US3214308A - Thermally stable propellant powders containing powdered polymeric materials and perchlorates - Google Patents

Thermally stable propellant powders containing powdered polymeric materials and perchlorates Download PDF

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US3214308A
US3214308A US244268A US24426862A US3214308A US 3214308 A US3214308 A US 3214308A US 244268 A US244268 A US 244268A US 24426862 A US24426862 A US 24426862A US 3214308 A US3214308 A US 3214308A
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weight
percent
thermally stable
propellant
perchlorates
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US244268A
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Howard E Rice
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ATK Launch Systems LLC
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Thiokol Corp
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    • 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
    • C06B29/00—Compositions containing an inorganic oxygen-halogen salt, e.g. chlorate, perchlorate
    • C06B29/02—Compositions containing an inorganic oxygen-halogen salt, e.g. chlorate, perchlorate of an alkali metal
    • C06B29/08—Compositions containing an inorganic oxygen-halogen salt, e.g. chlorate, perchlorate of an alkali metal with an organic non-explosive or an organic non-thermic component

Definitions

  • a further object is to provide a novel composition suitable for high temperature uses in oil well perforators.
  • a still further object is to provide a composition useful as a propellant and pyrotechnic ingredient for nose cones or missile warheads.
  • compositions of this invention are very stable at high temperatures for extended periods.
  • a preferred composition, utilizing polyacrylonitrile, has been stored at temperatures above 400' F. for several months and has exhibited no signs of decomposition or autoignition.
  • These compositions also have a low impact sensitivity in comparison with compositions of the prior art. They likewise are simpler and cheaper to prepare, as they are physical mixtures and thus do not require synthesis of expensive nitro substituted derivatives.
  • compositions of this invention can be conveniently prepared by admixture of the ingredients.
  • Preferred oxidizers are ammonium perchlorate, lithium perchlorate, sodium perchlorate and potassium perchlorate; while preferred fuels are polyacrylonitrile, polyacrylamide, poly- N-vinylcarbazole and phenol-formaldehyde polymer.
  • the fuel and oxidizer are combined in toichiometric ratio. However, other ratios ranging from 40-95 percent by weight of oxidizer and -60 percent by weight of fuel can be used.
  • burning rate modifiers such as ferric oxide, ammonium dichromate, copper chromite, and ammonium ferrocene sulfonate and anticaking agents such as finely divided silicon dioxide can be added as desired.
  • compositions of this invention differ from other propellants in that they are not cast and cured.
  • the fuels used are extremely high molecular weight compounds and are so viscous that they'are considered solids. They can be powdered in a hammer mill, for instance. Further, their viscosity does not decrease upon heating.
  • compositions when ignited by suitable means such as a squib, volatilize rapidly producing large volumes of gas rather slowly.
  • the compositions do not melt before volatilizing. It is therefore advantageous to have as much surface area available as possible.
  • the fuel and oxidizer can be reduced in particle size by means of a suitable apparatus, such as a hammer mill.
  • a suitable apparatus such as a hammer mill.
  • One fuel, polyacrylonitrile, as manufactured has a particle size ranging from 3 to microns. This is eminently suited for the purpose.
  • the other fuels. and oxidizers must be reduced in size before they are used.
  • the fuel and oxidizer are stirred until a homogeneous mixture is obtained.
  • the burning rate modifier and anticaking agent can be omitted altogether without affecting the properties of the propellant.
  • the fuel and oxidizer remain as discrete particles rather than the fuel becoming crosslinked, as in standard propellants. Since the fuel is already essentially a solid, no curing agent is required.
  • a small amount of plasticizer can be added to the mixture to aid pelletization, if desired. The amount of plasticizer added is dependent upon the end use of the composition and is easily ascertainable by one skilled in the art.
  • the composition is pressed into a cartridge or other device, equipped with a squib, lowered into the well and fired.
  • a squib There are several squibs, qualified at high temperatures, available for this purpose.
  • One such squib is obtainable from E. I. du Pont Company and is known as the 8-95 squib.
  • Example 1 A mixture of 12 parts of powdered polyacrylonitrile, 87 parts of ammonium perchlorate, 0.5 part of ferric oxide, and 0.5 part of finely divided silicon dioxide is stirred in a vertical planetary mixer for 30 minutes. A cover is placed over the mixingbowl so that the finely powdered material does. not escape during mixing. The mixture i checked visually to see that it is homogeneous. The propellant composition is then removed from the mixer and either placed in a tool or stored until needed.
  • this composition was placed in a cartridge and fired with a squib in wells 13,500 feet deep. The temperature was recorded at 350- 360 F. and the tool was in this environment for periods up to one hour. No misfirings occurred.
  • This composition has been held at 400 F. for one month and has shown no signs of decomposition or autoignition. Its autoignition temperature is about 520 F.
  • Example 2 Following the procedure described in Example 1, the following propellant formulations are obtained.
  • a propellant composition stable to autoignition and deformation at temperatures above 325 F. said propellant composition being an admixture of about 5 to 60 percent by weight of a thermally stable fuel binder, said fuel binder being selected from the group consisting of polyacrylonitrile, polyacrylamide and poly-N-vinylcarbazole, and 40 to 95 percent by weight of a solid perchlorate oxidizer, and up to 5 percent by weight of burning rate modifiers and anticaking agents.
  • a method of stabilizing propellant containing solid perchlorate oxidizer toward autoignition and deformation at temperatures above 325 F. comprising the steps of adding to said propellant containing solid perchlorate oxidizer component, burning rate modifier, anticaking component and the like, from about 5 to 60 percent by weight of a thermally stable fuel binder component, said thermally stable fuel binder being selected from the group consisting of polyacrylonitrile, polyacrylamide and, poly- N-vinylcarbazole and admixing said propellant components until a uniform and homogeneous propellant composition is produced.
  • a method of stabilizing ammonium perchlorate based propellants toward autoignition and deformation at temperatures above 325 F. comprising the steps of adding to 40 to 95 percent by weight of ammonium perchlorate oxidizer component from 5 to 60 percent by weight of polyacrylonitrile fuel binder, and admixing said mixed components until a uniform and homogeneous propellant composition is produced.
  • a propellant composition stable to autoignition and deformation at temperatures above 325 F. said propellant composition being an admixture of about 5 to 60 percent by weight of polyacrylonitrile fuel binder, and to 95 percent by weight of ammonium perchlorate oxidizer, and up to 5 percent by weight of burning rate modifiers and anticaking agents.
  • a propellant composition stable to autoignition and deformation at temperatures above 325 F. said propellant composition being an admixture of about 5 to percent by weight of polyacrylonitrile fuel binder, and 40 to percent by weight of potassium perchlorate oxidizer, and up to 5 percent by weight of burning rate modifiers and anticaking agents.
  • a propellant composition stable to autoignition and deformation at temperatures above 325 F. said propellant composition being an admixture of about 5 to 60 percent by weight of polyacrylonitrile fuel binder, and 40 to 95 percent by weight of lithium perchlorate oxidizer, and up to 5 percent by weight of burning rate modifiers and anticaking agents.

