US3808061A - Nitrocellulose solid propellant composition with load additive to reduce radar attenuation - Google Patents
Nitrocellulose solid propellant composition with load additive to reduce radar attenuation Download PDFInfo
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- US3808061A US3808061A US00370402A US37040264A US3808061A US 3808061 A US3808061 A US 3808061A US 00370402 A US00370402 A US 00370402A US 37040264 A US37040264 A US 37040264A US 3808061 A US3808061 A US 3808061A
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- Prior art keywords
- nitrocellulose
- lead
- weight
- plasticizer
- composition
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- 239000000203 mixture Substances 0.000 title claims abstract description 50
- 239000000020 Nitrocellulose Substances 0.000 title claims abstract description 39
- 229920001220 nitrocellulos Polymers 0.000 title claims abstract description 39
- 239000004449 solid propellant Substances 0.000 title claims description 7
- 239000000654 additive Substances 0.000 title description 2
- 230000000996 additive effect Effects 0.000 title description 2
- 239000003380 propellant Substances 0.000 claims abstract description 23
- MOUPNEIJQCETIW-UHFFFAOYSA-N lead chromate Chemical compound [Pb+2].[O-][Cr]([O-])(=O)=O MOUPNEIJQCETIW-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000004014 plasticizer Substances 0.000 claims abstract description 17
- 239000000446 fuel Substances 0.000 claims abstract description 11
- 239000003381 stabilizer Substances 0.000 claims abstract description 10
- 239000003607 modifier Substances 0.000 claims abstract description 9
- 239000002360 explosive Substances 0.000 claims abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000000006 Nitroglycerin Substances 0.000 claims description 8
- 229960003711 glyceryl trinitrate Drugs 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- SNIOPGDIGTZGOP-UHFFFAOYSA-N Nitroglycerin Chemical compound [O-][N+](=O)OCC(O[N+]([O-])=O)CO[N+]([O-])=O SNIOPGDIGTZGOP-UHFFFAOYSA-N 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 claims description 6
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 6
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 6
- URAYPUMNDPQOKB-UHFFFAOYSA-N triacetin Chemical compound CC(=O)OCC(OC(C)=O)COC(C)=O URAYPUMNDPQOKB-UHFFFAOYSA-N 0.000 claims description 6
- 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 claims description 5
- 150000005690 diesters Chemical class 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- RUKISNQKOIKZGT-UHFFFAOYSA-N 2-nitrodiphenylamine Chemical compound [O-][N+](=O)C1=CC=CC=C1NC1=CC=CC=C1 RUKISNQKOIKZGT-UHFFFAOYSA-N 0.000 claims description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- FOHIURCGHCHRHW-UHFFFAOYSA-N 1-ethyl-3-methyl-1,3-diphenylurea Chemical compound C=1C=CC=CC=1N(CC)C(=O)N(C)C1=CC=CC=C1 FOHIURCGHCHRHW-UHFFFAOYSA-N 0.000 claims description 3
- GDDNTTHUKVNJRA-UHFFFAOYSA-N 3-bromo-3,3-difluoroprop-1-ene Chemical compound FC(F)(Br)C=C GDDNTTHUKVNJRA-UHFFFAOYSA-N 0.000 claims description 3
- BSYNRYMUTXBXSQ-UHFFFAOYSA-N Aspirin Chemical compound CC(=O)OC1=CC=CC=C1C(O)=O BSYNRYMUTXBXSQ-UHFFFAOYSA-N 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 3
- 229940068372 acetyl salicylate Drugs 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 3
- 150000001540 azides Chemical class 0.000 claims description 3
- CNVULGHYDPMIHD-UHFFFAOYSA-L bis[(2-hydroxybenzoyl)oxy]lead Chemical compound [Pb+2].OC1=CC=CC=C1C([O-])=O.OC1=CC=CC=C1C([O-])=O CNVULGHYDPMIHD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 238000002485 combustion reaction Methods 0.000 claims description 3
- 230000003247 decreasing effect Effects 0.000 claims description 3
- UQLDLKMNUJERMK-UHFFFAOYSA-L di(octadecanoyloxy)lead Chemical compound [Pb+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O UQLDLKMNUJERMK-UHFFFAOYSA-L 0.000 claims description 3
- 239000001087 glyceryl triacetate Substances 0.000 claims description 3
- 235000013773 glyceryl triacetate Nutrition 0.000 claims description 3
- 229910000464 lead oxide Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 claims description 3
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 3
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical class OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 3
- -1 succinic acid, diesters Chemical class 0.000 claims description 3
- 229960002622 triacetin Drugs 0.000 claims description 3
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 2
- 239000001361 adipic acid Substances 0.000 claims description 2
- 235000011037 adipic acid Nutrition 0.000 claims description 2
