An Explosive is Defined as a Material

Explosives An explosive is defined as a material (chemical or nuclear) that can be initiated to undergo very rapid, self-propagating decomposition that results in the formation of more stable material, the liberation of heat, or the development of a sudden pressure effect through the action of heat on produced or adjacent gases. All of these outcomes produce energy; a weapon's effectiveness is measured by the quantity of energy - or damage potential - it delivers to the target. Modern weapons use both kinetic and potential energy to achieve maximum lethality. Kinetic energy systems rely on the conversion of kinetic energy to work, while potential energy systems use explosive energy directly in the form of heat and blast, or by accelerating metal as a shaped charge, EFP or case fragments to increase their kinetic energy and damage volume. Energy may be broadly classified as potential or kinetic. Potential energy is energy of configuration or position, or the capacity to perform work. For example, the relatively unstable chemical bonds among the atoms that comprise trinitrotoluene (TNT) possess chemical potential energy. Potential energy can, under suitable conditions, be transformed into kinetic energy, which is energy of motion. When a conventional explosive such as TNT is detonated, the relatively unstable chemical bonds are converted into bonds that are more stable, producing kinetic energy in the form of blast and thermal energies. This process of transforming a chemical system's bonds from lesser to greater stability is exothermic (there is a net production of energy). A chemical explosive is a compound or a mixture of compounds which, when subjected to heat, impact, friction, or shock, undergoes very rapid, self-propagating, heatproducing decomposition. This decomposition produces gases that exert tremendous pressures as they expand at the high temperature of the reaction. The work done by an explosive depends primarily on the amount of heat given off during the explosion. The term detonation indicates that the reaction is moving through the explosive faster than the speed of sound in the unreacted explosive; whereas, deflagration indicates a slower reaction (rapid burning). A high explosive will detonate; a low explosive will deflagrate. All commercial explosives except black powder are high explosives. Low-order explosives (LE) create a subsonic explosion [below 3,300 feet per second] and lack HE's over-pressurization wave. Examples of LE include pipe bombs, gunpowder, and most pure petroleum-based bombs such as Molotov cocktails or aircraft improvised as guided missiles. A High Explosive (HE) is a compound or mixture which, when initiated, is capable of sustaining a detonation shockwave to produce a powerful blast effect. A detonation is the powerful explosive effect caused by the propagation of a high-speed shockwave through a high explosive compound or mixture. During the process of detonation, the high explosive is largely decomposed into hot, rapidly expanding gas. The most important single property in rating an explosive is detonation velocity, which may be expressed for either confined or un-confined conditions. It is the speed at which the detonation wave travels through the explosive. Since explosives in boreholes are confined to some degree, the confined value is the more significant. Most manufacturers, however, measure the detonation velocity in an unconfined column of explosive 1- i/4 in. in diameter. The detonation velocity of an explosive is dependent on the density, ingredients, particle size, charge diameter, and degree of confinement. Decreased particle

size, increased charge diameter, and increased confinement all tend to increase the detonation velocity. Unconfined velocities are generally 70 to 80 percent of confined velocities. The confined detonation velocity of commercial explosives varies from 4,000 to 25,000 fps. With cartridge explosives the confined velocity is seldom attained. Some explosives and blasting agents are sensitive to diameter changes. As diameter is reduced, the velocity is reduced until at some critical diameter, propagation is no longer assured and misfires are likely. Relative effectiveness factor (R.E. factor) is a measurement of an explosive's power for military demolitions purposes. It measures the detonating velocity relative to that of TNT, which has an R.E. factor of 1.00. TNT equivalent is a measure of the energy released from the detonation of a nuclear weapon, or from the explosion of a given quantity of fissionable material, in terms of the amount of TNT (trinitrotoluene) which could release the same amount of energy when exploded. The twelve-kiloton Hiroshima atomic bomb had had a blast effect alone equivalent to some twenty-five million pounds of TNT-that's million. Denser explosives usually give higher detonation velocities and pressures. A dense explosive may be desirable for difficult blasting conditions or where fine fragmentation is required. Low-density ex-plosives will suffice in easily fragmented or closely jointed rocks and are preferred for quarrying coarse material. Energetic materials are made in two ways. The first is by physically mixing solid oxidizers and fuels, a process that, in its basics, has remained virtually unchanged for centuries. Such a process results in a composite energetic material such as black powder. The second process involves creating a monomolecular energetic material, such as TNT, in which each molecule contains an oxidizing component and a fuel component. For the composites, the total energy can be much greater than that of monomolecular materials. However, the rate at which this energy is released is relatively slow when compared to the release rate of monomolecular materials. Monomolecular materials such as TNT work fast and thus have greater power than composites, but they have only moderate energy densities-commonly half those of composites. Greater energy densities versus greater power-that's been the traditional trade-off. Ingredients of high explosives are classified as explosive bases, combustibles, oxygen carriers, antacids, and absorbents. Some ingredients perform more than one function. An explosive base is a solid or liquid which, upon the application of sufficient heat or shock, decomposes to gases with an accompanying release of considerable heat. A combustible combines with excess oxygen to prevent the formation of nitrogen oxides. An oxygen carrier assures complete oxidation of the carbon to prevent the formation of carbon monoxide. The formation of nitrogen oxides or carbon monoxide, in addition to being undesirable from the standpoint of fumes, results in lower heat of explosion and efficiency than when carbon dioxide and nitrogen are formed. Antacids increase stability in storage, and absorb-ents absorb liquid explosive bases. Explosives are classified as primary or secondary based on their susceptibility to initiation. Primary explosives, which include lead azide and lead styphnate, are highly susceptible to initiation. Primary explosives often are referred to as initiating explosives because they can be used to ignite secondary explosives. Secondary explosives, which include nitroaromatics and nitramines are much more prevalent at military sites than are

primary explosives. Because they are formulated to detonate only under specific circumstances, secondary explosives often are used as main charge or bolstering explosives. Secondary explosives can be loosely categorized into melt-pour explosives, which are based on nitroaromatics such as TNT, and plastic-bonded explosives which are based on a binder and crystalline explosive such as RDX. Propellants include both rocket and gun propellants. Most rocket propellants are composites based on a rubber binder, ammonium perchlorate oxidizer, and a powdered aluminum fuel; or composites based on a nitrate esters, usually nitroglycerine or nitrocellulose and nitramines. If a binder is used, it usually is an isocyanate-cured polyester or polyether. Some propellants also contain combustion modifiers, such as lead oxide. One group of gun propellants are called "single base" (principally nitrocellulose), "double base" (nitrocellulose and nitroglycerine), or "triple base" (nitrocellulose, nitroglycerine, and nitroguanidine). Some of the newer, lower vulnerability gun propellants contain polymer binders and crystalline nitramines. Pyrotechnics include illuminating flares, signaling flares, colored and white smoke generators, tracers, incendiary delays, fuses, and photo-flash compounds. Pyrotechnics usually are composed of an inorganic oxidizer and metal powder in a binder. Illuminating flares contain sodium nitrate, magnesium, and a binder. Signaling flares contain barium, strontium, or other metal nitrates. Explosive and incendiary (fire) bombs are further characterized based on their source. "Manufactured" implies standard military-issued, mass produced, and quality-tested weapons. "Improvised" describes weapons produced in small quantities, or use of a device outside its intended purpose, such as converting a commercial aircraft into a guided missile. Manufactured (military) explosive weapons are exclusively HE-based. Terrorists will use whatever is available - illegally obtained manufactured weapons or improvised explosive devices (also known as "IEDs") that may be composed of HE, LE, or both. Manufactured and improvised bombs cause markedly different injuries. Plastic explosive means an explosive material in flexible or elastic sheet form formulated with one or more high explosives which in their pure form has a vapor pressure less than 10-4 Pa at a temperature of 25 deg. C., is formulated with a binder material, and is as a mixture malleable or flexible at normal room temperature. The energetic materials used by the military as propellants and explosives are mostly organic compounds containing nitro (NO2) groups. The three major classes of these energetic materials are nitroaromatics (e.g., tri-nitrotoluene or TNT), nitramines (e.g., hexahydro-1,3,5 trinitroazine or RDX), and nitrate esters (e.g., nitrocellulose and nitroglycerine). Since the invention of the cannon, the explosive fills used to drive lethal mechanisms have been the subject of ever increasing interest and study. Traditionally, munitions designers have used such ex-plosives as Comp-B, TNT, or LX-14, depending upon the particular application. During the 1920s and into the 1940s, the Army's Picatinny Arsenal was instrumental in designing, modeling and evaluating such high explosive material as TNT, RDX, and Haleite. This work greatly influenced battlefield lethality during WWII where explosives exhibiting a higher brisance, or shattering effect, than TNT were in great demand. The 1960s brought new explosives such as HMX that was chemically analogous to RDX,

but even more powerful to give soldiers greater lethality capability. Picatinny laboratories also developed precision warheads for several missile systems, including the DRAGONMAW, a Medium Antiarmor Weapon. The Army uses Research Department Explosive (RDX) and High Melt Explosive (HMX) as basic explosives for munitions and tactical missiles as well as propellants for strategic missiles rather than TNT because of their superior energy. Most modern explosives are reasonably stable and require percussive shock or other triggering devices for detonation. Energetic materials are especially vulnerable to elevated temperature, with possible consequences ranging from mild decomposition to vigorous deflagration or detonation. Energetic materials can also be initiated by mechanical work through friction, impact, or electricity (e.g., current flow, spark, electrostatic discharge, or electromagnetic radiation). Other stimuli (e.g., focused laser light or chemical incompatibility) can have consequences ranging from mild decomposition to detonation. Explosives may be toxic, with exposure pathways being inhalation of dust or vapor, ingestion, or skin contact. Most explosives are not highly toxic, but improper handling can result in systemic poisoning, usually affecting the bone marrow (i.e., the blood cellproducing system) and the liver. Some explosives are vasodilators, which cause headaches, low blood pressure, chest pains, and possible heart attacks. Some explosives may irritate the skin. Some detonation or combustion products from explosives are toxic. Such products can be respiratory and skin irritants and lead to systemic effects following short-term exposure to high levels. Soot from detonated explosives is not mutagenic; however, soot from burned gun propellants may be mutagenic and is therefore treated as a mutagen. Fortunately, contamination usually occurs in dilute, aqueous solutions or in relatively low concentrations in the soil and present no explosion hazard. Masses of pure crystalline explosive material have, however, been encountered in soils associated with wastewater lagoons, leach pits, burn pits, and firing ranges. These materials remain hazardous for long periods of time and great care must be used during the investigation and remediation process. Molecular weights are moderate, of the order of a few hundreds of grams per mole. The molecular structure, particularly the types and positions of subsidiary functional groups, controls environmental behavior. All of the common explosives are solid at normal environmental temperatures and pressures. Melting point temperatures for explosives solids are moderate (50-205 0C). Melting points are of little direct value in predicting environmental fate and transport, but several parameter estimation relations for solids incorporate the influence of molecular crystal bonding by including a term dependent on the melting point. Melting points are not available for many of the breakdown products. Most of the explosives and associated contaminants have very low volatility, with vapor pressures estimated to be less than 6 x 10-4 torr. Henry's law constants (KH) range from 10-4 to 10-11 atm·m-2·mole-1. Only those with KH greater than 10-5 volatilize significantly from aqueous solution 12. Though explosives compounds may not be volatile, some of the transformation products, other key reactants, or products may be volatile to semivolatile. -----------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------

Primary Explosives The explosives used as initiating explosives are the primary high explosives mentioned previously in this chapter. They are used in varying amounts in the different primers and detonators used by the Navy and may differ some insensitivity and in the amount of heat given off. The explosives discussed in this section are lead azide, lead, styphnate, and diazodinitrophenol (DDNP). Lead Azide Lead azide has a high-ignition temperature and is today the most commonly used primary explosive. Lead azide is poisonous, slightly soluble in hot water and in alcohol, and highly soluble in a diluted solution of nitric or acetic acid in which a little sodium nitrate has been dissolved It reacts with copper, zinc, cadmium, or alloys containing such metals, forming an azide that is more sensitive than the original lead tide. Because lead azide does not react with aluminum, detonator capsules for lead azide are made of this metal. The hygroscopicity of lead azide is very low. Water does not reduce its impact sensitivity, as is the case with mercury fulminate. Ammonium acetate and sodium bichromate are used to destroy small quantities of lead azide. Lead tide may be used where detonation is caused by flame or heat. The velocity of detonation is approximately 17,500 feet per second (fps). Its color varies from white to buff. Lead azide is widely used as an initiating explosive in high-explosive detonator devices. Lead azide, when protected from humidity, is completely stable in stowage. Lead Styphnate There are two forms of lead styphnate-the normal that appears as six-sided monohydrate crystals and the basic that appears as small, rectangular crystals. Lead styphnate is particularly sensitive to fire and the discharge of static electricity. When the styphnate is dry, it can readily ignite by static discharges from the human body. The longer and narrower the crystals, the more susceptible the material is to static electricity. Lead styphnate does not react with metals. It is less sensitive to shock and fiction than lead azide. Lead styphnate is slightly soluble in water and methyl alcohol and may be neutralized by a solution of sodium carbonate. The velocity of detonation is approximately 17,000 fps. The color of lead styphnate varies from yellow to brown. Lead styphnate is used as an initiating explosive in propellant primer and high-explosive detonator devices. Diazodinitrophenol (DDNP) DDNP is a yellowish brown powder. It is soluble in acetic acid, acetone, strong hydrochloric acid, and most of the solvents, but is insoluble in water. A cold sodium hydroxide solution may be used to destroy it. DDNP is desensitized by immersion in water and does not react with it at normal temperatures. It is less sensitive to impact but more powerful than lead tide. The sensitivity of DDNPto friction is approximately the same as that of lead tide. DDNP is often used as an initiating explosive in propellant primer devices ----------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------

Booster Explosives Booster explosives are those components of the explosive train that function to transmit and augment the force and flame from the initiating explosive. They ensure the reliable detonation or burning of the main burster charge or propellant charge. Propelling charges

use a black powder booster, while high-explosive boosters use one of the following: Tetryl, CH-6, or Composition A-5. Tetryl (2,4,6-trinitrophenyl-methylnitramine) Tetryl is a nitramine booster explosive, though the use has been largely superseded by RDX. Tetryl is sensitive secondary high explosive used as a booster, a small charge placed next to the detonator in order to propagate the detonation into the main charge. While it is commonly known as Tetryl it is in fact Trinitrophenylmethylnitramine (derivative of Benzene). This is a standard booster explosive. Tetryl is a fine yellow crystalline material. When tetryl is heated, it first melts, then decomposes and explodes. It burns readily and is more easily detonated than explosive D. It is a yellow crystalline solid powder material, practically insoluble in water but soluble in Acetone, Benzene and other solvents. It burns readily and is more easily detonated than TNT or Ammonium Picrate (Explosive D), being about as sensitive as Picric Acid. It is detonated by friction, shock, or spark . It remains stable at all temperatures which may be encountered in storage. It is generally used in the form of pressed pellets, and has been approved as the standard bursting charge for small-caliber projectiles, since it gives much better fragmentation than TNT. It also has greater shattering ability than any other military high explosive, and must be properly protected from bullet fire . Its rate of detonation is 23,600-23,900 feet per second. Tetryl is the basis for the service Tetryl blasting caps necessary for positive detonation of TNT. A mixture of Fulminate of Mercury and Potassium Chlorate is included in the cap to insure detonation of Tetryl. The most toxic ordnance compounds, tetryl and 1,3,5-TNB, are also the most degradable. Therefore these chemicals are expected to be short-lived in nature, and environmental impacts would not be expected in areas that are not currently subject to chronic inputs of these chemicals. Tetryl decomposes rapidly in methanol/water solutions, as well as with heat. All aqueous samples expected to contain tetryl should be diluted with acetonitrile prior to filtration and acidified to pH <3. All samples expected to contain tetryl should not be exposed to temperatures above room temperature. In addition, degradation products of tetryl appear as a shoulder on the 2,4,6-TNT peak. Peak heights rather than peak areas should be used when tetryl is present in concentrations that are significant relative to the concentration of 2,4,6-TNT. CH-6 CH-6 is a mixture of 97.5% RDX (described in the next section), 1.5% calcium stearate, 0.5% polyisobutylene, and 0.5% graphite. It is a finely divided gray powder that is less toxic and more available than tetryl. Composition A-5 Composition A-5 is a mixture of 98.5% RDX and 1.5% stearic acid. NQ [Nitroguanidine / Picrate] Ammonium Picrate (Yellow D / Explosive D), or Picric Acid or 2,4,6-trinitrophenol, C6H2(NO2)3OH, a toxic yellow crystalline solid that melts at 122°C and is soluble in most organic solvents. Picric acid is a derivative of phenol. It reacts with metals to form metal picrates, which like picric acid itself are highly sensitive explosives that can be detonated by heat, flame, shock, or friction. The high explosives lyddite and melinite are composed mostly of compressed or fused picric acid. Picric acid is often used as a booster to detonate another, less sensitive explosive, such as TNT (trinitrotoluene ). Although picric acid, a nitramine explosive, can

be synthesized by nitration of phenol, higher yields are obtained if chlorobenzene is used as a starting material; the latter method involves several steps and the formation of several intermediate products. In addition to its use in explosives, picric acid has been used as a yellow dye, as an antiseptic, and in the synthesis of chloropicrin, or nitrotrichloromethane, CCl 3 NO 2 , a powerful insecticide. A UXO item without a fuze is relatively safe (crystallized bulk explosives, picrate salts, chemical, and white phosphorous rounds excepted). -------_____________________________________________________________________________ __________________________________________________________

Explosives - Nitroaromatics Nitroaromatics form an important group of recalcitrant xenobiotics. Only few aromatic compounds, bearing one nitro group as a substituent of the aromatic ring, are produced as secondary metabolites by microorganisms. The majority of nitroaromatic compounds in the biosphere are industrial chemicals such as explosives, dyes, polyurethane foams, herbicides, insecticides and solvents. Detection of unrecovered land mines is a growing international problem. Unrecoverd land mines are a legacy that continues to harm people long after the hostilities cease. The most widely used tool for land mine detection today is the hand-held metal detector. Other methods for landmine detection are limited due to their high false alarm rate. Chemical sensors have been investigated for mine detection. For chemical species having favorable spectral properties, remote sensing can be achieved by fluorescence light detection and ranging LIDAR. Nitroaromatic explosives exhibit strong ultraviolet absorption but low fluorescence, thus direct detection is not practical. Indirect detection in soil can be obtained using a synthetic chemical polymer that exhibits a change in fluorescence in the presence of an explosive compound. Penetration of nitroaromatic compounds through the skin is a major concern for the military. An important characteristic of nitroaromatic compounds is their ability to rapidly penetrate the skin. They can cause the formation of methemeglobin on acute exposures and anemia on chronic exposures. Additionally, local irritation, liver damage and bladder tumors have also been identified. These compounds are generally recalcitrant to biological treatment and remain in the biosphere, where they constitute a source of pollution due to both toxic and mutagenic effects on humans, fish, algae and microorganisms. However, relatively few microorganisms have been described as being able to use nitroaromatic compounds as nitrogen and/or carbon and energy source. However, relatively few microorganisms have been described as being able to use nitroaromatic compounds as nitrogen and/or carbon and energy source. The best-known nitroaromatic compound is the explosive TNT (2,4,6-trinitrotoluene). The optimal remediation strategy for nitroaromatic compounds depends on many sitespecific factors. Composting and the use of reactor systems lend themselves to treating soils contaminated with high levels of explosives (e.g. at former ammunition production facilities, where areas with a high contamination level are common). Compared to composting systems, bioreactors have the major advantage of a short treatment time, but the disadvantage of being more labour intensive and more expensive.

TNT [2,4,6-trinitrotoluene] TNT is one of the most common bulk explosives. 2,4,6 Trinitrotoluene (TNT) is an explosive used in military munitions and in civilian mining and quarrying activities. TNT was first used on a wide scale during World War I and is still used today. The United States military stopped production of TNT in the mid-1980s. TNT is classified as a secondary explosive because it is less susceptible to initiation and requires a primary or initiating explosive to ignite it. TNT can be used as a booster or as a bursting charge for high-explosive shells and bombs. Also, TNT may be mixed with other explosives such as Royal Demolition Explosive (RDX) and High Melting Explosive (HMX) and it is a constituent of many explosives, such as amatol, pentolite, tetrytol, torpex, tritonal, picratol, ednatol, and ¿Composition B¿. It has been used under such names as Triton, Trotyl, Trilite, Trinol, and Tritolo. The advantages of TNT include low cost, safety in handling, fairly high explosive power, good chemical and thermal stability, compatibility with other explosives, a low melting point favorable for melt casting operations and moderate toxicity. TNT is a crystalline substance. The importance of TNT as a military explosive is based upon its relative safety in manufacture, loading, transportation, and stowage, and upon its explosive properties. Manufacturing yields are high and production relatively economical. The chemical names for TNT are trinitrotoluene and trinitrotol. Other (commercial) names are Trilite, Tolite, Trinol, Trotyl, Tritolol, Tritone, Trotol, and Triton. TNT is toxic, odorless, comparatively stable, nonhygroscopic, and relatively insensitive. When TNT is pure, it is known as grade A TNT and varies from white to pale yellow. When the proportion of impurities is much greater, the color is darker, often brown, and the chemical is known as grade B TNT. It maybe ignited by impact, friction, spark, shock, or heat. TNT does not form sensitive compounds with most metals. The melting point varies between 80.6°C for grade A (refined TNT) and 76°C for grade B (crude TNT). TNT does not appear to be affected by acids but is affected by alkalies (lye, washing soda, and so on), becoming pink, red, or brown, and more sensitive. It is practically insoluble in water, but soluble in alcohol, ether, benzene, carbon disulfide, acetone, and certain other solvents. The velocity of detonation is approximately 22,300 fps. Exudate has been known to separate from cast TNT. It may appear pale yellow to brown and may vary in consistency from an oily liquid to a sticky substance. The amount and rate of separation depend primarily upon the purity of the TNT and, secondarily, upon the temperature of the stowage place. Grade B (low-melting point) TNT may exude considerable liquid and generate some gas. This exudation is accelerated with an increase in temperature. Pure TNT will not exude since exudate consists of impurities that have not been extracted in the refining process. Exudate is a mixture of lower melting isomers of TNT, nitrocompounds of toluene of lower nitration, and possible nitrocompounds of other aromatic hydrocarbons and alcohols. It is flammable and has high sensitivity to percussion when mixed with absorbents. Its presence does no appreciable harm to the stability but somewhat reduces the explosive force of the main charge. In some ammunition, an inert wax pad is used in the loading operation, and, in some cases, waxy material may ooze from the case. It should not be confused with the TNT exudate previously described. This material should, however, be tested for TNT to confirm its actual composition, TNT exudate, when mixed with a combustible material,

such as wood chips, sawdust, or cotton waste, will form a low explosive that is highly flammable and ignites easily from a small flame. It can be exploded in a reamer similar to a low grade of dynamite, but the main danger is its fire hazard. Accumulation of exudate is considered a great risk of explosion and fire. Its accumulation should always be avoided by continual removal and disposal as it occurs. While TNT is no longer used in Navy gun ammunition, some 3"/50, 40-mm, and 20-mm stocks loaded with TNT may still be in the inventory. These stocks should be identified and checked periodically for the presence of exudate. The exudate is soluble in acetone or alcohol. One of these solvents (requiring adequate ventilation) or clean, hot water should be used to facilitate removal and disposal of the exudate. Under no circumstances should soap or other alkaline preparations be used to remove this exudate. The addition of a small amount of hydroxide, caustic soda, or potash will sensitize TNT and cause it to explode if heated to 160°F. During production TNT is in the form of a liquid which is then cooled and washed with water to form solid flakes in the form of colorless crystals, though commercial crystals are yellow. The flakes can be remelted at low temperatures (180 degrees Fahrenheit) and poured into munitions shells and casings. TNT was widely used by the military because of its low melting point and its resistance to shock or friction which allows it to be handled, stored, and used with comparative safety. In order to detonate, TNT must be confined in a casing or shell and subjected to severe pressures and/or temperatures (936 degrees Fahrenheit) such as from a blasting cap or detonator. In fact, U.S. Army tests on pure TNT show that when struck by a rifle bullet TNT failed to detonate 96% of the time and when dropped from an altitude of 4,000 feet onto concrete, a TNT filled bomb failed to explode 92% of the time. 2,4,6-Trinitrotoluene (TNT) causes liver damage and aplastic anemia. Deaths from aplastic anemia and toxic hepatitis were reported in TNT workers prior to the 1950s. With improved industrial practices, there have been few reports of fatalities or serious health problems related to its use. Exposures at or below 0.5 mg/m3 have been reported to cause destruction of red blood cells. Among some groups of workers, there is a reduction in average hemoglobin and hematocrit values. Workers deficient in glucose-6-phosphate dehydrogenase may be particularly at risk of acute hemolytic disease. Three such cases occurred after a latent period of 2 to 4 days and were characterized by weakness, vertigo, headache, nausea, paleness, enlarged liver and spleen, dark urine, decreased hemoglobin levels, and reticulocytosis. Although no simultaneous measurements of atmospheric levels were available, measurement on other occasions showed exposure levels up to 3.0 mg/m3. Cataracts are also reportedly produced with chronic exposures for more than 5 years. The opacities did not interfere with visual acuity or visual fields. The induced cataracts may not regress once exposure ceases, although progression is arrested. The vapor or dust can cause irritation of mucous membranes resulting in sneezing, cough, and sore throat. Although intense or prolonged exposure to TNT may cause some cyanosis, it is not regarded as a strong producer of methemoglobin. Other occasional effects include leukocytosis or leukopenia, peripheral neuritis, muscular pains, cardiac irregularities, and renal irritation. Trinitrotoluene is absorbed through skin fairly rapidly, and reference to airborne levels of vapor or dust may underestimate total systemic exposure if skin exposure also occurs.

Apparent differences in dose-response relationships based only on airborne levels may be explained by differences in skin contact. TNT causes sensitization dermatitis; the hands, wrist, and forearms most commonly are affected, but skin at friction points such as the collar line, belt line, and ankles also is often involved. Erythema, papules, and an itchy eczema can be severe. The skin, hair, and nails of exposed workers may be stained yellow. Rats administered 50 mg/kg/day in their diets had anemia, splenic lesions, and liver and kidney damage. Hyperplasia and carcinoma of the urinary bladder also were observed in female rats. Historically, control of exposure to TNT has been accomplished through general safety and hygiene measures, yet additional, specific measures are necessary. The Hazard Communication Program, for example, should instruct workers about the need for strict personal and shop hygiene, and about the hazards of the particular operations that are conducted in that plant. In addition, soap that contains 5% to 10% potassium sulfite will not only help remove TNT dust from the skin, suds that turn red will also indicate any remaining contamination. Furthermore, respiratory protection equipment should be selected according to NIOSH guidance, and should be worn during operations that release dust, vapor, or fumes. Before WWII, research suggested that improving the nutritional status of TNT workers might help improve their resistance to toxic effects. However, in a World War II era cohort study, multivitamin capsules were not shown to be efficacious in preventing TNT toxicity. TNT interacts with certain medications - including isoniazid, phenylbutazone, phenytoin, and methotrexate. Anyone taking these medications while working with TNT should be closely followed by the occupational physician. Medical Monitoring. The U.S. Army currently recommends preplacement and periodic (semiannual) examinations of TNT workers. To identify workers with higher-than-normal sensitivity to TNT toxicity during the first three months of exposure, monthly hemoglobin, LDH, and AST should be done. The ACGIH TLV Committee for Chemical Substances recommended that the 8-hour TLV for TNT be lowered from 0.5 mg/m3 to 0.1 mg/m3 on 21 May 1997 after reviewing scientific reports of human and animal exposure. In some studies, evidence of liver toxicity, changes in blood cell production, and cataracts were noted when exposure levels ranged below 0.5 mg/m3 (the old ACGIH TLV). TNT workers should never be exposed to ambient levels of TNT above 0.1 mg/m3 for an 8-hour time weighted average (TWA) without appropriate respiratory protection. Based on the evidence reviewed by the ACGIH, the extra margin of safety afforded by this lowered TLV is necessary to protect workers health. Skin absorption has also been noted to be a significant means of exposure in several studies. Dermal exposure over an 8 hour period cannot be readily quantitated at a worksite, however use of protective clothing to include head cover and impermeable gloves is essential to prevent skin absorption of TNT. DNT (Dinitrotoluene) 2,4-DNT and 2,6-DNT are pale yellow solids with a slight odor and are two of the six forms of the chemical called dinitrotoluene (DNT). The other four forms (2,3-DNT, 2,5DNT, 3,4-DNT, and 3,5-DNT) only make up about 5% of the technical grade DNT. DNT is not a natural substance but rather is usually made by reacting toluene (a solvent) with

mixed nitric and sulfuric acids, which are strong acids. DNT is used to produce flexible polyurethane foams used in the bedding and furniture industry. DNT is also used to produce ammunition and explosives and to make dyes. It is also used in the air bags of automobiles. It has been found in the soil, surface water, and groundwater of at least 122 hazardous waste sites that contain buried ammunition wastes and wastes from manufacturing facilities that release DNT. DNT does not usually evaporate and is found in the air only in manufacturing plants. DNT also does not usually remain in the environment for a long time because it is broken down by sunlight and bacteria into substances such as carbon dioxide, water, and nitric acid. Workers who have been exposed to 2,4-DNT showed a higher than normal death rate from heart disease. However, these workers were exposed to other chemical as well. 2,4and 2,6-DNT may also affect the nervous system and the blood of exposed workers. One study showed that male workers exposed to DNT had reduced sperm counts, but other studies did not confirm this finding. TNB (1,3,5-Trinitrobenzene) The synthetic compound 1,3,5-TNB is used as a high explosive for commercial mining and military use, as a narrow-range pH indicator and as an agent to vulcanize natural rubber. The compound is a manufacturing by-product of the explosive, TNT, and is released to the environment in discharged wastewater. Additionally, any TNT itself that is present in the waste stream may be degraded to 1,3,5-TNB by photolysis under certain conditions of pH and organic matter content. The compound has a close structural relationship with the most widely produced military explosive, trinitrotoluene (TNT), of which it is a manufacturing by-product and an environmental degradation product. _____________________________________________________________________________ ______________________________________________________________

Explosives - Nitramines The nitramines are the most recently introduced class of organic nitrate explosives. The most prominent member of this class is RDX (research department explosive; hexahydro1,3,5-trinitro-1,3,5 triazine, which is also known as cyclonite); HMX (high melting explosive; octahydro-1,3,5,7-tetranitro-1,3,5,7 tetrazocine), nitroguanidine, and tetryl are also significant nitramines. In a class of explosives like nitramines, the higher density, bigger molecules will give more power because more realizable energy can be packed in the same space. Bigger molecules using the same proportion of elements are more dense because the formation of covalent bonds makes atoms come closer together than if they were just pushed together but from different molecules. HMX is a big ring molecule, same as RDX but with an extra CH2NNO2 unit. It has higher density (TMD 1.902) than RDX, 1.806, its det. vel is 9.11 km/sec vs. 8.70 for RDX. It is considered more powerful. Pollution from manufacturing processes of the major energetic materials currently used in the U.S., 1,3,5-trinitro-1,3,5-triazacyclohexane (RDX), 1,3,5,7-tetranitro-1,3,5,7 tetraazacyclooctane (HMX) was briefly evaluated. It was found that acetic acid was a major pollutant. It appeared that the British Process could be controlled to reduce the polluting effluents better than the Bachmann Process used in the U.S.

