US3236704A - Propellant composition - Google Patents
Propellant composition Download PDFInfo
- Publication number
- US3236704A US3236704A US3236704DA US3236704A US 3236704 A US3236704 A US 3236704A US 3236704D A US3236704D A US 3236704DA US 3236704 A US3236704 A US 3236704A
- Authority
- US
- United States
- Prior art keywords
- composition
- combustible
- propellant
- weight
- nitrocellulose
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000203 mixture Substances 0.000 title claims description 112
- 239000003380 propellant Substances 0.000 title claims description 86
- 239000000463 material Substances 0.000 claims description 58
- 239000000020 Nitrocellulose Substances 0.000 claims description 26
- 229920001220 nitrocellulos Polymers 0.000 claims description 26
- 229920000642 polymer Polymers 0.000 claims description 22
- 239000000843 powder Substances 0.000 claims description 20
- 230000003179 granulation Effects 0.000 claims description 12
- 238000005469 granulation Methods 0.000 claims description 8
- 239000004033 plastic Substances 0.000 claims description 6
- 229920003023 plastic Polymers 0.000 claims description 6
- 229920005989 resin Polymers 0.000 description 36
- 239000011347 resin Substances 0.000 description 36
- 239000011230 binding agent Substances 0.000 description 20
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 description 18
- 150000001875 compounds Chemical class 0.000 description 18
- 229920000728 polyester Polymers 0.000 description 12
- RMBFBMJGBANMMK-UHFFFAOYSA-N 2,4-Dinitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O RMBFBMJGBANMMK-UHFFFAOYSA-N 0.000 description 10
- 229920001342 Bakelite® Polymers 0.000 description 10
- 239000004637 bakelite Substances 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 10
- 239000004615 ingredient Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 238000002156 mixing Methods 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- DMBHHRLKUKUOEG-UHFFFAOYSA-N Diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 8
- 239000003431 cross linking reagent Substances 0.000 description 8
- 125000005442 diisocyanate group Chemical group 0.000 description 8
- 239000003822 epoxy resin Substances 0.000 description 8
- 238000009472 formulation Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 229920000647 polyepoxide Polymers 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 239000002253 acid Substances 0.000 description 6
- 150000008065 acid anhydrides Chemical class 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000011068 load Methods 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- VZCYOOQTPOCHFL-OWOJBTEDSA-N (E)-but-2-enedioate;hydron Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- SNIOPGDIGTZGOP-UHFFFAOYSA-N 1,2,3-propanetrioltrinitrate Chemical compound [O-][N+](=O)OCC(O[N+]([O-])=O)CO[N+]([O-])=O SNIOPGDIGTZGOP-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N Adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N Barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 4
- PZIMIYVOZBTARW-UHFFFAOYSA-N Centralite Chemical compound C=1C=CC=CC=1N(CC)C(=O)N(CC)C1=CC=CC=C1 PZIMIYVOZBTARW-UHFFFAOYSA-N 0.000 description 4
- 229960002380 Dibutyl Phthalate Drugs 0.000 description 4
- DOIRQSBPFJWKBE-UHFFFAOYSA-N Dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 4
- WZCQRUWWHSTZEM-UHFFFAOYSA-N M-Phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 4
- 239000000006 Nitroglycerin Substances 0.000 description 4
- 229940014995 Nitroglycerin Drugs 0.000 description 4
- 229950006286 Pentrinitrol Drugs 0.000 description 4
- OTYBMLCTZGSZBG-UHFFFAOYSA-L Potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 4
- BRBAEHHXGZRCBK-UHFFFAOYSA-N [2-(hydroxymethyl)-3-nitrooxy-2-(nitrooxymethyl)propyl] nitrate Chemical compound [O-][N+](=O)OCC(CO)(CO[N+]([O-])=O)CO[N+]([O-])=O BRBAEHHXGZRCBK-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 150000008064 anhydrides Chemical class 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 230000001419 dependent Effects 0.000 description 4
- 150000004985 diamines Chemical class 0.000 description 4
- 238000003379 elimination reaction Methods 0.000 description 4
- BRLQWZUYTZBJKN-UHFFFAOYSA-N epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 4
- 229960003711 glyceryl trinitrate Drugs 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 229920005749 polyurethane resin Polymers 0.000 description 4
- 229910052939 potassium sulfate Inorganic materials 0.000 description 4
- 235000011151 potassium sulphates Nutrition 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 229920001169 thermoplastic Polymers 0.000 description 4
- 239000004416 thermosoftening plastic Substances 0.000 description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N 1,2-ethanediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N 1,4-Butanediol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N Bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- 239000004641 Diallyl-phthalate Substances 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N Diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- VJZWIFWPGRIJSN-XRHABHTOSA-N Dilinoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O.CCCCC\C=C/C\C=C/CCCCCCCC(O)=O VJZWIFWPGRIJSN-XRHABHTOSA-N 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N Maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- IDCPFAYURAQKDZ-UHFFFAOYSA-N Nitroguanidine Chemical compound NC(=N)N[N+]([O-])=O IDCPFAYURAQKDZ-UHFFFAOYSA-N 0.000 description 2
- KDLBMFGTFLOMMG-UHFFFAOYSA-N OC1(CC=C(C=C1)O)C(C)(C)C1(CC=C(C=C1)O)O Chemical compound OC1(CC=C(C=C1)O)C(C)(C)C1(CC=C(C=C1)O)O KDLBMFGTFLOMMG-UHFFFAOYSA-N 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- REHXRBDMVPYGJX-UHFFFAOYSA-H Sodium hexafluoroaluminate Chemical compound [Na+].[Na+].[Na+].F[Al-3](F)(F)(F)(F)F REHXRBDMVPYGJX-UHFFFAOYSA-H 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N Toluene diisocyanate Chemical group CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- -1 aliphatic amines Chemical class 0.000 description 2