- 229920002301 cellulose acetate Polymers 0.000 claims description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 239000000084 colloidal system Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- 229910001430 chromium ion Inorganic materials 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000003574 free electron Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- QUAMCNNWODGSJA-UHFFFAOYSA-N 1,1-dinitrooxybutyl nitrate Chemical compound CCCC(O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O QUAMCNNWODGSJA-UHFFFAOYSA-N 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- XTJFFFGAUHQWII-UHFFFAOYSA-N Dibutyl adipate Chemical compound CCCCOC(=O)CCCCC(=O)OCCCC XTJFFFGAUHQWII-UHFFFAOYSA-N 0.000 description 1
- PYGXAGIECVVIOZ-UHFFFAOYSA-N Dibutyl decanedioate Chemical compound CCCCOC(=O)CCCCCCCCC(=O)OCCCC PYGXAGIECVVIOZ-UHFFFAOYSA-N 0.000 description 1
- YUXIBTJKHLUKBD-UHFFFAOYSA-N Dibutyl succinate Chemical compound CCCCOC(=O)CCC(=O)OCCCC YUXIBTJKHLUKBD-UHFFFAOYSA-N 0.000 description 1
- 229920001944 Plastisol Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical class [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 229940100539 dibutyl adipate Drugs 0.000 description 1
- 229960002097 dibutylsuccinate Drugs 0.000 description 1
- LYAGTVMJGHTIDH-UHFFFAOYSA-N diethylene glycol dinitrate Chemical compound [O-][N+](=O)OCCOCCO[N+]([O-])=O LYAGTVMJGHTIDH-UHFFFAOYSA-N 0.000 description 1
- OXHJBNINOWPTFT-UHFFFAOYSA-N dioctyl decanedioate;dioctyl hexanedioate Chemical compound CCCCCCCCOC(=O)CCCCC(=O)OCCCCCCCC.CCCCCCCCOC(=O)CCCCCCCCC(=O)OCCCCCCCC OXHJBNINOWPTFT-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000002816 fuel additive Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- YAFOVCNAQTZDQB-UHFFFAOYSA-N octyl diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)(OCCCCCCCC)OC1=CC=CC=C1 YAFOVCNAQTZDQB-UHFFFAOYSA-N 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 239000004999 plastisol Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- WTLBZVNBAKMVDP-UHFFFAOYSA-N tris(2-butoxyethyl) phosphate Chemical compound CCCCOCCOP(=O)(OCCOCCCC)OCCOCCCC WTLBZVNBAKMVDP-UHFFFAOYSA-N 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B23/00—Compositions characterised by non-explosive or non-thermic constituents
- C06B23/04—Compositions characterised by non-explosive or non-thermic constituents for cooling the explosion gases including antifouling and flash suppressing agents
-
- 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
- C06B25/18—Compositions containing a nitrated organic compound the compound being nitrocellulose present as 10% or more by weight of the total composition
- C06B25/24—Compositions containing a nitrated organic compound the compound being nitrocellulose present as 10% or more by weight of the total composition with nitroglycerine
- C06B25/26—Compositions containing a nitrated organic compound the compound being nitrocellulose present as 10% or more by weight of the total composition with nitroglycerine with an organic non-explosive or an organic non-thermic component
Definitions
- a nitrocellulose propellant composition consisting essentially of an intimate admixture of about 10% to about 60% nitrocellulose, about 20% to about 50% energizing plasticizer for nitrocellulose, 0% to about 25% of a metallic fuel, about 1% to about 15% of a non-explosive plasticizer for nitrocellulose, about 1% to about 5% of a stabilizer, 0% to about 5% of a burning rate modifier, and from about 0.5% to about 5.0% of lead chromate, all percentages expressing percent by weight of total compositions.
- the present invention relates to a method for decreasing the radar attenuation caused by the exhaust gases from a solid propellant rocket motor and to improved propellant compositions.
- the invention relates to a method for decreasing the amount of radar attenuation due to the combustion of nitrocellulose base propellant formulations and especially double-base propellant formulations by incorporating powdered lead chromate therein. Novel nitrocellulose base compositions containing lead chromate are also contemplated by the invention.
- the guidance of many missile systems depends on the effective transmission and receiving of ultra highfrequency waves. It has been found that the hot exhaust gases from these solid propellants attenuate the radar signal used in the guidance of the missile. For example, potassium and sodium salts present in the propellant as impurities cause attenuation of the radar signal. Furthermore, during combustion those propellants which utilize particulate metal as high energy fuel additives seriously weaken the radar signal. Therefore, a means of eliminating or substantially reducing the amount of attenuation is needed to improve the accuracy of the particular missile involved.
- a further object is to provide a method for reducing the radar attenuating effects of double-base propellants by incorporating lead chromate into the propellant compositions.