RDX [Cyclonite - Hexahydro-1,3,5-trinitro-1,3,5-triazine] RDX stands for Royal Demolition eXplosive. It is also known as cyclonite or hexogen. RDX is currently the most important military high explosive in the US. Cyclotrimethylenetrinitramine, C3H6N606 (RDX), is second in strength to nitroglycerin among common explosive substances. When compressed to a specific gravity of 1.70, it has a confined detonation velocity of about 27,000 fps. RDX is used as an explosive, usually in mixtures with other explosives, oils, or waxes. It has a high degree of stability in storage and is considered the most powerful and brisant of the military high explosives. RDX is used as a base charge in detonators and in blasting caps. RDX can be used alone or with other explosives, including PETN.t RDX can be mixed with plasticizers to make C-4, and the most common explosive combining RDX and PETN is Semtex. RDX forms the base for the following common military explosives: Composition A, Composition B, Composition C, HBX, H-6 and Cyclotol. Composition A consists of RDX melted with wax; in Composition B, RDX is mixed with TNT; and Composition C contains RDX blended with a non-explosive plasticizer. Pure RDX is used in press-loaded projectiles. Cast loading is accomplished by blending RDX with a relatively low melting point substance. RDX has both military and civilian applications. As a military explosive, RDX can be used alone as a base charge for detonators or mixed with another explosive such as TNT to form cyclotols, which produce a bursting charge for aerial bombs, mines, and torpedoes. Common military uses of RDX have been as an ingredient in plastic bonded explosives, or plastic explosives which have been used as explosive fill in almost all types of munition compounds. Civilian applications of RDX include use in fireworks, in demolition blocks, as a heating fuel for food rations, and as an occasional rodenticide. Combinations of RDX and HMX, another explosive, have been the chief ingredients in approximately 75 products. RDX is an explosive nitramine compound. It is in the form of a white powder with a density of 1.806 g/cc. Nitrogen content of 37.84%. The chemical name for RDX is 1,3,5trinitro-1,3,5-triazine. The chemical formula for RDX is C3H6N6O6 and the molecular weight is 222.117. Its melting point is 205°C. RDX has very low solubility in water and has an extremely low volatility. RDX does not sorb to soil very strongly and can move into the groundwater from soil. It can be broken down in air and water in a few hours, but breaks down more slowly in soil. Although RDX [Royal Demolition Explosive or Research Department Explosive] was first prepared in 1899, its explosive properties were not appreciated until 1920. RDX was used widely during World War II because petroleum was not needed as a raw ingredient. During and since World War II, RDX has become the second-most-widely used high explosive in the military, exceeded only by TNT. As with most military explosives, RDX is rarely used alone; it is widely used as a component of plastic explosives, detonators, high explosives in artillery rounds, Claymore mines, and demolition kits. RDX has limited civilian use as a rat poison. RDX can cause seizures in humans and animals when large amounts are inhaled or ingested. Nausea and vomiting have also been observed. The effects of long-term (365 days or longer), low-level exposure on the nervous system are not known. No other significant health effects have been reported in humans. Rats and mice that ate RDX for 3 months or more had decreased body weights and slight liver and kidney damage. It is not

known whether RDX causes birth defects in humans. It did not cause birth defects in rabbits, but did result in smaller offspring in rats. It is not known whether RDX affects reproduction in humans. The EPA has determined that RDX is a possible human carcinogen (Class C). In one study, RDX caused liver tumors in mice that were exposed to it in the diet. However, carcinogenic effects were not noted in rat studies and no human data are available. RDX does not bioaccumulate in fish or in humans. RDX has been produced several ways, but the most common method of manufacture used in the United States is the continuous Bachmann process. The Bachmann process involves reacting hexamine with nitric acid, ammonium nitrate, glacial acetic acid, and acetic anhydride. The crude product is filtered and recrystallized to form RDX. The byproducts of RDX manufacture include nitrogen oxides, sulfur oxides, acid mists, and unreacted ingredients. A second process that has been used to manufacture RDX, the direct nitration of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), has not yielded a percentage of RDX as high as the percentage produced in the Bachmann process (Army 1978; Merck 1989). Production of RDX peaked in the 1960s when it was ranked third in explosive production by volume in the United States. The average volume of RDX produced from 1969 to 1971 was 15 million pounds per month. However, production of RDX decreased to a yearly total of 16 million pounds for 1984. RDX is not produced commercially in the United States. Production in the United States is limited to Army ammunition plants such as Holston Army ammunition plant in Kingsport, Tennessee, which has been operating at 10-20% capacity. Several Army ammunition plants, such as Louisiana (Shreveport, Louisiana), Lone Star (Texarkana, Texas), Iowa (Middletown, Iowa), and Milan (Milan, Tennessee), also handle and package RDX. Since the release of RDX is not required to be reported under SARA Section 313, there are no data on RDX in the Toxics Release Inventory (TRI 1993). Waste-water treatment sludges resulting from the manufacture of RDX are classified as hazardous wastes and are subject to EPA regulations. Munitions such as RDX have been disposed of in the past by dumping in deep sea water. By-products of military explosives such as RDX have also been openly burned in many Army ammunition plants in the past. There are indications that in recent years as much as 80% of waste munitions and propellants have been disposed of by incineration. Wastes containing RDX have been incinerated by grinding the explosive wastes with a flying knife cutter and spraying the ground material with water to form a slurry. The types of incineration used to dispose of waste munitions containing RDX include rotary kiln incineration, fluidized bed incineration, and pyrolitic incineration. The primary disadvantage of open burning or incineration is that explosive contaminants are often released into the air, water, and soils. Soldiers and other workers have been exposed to RDX during its manufacture, in the field, and through the contamination of the environment. The main occupational exposure to RDX during its manufacture is through the inhalation of fine dust particles. Ingestion may also be a possible route of exposure, but it is poorly absorbed through the dermis. The greatest potential for occupational exposure to RDX occurs at ammunition plants with load, assemble and pack (LAP) operations, where workers involved with meltpouring and maintenance operations have the greatest potential for exposures. In 1962, five cases of convulsions or unconsciousness or both occurred at an RDX manufacturing plant in the United States. All five employees had convulsions during their

work shifts or within a few hours after their shifts were over. These patients exhibited little or no prodrome, and the postictal phase lasted up to 24 hours. No abnormal laboratory or physical findings were noted. Troops have also become intoxicated during field operations from exposure to composition C4 plastic explosive, which contains 91% RDX. These field exposures occurred because C4 was either chewed as an intoxicant or used as a fuel for cooking. Thus, the route of exposure was ingestion or inhalation. At least 40 American soldiers experienced convulsions due to RDX ingestion during the Vietnam War. After acute exposure by inhalation or ingestion, there is a latent period of a few hours, followed by a general sequence of intoxication that begins with a prodromal period of irritability. Neurological symptoms predominate and include restlessness and hyperirritability; headache; weakness; dizziness; hyperactive reflexes; nausea and vomiting; prolonged and recurrent generalized convulsions; muscle twitching and soreness; and stupor, delirium, and disorientation. Clinical findings in acute exposures may also include fever, tachycardia, hematuria, proteinuria, azotemia, mild anemia, neutrophilic leukocytosis, elevated AST, and electroencephalogram (EEG) abnormalities. These abnormal effects, transient and unreliable for diagnosis purposes, last at most a few days. In fact, all physical and laboratory tests may remain normal, even in the presence of seizures. EEGs made at the time of convulsions may show bilateral synchronous spike and wave complexes (2-3/sec) in the frontal areas with diffuse slow wave activity; normalization occurs within 1 to 3 months. RDX in the wastewater from manufacturing and loading operations has also contaminated the environment. Although contamination has appeared in soil and groundwater near some ammunition plants, RDX's low solubility in water has limited its migration in most cases. Although intensive research with animals has revealed some effects, few effects of chronic human exposure to RDX have been reported. Investigations into the mutagenicity and carcinogenicity of RDX have yielded conflicting results. RDX does not appear to be a mutagen, based on negative results in the Ames tests, the dominant lethal test, and the unscheduled deoxyribonucleic acid synthesis assay. RDX has not been found to be carcinogenic in gavage studies performed on rats, but increased hepatocellular carcinoma and adenoma were noted in females of one strain of mice. Due to this finding, the U.S. Environmental Protection Agency has classified RDX as a possible human carcinogen. Reproductive effects have been noted in rabbits and rats. A study performed on rabbits showed teratogenic effects at 2 mg/kg/day (10% of the dose that caused maternal toxicity). Similarly, a teratology study performed on pregnant rats exposed to RDX resulted in offspring with lower body weights and shorter body lengths than were found in the control group. These researchers therefore recommended that human females of childbearing age be protected from exposure to RDX. Despite the low toxicity of RDX, exposure should be maintained at the lowest levels possible due to its possible carcinogenicity. General medical surveillance examinations can be conducted (such as liver and kidney function tests), but specific testing for the effects of low level occupational exposure does not appear to be warranted, given the absence of abnormal results even in those patients with RDX-induced seizures. Surveillance for both males and females should also include a screening questionnaire for

reproductive history. Pregnant women should avoid exposure to RDX. HMX [Octogen - Octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine ] High Melting Explosive [HMX] is the highest-energy solid explosive produced on a large scale in the United States. It is also known as Octogen and cyclotetramethylenetetranitramine, as well as other names. HMX explodes violently at high temperatures (534°F and above). Because of this property, HMX is used exclusively for military purposes to implode fissionable material in nuclear devices, as a component of plasticbonded explosives, as a component of rocket propellant, and as a high explosive burster charge. The use of HMX as a propellant and in maximum-performance explosives is increasing. HMX was discovered as a by-product in the production of RDX. Although it is almost as sensitive and powerful as RDX, it is seldom used alone in military applications but is normally mixed with another compound, such as TNT. In the Navy, HMX is used as an ingredient in plastic-bonded explosives. HMX is produced by the nitration of hexamine with ammonium nitrate and nitric acid in an acetic acid/acetic anhydride solvent at 44°C. The raw materials are mixed in a twostep process and the product is purified by recrystallization. This is a modification of the Bachmann Process used to produce RDX, another explosive. The yield of HMX is about 55-60%, with RDX as an impurity. RDX produced by the Bachmann Process usually contains about 8-12% HMX as an acceptable byproduct. HMX is currently produced at only one facility in the United States, the Holston Army Ammunition Plant in Kingsport, Tennessee. The amount of HMX made and used in the United States at present is not known, but it is believed to be greater than 30 million pounds [15,000 tons] per year between 1969 and 1971. No estimates of current production volume were located, but it is estimated that its use is increasing. Processing may occur at load, assemble, and pack (LAP) facilities operated by the military. There were 10 facilities engaged in LAP operations in the United States in 1976 No information was located regarding import or export of HMX in the United States. Export of this chemical is regulated by the U.S. State Department. Wastes from explosive manufacturing processes are classified as hazardous wastes by EPA. Generators of these wastes must conform to EPA regulations for treatment, storage, and disposal. The waste water treatment sludges from processing of explosives are listed as hazardous wastes by EPA based only on reactivity. Waste water treatment may involve filtering through activated charcoal, photolytic degradation, and biodegradation. Rotary kiln or fluidized bed incineration methods are acceptable disposal methods for HMXcontaining wastes. At the Holston facility, waste waters are generated from the manufacturing areas and piped to an industrial water treatment plant on site. Following neutralization and nutrient addition, sludge is aerobically digested and dewatered. It was estimated that the facility generates a maximum of 3,800 tons (7.6 million pounds) of treated, dewatered sludge annually. Based on demonstration by Holston that this sludge is nonhazardous, the EPA proposed granting a petition to exclude the sludge from hazardous waste control. HMX is not listed on the Toxics Release Inventory (TRI) database, because it is not a chemical for which companies are required to report discharges to environmental media. HMX or octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine is an explosive polynitramine. The chemical formula is C4H8N8O8 and molecular weight is 296.20. It is a colorless

solid with a melting point of 276 to 286°C. HMX is made by the nitration of hexamine with ammonium nitrate and nitric acid in an acetic acid/acetic anhydride solvent. A small amount of HMX is also formed in making cyclotrimethylene-trinitramine (RDX), another explosive similar in structure to HMX. It dissolves slightly in water. Only a very small amount of HMX will evaporate into the air; however, it can occur in air attached to suspended particles or dust. The taste and smell of HMX are not known. HMX is a manmade chemical and does not occur naturally in the environment. It is made from other chemicals known as hexamine, ammonium nitrate, nitric acid, and acetic acid. A small amount of HMX is also formed in making cyclotrimethylene-trinitramine (RDX), another explosive similar in structure to HMX. HMX is only slightly soluble in water. It has low volatility and thus only a small amount of HMX will evaporate into the air; however, it can occur in air attached to suspended particles or dust. In surface water, HMX does not evaporate or bind to sediments to any large extent. Sunlight breaks down most of the HMX in surface water into other compounds, usually in a matter of days to weeks. HMX is likely to move from soil into groundwater, particularly in sandy soils. Exposure to HMX can occur during the manufacture and filling of munitions or through the environmental contamination of groundwater and soil. HMX, like RDX, is manufactured using the continuous Bachman process. Although its solubility in water is very low, HMX can be present in particulate form in water effluent from manufacturing, LAP, and demilitarization operations. Information on the adverse health effects of HMX is limited. In one study on humans, no adverse effects were reported in workers exposed to HMX in air. However, the concentrations of HMX in the workplace air were not reported in this study, and only a small number of workers and effects were investigated. Studies in rats, mice, and rabbits indicate that HMX may be harmful to the liver and central nervous system if it is swallowed or contacts the skin. The lowest dose producing any effects in animals was 100 milligrams per kilogram of body weight per day (mg/kg/day) orally and 165 mg/kg/day on the skin. Limited evidence suggests that even a single exposure to these dose levels harmed rabbits. The mechanism by which HMX causes adverse effects on the liver and nervous system is not understood. The reproductive and developmental effects of HMX have not been well studied in humans or animals. At present, the information needed to determine if HMX causes cancer is insufficient. Due to the lack of information, EPA has determined that HMX is not classifiable as to its human carcinogenicity. The data on the effects on human health of exposure to HMX are very limited. HMX causes CNS effects similar to those of RDX, but at considerably higher doses. In one study, volunteers submitted to patch testing, which produced skin irritation. Another study of a cohort of 93 workers at an ammunition plant found no hematological, hepatic, autoimmune, or renal diseases. However, the study did not quantify the levels of exposure to HMX. HMX exposure has been investigated in several studies on animals. Overall, the toxicity appears to be quite low. HMX is poorly absorbed by ingestion. When applied to the dermis, it induces mild skin irritation but not delayed contact sensitization. Various acute and subchronic neurobehavioral effects have been reported in rabbits and rodents,

including ataxia, sedation, hyperkinesia, and convulsions. The chronic effects of HMX that have been documented through animal studies include decreased hemoglobin, increased serum alkaline phosphatase, and decreased albumin. Pathological changes were also observed in the animals' livers and kidneys. No data are available concerning the possible reproductive, developmental, or carcinogenic effects of HMX. CL-20 / HNIW CL-20 [2,4,6,8,10,12-hexanitrohexaazaisowurtzitane (HNIW) ] is a new nitramine explosive that is 20 percent more powerful that HMX. CL20 was a breakthrough in energetic materials with higher performance, minimum signature, and reduced-hazard characteristics. CL-20 has numerous military and commercial applications. The trend today is to explore the possibilities that HNIW can provide to munitions;from high performance gun propellants , shaped charges etc. The only limitation is the cost of its production. Even there had been practical methods to nitrate the special reactant (acetyl Isowurtzitane derivatives) with mixed acid, but the effort of debenzylation of the condensation products of glyoxal and benzylamine still requires the expensive palladium catalyst. Therefore it will take some time before it can reach the level of comparatively lower cost needed to make HMX. CL-20 exists in four crystalline forms, stable at different temperatures. Only the e and the ß form are used in ex-ploitation. CL-20 has better detonation properties than octogen, higher den-sity and detonation rate but lower impact and friction sensitivity (of the PETN class). The CL-20 melting point is lower than in octogen, 240°C approximately. CL20, a high-energy explosive compound, is a polyazapolycyclic caged polynitramine. The combustion and detonation characteristics of CL20 can be improved if it is formed into nanoparticles of uniform size. A new, promising process for particulation of materials utilizes environmentally benign compressed gases as either solvents or anti-solvents. Predictive models are required to describe the solubility and phase behavior of supercritical solutions of CL20 and supercritical carbon dioxide and for process simulation and development. Here, the solubility of CL20 in supercritical carbon dioxide was evaluated using the Peng-Robinson cubic equation of state. Critical properties, vapor pressure, and other required thermodynamic properties were estimated using a variety of available estimation techniques. A Fortran program to predict the solubility of CL20 was developed. The program was validated using available literature data for the solubility of naphthalene and of biphenyl in supercritical carbon dioxide. The applicability of the estimation techniques employed for the critical properties for CL20 was established using these same techniques to estimate the critical properties of comparable compounds, including RDX and HMX. Solubility data for RDX in supercritical carbon dioxide reported in the literature were also used to establish the validity of the estimation approach. Solubility was predicted over the temperature range of 305.15 to 368.15 K and over the pressure range of 74 to 150 atm. In general, as the temperature increases, the solubility decreases, while as the pressure increases, the solubility increases. Fortunately, shortly after Dr. Arnold Nielson first synthesized Hexanitrohexaazaisowurtzitane [hexa-nitro-hexa-aza-iso-wurtzi-tane] in 1987 it was designated "CL-20," and talking and writing about this "most significant energetic ingredient in 50 years" was made much easier. And there has been alot of writing and discussion about the development of CL-20. Nielson's original discovery astonished the scientific community because he constructed the CL-20 cage using a single chemical

reaction and, in the process, established a new type of amine glyoxal chemistry. It was soon realized that CL-20 had greater energy output than existing (in-use) energetic ingredients while having an acceptable level of insensitivity to shock and other external stimuli. This fit in nicely with the Navy's 1989 decree for development of "insensitive munitions," capable of withstanding unplanned exposure to external forces. Further, CL20-based formulations were clean burning, with less signature and which also met requirements spawned by the government's then new-found emphasis of its role in preserving the natural environment. Seeing potential for the new molecule, early members of the team set about purifying and characterizing new polymorphic forms and scaling up to produce usable quantities. In 1993 some 48 members of the Research, Ordnance Systems and Range departments received a Team Award for their CL-20 efforts. Still more have been involved since then. On June 19, 1996, NAWCWD and Thiokol Corporation of Ogden, Utah, entered into a Cooperative Research and Development Agreement (CRADA), the ultimate goal of which is to test a warhead containing a CL-20-based explosive that will demonstrate performance significantly above that of existing explosives. Under the terms of the threeyear agreement NAWCWD will provide the personnel, facilities, equipment and materials necessary to characterize CL-20; formulate, test and evaluate CL-20-based explosives; and test and evaluate subscale warheads. Thiokol will provide the personnel, facilities, equipment and materials necessary, and will provide 250 lbs. Of epsilon (polymorph) CL-20 for this effort, to support preparation of subscale samples and other tasks. cost reduction is a major benefit expected to be gained from this CRADA. By successfully completing this CRADA and demonstrating the potential of CL-20, demand for the material will go up. With increased demand, and improved production processes for high-grade product that will also come from this CRADA, availability will go up. When that happens cost will go down. When Arnold Nielson first synthesized a few grams of CL-20, the extrapolated cost to produce a pound by that method would have been several thousand dollars. Thiokil has refined the production process to the point that customers were paying around $400 a pound in the mid-1990s, which was a considerable reduction. The hope at that time was to quarter that cost and get it down to around $100 a pound. As NAWCWD has been characterizing and refining the CL-20 molecule, other entities, including Thiokol, have been working on the CL-20 molecule produced from their own processes. Thiokol with continuous assistance and collaboration from China Lake researchers has scaled up its process to the point that it can now produce 1,000-plus pound batches of the ingredient. It has also been commercially marketing the basic ingredient as well as end-product formulations for explosives, gun propellants and, to a lesser degree, rocket propellants. While there have been other new ingredients over the years, none of them have been successfully scaled up to mass productionlevels. Thiokol has made the jump to mass production of CL-20. That's why many have called CL-20 the mostsignificant energetic ingredient in the past 50 years. It offers great potential to meet the performance, insensitive munitions and environmental requirements for future weapons systems. CL20-based shaped charges are already being used in the oil well industry. Other commercial applications he expects to see include specialty demolition, because CL-20

has good properties for use as a "cutter." And it will likely be used in high-rate detonating cord. _____________________________________________________________________________ _______________________________________________________________

Explosives - Nitrate esters Nitrate (NO3-) (CAS No. 014797-55-8) is an inorganic anion resulting from the oxidation of elemental nitrogen. It is an essential nutrient for plant protein synthesis and plays a critical role in the nitrogen cycle of soil and water. Nitrates are produced by natural biological and physical oxidations and therefore are ubiquitous in the environment (Ridder and Oehme 1974). Most nitrate compounds are strong oxidizing agents and some can react violently with oxidizable substances and may explode if exposed to heat or shock. Nitrates are produced by natural biological and physical oxidations and therefore are ubiquitous in the environment. Most of the excess nitrates in the environment originate from inorganic chemicals manufactured for agriculture. Organic molecules containing nitrate groups are manufactured primarily for explosives or for their pharmacological effects NC [Nitrocellulose] for many centuries gunpowder was the world's only explosive, and was not superseded until the discovery of guncotton. So long ago as 1832 Bracon discovered that woody fiber could be turned into an explosive by the action of concentrated nitric acid; and a few years later a French inventor, Dumas, tried to make cartridges of paper treated in similar fashion. If he had succeeded these would have been the first smokeless cartridges, but he failed; and it was not until 1845 that Schönbein, a German chemist, hit upon the proper method of treating cotton wool with nitric and sulphuric acids, so as to turn it into guncotton. In 1847 an English firm, Messrs. Hall and Son of Faversham, began to manufacture guncotton, and military experts hailed it as the new explosive which would take the place of gunpowder. But this explosive was so terribly powerful that, when used in a gun or rifle, it blew the barrel to pieces. Worse than that, it was most dangerous to manufacture. Two main problems had to be solved before it could be used as a gun propellant. First, the velocity of the explosion had to be reduced so that the charge weight required to propel the projectile would not shatter the gun tube. second, the density had to be increased so that a given charge weight would pack into a reasonable space. The first problem was solved in part by igniting NC instead of firing it with a detonator. The solution to the second problem actually solved both. In 1886, Vielle first colloided or gelatinized NC with alcohol and ether and, thus reduced the burning rate to acceptable levels. The procedure significantly increased the loading density of NC, establishing it as the foundational element in gun propellants used through the present day. Further developments resulted in materials that could be added to improve stowage qualities, reduce or eliminate flash, reduce hygroscopicity, reduce flame temperature, and even increase the propellant force or impetus. Munitions manufacturing processes may generate nitrocellulose (NC) fines. Disposal of these fines is difficult because of their reactive nature. Composting has potential to be a safe and cost effective means of disposal. Open burning is no longer permitted in several

states and is expected to banned nationally in the future. Open detonation is also the least acceptable form of disposal because of uncontrolled pollution by-products. In its role as the Department of Defense Manager for conventional munitions, Army must be able to dispose of Propellants/Explosives/Pyrotechnics production wastes. In composting, a controlled biological process, microorganisms convert biodegradable hazardous material to innocuous, stabilized by-products, typically at elevated temperatures between 50 - 55 °C. The increased temperatures result from heat produced by the microorganisms as they degrade the organic material in the waste. The NC fines are mixed with bulking agents and organic amendments, such as wood chips and animal and vegetable wastes, to enhance the porosity of the mixture. Maintaining moisture content, pH, oxygenation, temperature, and the carbon-to-nitrogen ratio achieves maximum degradation efficiency. NG [Nitroglycerin ] Nitroglycerin (NG) [Synonyms: 1,2,3-Propanetriol trinitrate; glycerol trinitrate; nitroglycerol; NG; trinitroglycerol; NTG; trinitrin] is an oily liquid at room temperature; colorless in pure form and pale yellow or brown in commercial form. It is used in manufacture of dynamite, gunpowder, and rocket propellants, and as a therapeutic agent primarily to alleviate angina pectoris. NG is used to make smokeless gun powder and rocket propellants. Single-base powders contain only nitrocellulose, double-base powders contain nitrocellulose and NG, and triple-base powders contain nitrocellulose, NG, and other combustible materials. In 1847 a new explosive came into being. This was nitroglycerine, made by treating glycerine with nitric and sulphuric acids. But at first it was even more dangerous to handle than guncotton, for the least shock exploded it, and its violence was terrific. The great chemist Alfred Nobel tried to improve it by mixing it with gunpowder, but the powder did not absorb all the nitroglycerine, and accidents of the most terrible kind became more and more frequent. Yet the new explosive, being liquid, could be poured into crevices in rocks, and was so useful as a blasting agent that its manufacture went on until a large vessel carrying cases of the explosive from Hamburg to Chili blew up at sea. The ship was blown to bits and her crew killed, and the disaster caused so great a sensation that the manufacture of nitroglycerine was prohibited in Sweden, Belgium, and in England. But Nobel still continued his experiments, and at last, after trying sawdust and all other sorts of absorbents in vain, found the perfect absorbent in the shape of keiselguhr-a sort of earth made of fossil shells. The mixture is what we know to-day as dynamite; and in spite of the fact that modern chemistry has produced very many new explosives, some of terrific power, dynamite remains the safest and most widely used of all explosives. Nitroglycerin (NG) is a vasodilator and has been associated with acute episodes of angina pectoris, myocardial infraction, and sudden death. Workers engaged in the production or use of dynamite are potentially exposed to mixed vapors of nitroglycerin (NG) and ethylene glycol dinitrate (EGDN). Initial exposure to NG (or NG:EGDN mixtures) characteristically results in an intense throbbing headache that begins in the forehead and moves to the occipital region. Volunteers developed mild headaches when exposed to NG:EGDN vapor at concentrations of 0.5mg/m^3 for 25 minutes. It has been suggested that at least some workers may develop headaches at concentrations in excess of 0.1 mg/m^3. Other signs and symptoms associated with initial exposure include dizziness, nausea, palpitations, and decreases in systolic, diastolic, and pulse pressures. These initial

