US3830671A - Thermally ignitable zirconium-plastic composition - Google Patents
Thermally ignitable zirconium-plastic composition Download PDFInfo
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- US3830671A US3830671A US00310920A US31092072A US3830671A US 3830671 A US3830671 A US 3830671A US 00310920 A US00310920 A US 00310920A US 31092072 A US31092072 A US 31092072A US 3830671 A US3830671 A US 3830671A
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- zirconium
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- 239000000203 mixture Substances 0.000 title claims abstract description 60
- 239000004033 plastic Substances 0.000 title claims abstract description 23
- 229920003023 plastic Polymers 0.000 title claims abstract description 23
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229920001225 polyester resin Polymers 0.000 claims abstract description 21
- 239000004645 polyester resin Substances 0.000 claims abstract description 21
- 239000002131 composite material Substances 0.000 claims description 18
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 4
- 239000011159 matrix material Substances 0.000 claims description 3
- 229920000704 biodegradable plastic Polymers 0.000 abstract description 2
- 229920005989 resin Polymers 0.000 description 14
- 239000011347 resin Substances 0.000 description 14
- 239000003054 catalyst Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000003086 colorant Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000008188 pellet Substances 0.000 description 4
- BOOBDAVNHSOIDB-UHFFFAOYSA-N (2,3-dichlorobenzoyl) 2,3-dichlorobenzenecarboperoxoate Chemical compound ClC1=CC=CC(C(=O)OOC(=O)C=2C(=C(Cl)C=CC=2)Cl)=C1Cl BOOBDAVNHSOIDB-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000002360 explosive Substances 0.000 description 3
- -1 maleic Chemical class 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 239000006187 pill Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- 229920003261 Durez Polymers 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 208000007101 Muscle Cramp Diseases 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 208000005392 Spasm Diseases 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 150000001279 adipic acids Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001536 azelaic acids Chemical class 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical class OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001869 cobalt compounds Chemical class 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005474 detonation Methods 0.000 description 1
- AXZAYXJCENRGIM-UHFFFAOYSA-J dipotassium;tetrabromoplatinum(2-) Chemical compound [K+].[K+].[Br-].[Br-].[Br-].[Br-].[Pt+2] AXZAYXJCENRGIM-UHFFFAOYSA-J 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 150000002531 isophthalic acids Chemical class 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229910001487 potassium perchlorate Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 239000000700 radioactive tracer Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- 229910001631 strontium chloride Inorganic materials 0.000 description 1
- 150000003438 strontium compounds Chemical class 0.000 description 1
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 description 1
- MXRFIUHRIOLIIV-UHFFFAOYSA-L strontium;diperchlorate Chemical compound [Sr+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O MXRFIUHRIOLIIV-UHFFFAOYSA-L 0.000 description 1
- 239000003826 tablet Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F42—AMMUNITION; BLASTING
- F42B—EXPLOSIVE CHARGES, e.g. FOR BLASTING, FIREWORKS, AMMUNITION
- F42B12/00—Projectiles, missiles or mines characterised by the warhead, the intended effect, or the material
- F42B12/02—Projectiles, missiles or mines characterised by the warhead, the intended effect, or the material characterised by the warhead or the intended effect
- F42B12/36—Projectiles, missiles or mines characterised by the warhead, the intended effect, or the material characterised by the warhead or the intended effect for dispensing materials; for producing chemical or physical reaction; for signalling ; for transmitting information
- F42B12/44—Projectiles, missiles or mines characterised by the warhead, the intended effect, or the material characterised by the warhead or the intended effect for dispensing materials; for producing chemical or physical reaction; for signalling ; for transmitting information of incendiary type
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B33/00—Compositions containing particulate metal, alloy, boron, silicon, selenium or tellurium with at least one oxygen supplying material which is either a metal oxide or a salt, organic or inorganic, capable of yielding a metal oxide
- C06B33/02—Compositions containing particulate metal, alloy, boron, silicon, selenium or tellurium with at least one oxygen supplying material which is either a metal oxide or a salt, organic or inorganic, capable of yielding a metal oxide with an organic non-explosive or an organic non-thermic component
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S149/00—Explosive and thermic compositions or charges
- Y10S149/11—Particle size of a component
- Y10S149/114—Inorganic fuel
Definitions
- ABSTCT A thermally ignitable zirconium-plastic composition comprising a thermally decomposable plastic having zirconium powder dispersed therethrough, the plastic being formed of a polyester resin.
