Explosive Properties of Primary Explosives

The chemical properties of primary and secondary nitramines are important in relation to their use as explosives. Primary nitramines contain acidic hydrogen in the form of —N//NO2 and, consequently, in the presence of moisture, primary nitramines corrode metals and form metal salts, some of which are primary explosives. This is one reason why powerful explosives like methyinitramine (1) have not found practical use. Ethylenedinitramine (EDNA) (2) suffers from similar problems but its high brisance (VOD 8240 m/s, d = 1.66 g/cm ) and low sensitivity to impact have seen it used for some applications. 

Handling of Explosives 406 407, Table 1. Properties of Primary Explosives... 

The explosive properties of sodium, calcium, strontium and barium azides have been investigated at the Chemisch-Technische Reichsanstalt [135]. These azides differ markedly from lead, silver and cupric azides in that they show none of the properties of primary explosives. All three may be ignited by a spark, a glowing wire or the flame of blackpowder. Calcium azide bums most rapidly and has distinctly marked explosive properties. Larger quantities of it may explode when ignited in a closed tin, while strontium and barium merely bum violently. Calcium azide detonates under the influence of a detonating cap. The sodium azide does not decompose in these conditions. The other azides show weak decomposition under the influence of a standard (No. 3) detonator. Their most important properties are tabulated below. 

Trinitrotriazidobenzene (IX) is the only representative of organic azides possessing properties of primary explosives which has some prospect of practical use. Turek [159] prepared it by the action of sodium azide on sym-trichlorotrinitrobenzene (Vol. I. p. 469) and on the basis of its properties which he himself determined he suggested its use as an initiator. 

As early as 1883 Berthelot [75] noticed that some salts of oxalic acid (e.g. mercuric or silver oxalates) have the properties of primary explosives. 

The heavy metal salts of acetylene have the properties of primary explosives, but only cuprous acetylide was found to be satisfactory for practical use. 

Section 3 (1953) 2nd Supplement (1953) 32)Kirk Othmer, Vol 4 (1949), 636 -62 A.F.Wells, Crystals 33)Armour Res Foundation of IIT, "Crystallographic Properties of Primary Explosives , Summary Rept... 

T.A-Erikson R.J.Hinch, Jr, "Investigation of Crystallographic Properties of Primary Explosives , Armour Res Foundation, IIT Quarterly Rept No 1 (1958), [Ord Proj TB3-0115A, Contract DA-11-022-501-ORD-2731] 36)W.C.McCrone Assoc Inc, "The Crystallography of Explosives , Final Rept (1962) (Contract DA-11-022-ORD-4090) 37)R.C.Evans,... 

Organic peroxides may be explosive. They are usually not manufactured for blasting purposes, but rather as catalysts for polymerization reactions. They are utilized in a safely phlegmatized condition. They will not be discussed in this book, except for two substances displaying properties of primary explosives -< Tricycloacetone Peroxide and -> Hexamethylenetriperoxide Diamine. 

This compound is formed from acetone in sulfuric acid solution when acted upon by 45% hydrogen peroxide. It displays the properties of primary explosives. It is not used in practice because of its tendency to sublimation. 

Krc, J. Jr. (1955). Crystallographic properties of primary explosives. Quarterly Progress Report No. 2, Armour Research Foundation, Chicago, Illinois. [279t]... 

Impurities may have a profound effect on the chemical and physical properties of primary explosives. Of particular importance are metals, such as copper, that sensitize lead azide. An increased knowledge of the effect of impurities on explosive properties emphasizes the need for accurate determinations of these impurities. 

Properties of other higher a-olefins and those of some commercially significant cycloolefins are given in Table 2. These monomers are fiquids at ambient temperature and pressure. They are highly combustible and can form explosive mixtures with air. The primary health hazards presented by these monomers are associated with inhalation or prolonged skin contact that can cause irritation. 

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