US3650856A - Red phosphorus castable smoke producing composition - Google Patents
Red phosphorus castable smoke producing composition Download PDFInfo
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- US3650856A US3650856A US864159A US3650856DA US3650856A US 3650856 A US3650856 A US 3650856A US 864159 A US864159 A US 864159A US 3650856D A US3650856D A US 3650856DA US 3650856 A US3650856 A US 3650856A
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- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B39/00—Compositions containing free phosphorus or a binary compound of phosphorus, except with oxygen
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- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06D—MEANS FOR GENERATING SMOKE OR MIST; GAS-ATTACK COMPOSITIONS; GENERATION OF GAS FOR BLASTING OR PROPULSION (CHEMICAL PART)
- C06D3/00—Generation of smoke or mist (chemical part)
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- 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
- Y10S149/117—Smoke or weather composition contains resin
Definitions
- ABSTRACT A castable pyrotechnic white smoke composition which comprises red phosphorous, an alkali metal nitrate, magnesium and a suitable castable polymeric binder.
- Smoke markers or grenades are very useful in both military and commercial applications. In military applications, smoke markers can be used to identify target sites. Additionally, in both commercial and military applications such smoke markers are used for rescue operations to identify parties being retrieved. In order for a smoke marker to be readily handleable, it should be capable of being placed in a closed can or container which in some instances can actually be a grenade. If the smoke composition is so disposed in an enclosed container, it must be susceptible to generating smoke without the presence of oxygen or air. In other words, the composition should be self-sustaining. Further, smoke composition should be preferably capable of slow dissipation of the smoke over a given period of time, to allow for identification of the area in which the smoke is originating.
- white phosphorous Prior to the herein invention, white phosphorous had often been utilized as the main smoke generating ingredient in various compositions.
- whitephosphorous has a drawback in that it is spontaneously combustible in air, which makes it extremely dangerous to handle. Further, white phosphorous rapidly dissipates smoke and does not allow for a gradual release thereof.
- red phosphorous smoke compositions Little effort had been directed in the past to the use of red phosphorous smoke compositions. When red phosphorous was used it was in the form of pressed powder and was not cast as a grain. This is an expensive, time consuming and sometimes dangerous process. Further, pressed powders do not have the structural integrity of cast grains. The previous pressed red phosphorous compositions additionally need air in order to burn and were not self-sustaining, and thus could not be used in closed containers where air could not reach the material.
- an object of this invention is to provide a self-sustaining castable white smoke composition.
- Another object of this invention is to provide a self-sustaining castable smoke composition containing red phosphorous.
- Still another object of this invention is to provide a castable -white smoke composition which has a long and controlled burn time.
- a novel castable white smoke composition of this invention based on red phosphorous which will burn in the absence of atmospheric oxygen.
- the composition of the invention contains red phosphorous as a primary fuel ingredient to generate the smoke.
- the composition additionally contains an alkaline metal nitrate as an oxidizer.
- the composition contains a metallic fuel, such as magnesium, in a relatively small amount.
- the composition is held together by a castable binder which additionally serves as a fuel.
- a castable binder which additionally serves as a fuel.
- Virtually any polymeric binder which is suitable for solid propellant utilization can be used. It is preferred that the binder have a relatively high oxygen content and that it cure to a rubbery state.
- a typical example of such a binder is the class of polysulphide rubbers.
- compositions can be present in the composition.
- the ingredients are typically mixed together in a suitable mixer, poured into the containers or hardware for the smoke composition, and cured at suitable curing conditions of temperature and pressure.
- a suitable mixer poured into the containers or hardware for the smoke composition, and cured at suitable curing conditions of temperature and pressure.
- red phosphorous The main component of the smoke composition of this invention is red phosphorous.
- red phosphorous was very seldom used in smoke compositions.
- U.S. Pat. No. 528,5]5 red phosphorous was combined with nitrate and pressed in one embodiment to form a composition which would produce a bright flash of light.
- red phosphorous has been previously used in an attempt to form a smoke generating composition, it additionally was in a pressed form, not cast, and required the presence of air to burn.
- White phosphorous has been used mostly in the past in smoke compositions. However, it is spontaneously combustible in air, as indicated, and does not provide a slow controlled dissipation of smoke.
- the red phosphorous used in this invention can vary from 31 to 47 weight percent of the smoke composition. Red phosphorous is normally in a fine particle form. It is not readily obtainable in various size particles. Because of this, one cannot readily achieve a high solid loading in a cast composition, and thus the upper limit of 47 weight percent of the material is determined by a solids loading capability for cast compositions.
- An alkali metal nitrate is used in the composition of this invention as an oxidizer.
- Typical nitrates include sodium and potassium nitrates.
- One of the primary problems in forming a suitable composition is an unwanted reaction between the oxidizer and the phosphorous. Thus, highly reactive materials, such as the chlorates and perchlorates, are not suitable for the compositions of this invention.
- the nitrate is used in a solid particulate form in amounts varying from 18 to 32 weight percent of the smoke composition.
- magnesium is added to the composition of the invention.
