RESEP: PATENT SPECIFICATION Index at aeceptance:—Class 9(2), D. 737,129 Na, 10346154 Date of Application ond fling Complete Specification April 8, 1954. ‘Application made in United States of America on June 9, 1953. Complete Specificetio Published: Sept. 12, 1956. COMPLETE SPECIFICATION ‘Improvements in or relating to Propellents and method of making same”. We, Quin Marreson Cifemtcat, Conpon- amios, a corporation organised under the laws of the State of Virginia, United States of America, of East Alton, ilinois, United 5States of America, do hereby declare the Inyestion, for which we pray that a patent ay be granted to us, and the method by which it is to be performed, to be. particu- larly deseribed in’ and by’ the following 10tatement: — “This invention relates generally to ex lasives and more particularly to a propel- lent. ‘The present invention provides a propel- 1Slent composed of extruded nitrocellulose base propellent grains, characterized in that the cut surfaces of ae eas are so spacgd that the surface area of the grains is from 75 to 84 square centimetres per gram thereof, 20 the web is from 0.015 to 0,025 inch, and at least 3%, by weight of the grain of a non- migratory deterrent is dispersed throughout the region of the grain which extends from each surface one-sixth of the web of the 25 grain, said deterrent having a negative heat of explosion constant greater than —200 calories per gram, The propellent_ grains preferably have a heat of explosion constant ‘of not more than 900 calories per gram. 30 The present invention also provides a ‘method for making the. propellents charac- terized by extruding nitrocellulose powder base through a die, sub-dividing the powder base into propellent grains having a surface 35 area of from 75 to 84 square centimetres per gram and 2 web of 0.015 inch to 0.025 inch and thereafter, treating with at Teast 3% of a non-migratory deterrent having 4 negative heat of explosion constant greater 40 than —200 calories per gram only the region of the grain which extends from the surface thereof one-sixth of the web of the grain, Propellent grains having various shapes and chemical composition have been pro- 45 posed, heretofore, for .30 inch and similar (rice 3)-). caliber cartridges but none of them have been found entirely suitable in practice. Of these various types of propellents, tubular propollent grains having 2 dinittotoluene ‘coating on the grain have the least number SO ‘of disadvantages and, consequently, grains of this type have been utilized almost ex- clusively in such cartridges. These. grains are eminently suitable for the purpose ex- capt for the fact that the accuracy and ss efficiency of the projectile is no longer ac: ceptable after a relatively small number of ceatiridges have been fired in a machine gun or other rapid firing guns. This decrease in accuracy has been found to be due to the 60 inner wall of the barrel substantially adja- cent the breech being eroded or otherwise ‘damaged by the gases developed by the ex: plosion of the propellent. Heretofore, the only remedy for this condition has been t065 cease firing and change the gun_ barrel, which is of disadvantage to the operator and has not alleviated the disadvantage of short barrel life. It is therefore an object of this invention 70 to provide @ novel propellent charge for rapid fire guns. Another object of the in- vention is to provide 2 propellent which has improved ballistic propertics. Still an- other object of the invention is to provide 75 fa propellent for .30 inch and similar sized cartridges having improved barrel erosion characteristics. A further object is to pro- vide a method for making an extruded pellent suitable for utilization in machine 80 ‘guns and other rapid fire guns of .30 inch caliber. Tn accordance with this invention, the fore- going objects, as well as others which will become apparent from the following des- 85 cription are achieved by providing a propel- Tent composed of nitrocellulose propellent grains formed by extrusion and having a surface area within the range of from 75 square centimeters to 84 square centimeters90per gram thereof and having localized ad- jacent each surface of each grain not less than 3 per cent of a non-migratory deter- rent based on the weight of the powder grain Sand having @ negative heat of explosion constant greater than 200 calories per gram Shere, Ordinarily not more than 12 pet cent deterrent will be required preferably 65%, is used. The web of the propellent 10 grains must be within the range of 0.015 inch to 0.025 inch and the deterrent must be dispersed only in that region of the grain extending from each surface of the grain not more than one-sixth of the web of the 1Sgrain, The invention thus contemplates shaping a nitrocellulose powder base by an extrusion process, subdividing the extruded powder base into propellent grains having a surface area of from 75 to 84 square csntic 20 meters per gram thereof and a web of from 0.015 inch to 0.025 inch, and thereafter dis- persing a non-migratory’ deterrent having a ‘ogative heat of explosion constant greater than —-200 ealories per gram throughout that 25region of the grain extending from each sur- thereof not more than one-sixth of the grain’s web. ‘The grain is preferably ex- truded through a die adapted to impart the desited web to the nitrocellulose but the 30.grain can be formed by an extrusion pro- cess, cut to length and thereafter rolled to the required web. For most practical pur- poses, deterrents having heat of explosion constants as low as —1000 to —250 calories 35 per gram are preferred although, as stated hereinbefore, deterrents having @ negative heat of explosion constant greater than —~200 calories per gram can be utilized, but ob- viously are not as eflective. 