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 229910001610 cryolite Inorganic materials 0.000 description 2
- 230000002939 deleterious Effects 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000003628 erosive Effects 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- 125000003916 ethylene diamine group Chemical group 0.000 description 2
- 239000002360 explosive Substances 0.000 description 2
- 230000036748 firing rate Effects 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N fumaric acid Chemical compound OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N oxane Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 239000004848 polyfunctional curative Substances 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 239000004323 potassium nitrate Substances 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Inorganic materials [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 235000010333 potassium nitrate Nutrition 0.000 description 2
- 239000001120 potassium sulphate Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000002760 rocket fuel Substances 0.000 description 2
- 239000004449 solid propellant Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000001384 succinic acid Substances 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- 239000012209 synthetic fiber Substances 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N tin hydride Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 2
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 2
- 239000011800 void material Substances 0.000 description 2
Classifications
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B21/00—Apparatus or methods for working-up explosives, e.g. forming, cutting, drying
- C06B21/0033—Shaping the mixture
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B45/00—Compositions or products which are defined by structure or arrangement of component of product
- C06B45/04—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive
- C06B45/06—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive the solid solution or matrix containing an organic component
- C06B45/10—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive the solid solution or matrix containing an organic component the organic component containing a resin
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B25/00—Compositions containing a nitrated organic compound
- C06B25/34—Compositions containing a nitrated organic compound the compound being a nitrated acyclic, alicyclic or heterocyclic amine
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S149/00—Explosive and thermic compositions or charges
- Y10S149/11—Particle size of a component
- Y10S149/111—Nitrated organic compound
Definitions
- the present invention relates to combustible casing material and to the methods of making the same. More particularly the invention is concerned with combustible casing material that may be formed in the shape of, and serve as, combustible cartridge cases or the like.
- Another disadvantage of the prior art material is that the combustible casing material has added no appreciable propelling effect to the shell thus in no way allowing for the reduction in the propellant loading.
- Yet another disadvantage of the prior art is that known combustible casings are formed of lamiuations and thus are not readily adaptable to cheap and fast mass production as by, for example, molding.
- a primary object of the present invention is the provision of a combustible cartridge case having the necessary strength characteristics and which will burn completely when fired in conventional weapons.
- Another object of this invention is to provide a combustible casing constructed of propellant grains bonded together with a binder, thus allowing a reduction in the propellant loading.
- Yet another object of this invention is to provide a composition of matter which may be molded into any desired shape and which will be smokeless when burned.
- the method of making the present invention consists of mixing one or more granulations and formulations of propellant grains with a resin binder so that the grains are held in a matrix of the resin.
- the quantity and size of the propellant grains which are held suspended in the resin matrix may be varied to give a uniformly porous structure to the combustible casing material.
- a combustible material can be obtained which, as further pointed out below, leads to the feature of a mass burning rate which is to only a small extent dependent on structure or wall thickness.
- the material may be formed into any desired shape or easing form by, for example, being molded in the shape of cartridge casings or rocket tubes which may then be filled with an appropri ate propellent material.
- the combustible casing material of the present invention should not be confused with prior combustible materials of the cast propellant type.
- cast propellants very careful attention is given to getting a propellant completely free of voids or porous structure and as homogeneous as possible in composition. Since cast propellants do not have a void or porous structure, it has a burning rate which is essentially dependent on the chemical composition. Thus, the mass burning rates of cast propellants, for a given grain size or web, are considerably lower than for the type of propellant composition disclosed in the present invention. Since cast propellants have a mass burning rate that is relatively low, there is a practical limitation on the size or thickness of a casing wall that may be constructed of the cast propellants.
- the resin or binder materials which may be used by the process of this invention may be chosen from the large group of binding substances including polyesters, polyurethane and epoxy resins.