- Magnesium reacts with the nitrate present to generate the heat required for continued combustion of the phosphorous without snuffing out. Further, the reaction of the magnesium with the nitrate helps to provide reliable ignition of the smoke composition. It has been found that from 4 to 5 weight percent magnesium in the smoke composition serves to accomplish the aforegoing purposes.
- a polymeric binder is used. Virtually any binder which has been found suitable for solid propellant compositions can be used herein. However, it is not desirable to have the smoke composition too rigid or brittle, since it is subject often to shock loads particularly when it is used as a grenade. In fact it is preferred that the polymer cure to a rubbery state.
- binders include the polysulfide rubbers, polysulfide-epoxy mixtures such as Thiokol LP-3/Dow Epoxy DER 321 and DER 736 and polyesters produced from the reaction of dibasic acids with dihydric alcohols.
- a typical polyester binder is hydroxy-terminated polyester resin R-l 8 as supplied by Mobay Chemical Co. formed from adipic acid and diethylene glycol. Additionally, hydroxy and carboxy terminated butadienes are further contemplated.
- any of the polymeric binders set forth can be used herein. Together with the polymer material, there is generally utilized a suitable plasticizer and cross-linking agent.
- plasticizers are contemplated, which are conventional and well known in the art depending upon the binder selected.
- Typical plasticizers include, for example, triacetin, bis-dinitropropylacrylate-formal (BDNPA-F), and trimethylolethanetrinitrate (TMETN).
- BDNPA-F bis-dinitropropylacrylate-formal
- TMETN trimethylolethanetrinitrate
- Various other plasticizers are contemplated and can be used.
- the binder composition will have a certain amount of cross-linking material added thereto.
- Preferred cross-linking material is PAPI which is polymethylene polyphenylisocyanate.
- Additional cross-linking agents could include, but are not limited to for example, trimethylolpropane, hexanetriol, castor oil, toluene diisocyanate, diphenyl-methane diisocyanate and MAP0 which is tris [l-(2-methyl)-aziridinyl] phosphine oxide.
- the binder and plasticizer if present, will constitute from 25 to 35 weight percent of the smoke composition.
- the weight ratio of plasticizer to hinder can vary from :1 to 1.521.
- the cross-linking agent will vary from to 20 weight percent of the active binder material, depending upon the materials used and the state of cure desired in the end product.
- FEAA ferric acetylacetonate
- EEAA ferric acetylacetonate
- Other accelerators can be used to hasten the cure time. Selection of fuel accelerators will depend on the composition chosen. For example, when TMETN is a plasticizer then trimethylolpropane TMP, is a most suitable accelerator together with FEAA.
- composition ranges set forth provide a smoke that is underoxidized.
- oxidizer present to furnish oxygen for the full combustion of the fuel components.
- This is very important to the herein invention in that it has been found that in fully oxidized or over oxidized compositions the smoke will burn too vigorously in an uncontrollable manner.
- the composition does provide a castable smoke which does burn in the absence of atmospheric oxygen.
- a castable red phosphorous smoke composition which will burn in the absence of air was not believed to be known.
- the formulation of the smoke is simple and straightforward. Generally the magnesium, phosphorous, plasticizer, and binder are first added to a mixer and mixed at a suitable temperature for a period of time to achieve homogeneity. The nitrate is then added and additional mixing under vacuum is accomplished at the mixed temperature. A vacuum is utilized at this stage to remove any air entrapped in the composition so that more dense castings can be made. Finally, after the nitrate has been mixed into the composition the cross-linking agent and other additives such as the FEAA are added and the final mix continued until all the materials have been thoroughly dispersed. It is preferred to vacuum cast the mixture into prepared hardware used, such as cans or grenades or any other suitable containers for the smoke composition. Casting conditions will of course vary depending upon the binder and cross-linking agents utilized. As indicated, the cure should provide a rubbery final composition as compared to a brittle or rigid one.
- the smoke composition of this invention can be ignited by virtually any ignition technique utilized for solid propellant ignition. These include a boron/potassium nitrate pellet, electric squibs, electric detonators and explosive materials such as Detacord, Primacord, and Pyroeore. Additionally a first fire mix or igniter mix can be coated onto a surface.
- a typical ignition composition is comprised of silicon, lead oxide and cuprous oxide which would be mixed with nitrocellulose in a suitable solvent to form a lacquer that is spread onto the surface to be ignited. It is believed that the invention will be further understood from the following detailed examples.
- a 5,000-gram batch of a smoke composition of this invention was prepared having the following composition expressed in weight percent.
- the percent accelerator is added above the entire composition of the A standard l-gallon Baker-Perkins vertical mixer commonly used for solid propellant mixing was used to mix the ingredients of this invention.
- the polyester binder, triacetin, magnesium, and phosphorous were all initially added to the mixer and mixed for 15 minutes at F.
- the mixing was then stopped and the sodium nitrate was then added and mixing continued for an additional 10 minutes under vacuum at F.
- the PAP! and FEAA were then finally added and the mixing was continued for an additional 10 minutes at 160 F. under vacuum.
- the composition was vacuum cast into polyethylene tubes which were 2% inches long and had a diameter of three-fourths of an inch.