signs and symptoms, including headache, are indicative of a shift in blood volume form the central to the peripheral circulatory system, initiated by dilation of the blood vessels. After 2 to 4 days of repeated NG exposure, tolerance to the vasodilatory activity occurs, probably as a result of compensatory vasoconstriction. Tolerance may be lost during periods without NG exposure, such as weekends and holidays. Chronic repeated exposures to NG and NG mixtures also have been associated with more serious cardiovascular effects, including angina pectoris and sudden death. Signs and symptoms of ischemic heart disease were observed in nine munitions workers involved in handling a nitroglycerin-cellulose mixture. Within 1 to 4 years of initial exposure, these workers developed nonexertional chest pain, which was relieved either by therapeutic nitroglycerin or by returning to work after the weekend. Coronary angiography performed in five of the patients showed no obstructive lesions. In one patient, observed while in a withdrawal state, coronary artery spasm was demonstrated and readily reversed by sublingual nitroglycerin. Sudden deaths in previously healthy workers have been reported among those exposed to NG or to NG: EGDN mixtures. Like the attacks of angina pectoris, sudden deaths occurred most frequently during brief periods away from work, in particular on Sunday nights or Monday mornings. In most cases, there were no premonitory signs or symptoms although some subjects had anginal episodes during brief periods away from work. Atherosclerotic plaques, with or without thrombosis, have been found in the coronary arteries of workers at autopsy, but their coronary arteries generally were not occluded to the same extent as those of unexposed workers who had died suddenly. The pathogenesis of the sudden death syndrome has been postulated to be due to withdrawal of coronary vasodilators (e.g. NG), resulting in vasoconstriction with acute hypertension, or with myocardial ischemia in workers adapted to and dependent on NG to maintain a minimum level of coronary flow. A second contributing mechanism for coronary artery toxicity due to NG may relate to so-called aging of the vessels due to repeated dilation. Other theories suggest that sudden deaths may be related to peripheral vasodilation consequent to reexposure of NG. Estimates of exposure levels associated with sudden death have not been made because workers typically absorb considerable amounts of NG through the skin in addition to inhalation. Employees handling NG should be given personal protective equipment to prevent the absorption of NG through the skin. However, neither natural rubber nor synthetic rubber gloves, including neoprene gloves, are impervious to NG. The wearing of such gloves tends to hold the chemical in contact with the skin, thus promoting its absorption. Preferably, cotton-lining gloves should be worn underneath nitrile gloves and both gloves changed ever 2-1/2 hours (USAEHA Technical Guide 24). More recent studies have suggested that the effects of long-term workplace exposure to NG may not be completely reversed after exposure is terminated. Former workers may be at increased risk for cardiovascular mortality for months to years after exposure has ceased. Individuals with preexisting ischemic heart disease should not be assigned to work where significant exposure to NG may occur. Early identification of cardiovascular disease is the primary goal of medical surveillance of nitroglycerin workers. A preplacement examination must be administered to all new employees occupational histories, a physical

examination, and indicated laboratory tests, record of their pulse rates. Periodic examinations should be conducted semiannually, with the same focus as the preplacement examination. During the periodic examination, the physician should be aware that headaches that occur during work shifts could indicate skin absorption of nitroglycerin, even if air concentrations of nitroglycerin are below the PEL. Examinations with similar content are necessary when exposure to nitroglycerin has been terminated, although surveillance should perhaps extend beyond employment, due to the latency of the withdrawal effects. Monitoring should include pulse, blood pressure, CBC, urinalysis, resting EKG and lipid profile. PETN [Pentaerythritol tetranitrate] Pentaerythritol tetranitrate, C5H8N4012 (PETN), has a specific gravity of solids of 1.76 and a confined detonation velocity of over 25,000 fps. PETN is used as a priming composition in detonators, a base charge in blasting caps, and a core load for detonating fuse. PETN is very much used in Detonating Cord of which it is the explosive core (Primacord), where it develops a velocity rate of 21,000 feet per second. Detonating cord is insensitive to friction and ordinary shock, but may be exploded by rifle fire. It also detonates sympathetically with the detonation of an adjacent high explosive. PETN is one of the strongest known high explosives with a relative effectiveness factor (R.E. factor) of 1.66. It is more sensitive to shock or friction than TNT or tetryl, and it is never used alone as a booster. It is primarily used in booster and bursting charges of small caliber ammunition, in upper charges of detonators in some land mines and shells, and as the explosive core of primacord. During World War II the M9A1 2.36" Rocket Launcher (Bazooka) charge, with 8 oz of pentolite, could penetrate up to 5 inches of armor. Demolition charge, M118, commonly called Flex-X or sheet explosive, consists of 4 halfpound sheets of flexible explosive packed in a plastic envelope. Each sheet is approximately 3 inches wide, 12 inches long, and 1/4 inch thick. Note: The exact explosive contained in an M118 charge varies with the manufacturer. At present, some manufacturers use PETN as the basic explosive. Others use RDX. Charges manufactured in the future may include other explosives. PETN does not occur naturally, so the production and use of this kind of compound can lead to contamination of the environment. PETN is subject to biodegradation in untreated or unpreserved urine and feces. There also have been some reports of its degradation by bacteria, whose PETN reductase sequentially denitrates PETN into tri- and dinitrates (French et al., 1996). The last compound shown in the pathway, pentaerythritol dinitrate, is degraded further to unknown products. In 1995 Haustein KO, Winkler U, Loffler A, Huller G. of the Abteilung Klinische Pharmakologie, Medizinische Hochschule Erfurt, Germany reported on a study of PETN's cardiovascular effects. The effects of 80 mg pentaerithrityl-tetranitrate (PETN) as suspension or formulated as tablets were compared to placebo in a single blind, randomized, crossover study in 18 healthy subjects (study A), and the bioequivalence of two tablet formulations (marketed Dilcoran 80 vs a new formulation) was studied in 24 healthy subjects after administration of single oral doses of 80 mg PETN according to a placebo controlled, randomized, double blind, two-way crossover study design (study B). The perfusion of the right middle finger was measured by rheography (altitude A of the changes of resistance and of the incisure D) before and 24 h post-dose, and blood

pressure and heart rate were measured in supine position at the same time. The values of area under curve (AUC) of the ratio A/D were calculated by the trapezoidal rule. In study A the mean A/D-values were reduced from about 2.0 to about 1.3 after intake of PETN (solution or tablet) with a minimum 60 to 90 min postdose (solution) and 2 h postdose (tablet). A significant reduction in this ratio was seen up to 8 (solution) or 12 h (tablet) post dose. Changes in blood pressure were not observed while the heart rate decreased in the subjects of all three groups 1 to 2 h postdose followed by an increase by 6 to 10 beats per min. After subtraction of the AUC values of placebo from the PETN-derived AUC values, mean values of 6.61 (SD 1.52, solution) and 7.25 (SD 1.48, A/D*h, tablet) were calculated (p > 0.1, study A). EGDN [ethylene glycol dinitrate] Ethylene Glycol Dinitrate [SYNONYM(s): Glycol dinitrate; Nitroglycol; Dinitroglycol; EGDN; Glycerin trinitrate] is a colorless to yellow, oily, odorless liquid. It is an explosive ingredient (60-80%) in dynamite along with nitroglycerine (40-20%). EGDN and NG are used with a mixture of sodium nitrate and an absorbent, often wood pulp, to produce dynamite. EGDN is added to lower the freezing point of the EGDN/NG mixture and is currently the major component. The EGDN/NG ratio is about 8/2 or 9/1. This is the only commercial use for EGDN. Because EGDN is more volatile than NG, there is usually more airborne EGDN than NG from the dynamite mixture. In 1976, about 250 million pounds of dynamite, containing 5 to 50% EGDN/NG, were produced by U.S. manufacturers. Headaches have developed in workers exposed to 0.4 to 0.67 mg/m3 for 25 minutes; all workers had decreases in blood pressure [Trainor and Jones 1966]. Ethylene glycol dinitrate and nitroglycerine are vasodilators and initial exposures result in headache, dizziness, nausea, or decreases in blood pressure; however, workers became tolerant of the vasodilatory activity after 2 to 4 days of exposure. Angina pectoris has been reported among workers who were exposed to EGDN and/or NG. In those affected, the angina usually occurred in periods away from work. Sudden deaths without any apparent cause have also been reported among these workers. The deaths, like the angina, occurred more frequently during periods away from work. In most cases, the workers who died suddenly had no symptoms other than angina during periods away from work. The deaths are thought to be related to compensatory vasoconstriction (tolerance) induced by repeated exposure to the substances. Vasoconstriction is thought to lead to spasms of the coronary arteries and then the related angina pectoris and sudden deaths. No data on acute inhalation toxicity are available on which to base the IDLH for ethylene glycol dinitrate (EGDN) and/or nitroglycerin. The chosen IDLH, therefore, is based on chronic toxicity data concerning the physiological response of animals to EGDN. According to Patty [1963], rats and guinea pigs survived 6 months of exposure to 500 mg/m3 (80 ppm) EGDN with the only effect being slight drowsiness and some Heinz body formation [Stein 1956]. Although Patty [1963] stated that EGDN is more toxic for cats and rabbits, the chosen IDLH is still probably conservative because cats given 2hour daily exposures to 21 ppm EGDN for 1,000 days exhibited only marked blood changes [von Oettingen 1946]. However, because of the assigned protection factor afforded by each device, 2,000 × the OSHA PEL of 0.1 mg/m3 (i.e., 200 mg/m3) is the concentration above which only the "most protective" respirators are permitted. _____________________________________________________________________________

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Explosives - Compositions In general, high explosives are compositions and mixtures of ingredients capable of instantaneously releasing large amounts of energy and doing work of various kinds on objects and bodies surrounding them. In some cases the useful work that is done is limited only by the energy content of the explosive composition, while in other cases the transfer of energy from the explosive composition to surrounding bodies is controlled to a large degree by the momentum or impulse released by the detonating explosive. Amatol Research and development during World War I yielded amatol (TNT plus ammonium nitrate), an explosive with three times the power of gunpowder. Amatol consists of TNT and ammonium nitrate mixed in either 20 /80 or 50 /50 ratios. When the U.S. entered the war, Amatol was adopted for loading high explosive shells. Owing to shortages of TNT and RDX (cyclonite) most World War II mines had had 50/50 ammonium nitrate and TNT (amatol) warheads. This was a low quality explosive but was later improved by the addition of about 20% aluminum to produce minol. This explosive is a mechanical mixture of Ammonium Nitrate and TNT. It is crystalline and yellow or brownish, moisture-absorbing, insensitive to friction, but may be detonated by severe impact. It is readily detonated by Mercury Fulminate and other high explosives. Amatol 50/50 has approximately the same rate of detonation and brisance as TNT. Amatol 80/20 (used in Bangalore Torpedoes), produces white smoke on detonation, while Amatol 50/50 produces a smoke, less black than straight TNT. Amatol is used as a substitute for TNT and is to be mainly found in large caliber shells. Driven by its liquid propellant engine, the V-2 had a range of approximately 200 miles. Its warhead consisted of 2,000 pounds of amatol. Baratol Baratol is a composition of barium nitrate and TNT. TNT is typically 25-33% of the mixture with 1% wax as a binder. The high density of barium nitrate gives baratol a density of at least 2.5. Early implosion atomic bombs, like the Gadget exploded at Trinity in 1945, the Soviet's Joe 1 in 1949, or India in 1972, used an Composition-B [RDX-TNT mixture] as the fast explosive, with baratol used as the slow explosive. Composition A Composition A is a was-coated, granular explosive consisting of RDX and plasticizing was. Composition A is used by the military in land mines and 2.75 and 5 inch rockets. Comp A-3 explosives are made from RDX and wax. Composition A-3 is a wax-coated, granular explosive, consisting of 91% RDX and 9% desensitizing wax. Composition A-3 is not melted or cast. It is pressed into projectiles. It is nonhygroscopic and possesses satisfactory stowage properties. Composition A-3 is appreciably more brisant and powerful than TNT; its velocity of detonation is approximately 27,000 fps. It may be white or buff, depending upon the color of the wax used to coat the powdered RDX. Composition A-3 is used as a fillerinprojectiles that contain a small burster cavity, such as antiaircraft projectiles. It can be used as compressed fillers for medium-caliber projectiles.

Composition B / Comp B Comp B explosives are made from TNT, RDX, and wax, such as 59.5 percent RDX, 39.5 percent TNT and 1 percent wax. Desensitizing agents are added. Composition B is used by the military in land mines, rockets and projectiles. Cast Composition B has a specific gravity of 1.65 and a detonation velocity of 'about 25,000 fps and is used as a primer and booster for blasting agents. Composition B is a mixture of 59% RDX, 40% TNT, and 1% wax. The TNT reduces the sensitivity of the RDX to a safe degree and, because of its melting point, allows the material to be cast-loaded. The blast energy of Composition B is slightly higher than that of TNT. Composition B is nonhygroscopic and remains stable in stowage. It has an extremely high-shaped-charge efficiency. The velocity of detonation is approximately 24,000 fps, and its color ranges from yellow to brown. Composition B has been used as a more powerful replacement for TNT in loading some of the rifle grenades and some rocket heads. It can be used where an explosive with more power and brisance is of tactical advantage and there is no objection to a slight increase of sensitivity. While no longer used in newer gun projectiles, some older stocks may be found with Composition B main charges. Factors for Equivalent Weight of Composition B Explosive Equivalent Factor Comp B 1.00 PBXN-109 1.19 Tritonal 1.09 AFX-777 1.47 AFX-757 1.39 PAX-28 1.62

Composition B-3 During the development of a series of melt-castable explosive formulations devoid of TNT, non-TNT formulations yielded self-heating temperatures significantly lower than predicted. In other tests, Composition B (59.5% RDX, 39.5% TNT, 1% wax) demonstrated an exceedingly low self-heating temperature that ultimately results in a violent final reaction. It is often processed above its self-heating temperature, yet it is safely processed in 300-gallon melt kettles. Researchers subjected Composition B and its individual energetic components to one-liter cook-off testing. They expanded their investigations to include neat TNT, neat RDX (HRDX), an insensitive RDX (IRDX) essentially absent of microinclusions and voids, and Composition B-3 (60% RDX, 40% TNT) made with IRDX. Following analysis of these tests, researchers also tested an HRDX/TNT (13% HRDX, 87% TNT) mixture. Neat TNT is thermally destabilized by the presence of RDX, either HRDX or IRDX, indicating that RDX is the trigger in the thermal decomposition process associated with Composition B (HRDX) and Composition B-3 (IRDX). The reaction violence of both neat HRDX and Composition B made with HRDX were exceedingly violent, with either partial detonation or detonation occurring. Additionally, researchers observed that the reaction of Composition B-3 (IRDX/TNT) was more violent than either neat TNT or neat IRDX. Once again, they hypothesized that solubilized RDX in molten TNT was the source of the effect. They believe the high-quality, defect-free crystals of IRDX were modified by a dynamic equilibrium in molten TNT, with IRDX solubilized and reprecipitated as ill-defined, voided crystals similar to HRDX. They suspect these ill-

defined RDX crystallites present at cook-off temperatures were the source of the reaction violence at cook-off. Composition C-3 Compositior C-3 is one of the Composition C series that has now been replaced by C-4, especially for loading shaped charges. However, quantities of Composition C-1 and Composition C-2 may be found in the field. Composition C-1 is 88.3% RDX and 11.7% plasticizing oil. Composition C-3 is 77% RDX, 3% tetryl, 4% TNT, 1% NC, 5% MNT (mononitrotoluol), and 10% DNT (dinitrotoluol). The last two compounds, while they are explosives, are oily liquids and plasticize the mixture. The essential difference between Composition C-3 and Composition C-2 is the substitution of 3% tetryl for 3% RDX, which improves the plastic qualities. The changes were made in an effort to obtain a plastic, puttylike composition to meet the requirements of an ideal explosive for molded and shaped charges that will maintain its plasticity over a wide range of temperatures and not exude oil. Composition C-3 is about 1.35 times as powerful as TNT. The melting point of Composition C-3 is 68°C, and it is soluble in acetone. The velocity of detonation is approximate y 26,000 fps. Its color is light brown. As with Composition B, Composition C is no longer being used as a gun projectile main charge. However, some stocks may still be in service with Composition C-3 used as a main charge. Composition C-4 / Comp C-4 Plastic Explosive The plasticized form of RDX, composition C-4, contains 91% RDX, 2.1% polyisobutylene, 1.6% motor oil, and 5.3% 2-ethylhexyl sebacate. The Demolition charge M183 is used primarily in breaching obstacles or demolition of large structures where large charges are required (Satchel Charge). The charge assembly M183 consists of 16 block demolition charges M112, four priming assemblies and carrying case M85. Each Priming assembly consists of a five-foot length of detonating cord assembled with two detonating cord clips and capped at each end with a booster. The components of the assembly are issued in the carrying case. The demolition charge M112 is a rectangular block of Composition C-4 approximately 2 inches by 1.5 inches and 11 inches long, weighing 1.25 Lbs. When the charge is detonated, the explosive is converted into compressed gas. The gas exerts pressure in the form of a shock wave, which demolishes the target by cutting, breaching, or cratering. Using explosives provides the easiest and fastest way to break the frozen ground. However, the use of demolitions will be restricted when under enemy observation. Composition C-4, tetrytol, and TNT are the best explosives for use in northern operations because they retain their effectiveness in cold weather. Dig a hole in the ground in which to place the explosive and tamp the charge with any material available to increase its effectiveness. Either electric or nonelectric circuits may be used to detonate the charge. For a foxhole, 10 pounds of explosive will usually be sufficient. Another formula is to use 2 pounds of explosive for every 30 cm (1') of penetration in frozen ground. DMDNB (2-3 dimethyl, 2-3 dinitrobutane) is a new, military unique compound used as a tagant in C-4 explosive. Therefore there is no OSHA or ACGIH standard. However, USACHPPM's Toxicology Directorate did a study to determine an Army Exposure Limit. There is no toxicological data for DMDNB's effects on the human body, but tests were done on laboratory animals and they showed a reversible liver hypertrophy in rats that were exposed to DMDNB. An exposure level was determined and a one thousand fold

safety factor was used to lower the Army exposure level to 0.15 mg/m^3. (At this level there are no warning properties, i.e. smell, taste, etc.) Composition H6 / COMP H6 H-6 is an Australian produced explosive composition. Composition H6 is a widely used main charge filling for underwater blast weapons such as mines, depth charges, torpedoes and mine disposal charges. The M21 AT mine is 230 millimeters in diameter and 206 millimeters high. It weighs 7.6 kilograms and has 4.95 kilograms of Composition H6 explosive. In weapon applications, computational models require experimental data to determine certain specific output parameters of H6 to predict various underwater blast scenarios. To this end, the critical diameter dc, which is the minimum diameter which will sustain a stable detonation, and the limiting value of the velocity of detonation at infinite charge diameter D-infinity, were determined for unconfined cylinders of H6. Cyclotol [Composition B] Cyclotol, which is a mixture of RDX and TNT, is an explosive used in shaped charge bombs. CXM-6 On 30 August 1999 Holston Army Ammunition Plant restarted production of new explosives to fill an order for Composition CXM-3. This is the first new explosive production by Royal Ordnance North America (RONA) as the operating contractor at Holston. CXM-3 will be supplied to Atlantic Research Corporation to fill warheads for the Tomahawk missile system. RONA is also planning to produce other RDX and HMX products, including approximately 800,000 pounds of Composition C-4, by the end of December. Detasheet Detasheet is a plastic explosives, manufactured by DuPont containing PETN with nitrocellulose and a binder. It is manufactured in thin flexible sheets with a rubbery texture, and is generally coloured either reddish/orange (commercial) or green (military). In use, it is typically cut to shape for precision engineering charges. Dynamite In 1847 a new explosive came into being. This was nitroglycerine, made by treating glycerine with nitric and sulphuric acids. But at first it was even more dangerous to handle than guncotton, for the least shock exploded it, and its violence was terrific. The great chemist Alfred Nobel tried to improve it by mixing it with gunpowder, but the powder did not absorb all the nitroglycerine, and accidents of the most terrible kind became more and more frequent. Yet the new explosive, being liquid, could be poured into crevices in rocks, and was so useful as a blasting agent that its manufacture went on until a large vessel carrying cases of the explosive from Hamburg to Chili blew up at sea. The ship was blown to bits and her crew killed, and the disaster caused so great a sensation that the manufacture of nitroglycerine was prohibited in Sweden, Belgium, and in England. But Nobel still continued his experiments, and at last, after trying sawdust and all other sorts of absorbents in vain, found the perfect absorbent in the shape of keiselguhr-a sort of earth made of fossil shells. The mixture is what we know to-day as dynamite; and in spite of the fact that modern chemistry has produced very many new explosives, some of terrific power, dynamite remains the safest and most widely used of all explosives.

Many attempts have been made to use dynamite in guns; and the Americans at one time built some huge air guns for the purpose of firing large shells, or rather aerial torpedoes, charged with dynamite. But these guns, of which one or two were used in the SpanishAmerican War, were very cumbersome and slow in use. Nor could they throw a projectile to a greater distance than a mile. So they were soon abandoned in favor of rifled cannonfiring shells loaded with explosives such as cordite or lyddite. Dynamite was originally a mixture of nitroglycerin and diato-mite, a porous, inert silica. Today, straight nitroglycerin dynamite consists of nitroglycerin, with sodium nitrate, antacid, carbonaceous fuel, and sometimes sulfur in place of the inert filler. It is most commonly manufactured in weight strengths of 20 to 60 percent. Because of the tendency of nitroglycerin to freeze at low working temperature, another explosive oil usually replaces part of the nitroglycerin in a straight dynamite. Straight dynamite has a high detonation velocity which gives a shattering action. It resists water well in the higher grades but poorly in the lower grades. Straight dynamite generally has poor fume qualities, and is unsuitable for use underground or in poorly ventilated spaces. The use of straight dynamite has declined because of high cost, sensitivity to shock and friction, and high flammability. Ammonia ("extra") dynamites have replaced straight dynamite in most applications. Ditching dynamite is a name given to 50 percent straight dynamite. Its high sensitivity is advantageous in ditching where sympathetic detonation eliminates the need for caps or detonating fuse with individual charges. Sixty percent straight dynamite is sometimes packaged in special cartridges for uncle rwater work. Ammonia dynamites (extra dynamite) are the most widely used cartridge explosives. An ammonia dynamite is similar to a straight dpmite except that ammonium nitrate replaces a portion of the nitroglycerin and sodium nitrate. High-density ammonia dynamite is commonly manufactured in weight strengths of 20 to 60 percent. It is generally lower in detonation velocity, less dense, better in fume qualities, and considerably less sensitive to shock and friction than straight dynamite. Extra dynamite can be used effectively where the rock is not extremely hard and water conditions are not severe. It is widely used in quarrying, stripping, and in well-ventilated mines for smaller diameter holes of small blasting operations. Low-density ammonia dynamite has a weight strength of approximately 65 percent and a cartridge strength from 20 to 50 percent. Like a high-density extra dynamite, it contains a low proportion of nitro-glycerin and a high proportion of ammonium nitrate. The different cartridge strengths are obtained by varying the density and grain size of the ingredients. Several manufacturers produce two series of low-density ammonia dynamite, a high- and a low-velocity series. Both series are of lower velocity and density than highdensity extra dynamite. Because of its slow, heaving action, the low-velocity series is well suited to blasting soft material such as clay- shale or where a coarse product such as riprap is desired. It is well suited for use in structural excavation blasting in certain rock types. Fume qualities and water resistance vary with the cartridge material. Wrappers sprayed with paraffin give fair to poor water resistance and fair fume rating, whereas a paraffinimpregnated wrapper gives very poor water resistance and a better fume rating. The explosive has little more water resistance than that provided by the wrapper. Low-density extra is the lowest cost cartridge explosive available. The composition of low-density

ammonia dynamites is similar to that of a 60 percent high-density extra dynamite with a lower proportion of nitroglycerin and a higher proportion of ammonium nitrate. Gelatin Blasting gelatin is a rubber-textured explosive made by adding nitrocellulose (guncotton) to nitroglycerin. An antacid is added for stability in storage. Wood meal is usually added to improve sensitivity. Blasting gelatin attains a very high detonation velocity and has excellent water resistance, but it emits large volumes of noxious fumes upon detonation. It is the most powerful of all commercial explosives. Blasting gelatin is also known as "oil well explosive." Nobel did much more than merely invent dynamite; he also invented blasting gelatine, gelatine dynamite, and gelignite, both of the latter being better suited for rock blasting than pure dynamite. Blasting gelatine was used to pierce the great St. Gothard Railway tunnel through rock so hard that without it the task could never have been accomplished. Blasting gelatine was tried in guns, but burst them, so Nobel set himself to discover an explosive less violent, yet equally clear and smokeless. By mixing nitroglycerine and guncotton he found a comparatively slow-burning powder which he called ballistite, and this, when he gave it to the world in 1888, caused a very great sensation. Straight gelatin is a dense, plastic explosive consisting of nitroglycerin or other explosive oil gelatinized with. nitrocellulose, an antacid, sodium nitrate, carbonaceous fuel, and sometimes sulfur. Since the gelatin tends to coat the other ingredients, straight gelatin is water-proof. Straight gelatin is the equivalent of straight dynamite in the dynamite category and is manufactured in weight strengths of 20 to 90 percent with corresponding cartridge strengths of 30 to 80 percent. The cartridge strength or the weight strength may be referred to by the manufacturer as the "grade" of the gelatin, a term which is confusing. Straight gelatin has been used in very hard rock or as a bottom charge in a column of explosives. It has been replaced in most applications by a more economical substitute such as ammonia gelatin, brit higher grades are still used in underwater blasting and in deep well shooting. Straight gelatin has two characteristic detonation velocities, the confined velocity and a much lower velocity which results from insufficient confinement, insufficient initiation, or high hydrostatic, pressure. Extremely high water pressures may cause a misfire. To overcome this disadvantage, high-velocity gelatin has been developed. High-velocity gelatin is very similar to straight gelatin except that it is slightly less dense, more sensitive to detonation, and always detonates near its rated velocity regardless of water pressure or degree of confinement. High-velocity gelatin is particularly useful as a seismic explosive, and is also used in deep well and underwater work. Ammonia gelatin (special gelatin or gelatin extra) has a portion of the nitroglycerin and sodium nitrate replaced by ammonium nitrate. Ammonia gelatin is comparable to a straight gelatin in the same way that a high-density ammonia dynamite is comparable to a straight dynamite, and was developed as a cheaper substitute. Ammonia gelatin is commonly manufactured in weight strengths of 30 to 80 percent with corresponding cartridge strengths of 35 to 72 percent. Compared with straight gelatin, ammonia gelatin has a somewhat lower detonation velocity, better fume qualities, and less water resistance, although it will fire efficiently even after standing in water for several days. It is suitable for underground work because of its good fume rating. The higher strengths (70 percent or higher) are efficient as primers for blasting agents.

