Explosives, starch nitrates

Ethynylmagnesium bromide, II, 115, 116 Euxanthic acid, III, 97 Explosives, starch nitrates as, I, 303... 

Nitric acid Nitric acid Nitro starch Nitro starch Nitrocellulose Mitrated cornstarch Improvised explosive mixture Nitrated cellulose, Gun cotton, CeUulosetrinitrate... 

The most important of the carbohydrate esters of nitric acid are the polysaccharide nitrates, particularly cellulose nitrate or nitrocellulose (NC) and starch nitrate ( nitrostarch ) which is much less used. Nitric esters prepared from other sugars such as saccharose and lactose are not of any importance as explosives. 

Solutions of synthetic polyglucoses have also been used for density-gradient centrifugation of viruses. 16 These substances are especially suited to this purpose, since they can be dissolved in water or buffer to yield solutions of high concentration and low intrinsic viscosity and a density similar to that of sucrose solutions. Because of their low rate of diffusion, polyglucoses form gradients that are more stable. A polyglucose nitrate possessed explosive properties, similar to those of starch nitrates and cellulose nitrates.200... 

Steelites. Cheddite type expls patented in 1902 in Ger by E. Steele and manufd in Engl by Steelite Explosives Ltd. They contained K chlorate 72.5 to 75.5, oxidized rosin 23.5 to 26.5 and castor oil 0,5 to 1.5%. See refs under Chlorate Explosives in Vol 2, C206-R. See also under Colophony-Starch Nitrated Mixture in Vol 3, C404-L... 

Starch acetates have been extensively investigated both as to manner of preparation and as to properties. This is in contrast to the other organic esters of starch of which only a few have been prepared, and, of these, only a few characterized. Among the inorganic esters, the starch nitrates have received the most attention and have risen to industrial importance because of their use in explosives. Partly because of this use and the secrecy attending their manufacture, a full disclosure of the preparation and properties of starch nitrates has not been published. 

Nitric acid esters of starch are the oldest known starch derivatives and are the only starch esters commercially produced on a large scale. Like cellulose nitrates, the starch nitrates are excellent explosives. They are used extensively in blasting compositions, for quarrying and for certain types of mining. Tapioca starch was used mainly for commercial nitrations in the United States until the advent of World War II and the disruption of supplies made it necessary to nitrate com starch. This transition has been accomplished with little difficulty, although the exact process used is a trade secret. 

Explosives, examination of finisheblack powder, 29 dinitrobenzene, 47 dinit rocdil or hydrin, 41 dinitroglycol, 40 industnal blasting explosives, 54 lead azide, 60 mercury fiilminate, 59 nitrated polysaccharides, 42 nitrocellulose, 32 nitro-compounds (additional), 48 nitroglycerine, 39 nitromannite, 43 nitronaphthaienes, 47 picric acid and picrates, 44 smokeless powders, 49 starch nitrate, 41... 

One of the earliest attempts to make commercial use of starch nitrate was advanced by Davey, who, in 1863, obtained a British patent for improvements in the manufacture of gunpowder and explosive compounds. His use of mixed acids in the proportion of 1 of nitric acid to 3 of sulfuric acid should have been fairly satisfactory, but he boiled the slurry Whatever resulted could hardly have contributed to the propellants of the day. 

According to Snelling, i starch nitrate was first made in the United States around 1888 as a constituent of Dr. Volney s powder. The du Ponts experimented with starch nitrate as early as 1899, but it was not until 1905 that a plant was erected for its manufacture and use in the non-freezing explosive called Nyalite. The manufacture (by Du Pont) of Arctic starch nitrate explosives was started about 1907, and this explosive was made and sold extensively for a period of more than ten years. Starch nitrate explosives were also made in Canada. The Trojan Powder Co. was manufacturing starch nitrate for commercial blasting in this pre-World War I era. In the construction of the Panama Canal, large amounts of starch nitrate based explosives were used. . . and produced by the Trojan Powder Co. at its Eastern and West Coast plants. This company is at present the principal, if not the sole, source of commercial starch nitrate. 

The all-important problem of stability was receiving further attention in the United States of America during this pre-World War I period. J. B. Bronstein took out a number of U. S. patents covering the stabilization of starch nitrate with borates, soda ash, lime, and the like. His contributions to the U. S. patent literature, for the purpose of improved stabilization treatments and for the increased efficiency of explosive compositions of starch nitrate, extended from 1907-26 and J. B. Bronstein, Jr., was granted a patent in 1939 for improving colloidal compositions of starch nitrate. 

Hough s method of nitration in the presence of sulfur trioxide was checked in 1910 by Berl and Biitler. They made intercomparisons of various starch nitrates and showed the very great difference in viscosities between a starch nitrate and a cellulose nitrate. An interesting departure in the techniques for stabilizing starch nitrate was indicated by Nathan, Rintoul, and Baker of the Nobel Explosives Company in 1912 British patents were issued covering the use of urea derivatives as stabilizers. 

In the same year in which Sadtler s patent appeared, W. O. Snelling became Director of Research at the Trojan Powder Company, and he remained in that capacity for 37 years, until his retirement in 1954. The use of starch nitrate as an exceptionally adaptable, military, high explosive, in two World Wars, is intimately associated with the work of Dr. Snelling, as is also its development for civil use through improvements in its stability and in its explosive compositions. His U. S. patent literature is extensive. ... 

Walter Snelling s last U. S. patent on starch nitrate was issued in 1945 and covered an explosive composition of ammonium nitrate partially sensitized by starch nitrate. His first patent was issued in 1918 and covered an explosive, fertilizer cartridge for treating soils. He patented starch nitrate as a water-insoluble fertilizer in 1922 and 1924. 

Commercial starch nitrate has an average nitrogen content of about 13.2%. Its efficiency as an explosive is a direct function of the nitrogen... 

Pyroxylin Starch nitrate UN0146 UN1337. A nitric ester of starch, probably the octonitrate used for blasting explosives, either alone, or by mixing 10% of it with a mixture of sodium nitrate and carbonaceous material. See pyroxylin [9004-70-0]. 

Derivatives of starch. The esters and ethers of starch do not find the wide field of uses of their cellulose counterparts. Starch nitrate is used as a high explosive. Slight derivatization of starch yields a number of commercially useful products. 

Miller Explosive. Consisted of two mixts, each of them relatively inert, but becoming an expl when mixed. They contd Na nitrate 35, K chlorate 35 and starch 2ps, K dichromate 3, sulfur 13 and charcoal 12ps Ref Daniel (1902), 439... 

G.L. Griffith W.L. Schwoyer, USP 3457128 (1969) CA 71, 72517 (1969). Particulate self-explosive nitrated materials, such as Nitro-starch, PETN, TNT,.and their mixts, can be made relatively safe to handle and transport thru formation of a uniform nongelled aq slurry containing 10—50% water and 0.5—10% partially hydrolyzed polyacrylamide suspending agent having 0.1—50% free acid, and = 50% unhydrolyzed amide groups, and a mw of 1,000,GOO-... 

Keil Explosive. A mixt of nitrodextroglucose (prepd from starch) with K nitrate or chlorate vegetable fibers Ref Daniel (1902), 391... 

Leuschel Explosives. Ger expls prepd by impregnating moss with glucose, starch, sugar or glycerin solns, drying the mixt and nitrating the resulting product Ref Daniel (1902), 405... 

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