- nitrocellulose-base solid propellant composition is intended to include any propellant composition based on a colloid of nitrocellulose and a plasticizer for the nitrocellulose.
- the plasticizer can be either the explosive or energizing type, the nonexplosive type, or a combination of the two. It is to be understood that while the invention is discussed in detail with relationship to double-base compositions, the invention is equally applicable to any nitrocellulose base composition. Therefore, by substituting one or more conventional plasticizers for nitrocellulose for all or part of the nitroglycerin in the double-base compositions discussed hereafter, a wide range of suitable nitrocellulose-base propellants can be prepared.
- Illustrative examples of the so-called energizing plasticizer include but are not limited to the nitrate esters of polyhydric alcohols such as nitroglycerin, butanetriol trinitrate, and diethyleneglycol dinitrate.
- double-base composition is intended to include those compositions based on a colloid of nitrocellulose and nitroglycerin; that is, compositions containing at least 40% by weight of the colloid.
- Such propellants are well known in the art with detailed examples being available in US. Pat. Nos. 2,967,098; 2,982,638; 3,093,523; 3,102,834; 3,103,458; 3,104,190.
- the invention contemplates compositions consisting essentially of about to about 99.5% of the nitrocellulose-nitroglycerin colloid and about 0.5% to about 5.0% powered lead chromate.
- the compositions can and normally will contain various amounts of stabilizers, modifier, additional plasticizers, and the like.
- the compositions will consist essentially of an intimate admixture of the following components in about the specified percentage ranges:
- the nitrocellulose will contain at least 12.5% nitrogen and may contain up to 13.5% nitrogen. Moreover, the nitrocellulose can be used in the form of ball powder.
- metallic fuels there can be used aluminum, boron, magnesium, alloys of these metals with each other, aluminum hydride, borohydrides, and the like. Generally, the metallic fuel will not exceed about 10% by weight of the composition. Of the metallic fuels, aluminum is the most preferred.
- non-explosive plasticizers for nitrocellulose which are suitable for use in the invention.
- organic phosphate esters such as tributoxyethyl phosphate and octyldiphenyl phosphate
- phthalate esters such as dioctyl phthalate, dimenthyl phthalate, and dibutyl phthalate
- the diesters of adipic are many art-recognized non-explosive plasticizers for nitrocellulose.
- organic phosphate esters such as tributoxyethyl phosphate and octyldiphenyl phosphate
- phthalate esters such as dioctyl phthalate, dimenthyl phthalate, and dibutyl phthalate
- the diesters of adipic such as dioctyl phthalate, dimenthyl phthalate, and dibutyl phthalate.
- the stabilizer can be one or more of the following compounds: 2-nitrodiphenylamine, symmetrical diethyl diphenyl urea, diphenylamine, methylethyldiphenyl urea, resoricinol, and the like.
- the preferred stabilizer system is based on the use of resorcinol and 2- nitrodiphenylamine in combination.
- At least one burning rate modifier may be incorporated into the compositions such as lead salicylate, lead acetylsalicylate, lead azide, lead stearate, lead oxide, ammonium perchlorate, various dyes, and the like.
- the compositions can also contain carbon black, candelia wax, and inert fillers.
- the radar attenuation of double-base propellant compositions of the type discussed hereinabove is reduced at least 20% by incorporating into the composition about 0.5% to 5.0% by weight of powdered lead chromate. In most instances, the amount of reduction is considerably higher and in some cases can approach 90%.
- This reduction in radar attenuation makes it possible to utilize the highly perfected double-base propellants in radarcontrolled missiles, particularly antimissile systems requiring the utmost in accuracy.
- the actual reduction in the amount of attenuation will depend on the amount of lead chromate used and the particular double-base propellant composition.
- the improved compositions of the invention are prepared according to two well known standard techniques. For example, using a water-jacketed Sigma blade mixer to insure uniform distribution of all ingredients, extruded grains can be made in the following manner.
- the nitrocellulose is wet with ethanol and the nitroglycerin desensitized with acetone. Thereafter, the nitroglycerin, nitrocellulose, metallic fuel, nonexplosive plasticizer, stabilizer, modifiers, and lead chromate are blended in the mixer. Additional acetone is added to the mixture to achieve a ratio of solvent to dry nitrocellulose of about 08:10. All the ingredients are mixed for several hours then partially dried. Subsequently, the mix is extruded into grains of the desired size by means of a hydraulic press. After a drying period of about 3 to days, the grains are cured (colloided) and substantially solvent free. Using this procedure, propellants having the following compositions are readily prepared.
