an explosive is defined as a material

8/14/2019 An Explosive is Defined as a Material

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ExplosivesAn explosive is defined as a material (chemical or nuclear) that can be initiated toundergo very rapid, self-propagating decomposition that results in the formation of morestable material, the liberation of heat, or the development of a sudden pressure effectthrough 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 damagepotential - 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 potentialenergy systems use explosive energy directly in the form of heat and blast, or byaccelerating metal as a shaped charge, EFP or case fragments to increase their kineticenergy and damage volume.Energy may be broadly classified as potential or kinetic. Potential energy is energy ofconfiguration or position, or the capacity to perform work. For example, the relativelyunstable chemical bonds among the atoms that comprise trinitrotoluene (TNT) possesschemical potential energy. Potential energy can, under suitable conditions, be transformed

into kinetic energy, which is energy of motion. When a conventional explosive such asTNT is detonated, the relatively unstable chemical bonds are converted into bonds thatare more stable, producing kinetic energy in the form of blast and thermal energies. Thisprocess of transforming a chemical system's bonds from lesser to greater stability isexothermic (there is a net production of energy).A chemical explosive is a compound or a mixture of compounds which, when subjectedto heat, impact, friction, or shock, undergoes very rapid, self-propagating, heat-producing decomposition. This decomposition produces gases that exert tremendouspressures as they expand at the high temperature of the reaction. The work done by anexplosive depends primarily on the amount of heat given off during the explosion. Theterm detonation indicates that the reaction is moving through the explosive faster than the

speed of sound in the unreacted explosive; whereas, deflagration indicates a slowerreaction (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] andlack HE's over-pressurization wave. Examples of LE include pipe bombs, gunpowder,and most pure petroleum-based bombs such as Molotov cocktails or aircraft improvisedas guided missiles.A High Explosive (HE) is a compound or mixture which, when initiated, is capable ofsustaining a detonation shockwave to produce a powerful blast effect. A detonation is thepowerful explosive effect caused by the propagation of a high-speed shockwave througha 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, whichmay be expressed for either confined or un-confined conditions. It is the speed at whichthe detonation wave travels through the explosive. Since explosives in boreholes areconfined 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


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size, increased charge diameter, and increased confinement all tend to increase thedetonation velocity. Unconfined velocities are generally 70 to 80 percent of confinedvelocities.The confined detonation velocity of commercial explosives varies from 4,000 to 25,000fps. With cartridge explosives the confined velocity is seldom attained. Some explosives

and blasting agents are sensitive to diameter changes. As diameter is reduced, the velocityis reduced until at some critical diameter, propagation is no longer assured and misfiresare likely.Relative effectiveness factor (R.E. factor) is a measurement of an explosive's power formilitary 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 releasedfrom the detonation of a nuclear weapon, or from the explosion of a given quantity offissionable material, in terms of the amount of TNT (trinitrotoluene) which could releasethe same amount of energy when exploded. The twelve-kiloton Hiroshima atomic bombhad had a blast effect alone equivalent to some twenty-five million pounds of TNT-that'smillion.

Denser explosives usually give higher detonation velocities and pressures. A denseexplosive may be desirable for difficult blasting conditions or where fine fragmentation isrequired. Low-density ex-plosives will suffice in easily fragmented or closely jointedrocks and are preferred for quarrying coarse material.Energetic materials are made in two ways. The first is by physically mixing solidoxidizers and fuels, a process that, in its basics, has remained virtually unchanged forcenturies. 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 thecomposites, 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 tothe release rate of monomolecular materials. Monomolecular materials such as TNT workfast and thus have greater power than composites, but they have only moderate energydensities-commonly half those of composites. Greater energy densities versus greaterpower-that's been the traditional trade-off.Ingredients of high explosives are classified as explosive bases, combustibles, oxygencarriers, antacids, and absorbents. Some ingredients perform more than one function. Anexplosive 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 combustiblecombines with excess oxygen to prevent the formation of nitrogen oxides. An oxygencarrier assures complete oxidation of the carbon to prevent the formation of carbonmonoxide. The formation of nitrogen oxides or carbon monoxide, in addition to beingundesirable from the standpoint of fumes, results in lower heat of explosion andefficiency than when carbon dioxide and nitrogen are formed. Antacids increase stabilityin storage, and absorb-ents absorb liquid explosive bases.Explosives are classified as primary or secondary based on their susceptibility toinitiation. Primary explosives, which include lead azide and lead styphnate, are highlysusceptible to initiation. Primary explosives often are referred to as initiating explosivesbecause they can be used to ignite secondary explosives. Secondary explosives, whichinclude nitroaromatics and nitramines are much more prevalent at military sites than are


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primary explosives. Because they are formulated to detonate only under specificcircumstances, secondary explosives often are used as main charge or bolsteringexplosives.Secondary explosives can be loosely categorized into melt-pour explosives, which arebased 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 arecomposites based on a rubber binder, ammonium perchlorate oxidizer, and a powderedaluminum fuel; or composites based on a nitrate esters, usually nitroglycerine ornitrocellulose and nitramines. If a binder is used, it usually is an isocyanate-curedpolyester or polyether. Some propellants also contain combustion modifiers, such as leadoxide. 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 gunpropellants 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. Pyrotechnicsusually are composed of an inorganic oxidizer and metal powder in a binder. Illuminatingflares 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-testedweapons. "Improvised" describes weapons produced in small quantities, or use of adevice outside its intended purpose, such as converting a commercial aircraft into aguided missile. Manufactured (military) explosive weapons are exclusively HE-based.Terrorists will use whatever is available - illegally obtained manufactured weapons orimprovised 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 formulatedwith one or more high explosives which in their pure form has a vapor pressure less than10-4 Pa at a temperature of 25 deg. C., is formulated with a binder material, and is as amixture malleable or flexible at normal room temperature.The energetic materials used by the military as propellants and explosives are mostlyorganic compounds containing nitro (NO2) groups. The three major classes of theseenergetic 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 andnitroglycerine).Since the invention of the cannon, the explosive fills used to drive lethal mechanismshave been the subject of ever increasing interest and study. Traditionally, munitionsdesigners have used such ex-plosives as Comp-B, TNT, or LX-14, depending upon theparticular application.During the 1920s and into the 1940s, the Army's Picatinny Arsenal was instrumental indesigning, modeling and evaluating such high explosive material as TNT, RDX, andHaleite. This work greatly influenced battlefield lethality during WWII where explosivesexhibiting 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,