- the filled tubes were placed in an oven and cured at 160 F. for 16 hours to a rubbery state.
- the aforegoing composition was determined to have a buming rate of 0.70 inch per minute. This composition was additionally found to have an autoignition temperature in excess of 500 F. and was insensitive to impact with a 5 pound weight from a height of at least 50 inches. The composition burned with a bright yellow flame and produced voluminous quantities of white smoke.
- EXAMPLE II A slow burning formulation was tested as compared to that described in Example 1.
- the composition of the smoke in this example comprised:
- EXAMPLE III A fast burning formulation in accord with this invention was formulated for this example using the procedures of Example I and the same polyethylene tubes for casting the grain.
- the composition used in this example comprised:
- a castable smoke producing composition comprising from 31 to 47 weight percent red phosphorous, from 18 to 32 weight percent alkali metal nitrate, from 4 to 5 weight percent magnesium and from to 35 weight percent of a castable polymeric binder.
- composition of claim 1 in which the castable polymeric binder is a castable polysulphide, polysulphideepoxy mixture, polyester or polybutadiene.
- composition of claim 5 in which the dibasic acid is adipic acid and the dihydric alcohol is diethylene glycol.
- composition of claim 7 in which the cross-linking agent is present in an amount of from 10 to 20 weight percent based on a total castable polymeric binder content.
- composition of claim 7 in which the plasticizer is trimethylolethanetrinitrate, triacetin, or bisdinitropropylacrylate-formal.
- composition otlciaim 7 in which the cross-linking agent is polymethylene polyphenylisocyanate.
- composition of claim 7 in which the composition includes from 0.001 to 0.01 weight percent of ferric acetylacetonate catalyst.
Abstract
A castable pyrotechnic white smoke composition which comprises red phosphorous, an alkali metal nitrate, magnesium and a suitable castable polymeric binder.
Description
Artz
ited States Patent [451 Mar. 21, 1972 RED PHOSPHORUS CASTABLE SMOKE PRODUCING COMPOSITION Glen D. Artz, Canoga Park, Calif.
North American Rockwell Corporation Oct. 6, 1969 Inventor:
Assignee:
Filed:
Appl. No.:
U.S. Cl ..149/19,149/30,149/38, 149/43, 149/44, 149/61, 149/62, 149/88 Int. Cl; 3.1.? ..L';'. .,C06d 3/00 Field of Search 149/29, 30, 19, 38, 43, 44, 149/61, 62, 88
References Cited UNITED STATES PATENTS 6/1922 Nichols 149/30 Primary Examiner-Carl D. Quarforth Assistant ExaminerE. A. Miller Attorney L. Lee Humphries and Thomas S. MacDonald [5 7] ABSTRACT A castable pyrotechnic white smoke composition which comprises red phosphorous, an alkali metal nitrate, magnesium and a suitable castable polymeric binder.
l 1 Claims, No Drawings RED PHOSPHORUS CASTABL'E SMOKE PRODUCING COMPOSITION Smoke markers or grenades are very useful in both military and commercial applications. In military applications, smoke markers can be used to identify target sites. Additionally, in both commercial and military applications such smoke markers are used for rescue operations to identify parties being retrieved. In order for a smoke marker to be readily handleable, it should be capable of being placed in a closed can or container which in some instances can actually be a grenade. If the smoke composition is so disposed in an enclosed container, it must be susceptible to generating smoke without the presence of oxygen or air. In other words, the composition should be self-sustaining. Further, smoke composition should be preferably capable of slow dissipation of the smoke over a given period of time, to allow for identification of the area in which the smoke is originating.
Prior to the herein invention, white phosphorous had often been utilized as the main smoke generating ingredient in various compositions. However, whitephosphorous has a drawback in that it is spontaneously combustible in air, which makes it extremely dangerous to handle. Further, white phosphorous rapidly dissipates smoke and does not allow for a gradual release thereof.
Little effort had been directed in the past to the use of red phosphorous smoke compositions. When red phosphorous was used it was in the form of pressed powder and was not cast as a grain. This is an expensive, time consuming and sometimes dangerous process. Further, pressed powders do not have the structural integrity of cast grains. The previous pressed red phosphorous compositions additionally need air in order to burn and were not self-sustaining, and thus could not be used in closed containers where air could not reach the material.
Thus an object of this invention is to provide a self-sustaining castable white smoke composition.
Another object of this invention is to provide a self-sustaining castable smoke composition containing red phosphorous.
Still another object of this invention is to provide a castable -white smoke composition which has a long and controlled burn time.
The above and other objects of this invention are accomplished by a novel castable white smoke composition of this invention based on red phosphorous which will burn in the absence of atmospheric oxygen. The composition of the invention contains red phosphorous as a primary fuel ingredient to generate the smoke. The composition additionally contains an alkaline metal nitrate as an oxidizer. Additionally, the composition contains a metallic fuel, such as magnesium, in a relatively small amount. Finally, the composition is held together by a castable binder which additionally serves as a fuel. Virtually any polymeric binder which is suitable for solid propellant utilization can be used. It is preferred that the binder have a relatively high oxygen content and that it cure to a rubbery state. A typical example of such a binder is the class of polysulphide rubbers. Additional other materials in small amounts, such as cross-linking agents, plasticizers, fillers and the'like can be present in the composition. The ingredients are typically mixed together in a suitable mixer, poured into the containers or hardware for the smoke composition, and cured at suitable curing conditions of temperature and pressure. By varying the composition and including the use of reactive plasticizers, one can subtly control the burning rate of the smoke compositions ofthis invention.