40. ‘The deterrent must be non-migratory at all temperatures to. which propellents” are ordinarily exposed in order that the deter- rent will remain substantially uniformly dis persed within the specified region of the 45 grain and no significant amouat theseof will penetrate into the grain’s core, Any non- Iigratory deterrent having a negative heat of explosion constant greater than —200 calories per gram can be utilized such as, S0for example, the diakyl phthalates like butyl phthalate and diemyl phthalate, the diaryl phthalates like diphenylphthalate, triphenyl phosphate, butyl. stearate, diaryl dialkylureas such as diethyl dipheny! urea, 55imethyl ethyl diphenyl urea and dimethyl diphenyl urea, glycerol sebacate, tricresyl phosphate. The provess disclosed by Mc- Bride in U.S. 1,955,927 whereby the depth cf penetration of the deterrent is controlled 6 by limiting the tumbling time and the tem- perature in the sweetie barrel, has been found to be particularly advantageous for properly locating the deterrent in the proper region of the propellent grain. 65 ‘The “heat of explosion” constant of a 757,129 constituent of powder grains is a well known ‘erm in the industry and has been deter- mined from the heat of combustion of the ‘material utilizing calculations involving the formulae published by dePauv in articles in70 “Zeitschrift far das gesamte Schiess-und Sprengstoffwesen” volume 32, pp. II, 36 and 60 (1937). Actually the value assigned as the heat of explosion of deterrents is a constant which represents the effect of the 75 ‘material on the heat emitted upon firing of the explosive constituents of the grain This constant can also be determined ex- perimentally. Tn such a method, a dried sample of 2 propellent powder not having 80 any deterrent in its composition is burned in ‘an adiabatic calorimeter bomb having a hitrogen atmosphere therein and the heat of combustion is measured by conventional procedures. Another dried sample of pro-85 pellent substantially identical with the one utilized in the foregoing with the exception that a known amount of deterrent is incor- porated in the grain is then burned in the bomb and the heat of combustion deter-90 mined. The difference between the heat of combustion of the untreated propelient and the treated propellent divided by the weight ‘of the deterrent is designated the heat of explosion of the deterrent, Thus the heat 95 of explosion constant of a deterrent isa measurement of the effect of the deterrent con the explosion temperature of a propel- Jent base material. “For example, to deter- mine the heat of explosion of dibutyl- 100 phthalate, a dried sample of a propellent Composed of about 90 per cent nitrocellu- lose and about 10 per cent nitroglycerine was burned in a calorimeter bomb having a nitrogen atmosphere. ‘Then another 105 sample of this propelient treated in accord. ance with this invention to contain about 7 per cent dibutylphthalate was burned under similar conditions. ‘The heat of explosion of the propellent without deterrent was110 found to be 1070 calories per gram of pro- pellent burned, while the heat of explosion of the propelent which contained the deter- rent was found to be 840 calories per gram ‘of propellent burned. Inasmuch as 93. per 115 cent of the grain” was nitrocellulose and nitroglycerine base material the heat due to the buming of this explosive portion of the charge of propellent having a deterrent should have been (93 x 1070) or 994199 calories. Subtracting 840 calories which was actually obtained in the test_ from 994 calories leaves 154 calories difference per gram between the heat of explosion between the two propellents. ‘This decrease is due to the deterrent since it was the only var able. There was only .07 grams of dibutyl phthalate per gram. of propellent so 154 Tnust be divided by .07 to determine the effect of the deterrent on propellenis in 130 25terms of grams of deterrent. In other words each gram of dibutylpbihslate will reduce the heat of explosion of a propellent about 2200 calories. In order to indicate that it Seduced the heat of explosion of the pro- pellent the number is referred to as a nega: tive number. “Hence the heat of explosion of dibutylphthalate is about —2200 calories Per_gram. . ; 10 The propellent grains are shaped into tubular or rod form by extruding partially or completely colloided nitrocellulose through a die and thereafter subdividing the rod or tube into grains of suitable length, 15 The grains may or may not have one of ‘more perforations therein. provided