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but even more powerful to give soldiers greater lethality capability. Picatinny laboratoriesalso developed precision warheads for several missile systems, including the DRAGON-MAW, 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 othertriggering devices for detonation. Energetic materials are especially vulnerable toelevated temperature, with possible consequences ranging from mild decomposition tovigorous deflagration or detonation. Energetic materials can also be initiated bymechanical work through friction, impact, or electricity (e.g., current flow, spark,electrostatic discharge, or electromagnetic radiation). Other stimuli (e.g., focused laserlight or chemical incompatibility) can have consequences ranging from milddecomposition 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 cell-producing system) and the liver. Some explosives are vasodilators, which causeheadaches, low blood pressure, chest pains, and possible heart attacks. Some explosivesmay irritate the skin.Some detonation or combustion products from explosives are toxic. Such products can berespiratory and skin irritants and lead to systemic effects following short-term exposureto high levels. Soot from detonated explosives is not mutagenic; however, soot fromburned gun propellants may be mutagenic and is therefore treated as a mutagen.Fortunately, contamination usually occurs in dilute, aqueous solutions or in relatively lowconcentrations in the soil and present no explosion hazard. Masses of pure crystallineexplosive material have, however, been encountered in soils associated with wastewaterlagoons, leach pits, burn pits, and firing ranges. These materials remain hazardous forlong periods of time and great care must be used during the investigation and remediationprocess.Molecular weights are moderate, of the order of a few hundreds of grams per mole. Themolecular structure, particularly the types and positions of subsidiary functional groups,controls environmental behavior.All of the common explosives are solid at normal environmental temperatures andpressures. Melting point temperatures for explosives solids are moderate (50-205 0C).Melting points are of little direct value in predicting environmental fate and transport, butseveral parameter estimation relations for solids incorporate the influence of molecularcrystal bonding by including a term dependent on the melting point. Melting points arenot available for many of the breakdown products. Most of the explosives and associatedcontaminants have very low volatility, with vapor pressures estimated to be less than 6 x10-4 torr. Henry's law constants (KH) range from 10-4 to 10-11 atmm-2mole-1. Onlythose 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.---------------------------------------------------------------------------------------------------------------------------------

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Primary ExplosivesThe explosives used as initiating explosives are the primary high explosives mentionedpreviously in this chapter. They are used in varying amounts in the different primers anddetonators used by the Navy and may differ some insensitivity and in the amount of heatgiven 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 primaryexplosive. Lead azide is poisonous, slightly soluble in hot water and in alcohol, andhighly soluble in a diluted solution of nitric or acetic acid in which a little sodium nitratehas 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 azidedoes 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 areused 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 persecond (fps). Its color varies from white to buff. Lead azide is widely used as an initiatingexplosive in high-explosive detonator devices. Lead azide, when protected fromhumidity, is completely stable in stowage.Lead Styphnate

There are two forms of lead styphnate-the normal that appears as six-sided monohydratecrystals and the basic that appears as small, rectangular crystals. Lead styphnate isparticularly sensitive to fire and the discharge of static electricity. When the styphnate isdry, it can readily ignite by static discharges from the human body. The longer andnarrower the crystals, the more susceptible the material is to static electricity. Leadstyphnate 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 beneutralized by a solution of sodium carbonate. The velocity of detonation isapproximately 17,000 fps. The color of lead styphnate varies from yellow to brown. Leadstyphnate is used as an initiating explosive in propellant primer and high-explosivedetonator devices.Diazodinitrophenol (DDNP)

DDNP is a yellowish brown powder. It is soluble in acetic acid, acetone, stronghydrochloric acid, and most of the solvents, but is insoluble in water. A cold sodiumhydroxide solution may be used to destroy it. DDNP is desensitized by immersion inwater and does not react with it at normal temperatures. It is less sensitive to impact butmore 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 propellantprimer devices---------------------------------------------------------------------------------------------------------------------------------

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


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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 byRDX. 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 yellowcrystalline material. When tetryl is heated, it first melts, then decomposes and explodes. Itburns readily and is more easily detonated than explosive D.It is a yellow crystalline solid powder material, practically insoluble in water but solublein Acetone, Benzene and other solvents. It burns readily and is more easily detonated thanTNT or Ammonium Picrate (Explosive D), being about as sensitive as Picric Acid. It isdetonated by friction, shock, or spark . It remains stable at all temperatures which may beencountered in storage. It is generally used in the form of pressed pellets, and has beenapproved 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 othermilitary high explosive, and must be properly protected from bullet fire . Its rate ofdetonation is 23,600-23,900 feet per second. Tetryl is the basis for the service Tetrylblasting caps necessary for positive detonation of TNT. A mixture of Fulminate ofMercury 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 environmentalimpacts would not be expected in areas that are not currently subject to chronic inputs ofthese chemicals. Tetryl decomposes rapidly in methanol/water solutions, as well as withheat. All aqueous samples expected to contain tetryl should be diluted with acetonitrileprior to filtration and acidified to pH


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be synthesized by nitration of phenol, higher yields are obtained if chlorobenzene is usedas a starting material; the latter method involves several steps and the formation ofseveral intermediate products. In addition to its use in explosives, picric acid has beenused as a yellow dye, as an antiseptic, and in the synthesis of chloropicrin, ornitrotrichloromethane, 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).--------

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Explosives - NitroaromaticsNitroaromatics form an important group of recalcitrant xenobiotics. Only few aromaticcompounds, bearing one nitro group as a substituent of the aromatic ring, are produced assecondary metabolites by microorganisms. The majority of nitroaromatic compounds inthe biosphere are industrial chemicals such as explosives, dyes, polyurethane foams,herbicides, insecticides and solvents.Detection of unrecovered land mines is a growing international problem. Unrecoverdland mines are a legacy that continues to harm people long after the hostilities cease. Themost 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 havingfavorable spectral properties, remote sensing can be achieved by fluorescence lightdetection and ranging LIDAR. Nitroaromatic explosives exhibit strong ultravioletabsorption but low fluorescence, thus direct detection is not practical. Indirect detectionin soil can be obtained using a synthetic chemical polymer that exhibits a change influorescence in the presence of an explosive compound.Penetration of nitroaromatic compounds through the skin is a major concern for themilitary. An important characteristic of nitroaromatic compounds is their ability to rapidlypenetrate the skin. They can cause the formation of methemeglobin on acute exposuresand anemia on chronic exposures. Additionally, local irritation, liver damage and bladdertumors have also been identified.These compounds are generally recalcitrant to biological treatment and remain in thebiosphere, where they constitute a source of pollution due to both toxic and mutageniceffects on humans, fish, algae and microorganisms. However, relatively fewmicroorganisms have been described as being able to use nitroaromatic compounds asnitrogen and/or carbon and energy source.However, relatively few microorganisms have been described as being able to usenitroaromatic 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 site-specific factors. Composting and the use of reactor systems lend themselves to treatingsoils contaminated with high levels of explosives (e.g. at former ammunition productionfacilities, where areas with a high contamination level are common). Compared tocomposting systems, bioreactors have the major advantage of a short treatment time, butthe disadvantage of being more labour intensive and more expensive.