- Petrin acrylate which is a nitropolymer may also be used as a binder.
- the petrin acrylate monomer is a solid which is fused, mixed with the propellant grains and then cured at an elevated temperature.
- nitropolymers which are known to be suitable for binder material.
- a number of granulations and formulations of propellant grains may be used with the binder material to form a combustible casing having controlled voids.
- the compositions of propellant grains which may be used are given below.
- Various other propellant agents may be used with the resin, as the only limitation on the propellants that may be used appears to be that they must be solids and chemically compatible with the resin used.
- the resins and propellant grains are mixed in a mixer of the type which will avoid crushing of the propellant grains since any crushing would result in a mixture whose ballistics would be unpredictable and, therefore undesirable.
- One mixer which has been found suitable for use in the present invention is the Sigma blade type.
- a Sigma blade mixer consists of a container in which two' arms, approximately in the shape of the letter Z, rotate in opposite directions to impart a kneading action to the material being mixed.
- the mixing operation of the present invention is not limited to the use of the Sigma blade mixer but any mixer which will not crush the propellant grains would be suitable.
- fibers of various types both natural and synthetic, such as, for example, nitrocellulose or cotton to the resin and propellant mixture.
- These various fibers give additional strength to the casing where such is necessary.
- Example I To 90 parts of a powder composition, which consists of:
- Epon 828 serves as a binder and is an epoxy resin manufactured by reacting epichlorohydrin with 2,2-bis(p-hydroxyphenyl) propane
- Versamid 125 which acts as a hardening agent is one of a group of Versamid polymers ranging from a polymer which is a liquid at room temperature to a polymer which is a solid at room temperature and which has a softening point of 190 C. They are prepared by the condensation of polymerized unsaturated fatty acids (e.g.
- dilinoleic acid with aliphatic amines such as ethylene diamine.
- This composition of three ingredients was blended in aSigma blade mixer until well blended.
- the composition was then cast into hollow tubes, or into the annulus between concentric tubes or in other suitable molds.
- the composition was then allowed to cure at temperatures from 50 F. to 212 F. for 45 minutes to 24 hours, depending on the curing temperature.
- Example II To 90 parts of a powder composition, which consists Nitrocellulose (13.15% N) 100.00%. Dinitrotoluene 8.00 parts added. Potassium sulphate 1.00 part added. Diphenylamine 0.7 part added.
- Epon 828 is described in greater detail in Example I and Versamid 115 is similar in composition and used interchangeably with the Versamid 125 described in Example I.
- This composition of three ingredients was blended in a Sigma blade type mixer until homogeneous. The composition was then cast into hollow tubes or other suitable molds. The composition was then allowed to cure at temperatures from 50 F. up to 212 F. for 45 minutes to 24 hours depending on the curing temperature.
- Example III To 87.5 parts of a powder composition, which is described in greater detail in Example I, having a granulation range of from 0.025" to 0.034", was added a mixture of 4 parts of Epon 828 and 0.8 part of Accelerator Z.
- Epon 828 is described in greater detail in Example I while Accelerator Z is a mixture of meta-phenylenediamine with a fluid resin.
- This composition of three ingredients was blended in a Sigma blade type of mixer until homogeneous. To the blend was then added 2.5 parts of a natural or synthetic fiber such as acetate rayon cut to /2" lengths. The mixing was then continued in the same mixer until the final formulation was Well blended. The formulation was then cast into the annulus between two concentric tubes and the composition was pressed at 4000 psi. Finally, the formulation was allowed to cure for 24 hours at 140 F. The tube was then removed from the mold.
- Example IV To parts of a powder composition, which consists of:
- Bakelite ERL 2795 is an epoxy resin made by reacting a polyfunctional compound such as, for example 2,2bis(p-dihydroxyphenyl) propane with epichlorohydrin.
- Bakelite ERL 2793 is an aliphatic amine used as a curing agent for Bakelite ERL 2795. This composition of three ingredients was blended in a Sigma blade mixer until homogeneous. To the blend was then added 2 parts of nitrocellulose fibers approximately 1" in length. The mixing was then continued until the formulation was well blended. The composition was then cast into a cylindrical mold and cured for 48 hours at room temperature. The cylinder was then removed from the mold.
- the resins that are used may be any liquid polymer or monomer or a solid polymer or monomer that may be fused below the maximum temperature at which a propellant may be safely handled. This temperature varies with different propellants but may be defined as the temperature at which the propellants may explode.
- Suitable unsaturated polyesters may be prepared by reacting a compound containing two or more hydroxyl groups with an acid or acid anhydride containing at least two carboxyl groups and at least one unsaturated ethylenic double bond. Examples of compounds containing two or more hydroxyl groups are ethylene glycol, glycerol, pentaerythritol, propylene glycol, butanediol-1,4 and others.