- Pyrotechnic devices are known for military use in which a metal is employed as fuel together with an oxidizer and binder. Such devices may comprise projectiles filled with magnesium or aluminum powder because of the high heat of oxidation of such metals. However, these materials, because of their low densities, do not exhibit good penetrating power when devices containing said materials are exploded.
- Zirconium metal powder is known to be a very incendiary material. However, this metal is very difficult and expensive to form into shapes by normal powder metalurgy techniques owing to its inherent galling characteristics.
- zirconium powder can be used in the production of pyrotechnic devices, incendiary elements, parts for projectiles, tracer elements and the like.
- Another object is to provide a thermally ignitable ar-- ticle of manufacture formed of a composite comprising zirconium powder as an essential ingredient.
- a still further object is to provide an incendiary projectile which includes a thermally ignitable zirconiumplastic composition as one of its elements of construction.
- FIG. 1 is illustrative of a flare comprising a thermally ignitable element produced by the invention
- FIG. 2 is an incendiary projectile partially broken away showing pills or small cylinders of a zirconium composite composition confined therein;
- FIG. 3 depicts a rod produced from the zirconium composite composition of the invention
- FIG. 4 is a hollow sleeve formed of the zirconium composite composition provided by the invention.
- FIG. 5 is another embodiment of an incendiary projectile in which the zirconium-plastic composition is employed as one of the elements of construction.
- the invention is directed to a thermally ignitable zirconium-plastic composition
- a thermally decomposable polyester resin having zirconium powder dispersed therethrough in an amount constituting at least about 40 percent by weight, and preferably at least about 50 percent by weight, substantially the balance of the composition comprising said polyester resin.
- the loading of zirconium powder in the resin may preferably range by weight from about 50 to 95 percent and, more preferably, from about 60 to 85 percent.
- a loading of about 70 to 75 percent zirconium powder has been found to be particularly useful in the production of incendiary devices of the type illustrated in the drawings to be discussed later.
- the novel zirconium-plastic composition comprising said polyester resin is capable of being formed into any desirable shape by casting and polymerization.
- shapes are pellets, tablets, pills, rods, cylinders, incendiary flares, sleeves or liners for use as inserts in ordnance projectiles, and the like.
- the composition while still in the fluid condition, can be dip-coated onto the inside or outside diameters of projectiles to provide a pyrophoric capability.
- Additional metallic or chemical additives may be included in the composite material to attain specific results.
- FIG. ll depicts a flare 10 comprising a handle 11 to which said flare is mounted and a pyrotechnic portion 12 comprising a hollow cylinder 13 of,
- FIG. 2 illustrates an incendiary ordnance projectile designated generally by the numeral 15 comprising a casing of fracturable metal 16, e.g. steel, which has an expolsive-containing chamber 17 in back of divider l8 screw-threaded to the inner wall of the casing to maintain its position.
- the divider is relatively thin and may be made of the same metal as the casing.
- the chamber 17 contains an explosive charge 19.
- the explosive charge may be of any desirable composition.
- the means for detonating the charge are well known and need not be shown or described here.
- the divider When the projectile is fired, the divider is ruptured and the heat and pressure released as a result of the detonation causes the casing to burst and the pellets to ignite.
- the burning pellets are dispersed over a broad path in the area of the target to provide the necessary incendiary capability of the projectile.
- FIG. 3 depicts an incendiary element 22 in the form of a rod produced by casting in a mold. Such elements may have use in the manufacture of pyrotechnic displays. Similarly, sleeves or liners 23 (FIG. 4) may be easily produced by casting in a mold provided with a center core corresponding to the inner diameter of the sleeve. The sleeve may be used as a liner in a projectile to provide incendiary capability similar to that described for FIG. 2. FIG.