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TNT [2,4,6-trinitrotoluene]

TNT is one of the most common bulk explosives. 2,4,6 Trinitrotoluene (TNT) is anexplosive used in military munitions and in civilian mining and quarrying activities. TNTwas first used on a wide scale during World War I and is still used today. The UnitedStates military stopped production of TNT in the mid-1980s.

TNT is classified as a secondary explosive because it is less susceptible to initiation andrequires a primary or initiating explosive to ignite it. TNT can be used as a booster or as abursting charge for high-explosive shells and bombs. Also, TNT may be mixed with otherexplosives 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 suchnames 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 meltingpoint 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 itsexplosive properties. Manufacturing yields are high and production relativelyeconomical. 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, andthe 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 meltingpoint varies between 80.6C for grade A (refined TNT) and 76C for grade B (crudeTNT).TNT does not appear to be affected by acids but is affected by alkalies (lye, washingsoda, and so on), becoming pink, red, or brown, and more sensitive. It is practicallyinsoluble in water, but soluble in alcohol, ether, benzene, carbon disulfide, acetone, andcertain 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 brownand may vary in consistency from an oily liquid to a sticky substance. The amount andrate of separation depend primarily upon the purity of the TNT and, secondarily, upon thetemperature of the stowage place. Grade B (low-melting point) TNT may exudeconsiderable liquid and generate some gas. This exudation is accelerated with an increasein temperature. Pure TNT will not exude since exudate consists of impurities that havenot been extracted in the refining process. Exudate is a mixture of lower melting isomersof TNT, nitrocompounds of toluene of lower nitration, and possible nitrocompounds ofother aromatic hydrocarbons and alcohols. It is flammable and has high sensitivity topercussion when mixed with absorbents. Its presence does no appreciable harm to thestability 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 somecases, waxy material may ooze from the case. It should not be confused with the TNTexudate previously described. This material should, however, be tested for TNT toconfirm its actual composition, TNT exudate, when mixed with a combustible material,


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such as wood chips, sawdust, or cotton waste, will form a low explosive that is highlyflammable and ignites easily from a small flame. It can be exploded in a reamer similar toa low grade of dynamite, but the main danger is its fire hazard. Accumulation of exudateis considered a great risk of explosion and fire. Its accumulation should always beavoided 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 maystill be in the inventory. These stocks should be identified and checked periodically forthe presence of exudate. The exudate is soluble in acetone or alcohol. One of thesesolvents (requiring adequate ventilation) or clean, hot water should be used to facilitateremoval and disposal of the exudate.Under no circumstances should soap or other alkaline preparations be used to remove thisexudate. The addition of a small amount of hydroxide, caustic soda, or potash willsensitize TNT and cause it to explode if heated to 160F.During production TNT is in the form of a liquid which is then cooled and washed withwater to form solid flakes in the form of colorless crystals, though commercial crystalsare 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 becauseof its low melting point and its resistance to shock or friction which allows it to behandled, stored, and used with comparative safety.In order to detonate, TNT must be confined in a casing or shell and subjected to severepressures and/or temperatures (936 degrees Fahrenheit) such as from a blasting cap ordetonator. In fact, U.S. Army tests on pure TNT show that when struck by a rifle bulletTNT failed to detonate 96% of the time and when dropped from an altitude of 4,000 feetonto concrete, a TNT filled bomb failed to explode 92% of the time.2,4,6-Trinitrotoluene (TNT) causes liver damage and aplastic anemia. Deaths fromaplastic anemia and toxic hepatitis were reported in TNT workers prior to the 1950s. Withimproved industrial practices, there have been few reports of fatalities or serious healthproblems related to its use.Exposures at or below 0.5 mg/m3 have been reported to cause destruction of red bloodcells. Among some groups of workers, there is a reduction in average hemoglobin andhematocrit values. Workers deficient in glucose-6-phosphate dehydrogenase may beparticularly at risk of acute hemolytic disease. Three such cases occurred after a latentperiod of 2 to 4 days and were characterized by weakness, vertigo, headache, nausea,paleness, enlarged liver and spleen, dark urine, decreased hemoglobin levels, andreticulocytosis. Although no simultaneous measurements of atmospheric levels wereavailable, 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. Theopacities did not interfere with visual acuity or visual fields. The induced cataracts maynot 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 somecyanosis, it is not regarded as a strong producer of methemoglobin. Other occasionaleffects include leukocytosis or leukopenia, peripheral neuritis, muscular pains, cardiacirregularities, and renal irritation.Trinitrotoluene is absorbed through skin fairly rapidly, and reference to airborne levels ofvapor or dust may underestimate total systemic exposure if skin exposure also occurs.


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Apparent differences in dose-response relationships based only on airborne levels may beexplained 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 thecollar line, belt line, and ankles also is often involved. Erythema, papules, and an itchyeczema 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 andkidney damage. Hyperplasia and carcinoma of the urinary bladder also were observed infemale rats.Historically, control of exposure to TNT has been accomplished through general safetyand hygiene measures, yet additional, specific measures are necessary. The HazardCommunication Program, for example, should instruct workers about the need for strictpersonal and shop hygiene, and about the hazards of the particular operations that areconducted in that plant. In addition, soap that contains 5% to 10% potassium sulfite willnot only help remove TNT dust from the skin, suds that turn red will also indicate anyremaining contamination. Furthermore, respiratory protection equipment should be

selected according to NIOSH guidance, and should be worn during operations thatrelease dust, vapor, or fumes.Before WWII, research suggested that improving the nutritional status of TNT workersmight help improve their resistance to toxic effects. However, in a World War II eracohort study, multivitamin capsules were not shown to be efficacious in preventing TNTtoxicity.TNT interacts with certain medications - including isoniazid, phenylbutazone, phenytoin,and methotrexate. Anyone taking these medications while working with TNT should beclosely 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-normalsensitivity to TNT toxicity during the first three months of exposure, monthlyhemoglobin, LDH, and AST should be done.The ACGIH TLV Committee for Chemical Substances recommended that the 8-hour TLVfor TNT be lowered from 0.5 mg/m3 to 0.1 mg/m3 on 21 May 1997 after reviewingscientific reports of human and animal exposure. In some studies, evidence of livertoxicity, changes in blood cell production, and cataracts were noted when exposure levelsranged below 0.5 mg/m3 (the old ACGIH TLV). TNT workers should never be exposedto 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 theACGIH, the extra margin of safety afforded by this lowered TLV is necessary to protectworkers health. Skin absorption has also been noted to be a significant means of exposurein several studies. Dermal exposure over an 8 hour period cannot be readily quantitated ata worksite, however use of protective clothing to include head cover and impermeablegloves 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 sixforms of the chemical called dinitrotoluene (DNT). The other four forms (2,3-DNT, 2,5-DNT, 3,4-DNT, and 3,5-DNT) only make up about 5% of the technical grade DNT. DNTis not a natural substance but rather is usually made by reacting toluene (a solvent) with