It is believed that the invention will be better understood from the following detailed description and examples.
The main component of the smoke composition of this invention is red phosphorous. As indicated, prior to this invention, red phosphorous was very seldom used in smoke compositions. For example, in an early patent, U.S. Pat. No. 528,5]5, red phosphorous was combined with nitrate and pressed in one embodiment to form a composition which would produce a bright flash of light. However, it was not disclosed as a smoke generating composition. Where red phosphorous has been previously used in an attempt to form a smoke generating composition, it additionally was in a pressed form, not cast, and required the presence of air to burn. White phosphorous, on the other hand, has been used mostly in the past in smoke compositions. However, it is spontaneously combustible in air, as indicated, and does not provide a slow controlled dissipation of smoke.
The red phosphorous used in this invention can vary from 31 to 47 weight percent of the smoke composition. Red phosphorous is normally in a fine particle form. It is not readily obtainable in various size particles. Because of this, one cannot readily achieve a high solid loading in a cast composition, and thus the upper limit of 47 weight percent of the material is determined by a solids loading capability for cast compositions.
An alkali metal nitrate is used in the composition of this invention as an oxidizer. Typical nitrates include sodium and potassium nitrates. One of the primary problems in forming a suitable composition is an unwanted reaction between the oxidizer and the phosphorous. Thus, highly reactive materials, such as the chlorates and perchlorates, are not suitable for the compositions of this invention. The nitrate is used in a solid particulate form in amounts varying from 18 to 32 weight percent of the smoke composition.
In order to generate a hot enough flame to sustain burning of the phosphorous, magnesium is added to the composition of the invention. Magnesium reacts with the nitrate present to generate the heat required for continued combustion of the phosphorous without snuffing out. Further, the reaction of the magnesium with the nitrate helps to provide reliable ignition of the smoke composition. It has been found that from 4 to 5 weight percent magnesium in the smoke composition serves to accomplish the aforegoing purposes.
In order to form a suitable castable smoke composition, a polymeric binder is used. Virtually any binder which has been found suitable for solid propellant compositions can be used herein. However, it is not desirable to have the smoke composition too rigid or brittle, since it is subject often to shock loads particularly when it is used as a grenade. In fact it is preferred that the polymer cure to a rubbery state.
Additionally, it has been found desirable to have a high oxygen containing binder because the quantity of solid oxidizer required can be reduced if the binder can supply some of the oxygen required for oxidation of the phosphorous and other fuels present in the composition. As a result, preferred binders include the polysulfide rubbers, polysulfide-epoxy mixtures such as Thiokol LP-3/Dow Epoxy DER 321 and DER 736 and polyesters produced from the reaction of dibasic acids with dihydric alcohols. A typical polyester binder is hydroxy-terminated polyester resin R-l 8 as supplied by Mobay Chemical Co. formed from adipic acid and diethylene glycol. Additionally, hydroxy and carboxy terminated butadienes are further contemplated. In fact, any of the polymeric binders set forth can be used herein. Together with the polymer material, there is generally utilized a suitable plasticizer and cross-linking agent.
Various suitable plasticizers are contemplated, which are conventional and well known in the art depending upon the binder selected. Typical plasticizers include, for example, triacetin, bis-dinitropropylacrylate-formal (BDNPA-F), and trimethylolethanetrinitrate (TMETN). Various other plasticizers, of course, are contemplated and can be used.
In addition to the plasticizers, the binder composition will have a certain amount of cross-linking material added thereto. Preferred cross-linking material is PAPI which is polymethylene polyphenylisocyanate. Additional cross-linking agents could include, but are not limited to for example, trimethylolpropane, hexanetriol, castor oil, toluene diisocyanate, diphenyl-methane diisocyanate and MAP0 which is tris [l-(2-methyl)-aziridinyl] phosphine oxide.
Generally, the binder and plasticizer, if present, will constitute from 25 to 35 weight percent of the smoke composition. The weight ratio of plasticizer to hinder can vary from :1 to 1.521. The cross-linking agent will vary from to 20 weight percent of the active binder material, depending upon the materials used and the state of cure desired in the end product.
Further, it has been found that FEAA, which is ferric acetylacetonate, can be added to the composition of this invention to provide accelerated cure. Generally from 0.001 to 0.01 weight percent of EEAA is added for this purpose. Other accelerators can be used to hasten the cure time. Selection of fuel accelerators will depend on the composition chosen. For example, when TMETN is a plasticizer then trimethylolpropane TMP, is a most suitable accelerator together with FEAA.