- FIG. 5 illustrates such a projectile in which the zirconium-plastic composition is employed as a sleeve, the projectile 24 comprising a casing 25 of fracturable steel, a longitudinally shaped charge 26 axially supported therein surrounded by a sleeve 27 of the zirconium-plastic composition and a nose 28 of heat treated steel having firing means associated therewith (not shown).
- the firing means causes the charge 26 to explode and fracture the casing.
- the sleeve of the zirconiumplastic composition is similarly caused to fracture and thermally ignite while being dispersed in a board path relative to the target.
- the invention also resides in an article of manufacture comprising an incendiary element, whether employed in the manufacture of flares, or as an element for a projectile, or even as an element for pyrotechnic display commonly employed in fireworks.
- the composite zirconium-plastic composition may be employed in incendiary projectiles in other forms.
- controlled amounts of the composition may be poured into the base of a shell to provide an incendiary plug in contact with the explosive charge; or, the shell may comprise substantial amounts of the zirconiumplastic composition without an initiator, the composition being thermally ignited when the shell is caused to absorb a high degree of kinetic energy, such as occurs under high velocity impact.
- the size of the zirconium powder employed in making the composite should be such as not to react pyrophorically under ambient conditions.
- the average size is preferably over about microns and may range up to about 4000 microns.
- a polyester resin referred to in the trade as Durez, type PR-130 may be employed (manufactured by Durex Plastic Division of the Hooker Chemical Corporation). This resin is syrupy and has a Brookfield viscosity at 77F of 1900, a specific gravity of 1.13 and is in the uncatalyzed state before use.
- organic peroxides are used as catalyst, such as benzoyl peroxide, dichlorobenzoyl peroxide, lauroyl peroxide, methyl ethyl ketone peroxide, and the like.
- the peroxide catalyst may be added in small but effective amounts of up to about 2 percent of the weight of the resin.
- polyester resins which may be employed in carrying out the invention embrace a broad range of compositions.
- the resins are produced by the reaction of dibasic acids with dihydric alcohols, although trifunctional monomers, such as glycerol or citric acid may be used.
- Polyester resins particularly apply to products made using a mixture of unsaturated dibasic acids, e.g. maleic, along with saturated dibasic acids.
- the unsaturated polyester resins can be further polymerized through cross linking because they are unsaturated.
- another unsaturated monomer such as styrene
- styrene is added during this second stage of polymerization which can be made to occur at ordinary temperatures with suitable peroxide catalysts. It is usual for the first stage of polymerization (the ester formation stage) to be carried out at the manufacturing plant and the second stage polymerization out in the field.
- maleic anhydride and fumaric acid are the usual unsaturated acid components, while phthalic anhydride, isophthalic, adipic or azelaic acids are the corresponding saturated materials.
- glycols are ethylene, propylene, diethylene, dipropylene and certain butylene glycols.
- the polymerizable monomers which may be added are styrene, vinyltoluene, diallylphthalate, methyl methacrylate, chlorostyrene, methyl styrene, divinylbenzine or triallyl cryanurate. Water is eliminated during the first stage combination of acid and glycol. The second stage polymerization out in the field produces no gas or liquid products. The curing stage is fairly rapid.
- polyester resins may be employed in producing the composite zirconium-plastic composition of the invention.
- a composite mixture is produced, by way of a specific embodiment, by mixing 80 percent by weight of zirconium powder of approximately 20 microns average size with 20 percent by weight of the resin. Since it is desirable not to exceed a curing temperature of 250C in view of the reactivity of finely dividedzirconium powder, an organic peroxide catalyst is selected which will effect curing at a relatively low temperature, provided the mixture is cast immediately into a mold after being catalyzed.
- the curing agent is first added to the resin and the mixture blended thoroughly.
- a typical catalyst is 0.2 percent of dichlorobenzoyl peroxide by weight of the resin.
- the powder is then preferably added to the resin mix 25 percent at a time, with the mixture being thoroughly blended after each addition. This produces a pourable syrupy mixture.