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mixed nitric and sulfuric acids, which are strong acids. DNT is used to produce flexiblepolyurethane foams used in the bedding and furniture industry. DNT is also used toproduce ammunition and explosives and to make dyes. It is also used in the air bags ofautomobiles.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 manufacturingfacilities that release DNT. DNT does not usually evaporate and is found in the air only inmanufacturing plants. DNT also does not usually remain in the environment for a longtime because it is broken down by sunlight and bacteria into substances such as carbondioxide, water, and nitric acid.Workers who have been exposed to 2,4-DNT showed a higher than normal death ratefrom heart disease. However, these workers were exposed to other chemical as well. 2,4-and 2,6-DNT may also affect the nervous system and the blood of exposed workers. Onestudy showed that male workers exposed to DNT had reduced sperm counts, but otherstudies 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 miningand military use, as a narrow-range pH indicator and as an agent to vulcanize naturalrubber. The compound is a manufacturing by-product of the explosive, TNT, and isreleased to the environment in discharged wastewater. Additionally, any TNT itself that ispresent in the waste stream may be degraded to 1,3,5-TNB by photolysis under certainconditions of pH and organic matter content. The compound has a close structuralrelationship with the most widely produced military explosive, trinitrotoluene (TNT), ofwhich it is a manufacturing by-product and an environmental degradation product._____________________________________________________________________________

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Explosives - NitraminesThe nitramines are the most recently introduced class of organic nitrate explosives. Themost prominent member of this class is RDX (research department explosive; hexahydro-1,3,5-trinitro-1,3,5 triazine, which is also known as cyclonite); HMX (high meltingexplosive; octahydro-1,3,5,7-tetranitro-1,3,5,7 tetrazocine), nitroguanidine, and tetryl arealso significant nitramines.In a class of explosives like nitramines, the higher density, bigger molecules will givemore power because more realizable energy can be packed in the same space. Biggermolecules using the same proportion of elements are more dense because the formationof covalent bonds makes atoms come closer together than if they were just pushedtogether but from different molecules. HMX is a big ring molecule, same as RDX butwith an extra CH2NNO2 unit. It has higher density (TMD 1.902) than RDX, 1.806, itsdet. 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 inthe U.S., 1,3,5-trinitro-1,3,5-triazacyclohexane (RDX), 1,3,5,7-tetranitro-1,3,5,7tetraazacyclooctane (HMX) was briefly evaluated. It was found that acetic acid was amajor pollutant. It appeared that the British Process could be controlled to reduce thepolluting effluents better than the Bachmann Process used in the U.S.


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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 nitroglycerinamong 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 stabilityin storage and is considered the most powerful and brisant of the military highexplosives. RDX is used as a base charge in detonators and in blasting caps. RDX can beused alone or with other explosives, including PETN.t RDX can be mixed withplasticizers to make C-4, and the most common explosive combining RDX and PETN isSemtex. RDX forms the base for the following common military explosives:Composition A, Composition B, Composition C, HBX, H-6 and Cyclotol. Composition Aconsists of RDX melted with wax; in Composition B, RDX is mixed with TNT; andComposition C contains RDX blended with a non-explosive plasticizer. Pure RDX isused 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 beused alone as a base charge for detonators or mixed with another explosive such as TNTto form cyclotols, which produce a bursting charge for aerial bombs, mines, andtorpedoes. Common military uses of RDX have been as an ingredient in plastic bondedexplosives, or plastic explosives which have been used as explosive fill in almost alltypes of munition compounds. Civilian applications of RDX include use in fireworks, indemolition 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 inapproximately 75 products.RDX is an explosive nitramine compound. It is in the form of a white powder with adensity of 1.806 g/cc. Nitrogen content of 37.84%. The chemical name for RDX is 1,3,5-trinitro-1,3,5-triazine. The chemical formula for RDX is C3H6N6O6 and the molecularweight is 222.117. Its melting point is 205C. RDX has very low solubility in water andhas an extremely low volatility. RDX does not sorb to soil very strongly and can moveinto the groundwater from soil. It can be broken down in air and water in a few hours, butbreaks down more slowly in soil.Although RDX [Royal Demolition Explosive or Research Department Explosive] wasfirst prepared in 1899, its explosive properties were not appreciated until 1920. RDX wasused 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 highexplosive in the military, exceeded only by TNT. As with most military explosives, RDXis 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 haslimited civilian use as a rat poison.RDX can cause seizures in humans and animals when large amounts are inhaled oringested. Nausea and vomiting have also been observed. The effects of long-term (365days or longer), low-level exposure on the nervous system are not known. No othersignificant health effects have been reported in humans. Rats and mice that ate RDX for 3months or more had decreased body weights and slight liver and kidney damage. It is not


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known whether RDX causes birth defects in humans. It did not cause birth defects inrabbits, but did result in smaller offspring in rats. It is not known whether RDX affectsreproduction in humans. The EPA has determined that RDX is a possible humancarcinogen (Class C). In one study, RDX caused liver tumors in mice that were exposedto 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 manufactureused in the United States is the continuous Bachmann process. The Bachmann processinvolves reacting hexamine with nitric acid, ammonium nitrate, glacial acetic acid, andacetic anhydride. The crude product is filtered and recrystallized to form RDX. Thebyproducts of RDX manufacture include nitrogen oxides, sulfur oxides, acid mists, andunreacted ingredients. A second process that has been used to manufacture RDX, thedirect nitration of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), has not yieldeda percentage of RDX as high as the percentage produced in the Bachmann process (Army1978; 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 to1971 was 15 million pounds per month. However, production of RDX decreased to ayearly total of 16 million pounds for 1984.RDX is not produced commercially in the United States. Production in the United Statesis limited to Army ammunition plants such as Holston Army ammunition plant inKingsport, Tennessee, which has been operating at 10-20% capacity. Several Armyammunition plants, such as Louisiana (Shreveport, Louisiana), Lone Star (Texarkana,Texas), Iowa (Middletown, Iowa), and Milan (Milan, Tennessee), also handle andpackage RDX. Since the release of RDX is not required to be reported under SARASection 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 ashazardous wastes and are subject to EPA regulations. Munitions such as RDX have beendisposed of in the past by dumping in deep sea water. By-products of military explosivessuch 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 andpropellants have been disposed of by incineration. Wastes containing RDX have beenincinerated by grinding the explosive wastes with a flying knife cutter and spraying theground material with water to form a slurry. The types of incineration used to dispose ofwaste munitions containing RDX include rotary kiln incineration, fluidized bedincineration, and pyrolitic incineration. The primary disadvantage of open burning orincineration 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 thefield, and through the contamination of the environment. The main occupational exposureto RDX during its manufacture is through the inhalation of fine dust particles. Ingestionmay 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 plantswith load, assemble and pack (LAP) operations, where workers involved with melt-pouring and maintenance operations have the greatest potential for exposures.In 1962, five cases of convulsions or unconsciousness or both occurred at an RDXmanufacturing plant in the United States. All five employees had convulsions during their