It should be pointed out that the aforegoing composition ranges set forth provide a smoke that is underoxidized. In other words, from a stoichiometric standpoint there is not enough oxidizer present to furnish oxygen for the full combustion of the fuel components. This is very important to the herein invention in that it has been found that in fully oxidized or over oxidized compositions the smoke will burn too vigorously in an uncontrollable manner. However, the composition does provide a castable smoke which does burn in the absence of atmospheric oxygen. Prior to the herein invention a castable red phosphorous smoke composition which will burn in the absence of air was not believed to be known.
The formulation of the smoke is simple and straightforward. Generally the magnesium, phosphorous, plasticizer, and binder are first added to a mixer and mixed at a suitable temperature for a period of time to achieve homogeneity. The nitrate is then added and additional mixing under vacuum is accomplished at the mixed temperature. A vacuum is utilized at this stage to remove any air entrapped in the composition so that more dense castings can be made. Finally, after the nitrate has been mixed into the composition the cross-linking agent and other additives such as the FEAA are added and the final mix continued until all the materials have been thoroughly dispersed. It is preferred to vacuum cast the mixture into prepared hardware used, such as cans or grenades or any other suitable containers for the smoke composition. Casting conditions will of course vary depending upon the binder and cross-linking agents utilized. As indicated, the cure should provide a rubbery final composition as compared to a brittle or rigid one.
In order to start or initially ignite the smoke composition an igniter is required. The smoke composition of this invention can be ignited by virtually any ignition technique utilized for solid propellant ignition. These include a boron/potassium nitrate pellet, electric squibs, electric detonators and explosive materials such as Detacord, Primacord, and Pyroeore. Additionally a first fire mix or igniter mix can be coated onto a surface. A typical ignition composition is comprised of silicon, lead oxide and cuprous oxide which would be mixed with nitrocellulose in a suitable solvent to form a lacquer that is spread onto the surface to be ignited. It is believed that the invention will be further understood from the following detailed examples.
EXAMPLE I A 5,000-gram batch of a smoke composition of this invention was prepared having the following composition expressed in weight percent. In this and the following examples the percent accelerator is added above the entire composition of the A standard l-gallon Baker-Perkins vertical mixer commonly used for solid propellant mixing was used to mix the ingredients of this invention. The polyester binder, triacetin, magnesium, and phosphorous were all initially added to the mixer and mixed for 15 minutes at F. The mixing was then stopped and the sodium nitrate was then added and mixing continued for an additional 10 minutes under vacuum at F. After completion of this time period the PAP! and FEAA were then finally added and the mixing was continued for an additional 10 minutes at 160 F. under vacuum. At this point, the mixing of the smoke composition was complete and ready for casting. The composition was vacuum cast into polyethylene tubes which were 2% inches long and had a diameter of three-fourths of an inch. The filled tubes were placed in an oven and cured at 160 F. for 16 hours to a rubbery state.
These filled tubes were ignited by an electric squib and the burn times evaluated by visual observation and a stopwatch. Standard solid propellant strand burning rate equipment (Atlantic Research Corp.), which provides automatic recording of burn times, has also been utilized for burn rate evaluation although open air tests are preferable for obvious reasons.
The aforegoing composition was determined to have a buming rate of 0.70 inch per minute. This composition was additionally found to have an autoignition temperature in excess of 500 F. and was insensitive to impact with a 5 pound weight from a height of at least 50 inches. The composition burned with a bright yellow flame and produced voluminous quantities of white smoke.
EXAMPLE II A slow burning formulation was tested as compared to that described in Example 1. The composition of the smoke in this example comprised:
Compound Wt.
Red Phosphorous 46.90 Sodium Nitrate 18.30 Magnesium 4.60 Mobay R-18 Polyester Binder 14.00 Triacetin 15.80 PAP] 1.40 FEAA (added) 0.02
EXAMPLE III A fast burning formulation in accord with this invention was formulated for this example using the procedures of Example I and the same polyethylene tubes for casting the grain. The composition used in this example comprised:
Compound Wt. 7:
Red Phosphorous 31.30 Sodium Nitrate 31.30 Magnesium 4.50 Mobay R-l8 Polyester Binder 1 1.60 PAPl 0.90 TMETN 20.30 TMP (added) 0.10 FEAA (added) 0.02
Because of the presence of the TMETN instead of the triacetin, together with the TMP, burning rates varying from 1.57 to 2.16 inches/minute were obtained from samples tested. This indicates that the burning rate of this composition was from two to three times as great as the composition set forth in Example I. Once again, this composition burned with a bright yellow flame producing large quantities of white smoke.
lclaim:
1. A castable smoke producing composition comprising from 31 to 47 weight percent red phosphorous, from 18 to 32 weight percent alkali metal nitrate, from 4 to 5 weight percent magnesium and from to 35 weight percent of a castable polymeric binder.
2. The composition of claim 1 in which said alkali metal nitrate is potassium nitrate or sodium nitrate.
31 The composition of claim 1 in which the castable polymeric binder is a castable polysulphide, polysulphideepoxy mixture, polyester or polybutadiene.