- a 25 inch vacuum is applied (based on mercury) to remove entrapped air.
- the mixture After removing the entrapped air from the syrupy composition, the mixture is then poured slowly into a vibrating mold to produce the desired shape depending on end use. Silicone or teflon-based release agents are coated onto the mold surfaces to assure easy removal of the cast composition.
- the mixture may be dip-coated onto fairly stiff wires of suitable length to produce sparklers for pyrotechnic display.
- the temperature may range from 200F to 275F. Preferably, the temperature should be as low as possible.
- the composition may include certain inorganic additives, such as oxidizers, coloring agents, and the like, depending on the end use of the composite.
- oxidizers are potassium perchlorate, sodium nitrate, sodium perchlorate, manganese dioxide and many others.
- coloring agents are the copper compounds, copper chloride, copper nitrate, etc., strontium perchlorate, strontium nitrate, strontium chloride and other strontium compounds; cobalt compounds, including cobalt chloride, cobalt nitrate; and many other coloring agents.
- the composition may contain at least one of the additives selected from the group consisting of oxidizers and coloring agents.
- Liquid polyester resin (Durez PR-l30) 30 wt.%
- the zirconium powder and plastic mix are compounded similarly as described above with about 0.2 percent of benzoyl peroxide by weight of the resin being used as the catalyst.
- the following illustrates a composition for use in producing pyrotechnic displays.
- (Durex PR-l30) agent Part of the formulated mixture is cast into long narrow rods for use in pyrotechnic display. In addition, the composition may be dip-coated onto suitable lengths of wire to produce sparklers common in fireworks display.
- polyester resin available in the market is one sold by Commercial Resins Division of lnterplastic Corporation, Minneapolis, Minnesota, under the trade name Corezyn 3 is a viscous liquid resin whose viscosity is over 100,000 cps and has a specific gravity of 1.23.
- oxidizers and/or coloring agents may or may not be added to the formulation, these additives, when present, may range in total amounts up to about 30% by weight of the final zirconium-plastic mixture.
- polyester resin is defined as comprising substantially the balance of the zirconium-plastic composiiton, it does not exclude the presence of such additives.
- a cast thermally ignitable zirconium-plastic composition consisting essentially by weight of about 60 to 85 percent zirconium powder of particle size falling within the range of about 15 to 4,000 microns dispersed through a cured matrix of about 15 to 40 percent of a polyester resin making up essentially the balance.
- a cast thermally ignitable composite article of manufacture comprising an incendiary element formed of a cured zirconium-plastic composition consisting essentially by weight of about 60 to percent zirconium powder of particle size falling within the range of about 15 to 4,000 microns dispersed through a cured matrix of about 15 to 40 percent of a polyester resin making up essentially the balance.
- thermoly ignitable composite article of claim 3 wherein the composition contains approximately 70 percent Zirconium.
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Abstract
A thermally ignitable zirconium-plastic composition is provided comprising a thermally decomposable plastic having zirconium powder dispersed therethrough, the plastic being formed of a polyester resin.
Description
[ Aug. 20, 1974 Elmiie @Efies Paiefii [191 cArdle 2,951,752 9/1960 Stevenson....................... 3,030,243 4/1962 Hart.,......... 3,291,665 12/1966 Jackson............................
[73] Assignee: American Metal Climax, The, New Prima'y Examiner-"Leland Sebastian York, NY.
Attorney, Agent, or FirmKasper T. Serijan; Eugene T. Kalil Appl. No.: 310,920
ABSTCT A thermally ignitable zirconium-plastic composition is provided comprising a thermally decomposable plastic having zirconium powder dispersed therethrough, the plastic being formed of a polyester resin.
[51] Int. C0611 1/02 [58] Field of Search..... 149/19, 42,43, 44, 114, 149/2, 19.5; 260/40 R [56] References Cited UNITED STATES PATENTS 4 Claims, 5 Drawing Figures 2,758,983 8/1956 Toulmin, Jr. 260/40 spasms-r1 Pmmmuczolm FICM THERMALLY KGNITABLE ZIRCONIIUM-PLASTIC COOSHTION This invention relates to a thermally ignitable zirconium-plastic composition and to a composite article of manufacture comprising said composition.