- Examples of compounds containing two or more carboxyl groups and at least one unsaturated bond are maleic anhydride, maleic acid, fumaric acid, and others.
- other dicarboxylic acids or acid anhydrides e.g. succinic acid, adipic acid, etc.
- succinic acid, adipic acid, etc. are simultaneously reacted with the above mentioned hydroxyl and carboxyl containing compounds to modify the properties of the resulting unsaturated polyester.
- the unsaturated polyester 1s then blended with a crosslinking agent such as styrene or diallyl phthalate.
- the crosslinking reaction is made to proceed under the influence of heat and/ or a peroxide catalyst agent.
- Polyurethane resins such as may be used in the present invention are formed when hydroxyl-containing compounds react with diisocyanates.
- the hydroxyl-containmg compounds may be glycols, polyols, hydroxyl-contaming polyesters or polyethers.
- the reaction may be s mply depicted for illustrative purposes by monofunctional reactants as follows:
- the diisocyanate used is usually one or a mixture of the tolylene diisocyanate group of isomers. However, other diisocyanates may be used.
- An alternate method of preparing polyurethane is by pre-reacting a polyester with an excess of diisocyanate and then crosslinking the residual isocyan-ate groups with an amine or other compound containing a reactive hydrogen.
- Epoxy resins such as may be used in the present invention may be prepared by condensation of epichloro- 'hydrin with a diphen-olic compound.
- a typical reaction of this type would be the following:
- propellant grains As stated above, various other propellant grains may be used with excellent results. Among these propellant grains are:
- Grain propellant consisting of Nitrocellulose (13.15% N) 85.00 Dinitrotoluene 10.00 Dibutylphthalate 5.00
- Grain propellant consisting of Nitrocellulose (13.15% N) 77.45 Nitroglycerin 19.50 Barium nitrate 1.4- Potassium nitrate 0.75 Ethyl centralite 0.60 Graphite 0.30
- Grain propellant consisting of- Nitrocellulose (13.15% N) 20.00 Nitroglycerin 19.00 Nitrogu-anidine 54.70 Ethyl centralite 6.00 Cryolite 0.30
- solid propellants may be used as long as the resin binder used does not cause any chemical break-down or deterioration of the propellant and the propellant does not interfere in a deleterious manner with the curing of the resin binder.
- the operable ratio range of resin to propellant grains is not restricted to the range given in the above examples but may vary from :95 to 45:55. However, the optimum ratio range of resin to propellant grains has been found to be from 10:90 to 35:65.
- the operable range of the propellant grain size is only limited in that the larger grain sizes generally yield physically weak structures. However, grains having a diameter as large as .080 can be successfully used. In some applications, the grain size must be selected to satisfy the particular burning time requirement, in accordance with the principles of the science of interior ballistics.
- compositions made in accordance with this invention are capable of being formed or shaped into tubes, solid cylinders or other shapes by the use of appropriate molds.
- the product resulting thereby is a combustible material suitable for use for such items as combustible cartridge cases, combustible primer-s, combustible initiators and other items where the combustion of the item in use is desirable or required.
- the compositions can be made ballistically smokeless.
- a composition for a combustible cartridge casing consisting essentially of about 90% by weight of a granular nitrocellulose base propellant intimately mixed and dispersed in about 10% by weight of a plastic consisting of cross-linked, three-dimensional polymers.
- a composition for a combustible cartridge case consisting essentially of about 90% of a particulate powder composition, the said powder composition having a granulation range of 0.025" to 0.034" and containing to by weight of nitrocellulose (13.15% N) and 0.8 to 10% by weight of dinitrotoluene, the said particulate powder composition being in intimate and uniform mixture with about 10% 'by weight of a cross-linked, three dimensional polymeric material.
- composition according to claim 2 in which the polymeric material is cross-linked with a diamine.
- composition according to claim 2 in which the polymeric material is cross-linked with the anhydride of a dibasic acid.
- a combustible cartridge casing resistant to deformation by cold flow prepared by molding the composition according to claim 2.
- crosslinking agent is meta-phenylene diamine.
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Description
United States Patent 3,236,704 PROPELLANT COMPOSITION Sydney Axelrod, New York, N.Y., and George Demitrack, Denville, N.J., assignors to the United States of America as represented by the Secretary of the Army No Drawing. Filed July 19, 1961, Ser. No. 126,843
8 Claims. (Cl. 149-19) (Granted under Title 35, US. Code (1952), see. 266) The invention described herein may be manufactured and used by or for the Government for governmental purposes without the payment to us of any royalty thereon.
The present invention relates to combustible casing material and to the methods of making the same. More particularly the invention is concerned with combustible casing material that may be formed in the shape of, and serve as, combustible cartridge cases or the like.