A semigelatin is comparable to an ammonia gelatin as a low-density ammonia dynamite is comparable to a high-density ammonia dynamite. Like low-density extras, semigelatin has a uniform weight strength (60 to 65 percent) with the cartridge strength varying with the density and grain size of the ingredients. Its properties fall betieen those of highdensity ammonia dynamite and ammonia gelatin, and it has great versatility. Semigelatin can be used to replace ammonia dynamite when more water resistance is needed. It is cheaper for wet work than ammonia gelatin, although its water resistance is not quite as high as that of ammonia gelatin. Semigelatin has a confined detonation velocity of 10,000 to 12,000 fps, which, b contrast to that of most explosives, is not seriously affected by lack of confinement. Very good fume qualities permit its use underground. The compositions are similar to ammonia gelatin with less nitroglycerin and sodium nitrate and more ammonium nitrate. H6 H-6 is a binary explosive that is a mixture of RDX, TNT, powered aluminum, and D-2 wax with calcium chloride added. H-6 is an Australian produced explosive composition used by the military for general purpose bombs. HBX [Hexahydro - 1, 3, 5 Trinitro-8-Triazine] HBX is a form of high explosive made from TNT, RDX, aluminum, lecithin, and wax. HBX was developed during WWII that replaced the more shock-sensitive TORPEX used in depth bombs and torpedoes. The warhead for the 2.75-inch "Mighty Mouse" rocket was filled with HBX (40 percent RDX, 38 percent TNT, 17 percent aluminum powder, and 5 percent desensitizers) or composition B (59 percent RDX, 40 percent TNT, and 1 percent wax). All Navy warhead filling activities in the TNT Plant ceased in early The major longer range improvements resulting were the Navy's development of HBX type explosives together with asphaltic, "hot melt" liners for bombs and other munitions. The hot melt liners were developed to coat and eliminate metal-to metal pinch points. After the Naval Magazine, Port Chicago, CA accident of 17 July 1944 , HBX and H-6 explosives were developed that incorporated wax and other chemicals to desensitize the explosive and hot melt liners were introduced for lining bombs and warheads to give some thermal protection and eliminate potential pinch points from cracks or fissures in the bomb or warhead case. Later, plastic-bonded explosives were developed for increased thermal protection and fragment impact resistance. LX-14 Minol Although ANFO is not generally suitable for military use, since it's troublesome to store without drying out, mixtures of AN and TNT known as "amatols" were used in both WWI and WWII as a means of stretching the supply of explosives. The proportion of AN in the mix ranged from 50% to 80%. A mix of ANFO, TNT, and powdered aluminum enhancer named "Minol" is still in use [40% TNT, 40% ammonium nitrate, 20% aluminum]. Owing to shortages of TNT and RDX (cyclonite) most World War II mines had had 50/50 ammonium nitrate and TNT (amatol) warheads. This was a low quality explosive but was later improved by the addition of about 20% aluminum to produce minol. Octol The melt-cast explosive Octol is a TNT-based explosive (70% HMX:30% TNT or 75 percent HMX, 25 percent TNT). Explosives to be stored on Navy ships must not contain

TNT or Octol. PBX The ideal high-energy explosive must balance different requirements. HE should be easy to form into parts but resistant to subsequent deformation through temperature, pressure, or mechanical stress. It should be easy to detonate on demand but difficult to explode accidentally. The explosive should also be compatible with all the materials it contacts, and it should retain all its desirable qualities indefinitely. No such explosive existed in 1944. While using what was available to meet wartime demands, scientists at Los Alamos began to develop a high-energy, relatively safe, dimensionally stable, and compositionally uniform explosive. By 1947, scientists at Los Alamos had created the first plastic-bonded explosive (PBX), an RDX*-polystyrene formulation later designated PBX 9205. Although other PBXs have since been successfully formulated for a wide range of applications, only a handful have displayed the combination of adequate energy content, mechanical properties, sensitivity, and chemical stability required for stockpile nuclear weapons. Since the 1960s, Livermore has been researching and developing safer HE for Livermore-designed weapons. The plastic coating that binds the explosive granules, typically 5 to 20% of each formulation by weight, is what gives each PBX its distinctive characteristics. Pressing a PBX molding powder converts it into a solid mass, with the polymer binder providing both mechanical rigidity and reduced sensitivity to accidental detonation. The choice of binder affects hardness, safety, and stability. Too brittle a PBX can sustain damage in normal handling and succumb to extreme temperature swings or thermal shocks, while too soft a PBX may be susceptible to creep and may lack dimensional stability or strength. PBXN-5 PBXN-5 is referred to as a plastic-bonded explosive because it is an explosive coated with plastic material. The composition is made of 95% HMX and 5% fluoroelastomers. The Anti-Personnel Obstacle Breaching System (APOBS) Detonating Cord Assembly consists of PBXN-8 explosive, silicone rubber, polyamide yarn type I and II, and composition A-5 explosive. Grenade Assembly consists of PBXN-5 explosive booster pellet, PBXN-9 explosive pellets, grenade tube, and male and female grenade shells. Grenade Assembly consists of PBXN-5 explosive booster pellet, PBXN-9 explosive pellets, grenade tube, unisex grenade shells, and ring clamp. PBXN-7 China Lake designed, developed, and qualified the Tomahawk Block III WDU-36 warhead in 48 months to meet evolving Tomahawk requirements of insensitive munitions ordnance compliance and range enhancement, while maintaining or enhancing ordnance effectiveness. The WDU-36 uses a new warhead material based upon prior China Lake warhead technology investigations, PBXN-107 explosive, the FMU-148 fuze (developed and qualified for this application), and the BBU-47 fuze booster (developed and qualified using the new PBXN-7 explosive). Block III was first used in the September 1995 Bosnia strike (Deliberate Force) and a year later in the Iraq strike (Desert Strike). PBXN-9 PBXN-9 Explosive is made for the HELLFIRE/Longbow Missile System. Because of its acceptance into a number of fleet uses, additional characterization and performance tests were conducted on PBXN-9 to support various warhead developmental efforts. Included

are the results of various explosive performance tests, such as detonation pressure, cylinder expansion (cylex),and wedge tests, as well as additional material sensitivity studies (large-scale gap test and small-scale gap test). The JASSM contains the WDU-42/B (J-1000), a 1000-pound class, penetrating warhead with 240 pounds of AFX-757. AFX-757 is an extremely insensitive explosive developed by the Air Force Research Laboratory/High Explosives Research and Development Facility, Eglin AFB, Fla. The fuze is the FMU-156/B employing a 150-gram PBXN-9 booster. The Anti-Personnel Obstacle Breaching System (APOBS) Detonating Cord Assembly consists of PBXN-8 explosive, silicone rubber, polyamide yarn type I and II, and composition A-5 explosive. Grenade Assembly consists of PBXN-5 explosive booster pellet, PBXN-9 explosive pellets, grenade tube, and male and female grenade shells. Grenade Assembly consists of PBXN-5 explosive booster pellet, PBXN-9 explosive pellets, grenade tube, unisex grenade shells, and ring clamp. A Low-Energy Exploding Foil Initiator (LEEFI) is a low-energy input device with highenergy output that can detonate a main charge of PBXN-9. PBXN-10 PBXN-106 This explosive is one of the new plastic-bonded explosives. It is a cast-cured explosive composition made from a homogeneous mixture of RDX in a plasticized polyurethane rubber matrix. Once cured, the material cannot be easily restored to a liquid state. The finished material is flexible and will absorb considerably more mechanical shock than conventional cast or pressed explosives. PBXN-107 PBXN-109 PE4 PE4 is a conventional plastic explosive, widely used for the production of improved energetic systems for defensive and offensive use. PE4 is RDX based and is available in cartridge and bulk form. An extrudable for DEMEX 400 is also available. Distinctive standard colours indicate the explosive component: C4, or PE4 ( British) is white and Semtex-H is orange. Pentolite Pentolite is a mixture of equal parts of TNT and PETN. When cast, it has a specific gratity of 1.65 and a confined detonation velocity of 24,000 to 25,000 fps. Cast pentolite is used as a primer and booster for blasting agents where its high detonation pressure assures efficient initiation of the blasting agent. Semtex Semtex is an explosive containing both RDX and PETN. Semtex, a Czech-made explosive, has been used in many terrorist bombings. Dynamite has been replaced by the more destructive and easily concealed Semtex. SEMTEX is a plastic explosive that is odorless. SEMTEX along with a detonating cap, can be inserted inside a 5" x 6" musical greeting card, undetected. Three pounds of Semtex plastique packs enough punch to raze a two-story building. Terrorists attack with no warning and no rationale. Their weapon of choice is a pliable, odorless substance that is twice as powerful as TNT and is virtually invisible to conventional security devices. It can be hidden in a brief case or a small cassette recorder.

Czechoslovakia was among the world's chief arms exporters. It sold hundreds of tanks, thousands of firearms and large quantities of Semtex to Iran, Iraq, Libya, Syria, Cambodia and other trouble spots, a practice that stopped long ago. In 1985 and 1986, the Irish Republican Army [IRA] took delivery of nearly 120 tons of arms and explosives from Libya, including a ton of Semtex explosive and 12 SAM-7 surface-to-air missiles. Some of those weapons and explosives have been used by the IRA in terrorist attacks in the United Kingdom and in other European countries. Libyan terrorists used Semtex in 1988 to down Pan Am Flight 103 over Lockerbie, Scotland, killing 270 persons. The on-again, off-again export of the general-purpose plastic explosive Semtex, manufactured in Czechoslovakia during the height of the Cold War and linked to terrorist groups around the world, resumed in 1994. The Czech Republic recently announced that exports were beginning to selected countries. The first Semtex shipment under the resumed exportswent to the British Defense Ministry. Czech reporting suggested that the British authorities intend to run experiments on the explosive that is often used by Irish Republican Army terrorists-including the October 1993 destruction of a building in Belfast. According to the 1991 international convention signed in Montreal, Semtex intended for industrial applications is to be a bright red-orange color and detectable by securitymonitoring equipment. Variants of the explosive produced for civilian purposes are also less powerful than the nearly odorless version that became a favorite weapon of terrorists. Despite this and the export ban that had earlier been in place, Semtex continues to be smuggled across borders. Substantial quantities of the explosive have been stolen from industrial enterprises in the Czech and Slovak republics for sale on the black market. Shortly before the most recent ban was lifted, Czech police seized 100 kilograms of industrial Semtex from a group of Czech citizens who were planning its illegal sale abroad. In Slovakia in October 1993, some 900 kilograms of the explosive were stolen from the warehouse of a private firm, together with more than 2,000 detonators. Czech officials candidly admit that they have no idea how much Semtex has been stolen or illegally diverted, and the continued black market trade in the explosive seems certain. Slurries Slurries, sometimes called water gels, contain ammonium nitrate partly in aqueous solution. Depending on the remainder of the ingredients, slurries can be classified as either blasting agents or explosives. Slurry blasting agents contain nonexplosive sensitizers or fuels such as carbon, sulfur, or aluminum, and are not cap sensitive; whereas slurry explosives contain cap- sensitive ingredients such as TNT and the mixture itself may be cap sensitive. Slurries are thickened and gelled with a gum, such as guar gum, to give considerable water resistance. Since most slurries are not cap sensitive, all slurries, even those containing TNT, are often grouped under the term blasting agent. This grouping is incorrect. A blasting agent, as defined by the National Fire Protection Association, shall contain no ingredient that is classified as an explosive. Slurry blasting agents require adequate priming with a high-velocity explosive to attain proper detonation velocities, and often require boosters of high explosive spaced along the borehole to as sure complete detonation. Slurry explosives may or may not require priming. The detonation velocities of slurries, between i2,000 and 18,000 fps, vary with

ingredients used, charge diameter, degree of confinement, and density. The detonation velocity of a slurry, however, is not as dependent on charge diameter as that of a dry blasting agent. The specific gratity varies from I.i to i.6. The consistency of most slurries ranges from fluid near iOOO F to rigid at freezing temperatures, although some slurries maintain their fluidity even at freezing temperatures. Slurries consequently give the same advantageous direct borehole coupling as dry blasting agents as well as a higher detonation velocity and a higher density. Thus, more energy can be loaded into a given volume of borehole. Saving in costs realized by drilling smaller holes or using larger burden and spacing will often more than offset the higher cost per pound of explosive. Adding powdered aluminum as a sensitizer to slurries greatly increases the heat of explosion or the energy release. Aluminized slurries have been used in extremely hard rock with excellent results. A slurry and a dry blasting agent may be used in the same borehole in "slurry boosting," with the buk of the charge being dry blasting agent. Boosters placed at regular intervals may improve fragmentation. In another application of slurry boosting, the slurry is placed in a position where fragmentation is difficult, such as a hard toe or a zone of hard rock in the burden. The combination will often give better overall economy than straight slurry or dry blasting agent. Tetrytol Tetrytol is a mixture of ~70% tetryl (2,4,6-trinitrophenyl-methylnitramine) and ~30% TNT (2,4,6-trinitrotoluene. In 1944 the M104 auxiliary booster was first given to Redstone Arsenal as an experimental order with instructions to develop a manufacturing procedure for loading it with tetrytol. The booster had heretofore been loaded with tetryl pellets. The tests that Redstone conducted showed that tetrytol-loaded M104 auxiliary boosters had a greater brisance than the tetryl-loaded ones but that a heavier booster charge was required for detonation. Since such a booster charge was already available, the tetrytol-loaded auxiliary booster was considered more satisfactory than the tetrylloaded one. TORPEX TORPEX is an explosive based on trinitrotoluene (TNT) that gave a greater blast than TNT, but was more sensitive. It was replaced by HBX or HBX-1 later in WWII. Torpex is RDX/TNT/Aluminum/Wax desensitizer. It was used in several types of torpedoes and mines. Due to it sensitivity to bullet impact, the first weapons loaded were ones for which there would be the least possibility of rifle bullet and fragment attack, namely, submarine delivered mines and torpedoes. The loading stations were advised that they must take adequate care in mixing and loading and in the handling of the loaded items. It was declared that the British had been able to handle it without incident for 2 years and that the risk was worth the advantage gained in its underwater power. Tritonal The GBU-28 contains only six hundred pounds of Tritonal. The BLU-109/B was an improved 2,000-pound-class penetrator bomb designed for attacking the most hardened targets. Its skin was much harder than that of a standard iron bomb, consisting of a singlepiece, forged warhead casing of one-inch, high-grade steel. The bomb featured a 550 pound tritonal high-explosive blast warhead and was always mated with a laser guidance kit to form a laser-guided bomb. The Tritonal filling of the BLU-109/B is similar in size to the warhead of the Mk.48 series torpedo. Explosive (NEW) 535 lbs. Tritonal in the

BLU-109 and 945 lbs. of Tritonal on the MK 84. The Munitions Directorate's successful completion of the Miniaturized Munition Technology Demonstration (MMTD) Program, has provided an innovative weapon called the Small Smart Bomb. The miniaturized munition concept includes a weapon that issix feet long, six inches in diameter, and weighs only 250 pounds with approximately fifty pounds of Tritonal explosive material. The weapon is effective against a majority of hardened targets previously vulnerable only to munitions in the 2,000 pound class. The Air Force Research Laboratory's Munitions Directorate has set the baseline for small bomb development by successfully demonstrating the technology that will be used to further the development of a 250-pound class munition. Small Smart Bomb's size will allow future fighter and bomber aircraft to carry more weapons in their weapons bays. Polynitrocubane Super Explosives are a family of new energetics. In FY96, the Army initiated the synthesis of a more powerful polynitrocubane explosive. In FY97, the Army scaled up the polynitrocubane explosive to pound level. In FY98, scale up the polynitrocubane explosive to pilot plant quantity and initiate formulation study for antiarmor warhead (Shaped Charge or explosively Formed Penetrator) loading. In FY99, conduct static warhead test using the polynitrocubane explosive to show increase in energy performance by up to 25 percent and with comparable sensitivity to LX-14. The current winner in the most powerful explosives debate is heptanitrocubane (HpNC). It has beat out the theoretically more powerful octanitrocubane (ONC) in actual tests recently performed. ONC has only been synthesized in the last year, but it has been calculated to have the greatest density of any explosive we could make. In reality ONC does not achieve this theoretical density. Since it has existed for such a short time, researchers conclude that they simply have yet to find its most dense crystalline form. The default winner is the next best thing, HpNC. Further conjecture into nitro cubane chemistry has hypothesized at the possibility of polynitrocubane molecules which could achieve even greater densities. _____________________________________________________________________________ ________________________________________________________________

Explosives - ANFO (Ammonium Nitrate - Fuel Oil) Ammonium nitrate-fuel oil (ANFO) blasting agents represent the largest industrial explosive manufactured (in terms of quantity) in the United States. This product is used primarily in mining and quarrying operations. The components are generally mixed at or near the point of use for safety reasons. The mixed product is relatively safe and easily handled and can be poured into drill holes in the mass or object to be blasted. Melvin A. Cook's life is intimately connected with the history of explosives, he is a scientist,, inventor, teacher, businessman, theorist, consultant, expert witness, entrepreneur, and author. Cook, a professor of metallurgy at the University of Utah, was a businessman and author of works on explosives. He also published works on creationism, particularly on the relationship between science and Mormonism. Cook's personal involvement in both the theoretical and practical aspects of the field of explosives spans more than fifty years. Cook's greatest commercial explosives invention was formulated in December of 1956, when he created a new blasting agent using an unusual mixture of ammonium nitrate, aluminum powder, and water. The safety and efficiency of this new explosive were

apparent, and the use of water was revolutionary. Tests that followed resulted in the development of a new field of explosives: slurry explosives. This invention converted the commercial explosives industry from "dangerous dynamite" to "safe slurry" and dry blasting agents [ANFO]. In 1972 Cook developed the BLU-82, the largest and most powerful chemical bomb, using aluminized slurry. Blasting agents consist of mixtures of fuels and oxidizers, none of which are classified as explosive. Nitrocarbonitrate is a classification given to a blasting agent under the US Department of Transportation regulations on packaging and shipping. A blasting agent consists of inorganic nitrates and carbonaceous fuels and may contain additional nonexplosive substances such as powdered aluminum or ferrosilicon to increase density. The addition of an explosive ingredient such as TNT changes the classification from a blasting agent to an explosive. Blasting agents may be dry or in slurry forms. Because of their insensitivity, blasting agents should be detonated by a primer of high explosive. Ammonium nitrate- fuel oil has largely replaced dynamites and gelatins in bench blasting. Denser slurry blasting agents are supplanting dynamite and gelatin and dry blasting agents. The most widely used dry blasting agent is a mixture of ammonium nitrate prills (porous grains) and fuel oil. The fuel oil is not precisely CH2, but this is sufficiently accurate to characterize the reaction. The right side of the equation contains only the desirable gases of detonation, although some CO and N02 are always formed. Weight proportions of ingredients for the equation are 94.5 percent ammonium nitrate and 5.5 percent fuel oil. In actual practice the proportions are 94 percent and 6 percent to assure an efficient chemical reaction of the nitrate. Uniform mixing of oil and ammonium nitrate is essential to development of full explosive force. Some blasting agents are premixed and packaged by the manufacturer. Where not premixed, several methods of mixing in the field can be employed to achieve uniformity. The best method, although not always the most practical one, is by mechanical tier. A more common and almost as effective method of mixing is by uniformly soaking prills in opened bags with 8 to 1O percent of their weight of oil. After draining for at least a half hour the prills will have retained about the correct amount of fuel oil. Fuel oil can also be poured onto the ammonium nitrate in approximately the correct proportions as it is poured into the blasthole. For this purpose, about i gal of fuel oil for each 100 lb of ammonium nitrate will equal approximately 6 percent by weight of oil. The oil can be added after each bag or two of prills, and it will disperse relatively rapidly and uniformly. Inadequate priming imparts a low initial detonation velocity to a blasting agent, and the reaction may die out and cause a misfire. High explosive boosters are sometimes spaced along the borehole to as sure propagation throughout the column. As in other combustion reactions, a deficiency of oxygen favors the formation of carbon monoxide and unburned organic compounds and produces little, if any, nitrogen oxides. An excess of oxygen causes more nitrogen oxides and less carbon monoxide and other unburned organics. For ammonium nitrate and fuel oil (ANFO) mixtures, a fuel oil content of more than 5.5 percent creates a deficiency of oxygen. Ammonium nitrate and fuel oil (ANFO) has a broad spectrum of Velocities of Detonation according to numerous references. However, some of these references are more specific when establishing parameters. A military catering charge lists a VOD of 10,700 feet per second (fps). A 4" diameter steel tube confinement is at 10,000 fps, while a 16" diameter

tube is at 16,000 fps. In charge diameters of 6 in. or more, dry blasting agents attain confined detonation velocities of more than i2,000 fps, but in a diameter of 1- 1/2 in., the velocity is reduced to 60 percent. When ANFO is used in boreholeing, the VOD has a positive slope as a function of depth, the VOD increases as the detonation front progresses down the borehole. Enhanced effects of very large quantities, which is essentially self tamping, the VOD is expected to be in the 13,000-15,000 fps range. A ballpark approximation for very large quantities of blasting agents, which is accepted in the commercial industry, is roughly half the VOD of C-4/plastics, which equates to 13,000 fps. The recognized VOD of urea nitrate, however, is 11,155 to 15,420 fps. The specific gravity of ANFO varies from 0.75 to 0.95 depending on the particle density and sizes. Confined detonation velocity and charge concentration of ANFO vary with borehole diameter. Pneumatic loading results in high detonation velocities and higher charge concentrations, particularly in holes smaller than 3 in. (otherwise such small holes are not usually recommended for ANFO blasting). _The simple removal of a tree stump might be done with a 2-step train made up of an electric blasting cap and a stick of dynamite. The detonation wave from the blasting cap would cause detonation of the dynamite. To make a large hole in the earth, an inexpensive explosive such as ANFO might be used. In this case, the detonation wave from the blasting cap is not powerful enough to cause detonation, so a booster must be used in a 3- or 4-step train. The yield from the blasting caps and safety fuses used in these trains are usually small compared to those from the main charge, because the yields are roughly proportional to the weight of explosive used, and the main charge makes up most of the total weight. Advantages of insensitive dry blasting agents are their safety, ease of loading, and low price. In the free-flowing form, they have a great advantage over cartridge explosives because they completely fill the borehole. This direct coupling to the walls assures efficient use of explosive energy. Ammonium nitrate is water soluble so that in wet holes, some blasters pump the water from the hole, insert a plastic sleeve, and load the blasting agent into the sleeve. Special precautions should be taken to avoid a possible building up of static electrical charge, particularly when loading pneumatically. When properly oxygen- balanced, the fume qualities of dry blasting agents permit their use underground. Canned blasting agents, once widely used, have unlimited water resist-ance, but lack advantages of loading ease and direct coupling to the borehole. In 2001, US explosives production was 2.38 million metric tons (Mt), 7% less than that in 2000; sales of explosives were reported in all States. Coal mining, with 69% of total consumption, continued to be the dominant use for explosives in the United States. Kentucky, West Virginia, Indiana, Wyoming, and Virginia, in descending order, were the largest consuming States, with a combined total of 46% of US sales. After completing an investigation into dumping of ammonium nitrate from Ukraine that was begun in 2000, the US International Trade Commission (ITC) issued its final determination in August 2001. The ITC determined that imports of ammonium nitrate from Ukraine were sold in the United States at less than fair market value and that critical circumstances did not exist with regard to these imports. As a result of the negative determination regarding critical circumstances, the duties were not retroactive and only apply to ammonium nitrate that has been imported since March 5, 2001. The antidumping duty of 156.29% ad valorem that was finalized by the International Trade Administration

in July 2001 was applied. Sales of ammonium-nitrate-based explosives (blasting agents and oxidizers) were 2.34 Mt in 2001, which was an 8% decrease from that of 2000, and accounted for 98% of US industrial explosives sales. Sales of permissibles and other high explosives increased slightly. Data for 2001 are not exactly comparable to the 2000 data. One company, Nelson Brothers LLC, did not provide data to the Institute of Makers of Explosives (IME) in 2001, and no estimate for its sales was included in the totals. By 2001 engineers in the Fuels and Lubricants Group of Shell Co. of Australia developed a technique to blend waste oil with ANFO for a product that can be used in blasting. Mines throughout the world produce thousands of liters of waste fuel oil that needs to be disposed of in an environmentally safe manner. By using the fuel oil in a blasting compound, transporting the waste oil is eliminated, the quantity of fuel oil needed for blasting is reduced, and potentially toxic hydrocarbons in waste oil can be destroyed by the high blast temperature. Shell tested the ANFO-waste oil blend at Hamersley Iron's Marandoo mine site, and found that the ratio of waste oil to ANFO blend could be as much as 50-50 without any detrimental effect to the final blasting performance. Urea nitrate is also considered a type of fertilizer-based explosive, although, in this case, the two constituents are nitric acid (one of the ten most produced chemicals in the world) and urea. A common source of urea is the prill used for de-icing sidewalks. Urea can also be derived from concentrated urine. This is a common variation used in South America and the Middle East by terrorists. Often, sulfuric acid is added to assist with catalyzing the constituents. A bucket containing the urea is used surrounded by an ice bath. The ice serves in assisting with the chemical conversion when the nitric acid is added. The resulting explosive can be blasting cap sensitive. Urea nitrate has a destructive power similar to ammonium nitrate. By one estimate, the bomb used to attack the Alfred Murrah Federal Building in Oklahoma City on April 19, 1995 consisted of an ANFO explosive main charge of approximately 4,000 pounds, based on an estimate of the Velocities of Detonation [VOD] of approximately 13,000 fps. Other estimates claim that the 1995 explosion that collapsed portions of the Murrah Federal Building in Oklahoma City contained 4,800 pounds of ammonium nitrate and fuel oil. Later estimates suggested that the bomb had in excess of 6,200 pounds of various energetic materials, including explosives other than ANFO, equivalent to 5,000 pounds of TNT. In the Salameh World Trade Center bombing case resulting from the bombing of the World Trade Center (WTC) on February 26, 1993, FBI Explosives Unit examiner David Williams opined that the main explosive used in the bombing consisted of 1,200 pounds of urea nitrate explosive. The FBI chemists specializing in the examination of explosive residue, however, did not find any residue identifying the explosive at the World Trade Center. Not all large truck bombs have used ANFO. On June 25, 1996, Saudi terrorists sponsored by Iran attacked the Khobar Towers barracks, a high-rise building complex in a densely populated urban environment in Saudi Arabia. T tanker truck loaded with at least 5,000 pounds of plastic explosives was driven into the parking lot in front of the Khobar Towers residential complex in Dhahran. Nineteen American service members were killed in the blast, and hundreds of other service members and Saudis were injured. There is no doubt that the extent of the casualties at Khobar Towers resulted, in part, from the extraordinary size of the terrorist bomb. Reports initially estimated that the bomb contained the

equivalent of 3,000 to 8,000 pounds of TNT, but a study by the Defense Special Weapons Agency concluded that the power of the bomb was actually closer to 20,000 pounds of TNT. _____________________________________________________________________________ _______________________________________________________________

Explosives - Mining Types Most of the explosives and blasting agents sold in the US are used in mining. There are two classifications of explosives and blasting agents. High explosives include permissibles and other high explosives. Permissibles are explosives that the Mine Safety and Health Administration approved. Blasting Agents and Oxidizers include ammonium nitrate-fuel oil (ANFO) mixtures, regardless of density; slurries, water gels, or emulsions; ANFO blends containing slurries, water gels, or emulsions; and ammonium nitrate in prilled, grained, or liquor form. Bulk and packaged forms of these materials are contained in this category. In 1998, about 95% of the total blasting agents and oxidizer were in bulk form. The principle distinction between high explosives and blasting agents is their sensitivity to initiation. High explosives are cap sensitive, whereas blasting agents are not. Many coal mines use explosives to loosen the rock and coal. In surface mining, holes are drilled through the overburden, loaded with explosives, and discharged, shattering the rock in the overburden. In one underground mining method, the coal is blasted off the bed without any undercutting to help break it down. The drawback to this method is that a dangerously large explosive charge is needed, and much dust and fine coal are produced. In another underground mining method using explosives to break down the coal, shot holes are drilled at intervals along the face of the coal bed. The explosives are inserted in these holes or shots. When the explosion occurs, the coal wall cracks into pieces. Coal mines use cylinders of compressed air, liquid carbon dioxide, or chemical explosives. Approximately 1.72 million metric tons (Mt) of explosives used for coal mining in 2000. This accounted for 67 percent of total U.S. explosives consumption. The largest coal producing states, Wyoming, West Virginia, and Kentucky were also the largest explosives-consuming states, accounting for 41 percent of total U.S. explosive sales. Quarrying and nonmetal mining, the second-largest explosives-consuming industries, accounted for 14 percent of total explosives sales and metal mining accounted for 9 percent. Kentucky, Wyoming, West Virginia, Virginia, and Indiana, in descending order, were the largest consuming states, with a combined total of 51 percent of total US sales of explosives.

Cast Blasts Explosive casting is the technique used by many surface coal mines to control the displacement of overburden by means of explosive energy. The casting moves 30-80% of the overburden into the mined-out pit, while the remaining spoil is removed by draglines or other machinery. A blasting engineer must consider bench height, pit width, borehole diameter, and geologic formation when designing a cast blast. In most cases, the blaster uses a complicated sequence of downhole and surface delays to minimize the ground roll associated with the large amounts of explosives (between 0.5-8 million pounds, ie, 500 to 4,000 tons, of Ammonium Nitrate Fuel Oil ANFO) used in a cast blast. The casting of the overburden into the pit creates both horizontal and vertical spall force components that influence the generation of surface waves. Kiloton class mine blasts are not uncommon in numerous regions worldwide such as Wyoming, Kentucky and, at least historically, the Kuzbass mining region in Russia. These use delay-firing and thus a considerable explosive yield is spread out over several seconds and seismic amplitudes are reduced. It is well known that minor deviations from the planned shot pattern are obiquitous. A small subset of these events, however, include a significant detonation anomaly.

Fragmentation Blasts The majority of hard rock open-pit mines design blasts that will optimize the insitu fragmentation of the material. This is accomplished by loading the holes with two different energy levels: higher energy explosives in the bottom and lower energy near the top. The result is that the material is not thrown into the mined-out pit as in the cast blasts. Instead, the material is fractured in place and removed with shovels and haul trucks. Seismic waves generated from a fragmentation blast should be influenced only by the explosion point and vertical component spall forces.

Quarry Blasts A third type of explosion used in the mining industry is for quarrying materials such as limestone, gravels, and igneous rocks. On average, quarry blasts are smaller in spatial extent and explosives content than fragmentation and cast blasts. Since these operations usually involve the crushing of the rock, efficient fragmentation of the rock into small pieces is required for use in a rock crusher. For ease in extraction of the materials, the rocks are usually blasted into the mined-out pit. Quarrry blasts seismograms will thus have both horizontal and vertical spall forces effecting the regional seismograms.