the specific surface is within the range of 75 square centimeters to 84 square centimeters pet gram of propellent. If the grain is per- 20 crated, the walls of the perforation must be deierrent treated along with the other sur- faces of the grain and, for that reason, solid grains or perforated grains wherein the dimensions of the perforation are such as 25 o facilitate coating the walls thereof are preferred. Best results are obtained i the Tength of the grain is substantially equal to the thickness thereof. with the well known ing deterrents and energiz- ing modifiers to obtain the desired ballistic effects with nitrocellulose propellents, the deterrent may be adjusted within the 3 per cent to 12 per cent limit specified herein- 35 before to obtain the ballisties essential for the partictular 0.30. inch caliber and, if necessary or desired to. produce particular ballistic effects the propellent grains may be impregnated with an energizing modifier, 40for example a liquid explosive nitric ester ‘of a polyhydric. alcohol, such as_nitro- slycerine before treatment with the deter- rent. Ordinarily, powder grains having a specific gravity of about 1.5 are utilized, but 45 the powder grains of this invention having a lower specific gravity are also less erosive to the gun barrel. The amount of energiz~ ing modifier required for double base pro- pellent is usually within the range of 10 to 50 20 per cent by weight of the propellent grain preferably 10° nitroglycerine. By “web” as utilized herein and in the appended claims is meant the minimum thickness between any two surfaces of solid 5Sor perforated grains. Hence, the web of a tubular grain may be the minimum distance between the wall bounding a perforation and ‘another surface of the grain or it may be the distance between two extemal surfaces of 40the grain depending upon which distance is the smaller and the word web is used here in its usual sense in the art, No definite explanation has been resolved as to why the propellent of this invention “65is less erosive 10 the breech end of a gun barrel than the hereiofore conventional pro- pplents incorporating deterrents having a negative heat of explosion constant less than 200 calories per gram and having a surface area of only one-talf or less of that of the 70 propellent of this invention, However, it hhas been found that cartridges loaded with the propellent of the type provided by this invention exhibit 2 phenomenal improvement over similar cariidges loaded with a powder 75 charge composed of perforated grains made in accordance with the process disclosed in ‘Technical Manual No, 9-290 entitled Military Explosives” published August 29, 1940 by the War Department of the80 United States Government. In this test the barrel is considered no longer suitable when the flight of the projectile indicates a yaw of at Teast ten degrees or when the muzzle velocity of the projectile has decreased more 85 than 200 feet per second In order to further clarify the invention, the following is a detail description of an embodiment thereo. ‘A Powder base having an average nitro-90 agen content of about 13.2 por cent is ob- tained by mixing about 3 parts by weight nitrocellulose having a nitrogen coxient of about 13.4 per cent with about one part nitrocellulose having nitrogen content of 95 about 12.6 per cent. About 100 parts by Weight of the resulting nitrocellulose is de- hydrated with about 125 parts of ethyl al- echol in a conventional dehydrating press. The resulting block of about 100 parts nitro- 100 cellulose and about 33 parts aleohol is broken up and 66 parts diethyl ether is added thereto to partially colloid the mass. Daring the agitation 10 completely mix the solvent with the nitrocellulose, about one 105, part diphenylamine is added. "The colloid Js next pressed into a block, foreed through an extrision die and again ‘blocked in cot ventional equipment and finally grained by extruding through a die adapted to produce 110 a solid tod, the die~ having an. internal diamoter of about 01042 inch, The solid rod is cut to lengths substantially equal to. its diameter to form solid, substantially ey drical propelient grains. The ether-aloohol 115 and other volatiles are removed by air diy- ing in trays stored in 2 room having en average temperature of about 30°C. the first 24 hours, about 40°C. the next 24 hours and about 45°C. for about one week. About 100 patts of the resulting propel- lent grains ate suspended in abcut 330 parts water. “About 22 parts of an emulsion of about 11 parts nitroglycerine, about 4 parts ethyl acetate and about 7 paris toluene and 195 about 0.1 part gum arabic in about 75 parts water are added and the temperature of the slurry is raised to about 65°C. and further increased to about 70°C. in a period of about four hours. The ethyl acetate and 130 120757,129 toluene are then removed by passing ait through the slurry while continuing the agi- tation thereof. About 13 hours are required for substantially complete removal of ‘the Solvent after which the temperature is raised to about 72°C. and about 14 parts gum arabic are added. ‘An emulsion of about 72 parts dibutyl- phthalate