Description

United States Patent 3,214,308 THERMALLY STABLE PROPELLANT POWDERS CONTAINING PDWDERED POLYMERIC MA- TERIALS AND PERCHLURATES Howard E. Rice, Elkton, Md., assignor to Thiokol Chemical Corporation, Bristol, Pa., a corporation of Delaware No Drawing. Filed Dec. 13, 1962, Ser. No. 244,268 6 Claims. (Cl. 149-76) The present invention relates to novel compositions of matter and more particularly to propellant powders which are stable for extended periods of time at high temperature.
There has been a pressing need in the oil drilling industry for propellants of high heat stability for the purpose of shattering and piercing oil well casings. Numerous types of devices, commonly known as oil well gun perforators, have been developed for this purpose. Gun powder and ball powder have been used in such devices, but they have several serious deficiencies. Gun powder is relatively heat sensitive so that upon being lowered to great depths, premature firing and the like have occurred. The temperature of oil wells increases, of course, as the well becomes deeper. Many wells are now at the 12,000 to 15,000 foot level, where the temperature is in the neighborhood of 325-375 F. Presently the deepest ones are at the 26,000 foot level and show temperatures of about 465 F. The compositions of the prior art are unstable at temperature above 250 F. and thus cannot be used with reliability. Furthermore, these compounds require the synthesis of expensive nitro substituted derivatives.
It is therefore an object of this invention to provide a novel propellant suitable for use at high temperatures. A further object is to provide a novel composition suitable for high temperature uses in oil well perforators. A still further object is to provide a composition useful as a propellant and pyrotechnic ingredient for nose cones or missile warheads.
The compositions of this invention are very stable at high temperatures for extended periods. A preferred composition, utilizing polyacrylonitrile, has been stored at temperatures above 400' F. for several months and has exhibited no signs of decomposition or autoignition. These compositions also have a low impact sensitivity in comparison with compositions of the prior art. They likewise are simpler and cheaper to prepare, as they are physical mixtures and thus do not require synthesis of expensive nitro substituted derivatives.
The compositions of this invention can be conveniently prepared by admixture of the ingredients. Preferred oxidizers are ammonium perchlorate, lithium perchlorate, sodium perchlorate and potassium perchlorate; while preferred fuels are polyacrylonitrile, polyacrylamide, poly- N-vinylcarbazole and phenol-formaldehyde polymer. For best results, the fuel and oxidizer are combined in toichiometric ratio. However, other ratios ranging from 40-95 percent by weight of oxidizer and -60 percent by weight of fuel can be used. In addition, burning rate modifiers such as ferric oxide, ammonium dichromate, copper chromite, and ammonium ferrocene sulfonate and anticaking agents such as finely divided silicon dioxide can be added as desired.
The compositions of this invention differ from other propellants in that they are not cast and cured. The fuels used are extremely high molecular weight compounds and are so viscous that they'are considered solids. They can be powdered in a hammer mill, for instance. Further, their viscosity does not decrease upon heating.
These compositions, when ignited by suitable means such as a squib, volatilize rapidly producing large volumes of gas rather slowly. The compositions do not melt before volatilizing. It is therefore advantageous to have as much surface area available as possible. The fuel and oxidizer can be reduced in particle size by means of a suitable apparatus, such as a hammer mill. One fuel, polyacrylonitrile, as manufactured, has a particle size ranging from 3 to microns. This is eminently suited for the purpose. The other fuels. and oxidizers must be reduced in size before they are used.
The fuel and oxidizer are stirred until a homogeneous mixture is obtained. The burning rate modifier and anticaking agent can be omitted altogether without affecting the properties of the propellant. After stirring, the fuel and oxidizer remain as discrete particles rather than the fuel becoming crosslinked, as in standard propellants. Since the fuel is already essentially a solid, no curing agent is required. A small amount of plasticizer can be added to the mixture to aid pelletization, if desired. The amount of plasticizer added is dependent upon the end use of the composition and is easily ascertainable by one skilled in the art.
