporation of the triazole [(VI)], 18 5,5’-dinitro-3,3’-bi-l,2,4-triazolyl components.’ A recent demonstration by Finger et [(vu) ],” and 5-nitrotetrazole [(VIII)]” were al, showed that mixtures of gelled nitromethane prepared by bubbling ammonia gas through a solu- with 200-ym particles of ammonium perchlorate tion of the nitroheterocycle in ether or were distinctly nonideal; however, mixtures con- ether/ethanol. The solids were collected and taining 5-~m ammonium perchlorate were nearly recrystallized from acetone/ethyl acetate to give ideal.”s products with acceptable elemental analyses. The Pursuing the hypothesis that variatlw s structures plus physical and explosive properties timacy of mixing could be used to control sensitivity determined for these salts are given in Table L The and performance, the Los Alamos Scientific references (14-19) give the preparations of the Laboratory (LASL) has long supported a study on parent compounds. crystallography and phase relationships of ex- The composite explosives were prepared by plosives. It was assumed that maximum perfor- grinding together the appropriate amounts of AN mance would be obtained when components were and the ammonium salt of the nitroheterocycle, combined in a continuous solid solution; however, Each AN/ammonium salt mixture was heated with no cost-effective, practical, solid-solution system stirringat -5° C above its melting point until a clear has been found. Recent work at Picatinny Arsenal solution was obtained; then it was cooled to room and LASL has indicated that eutectic incorporation temperature. The resulting solid was ground to a of components greatly improved performance,etio’ii powder, which was used to obtain the eutectic data but did not produce ideal performance. in Table I. We studied primarily the mixtures of AN These recent studiesg,llinvolved consolidification and ADNT [(II)], because their relatively low of AN with amine nitrates, in an attempt to promote melting points and good thermal stabilities implied eutectic formation by the common nitrate ion. Our that they might be useful components of a castable most recent approach is to use ammonium salts of explosive. In addition, these mixtures were found to nitroheterocycles as fuels with the hope that the be more sensitive to impact than ADNT. This ob- common ammonium ion will produce advantageous servation was unexpected, because mixing other phase relationships. common explosives with AN generally gives a com- We first studied the ammonium salt of 2,4,5- posite that is less sensitive than the pure explosive. trinitroimidazole (ATNI) .12 Although ATNI is a Explosives based on mixtures of ammonium nitrate very stable and energetic compound,l’ work on this and ammonium 3,5-dinitro-l,2,4 -triazolate are code material was discontinued when we discovered that named Fairy Dust and their compositions and ex- it could not be economically produced and that it plosive properties are classified CNSI. would not form a low-melting eutectic with AN A plate-dent testm was run on an unconfined (Sec. VI). We have now prepared ammonium salts pressed charge of the COZ-balanced, fused mixture of other nitroheterocycles, and we have evaluated (2/1 of AN/ADNT)* with a density of 1.590 g/cm’. the physical and explosive properties of mixtures of ———— these compounds with AN. “All ratios are molar ratios. w APPROVED FOR PUBLIC RELEASE APPROVED FOR PUBLIC RELEASE PROPERTIES OF AMMONIUM SALTS OF NITROHIF17EROCYCLES N— N—N NH,+ <0)- N02 NH4+02 N<0) – N02 N N (I) (II) m (n?) (x) —N NH, + — N02 @ Nb2 m) (m) (m Properties I II III Iv v VI VII VIII —. — — — _ Melting point (“C) 158-216 165-168 186-232 185-188 225-226 107-125 unstable 205dec. DTA (endotherm, ‘C) 140,175 168 280 exe-235 226 180 exo-280 67,112,205 AN eutectic mu (“C) 120 112 167 165 152 120 110 Density (g/cm~ 1.63 1.67 Impact sensitivity Type 12 (cm) >320 110 158 77.5 235 30 Type 12B (cm) 124 135 62.6 302 75 The estimated detonation pressure [Chapman- 111. AN/ADNT AS A BINDER FOR MILITARY Jouget (CJ) pressure (Pc~)] agreed quite closely with EXPLOSIVES that obtained from a BKW calculation that assumed an ideal system.zi A second charge of the We found that ANIADNT mixtures can be used same formulation pressed at 100”C to a density of as energetic, oxygen-rich binders for RDX, HMX, 1.645 g/cma gave a lower detonation pressure than nitroguanidine (NQ), and other explosives. The the first in the 1.27-cm (0.5-in.) plate-dent test, melt dissolves an appreciable amount of explosive because it partially failed. Generally, failure and holds an additional amount as a slurry. Upon diameter increasesas the density increases. We were cooling, the slurry solidifies to form a uniform solid. fortunate that the first pressing did not fail, because We have pulverized these solids and pressed them explosives containing AN usually have failure into cylinders for test-firing samples.
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