and about 0.05 parts emulsifying io agent such as gum arabie in about 20 parts water is added and the resulting slurry agi- fated for about 5 hours after which the copellent grains are separated from the Figuid. About 1000. parts of the resulting 1Sgrains are coated with about 5.0 parts potassium nitrate, about 2.5 parts diphenyl- thalate and about one-half part dinitro- luene by tumbling the grains therewith in a. sweetie barrel for about 30 minutes at 2055°C. after which about 0.4 parts graphite are added and tumbling js continued for an additional 30 minutes. ‘The resulting grains have a surface area of about 77 square centi- meters per gram of propellent, have a web 25of about 0.016 inch and contain about 65 per cent by weight of dibutylphthalate dis- persed in that region of the grain extending From each surface thereof about 0.0025 inch. "While the foregoing embodiment has been 20 described in detail with rexpet to 0.30 inch ibet_propellents, propellent, charges. for other guns in this range of calibers such us caliber 303, 7.92 millimeter, 7. millimeter are contemplated by the invention, 35” ‘The invention has been described in de- tail in the foregoing for the purpose of illustration and variations therein will occur to those skilled in the art and can be made without departing from the scope of the 40 appended claims. For example, other suit- able methods can be utilized Tor treating the propellent grains with the deterrent. Likewise, if a double base propellent is de- sired, any suitable method for incorporating 45 tho energizing modifier in the grain can be utilized, As pointed out hereinbefore, how- ever, single base. nitrocellulose propellents are Suitable for the purpose. Furthermore, for some purposes, it might be desirable to Sinclude certain ballistics modifiers such as carbon black, ‘What we claim is: — 1. A propellent composed of extruded nitrocellulose base propellent grains, char- SS acterized in that the cut surfaces of said grains are so spaced that the surface area Of the grains is from 75 to 84 square centi- meiets per gram thereof, the web is from 0.015 to 0.025 inch, and at least 3% by Oweight of the grain of a non-migratory de- terrent is dispersed throughout the region of the grain which extends from each sur- face one-sixth of the web of the grain, said deterrent having 2 negative heat of explo- 65sion constant greater than —200 calories per gram. 2, A propellent according to Claim 1, characterized by the feature that said pro- pellent has a heat of explosion constant of Hot more than SOD calories per gram thre-70 3._A propellent according to Claim 1 or 2, characterized by the feature that said grains have a surface area of 77 square centimeters per gram thereof and a web of 75 0.016 inch, 4, A propellent according to Csi 1, 2 or 3, characterized by the feature that the ‘grains each contain 6.5 per cent of the non- migratory deterrent. 80 5. A propellent according to any of the preceding claims, characterized by the feature. that said ‘deterrent has a negative hheat of explosion constant greater’ than —1000 calories per gram. 6. A propellent according to Claims 2, 3 and 4, characterized by the feature that 6.5%, dibutylphthalate is dispersed through- oat the region of the grain which extends from each surface 0.0025 inch, 7. A propellent according to any of Claims 1 to 5, characterized by the feature that said grains are solid substantially cylin~ Grical propellent grains. 8. A propellent according to any of the 95 preceding claims, characterized by the feature that it contains from 3 to 12% of said deterrent 9. A method for making the propellents characterized by extruding nitrocellulose 100, powder base through a dio, subdividing the powder base into propellent grains having a surface area of from 75 to 84 square centi- meters per gram and a web of 0.015 inch to 0.025 inch and thereafter, treating with 105 at least 3% of a non-migratory deterrent hhaving a negative heat of explosion con- stant greater than —200 calories per gram only the region of tho grain which exends from each surface thereof one-sixth of the 110 web of the grain 10. A method according to Claim 9, characterized by the feature that said powder base is gelatinized nitrocellulose powder base. Il. A method according to Claim 9 or 10, which is further characterized by im- pregnating the grains with a liquid explosive nitric ester of a polyhydric alcohol and thereafter treating them with the non- 120 migratory deterrent. 12, A method according to Claim 9, 10 or Ii which is further characterized by im- pregnating the grains with 10 to 20 per cent nitroglycerine and thereafter treating with 125 65 per cent of the dibutylphthalate deter- rent only the region of the grain which ‘extends from each surface thereof 0.0025 inch, 13. A propellent substantially as herein 130 85 » us75129 described. STEVENS, LANGNER, PARRY & 14 A method of making propellonts 'ROLLINSON, substantially as herein described. ‘Chartered Patent Agents, Agents for the Applicants. Printed for Her Majesty's Stationery Office by Maximus Printing jPortsmouth. 335 uted ae ue! Oe, 23, Souampion ul ‘ide fon, W.C2, from which copies