The advantages of combustible cartridge cases will be apparent to those skilled in the art. The firing rates of weapons in which combustible cartridge cases are used may be increased substantially due to the elimination of the ejection operation which would also result in a saving of weight and space in the weapon. The problem of disposal of metal shell cases is eliminated, creating thereby a saving of metals which might become critically short in supply during times of emergency. Furthermore, the elimination of .the conventional metal case results in a considerable saving in weight. An additional advantage of combustible cartridge cases may involve the possible reduction in gun erosion. Yet another use of combustible casing material would be in the manufacture of rocket casing that would be consumed as the rocket fuel was burned, thus eliminating a considerable dead weight found in prior metal rocket casings.
Prior methods and materials used for the manufacture of combustible casings have had the disadvantage that it has been difiicult to maintain the stability, strength and ballistic properties of the combustible material. This is particularly true where non-crystalline thermoplastic material was used, since these materials undergo an extensive amount of creep under normal storage conditions. This creep is a cold-flow process which is proportional to temperature and applied load. These non-crystalline thermoplastic materials have proven unsuccessful as combustible casing material since they will quite readily deform under their own weight.
Another disadvantage of the prior art material is that the combustible casing material has added no appreciable propelling effect to the shell thus in no way allowing for the reduction in the propellant loading. Yet another disadvantage of the prior art is that known combustible casings are formed of lamiuations and thus are not readily adaptable to cheap and fast mass production as by, for example, molding.
Accordingly, a primary object of the present invention is the provision of a combustible cartridge case having the necessary strength characteristics and which will burn completely when fired in conventional weapons.
Another object of this invention is to provide a combustible casing constructed of propellant grains bonded together with a binder, thus allowing a reduction in the propellant loading.
Yet another object of this invention is to provide a composition of matter which may be molded into any desired shape and which will be smokeless when burned.
Other objects and advantages of the present invention will become apparent to those skilled in the art from a study of the accompanying disclosure.
In one of its broad aspects, the method of making the present invention consists of mixing one or more granulations and formulations of propellant grains with a resin binder so that the grains are held in a matrix of the resin. The quantity and size of the propellant grains which are held suspended in the resin matrix may be varied to give a uniformly porous structure to the combustible casing material. By using this method, a combustible material can be obtained which, as further pointed out below, leads to the feature of a mass burning rate which is to only a small extent dependent on structure or wall thickness. As previously indicated, the material may be formed into any desired shape or easing form by, for example, being molded in the shape of cartridge casings or rocket tubes which may then be filled with an appropri ate propellent material.
The combustible casing material of the present invention should not be confused with prior combustible materials of the cast propellant type. In cast propellants, very careful attention is given to getting a propellant completely free of voids or porous structure and as homogeneous as possible in composition. Since cast propellants do not have a void or porous structure, it has a burning rate which is essentially dependent on the chemical composition. Thus, the mass burning rates of cast propellants, for a given grain size or web, are considerably lower than for the type of propellant composition disclosed in the present invention. Since cast propellants have a mass burning rate that is relatively low, there is a practical limitation on the size or thickness of a casing wall that may be constructed of the cast propellants. However, because of the burning properties of the propellant composition described herein, which are brought about by the introduction of controlled voids in the porous structure of the propellant material, and the size of the propellant grains suspended in the resin matrix it is ideally suited for applications where a heavy wall for structural strength and a short burning time is required.
The resin or binder materials which may be used by the process of this invention may be chosen from the large group of binding substances including polyesters, polyurethane and epoxy resins. Petrin acrylate which is a nitropolymer may also be used as a binder. The petrin acrylate monomer is a solid which is fused, mixed with the propellant grains and then cured at an elevated temperature. There are also other nitropolymers which are known to be suitable for binder material.
A number of granulations and formulations of propellant grains may be used with the binder material to form a combustible casing having controlled voids. The compositions of propellant grains which may be used are given below. Various other propellant agents may be used with the resin, as the only limitation on the propellants that may be used appears to be that they must be solids and chemically compatible with the resin used.
The resins and propellant grains are mixed in a mixer of the type which will avoid crushing of the propellant grains since any crushing would result in a mixture whose ballistics would be unpredictable and, therefore undesirable. One mixer which has been found suitable for use in the present invention is the Sigma blade type. A Sigma blade mixer consists of a container in which two' arms, approximately in the shape of the letter Z, rotate in opposite directions to impart a kneading action to the material being mixed. However, the mixing operation of the present invention is not limited to the use of the Sigma blade mixer but any mixer which will not crush the propellant grains would be suitable.
In some cases it has been found desirable to add fibers of various types, both natural and synthetic, such as, for example, nitrocellulose or cotton to the resin and propellant mixture. These various fibers give additional strength to the casing where such is necessary.
In order to point out more fully the nature of the present invention, the following specific examples are given of illustrative methods of preparing combustible casing materials falling within the scope of the present invention.