- a nitrocellulose propellant composition consisting essentially of an intimate admixture of about 10% to about 60% nitrocellulose, about 20% to about energizing plasticizer for nitrocellulose, 0% to about 25% of a metallic fuel, about 1% to about 15% of a nonexplosive plasticizer for nitrocellulose, about 1% to about 5% of a stabilizer, 0% to about 5% of a burning rate modifier, and from about 0.5% to about 5.0% of lead chromate, all percentages expressing percent by weight of total compositions.
- a double-base propellant composition consisting essentially of an intimate admixture of about 10% to about 60% nitrocellulose with said nitrocellulose containing about 12.5% to about 13.5% by weight nitro- Weight Percent of Ingredient in Composition 11
- Slurry or Plastisol type propellants are prepared using ball powder as the source for nitrocellulose. All the ingredients are mixed at ambient temperature for 10 to 60 minutes, poured into molds or motors, and cured at elevated temperatures.
- Typical Slurry cast propellant compositions are as follows:
- the chromium ions gen about 20% to about 50% nitroglycerin, 0% to about 25% of a metallic fuel selected from the group consisting of aluminum, boron, magnesium, alloys of these metals with each other, aluminum hydride, and borohydrides, about 1% to about 15% of a nonexplosive plasticizer for said nitrocellulose selected from the group consisting of organic phosphate esters, phthalate esters, diesters of adipic acid, diesters of succinic acid, diesters of sebacic acid, triacetin, triethylene glycol, orthonitrobiphenyl, and di-Z-ethyl butyrate, about 1% to about 5% of at least one stabilizer selected from the group consisting of 2-nitrodiphenylamine, symmetrical diethyl diphenyl urea, res
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Abstract
1. A nitrocellulose propellant composition consisting essentially of an intimate admixture of about 10% to about 60% nitrocellulose, about 20% to about 50% energizing plasticizer for nitrocellulose, 0% to about 25% of a metallic fuel, about 1% to about 15% of a non-explosive plasticizer for nitrocellulose, about 1% to about 5% of a stabilizer, 0% to about 5% of a burning rate modifier, and from about 0.5% to about 5.0% of lead chromate, all percentages expressing percent by weight of total compositions.
Description
United States Patent [191 Pierce Apr. 30, 1974 [75] Inventor:
[73] Assignee: The United States of America as represented by the Secretary of the Army, Washington, DC.
[22] Filed: May 22, 1964 [21] Appl. No.: 370,402
Everette M. Pierce, Somerville, Ala.
[52] US. Cl 149/18, 149/19, 149/20, 149/22, 149/35, 149/38, 149/39,
[51] Int. Cl C06d 5/06 [58] Field of Search 149/96, 97, 98, 99, 35, 149/38, 18, 19, 22, 20, 39
[56] References Cited UNITED STATES PATENTS 2,916,775 12/1959 O'Neill ..149/96 2/1961 Ryker 149/96 6/1964 Camp et al. 149/ Primary ExaminerBenjamin R. Padgett Attorney, Agent, or FirmEdward J. Kelly; Herbert Berl EXEMPLARY CLAIM 1. A nitrocellulose propellant composition consisting essentially of an intimate admixture of about 10% to about 60% nitrocellulose, about 20% to about 50% energizing plasticizer for nitrocellulose, 0% to about 25% of a metallic fuel, about 1% to about 15% of a non-explosive plasticizer for nitrocellulose, about 1% to about 5% of a stabilizer, 0% to about 5% of a burning rate modifier, and from about 0.5% to about 5.0% of lead chromate, all percentages expressing percent by weight of total compositions.
4 Claims, No Drawings NITROCELLULOSE SOLID PROPELLANT COMPOSITION WITH LOAD ADDITIVE TO REDUCE RADAR ATTENUATION The invention described herein may be manufactured and used by or for the Government for governmental purposes without the payment of any royalty thereon.
The present invention relates to a method for decreasing the radar attenuation caused by the exhaust gases from a solid propellant rocket motor and to improved propellant compositions. Particularly, the invention relates to a method for decreasing the amount of radar attenuation due to the combustion of nitrocellulose base propellant formulations and especially double-base propellant formulations by incorporating powdered lead chromate therein. Novel nitrocellulose base compositions containing lead chromate are also contemplated by the invention.
The guidance of many missile systems depends on the effective transmission and receiving of ultra highfrequency waves. It has been found that the hot exhaust gases from these solid propellants attenuate the radar signal used in the guidance of the missile. For example, potassium and sodium salts present in the propellant as impurities cause attenuation of the radar signal. Furthermore, during combustion those propellants which utilize particulate metal as high energy fuel additives seriously weaken the radar signal. Therefore, a means of eliminating or substantially reducing the amount of attenuation is needed to improve the accuracy of the particular missile involved.
It has now been determined that a small amount of lead chromate incorporated into nitrocellulose-base propellant compositions greatly reduces the attenuating effect of the exhaust gases. Moreover, the lead chromate even reduces the attenuating effect in those compositions which contain high energy metallic fuels.