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work shifts or within a few hours after their shifts were over. These patients exhibitedlittle or no prodrome, and the postictal phase lasted up to 24 hours. No abnormallaboratory or physical findings were noted.Troops have also become intoxicated during field operations from exposure tocomposition 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 soldiersexperienced 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 ofirritability. Neurological symptoms predominate and include restlessness andhyperirritability; headache; weakness; dizziness; hyperactive reflexes; nausea andvomiting; prolonged and recurrent generalized convulsions; muscle twitching andsoreness; 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 andunreliable for diagnosis purposes, last at most a few days. In fact, all physical andlaboratory tests may remain normal, even in the presence of seizures. EEGs made at thetime 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 3months.RDX in the wastewater from manufacturing and loading operations has alsocontaminated the environment. Although contamination has appeared in soil andgroundwater near some ammunition plants, RDX's low solubility in water has limited itsmigration in most cases.Although intensive research with animals has revealed some effects, few effects ofchronic human exposure to RDX have been reported. Investigations into the mutagenicityand carcinogenicity of RDX have yielded conflicting results. RDX does not appear to bea mutagen, based on negative results in the Ames tests, the dominant lethal test, and theunscheduled deoxyribonucleic acid synthesis assay. RDX has not been found to becarcinogenic in gavage studies performed on rats, but increased hepatocellular carcinomaand 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 rabbitsshowed teratogenic effects at 2 mg/kg/day (10% of the dose that caused maternaltoxicity). Similarly, a teratology study performed on pregnant rats exposed to RDXresulted in offspring with lower body weights and shorter body lengths than were foundin the control group. These researchers therefore recommended that human females ofchildbearing age be protected from exposure to RDX.Despite the low toxicity of RDX, exposure should be maintained at the lowest levelspossible due to its possible carcinogenicity. General medical surveillance examinationscan be conducted (such as liver and kidney function tests), but specific testing for theeffects of low level occupational exposure does not appear to be warranted, given theabsence of abnormal results even in those patients with RDX-induced seizures.Surveillance for both males and females should also include a screening questionnaire for


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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 largescale in the United States. It is also known as Octogen and cyclotetramethylene-tetranitramine, as well as other names. HMX explodes violently at high temperatures

(534F and above). Because of this property, HMX is used exclusively for militarypurposes to implode fissionable material in nuclear devices, as a component of plastic-bonded explosives, as a component of rocket propellant, and as a high explosive burstercharge. The use of HMX as a propellant and in maximum-performance explosives isincreasing.HMX was discovered as a by-product in the production of RDX. Although it is almost assensitive and powerful as RDX, it is seldom used alone in military applications but isnormally mixed with another compound, such as TNT. In the Navy, HMX is used as aningredient in plastic-bonded explosives.HMX is produced by the nitration of hexamine with ammonium nitrate and nitric acid inan acetic acid/acetic anhydride solvent at 44C. The raw materials are mixed in a two-

step process and the product is purified by recrystallization. This is a modification of theBachmann Process used to produce RDX, another explosive. The yield of HMX is about55-60%, with RDX as an impurity. RDX produced by the Bachmann Process usuallycontains about 8-12% HMX as an acceptable byproduct.HMX is currently produced at only one facility in the United States, the Holston ArmyAmmunition Plant in Kingsport, Tennessee. The amount of HMX made and used in theUnited States at present is not known, but it is believed to be greater than 30 millionpounds [15,000 tons] per year between 1969 and 1971. No estimates of currentproduction volume were located, but it is estimated that its use is increasing. Processingmay occur at load, assemble, and pack (LAP) facilities operated by the military. Therewere 10 facilities engaged in LAP operations in the United States in 1976No 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 byEPA. Generators of these wastes must conform to EPA regulations for treatment, storage,and disposal. The waste water treatment sludges from processing of explosives are listedas hazardous wastes by EPA based only on reactivity. Waste water treatment may involvefiltering through activated charcoal, photolytic degradation, and biodegradation. Rotarykiln or fluidized bed incineration methods are acceptable disposal methods for HMX-containing wastes. At the Holston facility, waste waters are generated from themanufacturing areas and piped to an industrial water treatment plant on site. Followingneutralization and nutrient addition, sludge is aerobically digested and dewatered. It wasestimated that the facility generates a maximum of 3,800 tons (7.6 million pounds) oftreated, dewatered sludge annually. Based on demonstration by Holston that this sludge isnonhazardous, the EPA proposed granting a petition to exclude the sludge from hazardouswaste 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 toenvironmental 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


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solid with a melting point of 276 to 286C. HMX is made by the nitration of hexaminewith ammonium nitrate and nitric acid in an acetic acid/acetic anhydride solvent. A smallamount of HMX is also formed in making cyclotrimethylene-trinitramine (RDX), anotherexplosive 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 andsmell of HMX are not known.HMX is a manmade chemical and does not occur naturally in the environment. It is madefrom 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 amountof HMX will evaporate into the air; however, it can occur in air attached to suspendedparticles or dust. In surface water, HMX does not evaporate or bind to sediments to anylarge extent. Sunlight breaks down most of the HMX in surface water into othercompounds, 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 throughthe environmental contamination of groundwater and soil. HMX, like RDX, ismanufactured using the continuous Bachman process. Although its solubility in water isvery 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, noadverse effects were reported in workers exposed to HMX in air. However, theconcentrations of HMX in the workplace air were not reported in this study, and only asmall number of workers and effects were investigated.Studies in rats, mice, and rabbits indicate that HMX may be harmful to the liver andcentral nervous system if it is swallowed or contacts the skin. The lowest dose producingany 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 asingle exposure to these dose levels harmed rabbits. The mechanism by which HMXcauses adverse effects on the liver and nervous system is not understood.The reproductive and developmental effects of HMX have not been well studied inhumans or animals. At present, the information needed to determine if HMX causescancer is insufficient. Due to the lack of information, EPA has determined that HMX isnot classifiable as to its human carcinogenicity.The data on the effects on human health of exposure to HMX are very limited. HMXcauses CNS effects similar to those of RDX, but at considerably higher doses. In onestudy, volunteers submitted to patch testing, which produced skin irritation. Anotherstudy 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 ofexposure to HMX.HMX exposure has been investigated in several studies on animals. Overall, the toxicityappears to be quite low. HMX is poorly absorbed by ingestion. When applied to thedermis, it induces mild skin irritation but not delayed contact sensitization. Various acuteand subchronic neurobehavioral effects have been reported in rabbits and rodents,


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including ataxia, sedation, hyperkinesia, and convulsions. The chronic effects of HMXthat have been documented through animal studies include decreased hemoglobin,increased serum alkaline phosphatase, and decreased albumin. Pathological changes werealso observed in the animals' livers and kidneys. No data are available concerning thepossible reproductive, developmental, or carcinogenic effects of HMX.