Example I To 90 parts of a powder composition, which consists of:
Percent. Nitrocellulose (13.15% N) 87.0:20 Dinitrotoluene 10.0:20 Dibutyl phthalate 3.0:10
Diphenylamine, 1 part added.
and having a granulation range of from 0.025" to 0.034", was added a mixture consisting of 5 parts of Epon 828 and 5 parts of Versamid 125. The Epon 828 serves as a binder and is an epoxy resin manufactured by reacting epichlorohydrin with 2,2-bis(p-hydroxyphenyl) propane, while Versamid 125 which acts as a hardening agent is one of a group of Versamid polymers ranging from a polymer which is a liquid at room temperature to a polymer which is a solid at room temperature and which has a softening point of 190 C. They are prepared by the condensation of polymerized unsaturated fatty acids (e.g. dilinoleic acid) with aliphatic amines such as ethylene diamine. This composition of three ingredients was blended in aSigma blade mixer until well blended. The composition was then cast into hollow tubes, or into the annulus between concentric tubes or in other suitable molds. The composition was then allowed to cure at temperatures from 50 F. to 212 F. for 45 minutes to 24 hours, depending on the curing temperature.
Example II To 90 parts of a powder composition, which consists Nitrocellulose (13.15% N) 100.00%. Dinitrotoluene 8.00 parts added. Potassium sulphate 1.00 part added. Diphenylamine 0.7 part added.
was added a mixture of 2.5 parts of Epon 828 and 7.5 parts of Versamid 115. Epon 828 is described in greater detail in Example I and Versamid 115 is similar in composition and used interchangeably with the Versamid 125 described in Example I. This composition of three ingredients was blended in a Sigma blade type mixer until homogeneous. The composition was then cast into hollow tubes or other suitable molds. The composition was then allowed to cure at temperatures from 50 F. up to 212 F. for 45 minutes to 24 hours depending on the curing temperature.
Example III To 87.5 parts of a powder composition, which is described in greater detail in Example I, having a granulation range of from 0.025" to 0.034", was added a mixture of 4 parts of Epon 828 and 0.8 part of Accelerator Z. Epon 828 is described in greater detail in Example I while Accelerator Z is a mixture of meta-phenylenediamine with a fluid resin. This composition of three ingredients was blended in a Sigma blade type of mixer until homogeneous. To the blend was then added 2.5 parts of a natural or synthetic fiber such as acetate rayon cut to /2" lengths. The mixing was then continued in the same mixer until the final formulation was Well blended. The formulation was then cast into the annulus between two concentric tubes and the composition was pressed at 4000 psi. Finally, the formulation was allowed to cure for 24 hours at 140 F. The tube was then removed from the mold.
Example IV To parts of a powder composition, which consists of:
Percent Nitrocellulose (13.15% N) 97.7 Potassium sulfate 0.75 Tin 0.75 Diphenylamine 0.80
Dinitrotoluene, 8.00 parts added.
was added a mixture of 10 parts of Bakelite ERL 2795 resin binder and 2.5 parts Bakelite ERL 2793 hardening agent. The Bakelite ERL 2795 is an epoxy resin made by reacting a polyfunctional compound such as, for example 2,2bis(p-dihydroxyphenyl) propane with epichlorohydrin. Bakelite ERL 2793 is an aliphatic amine used as a curing agent for Bakelite ERL 2795. This composition of three ingredients was blended in a Sigma blade mixer until homogeneous. To the blend was then added 2 parts of nitrocellulose fibers approximately 1" in length. The mixing was then continued until the formulation was well blended. The composition was then cast into a cylindrical mold and cured for 48 hours at room temperature. The cylinder was then removed from the mold.
The resins that are used may be any liquid polymer or monomer or a solid polymer or monomer that may be fused below the maximum temperature at which a propellant may be safely handled. This temperature varies with different propellants but may be defined as the temperature at which the propellants may explode. Suitable unsaturated polyesters may be prepared by reacting a compound containing two or more hydroxyl groups with an acid or acid anhydride containing at least two carboxyl groups and at least one unsaturated ethylenic double bond. Examples of compounds containing two or more hydroxyl groups are ethylene glycol, glycerol, pentaerythritol, propylene glycol, butanediol-1,4 and others. Examples of compounds containing two or more carboxyl groups and at least one unsaturated bond are maleic anhydride, maleic acid, fumaric acid, and others. In addition, other dicarboxylic acids or acid anhydrides (e.g. succinic acid, adipic acid, etc.) are simultaneously reacted with the above mentioned hydroxyl and carboxyl containing compounds to modify the properties of the resulting unsaturated polyester. The unsaturated polyester 1s then blended with a crosslinking agent such as styrene or diallyl phthalate. The crosslinking reaction is made to proceed under the influence of heat and/ or a peroxide catalyst agent.