4. The composition of claim 3 in which the polybutadiene is a hydroxy or carboxy terminated polybutadiene.
5. The composition of claim 3 in which the polyester is prepared by the reaction of a dibasic acid with a dihydric a1- cohol.
6. The composition of claim 5 in which the dibasic acid is adipic acid and the dihydric alcohol is diethylene glycol.
7. The composition of claim 1 in which the castable polymeric binder includes a suitable plasticizer and cross-linking agent.
8. The composition of claim 7 in which the cross-linking agent is present in an amount of from 10 to 20 weight percent based on a total castable polymeric binder content.
9. The composition of claim 7 in which the plasticizer is trimethylolethanetrinitrate, triacetin, or bisdinitropropylacrylate-formal.
10. The composition otlciaim 7 in whichthe cross-linking agent is polymethylene polyphenylisocyanate.
l 1. The composition of claim 7 in which the composition includes from 0.001 to 0.01 weight percent of ferric acetylacetonate catalyst.
Claims (10)
- 2. The composition of claim 1 in which said alkali metal nitrate is potassium nitrate or sodium nitrate.
- 3. The composition of claim 1 in which the castable polymeric binder is a castable polysulphide, polysulphide-epoxy mixture, polyester or polybutadiene.
- 4. The composition of claim 3 in which the polybutadiene is a hydroxy or carboxy terminated polybutadiene.
- 5. The composition of claim 3 in which the polyester is prepared by the reaction of a dibasic acid with a dihydric alcohol.
- 6. The composition of claim 5 in which the dibasic acid is adipic acid and the dihydric alcohol is diethylene glycol.
- 7. The composition of claim 1 in which the castable polymeric binder includes a suitable plasticizer and cross-linking agent.
- 8. The composition of claim 7 in which the cross-linking agent is present in an amount of from 10 to 20 weight percent based on a total castable polymeric binder content.
- 9. The composition of claim 7 in which the plasticizer is trimethylolethanetrinitrate, triacetin, or bis-dinitropropylacrylate-formal.
- 10. The composition of claim 7 in which the cross-linking agent is polymethylene polyphenylisocyanate.
- 11. The composition of claim 7 in which the composition includes from 0.001 to 0.01 weight percent of ferric acetylacetonate catalyst.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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US86415969A | 1969-10-06 | 1969-10-06 |
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US3650856A true US3650856A (en) | 1972-03-21 |
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US864159A Expired - Lifetime US3650856A (en) | 1969-10-06 | 1969-10-06 | Red phosphorus castable smoke producing composition |
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US (1) | US3650856A (en) |
JP (1) | JPS497207B1 (en) |
AU (1) | AU2055370A (en) |
BE (1) | BE757039A (en) |
CA (1) | CA931041A (en) |
DE (1) | DE2048583A1 (en) |
GB (1) | GB1325450A (en) |
Cited By (19)
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US3726225A (en) * | 1970-11-27 | 1973-04-10 | Us Army | Plastic bonded smoke |
US3986907A (en) * | 1975-03-07 | 1976-10-19 | Thiokol Corporation | Illuminating flare composition containing tetranitrocarbazole |
US4129465A (en) * | 1977-07-21 | 1978-12-12 | The United States Of America As Represented By The Secretary Of The Navy | Smoke-generating composition |
US4151233A (en) * | 1977-10-19 | 1979-04-24 | The United States Of America As Represented By The Secretary Of The Army | Method for preparing a smoke agent |
US4503004A (en) * | 1984-03-12 | 1985-03-05 | The United States Of America As Represented By The Secretary Of The Army | Method of molding a red phosphorous pyrotechnic composition |
US4534810A (en) * | 1984-01-30 | 1985-08-13 | The United States Of America As Represented By The Secretary Of The Army | Red phosphorous smoke producing composition |
US4860657A (en) * | 1978-05-05 | 1989-08-29 | Buck Chemisch-Technische Werke Gmbh & Co. | Projectile |
US5522320A (en) * | 1993-07-12 | 1996-06-04 | Thiokol Corporation | Low-toxicity obscuring smoke formulation |
US20080245252A1 (en) * | 2007-02-09 | 2008-10-09 | Alliant Techsystems Inc. | Non-toxic percussion primers and methods of preparing the same |
US7700679B2 (en) | 2005-02-18 | 2010-04-20 | Tyco Electronics Corporation | Heat-recoverable article and composition therefor |
DE102008060573A1 (en) * | 2008-12-04 | 2010-06-10 | Diehl Bgt Defence Gmbh & Co. Kg | Pyrotechnic active mass, useful to produce a smokescreen, comprises red phosphorus in surplus, metal nitrate, preferably e.g. sodium nitrate, silicon in porous or powdered single-crystalline state and binder preferably e.g. polyacrylate |