After preparation, the composition is pressed into a cartridge or other device, equipped with a squib, lowered into the well and fired. There are several squibs, qualified at high temperatures, available for this purpose. One such squib is obtainable from E. I. du Pont Company and is known as the 8-95 squib.
It will be apparent to those skilled in the art that many modifications, both of materials and methods, can be practical without departing from the invention. The following examples are illustrative only, and are not to be construed as limiting the invention either in spirit or in scope. In these examples temperatures are given in degrees Fahrenheit F.) and amounts of materials in parts by Weight.
Example 1 A mixture of 12 parts of powdered polyacrylonitrile, 87 parts of ammonium perchlorate, 0.5 part of ferric oxide, and 0.5 part of finely divided silicon dioxide is stirred in a vertical planetary mixer for 30 minutes. A cover is placed over the mixingbowl so that the finely powdered material does. not escape during mixing. The mixture i checked visually to see that it is homogeneous. The propellant composition is then removed from the mixer and either placed in a tool or stored until needed.
These compounds have been tested for their ability to power devices which are used to pierce oil well casings at elevated temperatures. For example, this composition was placed in a cartridge and fired with a squib in wells 13,500 feet deep. The temperature was recorded at 350- 360 F. and the tool was in this environment for periods up to one hour. No misfirings occurred. This composition has been held at 400 F. for one month and has shown no signs of decomposition or autoignition. Its autoignition temperature is about 520 F.
Example 2 Following the procedure described in Example 1, the following propellant formulations are obtained.
No. 2 No. 3
Polyacrylamide powder Poly-N-vinylcarbazole powder Phenol-formaldehyde powder Lithium perchlorate Sodium perchlorate Potassium perchlorate.-- Ferric oxide Silicon dioxide What is claimed is:
1. A propellant composition stable to autoignition and deformation at temperatures above 325 F., said propellant composition being an admixture of about 5 to 60 percent by weight of a thermally stable fuel binder, said fuel binder being selected from the group consisting of polyacrylonitrile, polyacrylamide and poly-N-vinylcarbazole, and 40 to 95 percent by weight of a solid perchlorate oxidizer, and up to 5 percent by weight of burning rate modifiers and anticaking agents.
2. A method of stabilizing propellant containing solid perchlorate oxidizer toward autoignition and deformation at temperatures above 325 F. comprising the steps of adding to said propellant containing solid perchlorate oxidizer component, burning rate modifier, anticaking component and the like, from about 5 to 60 percent by weight of a thermally stable fuel binder component, said thermally stable fuel binder being selected from the group consisting of polyacrylonitrile, polyacrylamide and, poly- N-vinylcarbazole and admixing said propellant components until a uniform and homogeneous propellant composition is produced.
3. A method of stabilizing ammonium perchlorate based propellants toward autoignition and deformation at temperatures above 325 F. comprising the steps of adding to 40 to 95 percent by weight of ammonium perchlorate oxidizer component from 5 to 60 percent by weight of polyacrylonitrile fuel binder, and admixing said mixed components until a uniform and homogeneous propellant composition is produced.
til
4. A propellant composition stable to autoignition and deformation at temperatures above 325 F., said propellant composition being an admixture of about 5 to 60 percent by weight of polyacrylonitrile fuel binder, and to 95 percent by weight of ammonium perchlorate oxidizer, and up to 5 percent by weight of burning rate modifiers and anticaking agents. I
5. A propellant composition stable to autoignition and deformation at temperatures above 325 F., said propellant composition being an admixture of about 5 to percent by weight of polyacrylonitrile fuel binder, and 40 to percent by weight of potassium perchlorate oxidizer, and up to 5 percent by weight of burning rate modifiers and anticaking agents.
6. A propellant composition stable to autoignition and deformation at temperatures above 325 F., said propellant composition being an admixture of about 5 to 60 percent by weight of polyacrylonitrile fuel binder, and 40 to 95 percent by weight of lithium perchlorate oxidizer, and up to 5 percent by weight of burning rate modifiers and anticaking agents.
References Cited by the Examiner UNITED STATES PATENTS 1,700,085 1/29 Scott 149 s3 11,964,222 6/34 Scott 149 s3 X 2,931,437 4/60 Smith 149-76 CARL D. QUARFORTH, Primary Examiner.

