HMX—

RDX and HMX are rather more recalcitrant, especially under aerobic conditions, but there are promising indications that biodegradation can occur under some conditions, especially composting (67). Several strains of bacteria able to use RDX (and Triazine) as a sole source of nitrogen for growth have recentiy been isolated, and this is an area where rapid progress is being made. 

Only relatively few compounds can act as primary explosives and still meet the restrictive military and industrial requirements for reflabiUty, ease of manufacture, low cost, compatibiUty, and long-term storage stabiUty under adverse environmental conditions. Most initiator explosives are dense, metaHoorganic compounds. In the United States, the most commonly used explosives for detonators include lead azide, PETN, and HMX. 2,4,6-Triamino-l,3,5-triuitrobenzene (TATB) is also used in electric detonators specially designed for use where stabiUty at elevated temperatures is essential. 

Both RDX and HMX are stable, crystalline soHds, somewhat less sensitive to impact than PETN. Both may be handled with no physiological effect if appropriate precautions are taken to assure cleanliness of operations. Both RDX and HMX detonate to form mostiy gaseous, low molecular weight products and some intermediate formation of soHd carbons. The calculated molar detonation products of RDX are 3.00 H2O, 3.00 N2, 1.49 CO2, and 0.02 CO. RDX has been stored for as long as 10 months at 85°C without perceptible deterioration. 

HMX, the highest density and highest energy soHd explosive produced on a large scale, primarily for military use, exists in four polymorphic forms. The beta form is the least sensitive, most stable, and the type requited for military use. The mole fraction products of detonation of HMX in a calorimetric bomb are 3.68 N2, 3.18 H2, 1.92 CO2, 1.06 CO, 0.97 C, 0.395 NH3, and 0.30 H2. 

Both RDX and HMX are substantially desensitized by mixing with TNT to form cyclotols (RDX) and octols (HMX) or by coating with waxes, synthetic polymers, and elastomeric biaders. Most of the RDX made ia the United States is converted to Composition B (60% RDX, 40% TNT, 1 part wax added). Composition A5 (RDX 98.5/stearic acid 1.5) and composition C4 (RDX91/nonexplosive plasticizer) account for the next largest uses. HMX is used as a propellant and ia maximum-performance plastic bonded explosives such as PBX 9401 and PBX N5 and the octols (147—150). 

Ma.nufa.cture. The two most common processes for making RDX and HMX use hexamethylenetetramine (hexamine) as starting material. The Woolwich or direct nitrolysis process used ia the United Kingdom proceeds according to ... 

In the Bachmann process an 80—84% yield is obtained, ca 10% of which is cyclotetramethylenetetranitramine (HMX). The Woolwich process gives a 70—75% yield containing only a trace of HMX. 

Military. The single-component explosives most commonly used for military compositions are TNT, RDX or HMX, nitrocellulose, and nitroglycerin. The last two are used almost exclusively to make propellants. The production volume of TNT far exceeds that of any other explosive. It is used as manufactured, as a base of biaary slurries with other high melting explosives, or ia ternary systems generally containing a biaary mix and aluminum. 

Calculated relative energy of explosive released on detonation and subsequent expansion of detonation gases relative to HMX. 

J. T. Rogers, Physical and Chemical Properties ofEDX and HMX, Control Rpt. 20-P-26A, Holston Defense Corp., Kingsport, Tex., 1962. 

J. Solomon, Pi Study of the Nitrolysis of Hexamine to Increase HMX Yields, Illinois Institute of Technology, Chicago, 1973. 

R. Robbins, The Preparation, Properties, and Uses of HMX, Rpt. RR-GC-149, Holston Defense Corp., Kingsport, Term., 1958. 

D. Burrows, Eiterature Eeview of the Toxicity ofEDX and HMX, U.S. Army Medical and Bioengineering Research and Development Lab., Washington, D.C., 1973. 

Polymer-based rocket propellants are generally referred to as composite propellants, and often identified by the elastomer used, eg, urethane propellants or carboxy- (CTPB) or hydroxy- (HTPB) terrninated polybutadiene propellants. The cross-linked polymers act as a viscoelastic matrix to provide mechanical strength, and as a fuel to react with the oxidizers present. Ammonium perchlorate and ammonium nitrate are the most common oxidizers used nitramines such as HMX or RDX may be added to react with the fuels and increase the impulse produced. Many other substances may be added including metallic fuels, plasticizers, stabilizers, catalysts, ballistic modifiers, and bonding agents. Typical components are Hsted in Table 1. 

Oxidizers. The characteristics of the oxidizer affect the baUistic and mechanical properties of a composite propellant as well as the processibihty. Oxidizers are selected to provide the best combination of available oxygen, high density, low heat of formation, and maximum gas volume in reaction with binders. Increases in oxidizer content increase the density, the adiabatic flame temperature, and the specific impulse of a propellant up to a maximum. The most commonly used inorganic oxidizer in both composite and nitroceUulose-based rocket propellant is ammonium perchlorate. The primary combustion products of an ammonium perchlorate propellant and a polymeric binder containing C, H, and O are CO2, H2, O2, and HCl. Ammonium nitrate has been used in slow burning propellants, and where a smokeless exhaust is requited. Nitramines such as RDX and HMX have also been used where maximum energy is essential. 

Gun Propellents. Low sensitivity gun propeUants, often referred to as LOVA (low vulnerabUity ammunition), use RDX or HMX as the principal energy components, and desensitizing binders such as ceUulose acetate butyrate or thermoplastic elastomers (TPE) including poly acetal—polyurethane block copolymers, polystyrene—polyacrjiate copolymers, and glycidyl azide polymers (GAP) to provide the required mechanical... 

A significant advantage of the PLM is in the differentiation and recognition of various forms of the same chemical substance polymorphic forms, eg, brookite, mtile, and anatase, three forms of titanium dioxide calcite, aragonite and vaterite, all forms of calcium carbonate Eorms I, II, III, and IV of HMX (a high explosive), etc. This is an important appHcation because most elements and compounds possess different crystal forms with very different physical properties. PLM is the only instmment mandated by the U.S. Environmental Protection Agency (EPA) for the detection and identification of the six forms of asbestos (qv) and other fibers in bulk samples. 

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