US20100288403A1 (en) * | 2006-03-02 | 2010-11-18 | Busky Randall T | Nontoxic, noncorrosive phosphorus-based primer compositions |
US20110000390A1 (en) * | 2007-02-09 | 2011-01-06 | Alliant Techsystems Inc. | Non-toxic percussion primers and methods of preparing the same |
US8206522B2 (en) | 2010-03-31 | 2012-06-26 | Alliant Techsystems Inc. | Non-toxic, heavy-metal free sensitized explosive percussion primers and methods of preparing the same |
RU2472763C1 (en) * | 2011-10-10 | 2013-01-20 | Открытое акционерное общество "Чебоксарское производственное объединение им. В.И. Чапаева" | Aerosol-generating composition for creation of smoke masking curtains |
RU2478600C1 (en) * | 2011-10-10 | 2013-04-10 | Открытое акционерное общество "Чебоксарское производственное объединение им. В.И. Чапаева" | Composition for forming smokescreen |
US8460486B1 (en) | 2005-03-30 | 2013-06-11 | Alliant Techsystems Inc. | Percussion primer composition and systems incorporating same |
US8540828B2 (en) | 2008-08-19 | 2013-09-24 | Alliant Techsystems Inc. | Nontoxic, noncorrosive phosphorus-based primer compositions and an ordnance element including the same |
US8641842B2 (en) | 2011-08-31 | 2014-02-04 | Alliant Techsystems Inc. | Propellant compositions including stabilized red phosphorus, a method of forming same, and an ordnance element including the same |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3028933C1 (en) * | 1980-07-30 | 1989-11-23 | Buck Chem Tech Werke | Heavy-duty molded fog body with broadband camouflage |
GB2188921B (en) * | 1983-04-05 | 1988-03-09 | Haley & Weller Ltd | Pyrotechnic composition for producing radiation-blocking screen |
JP4969841B2 (en) * | 2005-01-19 | 2012-07-04 | 日本工機株式会社 | Infrared shielding fuming composition |
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US1419295A (en) * | 1921-03-30 | 1922-06-13 | Harry J Nichols | Pyrotechnic composition |
US2658874A (en) * | 1944-11-07 | 1953-11-10 | John P Clay | Smoke agent |
US3147161A (en) * | 1961-06-19 | 1964-09-01 | Minnesota Mining & Mfg | Propellant composition cured with aziridinyl compounds |
US3193422A (en) * | 1962-02-19 | 1965-07-06 | Buck Hedwig | Smoke agents |
US3245849A (en) * | 1959-07-20 | 1966-04-12 | Aerojet General Co | Solid propellant compositions containing polyurethane resins of low cure temperature |
US3418184A (en) * | 1968-01-16 | 1968-12-24 | Navy Usa | Smoke producing propellant |
US3431153A (en) * | 1967-10-16 | 1969-03-04 | Us Army | Solidified plastic matrix containing white phosphorous |
US3467558A (en) * | 1967-09-01 | 1969-09-16 | Dow Chemical Co | Pyrotechnic disseminating composition containing an agent to be disseminated |
US3488711A (en) * | 1966-06-24 | 1970-01-06 | Knapsack Ag | Process for impregnating red phosphorus |
-
0
- BE BE757039D patent/BE757039A/en unknown
-
1969
- 1969-10-06 US US864159A patent/US3650856A/en not_active Expired - Lifetime
-
1970
- 1970-09-17 CA CA093348A patent/CA931041A/en not_active Expired
- 1970-09-17 GB GB4448470A patent/GB1325450A/en not_active Expired
- 1970-09-30 AU AU20553/70A patent/AU2055370A/en not_active Expired
- 1970-10-02 DE DE19702048583 patent/DE2048583A1/en active Pending
- 1970-10-06 JP JP45087184A patent/JPS497207B1/ja active Pending
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
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US1419295A (en) * | 1921-03-30 | 1922-06-13 | Harry J Nichols | Pyrotechnic composition |
US2658874A (en) * | 1944-11-07 | 1953-11-10 | John P Clay | Smoke agent |
US3245849A (en) * | 1959-07-20 | 1966-04-12 | Aerojet General Co | Solid propellant compositions containing polyurethane resins of low cure temperature |
US3147161A (en) * | 1961-06-19 | 1964-09-01 | Minnesota Mining & Mfg | Propellant composition cured with aziridinyl compounds |
US3193422A (en) * | 1962-02-19 | 1965-07-06 | Buck Hedwig | Smoke agents |
US3488711A (en) * | 1966-06-24 | 1970-01-06 | Knapsack Ag | Process for impregnating red phosphorus |
US3467558A (en) * | 1967-09-01 | 1969-09-16 | Dow Chemical Co | Pyrotechnic disseminating composition containing an agent to be disseminated |
US3431153A (en) * | 1967-10-16 | 1969-03-04 | Us Army | Solidified plastic matrix containing white phosphorous |
US3418184A (en) * | 1968-01-16 | 1968-12-24 | Navy Usa | Smoke producing propellant |
Cited By (29)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3726225A (en) * | 1970-11-27 | 1973-04-10 | Us Army | Plastic bonded smoke |
US3986907A (en) * | 1975-03-07 | 1976-10-19 | Thiokol Corporation | Illuminating flare composition containing tetranitrocarbazole |