Polyurethane resins such as may be used in the present invention are formed when hydroxyl-containing compounds react with diisocyanates. The hydroxyl-containmg compounds may be glycols, polyols, hydroxyl-contaming polyesters or polyethers. The reaction may be s mply depicted for illustrative purposes by monofunctional reactants as follows:
When polyfunctional chemicals are used, polymers are formed. The diisocyanate used is usually one or a mixture of the tolylene diisocyanate group of isomers. However, other diisocyanates may be used. An alternate method of preparing polyurethane is by pre-reacting a polyester with an excess of diisocyanate and then crosslinking the residual isocyan-ate groups with an amine or other compound containing a reactive hydrogen.
Epoxy resins such as may be used in the present invention may be prepared by condensation of epichloro- 'hydrin with a diphen-olic compound. A typical reaction of this type would be the following:
Other widely difierent embodiments of this invention may be made without departing from the spirit and scope where n is varied to obtain resins of desired viscosity. This resin is then crosslinked with an amine, an acid anhydride hardener or other suitable reagent.
As stated above, various other propellant grains may be used with excellent results. Among these propellant grains are:
Grain propellant consisting of Nitrocellulose (13.15% N) 85.00 Dinitrotoluene 10.00 Dibutylphthalate 5.00
Diphenylamine, 1.00 part added.
Grain propellant consisting of Nitrocellulose (13.15% N) 77.45 Nitroglycerin 19.50 Barium nitrate 1.4- Potassium nitrate 0.75 Ethyl centralite 0.60 Graphite 0.30
Grain propellant consisting of- Nitrocellulose (13.15% N) 20.00 Nitroglycerin 19.00 Nitrogu-anidine 54.70 Ethyl centralite 6.00 Cryolite 0.30
Other solid propellants may be used as long as the resin binder used does not cause any chemical break-down or deterioration of the propellant and the propellant does not interfere in a deleterious manner with the curing of the resin binder.
It should be noted that the operable ratio range of resin to propellant grains is not restricted to the range given in the above examples but may vary from :95 to 45:55. However, the optimum ratio range of resin to propellant grains has been found to be from 10:90 to 35:65. The operable range of the propellant grain size is only limited in that the larger grain sizes generally yield physically weak structures. However, grains having a diameter as large as .080 can be successfully used. In some applications, the grain size must be selected to satisfy the particular burning time requirement, in accordance with the principles of the science of interior ballistics.
From the above examples and disclosure it is apparent that compositions made in accordance with this invention are capable of being formed or shaped into tubes, solid cylinders or other shapes by the use of appropriate molds. The product resulting thereby is a combustible material suitable for use for such items as combustible cartridge cases, combustible primer-s, combustible initiators and other items where the combustion of the item in use is desirable or required. By the judicious selection of ingredients, the compositions can be made ballistically smokeless.
thereof, it being understood that the invention is not limited except as defined in the appended claims,
What is claimed is:
l. A composition for a combustible cartridge casing consisting essentially of about 90% by weight of a granular nitrocellulose base propellant intimately mixed and dispersed in about 10% by weight of a plastic consisting of cross-linked, three-dimensional polymers.
2. A composition for a combustible cartridge case consisting essentially of about 90% of a particulate powder composition, the said powder composition having a granulation range of 0.025" to 0.034" and containing to by weight of nitrocellulose (13.15% N) and 0.8 to 10% by weight of dinitrotoluene, the said particulate powder composition being in intimate and uniform mixture with about 10% 'by weight of a cross-linked, three dimensional polymeric material.
3. The composition according to claim 2 in which the polymeric material is cross-linked with a diamine.
4. The composition according to claim 2 in which the polymeric material is cross-linked with the anhydride of a dibasic acid.
5. A combustible cartridge casing resistant to deformation by cold flow prepared by molding the composition according to claim 2.
6. In the preparation of combustible cartridge casings resistant to deformation by cold flow and composed of a particulate crystalline explosive and a rigid three-dimensional plastic material consisting of a cross-linked linear polymer, the process which comprises adding a nitrocellulose base propellant in .a powdered form to a liquid polymer selected from the group consisting of linear chains of epoxy and urethane polymers, adding a cross-linking agent reactive to hydroxy groups and active hydrogen and selected from the group consisting of diamines and the anhydrides of dibasic acids, mixing, and curing in molds at temperatures of 50 to 212 F. for periods ranging from about 45 minutes at 212 to 24 hours at 50 F.
7. The process according to claim 6 wherein the crosslinking agent is meta-phenylene diamine.
8. The process according to claim 6 wherein the crosslinking agent is ethylene diamine.
References (Iited by the Examiner UNITED STATES PATENTS 2,965,466 12/1960 Ball 14992 2,977,885 4/1961 Perry et al. 10298 2,991,168 7/1961 Nadel 149-100 3,000,308 9/1961 Land et al 14919 LEON D. ROSDOL, Primary Examiner. ROGER L. CAMPBELL, CARL D. QUARFORTH,
Examiners. BENJAMIN R. PADGETT, Assistant Examiner.