In accordance with the foregoing, it is an object of the present invention to provide improved nitrocellulose base solid propellant compositions containing lead chromate, these compositions having greatly reduced radar attenuating effects.
A further object is to provide a method for reducing the radar attenuating effects of double-base propellants by incorporating lead chromate into the propellant compositions.
The manner in which these as well as other objects can be accomplished will become apparent from the following detailed description.
The terminology nitrocellulose-base solid propellant composition is intended to include any propellant composition based on a colloid of nitrocellulose and a plasticizer for the nitrocellulose. The plasticizer can be either the explosive or energizing type, the nonexplosive type, or a combination of the two. It is to be understood that while the invention is discussed in detail with relationship to double-base compositions, the invention is equally applicable to any nitrocellulose base composition. Therefore, by substituting one or more conventional plasticizers for nitrocellulose for all or part of the nitroglycerin in the double-base compositions discussed hereafter, a wide range of suitable nitrocellulose-base propellants can be prepared.
Illustrative examples of the so-called energizing plasticizer include but are not limited to the nitrate esters of polyhydric alcohols such as nitroglycerin, butanetriol trinitrate, and diethyleneglycol dinitrate.
As used herein, the term double-base composition is intended to include those compositions based on a colloid of nitrocellulose and nitroglycerin; that is, compositions containing at least 40% by weight of the colloid. Such propellants are well known in the art with detailed examples being available in US. Pat. Nos. 2,967,098; 2,982,638; 3,093,523; 3,102,834; 3,103,458; 3,104,190. In its basic form, the invention contemplates compositions consisting essentially of about to about 99.5% of the nitrocellulose-nitroglycerin colloid and about 0.5% to about 5.0% powered lead chromate. However, the compositions can and normally will contain various amounts of stabilizers, modifier, additional plasticizers, and the like. Preferably, the compositions will consist essentially of an intimate admixture of the following components in about the specified percentage ranges:
The nitrocellulose will contain at least 12.5% nitrogen and may contain up to 13.5% nitrogen. Moreover, the nitrocellulose can be used in the form of ball powder. As metallic fuels, there can be used aluminum, boron, magnesium, alloys of these metals with each other, aluminum hydride, borohydrides, and the like. Generally, the metallic fuel will not exceed about 10% by weight of the composition. Of the metallic fuels, aluminum is the most preferred.
There are many art-recognized non-explosive plasticizers for nitrocellulose which are suitable for use in the invention. Among these are the following: organic phosphate esters such as tributoxyethyl phosphate and octyldiphenyl phosphate; phthalate esters such as dioctyl phthalate, dimenthyl phthalate, and dibutyl phthalate; the diesters of adipic. acid, succinic acid, and sebacic acid as exemplified by dibutyl succinate, dibutyl adipate, dioctyl sebacate dioctyl adipate, and dibutyl sebacate; triacetin; triethylene glycol, orthonitrobiphenyl, and di-2-ethyl butyrate.
The stabilizer can be one or more of the following compounds: 2-nitrodiphenylamine, symmetrical diethyl diphenyl urea, diphenylamine, methylethyldiphenyl urea, resoricinol, and the like. The preferred stabilizer system is based on the use of resorcinol and 2- nitrodiphenylamine in combination.
At least one burning rate modifier may be incorporated into the compositions such as lead salicylate, lead acetylsalicylate, lead azide, lead stearate, lead oxide, ammonium perchlorate, various dyes, and the like. The compositions can also contain carbon black, candelia wax, and inert fillers.
According to the present invention, the radar attenuation of double-base propellant compositions of the type discussed hereinabove is reduced at least 20% by incorporating into the composition about 0.5% to 5.0% by weight of powdered lead chromate. In most instances, the amount of reduction is considerably higher and in some cases can approach 90%. This reduction in radar attenuation makes it possible to utilize the highly perfected double-base propellants in radarcontrolled missiles, particularly antimissile systems requiring the utmost in accuracy. As previously stated, the actual reduction in the amount of attenuation will depend on the amount of lead chromate used and the particular double-base propellant composition.
The improved compositions of the invention are prepared according to two well known standard techniques. For example, using a water-jacketed Sigma blade mixer to insure uniform distribution of all ingredients, extruded grains can be made in the following manner. The nitrocellulose is wet with ethanol and the nitroglycerin desensitized with acetone. Thereafter, the nitroglycerin, nitrocellulose, metallic fuel, nonexplosive plasticizer, stabilizer, modifiers, and lead chromate are blended in the mixer. Additional acetone is added to the mixture to achieve a ratio of solvent to dry nitrocellulose of about 08:10. All the ingredients are mixed for several hours then partially dried. Subsequently, the mix is extruded into grains of the desired size by means of a hydraulic press. After a drying period of about 3 to days, the grains are cured (colloided) and substantially solvent free. Using this procedure, propellants having the following compositions are readily prepared.
enter the exhaust stream with a valence of six. Free electrons in the exhaust stream (which are at least responsible for some of the attenuation) are picked up by the chromium ions. If there are enough free electrons in the exhaust gases, the chromium ions probably collect up to three electrons with a corresponding valence change to three. For this reason, it is very possible that other chromate salts can accomplish a similar reduction in the amount of radar attenuation.