Classification of Mining Explosions When the eject angle is 0°, there is no horizontal spall component and the blast is analogous to a fragmentation shot. For quarry blasts, there is some material cast into the pit at eject angles greater than 45°, however, a additional amount of the spalled material is cast into the air at angles between 0 and 30°. Finally, for cast blasts, the majority of the material is ejected at angles greater than 30°. Cast blasts will have the largest deviation from an isotropic source (i.e., a fragmentation blast) with the magnitude of the azimuthal variations being dependent upon the eject angle. In all cases, there is a slight increase in the amplitudes in the direction of the delay-firing. For the cast blasts to take on a more dipolar ("peanut-shaped") radiation pattern, the mass of the horizontal spall must be increased. By adding additional rows of explosives with different interrow and interhole delays, the characteristics can become markedly different. _____________________________________________________________________________

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Explosives - ANFO (Ammonium Nitrate - Fuel Oil) Mining is the search for, extraction, and beneficiation and processing of solid minerals from the earth. The kinds of minerals extracted from the earth vary widely. For thousands of years, these and other minerals have provided the raw materials with which human civilizations have been built. The vitality of the U.S. economy depends on key mineral resources. In the course of a lifetime, each American will use 3.5 million pounds of minerals, metals, and fuels. Every year, 46,000 pounds of new minerals including 7,500 pounds of coal energy must be provided for every person in the U.S. to maintain a high standard of living. Low-cost coal is used to generate a large portion of the nation's electricity supply, helping to keep U.S. electricity costs among the lowest in the world and thereby enhancing the competitiveness of U.S. industry. The contribution that the mining industry has made to the economic health, well being, and security of the U.S. throughout its history is unquestioned. Surface mining and underground mining are the prevailing mining methods. The method selected depends on a variety of factors including the nature and location of the deposit as well as the size, depth, and grade of the minerals. Both surface and underground mining are widely used in the extraction of coal. In 2000, the total amount of coal produced was 1.07 billion tons. Of this, 373 million tons or 35 percent came from underground mines and the remaining 699 million tons or 65 percent came from surface mines. Of the 1.3 billion crude metal ore produced in the US in 2000, 1.2 billion tons or 92 percent came from surface mining. Most of the industrial minerals in the US are extracted by surface mining. In 2000, the total amount of crude industrial ore mined in the US was 3.2 billion tons. Of this, 3.1 billion or 96 percent came from surface mines. Bingham Canyon near Salt Lake City, Utah, is probably the best-known example of a surface mine in the U.S. It is also the largest surface mine in the US, measuring approximately 2 miles in diameter and a little more than a half mile deep. Conical in shape and used for near-surface ore bodies, these mines feature a series of benches winding down into the pit. The benches are used as working areas and haul roads. The rock is drilled, blasted and loaded into large haul trucks that take it to a processing facility. Underground mining is used when mineralization is deep beneath the surface and/or when ore grade or quality is sufficient to justify more targeted mining. In order to get to the ore body, a vertical shaft, horizontal adit, or inclined passageway must be drilled remove ore and waste and provide ventilation. Once the ore body is exposed, several levels of horizontal tunnels called drifts and crosscuts are created to provide access to mining areas called stopes. The area actually being mined at any given time is called the face. Broken rock is hauled from the face by trains, loaders, or trucks that go directly to the surface, or to the shaft where it is hoisted to the surface and sent to a processing facility. There are seven general phases of the mining process. These are: 1) mine exploration; 2) design; 3) construction, which includes mine site preparation; 4) extraction operations in either underground or surface mines; 5) beneficiation operations consisting of crushing and grinding, separations, solvent extraction/electrowinning; 6) processing, which

consists of smelting and/or refining depending on the mineral and the final product; and 7) reclamation (closure and post-closure). In each of these stages, there are a variety of equipment and materials used.

Exposives and Coal Mining Coal is extracted principally in two ways: surface mining and underground mining. The mining method used depends primarily on the depth of the coal bed from the surface and the surrounding terrain. Coal beds deeper than 100 to 200 feet or on hilly terrain are usually mined by underground methods, while those at lesser depths are surface mined. Surface mining accounts for about 60 percent of the total U.S. coal production of 1 billion tons/year. A large surface mine can be three miles long and a mile wide. Underground mining accounted for 430 million short tons in 1998, about 40 percent of total US coal production that year. Coal fields in the eastern U.S. are characterized by relatively thin seams of deeply buried coal. Eastern coal generally has a high heating value. Conversely, relatively thick seams of shallow reserves characterize the coalfields in the western U.S. Western coal generally has a low heating value. These deposit characteristics also greatly influence the mining method used. Underground mining is more frequently used on the thinner seams of the eastern coalfields. However, surface mining is most frequently used in the West. These deposits require relatively low-volume, shallow digging to expose thick coal seams for recovery. In general, where favorable coal seam conditions exist, surface mining is the least expensive and most productive method of taking coal from the ground. Used when the coal seam is relatively close to the surface, it can result in the removal of as much as 95 percent of the total coal from a particular deposit. Area surface mining is done on relatively flat land under which the coal is buried at roughly uniform depth. In this method, the overburden from a 100- to 200-foot-wide cut is used to fill the mined-out area of the preceding cut. Contour surface mining follows coal beds lying in hillsides. Excavation begins at a location where coal and surface elevations are the same. It proceeds towards the center of the hill or mountain until the overburden becomes too thick to remove economically. Mountain top removal mining is used to recover coal buried at or near the summit of a large hill or mountain by entirely removing the elevated area. Most surface mines follow the same basic steps to produce coal. Bulldozers clear and level the mining area; topsoil is removed and stored for later use in the reclamation process; holes are drilled through the overburden, loaded with explosives and discharged, shattering the rock in the overburden; power shovels or draglines clear away the overburden until the coal is exposed. The dragline has a large bucket suspended from the end of a boom, which may be as long as 300 feet. The bucket, which is suspended by cables, is able to scoop up to 250 tons of overburden as it is dragged across the excavation area. The dragline is one of the largest land-based machines in the world. Smaller shovels then scoop up the coal and load it onto trucks, which carry the coal to the preparation plant.

Exposives and Iron Mining Iron is found in every state in the United States and in almost every country in the world. However, the ore must contain commercially recoverable amounts of iron in relatively large deposits or ranges if it is to be mined economically. The characteristics of iron-

bearing ores vary geographically. Specifically, magnetite and hematite are the main ironbearing ores in the Lake Superior district and in the northeastern United States, while hematite and hematite-magnetite mixtures tend to be found in ores in Alabama and the Southwest. To be competitive, iron mining must be done on a very large scale. Surface mining is the preferred choice, although there are exceptions. Small, low-capacity mines have rapidly disappeared. In 2000, twelve iron ore production complexes with 12 mines, 10 concentration plants, and 10 pelletizing plants were operating in Minnesota, Michigan, and six other States. The mines included eleven surface and one underground operation. Virtually all ore was concentrated before shipment. Nine mines operated by five companies accounted for 99 percent of production. When the iron ore lies close to the surface, it often can be uncovered by stripping away a layer of dirt, sometimes only a few feet thick. The ore is mined from large open pits by progressive extraction along steps or benches. The benches provide access to progressively deeper ore, as upper-level ore is removed. After the soil and overlying rock are cleared, the ore is drilled and blasted. The portion of the ore body to be removed is first drilled in a specific pattern, and the holes are loaded with explosive mixtures and blasted. Following blasting, the fractured ore is loaded by huge electrical shovels, hydraulic excavators, or front-end loaders onto large dump trucks. The wide holes in the ground created by drilling, blasting, and ore removal are referred to as "open pits".

Exposives and Copper Mining For nearly 5,000 years, copper was the only metal known to man. It remains one of the most used and reused of all metals. The demand for copper is due to its good strength and fatigue resistance, excellent electrical and thermal conductivity, outstanding resistance to corrosion, and ease of fabrication. Copper offers moderate levels of density, elastic modulus, and low melting temperature. It is used in electrical cables and wires, switches, plumbing, heating, roofing and building construction, chemical and pharmaceutical machinery. It is also used in alloys such as brass and bronze, alloy castings, and electroplated protective coating in undercoats of nickel, chromium, and zinc. Copper is commonly extracted from surface, underground and increasingly, from in situ operations. In 2000, the principal mining States, in descending order, Arizona, Utah, New Mexico, and Montana, accounted for 99 percent of domestic production. Copper was also recovered at mines in three other States. Although copper was recovered at about 30 mines operating in the United States, 15 mines accounted for about 99 percent of production. At 2001 year end, four primary smelters, four electrolytic and four fire refineries, and 15 solvent extraction-electrowinning facilities were operating. Surface mining requires extensive blasting as well as rock, soil, vegetation, and overburden removal to reach lode deposits. Benches are cut into the walls of the mine to provide access to progressively deeper ore as upper-level ore is depleted. Ore is removed from the mine and transported to beneficiation plants for milling and concentrating. The concentrate is then smelted and refined. Open-pit mining is the primary domestic source of copper.

Exposives and Crushed RockMining Crushed rock is one of the most accessible natural resources and a major basic raw material. It is used in construction, agriculture, and other industries using complex

chemical and metallurgical processes. Despite the low value of its basic products, the crushed rock industry is a major contributor to and an indicator of the economic well being of the nation. Most crushed and broken stone is mined from open quarries; however, in many areas, factors favoring large-scale production by underground mining are becoming more frequent and prominent. Surface mining equipment varies with the kind of stone mined, the production capacity needed, the size and shape of the deposit, estimated life of the operation, location of the deposit with respect to urban centers, and other important factors. Typically, drilling is done with tricone rotary drills, long-hole percussion drills, and churn drills. Blasting in smaller operations may be done with dynamite, but in most medium-to large-size operations, ammonium nitrate fuel oil mixture (AN-FO) is used as a low cost explosive. The rock is then extracted using power shovels or bulldozers. Typical blasts at quarries use a 3½ inch diameter hole approximately 40 feet deep. The explosive most commonly used is ANFO and the top part is stemmed with sand/gravel or drilling cuttings poured on top of the ANFO to help force the blast energy into the rock. The amounts of ANFO and stemming vary depending on the location of the hole in the blast pattern, site conditions, the hardness of the rock to be blasted, and of course, on PPV limitations for surrounding structures. Generally, a minimum amount of stemming for a 3½ inch diameter, 40 foot hole would be approximately 7 feet, which would leave 33 feet of hole for ANFO. The weight of explosives in the hole would be approximately 115 pounds. About three-quarters of the crushed stone production is limestone and dolomite, followed by, in descending order of tonnage: granite, traprock, sandstone and quartzite, miscellaneous stone, marble, slate, calcareous marl, shell, volcanic cinder and scoria. Limestone, one of the largest produced crushed rock, is a sedimentary rock composed mostly of the mineral calcite and comprising about 15 percent of the earth's sedimentary crust. This mineral is a basic building block of the construction industry and the chief material from which aggregate, cement, lime, and building stone are made. For the purposes of this report, limestone will be used as a sample for crushed rock. One product of limestone mining is lime. A wide range of industries use lime for a myriad of uses. It is used in many of the products and materials Americans use every day, including paper, steel, sugar, plastics, paint, and many more. The largest single use of lime is in steel manufacturing, for which it serves as a flux for removing impurities (silica, phosphorus and sulfur) in refining steel. _______________________________________________________________________ ____________________________________________________

Liquid Explosives Nitroglycerine is a colorless to pale-yellow, viscous liquid or solid (below 56°F). It is an explosive ingredient in dynamite (20-40%) with ethylene glycol dinitrate (80-60%). It has a high nitrogen content( 18.5%) and contains more than enough oxigen atoms to oxidize the carbon and hydrogen atoms while nitrogen is beeing liberated, so it is one of the most powerful explosives known. Its detonation generates gases that would occupy more than 1,200 times the original volume at room temperature. Astrolite explosives, frequently and not too precisely called the world's most powerful

non-nuclear explosive, were discovered in the 1960's. Astrolite explosives are formed when ammonium nitrate is mixed with anhydrous hydrazine. This produces a clear liquid explosive called Astrolite G. When aluminum powder (100 mesh or finer) is added to the Hydrazinium Nitrate slurry, it forms Astrolite A-1-5. Astrolite G is a clear liquid explosive that produces a very high detonation velocity, almost twice as powerful as TNT. Explosive compositions comprising nitromethane and a sensitizer for the nitromethane are well known in the art. These compositions are formed by combining nitromethane with a sensitizing chemical compound. Various chemical compounds serve as effective sensitizers for nitromethane. For example, liquid explosive compositions containing nitromethane sensitized with amines or polyamines such as diethylamine, triethylamine, ethanolamine, ethylenediamine and morpholine. Likewise, non-chemical, air entrapping structures, such as resin micro balloons and polymeric foam, are effective nitromethane sensitizers. Nitromethane was first synthesized by Kolbe in 1872. It is so insensitive that it was not until 1938 that its detonation property was revealed by McKittrick. Once this detonation property was discovered, research was initiated to find sensitizers to increase its ease of detonation. World War II research produced sensitizers, primarily amines, which made nitromethane detonatable with a blasting cap. In 1945, Ericksen and Rowen listed over one dozen nitromethane - amine mixtures along with their explosive ability. Normally, liquid nitromethane based explosive compositions are converted into a semisolid or gelled state by the addition of a gelling agent. This conversion increases the density and, therefore, the detonation pressure of the semi-solid or gelled compositions. Although the semi-solid or gelled compositions have a higher detonation pressure than liquid compositions, they are not as effective in situations requiring a fluid material capable of conforming to any shape or structure. As a result, one must choose between the higher detonation pressure found in a semi-solid or gelled composition and the versatility of a liquid composition. Nitromethane known to reduce the sensitivity of nitroglycerine. Nitromethane may be added to compositions containing nitroglycerine. The reference further teaches that trinitrotoluene may be added to said compositions. Pyridine is known to be a highly effective solvent for trinitrotoluene. It is also a well-known sensitizer for nitromethane; however, it is seldom used for its sensitizer properties because more effective sensitizers are known and available. Trinitrotoluene was found to be soluble in nitromethane. The US Army Ballistic Research Laboratory was not aware of this property until 1987. In the field of explosives and explosives manufacturing, there are many types of explosives made for various applications. A few of these applications are for mining, construction, demolition, law enforcement and military uses. There are a multitude of explosive products available to satisfy the requirements in these fields. For example, for blasting rock in mining and construction work, the user can choose from cartridged explosives such as dynamite, water-gels and emulsions which are used for small diameter bore holes (up to 3 inches). For larger boreholes, blasting agents are used in the form of Ammonium Nitrate/Fuel Oil mixtures (ANFO), which are poured or pumped into position. Unlike the smaller, "cap-sensitive" cartridged explosives, these blasting agents (by definition) require a small, high explosive booster to initiate the detonation thereof. For commercial demolition applications, cartridged explosives are placed in small

boreholes within concrete columns and beams in the case of buildings, bridges and other similar structures. Where steel needs to be cut, small but powerful high explosive shaped charges are used to sever critical points in order to complete the demolition. Military applications for explosives are many. However, they tend to fall into two main groups. The first is for bombs, artillery shells, mortars, mines, etc. For these uses, the explosives are generally placed into the devices by means of a melt-pour operation. The second group are explosives used for demolition and breaching by Special Forces and engineering groups. Although some of the explosive charges are pre-made devices incorporating shaped charge or Explosively Formed Projectile (EFP) technology, most are simply bulk explosives in the form of blocks (C-4, and TNT) or sheets (Deta-Sheet). Another military related use of explosives is demining operations and unexploded ordnance (UXO) clearing operations where explosive charges are used to sympathetically detonate and destroy landmines as well as "dud" bombs and artillery shells. Similar type work conducted by civilian contractors after a conflict has been termed "Humanitarian Demining". Clearing of old military firing ranges by these contractors is called remediation. Although the previously mentioned applications consume the bulk of the explosives used in the world, smaller quantities are also used for agricultural blasting such as tree stump removal, irrigation and drainage ditch blasting and beaver dam control; Avalanche control; Metal hardening; Forest fire fighting; Submarine (underwater) blasting; Seismic work; Secondary blasting such as boulder breaking; Law enforcement applications such as tactical breaching and bomb squad work. Due to threats of terrorism and increased attention to accident prevention, regulations concerning the transportation, storage, use and transfer relating to explosives have steadily increased over the last few years. Along with this has come an increase in the cost of using explosives, particularly, in the area of transportation. Where explosives are used in volume, such as mines and quarries, the cost of transporting a truckload of explosives is not much more than a truckload of any other material. However, where small amounts of explosives are required, the transportation costs can far exceed the cost of the product. For example, it costs just as much to transport one stick of dynamite by commercial truck as it does two thousand pounds of dynamite. In order to accommodate the user who needs smaller quantities to do a job, "binary" or "two-part" explosives are available. One popular brand is called Kinepak. As embodied in the commercially available product Kinepak, two individual, nonexplosive components are combined by the user to form a cap sensitive explosive. The first component, referred to as "the liquid" is predominantly nitromethane (NM). The other component, referred to as "the solid" is primarily finely divided ammonium nitrate (AN). The commercial product Kinepak is packaged in several different sizes and shapes of plastic bottles as well as foil pouches (bags) which are intended for various applications. In each case, the solid component container is supplied with an appropriate amount of premeasured liquid in another individual container. The liquid component of the Kinepak is classified as a "Flammable Liquid" for transportation purposes. The solid component is classified as an "Oxidizer". Although both are considered hazardous materials, neither is defined as an explosive for transportation (U.S. Department of Transportation, DOT regulations) or storage (U.S. Bureau of Alcohol, Tobacco and Firearms, ATF regulations).

In order to use Kinepak, the liquid component is simply poured into the solid component. Within about five to fifteen minutes, the liquid (which is usually colored red) will soak down to the bottom of the container, as evidenced by the pink color. At this point, it has the consistency of moist powder and is a cap sensitive, high explosive. It can be used in most situations where it would be suitable to use cartridged explosives such as dynamite, water gels and small diameter emulsions. Kinepak is used as an example here because it is, at the time of this writing, one of the only two commercially available two-component explosives. The only other known commercial product is marketed under the name Binex. Binex uses a two component system of an aqueous solution of sodium perchlorate and aluminum powder. When these two components are combined, a liquid explosive is formed that is cap sensitive. It is believed that this composition would not be a viable product as a replacement for cartridged explosives because of the high cost and the environmental concerns with the sodium perchlorate solution. However, there is a current military application where this product is used to blast fox holes in conjunction with an entrenchment kit for soldiers. It is known that this explosive has detonation velocity that is much lower than Kinepak and other commercial cartridged explosives. In the case of the military application, this is an advantage as lower velocity explosives are generally better for cratering in soil. There are many other possible candidates for use as binary explosives. However, most of these others would not be viable for consideration as commercial products for the following reasons: toxicity of the components and/or detonation products; stability of the components before and after mixing; shelf life; cost; ease/difficulty of mixing; no advantages when compared to ammonium nitrate/nitromethane systems (Kinepak). In most binary systems, one of the components is an oxidizer (ammonium nitrate, sodium perchlorate) and the other is a fuel (nitromethane, aluminum). As with all explosives, the potential uses and effects are determined by several properties such as detonation velocity, density, gas production, etc. Effects on a specific target can be influenced by container size, shape and confinement. For example, configuring the explosive in a shaped charge container will cause more of the available energy to be focused toward a given target than would be possible otherwise. The type of initiation system required and utilized will also have an effect, especially with blasting agents such as ANFO. Ammonium nitrate and nitromethane (AN-NM) binary systems such as Kinepak work very well for their intended purpose. They have the following advantages over conventional explosives: The components are not explosives before mixing; The components do not have to be transported as explosives; The components do not have to be stored as explosives (in most places) therefore do not require expensive storage "magazines". These advantages are due to the fact that they are mixed on site just before using. However, there are a few disadvantages: Mixing can be time consuming; Shelf life of the ammonium nitrate powder can be short depending on conditions, particularly temperature; Can cost 2 to 3 times more than conventional explosives . Although other systems besides AN-NM exist, there has not been a commercially viable product available as a substitute for conventional small diameter cartridge explosives. There are other binary systems based on nitroparaffins such as nitromethane, nitroethane, nitropropanes, etc. These nitroparaffins are very interesting materials. Under the right circumstances, they can act as a fuel (as when combined with ammonium nitrate) an

oxidizer or a stand alone explosive, especially nitromethane. However, they are too insensitive to be used as explosives as is. There are ways to utilize nitroparaffins as the basis of a binary system. A stable explosive composition can be made by adding a sensitizer, in the form of resin balloons, to nitromethane. It is well known that amines (particularly ethylenediamine) will sensitize nitromethane so that it will detonate with a blasting cap. These mixtures become unstable and decompose after a few days. Most of these sensitizing agents are very toxic and difficult to work with safely. The basis of this patent is that by entrapping air into the nitromethane liquid, by means of micro balloons (resin, glass, etc.), it can be made capsensitive. However since the balloons will float to the surface of pure nitromethane, a thickening (gelling) agent must be added to prevent this. A foamable nitromethane composition can be made by the addition of stabilizers, thickeners, sensitizing and foaming agents. It also teaches the addition of metals, including aluminum, to enhance the total energy of the system. The idea is that the foam would be applied to a mine field and then detonated. Two problems with this method is the very low density of the foam, thus low velocity. Another problem is the useable life of the foam after its application. This would greatly vary depending on conditions such as temperature, wind, sunlight, etc. It is commonly known that the addition of aluminum to many explosive compositions (usually water gels) not only adds energy, but also increases its sensitivity. The addition of aluminum to typical water gel mixtures uses aluminum coated with stearic acid which give it a hydrophobic property. This causes air bubbles to cling to the surface of the aluminum particles. The incorporation of air bubbles into explosive mixtures increases the sensitivity. Mixtures of nitromethane and nitroethane are used as an oxidizing liquid and aluminum fuel granules having an average particle size within the range of 1/64 to 1/4 inch and an average bulk density within the range of 0.2 to 1.0 grams/cc. The resultant explosive is a blasting agent requiring a one pound booster for initiation, not a cap sensitive, small diameter mixture. Pure nitromethane is actually a very powerful explosive. However, without the addition of some additives or modifiers, it is so insensitive that it is classified as a "Flammable Liquid" for transportation purposes. Pure nitromethane will not usually detonate unless it is subjected to extreme shock and/or confinement at elevated temperatures. Most of the efforts to make a usable nitromethane based explosive have centered on adding dangerous amine compounds and/or incorporating entrapped air bubbles by some means. These air bubbles, while having the desired result of sensitization, have the undesired result of decreasing the density, and thereby lowering the velocity. Further, since these air bubble means are non-energetic, the per unit volume energy is also decreased. Although ammonium nitrate and nitromethane systems provide a good product, a binary explosive with a higher velocity and total energy would be able to perform tasks that are currently not possible. There are many commercial and military applications where such an explosive would be very useful. If this new binary explosive was in liquid form after mixing, it would be particularly attractive because of its ability to be poured into and fill any container. _____________________________________________________________________________ ______________________________________________________________

Novel Energetic Materials Novel Energetic Materials consists of fundamental research programs to expand and validate physics-based models and experimental techniques to devise chemical formulations that will enable the design of novel insensitive high-energy propellants and explosives with tailored energy release for revolutionary Future Force lethality and survivability. This program supports demonstration of advanced energetic materials with ability to tune energy release for precision munition & counter-munition applications (e.g., propellants, explosives, thermobarics, multi-purpose warhead, APS). These energetic materials may have the potential of providing factors of 3 to 4 in increased energy release rate compared with conventional formulations. The Army's Novel Energetic Materials for the Objective Force effort seeks to mature advanced energetic materials to provide a 40% increase in deliverable energy from advanced gun propellant systems and a 20-50% increase in warhead effectiveness (munitions, active protection). DoD and DOE continue to have very similar requirements for energetic materials. Both agencies desire high explosives with increased or tailored performance and decreased sensitivity, and recent accomplishments have benefited both agencies. Like advanced initiation, improved energetic materials are enabling technology for the next generation of weapon systems that will be safer, smaller and more lethal. Under this program a combination of evolutionary and novel technologies are under development. Conventional chemistry has been used to develop more powerful, less sensitive explosives. Nano-structured and engineered materials are being explored to increase energy density and energy on target by factors of three or more. Higher risk efforts are also underway to explore the possibility of metastable High Energy Density Materials (HEDM). Using conventional chemistry, a number of new candidate molecules have been synthesized, characterized and formulated. The development of new materials is based on theoretical molecular design. The structure, performance and sensitivity of new molecules are predicted computationally, then synthesis is attempted. The focus is in two areas: molecules with significantly increased energy over current materials and very insensitive materials with reasonable energies. Energetic materials consist of fuels and oxidizers which are intimately mixed. This is done by incorporating fuels and oxidizers within one molecule or through chemical and physical mixtures of separate fuel and oxidizer ingredients. The material may also contain other constituents such as binders, plasticizers, stabilizers, pigments, etc. Traditional manufacturing of energetic materials involves processing granular solids into parts. Materials may be pressed or cast to shape. Performance properties are strongly dependent on particle size distribution, surface area of the constituents, and void volume. In many cases achieving fast energy release rates, as well as insensitivity to unintended initiation, necessitates the use of small particles (.ltoreq.100 .mu.m) which are intimately mixed. Reproducibility in performance is adversely affected by the difficulties of synthesizing and processing materials with the same particle morphology and distribution uniformity. Manufacturing these granular substances into complex shapes is often difficult due to limitations in processing highly solid filled materials. An example of an existing limitation of processing granular solids is in manufacturing

energetic materials for detonators. The state-of-the-art now requires the precise synthesis and recrystallization of explosive powders. These powders typically have high surface areas (e.g., >1 m.sup.2/g). The powders are weighed and compacted at high pressures to make pellets. Handling fine grain powders is very difficult. Dimensional and mechanical tolerances may be very poor as the pellets may contain little or no binder. Changes in the density and dimensions of the pellets affect both initiation and detonation properties. Manufacturing rates are also low as the process is usually done one at a time. Certification of material is typically done by expensive, end-use detonation performance testing and not solely by chemical and physical characterization of the explosive powder. As these detonators or initiating explosives are sensitive, machining to shape pressed pellets is typically not done. Another current limitation is producing precise intimate mixtures of fuels and oxidizers. The energy release rates of energetic materials are determined by the overall chemical reaction rate. Monomolecular energetic materials have the highest power as the energy release rates are primarily determined by intramolecular reactions. However, energy densities can be significantly higher in composite energetic materials. Reaction rates (power) in these systems are typically controlled by mass transport rates of reactants. In general, initiation and detonation properties of energetic materials are dramatically affected by their microstructural properties. It is generally known in material science that the mechanical, acoustic, electronic, and optical properties are significantly and favorably altered in materials called "nanostructures," which are made from nanometer-scale building blocks. Modern technology, through sol-gel chemistry, provides an approach to control structures at the nanometer scale, thus enabling the formation of new energetic materials, generally having improved, exceptional, or entirely new properties. Since the invention of black powder the technology for making solid energetic materials has remained either the physical mixing of solid oxidizers and fuels, referred to as composite energetic materials (e.g., black powder); or the incorporation of oxidizing and fuel moieties into one molecule, referred to as monomolecular energetic materials (e.g., trinitrotoluene, TNT). The basic distinctions between these prior known energetic composites and energetic materials made from monomolecular approaches are as follows. In composite systems, desired energy properties can be attained through readily varied ratios of oxidizer and fuels. A complete balance between the oxidizer and fuel may be reached to maximize energy density. Current composite energetic materials can store energy as densely as >23 kJ/cm.sup.3. However, due to the granular nature of composite energetic materials, reaction kinetics are typically controlled by the mass transport rates between reactants. Hence, although composites may have extreme energy densities, the release rate of that energy is below that which may be attained in a chemical kinetics controlled process. In monomolecular energetic materials the rate of energy release is primarily controlled by chemical kinetics, not by mass transport. Therefore, monomulecular materials can have much greater power than composite energetic materials. A major limitation with these monomolecular energetic materials is the total energy density achievable. Currently, the highest energy density for monomolecular materials is approximately 12 kJ/cm.sup.3, about half that achievable in composite systems. The reason for this is that the requirement for a chemically stable material and the current state of the art synthetic procedures limit both the oxidizer-fuel balance and the physical density of the material.