Claims (2)
1. A COMPOSITION FOR A COMBUSTIBLE CARRTRIGDE CASING CONSISTING ESSENTIALLY OF ABOUT 90% BY WEIGHT OF A GRANULAR NITROCELLULOSE BASE PROPELLANT INTIMATELY MIXED AND DISPERSED IN ABOUT 10% BY WEIGHT OF A PLASTIC CONSISTING OF CROSS-LINKED, THREE-DIMENSIONAL POLYMERS.
2. A COMPOSITION FOR A COMBUSTIBLE CARTRIDGE CASE CONSISTING ESSENTIALLY OF ABOUT 90% OF A PARTICULATE POWDER COMPOSITION, THE SAID POWDER COMPOSITION HAVING A GRANULATION RANGE OF 0.025''" TO 0.034" AND CONTAINING 75 TO 85% BY WEIGHT OF NITROCELLULOSE (13.15% N) AND 0.8 TO 10% BY WEIGHT OF DINITROLUENE, THE SAID PARTICULATE POWDER COMPOSITION BEING IN INTIMATE AND UNIFORM MIXTURE WITH ABOUT 10% BY WEIGHT OF A CROSS-LINKED, THREE DIMENSIONAL POLYMERIC MATERIAL.
Publications (1)
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US3236704A true US3236704A (en) | 1966-02-22 |
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Family Applications (1)
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US3236704D Expired - Lifetime US3236704A (en) | Propellant composition |
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Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3280746A (en) * | 1965-04-26 | 1966-10-25 | Atlantic Res Corp | Combustible cartridge case of felted fibrous material with synthetic resin and process |
US3376174A (en) * | 1965-09-21 | 1968-04-02 | France Etat | Powder containing nitrocellulose, metal or metal hydride and a superficial layer of moderating agent |
US3711344A (en) * | 1970-09-23 | 1973-01-16 | Us Army | Processing of crosslinked nitrocellulose propellants |
US3720553A (en) * | 1969-02-07 | 1973-03-13 | Standard Oil Co | Ammonium nitrate propellant compositions |
US3882784A (en) * | 1972-07-03 | 1975-05-13 | Us Navy | Nitroester propellant, casing, and liner of an epoxy-polyamide copolymer containing a stabilizer |
US3890175A (en) * | 1964-09-04 | 1975-06-17 | Us Army | Nitrocellulose base propellants |
US3979486A (en) * | 1973-07-27 | 1976-09-07 | Societe Nationale Des Poudres Et Explosifs | Process for controlling the ballistic characteristics of double-base propellants |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2965466A (en) * | 1959-04-22 | 1960-12-20 | Hercules Powder Co Ltd | Explosive |
US2977885A (en) * | 1955-03-07 | 1961-04-04 | Jr Henry A Perry | Explosive bomb or weapon casing |
US2991168A (en) * | 1957-11-18 | 1961-07-04 | Isidore G Nadel | Fibrous solid propellants in sheet form |
US3000308A (en) * | 1956-03-07 | 1961-09-19 | William E Land | High explosive composition |
-
0
- US US3236704D patent/US3236704A/en not_active Expired - Lifetime
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2977885A (en) * | 1955-03-07 | 1961-04-04 | Jr Henry A Perry | Explosive bomb or weapon casing |
US3000308A (en) * | 1956-03-07 | 1961-09-19 | William E Land | High explosive composition |
US2991168A (en) * | 1957-11-18 | 1961-07-04 | Isidore G Nadel | Fibrous solid propellants in sheet form |
US2965466A (en) * | 1959-04-22 | 1960-12-20 | Hercules Powder Co Ltd | Explosive |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3890175A (en) * | 1964-09-04 | 1975-06-17 | Us Army | Nitrocellulose base propellants |
US3280746A (en) * | 1965-04-26 | 1966-10-25 | Atlantic Res Corp | Combustible cartridge case of felted fibrous material with synthetic resin and process |
US3376174A (en) * | 1965-09-21 | 1968-04-02 | France Etat | Powder containing nitrocellulose, metal or metal hydride and a superficial layer of moderating agent |
US3720553A (en) * | 1969-02-07 | 1973-03-13 | Standard Oil Co | Ammonium nitrate propellant compositions |
US3711344A (en) * | 1970-09-23 | 1973-01-16 | Us Army | Processing of crosslinked nitrocellulose propellants |
US3882784A (en) * | 1972-07-03 | 1975-05-13 | Us Navy | Nitroester propellant, casing, and liner of an epoxy-polyamide copolymer containing a stabilizer |
US3979486A (en) * | 1973-07-27 | 1976-09-07 | Societe Nationale Des Poudres Et Explosifs | Process for controlling the ballistic characteristics of double-base propellants |
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