US4129465A (en) * | 1977-07-21 | 1978-12-12 | The United States Of America As Represented By The Secretary Of The Navy | Smoke-generating composition |
US4151233A (en) * | 1977-10-19 | 1979-04-24 | The United States Of America As Represented By The Secretary Of The Army | Method for preparing a smoke agent |
US4860657A (en) * | 1978-05-05 | 1989-08-29 | Buck Chemisch-Technische Werke Gmbh & Co. | Projectile |
US4534810A (en) * | 1984-01-30 | 1985-08-13 | The United States Of America As Represented By The Secretary Of The Army | Red phosphorous smoke producing composition |
US4503004A (en) * | 1984-03-12 | 1985-03-05 | The United States Of America As Represented By The Secretary Of The Army | Method of molding a red phosphorous pyrotechnic composition |
US5522320A (en) * | 1993-07-12 | 1996-06-04 | Thiokol Corporation | Low-toxicity obscuring smoke formulation |
US7700679B2 (en) | 2005-02-18 | 2010-04-20 | Tyco Electronics Corporation | Heat-recoverable article and composition therefor |
US8460486B1 (en) | 2005-03-30 | 2013-06-11 | Alliant Techsystems Inc. | Percussion primer composition and systems incorporating same |
US20110100246A1 (en) * | 2006-03-02 | 2011-05-05 | Alliant Techsystems Inc. | Percussion primers comprising a primer composition and ordnance including the same |
US7857921B2 (en) * | 2006-03-02 | 2010-12-28 | Alliant Techsystems Inc. | Nontoxic, noncorrosive phosphorus-based primer compositions |
US8524018B2 (en) * | 2006-03-02 | 2013-09-03 | Alliant Techsystems Inc. | Percussion primers comprising a primer composition and ordnance including the same |
US20100288403A1 (en) * | 2006-03-02 | 2010-11-18 | Busky Randall T | Nontoxic, noncorrosive phosphorus-based primer compositions |
US9199887B2 (en) | 2006-03-02 | 2015-12-01 | Orbital Atk, Inc. | Propellant compositions including stabilized red phosphorus and methods of forming same |
US20080245252A1 (en) * | 2007-02-09 | 2008-10-09 | Alliant Techsystems Inc. | Non-toxic percussion primers and methods of preparing the same |
US20110000390A1 (en) * | 2007-02-09 | 2011-01-06 | Alliant Techsystems Inc. | Non-toxic percussion primers and methods of preparing the same |
US8192568B2 (en) | 2007-02-09 | 2012-06-05 | Alliant Techsystems Inc. | Non-toxic percussion primers and methods of preparing the same |
US8202377B2 (en) | 2007-02-09 | 2012-06-19 | Alliant Techsystems Inc. | Non-toxic percussion primers and methods of preparing the same |
US8454770B1 (en) | 2007-02-09 | 2013-06-04 | Alliant Techsystems Inc. | Non-toxic percussion primers and methods of preparing the same |
US8454769B2 (en) | 2007-02-09 | 2013-06-04 | Alliant Techsystems Inc. | Non-toxic percussion primers and methods of preparing the same |
US8540828B2 (en) | 2008-08-19 | 2013-09-24 | Alliant Techsystems Inc. | Nontoxic, noncorrosive phosphorus-based primer compositions and an ordnance element including the same |
DE102008060573A1 (en) * | 2008-12-04 | 2010-06-10 | Diehl Bgt Defence Gmbh & Co. Kg | Pyrotechnic active mass, useful to produce a smokescreen, comprises red phosphorus in surplus, metal nitrate, preferably e.g. sodium nitrate, silicon in porous or powdered single-crystalline state and binder preferably e.g. polyacrylate |
DE102008060573B4 (en) * | 2008-12-04 | 2016-08-11 | Diehl Bgt Defence Gmbh & Co. Kg | Pyrotechnic active mass for the production of a camouflage nebula |
US8470107B2 (en) | 2010-03-31 | 2013-06-25 | Alliant Techsystems Inc. | Non-toxic, heavy-metal free explosive percussion primers and methods of preparing the same |
US8206522B2 (en) | 2010-03-31 | 2012-06-26 | Alliant Techsystems Inc. | Non-toxic, heavy-metal free sensitized explosive percussion primers and methods of preparing the same |
US8641842B2 (en) | 2011-08-31 | 2014-02-04 | Alliant Techsystems Inc. | Propellant compositions including stabilized red phosphorus, a method of forming same, and an ordnance element including the same |
RU2478600C1 (en) * | 2011-10-10 | 2013-04-10 | Открытое акционерное общество "Чебоксарское производственное объединение им. В.И. Чапаева" | Composition for forming smokescreen |
RU2472763C1 (en) * | 2011-10-10 | 2013-01-20 | Открытое акционерное общество "Чебоксарское производственное объединение им. В.И. Чапаева" | Aerosol-generating composition for creation of smoke masking curtains |
Also Published As
Publication number | Publication date |
---|---|
AU2055370A (en) | 1972-04-13 |
DE2048583A1 (en) | 1971-04-15 |
GB1325450A (en) | 1973-08-01 |
CA931041A (en) | 1973-07-31 |
BE757039A (en) | 1971-03-16 |
JPS497207B1 (en) | 1974-02-19 |
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