The overall goal is to engineer multi-dimensional nanoscale energetic materials systems whose energy release can be controlled in terms of its type, rate, spatial distribution, and temporal history. The goal is to manipulate individual atoms and molecules and control their assembly into a large-scale bulk energetic material. The possibility exists to build large-scale energetic materials with a very high degree of uniformity (few/no defects, perfect crystalline structure, composites with molecularly engineered uniformity, laminated composites with structures built molecularly controlled and selectable layers - no stirring, mixing - - all done through self-assembly). It is also possible to embed molecular scale devices within the energetic matrix (embedded smart devices and sensors). The current emphasis in the nanoscale energetic materials area is on the preparation and characterization of single nanoscale energetic particles. These particles are then utilized in an otherwise conventional composite formulation, incorporating the nanoparticles (typically aluminum, the fuel) in a matrix with micron-sized oxidizer particles. While there is some performance improvement, the full extent of the anticipated performance gains of the nanoscale materials have not been realized. In large measure this is due the incompatibility of the length scales. What is needed is a formulation with all constituents at the nanoscale. If this were accomplished, the reactivity of the material would be characterized by the almost premixed gas-phase reaction rates of the nanomaterials; not limited by the slower, diffusion dominated reactions of micron-sized constituents. It may also be expected that the much smaller crystalline sizes of nanomaterials would be much less susceptible to shear-induced initiation and may be less responsive to some hazards. Macroscale formulations of energetic materials that preserve the intrinsic nanoscale structure of the individual components are needed to realize the true potential of nanoscale energetic materials. An optimal material may be a macroscale threedimensional, ordered array of nanoscale constituents, with spacing and interstitial/bonding materials chosen to optimize both stability and reactivity. At a minimum, these macroscale units would be on the order of millimeter size, which could then be processed into the centimeter to meter sizes needed for practical propellants and explosives. The advantages of this “bottom-up” approach to energetic materials are: a) developing a fundamental understanding of the evolution of properties with the size of the system, b) understanding the effects of the interaction of matter at different molecular-length scale with external stimuli, and c) developing a detailed understanding of the functionalities of matter at molecular-length scale. The chemistry, physics and materials science of nanoscale energetic material preparation need to be developed, focusing on those processes that lead to well ordered structures, e.g. self-assembly, vapor deposition, etc. Computational methods are needed to assess the reactivity of candidate structures and to predict the stability of the energetic material structure, to both hazards (shock, spark, etc.) and to long-term degradation. These computations should also provide guidance to and receive validation from the experimental aspects of the program, specifically the formulation and characterization activities. Experimental methods of characterizing nanoenergetic structures are needed to verify structure and performance. This includes developments of techniques capable of the determination of the threedimensional structure of the nanoscale assembly and the orientation and bonding of the constituents. Characterization of reaction front progress

through the nanostucture is also desirable. This research program will enable molecularly manipulated energetic materials and formulations with tuned chemical and physical properties, high performance, low sensitivity, and multifunctionality (a single smart material that can function as a structural material, embedded sensor, and have real-time selectable propellant, explosive, or nonlethal functionality within a precision munition). Novel Energetic Materials science and technology is recognized as a critical enabler in support of changing force structure for advanced weapons platforms. Nanoenergetic materials are a key area highlighted by the DDR&E/ OUSD (S&T) “National Advanced Energetics Program”. That initiative is funding the first generation materials. The program supports the ARL-led STO IV.WP.2003.01 “Novel Energetic Materials for the Objective Force”, the DTO WE.70 “Novel Energetics” in which ARL is a partner, the provisional SRO “Insensitive High Energy Materials” which ARL leads, the OSD Office of Munitions efforts on “Insensitive Munitions”, and DTAP/Reliance “Advanced Gun Propulsion” which ARL leads. This program will provide the next generation novel energetic materials. One new explosive under development is LLM-105. It is dense, thermally stable and very insensitive. With 30% more energy than TNT it has possible detonator and booster applications and is an alternative to TATB in special purpose weapons such as hard target penetrators that have to survive high shock loading. The synthesis, scale-up, and characterization of this material have been completed and its use as insensitive booster material for Navy weapons applications is now being evaluated. Efforts to crystallize the pure form of a newly synthesized energetic material with predicted energy greater than CL-20, LLM-121 continued in FY 2001. Two other very fast burning materials, BTATz and DHT, have been successfully synthesized and are under evaluation as enhanced performance gun and rocket propellant ingredients. Metastable Intermolecular Composites (MIC) developed under this program were the first successful examples of nano-structured energetic materials with significantly enhanced performance. They demonstrated that tailored, ultra-fine reactant particles could dramatically increase the energy release rate of thermite-like materials and provide twice the total energy of high explosives. The first application of this technology is for lead-free percussion primers for small arms ammunition, and this program is now in engineering development under SERDP funding. The current focus is on the optimization of this material for other weapons applications via better diagnostic and measurement methods. A new bulk process for manufacturing nano-structured energetic materials using sol-gel chemistry has been developed with the promise of precise control of material homogeneity, properties, and geometry. Samples of this material were manufactured this year for testing and evaluation in support of reactive warheads that better couple energy to the target and applications that require very high thermal loading. Extended solid HEDMs are also under development. This work uses intense pressure and temperature to force elements into highly energetic bonding states that can be recovered to ambient conditions. Current synthesis techniques have produced CO-derived solids and a family of novel nitrogen materials, but in very small quantities. These materials are expected to be highly energetic, but characterizing them, and particularly verifying the energy content, has been difficult due to the microscopic quantities of material available.

In 2001 the energy content of laboratory produced high energy density material was preliminarily measured. A special press was installed for production of milligram sample sizes, which can then be characterized more accurately using standard and improved techniques. The creation of the thermochemical code Cheetah represents a major accomplishment of this program. The code predicts the performance of energetic materials including high explosives, propellants and pyrotechnics and reduces the number of tests necessary to develop a new material. Cheetah 3.0 was released in 2001 to DoD, DOE and DoD contractor users. This version includes new equations of state resulting in greatly enhanced stability and accuracy of the code. A major effort is also underway to develop a suite of codes for use in predicting the response of energetic materials in weapon systems subjected to thermal and mechanical insult. The objective is to reduce the number and cost of the current go/no-go insensitive munitions test protocols required to qualify a new system for military use and to improve our understanding of the physical mechanisms and safety margins. A collaborative effort with the Navy was initiated to experimentally assess and validate codes for use in predicting the response of weapon systems including the violence of reaction in cookoff accidents. Quantitative data on cookoff violence have been generated by both the Navy in small-scale experiments and by DOE in the scaled thermal explosion experiments. Data on both HMX based explosives and PBX-109 have been obtained for use in establishing the accuracy and range of validity of the predictive models. The measured properties were used this year to successfully predict the time to explosion in cookoff tests performed by the Navy. In order to preserve and transition the energetic materials technology generated under this program, two explosives databases have been distributed to government laboratories and contractors. One database, HEAT1, contains over 3,000 chemical structures, and is a compilation of measured heats of formation for a wide range of organic molecules of interest to researchers in the weapons community. A second database is APEX, A Pure Explosives Database. This database contains over 500 energetic materials of different molecular structure to guide the synthesis of new materials and ensure the retention of important characterization data. Work in energetic materials was aligned with the recommendations from the DoD 2000 Weapons Technology Area Review and Assessment (TARA) and, in particular, was coordinated with the national initiative in advanced energetic materials. Concern from the DoD 2000 Weapons TARA regarding the need to maintain weapon lethality as weapon and platform size decrease continued to be addressed in efforts to synthesize, characterize and scale-up new energetic materials with increased or tailored performance and decreased sensitivity. The development and characterization of new insensitive and new high-energy, high power materials continued with synthesis based on theoretical molecular design. Efforts to crystallize the new high energy molecule, LLM-121, in its pure form continued. Efforts sponsored under this program continued to exploit opportunities in nano-energetics by developing nano-structured and engineered energetic materials, including sol-gel derived materials, and evaluating their effectiveness and utility for warhead applications. With the completion of the LLM-105 synthesis and scale-up work, efforts will focused on formulation for evaluation and eventual qualification as a Navy booster material. The creation of new HEDMs continued, along with the development and implementation of accurate techniques for determining crystal structure and energy

content of the newly synthesized materials. With the installation of a special press in FY 2001 designed to produce sample sizes of 100mm3, the feasibility of bulk synthesis on CO-derived and nitrogen HEDMs was demonstrated and initial measurements of their energy content with larger sample sizes was completed. The synthesis of additional extended solid HEDMs was explored. With the release of Cheetah 3.0, the emphasis in Cheetah development will turn towards implementing more sophisticated kinetic models into the code that account for differences in explosive microstructure including explosive particle morphology and towards generating more accurate equations of state for detonation products. To support this work, a new impulsive stimulated light scattering spectrometer was used to conduct measurements in a diamond anvil cell to monitor the onset of chemical reactivity at extreme conditions with great accuracy. Efforts to develop and validate computational tools for predicting munition system response to operational threat and accident environments will continue. The first generation of simulation tools for munitions response to accident environments will be exercised against test data to validate the codes and expand their ability to predict weapon system performance and response in accident situations. The joint experimental program with Navy to measure the violence of reaction in cookoff accidents will be expanded to testing and analyses of a full weapon systems. Experiments to determine mechanical property of both fielded high explosives and their constituents continued for development and validation of high explosive mechanical response models. _____________________________________________________________________________ _______________________________________________________________

Insensitive High Explosives [IHE] In an effort to improve munitions survivability and safety, the Department of Defense (through the Joint Requirements Oversight Council) several years ago established a policy requiring all new munitions be capable of withstanding accidents, fires, or enemy attack. One method of addressing this requirement, the use of "Insensitive Munitions" (IM), including propellants and explosives, was mandated. Thus a new class of IM explosives has been developed over the past decade. Because these IM formulations differ somewhat from each other in a variety of ways (physical properties, explosive output, manufacturing process and cost, sensitivity and toxicity, etc.,) the explosive selection process for a given munition has become more complex. They must meet MILSTD-2105, Hazard Assessment Tests, Non-Nuclear Munitions. The US Air Force is developing an insensitive explosive fill for its general use bombs using a mixture of trinitrotoluene (TNT) and aluminum. Since the insensitive fill is not ready to be used in tactical bombs, and there is no available TNT in the stockpile, Joint Munitions Command (JMC) Bombs/Energetics Division awarded an indefinite delivery/indefinite quantity (IDIQ) contract for supply of TNT over a 5-year period to Alliant Ammunition and Powder Co. (AAPC). Virgin TNT will be supplied from a National Technology Industrial Base source, reclaimed and OCONUS TNT. The facility that produces the virgin TNT can be easily modified to produce other energetic materials, notably insensitive explosives. The IDIQ is delivering sufficient quantities of TNT to meet increased requirements. Partnering with major contractors has proved beneficial for current program execution. New partnerships are now being established with AAPC for

TNT and General Dynamics Tactical and Ordnance Systems for bombs. Through these partnerships, communications will be improved, expectations will be better understood, common goals can be set, delivery times improved and problems identified so they can be resolved early on. AFX-757 The Joint Air-to-Surface Stand-off Missile (JASSM) may become the first munition item to obtain insensitive munition (IM) certification and a 1.2.3 hazard classification. Currently, almost all munition items are hazard classified 1.1. This certification and classification reflect improvements in the munition that greatly reduce both the threat for accidental initiation of the item and the severity in case of an inadvertent initiation. The safety implications and reduced costs associated withstorage of such IM-compliant munitions are of significant benefit to boththe US Air Force and Navy customers. With full support of the Air Force Research Laboratory Munitions Directorate's EnergeticMaterials Branch, the JASSM warhead and All-Up-Round passed some of the most difficult tests for obtaining IM certification and a reducedexplosive hazard classification (1.2.3). After a disappointing failure of the first JASSM warhead during sympathetic detonation testing, engineers from Lockheed Martin asked the Energetic Materials Branch to analyze the failure. Drawing on previous experiencein the development of IM-compliant Mk-82 bombs filled with the newly developed AFX-645 explosive, the directorate recommended a non-standard pallet stacking arrangement. This new stacking arrangement mitigates the energy transferred during sympathetic detonation from onemunition to the next. Lockheed Martin engineers tested this configuration in a hydrocode studyand confirmed that the directorate's suggestions did provide a significant improvement for survival. Lockheed Martin further improved this conceptby positioning the JASSM warheads side by side in a nose-to-tailconfiguration. The engineers placed the warhead casings as close aspossible, preventing a sympathetic detonation from occuring. Lockheed Martin engineers performed a new test using this storage configurationand successfully passed the sympathetic detonation criterion. The directorate and Lockheed Martin have accomplished all required IM classification testing. This is a major milestone since it is the first time amajor Air Force weapon system has passed all required IM testing. The Energetic Materials Branch developed AFX-757, the explosive fill used in JASSM, as a replacement for tritonal in the Miniature MunitionTechnology program. Lockheed Martin, the JASSM contractor, chose AFX-757 for their warhead because of its increased blast energy andpotential insensitivity. DNI Dinitroimidazoles Dinitroimidazoles, such as DNI (2,4-dinitroimidazole), are a group of very insensitive explosives. 4,5-dinitroimidazole (45DNI) crystallizes with two crystallographically unique molecules in the monoclinic space group P21/n (#14) with unit-cell parameters a = 11.5360(8) Å, b = 9.071(1) Å, c = 11.822(1) Å, ß = 107.640(6)°, Z = 8, and has a density of 1.781 g/cm3. The molecular packing consists of infinite one-dimensional chains of 45DNI molecules approximately oriented in the ac direction which are linked by two different hydrogen bonds, {\rm [N(1)-\hbox{-}H(1)\cdots N(31)} and {\rm N(11)-H(11)\cdots N(3)]}. In the lateral directions the chains are held together by molecular forces. LX-17 Only the TATB-based formulations of Livermore's LX-17 and Los Alamos's PBX 9502

are considered "insensitive" high explosives (IHE) for nuclear weapons; others are termed "conventional." MNX-194 MNX-194 in a melt castable, wax binder explosive fill to replace TNT in Army M107/M795 155 mm artillery rounds. Munitions Directorate researchers, funded by the US Army Tank-Automotive and Armaments Command/Armament Research, Development and Engineering Center, developed MNX-194, a qualified replacement for Trinitrotoluene (TNT) in both the M107 and M795 155 mm artillery rounds. Directorate researchers from the High Explosives Research and Development Facility developed three compositionally equivalent versions of MNX-194 in which Cyclotrimethylenetrinitramine (RDX) is the sole energetic component. The primary difference between the three versions is the source and/or pretreatment of the RDX component. Directorate researchers characterized all of these novel wax binder explosive formulations for both small-scale safety and shock sensitivity, and performance. Their research also shows RDX is more powerful than TNT in similar test configurations. Additional characterization and optimization work is currently under way. Beyond MNX-194 applications for artillery hardware, the Air Force is considering this formulation as a fill for other Air Force applications. In particular, the directorate is developing an aluminized version of the MNX-194 binder matrix as a potential candidate replacement for the TNT-based fill in Mk-series bombs. The current usage rates and depletion of the Department of Defense stockpile of TNT is causing many program managers to revisit formulation options such as the directorate's bomb fill replacement effort. With a melting temperature similar to that of TNT (~80°C) and the ease of processing this wax binder system, the Air Force considers MNX-194, or modifications thereof, an ideal contender for any TNT replacement program. PAX Since the mid 1980s, Picatinny has developed over 24 Picatinny Arsenal Explosive (PAX) formulations. New combinations of energetic "fill" binders and, in some cases, plasticizers continue to be evaluated in search of the Army's next generation more powerful explosive. One of the most significant challenges to Picatinny was the development of a new main charge melt-pour energetic, PAX-21. This new explosive is designed to be low cost and requires little or no refacilitization for production or projectile filling. It contains no TNT and is slightly less toxic than the Composition-B it replaces. Not only is it safe for use in production, PAX-21 also exhibits good IM and thermal stress characteristics and low shock sensitivity. PAX-2A was the Army's first high performing IM (insensitive munition) explosive. It is less sensitive to initiation by outside stimuli, but retains all the requisite performance capabilities of the high explosive that was used in the past. It has matured through extensive loading, performance testing and hazard threat analysis testing in various current and future warhead configuration of the Army, Navy, and Air Force munitions systems. This IM explosive is now considered to be a viable alternative to current HMX formulations and has been successfully demonstrated in Hellfire, Javelin, M830A1, HEWAM, SADARM, and XM915 Dual Purpose Improved Conventional Munitions (DPICM) XM80 grenade submunitions. The vast majority of cannon lunched unitary warheads use melt pour explosives for cost

and surge capability. Traditional melt pour explosives have focused on fragmentation capability. A new family of low cost reduced sensitivity melt pour explosives based on 2,4-dinitroanisole, RDX or HMX and AP has been developed in response to Insensitive Munition [IM] requirements. Development of Insensitive Munition [IM] melt pour explosives has been next to none. Picatinny Arsenal and Thiokol Propulsion developed the first melt pour explosive (PAX21) to exhibit IM properties (currently in production). The PAX-21 success led to increased interest in all areas of IM melt pour explosives I.e., cost, producibility, facilitization, etc. Family of PAX • PAX-21- Comp B replacement: RDX, DNAN, AP and trace amounts of MNA (for processability) currently in production • PAX-24 - TNT replacement: DNAN, AP and MNA • PAX-25 - Comp B replacement: RDX, DNAN, AP and MNA (different proportions for RDX, DNAN, and AP) better performance than PAX-21 • PAX-26 - Tritonal replacement: DNAN, Al, AP, MNA • PAX-28 - Unitary warheads: RDX, DNAN, Al, AP, MNA. An equivalency factor of 1.62 was determined between Composition B and PAX-28 • PAX-40 - Octol replacement: HMX, DNAN, MNA • PAX-41 - Cyclotol replacement: RDX, DNAN, MNA One advantage is the ease of loading of melt pour explosives into various munition items. Typically less expensive than pressed explosives to manufacture, load and facilitization. Increased IM characteristics without decreasing performance. Performance and shock sensitivity can be tailored for a given system based on particle size and the percentage of ingredients. PAX-40 & 41 exceed COMP B's detonation velocity. PAX-40 & 41 are less shock sensitive than COMP B. PBXIH-135 The navy's insensitive munitions advanced development program for high explosives (IMAD/HE) has developed a new insensitive, cast-cured pbx called PBXIH-135. PBXIH135 has enhanced internal blast performance and improved vulnerability and penetration survivability characteristics compared to PBXN-109. PBXIH-135 was subjected to insensitive detonating substance (EIDS) testing to include cap, gap, external Fire, slow cookoff, and friability. The Navy began developing thermobaric explosives in the late 1980's and resumed research and development in the mid 1990's, responding to the need for internal blast explosives to defeat hard and deeply buried structures as evidenced during Operation Desert Storm. NSWC Indian Head scientists developed the PBXIH-135 thermobaric explosive, which not only offers effective blast and thermal effects, but also is extremely insensitive to factors that may cause accidental detonation during transit or storage. The secret to PBXIH-135 is the addition of a precise mixture of aluminum powder, which burns in the hot gases. Long after the initial shock wave, the burning aluminum sends heat and pressure bounding through corridors. In response to the Sept. 11, 2001 terrorist attacks on the United States, the Defense Threat Reduction Agency (DTRA) organized a 60-day joint project with NSWC Indian Head, the Air Force and Department of Energy to identify, test and integrate a solution to deliver a new capability for tunnel defeat. NSWC Indian Head was responsible for the

payload and booster design, as well as loading of the new bombs. After static and flight tests at full-scale tunnel facilities at the Department of Energy's Nevada test site, the program culminated in December with a successful flight test of a laser-guided weapon, containing Indian Head's PBXIH-135 thermobaric explosive, launched from an F-15E Strike Eagle. NSWC Indian Head, along with DTRA and the Air Force, are engaged in a three-year advanced Concept Technical Demonstration of another thermobaric weapon. Indian Head is developing the new payload, which will have superior performance to that of PBXIH-135. PBXN-109 Two different energetic composite formulations can be used in hard target penetrator warheads: PBXN-109 and AFX-757. Four explosive formulations have been evaluated for the Mk-83 warhead. The four candidate formulations: AFX-777, AFX-757, PBXN111 and PBXW-129 were tested against the Mk-83 baseline fill, PBXN-109. Two test series involving the static detonation of a new design Hellfire missile warhead, now designated as a type N thermobaric warhead, were conducted in 2002 to determine fragment spatial, mass, and velocity distributions. The data from the type N tests are compared with the performance of a hellfire type M blast-frag warhead (BFWH) loaded with the conventional explosive PBXN-109. Of particular interest in the tests was the assessment of thermobaric phenomena with regard to warhead effectiveness. The cookoff of energetic materials involves the combined effects of several physical and chemical processes. These processes include heat transfer, chemical decomposition, and mechanical response. The interaction and coupling between these processes influence both the time-to-event and the violence of reaction. The prediction of the behavior of explosives during cookoff, particularly with respect to reaction violence, is a challenging task. To this end, a joint DoD/DOE program has been initiated to develop models for cookoff, and to perform experiments to validate those models. In this paper, a series of cookoff analyses are presented and compared with data from a number of experiments for the aluminized, RDX-based, Navy explosive PBXN-109. Computational tools are being developed to predict the response of Navy ordnance to abnormal thermal (cookoff) events. The Naval Air Warfare Center 1 (NAWC) and Naval Surface Warfare Center (NSWC) are performing cookoff experiments to help validate DOE computer codes and associated thermal, chemical, and mechanical models. Initial work at the NAWC is focused on the cookoff of an aluminized, RDX-based explosive, PBXN-109 that is initially confined in a tube with sealed ends. The tube is slowly heated until ignition occurs. The response is characterized using thermocouples, strain gauges, and high-speed cameras. A modified version of this system is being developed at the NSWC. The designs of these cookoff systems are relatively simple to facilitate initial model development. An effort is being made to achieve a wide range of results for reaction violence. Lawrence Livermore National Laboratories (LLNL) and Sandia National Laboratories (SNL) are developing computer codes and materials models to simulate cookoff for ordnance safety evaluations. The computer program ALE3D from LLNL is being used to simulate the coupled thermal transport, chemical reactions, and mechanical response during heating and explosion 2 . SNL is employing multiple computer codes in a parallel effort 3,4,5 . For the analysis of PBXN-109 cookoff, Schmitt et al.6 performed an initial survey of measured materials properties and provided estimates for several others.

RS-RDX Reduced Sensitivity RDX In the late 1990s SNPE (SME now Eurenco) marketed an "insensitive" form of RDX (IRDX®) produced by the Woolwich synthesis. It employed proprietary recrystallization process. This produced RDX that displayed reduced sensitivity to shock initiation as measured by Large Scale Gap Test. In 2001 Army pursued an FCT program to evaluate IRDX® in 155 mm projectile with the goal to determine whether IRDX® would improve the IM characteristics of the projectile and to determine whether the SNPE crystallization process could be implemented at Holston (Bachmann synthesis) to produce reduced sensitivity RDX. SNPE recrystallized HSAAP RDX into IRDX®. The US Army, Navy and AF evaluated 2 formulations using both IRDX® and HSAAP IRDX®: Wax-based melt castable explosive (Air Force); and Cast curable PBX explosive (Navy). They conducted performance and IM testing. Upon aging, the HSAAP RDX recrystallized by SNPE did not retain the original "insensitive" characteristics. Subsequently, other manufacturers claimed to produce forms of RDX that exhibit reduced sensitivity to shock relative to conventional RDX as produced by the Bachman process. In 2003, Army published a sources sought solicitation. The following manufacturers are now claiming to make Reduced Sensitivity RDX (RS-RDX): EUROENCO (aka SNPE): IRDX®; Australian Defence Industries (ADI): Grade A RDX; Royal Ordnance Defence (RO): Type I RDX; and Dyno Nobel: RS-RDX. Of these, only Dyno employs the Bachman process. What makes RDX insensitive? No definitive explanation has been offered for the insensitivity of the RDX from these manufacturers. Crystal quality of some sort appears to be involved. No parameter that can be measured on the crystalline material has been identified that will enable one to distinguish between relatively more sensitive and relatively less sensitive forms. TATB (triamino-trinitrobenzene) One of the most important accomplishments made by nuclear weapons laboratories' chemists in the past two decades has been the formulation of powerful conventional high explosives that are remarkably insensitive to high temperatures, shock, and impact. These insensitive high explosives (IHEs) significantly improve the safety and survivability of munitions, weapons, and personnel. The Department of Energy's most important IHE for use in modern nuclear warheads is TATB (triamino-trinitrobenzene) because its resistance to heat and physical shock is greater than that of any other known material of comparable energy. The Department of Energy currently maintains an estimated five-year supply of TATB for its Stockpile Stewardship and Management Program, which is designed to ensure the safety, security, and reliability of the U.S. nuclear stockpile. The Department of Defense is also studying the possible use of TATB as an insensitive booster material, because even with its safety characteristics, a given amount of that explosive has more power than an equivalent volume of TNT. The compound 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) is a reasonably powerful high explosive (HE) whose thermal and shock stability is considerably greater than that of any other known material of comparable energy. The high stability of TATB favors its use in military2 and civilian applications3 when insensitive high explosives are required. In addition to its applications as a HE, TATB is used to produce the important intermediate benzenehexamine. Benzenehexamine has been used in the preparation of

ferromagnetic organic salts and in the synthesis of new heteropolycyclic molecules such as 1,4,5,8,9,12-hexaazatriphenylene (HAT) that serve as strong electron acceptor ligands for low-valence transition metals. In addition to its military uses, TATB has been proposed for use as a reagent in the manufacturing of components for liquid crystal computer displays. The use of TATB to prepare components of lyotropic liquid-crystal phases for use in display devices is the subject of a German patent. There is also interest in employing the explosive in the civilian sector for deep oil well explorations where heat-insensitive explosives are required. Despite its broad potential, the high cost of manufacturing TATB has limited its use. Several years ago, TATB produced on an industrial scale in the U.S. was priced at $90 to $250 per kilogram. Today it is available to customers outside DOE for about $200 per kilogram. In response to a need for a more economical product, chemists at Lawrence Livermore have developed a flexible and convenient means of synthesizing TATB as well as DATB (diamino-trinitrobenzene), a closely related but less well known IHE developed by the U.S. Navy. The initial phase of this work was funded by the Department of Defense (U.S. Navy) to explore the chemical conversion of surplus energetic materials to higher value products as an alternative to detonation. The Lawrence Livermore process--also called the VNS (vicarious nucleophilic substitution) process--should be able to produce TATB for less than $90 a kilogram on an industrial scale in about 40% less manufacturing time. The process also offers significant advantages over the current method of synthesis in environmental friendliness, for example, by avoiding chlorinated starting materials. TNAZ 1,1,3 Trinitroazetidine (TNAZ) is a material that is more powerful, but less-sensitive than HMX. The advent of the new high-energy explosive CL-20 and TNAZ present the possibility of increased performance high explosives with reduced sensitivity. A nitrogen-rich compound, TNAZ can itself be melted and moulded. But money was an issue. It costs just a few tens of dollars to produce a kilogram of HMX or RDX, but about $200 to create the same amount of TNAZ. Most of the effort for producing the next generation of energetic materials is currently centered around the production of 1,3,3-trinitroazetidine (TNAZ). Researchers have evaluated five synthetic routes for producing TNAZ. The two most likely methods to manufacture TNAZ in a sustainable green manufacturing process are those due to Axenrod, and Coburn and Hiskey. work funded by ARDEC led to the synthesis and process for the commercial scale-up of 3,3,1-trinitroazetidine (TNAZ), a strained ring Heterocyclic nitramine. TNAZ is one of the few new energetic materials found to be thermally stable above its melting point. However, in formulations studies, it has been found that TNAZ has high volatility that will severely inhibit its utility in military explosive and propellant applications. Further limitations to its use include the processing, polymorph, and material costs. _____________________________________________________________________________ ______________________________________________________________