CL-20 / HNIWCL-20 [2,4,6,8,10,12-hexanitrohexaazaisowurtzitane (HNIW) ] is a new nitramineexplosive that is 20 percent more powerful that HMX. CL20 was a breakthrough inenergetic materials with higher performance, minimum signature, and reduced-hazardcharacteristics. CL-20 has numerous military and commercial applications. The trendtoday is to explore the possibilities that HNIW can provide to munitions;from highperformance gun propellants , shaped charges etc. The only limitation is the cost of itsproduction. Even there had been practical methods to nitrate the special reactant (acetylIsowurtzitane derivatives) with mixed acid, but the effort of debenzylation of thecondensation products of glyoxal and benzylamine still requires the expensive palladiumcatalyst. 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 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 PETNclass). The CL-20 melting point is lower than in octogen, 240C 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 formedinto nanoparticles of uniform size. A new, promising process for particulation of materialsutilizes environmentally benign compressed gases as either solvents or anti-solvents.Predictive models are required to describe the solubility and phase behavior ofsupercritical solutions of CL20 and supercritical carbon dioxide and for processsimulation and development. Here, the solubility of CL20 in supercritical carbon dioxidewas evaluated using the Peng-Robinson cubic equation of state. Critical properties, vaporpressure, and other required thermodynamic properties were estimated using a variety ofavailable estimation techniques. A Fortran program to predict the solubility of CL20 wasdeveloped. The program was validated using available literature data for the solubility ofnaphthalene and of biphenyl in supercritical carbon dioxide. The applicability of theestimation techniques employed for the critical properties for CL20 was established usingthese same techniques to estimate the critical properties of comparable compounds,including RDX and HMX. Solubility data for RDX in supercritical carbon dioxidereported in the literature were also used to establish the validity of the estimationapproach. Solubility was predicted over the temperature range of 305.15 to 368.15 K andover the pressure range of 74 to 150 atm. In general, as the temperature increases, thesolubility decreases, while as the pressure increases, the solubility increases.Fortunately, shortly after Dr. Arnold Nielson first synthesizedHexanitrohexaazaisowurtzitane [hexa-nitro-hexa-aza-iso-wurtzi-tane] in 1987 it wasdesignated "CL-20," and talking and writing about this "most significant energeticingredient in 50 years" was made much easier. And there has been alot of writing anddiscussion about the development of CL-20. Nielson's original discovery astonished thescientific community because he constructed the CL-20 cage using a single chemical


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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) energeticingredients while having an acceptable level of insensitivity to shock and other externalstimuli. This fit in nicely with the Navy's 1989 decree for development of "insensitivemunitions," capable of withstanding unplanned exposure to external forces. Further, CL-

20-based formulations were clean burning, with less signature and which also metrequirements spawned by the government's then new-found emphasis of its role inpreserving the natural environment.Seeing potential for the new molecule, early members of the team set about purifying andcharacterizing new polymorphic forms and scaling up to produce usable quantities. In1993 some 48 members of the Research, Ordnance Systems and Range departmentsreceived 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 aCooperative Research and Development Agreement (CRADA), the ultimate goal ofwhich is to test a warhead containing a CL-20-based explosive that will demonstrateperformance significantly above that of existing explosives. Under the terms of the three-

year agreement NAWCWD will provide the personnel, facilities, equipment andmaterials necessary to characterize CL-20; formulate, test and evaluate CL-20-basedexplosives; 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 othertasks.cost reduction is a major benefit expected to be gained from this CRADA. Bysuccessfully completing this CRADA and demonstrating the potential of CL-20, demandfor the material will go up. With increased demand, and improved production processesfor 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 fewgrams of CL-20, the extrapolated cost to produce a pound by that method would havebeen several thousand dollars. Thiokil has refined the production process to the point thatcustomers were paying around $400 a pound in the mid-1990s, which was a considerablereduction. The hope at that time was to quarter that cost and get it down to around $100 apound.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 ownprocesses. Thiokol with continuous assistance and collaboration from China Lakeresearchers has scaled up its process to the point that it can now produce 1,000-pluspound batches of the ingredient. It has also been commercially marketing the basicingredient as well as end-product formulations for explosives, gun propellants and, to alesser degree, rocket propellants.While there have been other new ingredients over the years, none of them have beensuccessfully scaled up to mass productionlevels. Thiokol has made the jump to massproduction of CL-20. That's why many have called CL-20 the mostsignificant energeticingredient in the past 50 years. It offers great potential to meet the performance,insensitive munitions and environmental requirements for future weapons systems. CL-20-based shaped charges are already being used in the oil well industry. Othercommercial applications he expects to see include specialty demolition, because CL-20


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

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Explosives - Nitrate estersNitrate (NO3-) (CAS No. 014797-55-8) is an inorganic anion resulting from theoxidation of elemental nitrogen. It is an essential nutrient for plant protein synthesis andplays a critical role in the nitrogen cycle of soil and water. Nitrates are produced bynatural biological and physical oxidations and therefore are ubiquitous in theenvironment (Ridder and Oehme 1974). Most nitrate compounds are strong oxidizingagents and some can react violently with oxidizable substances and may explode ifexposed to heat or shock.Nitrates are produced by natural biological and physical oxidations and therefore areubiquitous in the environment. Most of the excess nitrates in the environment originatefrom inorganic chemicals manufactured for agriculture. Organic molecules containing

nitrate groups are manufactured primarily for explosives or for their pharmacologicaleffectsNC [Nitrocellulose]