The above detailed description is for purposes of illustration only and no undue limitation should be ascribed to the invention as a result thereof except as reflected in the appended claims.
1 claim:
1. A nitrocellulose propellant composition consisting essentially of an intimate admixture of about 10% to about 60% nitrocellulose, about 20% to about energizing plasticizer for nitrocellulose, 0% to about 25% of a metallic fuel, about 1% to about 15% of a nonexplosive plasticizer for nitrocellulose, about 1% to about 5% of a stabilizer, 0% to about 5% of a burning rate modifier, and from about 0.5% to about 5.0% of lead chromate, all percentages expressing percent by weight of total compositions.
2. A double-base propellant composition consisting essentially of an intimate admixture of about 10% to about 60% nitrocellulose with said nitrocellulose containing about 12.5% to about 13.5% by weight nitro- Weight Percent of Ingredient in Composition 11 Ill Nitrogen content of nitrocellulose: l-l2.6%N; 1I-13.1%N; Ill-12.5%N
Using conventional mixing equipment, the Slurry" or Plastisol type propellants are prepared using ball powder as the source for nitrocellulose. All the ingredients are mixed at ambient temperature for 10 to 60 minutes, poured into molds or motors, and cured at elevated temperatures. Typical Slurry cast propellant compositions are as follows:
Z-Nitrodyphenylamine 2% The exact mechanism by which the lead chromatc decreases the amount of radar attenuation is not understood. However, it is believed that the chromium ions gen, about 20% to about 50% nitroglycerin, 0% to about 25% of a metallic fuel selected from the group consisting of aluminum, boron, magnesium, alloys of these metals with each other, aluminum hydride, and borohydrides, about 1% to about 15% of a nonexplosive plasticizer for said nitrocellulose selected from the group consisting of organic phosphate esters, phthalate esters, diesters of adipic acid, diesters of succinic acid, diesters of sebacic acid, triacetin, triethylene glycol, orthonitrobiphenyl, and di-Z-ethyl butyrate, about 1% to about 5% of at least one stabilizer selected from the group consisting of 2-nitrodiphenylamine, symmetrical diethyl diphenyl urea, resorcinol, diphenylamine, and methylethyldiphenyl urea, 0% to about 5% of at least one burning rate modifier selected from the group consisting of lead salicylate, lead acetylsalicylate, lead azide, lead stearate, lead oxide, ethyl centralite, cellulose acetate, ammonium nitrate, and ammonium perchlorate, and about 0.5% to about 5.0% lead chromate, all percentages expressing percent by weight of total composition.
6 4. The method according to claim 3 wherein said lead chromate is present in an amount equal to about 0.5% to about 5.0% by weight of the total weight of said composition including the weight of said lead chromate.
Claims (4)
1. A NITROCELLULOSE PROPELLANT COMPOSITION CONSISTING ESSENTIALLY OF AN INTIMATE ADMIXTURE OF ABOUT 10% TO ABOUT 60% NITROCELLULOSE, 0% TO ABOUT 25% OF A METALLIC PLASTICIZER FOR NITROCELLULOSE, 0% TO ABOUT 25% OF METALLIC FUEL, ABOUT 1% TO ABOUT 15% OF A NON-EXPOLSIVE PLASTICIZER FOR INTROCELULOSE, ABOUT 1% TO ABOUT 5% OF A STABILIZER, 0% TO ABOUT 5% OF A BURNING RATE MODIFIER, AND FROM ABOUT 0.5% TO ABOUT 50.% OF LEAD CHROMATE, ALL PERCENTAGES EXPRESSING PERCENT BY WEIGHT OF TOTAL COMPOSITIONS.