Insensitive Munitions (IM) Under their normal conditions of use, modern munitions are both effective—they provide an essential military capability— and relatively safe—they are very unlikely to explode

or burn spontaneously-despite the fact that they are composed primarily of very hazardous material. Under very severe conditions, however, their dangerous nature comes to light. The energetic materials—high explosives, gun propellants, rocket propellants—that are found in munitions of all types are sensitive to heat and to mechanical shock, so they may be triggered by fire or by impact with bullets or fragments. Such secondary effects are significant: in the Gulf War, for example, most of the disabling damage to fighting vehicles was found to be caused by their own munition payloads, inadvertently triggered by unwanted stimuli. A range of energetic materials can be used in low-risk munitions: explosives and propellants less vulnerable than their predecessors to both slow and rapid heating ("cook off") and to impact by bullets or fragments of exploding shells. For warheads, efforts concentrate on the replacement of explosives such as TNT, which is very sensitive to heat and shock, by more stable plastic-bonded explosives, which are better able to withstand adverse condi-tions. For gun propellants, the single, double and triple-base formulations now in service can be replaced by others based on components that are more energetic, but less sensitive. These new explosives and gun propellants are made primarily with energetic crystals such as RDX and HMX, contained in new energetic binders and plasticizers. Some of these formulations not only match the performance of the munitions they replace, they improve on it. An insensitive munition is one that will not detonate under any conditions other than its intended mission to destroy a target. If it is struck by fragments from an explosion or hit by a bullet, it will not detonate. It also will not detonate if it is in close proximity to a target that is hit. In extreme temperatures, the missile will only burn (no detonation or explosion). This increased safety allows greater numbers of missiles to be packaged, handled, stored, and transported in smaller containers. Passing these requirements addresses higher levels of safety performance and means the system is safer to operate in any environment while maintaining its highly lethal performance. It also allows for cost saving opportunities for the government. To reduce the chance of accidental explosions and fires, the Navy, Air Force, and Army are replacing existing main charge explosives with new, more insensitive explosives such as PBXN-103 and PBXN-109. For safety, the Navy, Air Force, and Army are replacing present main charge explosives with insensitive main charge explosives having critical diameters greater than 1 inch. The critical diameter for an explosive is the minimum diameter mass of that explosive that can be detonated without being heavily confined. Future underwater and bombfill explosives will have critical diameters greater than one inch. Two examples of these insensitive main charge explosives are PBXW-124 (27% NTO, 20% RDX, 20% aluminum, 20% ammonium perchlorate, and 13% binder by weight) which has a critical diameter of between 3 and 4 inches, and PBXW-122 (47% NTO, 5% RDX, 15% aluminum, 20% ammonium perchlorate, and 13% binder by weight) which has a critical diameter of 7 inches. Existing booster explosives and fuses have insufficient energy output to reliably initiate the new insensitive main charge explosives. Increasing the amount of booster explosive will increase the weapon's sensitivity and the chance of an accidental detonation. Moreover, the existing Department of Defense (DOD) inventory of fuses and booster explosives is very large and cannot be replaced without considerable cost. What is needed

is an inexpensive method of reliably initiating the new, more insensitive main charge explosive while at the same time reducing the chance of the accidental initiation of a fuse booster system. There is a desire to move away from trinitrotoluene (TNT) based fills since there is no longer a CONUS producer of TNT in existence. Therefore, it is desirable to develop General Purpose (GP) bombs (500 and 2000 pound class), which contain a non-TNT based high explosive fill that also meets all of the IM criteria as specified in MIL-STD2105B. Reaching a 1.2.3J hazard classification allows for significantly higher storage densities than the previous highest classification, which means that it saves in facility storage, handling, and transportation expenditures. _____________________________________________________________________________ ______________________________________________________________

Dense Inert Metal Explosive (DIME) In mid-October 2006 a team of investigative journalists at RAI Italian television reported that Israel had been using a new weapon in the Gaza Strip, similar to DIME – dense inert metal explosive. The report was produced by the same journalists who claimed without foundation that the US used White Phosphorus (WP) against civilians during attacks on Fallujah. According to the Israeli daily Haaretz, the weapon was launched from drones in the summer of 2006, most of them in July, and led to "abnormally serious" physical injuries. Physicians in the Gaza Strip noted the pattern of wounds they were treating were unusual, with severed legs that showed signs of severe heat at the point of amputation but no metal shrapnel. The American version is still in a testing stage and had not been used on the battlefield at that time. It has not been "declared an illegal weapon", though the weapon was claimed [without described basis] to be "highly carcinogenic and harmful to the environment". Dense Inert Metal Explosive (DIME) is uniquely suited for Low Collateral Damage. It produces lower pressure but increased impulse in the near field. Far Field damage is reduced (no frags/ impulse rolloff). The lethal footprint can be tuned to precision footprint. Strike Weapon Scaling Tests were completed in August of 2004), and full-scale Mk-82 tests were in the planning stage as of early 2005. DARPA funded RPG defense system feasibility tests in January 2005, which were successful. Additional Small Diameter Bomb funding would allow the facilities to continue development of a Focused Lethality Munition (FLM) using the Dense Inert Metal Explosive technology integrated into SDB I. With lawmakers' approval, the dollars would allow AFRL to "continue to mature FLM technology. The armament center would integrate the technology with the SDB I baseline model within the advanced technology demonstration construct and demonstrates utility through a flight test program. AFRL is currently utilizing high-fidelity physics-based simulations to aid in the design and testing of low-collateral-damage (LCD) munitions. LCD munitions will benefit the warfighter during urban conflicts where standard munitions would inflict unacceptable collateral damage levels. AFRL partnered with Lawrence Livermore National Laboratory to employ a physics-based code in the design and evaluation of the munitions, which are based on a dense inert metal explosive (DIME) technology. The code requires a DIMEspecific multiphase flow capability to accurately simulate the DIME-type munitions. The laboratory is continually validating this new capability as the program progresses.

AFRL is utilizing this new capability to assist in the design and validation of LCD weapon concepts. The unique simulations provide the testing community with valuable insight in the areas of weapon detonation physics and blast wave interaction with the test's structural targets. The physical fidelity of the code provides valuable data that allows the researchers to accurately quantify the differences between standard and LCD munitions. This capability allows the team to make timely, informed concept decisions and is more cost effective than trial-and-error testing. Increased attention to the employment of precision weapons has decreased the occurrence of unintentional collateral damage. Until now, the development of new munitions to do the same has fallen behind. The AFRL's Munitions Directorate dense inert metal explosive (DIME) concept team successfully demonstrated an effective mechanism to reduce collateral damage, helping the warfighter to prevent the loss of public support and more importantly, the loss of innocent life. AFRL encountered survivability problems of conventional air-blast transducers while measuring the close-in blast environment from DIME charges. In 2002, a specially designed Hopkinson bar gauge was utilized to obtain near-field blast measurements from a DIME charge. However, the 2002 tests produced data at only one distance at normal incidence. AFRL's 20-charge test series in 2004 corrected that problem and produced reflected pressure and impulse data from various distances and angles of incidence, facilitating a lethality analysis of the DIME concept. Scientists used this data to create pressure and impulse maps that detail the near- and far-field magnitudes versus distance and angle of incidence, effectively validating the DIME charge as a low-collateral-damage munition. The Air Force is demonstrating a low collateral damage warhead, allowing a "behind-thewall" threat prosecution with a highly localized lethal footprint. The warhead case consists of a low-density, wrapped carbon-fiber/epoxy matrix integrated with a steel nose and base. The low-density composite case can survive penetration into a one-foot hardened concrete wall. Upon detonation, the carbon-fiber warhead case disintegrates into small non-lethal fibers with little or no metallic fragments, thus significantly reducing collateral damage to people and structures. The warhead explosive fill is a dense inert metal explosive containing fine tungsten particles to provide a ballasted payload with sufficient penetration mass. The tungsten displaces energetic material so as to reduce the total energetic used. The net results are higher dynamic energy impulse all within a small lethal footprint. Previous scaled tests show that the carbon composite casing breaks up into small harmless fibers during the detonation event, effectively removing fragmentation as a lethal mechanism to nearby collateral assets. Thus, near-field airblast with entrained high-velocity inert metal particles are the damage mechanisms for carbon composite cased munitions with DIME fills. Characterization of blast loads from this class of concept munition is essential to verify effectiveness against targets of interest while minimizing collateral damage. Unfortunately, the high-velocity, high temperature inert metal particles found in DIME fills have proved to be extremely damaging to traditional pressure measurement instruments. Hence, new measurement diagnostics had to be developed to investigate DIME formulations. Previous experiments have demonstrated that specially-designed pressure bar gages outfitted with strain gages were capable of measuring applied blast loads from DIME

charges. In 2005, this measurement technology was applied to a series of nine experiments involving full-scale charges with carbon composite casings. Explosive mass and explosive type (two DIME formulations and one conventional high explosive) were varied in the test series. Three pressure bar gages were fielded on each test to characterize the airblast environment produced by each carbon composite cased explosive charge. This paper describes the pressure bar implementation during these experiments, presents results, and comments on the performance of the pressure bars as a measurement diagnostic for this novel class of explosives. _____________________________________________________________________________ ________________________________________________________________

Triacetone Triperoxide (TATP) A new terrorist explosive, triacetone triperoxide (TATP), has recently appeared as a weapon in the Middle East. TATP has been used by suicide bombers in Israel, and was chosen as a detonator in 2001 by the thwarted "shoe bomber" Richard Reid. It can be as or more powerful than military analogs. TATP is one of the most sensitive explosives known, being extremely sensitive to impact, temperature change and friction. Another peroxide-type explosive is hexamethylene triperoxide diamine (HMTD), which is less sensitive than TATP but still dangerous. HMTD is somewhat more sensitive to impact than TCPT, but both are very sensitive explosives. The explosion of TATP is not a thermochemically highly favored event. In conventional high explosives such as TNT, each molecule contains both a fuel component and an oxidising component. When the explosive detonates, the fuel part is oxidised and as this combustion reaction spreads it releases large amounts of heat. The explosion of TATP involves entropy burst, which is the result of formation of one ozone and three acetone molecules from every molecule of TATP in the solid state. Just a few hundred grams of the material produce hundreds of litres of gas in a fraction of a second. The explosion of TATP is similar to the decomposition of azide, for example, which produces nitrogen gas but little heat, is used to fill airbags for cars. TATP is the most extreme example currently known, but it may be possible to design molecules that behave as an even more powerful explosive. TATP can be easily prepared in a basement lab using commercially available starting materials obtained from, e.g., hardware stores, pharmacies, and stores selling cosmetics. TATP is a fairly easy explosive to make, as far as explosives manufacturing goes. All it takes is acetone, hydrogen peroxide (3% medicinal peroxide is not concentrated enough), and a strong acid like hydrochloric or sulfuric acid. I don't recommended mixing up a batch for Independence Day celebrations because it's easy to blow yourself up when you make it. On Dec. 22, 2001, American Airlines Flight 63, carrying a crew of 14 and a passenger complement of 184, including "shoe bomber" Richard Reid, departed Charles de Gaulle Airport in Paris, France, bound for Miami, Florida. Approximately one and a half hours into the flight, a flight attendant smelled what she thought was a burnt match. After the flight attendant determined that it was coming from where Reid was seated, she confronted Reid, at which time he put a match into his mouth. The flight attendant alerted the captain over the intercom system. Reid went on to light another match in an apparent attempt to set fire to his shoe. The flight attendant then noticed a wire protruding from the

shoe. A struggle ensued among several of the flight attendants, passengers and Reid. Ultimately Reid was subdued and restrained for the remainder of the flight. The flight was diverted for landing to Boston's Logan International Airport, where Reid was taken into federal custody. Later analysis by the FBI laboratory in Washington determined that there were two functional improvised explosive devices hidden in Reid's shoes made of the explosive material triacetone triperoxide, known as "TATP," and other components. Richard Reid's shoe had 8 or 10 ounces of triacetone triperoxide and PETN. Because of the wide range of energetic materials and the many differences in their physical properties, several detection devices detect only certain types of explosives and fail to detect others. For example, many detection devices readily detect conventional explosives made of organic nitro and nitrate compounds, but fail to detect explosives made of inorganic nitrates or non-nitrogeneous compounds. In particular, many nitrogenbased detection devices fail to detect explosives such as ANFO (ammonium nitrate in fuel oil), Black Powder ("gun powder" formed from potassium nitrate, sulfur, and charcoal), and triacetone triperoxide (TATP). As a result, such explosives are sometimes referred to as "transparent." _____________________________________________________________________________ _______________________________________________________________

Explosives - Injuries Bombs and explosions can cause unique patterns of injury seldom seen outside combat. The predominant post explosion injuries among survivors involve standard penetrating and blunt trauma. Blast lung is the most common fatal injury among initial survivors. Explosions in confined spaces (mines, buildings, or large vehicles) and/or structural collapse are associated with greater morbidity and mortality. Half of all initial casualties will seek medical care over a one-hour period. This can be useful to predict demand for care and resource needs. Care providers expect an “upside-down” triage - the most severely injured arrive after the less injured, who bypass EMS triage and go directly to the closest hospitals.

Background Explosions can produce unique patterns of injury seldom seen outside combat. When they do occur, they have the potential to inflict multi-system life-threatening injuries on many persons simultaneously. The injury patterns following such events are a product of the composition and amount of the materials involved, the surrounding environment, delivery method (if a bomb), the distance between the victim and the blast, and any intervening protective barriers or environmental hazards. Because explosions are relatively infrequent, blast-related injuries can present unique triage, diagnostic, and management challenges to providers of emergency care. Few U.S. health professionals have experience with explosive-related injuries. Vietnam era physicians are retiring, other armed conflicts have been short-lived, and until this past decade, the U.S. was largely spared of the scourge of mega-terrorist attacks. This primer introduces information relevant to the care of casualties from explosives and blast injuries.

Classification of Explosives Explosives are categorized as high-order explosives (HE) or low-order explosives (LE). HE produce a defining supersonic over-pressurization shock wave. Examples of HE include TNT, C-4, Semtex, nitroglycerin, dynamite, and ammonium nitrate fuel oil (ANFO). LE create a subsonic explosion and lack HE’s over-pressurization wave. Examples of LE include pipe bombs, gunpowder, and most pure petroleum-based bombs such as Molotov cocktails or aircraft improvised as guided missiles. HE and LE cause different injury patterns. Explosive and incendiary (fire) bombs are further characterized based on their source. “Manufactured” implies standard military-issued, mass produced, and quality-tested weapons. “Improvised” describes weapons produced in small quantities, or use of a device outside its intended purpose, such as converting a commercial aircraft into a guided missile. Manufactured (military) explosive weapons are exclusively HE-based. Terrorists will use whatever is available – illegally obtained manufactured weapons or improvised explosive devices (also known as “IEDs”) that may be composed of HE, LE, or both. Manufactured and improvised bombs cause markedly different injuries.

Blast Injuries The four basic mechanisms of blast injury are termed as primary, secondary, tertiary, and quaternary (Table 1). “Blast Wave” (primary) refers to the intense over-pressurization impulse created by a detonated HE. Blast injuries are characterized by anatomical and physiological changes from the direct or reflective over-pressurization force impacting the body’s surface. The HE “blast wave” (over-pressure component) should be distinguished from “blast wind” (forced super-heated air flow). The latter may be encountered with both HE and LE. Table 1: Mechanisms of Blast Injury C at e g Characteristics o r y P ri m a r y

Unique to HE, results from the impact of the overpressurization wave with body surfaces.

Body Part Affected

Types of Injuries

Gas filled structures are most susceptible lungs, GI tract, and middle ear.

Blast lung (pulmonary barotrauma) TM rupture and middle ear damage Abdominal hemorrhage and perforation - Globe (eye) rupture- Concussion (TBI without physical signs of head injury)

S Results from flying debris and e bomb fragments. c o n d a r y

Any body part may be affected.

T Results from individuals being e thrown by the blast wind. rt ia r y

Any body part may be affected.

Q u at e r n a r y

Any body part may be affected.

All explosion-related injuries, illnesses, or diseases not due to primary, secondary, or tertiary mechanisms. Includes exacerbation or complications of existing conditions.

Penetrating ballistic (fragmentation) or blunt injuries Eye penetration (can be occult)

Fracture and traumatic amputation Closed and open brain injury

Burns (flash, partial, and full thickness) Crush injuries Closed and open brain injury Asthma, COPD, or other breathing problems from dust, smoke, or toxic fumes Angina Hyperglycemia, hypertension

LE are classified differently because they lack the self-defining HE over-pressurization wave. LE’s mechanisms of injuries are characterized as due from ballistics (fragmentation), blast wind (not blast wave), and thermal. There is some overlap between LE descriptive mechanisms and HE’s Secondary, Tertiary, and Quaternary mechanisms. Table 2: Overview of Explosive-Related Injuries Syst em Aud itor y Eye , Orb it,

Injury or Condition TM rupture, ossicular disruption, cochlear damage, foreign body Perforated globe, foreign body, air embolism, fractures

Fac e Res pira tory Dig esti ve Circ ulat ory CN S Inju ry Ren al Inju ry Extr emi ty Inju ry

Blast lung, hemothorax, pneumothorax, pulmonary contusion and hemorrhage, A-V fistulas (source of air embolism), airway epithelial damage, aspiration pneumonitis, sepsis Bowel perforation, hemorrhage, ruptured liver or spleen, sepsis, mesenteric ischemia from air embolism Cardiac contusion, myocardial infarction from air embolism, shock, vasovagal hypotension, peripheral vascular injury, air embolism-induced injury Concussion, closed and open brain injury, stroke, spinal cord injury, air embolism-induced injury

Renal contusion, laceration, acute renal failure due to rhabdomyolysis, hypotension, and hypovolemia Traumatic amputation, fractures, crush injuries, compartment syndrome, burns, cuts, lacerations, acute arterial occlusion, air embolism-induced injury

Note: Up to 10% of all blast survivors have significant eye injuries. These injuries involve perforations from high-velocity projectiles, can occur with minimal initial discomfort, and present for care days, weeks, or months after the event. Symptoms include eye pain or irritation, foreign body sensation, altered vision, periorbital swelling or contusions. Findings can include decreased visual acuity, hyphema, globe perforation, subconjunctival hemorrhage, foreign body, or lid lacerations. Liberal referral for ophthalmologic screening is encouraged.

Selected Blast Injuries •

•

Lung Injury “Blast lung” is a direct consequence of the HE over-pressurization wave. It is the most common fatal primary blast injury among initial survivors. Signs of blast lung are usually present at the time of initial evaluation, but they have been reported as late as 48 hours after the explosion. Blast lung is characterized by the clinical triad of apnea, bradycardia, and hypotension. Pulmonary injuries vary from scattered petechae to confluent hemorrhages. Blast lung should be suspected for anyone with dyspnea, cough, hemoptysis, or chest pain following blast exposure. Blast lung produces a characteristic “butterfly” pattern on chest X-ray. A chest X-ray is recommended for all exposed persons and a prophylactic chest tube (thoracostomy) is recommended before general anesthesia or air transport is indicated if blast lung is suspected. Ear Injury Primary blast injuries of the auditory system cause significant morbidity, but are

•

•

easily overlooked. Injury is dependent on the orientation of the ear to the blast. TM perforation is the most common injury to the middle ear. Signs of ear injury are usually present at time of initial evaluation and should be suspected for anyone presenting with hearing loss, tinnitus, otalgia, vertigo, bleeding from the external canal, TM rupture, or mucopurulent otorhea. All patients exposed to blast should have an otologic assessment and audiometry. Abdominal Injury Gas-containing sections of the GI tract are most vulnerable to primary blast effect. This can cause immediate bowel perforation, hemorrhage (ranging from small petechiae to large hematomas), mesenteric shear injuries, solid organ lacerations, and testicular rupture. Blast abdominal injury should be suspected in anyone exposed to an explosion with abdominal pain, nausea, vomiting, hematemesis, rectal pain, tenesmus, testicular pain, unexplained hypovolemia, or any findings suggestive of an acute abdomen. Clinical findings may be absent until the onset of complications. Brain Injury Primary blast waves can cause concussions or mild traumatic brain injury (MTBI) without a direct blow to the head. Consider the proximity of the victim to the blast particularly when given complaints of headache, fatigue, poor concentration, lethargy, depression, anxiety, insomnia, or other constitutional symptoms. The symptoms of concussion and post traumatic stress disorder can be similar.

Emergency Management Options • • • •

•

Follow your hospital’s and regional disaster system’s plan. Expect an “upside-down” triage - the most severely injured arrive after the less injured, who by-pass EMS triage and go directly to the closest hospitals. Double the first hour’s casualties for a rough prediction of total “first wave” of casualties. Obtain and record details about the nature of the explosion, potential toxic exposures and environmental hazards, and casualty location from police, fire, EMS, ICS Commander, regional EMA, health department, and reliable news sources. If structural collapse occurs, expect increased severity and delayed arrival of casualties.

Medical Management Options; • • •

•

Blast injuries are not confined to the battlefield. They should be considered for any victim exposed to an explosive force. Clinical signs of blast-related abdominal injuries can be initially silent until signs of acute abdomen or sepsis are advanced. Standard penetrating and blunt trauma to any body surface is the most common injury seen among survivors. Primary blast lung and blast abdomen are associated with a high mortality rate. “Blast Lung” is the most common fatal injury among initial survivors. Blast lung presents soon after exposure. It can be confirmed by finding a “butterfly” pattern on chest X-ray. Prophylactic chest tubes (thoracostomy) are recommended prior to general anesthesia and/or air transport.

• • • • • • •

Auditory system injuries and concussions are easily overlooked. The symptoms of mild TBI and post traumatic stress disorder can be identical. Isolated TM rupture is not a marker of morbidity; however, traumatic amputation of any limb is a marker for multi-system injuries. Air embolism is common, and can present as stroke, MI, acute abdomen, blindness, deafness, spinal cord injury, or claudication. Hyperbaric oxygen therapy may be effective in some cases. Compartment syndrome, rhabdomyolysis, and acute renal failure are associated with structural collapse, prolonged extrication, severe burns, and some poisonings. Consider the possibility of exposure to inhaled toxins and poisonings (e.g., CO, CN, MetHgb) in both industrial and criminal explosions. Wounds can be grossly contaminated. Consider delayed primary closure and assess tetanus status. Ensure close follow-up of wounds, head injuries, eye, ear, and stress-related complaints. Communications and instructions may need to be written because of tinnitus and sudden temporary or permanent deafness.

Selected Readings Auf der Heide E. Disaster Response: Principles of Preparation and Coordination Disaster Response: Principles of Preparation and Coordination. Quenemoen LE, Davis, YM, Malilay J, Sinks T, Noji EK, and Klitzman S. The World Trade Center bombing: injury prevention strategies for high-rise building fires. Disasters 1996;20:125–32. Wightman JM and Gladish SL. Explosions and blast injuries. Annals of Emergency Medicine; June 2001; 37(6): 664-p678. Stein M and Hirshberg A. Trauma Care in the New Millinium: Medical Consequences of Terrorism, the Conventional Weapon Threat. Surgical Clinics of North America. Dec 1999; Vol 79 (6). Phillips YY. Primary Blast Injuries. Annals of Emergency Medicine; 1986, Dec; 106 (15); 1446-50. Hogan D, et al. Emergency Department Impact of the Oklahoma City Terrorist Bombing. Annals of Emergency Medicine; August 1999; 34 (2), pp Mallonee S, et al. Physical Injuries and Fatalities Resulting From the Oklahoma City Bombing. Journal of the American Medical Association; August 7, 1996; 276 (5); 382387. Leibovici D, et al. Blast injuries: bus versus open-air bombings—a comparative study of injuries in survivors of open-air versus confined-space explosions. J Trauma; 1996, Dec; 41 (6): 1030-5.

Katz E, et al. Primary blast injury after a bomb explosion in a civilian bus. Ann Surg; 1989 Apr; 209 (4): 484-8. Hill JF. Blast injury with particular reference to recent terrorists bombing incidents. Annals of the Royal College of Surgeons of England 1979;61:411. Landesman LY, Malilay J, Bissell RA, Becker SM, Roberts L, Ascher MS. Roles and responsibilities of public health in disaster preparedness and response. In: Novick LF, Mays GP, editors. Public Health Administration: Principles for Population-based Management. Gaithersburg (MD): Aspen Publishers; 2001.

Hazard Classification Code The UN hazard classification system for classifying explosive materials and explosive components is recognized internationally and is used universally by the Department of Defense (DoD), other Department of Energy (DOE) contractors, and the Department of Transportation (DOT). The UN system consists of nine classes of dangerous materials, with explosives designated as Class 1. The explosives hazard class is further subdivided into six divisions, which are used for segregating ammunition and explosives on the basis of similarity of characteristics, properties, and accident effects potential. Hazard class/division 1.1

Mass explosion

1.2

Nonmass explosion, fragment-producing

1.3

Mass fire, minor blast or fragment

1.4

Moderate fire, no blast or fragment

1.5

Explosive substance, very insensitive (with a mass explosion hazard) Explosive article, extremely insensitive

1.6

Unit ed Nati ons Seri al Num ber

Hazard description

Article

Hazar d Classi ficati on Code

354 355 356 350 351 352 353 349 224

ARTICLES, EXPLOSIVE, N.O.S. ARTICLES, EXPLOSIVE, N.O.S. ARTICLES, EXPLOSIVE, N.O.S. ARTICLES, EXPLOSIVE, N.O.S. ARTICLES, EXPLOSIVE, N.O.S. ARTICLES, EXPLOSIVE, N.O.S. ARTICLES, EXPLOSIVE, N.O.S. ARTICLES, EXPLOSIVE, N.O.S. BARIUM AZIDE, dry or wetted with less than 50 per cent water, by weight.

1.1 L 1.2 L 1.3 L 1.4 B 1.4 C 1.4 D 1.4 G 1.4 S 1.1 A

28

BLACK POWDER (GUNPOWDER) COMPRESSED, or BLACK POWDER (GUNPOWDER) IN PELLETS.

1.1 D

27

BLACK POWDER (GUNPOWDER) granular or as a meal.

1.1 D

268 225 42 283 48 444

BOOSTERS WITH DETONATOR. BOOSTERS WITH DETONATOR. BOOSTERS without detonator. BOOSTERS without detonator. CHARGES, DEMOLITION. CHARGES, EXPLOSIVE, COMMERCIAL without detonator.

1.2 B 1.1 B 1.1D 1.2 D 1.1D 1.4 D

445

CHARGES, EXPLOSIVE, COMMERCIAL without detonator.

1.4 S

443

CHARGES, EXPLOSIVE, COMMERCIAL without detonator.

1.2 D

442

CHARGES, EXPLOSIVE, COMMERCIAL without detonator.

1.1 D

59

CHARGES, SHAPED, COMMERCIAL without detonator.

1.1D

441

CHARGES, SHAPED, COMMERCIAL without detonator.

1.4 S

439

CHARGES, SHAPED, COMMERCIAL without detonator.

1.2 D

440

CHARGES, SHAPED, COMMERCIAL without detonator.

1.4 D

288

CHARGES, SHAPED, FLEXIBLE, LINEAR metal clad.

1.1D

237

CHARGES, SHAPED, FLEXIBLE, LINEAR metal clad.

1.4 D

60 383 382 384 249

CHARGES, SUPPLEMENTARY, EXPLOSIVE. COMPONENTS, EXPLOSIVE TRAIN, N.O.S. COMPONENTS, EXPLOSIVE TRAIN, N.O.S. COMPONENTS, EXPLOSIVE TRAIN, N.O.S. CONTRIVANCES, WATER-ACTIVATED with burster, expelling charge or propelling charge.

1.1D 1.4 B 1.2 B 1.4 S 1.3 L

248

CONTRIVANCES, WATER-ACTIVATED with burster, expelling charge or propelling charge.

1.2 L

102 290

CORD (FUSE), DETONATING, metal clad. CORD (FUSE), DETONATING, metal clad.

1.2 D 1.1D

104

CORD (FUSE), DETONATING, mild effect, metal clad.

1.4 D

65 289 66 226

CORD, DETONATING, flexible. CORD, DETONATING, flexible. CORD, IGNITER. CYCLOTETRAMETHYLENETETRANITRAMIN E (HMX; OCTOGEN), WETTED with not less than 15 per cent water, by weight, or CYCLOTETRAMETHYLENETETRANITRAMIN E (HMX; OCTOGEN), DESENSITIZED with not less than 10 per cent phlegmatiser, by weight.

1.1D 1.4 D 1.4 G 1.1 D

391

CYCLOTRIMETHYLENETRINITRAMINE (CYCLONITE; HEXOGEN; RDX) AND CYCLOTETRAMETHYLENETETRANITRAMIN E (HMX; OCTOGEN) MIXTURES, WETTED with not less than 15 percent water by weight, or CYCLOTRIMETHYLENETRINITRAMINE (CYCLONITE; HEXOGEN; RDX) AND CYCLOTETRAMETHYLENETETRANITRAMIN E (HMX; OCTOGEN) MIXTURES, DESENSITIZED with not less than 10 per cent phlegmatiser, by weight.

1.1 D

72

CYCLOTRIMETHYLENETRINITRAMINE (CYCLONITE; HEXOGEN; RDX), WETTED with not less than 15 per cent water, by weight, or CYCLOTRIMETHYLENETRINITRAMINE (CYCLONITE; HEXOGEN; RDX), DESENSITIZED with not less than 10 per cent phlegmatiser, by weight.

1.1 D

630

DETONATOR, ASSEMBLIES, NON-ELECTRIC for blasting.

1.1 B

361

DETONATOR, ASSEMBLIES, NON-ELECTRIC for blasting.

1.4 B

255 30 267 29 74

DETONATORS, ELECTRIC for blasting. DETONATORS, ELECTRIC for blasting. DETONATORS, NON-ELECTRIC for blasting. DETONATORS, NON-ELECTRIC for blasting. DIAZODINITROPHENOL, WETTED with not less than 40 per cent water, by weight (or mixture of alcohol and water).

1.4 B 1.1 B 1.4 B 1.1 B 1.1 A

81 331 82 84 332 241 83 99

EXPLOSIVE, BLASTING, TYPE A. EXPLOSIVE, BLASTING, TYPE B. EXPLOSIVE, BLASTING, TYPE B. EXPLOSIVE, BLASTING, TYPE D. EXPLOSIVE, BLASTING, TYPE E. EXPLOSIVE, BLASTING, TYPE E. EXPLOSIVE, BLASTING,TYPE C. FRACTURING DEVICES, EXPLOSIVE, for oil wells, without detonator.