Claims (1)

1. A PROPELLANT COMPOSITION STABLE TO AUTOIGNITION AND DEFORMATION AT TEMPERATURES ABOVE 325*F., SAID PROPELLANT COMPOSITION BEING AN ADMIXTURE OF ABOUT 5 TO 60 PERCENT BY WEIGHT OF A THERMALLY STABLE FUEL BINDER, SAID FUEL BINDER BEING SELECTED FROM THE GROUP CONSISTING OF POLYACRYLONITRILE, POLYACRYLAMIDE AND POLY-N-VINYLCARBOZOLE, AND 40 TO 95 PERCENT BY WEIGHT OF A SOLID PERCHLORATE OXIDIZER, AND UP TO 5 PERCENT BY WEIGHT OF BURNING RATE MODIFIERS AND ANTICAKING AGENTS.
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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3798088A (en) * 1973-03-05 1974-03-19 Us Navy Cocrystallization of ammonium perchlorate and stabilization of solid propellants
US3964256A (en) * 1972-10-17 1976-06-22 Societe Nationale Des Poudres Et Explosifs Production of non-toxic gas by combustion of solid propellant
DE19932466A1 (en) * 1999-07-12 2001-01-18 Trw Airbag Sys Gmbh & Co Kg Azide free gas generating composition
DE10224859A1 (en) * 2002-06-05 2003-12-24 Fraunhofer Ges Forschung Production of free-running perchlorate, used as propellant, explosive and oxidant, e.g. in solid propellant or pyrotechnics, involves mixing with anticaking agent, transfer to inert carrier gas stream and hammer milling
US6709537B2 (en) 2001-10-05 2004-03-23 Autoliv Asp, Inc, Low firing energy initiator pyrotechnic mixture
US6758922B2 (en) 2001-10-05 2004-07-06 Autoliv Asp, Inc. Low firing energy initiator pyrotechnic mixture
US8932417B1 (en) * 2007-06-11 2015-01-13 Pacific Scientific Energetic Materials Company Methods and systems for manufacturing propellants

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1700085A (en) * 1924-11-29 1929-01-22 Mexco Ltd Explosive
US1964222A (en) * 1931-11-11 1934-06-26 Heaters Ltd Explosive
US2931437A (en) * 1956-02-23 1960-04-05 Phillips Petroleum Co Method and apparatus for initiating subterranean combustion

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1700085A (en) * 1924-11-29 1929-01-22 Mexco Ltd Explosive
US1964222A (en) * 1931-11-11 1934-06-26 Heaters Ltd Explosive
US2931437A (en) * 1956-02-23 1960-04-05 Phillips Petroleum Co Method and apparatus for initiating subterranean combustion

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3964256A (en) * 1972-10-17 1976-06-22 Societe Nationale Des Poudres Et Explosifs Production of non-toxic gas by combustion of solid propellant
US3798088A (en) * 1973-03-05 1974-03-19 Us Navy Cocrystallization of ammonium perchlorate and stabilization of solid propellants
DE19932466A1 (en) * 1999-07-12 2001-01-18 Trw Airbag Sys Gmbh & Co Kg Azide free gas generating composition
US6709537B2 (en) 2001-10-05 2004-03-23 Autoliv Asp, Inc, Low firing energy initiator pyrotechnic mixture
US6758922B2 (en) 2001-10-05 2004-07-06 Autoliv Asp, Inc. Low firing energy initiator pyrotechnic mixture
DE10224859A1 (en) * 2002-06-05 2003-12-24 Fraunhofer Ges Forschung Production of free-running perchlorate, used as propellant, explosive and oxidant, e.g. in solid propellant or pyrotechnics, involves mixing with anticaking agent, transfer to inert carrier gas stream and hammer milling
US8932417B1 (en) * 2007-06-11 2015-01-13 Pacific Scientific Energetic Materials Company Methods and systems for manufacturing propellants

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