Pyrotechnic devices are known for military use in which a metal is employed as fuel together with an oxidizer and binder. Such devices may comprise projectiles filled with magnesium or aluminum powder because of the high heat of oxidation of such metals. However, these materials, because of their low densities, do not exhibit good penetrating power when devices containing said materials are exploded.
Zirconium metal powder is known to be a very incendiary material. However, this metal is very difficult and expensive to form into shapes by normal powder metalurgy techniques owing to its inherent galling characteristics.
It would be desirable therefore to provide a method by which zirconium powder can be used in the production of pyrotechnic devices, incendiary elements, parts for projectiles, tracer elements and the like.
OBJECTS OF THE INVENTION It is an object of the invention to provide a thermally ignitable zirconium composition capable of being formed in any desirable shape.
Another object is to provide a thermally ignitable ar-- ticle of manufacture formed of a composite comprising zirconium powder as an essential ingredient.
A still further object is to provide an incendiary projectile which includes a thermally ignitable zirconiumplastic composition as one of its elements of construction.
These and other objects will more clearly appear when taken in conjunction with the following disclosure and the accompanying drawing, wherein:
FIG. 1 is illustrative of a flare comprising a thermally ignitable element produced by the invention;
FIG. 2 is an incendiary projectile partially broken away showing pills or small cylinders of a zirconium composite composition confined therein;
FIG. 3 depicts a rod produced from the zirconium composite composition of the invention;
FIG. 4 is a hollow sleeve formed of the zirconium composite composition provided by the invention; and
FIG. 5 is another embodiment of an incendiary projectile in which the zirconium-plastic composition is employed as one of the elements of construction.
STATEMENT OF THE INVENTION Stating it broadly, the invention is directed to a thermally ignitable zirconium-plastic composition comprising a thermally decomposable polyester resin having zirconium powder dispersed therethrough in an amount constituting at least about 40 percent by weight, and preferably at least about 50 percent by weight, substantially the balance of the composition comprising said polyester resin.
The loading of zirconium powder in the resin may preferably range by weight from about 50 to 95 percent and, more preferably, from about 60 to 85 percent. A loading of about 70 to 75 percent zirconium powder has been found to be particularly useful in the production of incendiary devices of the type illustrated in the drawings to be discussed later.
The novel zirconium-plastic composition comprising said polyester resin is capable of being formed into any desirable shape by casting and polymerization. Examples of shapes are pellets, tablets, pills, rods, cylinders, incendiary flares, sleeves or liners for use as inserts in ordnance projectiles, and the like. Or, if desired, the composition while still in the fluid condition, can be dip-coated onto the inside or outside diameters of projectiles to provide a pyrophoric capability.
Additional metallic or chemical additives may be included in the composite material to attain specific results.
Examples of uses of the composite are illustrated in FIGS. 1 to 5. FIG. ll depicts a flare 10 comprising a handle 11 to which said flare is mounted and a pyrotechnic portion 12 comprising a hollow cylinder 13 of,
for example, combustible wax-impregnated composition paper into which is cast the composite zirconiumplastic composition 14 of the invention. This flare is particularly advantageous because of the intense and penetrating lighting effects achievable with it.
FIG. 2 illustrates an incendiary ordnance projectile designated generally by the numeral 15 comprising a casing of fracturable metal 16, e.g. steel, which has an expolsive-containing chamber 17 in back of divider l8 screw-threaded to the inner wall of the casing to maintain its position. The divider is relatively thin and may be made of the same metal as the casing.
The chamber 17 contains an explosive charge 19. In the forward chamber 20 of the projectile is confined a plurality of pellets 21 formed from the composition of the invention. The explosive charge may be of any desirable composition. The means for detonating the charge are well known and need not be shown or described here.
When the projectile is fired, the divider is ruptured and the heat and pressure released as a result of the detonation causes the casing to burst and the pellets to ignite. The burning pellets are dispersed over a broad path in the area of the target to provide the necessary incendiary capability of the projectile.