2. A double-base propellant composition consisting essentially of an intimate admixture of about 10% to about 60% nitrocellulose with said nitrocellulose containing about 12.5% to about 13.5% by weight nitrogen, about 20% to about 50% nitroglycerin, 0% to about 25% of a metallic fuel selected from the group consisting of aluminum, boron, magnesium, alloys of these metals with each other, aluminum hydride, and borohydrides, about 1% to about 15% of a non-explosive plasticizer for said nitrocellulose selected from the group consisting of organic phosphate esters, phthalate esters, diesters of adipic acid, diesters of succinic acid, diesters of sebacic acid, triacetin, triethylene glycol, orthonitrobiphenyl, and di-2-ethyl butyrate, about 1% to about 5% of at least one stabilizer selected from the group consisting of 2-nitrodiphenylamine, symmetrical diethyl diphenyl urea, resorcinol, diphenylamine, and methylethyldiphenyl urea, 0% to about 5% of at least one burning rate modifier selected from the group consisting of lead salicylate, lead acetylsalicylate, lead azide, lead stearate, lead oxide, ethyl centralite, cellulose acetate, ammonium nitrate, and ammonium perchlorate, and about 0.5% to about 5.0% lead chromate, all percentages expressing percent by weight of total composition.
3. In rocket motors, the method for decreasing the amount of radar attenuation due to the exhaust gases for burning, double-base, solid propellant compositions, said method comprising incorporating into said composition and uniformly dispersing therethrough before combustion powdered lead chromate.
4. The method according to claim 3 wherein said lead chromate is present in an amount equal to about 0.5% to about 5.0% by weight of the total weight of said composition including the weight of said lead chromate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US00370402A US3808061A (en) | 1964-05-22 | 1964-05-22 | Nitrocellulose solid propellant composition with load additive to reduce radar attenuation |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US00370402A US3808061A (en) | 1964-05-22 | 1964-05-22 | Nitrocellulose solid propellant composition with load additive to reduce radar attenuation |
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| US3808061A true US3808061A (en) | 1974-04-30 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US00370402A Expired - Lifetime US3808061A (en) | 1964-05-22 | 1964-05-22 | Nitrocellulose solid propellant composition with load additive to reduce radar attenuation |
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Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4139404A (en) * | 1975-07-02 | 1979-02-13 | Teledyne Mccormick Selph | Active binder propellants incorporating burning rate catalysts |
| US4568399A (en) * | 1985-03-22 | 1986-02-04 | The United States Of America As Represented By The Secretary Of The Army | Propellant compositions |
| US5468313A (en) * | 1994-11-29 | 1995-11-21 | Thiokol Corporation | Plastisol explosive |
| US5756006A (en) * | 1994-12-07 | 1998-05-26 | The United States Of America As Represented By The Secretary Of The Navy | Inert simulants for energetic materials |
| US6066213A (en) * | 1998-09-18 | 2000-05-23 | Atlantic Research Corporation | Minimum smoke propellant composition |
| US6126763A (en) * | 1998-12-01 | 2000-10-03 | Atlantic Research Corporation | Minimum smoke propellant composition |
| RU2183607C2 (en) * | 2000-04-07 | 2002-06-20 | Федеральное государственное унитарное предприятие "Пермский завод им. С.М. Кирова" | Smokeless solid rocket fuel |
| RU2185356C1 (en) * | 2000-11-10 | 2002-07-20 | Государственное унитарное предприятие "Научно-исследовательский институт полимерных материалов" | Ballistic-type solid propellant |
| RU2191765C1 (en) * | 2001-04-23 | 2002-10-27 | Федеральное государственное унитарное предприятие "Научно-исследовательский институт полимерных материалов" | Ballistite propellant |
| RU2245314C2 (en) * | 2003-04-09 | 2005-01-27 | Федеральное государственное унитарное предприятие "Научно-исследовательский институт полимерных материалов" | Method for production of lead dioxide on nitrocellulose fibers |
| RU2256637C1 (en) * | 2004-03-18 | 2005-07-20 | Федеральное государственное унитарное предприятие "Научно-исследовательский институт полимерных материалов" | Method for preparing copper oxide dispersion on nitrocellulose fibers |
| RU2287511C1 (en) * | 2005-07-18 | 2006-11-20 | Федеральное государственное унитарное предприятие "Научно-исследовательский институт полимерных материалов" | Method of deposition of the copper oxide dispersion on the nitrocellulose filaments |
| US8673211B1 (en) * | 2011-06-01 | 2014-03-18 | The United States of America as repesented by the Secretary of Navy | Method to reduce corrosion of aluminum alloys exposed to seawater |