for many centuries gunpowder was the world's only explosive, and was not supersededuntil the discovery of guncotton. So long ago as 1832 Bracon discovered that woody fibercould be turned into an explosive by the action of concentrated nitric acid; and a fewyears later a French inventor, Dumas, tried to make cartridges of paper treated in similarfashion. If he had succeeded these would have been the first smokeless cartridges, but hefailed; and it was not until 1845 that Schnbein, a German chemist, hit upon the propermethod of treating cotton wool with nitric and sulphuric acids, so as to turn it intoguncotton.In 1847 an English firm, Messrs. Hall and Son of Faversham, began to manufactureguncotton, and military experts hailed it as the new explosive which would take the placeof gunpowder. But this explosive was so terribly powerful that, when used in a gun orrifle, 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 topropel the projectile would not shatter the gun tube. second, the density had to beincreased so that a given charge weight would pack into a reasonable space. The firstproblem was solved in part by igniting NC instead of firing it with a detonator. Thesolution to the second problem actually solved both. In 1886, Vielle first colloided orgelatinized NC with alcohol and ether and, thus reduced the burning rate to acceptablelevels. The procedure significantly increased the loading density of NC, establishing it asthe foundational element in gun propellants used through the present day. Furtherdevelopments resulted in materials that could be added to improve stowage qualities,reduce or eliminate flash, reduce hygroscopicity, reduce flame temperature, and evenincrease the propellant force or impetus.Munitions manufacturing processes may generate nitrocellulose (NC) fines. Disposal ofthese fines is difficult because of their reactive nature. Composting has potential to be asafe and cost effective means of disposal. Open burning is no longer permitted in several


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states and is expected to banned nationally in the future. Open detonation is also the leastacceptable form of disposal because of uncontrolled pollution by-products. In its role asthe Department of Defense Manager for conventional munitions, Army must be able todispose of Propellants/Explosives/Pyrotechnics production wastes. In composting, acontrolled biological process, microorganisms convert biodegradable hazardous material

to innocuous, stabilized by-products, typically at elevated temperatures between 50 - 55C. The increased temperatures result from heat produced by the microorganisms as theydegrade the organic material in the waste. The NC fines are mixed with bulking agentsand organic amendments, such as wood chips and animal and vegetable wastes, toenhance 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 inmanufacture of dynamite, gunpowder, and rocket propellants, and as a therapeutic agent

primarily to alleviate angina pectoris. NG is used to make smokeless gun powder androcket propellants. Single-base powders contain only nitrocellulose, double-base powderscontain nitrocellulose and NG, and triple-base powders contain nitrocellulose, NG, andother combustible materials.In 1847 a new explosive came into being. This was nitroglycerine, made by treatingglycerine with nitric and sulphuric acids. But at first it was even more dangerous tohandle 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 thepowder did not absorb all the nitroglycerine, and accidents of the most terrible kindbecame more and more frequent. Yet the new explosive, being liquid, could be pouredinto crevices in rocks, and was so useful as a blasting agent that its manufacture went onuntil 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 asensation that the manufacture of nitroglycerine was prohibited in Sweden, Belgium, andin England. But Nobel still continued his experiments, and at last, after trying sawdustand all other sorts of absorbents in vain, found the perfect absorbent in the shape ofkeiselguhr-a sort of earth made of fossil shells. The mixture is what we know to-day asdynamite; and in spite of the fact that modern chemistry has produced very many newexplosives, some of terrific power, dynamite remains the safest and most widely used ofall explosives.Nitroglycerin (NG) is a vasodilator and has been associated with acute episodes of anginapectoris, myocardial infraction, and sudden death. Workers engaged in the production oruse of dynamite are potentially exposed to mixed vapors of nitroglycerin (NG) andethylene glycol dinitrate (EGDN). Initial exposure to NG (or NG:EGDN mixtures)characteristically results in an intense throbbing headache that begins in the forehead andmoves to the occipital region. Volunteers developed mild headaches when exposed toNG:EGDN vapor at concentrations of 0.5mg/m^3 for 25 minutes. It has been suggestedthat at least some workers may develop headaches at concentrations in excess of 0.1mg/m^3. Other signs and symptoms associated with initial exposure include dizziness,nausea, palpitations, and decreases in systolic, diastolic, and pulse pressures. These initial


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signs and symptoms, including headache, are indicative of a shift in blood volume formthe 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 duringperiods without NG exposure, such as weekends and holidays. Chronic repeated

exposures to NG and NG mixtures also have been associated with more seriouscardiovascular effects, including angina pectoris and sudden death.Signs and symptoms of ischemic heart disease were observed in nine munitions workersinvolved in handling a nitroglycerin-cellulose mixture. Within 1 to 4 years of initialexposure, these workers developed nonexertional chest pain, which was relieved eitherby therapeutic nitroglycerin or by returning to work after the weekend. Coronaryangiography performed in five of the patients showed no obstructive lesions. In onepatient, observed while in a withdrawal state, coronary artery spasm was demonstratedand readily reversed by sublingual nitroglycerin.Sudden deaths in previously healthy workers have been reported among those exposed toNG 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 Sundaynights or Monday mornings. In most cases, there were no premonitory signs or symptomsalthough some subjects had anginal episodes during brief periods away from work.Atherosclerotic plaques, with or without thrombosis, have been found in the coronaryarteries of workers at autopsy, but their coronary arteries generally were not occluded tothe same extent as those of unexposed workers who had died suddenly.The pathogenesis of the sudden death syndrome has been postulated to be due towithdrawal of coronary vasodilators (e.g. NG), resulting in vasoconstriction with acutehypertension, or with myocardial ischemia in workers adapted to and dependent on NG tomaintain a minimum level of coronary flow. A second contributing mechanism forcoronary artery toxicity due to NG may relate to so-called aging of the vessels due torepeated dilation. Other theories suggest that sudden deaths may be related to peripheralvasodilation consequent to reexposure of NG.Estimates of exposure levels associated with sudden death have not been made becauseworkers typically absorb considerable amounts of NG through the skin in addition toinhalation.Employees handling NG should be given personal protective equipment to prevent theabsorption of NG through the skin. However, neither natural rubber nor synthetic rubbergloves, including neoprene gloves, are impervious to NG. The wearing of such glovestends 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 gloveschanged ever 2-1/2 hours (USAEHA Technical Guide 24).More recent studies have suggested that the effects of long-term workplace exposure toNG may not be completely reversed after exposure is terminated. Former workers may beat increased risk for cardiovascular mortality for months to years after exposure hasceased.Individuals with preexisting ischemic heart disease should not be assigned to work wheresignificant exposure to NG may occur. Early identification of cardiovascular disease isthe primary goal of medical surveillance of nitroglycerin workers. A preplacementexamination must be administered to all new employees occupational histories, a physical