FIG. 3 depicts an incendiary element 22 in the form of a rod produced by casting in a mold. Such elements may have use in the manufacture of pyrotechnic displays. Similarly, sleeves or liners 23 (FIG. 4) may be easily produced by casting in a mold provided with a center core corresponding to the inner diameter of the sleeve. The sleeve may be used as a liner in a projectile to provide incendiary capability similar to that described for FIG. 2. FIG. 5 illustrates such a projectile in which the zirconium-plastic composition is employed as a sleeve, the projectile 24 comprising a casing 25 of fracturable steel, a longitudinally shaped charge 26 axially supported therein surrounded by a sleeve 27 of the zirconium-plastic composition and a nose 28 of heat treated steel having firing means associated therewith (not shown). When the projectile strikes the target, the firing means causes the charge 26 to explode and fracture the casing. The sleeve of the zirconiumplastic composition is similarly caused to fracture and thermally ignite while being dispersed in a board path relative to the target.
As will clearly appear from the foregoing, the invention also resides in an article of manufacture comprising an incendiary element, whether employed in the manufacture of flares, or as an element for a projectile, or even as an element for pyrotechnic display commonly employed in fireworks.
The composite zirconium-plastic composition may be employed in incendiary projectiles in other forms. For example, controlled amounts of the composition may be poured into the base of a shell to provide an incendiary plug in contact with the explosive charge; or, the shell may comprise substantial amounts of the zirconiumplastic composition without an initiator, the composition being thermally ignited when the shell is caused to absorb a high degree of kinetic energy, such as occurs under high velocity impact.
The size of the zirconium powder employed in making the composite should be such as not to react pyrophorically under ambient conditions. The average size is preferably over about microns and may range up to about 4000 microns.
ln producing the composite composition using zirconium powder and polyester resin as the materials, a polyester resin referred to in the trade as Durez, type PR-130, may be employed (manufactured by Durex Plastic Division of the Hooker Chemical Corporation). This resin is syrupy and has a Brookfield viscosity at 77F of 1900, a specific gravity of 1.13 and is in the uncatalyzed state before use. Generally, organic peroxides are used as catalyst, such as benzoyl peroxide, dichlorobenzoyl peroxide, lauroyl peroxide, methyl ethyl ketone peroxide, and the like. The peroxide catalyst may be added in small but effective amounts of up to about 2 percent of the weight of the resin.
The polyester resins which may be employed in carrying out the invention embrace a broad range of compositions. Generally, the resins are produced by the reaction of dibasic acids with dihydric alcohols, although trifunctional monomers, such as glycerol or citric acid may be used. Polyester resins particularly apply to products made using a mixture of unsaturated dibasic acids, e.g. maleic, along with saturated dibasic acids.
The unsaturated polyester resins can be further polymerized through cross linking because they are unsaturated. Generally, another unsaturated monomer, such as styrene, is added during this second stage of polymerization which can be made to occur at ordinary temperatures with suitable peroxide catalysts. It is usual for the first stage of polymerization (the ester formation stage) to be carried out at the manufacturing plant and the second stage polymerization out in the field.
Generally speaking, maleic anhydride and fumaric acid are the usual unsaturated acid components, while phthalic anhydride, isophthalic, adipic or azelaic acids are the corresponding saturated materials. The commonly used glycols are ethylene, propylene, diethylene, dipropylene and certain butylene glycols. The polymerizable monomers which may be added are styrene, vinyltoluene, diallylphthalate, methyl methacrylate, chlorostyrene, methyl styrene, divinylbenzine or triallyl cryanurate. Water is eliminated during the first stage combination of acid and glycol. The second stage polymerization out in the field produces no gas or liquid products. The curing stage is fairly rapid.
As will be apparent, a broad range of polyester resins may be employed in producing the composite zirconium-plastic composition of the invention.