| US20150259262A1 (en) * | 2014-02-26 | 2015-09-17 | Orbital Atk, Inc. | Compositions usable as flare compositions, countermeasure devices containing the flare compositions, and related methods |
| WO2018235112A1 (en) * | 2017-06-23 | 2018-12-27 | Simmel Difesa S.P.A. | COMPOSITION FOR SINGLE-BASED PROPULSIVE POWDER FOR MUNITION AND MUNITION COMPRISING SUCH A COMPOSITION |
| CN109184954A (en) * | 2018-07-24 | 2019-01-11 | 北京理工大学 | A kind of auxiliary agent reducing solid engines slow cook-off responsiveness |
| US10415938B2 (en) | 2017-01-16 | 2019-09-17 | Spectre Enterprises, Inc. | Propellant |
| US11112222B2 (en) | 2019-01-21 | 2021-09-07 | Spectre Materials Sciences, Inc. | Propellant with pattern-controlled burn rate |
| US11650037B2 (en) | 2021-02-16 | 2023-05-16 | Spectre Materials Sciences, Inc. | Primer for firearms and other munitions |
| US12234198B2 (en) | 2020-08-05 | 2025-02-25 | Spectre Enterprises, Inc. | Passivated fuel |
| US12385727B2 (en) | 2023-04-29 | 2025-08-12 | Spectre Primer Technologies, Inc. | Fuzzy interface layer for thermite and primer made from thermite with fuzzy layer |
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Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4139404A (en) * | 1975-07-02 | 1979-02-13 | Teledyne Mccormick Selph | Active binder propellants incorporating burning rate catalysts |
| US4568399A (en) * | 1985-03-22 | 1986-02-04 | The United States Of America As Represented By The Secretary Of The Army | Propellant compositions |
| US5468313A (en) * | 1994-11-29 | 1995-11-21 | Thiokol Corporation | Plastisol explosive |
| US5756006A (en) * | 1994-12-07 | 1998-05-26 | The United States Of America As Represented By The Secretary Of The Navy | Inert simulants for energetic materials |
| US6066213A (en) * | 1998-09-18 | 2000-05-23 | Atlantic Research Corporation | Minimum smoke propellant composition |
| US6126763A (en) * | 1998-12-01 | 2000-10-03 | Atlantic Research Corporation | Minimum smoke propellant composition |
| RU2183607C2 (en) * | 2000-04-07 | 2002-06-20 | Федеральное государственное унитарное предприятие "Пермский завод им. С.М. Кирова" | Smokeless solid rocket fuel |
| RU2185356C1 (en) * | 2000-11-10 | 2002-07-20 | Государственное унитарное предприятие "Научно-исследовательский институт полимерных материалов" | Ballistic-type solid propellant |
| RU2191765C1 (en) * | 2001-04-23 | 2002-10-27 | Федеральное государственное унитарное предприятие "Научно-исследовательский институт полимерных материалов" | Ballistite propellant |
| RU2245314C2 (en) * | 2003-04-09 | 2005-01-27 | Федеральное государственное унитарное предприятие "Научно-исследовательский институт полимерных материалов" | Method for production of lead dioxide on nitrocellulose fibers |
| RU2256637C1 (en) * | 2004-03-18 | 2005-07-20 | Федеральное государственное унитарное предприятие "Научно-исследовательский институт полимерных материалов" | Method for preparing copper oxide dispersion on nitrocellulose fibers |
| RU2287511C1 (en) * | 2005-07-18 | 2006-11-20 | Федеральное государственное унитарное предприятие "Научно-исследовательский институт полимерных материалов" | Method of deposition of the copper oxide dispersion on the nitrocellulose filaments |
| US8673211B1 (en) * | 2011-06-01 | 2014-03-18 | The United States of America as repesented by the Secretary of Navy | Method to reduce corrosion of aluminum alloys exposed to seawater |
| US20150259262A1 (en) * | 2014-02-26 | 2015-09-17 | Orbital Atk, Inc. | Compositions usable as flare compositions, countermeasure devices containing the flare compositions, and related methods |
| US11920910B2 (en) * | 2014-02-26 | 2024-03-05 | Northrop Grumman Systems Corporation | Compositions usable as flare compositions, countermeasure devices containing the flare compositions, and related methods |
| US10415938B2 (en) | 2017-01-16 | 2019-09-17 | Spectre Enterprises, Inc. | Propellant |
| WO2018235112A1 (en) * | 2017-06-23 | 2018-12-27 | Simmel Difesa S.P.A. | COMPOSITION FOR SINGLE-BASED PROPULSIVE POWDER FOR MUNITION AND MUNITION COMPRISING SUCH A COMPOSITION |
| CN109184954A (en) * | 2018-07-24 | 2019-01-11 | 北京理工大学 | A kind of auxiliary agent reducing solid engines slow cook-off responsiveness |
| US11112222B2 (en) | 2019-01-21 | 2021-09-07 | Spectre Materials Sciences, Inc. | Propellant with pattern-controlled burn rate |
| US12234198B2 (en) | 2020-08-05 | 2025-02-25 | Spectre Enterprises, Inc. | Passivated fuel |
| US11650037B2 (en) | 2021-02-16 | 2023-05-16 | Spectre Materials Sciences, Inc. | Primer for firearms and other munitions |
| US12385727B2 (en) | 2023-04-29 | 2025-08-12 | Spectre Primer Technologies, Inc. | Fuzzy interface layer for thermite and primer made from thermite with fuzzy layer |
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