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examination, and indicated laboratory tests, record of their pulse rates. Periodicexaminations should be conducted semiannually, with the same focus as the preplacementexamination. During the periodic examination, the physician should be aware thatheadaches 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, althoughsurveillance should perhaps extend beyond employment, due to the latency of thewithdrawal 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 1.76and a confined detonation velocity of over 25,000 fps. PETN is used as a primingcomposition in detonators, a base charge in blasting caps, and a core load for detonatingfuse. 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 cordis 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 isnever used alone as a booster. It is primarily used in booster and bursting charges of smallcaliber ammunition, in upper charges of detonators in some land mines and shells, and asthe explosive core of primacord.During World War II the M9A1 2.36" Rocket Launcher (Bazooka) charge, with 8 oz ofpentolite, could penetrate up to 5 inches of armor.Demolition charge, M118, commonly called Flex-X or sheet explosive, consists of 4 half-pound sheets of flexible explosive packed in a plastic envelope. Each sheet isapproximately 3 inches wide, 12 inches long, and 1/4 inch thick. Note: The exactexplosive contained in an M118 charge varies with the manufacturer. At present, somemanufacturers use PETN as the basic explosive. Others use RDX. Charges manufacturedin the future may include other explosives.PETN does not occur naturally, so the production and use of this kind of compound canlead to contamination of the environment. PETN is subject to biodegradation in untreatedor unpreserved urine and feces. There also have been some reports of its degradation bybacteria, 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 KlinischePharmakologie, Medizinische Hochschule Erfurt, Germany reported on a study ofPETN's cardiovascular effects. The effects of 80 mg pentaerithrityl-tetranitrate (PETN) assuspension or formulated as tablets were compared to placebo in a single blind,randomized, crossover study in 18 healthy subjects (study A), and the bioequivalence oftwo tablet formulations (marketed Dilcoran 80 vs a new formulation) was studied in 24healthy subjects after administration of single oral doses of 80 mg PETN according to aplacebo 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 thechanges of resistance and of the incisure D) before and 24 h post-dose, and blood


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pressure and heart rate were measured in supine position at the same time. The values ofarea under curve (AUC) of the ratio A/D were calculated by the trapezoidal rule. In studyA 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 inthe subjects of all three groups 1 to 2 h postdose followed by an increase by 6 to 10 beatsper min. After subtraction of the AUC values of placebo from the PETN-derived AUCvalues, mean values of 6.61 (SD 1.52, solution) and 7.25 (SD 1.48, A/D*h, tablet) werecalculated (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 explosiveingredient (60-80%) in dynamite along with nitroglycerine (40-20%).EGDN and NG are used with a mixture of sodium nitrate and an absorbent, often woodpulp, 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, about250 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; allworkers had decreases in blood pressure [Trainor and Jones 1966]. Ethylene glycoldinitrate and nitroglycerine are vasodilators and initial exposures result in headache,dizziness, nausea, or decreases in blood pressure; however, workers became tolerant ofthe vasodilatory activity after 2 to 4 days of exposure.Angina pectoris has been reported among workers who were exposed to EGDN and/orNG. In those affected, the angina usually occurred in periods away from work. Suddendeaths without any apparent cause have also been reported among these workers. Thedeaths, like the angina, occurred more frequently during periods away from work. Inmost cases, the workers who died suddenly had no symptoms other than angina duringperiods away from work. The deaths are thought to be related to compensatoryvasoconstriction (tolerance) induced by repeated exposure to the substances.Vasoconstriction is thought to lead to spasms of the coronary arteries and then the relatedangina pectoris and sudden deaths.No data on acute inhalation toxicity are available on which to base the IDLH for ethyleneglycol dinitrate (EGDN) and/or nitroglycerin. The chosen IDLH, therefore, is based onchronic toxicity data concerning the physiological response of animals to EGDN.According to Patty [1963], rats and guinea pigs survived 6 months of exposure to 500mg/m3 (80 ppm) EGDN with the only effect being slight drowsiness and some Heinzbody formation [Stein 1956]. Although Patty [1963] stated that EGDN is more toxic forcats and rabbits, the chosen IDLH is still probably conservative because cats given 2hourdaily 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 byeach device, 2,000 the OSHA PEL of 0.1 mg/m3 (i.e., 200 mg/m3) is the concentrationabove which only the "most protective" respirators are permitted._____________________________________________________________________________


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Explosives - CompositionsIn general, high explosives are compositions and mixtures of ingredients capable ofinstantaneously 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 islimited only by the energy content of the explosive composition, while in other cases thetransfer of energy from the explosive composition to surrounding bodies is controlled to alarge degree by the momentum or impulse released by the detonating explosive.Amatol

Research and development during World War I yielded amatol (TNT plus ammoniumnitrate), an explosive with three times the power of gunpowder. Amatol consists of TNTand ammonium nitrate mixed in either 20 /80 or 50 /50 ratios. When the U.S. entered thewar, Amatol was adopted for loading high explosive shells. Owing to shortages of TNTand RDX (cyclonite) most World War II mines had had 50/50 ammonium nitrate andTNT (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 crystallineand yellow or brownish, moisture-absorbing, insensitive to friction, but may be detonatedby 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, whileAmatol 50/50 produces a smoke, less black than straight TNT. Amatol is used as asubstitute 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 themixture with 1% wax as a binder. The high density of barium nitrate gives baratol adensity of at least 2.5.Early implosion atomic bombs, like the Gadget exploded at Trinity in 1945, the Soviet'sJoe 1 in 1949, or India in 1972, used an Composition-B [RDX-TNT mixture] as the fastexplosive, with baratol used as the slow explosive.Composition A

Composition A is a was-coated, granular explosive consisting of RDX and plasticizingwas. 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 possessessatisfactory stowage properties. Composition A-3 is appreciably more brisant andpowerful than TNT; its velocity of detonation is approximately 27,000 fps. It may bewhite 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 asantiaircraft projectiles. It can be used as compressed fillers for medium-caliberprojectiles.


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defined RDX crystallites present at cook-off temperatures were the source of the reactionviolence 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 areexplosives, are oily liquids and plasticize the mixture. The essential difference betweenComposition 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 aplastic, puttylike composition to meet the requirements of an ideal explosive for moldedand shaped charges that will maintain its plasticity over a wide range of temperatures andnot exude oil.Composition C-3 is about 1.35 times as powerful as TNT. The melting point ofComposition C-3 is 68C, 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, CompositionC is no longer being used as a gun projectile main charge. However, some stocks maystill 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 oflarge structures where large charges are required (Satchel Charge). The charge assemblyM183 consists of 16 block demolition charges M112, four priming assemblies andcarrying case M85. Each Priming assembly consists of a five-foot length of detonatingcord 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 chargeM112 is a rectangular block of Composition C-4 approximately 2 inches by 1.5 inchesand 11 inches long, weighing 1.25 Lbs. When the charge is detonated, the explosive isconverted 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 operationsbecause they retain their effectiveness in cold weather. Dig a hole in the ground in whichto place the explosive and tamp the charge with any material available to increase itseffectiveness. 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 touse 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 atagant 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 weredone on laboratory animals and they showed a rever

an explosive is defined as a material

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