A composite mixture is produced, by way of a specific embodiment, by mixing 80 percent by weight of zirconium powder of approximately 20 microns average size with 20 percent by weight of the resin. Since it is desirable not to exceed a curing temperature of 250C in view of the reactivity of finely dividedzirconium powder, an organic peroxide catalyst is selected which will effect curing at a relatively low temperature, provided the mixture is cast immediately into a mold after being catalyzed.
lt is preferred to add the curing agent to the resin before adding the zirconium powder. Depending upon the particle size, the zirconium powder should be handled carefully, since friction can cause the powder to ignite. Thus, the curing agent is first added to the resin and the mixture blended thoroughly. A typical catalyst is 0.2 percent of dichlorobenzoyl peroxide by weight of the resin. The powder is then preferably added to the resin mix 25 percent at a time, with the mixture being thoroughly blended after each addition. This produces a pourable syrupy mixture. A 25 inch vacuum is applied (based on mercury) to remove entrapped air.
After removing the entrapped air from the syrupy composition, the mixture is then poured slowly into a vibrating mold to produce the desired shape depending on end use. Silicone or teflon-based release agents are coated onto the mold surfaces to assure easy removal of the cast composition. As stated hereinabove, the mixture may be dip-coated onto fairly stiff wires of suitable length to produce sparklers for pyrotechnic display. Where heat is relied upon to cure the mix in the mold, the temperature may range from 200F to 275F. Preferably, the temperature should be as low as possible.
As has already been stated hereinbefore, the composition may include certain inorganic additives, such as oxidizers, coloring agents, and the like, depending on the end use of the composite. Examples of oxidizers are potassium perchlorate, sodium nitrate, sodium perchlorate, manganese dioxide and many others. Examples of coloring agents are the copper compounds, copper chloride, copper nitrate, etc., strontium perchlorate, strontium nitrate, strontium chloride and other strontium compounds; cobalt compounds, including cobalt chloride, cobalt nitrate; and many other coloring agents.
Thus, the composition may contain at least one of the additives selected from the group consisting of oxidizers and coloring agents.
As illustrative of various compositions which are provided by the invention, the following examples are given:
EXAMPLE 1 Zirconium powder (20 microns average size) wt.%
Liquid polyester resin (Durez PR-l30) 30 wt.%
To the polyester resin maintained at room temperature is added about 0.3 percent by weight of dichlorobenzoylperoxide. The two ingredients are well mixed as described hereinbefore, the zirconium powder added and mixed and the uniform mixture after removal of entrapped air then poured into a vibrating mold containing a plurality of cavities corresponding to a rod of the type illustrated in FIG. 3. The mixture is allowed to cure in the mold, following which the mold is disassembled and the cast rods removed.
EXAMPLE 2 (l) Zirconium powder 60 wt.%
(about 50 microns) Liquid polyester resin 40 wt.% (Durez PR-l30) (2) Zirconium powder 85 wt.%
(about 100 microns) Liquid polyester resin wt.%
(Durez PR-l30) The foregoing compositions are formulated as in Example 1, methyl ethyl ketone peroxide in an amount of about 1 percent by weight of the resin being used to cure the resin. Another example is as follows:
EXAMPLE 3 Zirconium powder 80 wt.% (from 75 to 150 microns) Liquid polyester resin l5 wt.%
Unsaturated styrene monomer .5 wt.%
The zirconium powder and plastic mix are compounded similarly as described above with about 0.2 percent of benzoyl peroxide by weight of the resin being used as the catalyst.
The following illustrates a composition for use in producing pyrotechnic displays.
EXAMPLE 4 Zirconium powder 65 wt.% (about microns) Polyester resin 35 wt.%
(Durex PR-l30) agent. Part of the formulated mixture is cast into long narrow rods for use in pyrotechnic display. In addition, the composition may be dip-coated onto suitable lengths of wire to produce sparklers common in fireworks display.
An example of another polyester resin available in the market is one sold by Commercial Resins Division of lnterplastic Corporation, Minneapolis, Minnesota, under the trade name Corezyn 3 is a viscous liquid resin whose viscosity is over 100,000 cps and has a specific gravity of 1.23.