1.1 D 1.5 D 1.1 D 1.1 D 1.5 D 1.1 D 1.1 D 1.1 D

103 101 105 408 410 409 107 257 106 367 113

FUSE, IGNITER, tubular, metal clad. FUSE, INSTANTANEOUS, NON-DETONATING. FUSE, SAFETY. FUZES, DETONATING with protective features. FUZES, DETONATING with protective features. FUZES, DETONATING with protective features. FUZES, DETONATING. FUZES, DETONATING. FUZES, DETONATING. FUZES, DETONATING. GUANYL NITROSAMINOGUANYLIDENE HYDRAZINE, WETTED with not less than 30 per cent water, by weight

1.4 G 1.3 G 1.4 S 1.1 D 1.4 D 1.2 D 1.2 B 1.4 B 1.1 B 1.4 S 1.1 A

114

GUANYL NITROSAMINOGUANYLTETRAZENE (TETRAZENE), WETTED with not less than 30 per cent water, by weight (or mixture of alcohol and water)

1.1 A

79

HEXANITRODIPHENYLAMINE (DIPICRYLAMINE; HEXYL).

1.1 D

392 393 118

HEXANITROSTILBENE. HEXATONAL, CAST. HEXOLITE, dry or wetted with less than 15 per cent water, by weight.

1.1 D 1.1 D 1.1 D

325 315 314 121 124

IGNITERS. IGNITERS. IGNITERS. IGNITERS. JET PERFORATING GUNS, CHARGED, oil well, without detonator.

1.4 G 1.3 G 1.2 G 1.1 G 1.1D

129

LEAD AZIDE, WETTED with not less than 20 per cent water, by weight (or mixture of alcohol and water).

1.1 A

130

LEAD STYPHNATE (LEAD TRINITRORESORCINATE), WETTED with not less than 20 per cent water, by weight (or mixture of alcohol and water).

1.1 A

133

MANNITOL HEXANITRATE (NITROMANNAITE), WETTED with not less than 40 per cent water, by weight (or mixture of alcohol and water).

1.1 D

135

MERCURY FULMINATE, WETTED with not less than 20 per cent water, by weight (or mixture of alcohol and water).

1.1 A

147 340

NITRO UREA. NITROCELLULOSE, dry or wetted with less than 25 per cent water (or alcohol), by weight.

1.1 D 1.1 D

343

NITROCELLULOSE, PLASTICIZED with not less than 18 per cent plasticizing substance by weight.

1.3 C

341

NITROCELLULOSE, unmodified or plasticized with less than 18 per cent plasticizing substance by weight. NITROCELLULOSE, WETTED with not less than 25 per cent alcohol, by weight.

1.1 D

NITROGLYCERIN, DESENSITIZED, with not less than 40 per cent non-volatile water-insoluble phlegmatiser, by weight.

1.1 D

342 143

1.3C

144

NITROGLYCERIN, SPIRIT OF, with more than 1 per cent but not more than 10 per cent nitroglycerin in solution in alcohol.

1.1D

282

NITROGUANIDINE, (PICRITE), dry or wetted with less than 20 per cent water, by weight.

1.1 D

146

NITROSTARCH, dry or wetted with less than 20 per cent water, by weight.

1.1 D

266

OCTOLITE, (OCTOL), dry or wetted with less than 15 per cent water, by weight.

1.1 D

150

PENTAERYTHRITE TETRANITRATE (PENTAERYTHRITOL TETRANITRATE; PETN), WETTED with not less than 25 per cent water, by weight, or PENTAERYTHRITE TETRANITRATE (PENTAERYTHRITOL TETRANITRATE; PETN), DESENSITIZED with not less than 15 per cent phlegmatiser, by weight.

1.1D

411

PENTAERYTHRITE TETRANITRATE (PETN) with not less than 7 per cent wax, by weight.

1.1 D

151

PENTOLITE, dry or wetted with less than 15 per cent water, by weight.

1.1D

159

POWDER CAKE (POWDER PASTE), WETTED with not less than 35 per cent water, by weight.

1.3 C

433

POWDER CAKE, WETTED with not less than 17 per cent alcohol, by weight.

1.1 C

161 160 173 190

POWDER, SMOKELESS. POWDER, SMOKELESS. RELEASE DEVICES, EXPLOSIVE. SAMPLES, EXPLOSIVE, other than initiating explosive.

1.3 C 1.1 C 1.4 S As appro priate

374 204 375 296 357 358 359 208

SOUNDING DEVICES, EXPLOSIVE. SOUNDING DEVICES, EXPLOSIVE. SOUNDING DEVICES, EXPLOSIVE. SOUNDING DEVICES, EXPLOSIVE. SUBSTANCES, EXPLOSIVE, N.O.S. SUBSTANCES, EXPLOSIVE, N.O.S. SUBSTANCES, EXPLOSIVE, N.O.S. TRINITROPHENYLMETHYLNITRAMINE (TETRYL).

1.1 E 1.2F 1.2 E 1.1F 1.1 L 1.3 L 1.3 L 1.1 D

388

TRINITROTOLUENE (TNT) AND TRINITROTOLUENE MIXTURES OR TRINITROTOLUENE (TNT) AND HEXANITROSTILBENE MIXTURES.

1.1 D

389

TRINITROTOLUENE (TNT) MIXTURES CONTAINING TRINITROBENZENE AND HEXANITROSTILBENE

1.1 D

209

TRINITROTOULENE (TNT), dry or wetted with less than 30 per cent water, by weight.

1.1D

390 220

TRITONAL. UREA NITRATE, dry or wetted with less than 20 per cent water, by weight.

1.1 D 1.1 D

DEPARTMENT OF THE TREASURY Bureau of Alcohol, Tobacco and Firearms COMMERCE IN EXPLOSIVES Commerce in Explosives; List of Explosive Materials Updated: 4/26/02 Pursuant to the provisions of section 841(d) of title 18, United States Code (U.S.C.), and 27 CFR 55.23, the Director, Bureau of Alcohol, Tobacco and Firearms, must publish and revise at least annually in the Federal Register a list of explosives determined to be within the coverage of 18 U.S.C. chapter 40, Importation, Manufacture, Distribution, and Storage of Explosive Materials. This chapter covers not only explosives, but also blasting agents and detonators, all of which are defined as explosive materials in section 841(c) of title 18, U.S.C. Accordingly, the following is the 2002 List of Explosive Materials subject to regulation under 18 U.S.C. chapter 40. It includes both the list of explosives (including detonators) required to be published in the Federal Register and blasting agents. The list is intended to include any and all mixtures containing any of the materials on the list. Materials constituting blasting agents are marked by an asterisk. While the list is comprehensive, it is not all inclusive. The fact that an explosive material may not be on the list does not mean that it is not within the coverage of the law if it otherwise meets the statutory definitions in section 841 of title 18, U.S.C. Explosive materials are listed alphabetically by their common names followed, where applicable, by chemical names and synonyms in brackets. In the 2002 List of Explosive Materials, ATF has added five terms to the list of explosives, has further defined two explosive materials, and has made amendments to two explosive materials to more accurately reference these materials. The five additions to the list are as follows: 1. Azide explosives 2. HMTD [hexamethylenetriperoxidediamine]

3. Nitrate explosive mixtures 4. Picrate explosives 5. TATP [triacetonetriperoxide] We have added these explosive materials to the List because their primary or common purpose is to function by explosion. ATF has encountered the criminal use of some of these materials in improvised devices. ``Nitrate explosive mixtures'' is intended to be an all-encompassing term, including all forms of sodium, potassium, barium, calcium, and strontium nitrate explosive mixtures. The two explosive materials that we have further defined by including their chemical names are listed as follows: 1. DIPAM [dipicramide; diaminohexanitrobiphenyl] 2. EDNA [ethylenedinitramine] The two amendments to previously listed explosive materials are as follows: 1. ``Nitrates of soda explosive mixtures'' has been deleted and replaced with ``Sodium nitrate explosive mixtures'' to reflect current terminology. 2. PBX was previously defined as ``RDX and plasticizer.'' We are changing the definition to reflect that PBX is an acronym for ``plastic bonded explosive.'' This revised list supersedes the List of Explosive Materials dated September 14, 1999 (Notice No. 880, 64 FR 49840; correction notice of September 28, 1999, 64 FR 52378) and will be effective on April 26, 2002. List of Explosive Materials A Acetylides of heavy metals. Aluminum containing polymeric propellant. Aluminum ophorite explosive. Amatex. Amatol. Ammonal. Ammonium nitrate explosive mixtures (cap sensitive). *Ammonium nitrate explosive mixtures (non-cap sensitive). Ammonium perchlorate composite propellant. Ammonium perchlorate explosive mixtures. Ammonium picrate [picrate of ammonia, Explosive D]. Ammonium salt lattice with isomorphously substituted inorganic salts. *ANFO [ammonium nitrate-fuel oil]. Aromatic nitro-compound explosive mixtures. Azide explosives. B Baranol. Baratol. BEAF [1, 2-bis (2, 2-difluoro-2-nitroacetoxyethane)]. Black powder. Black powder based explosive mixtures. *Blasting agents, nitro-carbo-nitrates, including non-cap sensitive slurry and water gel explosives.

Blasting caps. Blasting gelatin. Blasting powder. BTNEC [bis (trinitroethyl) carbonate]. BTNEN [bis (trinitroethyl) nitramine]. BTTN [1,2,4 butanetriol trinitrate]. Bulk salutes. Butyl tetryl. C Calcium nitrate explosive mixture. Cellulose hexanitrate explosive mixture. Chlorate explosive mixtures. Composition A and variations. Composition B and variations. Composition C and variations. Copper acetylide. Cyanuric triazide. Cyclonite [RDX]. Cyclotetramethylenetetranitramine [HMX]. Cyclotol. Cyclotrimethylenetrinitramine [RDX]. D DATB [diaminotrinitrobenzene]. DDNP [diazodinitrophenol]. DEGDN [diethyleneglycol dinitrate]. Detonating cord. Detonators. Dimethylol dimethyl methane dinitrate composition. Dinitroethyleneurea. Dinitroglycerine [glycerol dinitrate]. Dinitrophenol. Dinitrophenolates. Dinitrophenyl hydrazine. Dinitroresorcinol. Dinitrotoluene-sodium nitrate explosive mixtures. DIPAM [dipicramide; diaminohexanitrobiphenyl]. Dipicryl sulfone. Dipicrylamine. Display fireworks. DNPA [2,2-dinitropropyl acrylate]. DNPD [dinitropentano nitrile]. Dynamite. E EDDN [ethylene diamine dinitrate]. EDNA [ethylenedinitramine]. Ednatol.

EDNP [ethyl 4,4-dinitropentanoate]. EGDN [ethylene glycol dinitrate]. Erythritol tetranitrate explosives. Esters of nitro-substituted alcohols. Ethyl-tetryl. Explosive conitrates. Explosive gelatins. Explosive liquids. Explosive mixtures containing oxygen-releasing inorganic salts and hydrocarbons. Explosive mixtures containing oxygen-releasing inorganic salts and nitro bodies. Explosive mixtures containing oxygen-releasing inorganic salts and water insoluble fuels. Explosive mixtures containing oxygen-releasing inorganic salts and water soluble fuels. Explosive mixtures containing sensitized nitromethane. Explosive mixtures containing tetranitromethane (nitroform). Explosive nitro compounds of aromatic hydrocarbons. Explosive organic nitrate mixtures. Explosive powders. F Flash powder. Fulminate of mercury. Fulminate of silver. Fulminating gold. Fulminating mercury. Fulminating platinum. Fulminating silver. G Gelatinized nitrocellulose. Gem-dinitro aliphatic explosive mixtures. Guanyl nitrosamino guanyl tetrazene. Guanyl nitrosamino guanylidene hydrazine. Guncotton. H Heavy metal azides. Hexanite. Hexanitrodiphenylamine. Hexanitrostilbene. Hexogen [RDX]. Hexogene or octogene and a nitrated N-methylaniline. Hexolites. HMTD [hexamethylenetriperoxidediamine]. HMX [cyclo-1,3,5,7-tetramethylene 2,4,6,8-tetranitramine; Octogen]. Hydrazinium nitrate/hydrazine/aluminum explosive system. Hydrazoic acid. I Igniter cord. Igniters.

Initiating tube systems. K KDNBF [potassium dinitrobenzo-furoxane]. [[Page 20866]] L Lead azide. Lead mannite. Lead mononitroresorcinate. Lead picrate. Lead salts, explosive. Lead styphnate [styphnate of lead, lead trinitroresorcinate]. Liquid nitrated polyol and trimethylolethane. Liquid oxygen explosives. M Magnesium ophorite explosives. Mannitol hexanitrate. MDNP [methyl 4,4-dinitropentanoate]. MEAN [monoethanolamine nitrate]. Mercuric fulminate. Mercury oxalate. Mercury tartrate. Metriol trinitrate. Minol-2 [40% TNT, 40% ammonium nitrate, 20% aluminum]. MMAN [monomethylamine nitrate]; methylamine nitrate. Mononitrotoluene-nitroglycerin mixture. Monopropellants. N NIBTN [nitroisobutametriol trinitrate]. Nitrate explosive mixtures. Nitrate sensitized with gelled nitroparaffin. Nitrated carbohydrate explosive. Nitrated glucoside explosive. Nitrated polyhydric alcohol explosives. Nitric acid and a nitro aromatic compound explosive. Nitric acid and carboxylic fuel explosive. Nitric acid explosive mixtures. Nitro aromatic explosive mixtures. Nitro compounds of furane explosive mixtures. Nitrocellulose explosive. Nitroderivative of urea explosive mixture. Nitrogelatin explosive. Nitrogen trichloride. Nitrogen tri-iodide. Nitroglycerine [NG, RNG, nitro, glyceryl trinitrate, trinitroglycerine]. Nitroglycide.

Nitroglycol [ethylene glycol dinitrate, EGDN]. Nitroguanidine explosives. Nitronium perchlorate propellant mixtures. Nitroparaffins Explosive Grade and ammonium nitrate mixtures. Nitrostarch. Nitro-substituted carboxylic acids. Nitrourea. O Octogen [HMX]. Octol [75 percent HMX, 25 percent TNT]. Organic amine nitrates. Organic nitramines. P PBX [plastic bonded explosives]. Pellet powder. Penthrinite composition. Pentolite. Perchlorate explosive mixtures. Peroxide based explosive mixtures. PETN [nitropentaerythrite, pentaerythrite tetranitrate, pentaerythritol tetranitrate]. Picramic acid and its salts. Picramide. Picrate explosives. Picrate of potassium explosive mixtures. Picratol. Picric acid (manufactured as an explosive). Picryl chloride. Picryl fluoride. PLX [95% nitromethane, 5% ethylenediamine]. Polynitro aliphatic compounds. Polyolpolynitrate-nitrocellulose explosive gels. Potassium chlorate and lead sulfocyanate explosive. Potassium nitrate explosive mixtures. Potassium nitroaminotetrazole. Pyrotechnic compositions. PYX [2,6-bis(picrylamino)]-3,5-dinitropyridine. R RDX [cyclonite, hexogen, T4, cyclo-1,3,5,-trimethylene-2,4,6,-trinitramine; hexahydro1,3,5-trinitro-S-triazine]. S Safety fuse. Salts of organic amino sulfonic acid explosive mixture. Salutes (bulk). Silver acetylide. Silver azide.

Silver fulminate. Silver oxalate explosive mixtures. Silver styphnate. Silver tartrate explosive mixtures. Silver tetrazene. Slurried explosive mixtures of water, inorganic oxidizing salt, gelling agent, fuel, and sensitizer (cap sensitive). Smokeless powder. Sodatol. Sodium amatol. Sodium azide explosive mixture. Sodium dinitro-ortho-cresolate. Sodium nitrate explosive mixtures. Sodium nitrate-potassium nitrate explosive mixture. Sodium picramate. Special fireworks. Squibs. Styphnic acid explosives. T Tacot [tetranitro-2,3,5,6-dibenzo- 1,3a,4,6a tetrazapentalene]. TATB [triaminotrinitrobenzene]. TATP [triacetonetriperoxide]. TEGDN [triethylene glycol dinitrate]. Tetranitrocarbazole. Tetrazene [tetracene, tetrazine, 1(5-tetrazolyl)-4-guanyl tetrazene hydrate]. Tetryl [2,4,6 tetranitro-N-methylaniline]. Tetrytol. Thickened inorganic oxidizer salt slurried explosive mixture. TMETN [trimethylolethane trinitrate]. TNEF [trinitroethyl formal]. TNEOC [trinitroethylorthocarbonate]. TNEOF [trinitroethylorthoformate]. TNT [trinitrotoluene, trotyl, trilite, triton]. Torpex. Tridite. Trimethylol ethyl methane trinitrate composition. Trimethylolthane trinitrate-nitrocellulose. Trimonite. Trinitroanisole. Trinitrobenzene. Trinitrobenzoic acid. Trinitrocresol. Trinitro-meta-cresol. Trinitronaphthalene. Trinitrophenetol.

Trinitrophloroglucinol. Trinitroresorcinol. Tritonal. U Urea nitrate. W Water-bearing explosives having salts of oxidizing acids and nitrogen bases, sulfates, or sulfamates (cap sensitive). Water-in-oil emulsion explosive compositions. X Xanthamonas hydrophilic colloid explosive mixture. FOR FURTHER INFORMATION CONTACT: Chad Yoder, ATF Specialist, Arson and Explosives Programs Division, Bureau of Alcohol, Tobacco and Firearms, 650 Massachusetts Avenue, NW., Washington, DC 20226 (202-927-7930). Signed: April 19, 2002. Bradley A. Buckles, Director. [FR Doc. 02-10324 Filed 4-25-02; 8:45 am] BILLING CODE 4810-31-P _____________________________________________________________________________ _______________________________________________________________

UN Storage Compatibility Groupings Under the UNO system, there are 13 storage compatibility groupings, which further categorize Class 1 explosives by their form or composition, ease of ignition, and sensitivity to detonation. • SCG A--Bulk-initiating explosives that have the necessary sensitivity to friction, heat, or percussion (shock) to make them suitable for use as initiating elements in an explosive train. A distinction is made between primary initiating explosives and nonprimary initiating explosives. Examples of primary initiating explosives are lead azide, lead styphnate, mercury fulminate, and tetracene. Examples of nonprimary initiating explosives are dry forms of cyclotetramethylene tetranitramine (HMX), cyclotrimethylene trinitramine (RDX), and pentaerythritol tetranitrate (PETN). •

•

SCG B--Detonators and similar initiating devices that do not contain two or more independent safety features. This group also consists of items that contain initiating explosives designed to initiate or continue the functioning of an explosives train. Examples are blasting caps, small arms primers, fuzes, and detonators of all types. SCG C--Bulk propellants, propelling charges, and devices containing propellant with or without their own means of initiation. Upon initiation, these items will deflagrate, explode, or detonate. Examples are single-, double-, and triple-base propellants; composite propellants; rocket motors (solid propellant); and ammunition with inert projectiles.

•

SCG D--High explosives (HE) and devices containing HE without their own means of initiation and without a propelling charge. This group includes explosives and ammunition that can be expected to explode or detonate when any given item or component thereof is initiated. This group does not include devices containing initiating explosives with independent safety features. Examples are wet HMX, plastic-bonded explosives (explosives formulated with a desensitizing plastic binder), trinitrotoluene (TNT), and black powder.

•

SCG E--Explosives devices that lack their own means of initiation but contain or have a propelling charge (other than one containing a flammable or hypergolic liquid). Examples are artillery ammunition, rockets, and guided missiles.

•

SCG F--Explosives devices that have their own means of initiation and with or without propelling charge. Examples are grenades, sounding devices, and similar items with an in-line explosive train in the initiator.

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SCG G--Pyrotechnic materials and devices containing pyrotechnic materials. Examples are devices that, when functioning, result in illumination, smoke, or an incendiary, lachrymatory, or sound effect.

•

SCG H--Ammunition containing both explosives and white phosphorus (WP) or other pyrophoric material. Ammunition in this group contains fillers that are spontaneously flammable when exposed to the atmosphere. Examples are WP, plasticized white phosphorus (PWP), or other ammunition containing pyrophoric material.

•

SCG J--Ammunition containing both explosives and flammable liquids or gels. Ammunition in this group contains flammable liquids or gels other than those that are spontaneously flammable when exposed to water or the atmosphere. Examples are liquid- or gel-filled incendiary ammunition, fuel-air explosive (FAE) devices, flammable liquid-fueled missiles, and torpedoes.

•

SCG K--Ammunition containing both explosives and toxic chemical agents. Ammunition in this group contains chemicals specifically designed for incapacitating effects more severe than lachrymation. Examples are artillery or mortar ammunition (fuzed or unfuzed), grenades, and rockets or bombs filled with a lethal or incapacitating chemical agent.

•

SCG L--Explosives or ammunition not included in other SC/HC groups. This group includes explosives or ammunition with characteristics that do not permit storage with other similar or dissimilar materials. Examples are damaged or suspect explosives devices or containers, explosives that have undergone severe testing, fuel-air explosive devices, and water-activated devices. Also included are experimental explosives, explosives of temporary interest, newly synthesized compounds, new mixtures, and salvaged explosives, unless established asbeing compatible with the original materials. Types of explosives in this group

presenting similar hazards may be stored together. •

SCG N--Hazard Division 1.6 ammunition containing only extremely insensitive detonating substances (IEDS). Examples are bombs and warheads. If dissimilar Group N munitions, such as MK 82 and MK 84 bombs, are mixed together and have not been tested to assure nonpropagation, the mixed munitions are considered to be Hazard Division 1.2, Storage and Compatibility Group D, for purposes of transportation and storage.

•

SCG S--Explosives, explosives devices, or ammunition presenting no significant hazard. Explosives ammunition, so designated or packed that, when in storage, all hazardous explosives effects are confined and self-contained within the item or package. Materials in this group are such that an incident that destroys all items in a single pack will not be communicated to other packs. Examples are thermal batteries, cable cutters, explosive actuators, and other ammunition items packaged to meet the criteria of this group. Group A--Initiating explosives (* indicates primary initiating explosives) CL-20 (Hexanitrohexaazaisowurtzitane; dry) CP (5-Cyanotetrazolpentaamine Cobalt III perchlorate) HMX (Cyclotetramethylene tetranitramine; dry) *Lead azide *Lead styphnate *Mercury fulminate *Nitrocellulose (dry) PETN (Pentaerythritol tetranitrate; dry) RDX (Cyclotrimethylene trinitramine; dry) *TATNB (Triazidotrinitrobenzene) *Tetracene Group B--Detonators and similar initiating devices Blasting caps Detonators (excluding EBW and slapper) Explosive bolts Fragmenting actuators Ignitors Low-energy initiators (LEIs) MDF (mild detonating fuze) detonator assemblies Pressure cartridges Primers Squibs Group C--Bulk propellant, propellant charges, and devices containing propellants with or without their own means of initiation Smokeless powder Pistol and rifle powder Rocket-motor solid propellants

Group D--High explosives and devices containing explosives without their own means of initiation (* indicates that classification may change depending on nitrogen and moisture content. Contact Hazards Control Department explosives safety personnel for additional guidance.) Ammonium picrate Baratol Black Powder Boracitol Chemical lenses CL-20 (Hexanitrohexaazaisowurtzitane; wet) Compositions A, B, and C (all types) Cyclotols (< 85% RDX) DATB (Diaminotrinitrobenzene) Detasheet Detonating cord (primacord or mild detonating fuze) bis-Dinitropropyl adipate bis-Dinitropropyl glutarate bis-Dinitropropyl maleate Dinitropropane Dinitropropanol Dinitropropyl acrylate monomer (DNPA) Dinitroproply acrylate polymer (PDNPA) EBW and slapper detonators Elastomeric plastic bonded explosives Explosive D GAP (Glyceryl azide polymer) HMX (Cyclotetramethylene tetranitramine; wet) HMX/wax (formulated with at least 1% wax) HNS (Hexanitrostilbene; wet or dry) Linear-shaped charge Methyl dinitropentanoate Mild detonating fuze (MDF) NG/TA (Nitroglycerine-triacetine) *Nitrocellulose (wet) Nitroguanidine (NQ) Octol (< 75% HMX) Pentolite PETN (Pentaerythritol tetranitrate; wet) PETN/extrudable binder PGN (Polyglycidyl nitrate) Plane wave lenses (composed of SC/HC Group D explosives) Plastic-bonded explosive, PBX (a SC/HC Group D formulated with a desensitizing binder)

Potassium picrate Primacord RDX (Cyclotrimethylene trinitramine; wet) Shaped charges (composed of SC/HC Group D explosives) TATB (Triamino trinitrobenzene) TATB/DATB mixtures TEGDN (Triethylene glycol dinitrate) Tetryl TMETN (Trimethylolethane trinitrate) TNAZ (Trinitoazetidine) TNT (Trinitrotoluene) Group E--Explosives devices without their own means of initiation and with propelling charge Artillery ammunition Rockets (e.g., M66 LAW) Group F--Explosives devices with detonators and detonating trains assembled to the devices and with propelling charge Grenades Sounding devices Group G--Pyrotechnic material and devices that produce an incendiary, illumination, lachrymatory, smoke, or sound effect Smoke pots/grenades Flares Incendiary ammunition Group H--Ammunition containing both explosives and white phosphorus (WP) or other pyrophoric material White phosphorus Plasticized white phosphorus Group J--Ammunition containing both explosives and flammable liquids or gels. Liquid- or gel-filled incendiary ammunition Fuel-air explosive (FAE) devices Flammable liquid-fueled missiles Torpedoes Group K--Ammunition containing both explosives and toxic chemicals Artillery or mortar ammunition (fuzed or unfuzed), grenades, rockets, or bombs filled with a lethal or incapacitating agent Group L--Explosives or other ammunition not included in other storage compatibility groups Damaged or suspect explosives devices or containers Explosives that have undergone severe testing Experimental explosives, explosives of temporary interest, newly synthesized compounds, new mixtures, and some salvaged explosives

Group N--Hazard Class/Division 1.6 ammunition containing only extremely insensitive detonating substances (EIDS) Bombs Warheads Group S--Explosives, explosives devices, or ammunition presenting no significant hazard Propellant cartridge-actuated devices (which yield a nonfragmenting, nonflame-producing controlled reaction). Examples include cable cutters, cartridge-actuated valves, and linear actuators (e.g., dimple, piston, or bellows motors) Safety fuse Most small arms ammunition below 50 caliber Thermal batteries

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Explosives & the Environment Secondary explosives (TNT, HMX, and RDX) have historically been discussed within the realm of safety related issues versus an HTRW waste classification perspective. Explosives-contaminated process waste waters can be subdivided into two categories: red water from the manufacture of TNT and pink water which includes any washwater associated with load, assemble, and pack operations or with the demilitarization of munitions involving contact with finished explosive. Despite their names, red and pink water cannot be identified by color. Both are clear when they emerge from their respective processes and subsequently turn pink, light red, dark red, or black when exposed to light. The chemical composition of pink water varies depending on the process and explosive operation from which it is derived; red water has a more defined chemical composition. Pinkwater is a wastewater generated in the production and handling of high explosive munitions. The principal contaminants in pinkwater are trinitrotoluene (TNT) and cyclo trimethylene trinitramine (RDX); they are transferred to water in washdown operations, and washout and steamout of old munitions. TNT and RDX are persistent contaminants that are regulated in discharges from Army Ammunition Plants. Chemical compounds such as TNT and RDX are resistant to aerobic attack because the nitro compounds act as electron-withdrawing substituents. Other substituents that cause the same effect are halogens, such as chlorine, which is often found in synthetic organic compounds persistent in the natural environment. Under ambient environmental conditions, explosives are highly persistent in soils and groundwater, exhibiting a resistance to naturally occurring volatilization, bio-degradation, and hydrolysis. Where biodegradation of TNT occurs, 2-AmDNT and 4-AmDNT are the most commonly identified transformation products. Photochemical decomposition of TNT to TNB occurs in the presence of sunlight and water, with TNB being generally

resistant to further photodegradation. TNB is subject to biotransformation to 3,5dinitroaniline, which has been recommended as an additional target analyte in EPA Method 8330. Picrate is a hydrolysis transformation product of tetryl, and is expected in environmental samples contaminated with tetryl. Site investigations indicate that TNT is the least mobile of the explosives and most frequently occurring soil contamination problem. RDX and HMX are the most mobile explosives and present the largest groundwater contamination problem. TNB, DNTs, and tetryl are of intermediate mobility and frequently occur as co-contaminants in soil and groundwater. Metals are cocontaminants at facilities where munitions compounds were handled, particularly at OB/OD sites.