While oxidizers and/or coloring agents may or may not be added to the formulation, these additives, when present, may range in total amounts up to about 30% by weight of the final zirconium-plastic mixture. Where the polyester resin is defined as comprising substantially the balance of the zirconium-plastic composiiton, it does not exclude the presence of such additives.
Although the present invention has been described in conjunction with preferred embodiments, it is to be understood that modifications and variations may be resorted to without departing from the spirit and scope of the invention as those skilled in the art will readily understand. Such modifications and variations are considered to be within the purview and scope of the invention and the appended claims.
What is claimed is:
l. A cast thermally ignitable zirconium-plastic composition consisting essentially by weight of about 60 to 85 percent zirconium powder of particle size falling within the range of about 15 to 4,000 microns dispersed through a cured matrix of about 15 to 40 percent of a polyester resin making up essentially the balance.
2. The zirconium-plastic composition of claim 1, wherein the amount of zirconium powder is approximately percent.
3. A cast thermally ignitable composite article of manufacture comprising an incendiary element formed of a cured zirconium-plastic composition consisting essentially by weight of about 60 to percent zirconium powder of particle size falling within the range of about 15 to 4,000 microns dispersed through a cured matrix of about 15 to 40 percent of a polyester resin making up essentially the balance.
4. The thermally ignitable composite article of claim 3, wherein the composition contains approximately 70 percent Zirconium.
Claims (3)
- 2. The zirconium-plastic composition of claim 1, wherein the amount of zirconium powder is approximately 70 percent.
- 3. A cast thermally ignitable composite article of manufacture comprising an incendiary element formed of a cured zirconium-plastic composition consisting essentially by weight of about 60 to 85 percent zirconium powder of particle size falling within the range of about 15 to 4,000 microns dispersed through a cured matrix of about 15 to 40 percent of a polyester resin making up essentially the balance.
- 4. The thermally ignitable composite article of claim 3, wherein the composition contains approximately 70 percent zirconium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US00310920A US3830671A (en) | 1972-11-30 | 1972-11-30 | Thermally ignitable zirconium-plastic composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US00310920A US3830671A (en) | 1972-11-30 | 1972-11-30 | Thermally ignitable zirconium-plastic composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3830671A true US3830671A (en) | 1974-08-20 |
Family
ID=23204632
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US00310920A Expired - Lifetime US3830671A (en) | 1972-11-30 | 1972-11-30 | Thermally ignitable zirconium-plastic composition |
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| US (1) | US3830671A (en) |
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4015529A (en) * | 1975-06-04 | 1977-04-05 | The United States Of America As Represented By The Secretary Of The Army | Illuminative and incendiary explosive munitions |
| US4152987A (en) * | 1977-02-18 | 1979-05-08 | The United States Of America As Represented By The Secretary Of The Navy | Impermeable polymer bomb liner for use with TNT containing explosives |
| US4256521A (en) * | 1973-09-05 | 1981-03-17 | Metal Sales Company (Proprietary) Limited | Porous metal agglomerates |
| US4351240A (en) * | 1975-02-28 | 1982-09-28 | The United States Of America As Represented By The Secretary Of The Navy | Incendiary fragmentary warhead |
| US4351239A (en) * | 1975-02-28 | 1982-09-28 | The United States Of America As Represented By The Secretary Of The Navy | Warhead, incendiary |
| US4381692A (en) * | 1977-05-11 | 1983-05-03 | Quantic Industries, Inc. | Method of making an incendiary munition |
| EP0255578A3 (en) * | 1986-05-28 | 1988-02-24 | Dynamit Nobel Aktiengesellschaft | Ammunition for producing smoke or an irritant agent |
| US5049883A (en) * | 1978-05-30 | 1991-09-17 | The United States Of America As Represented By The Secretary Of The Navy | Combined microwave and infrared chaff |
| US5054399A (en) * | 1988-07-05 | 1991-10-08 | The United States Of America As Represented By The Secretary Of The Air Force | Bomb or ordnance with internal shock attenuation barrier |
| US5076169A (en) * | 1989-12-06 | 1991-12-31 | Schweizerische Eidgenossenschaft Vertreten Durch Die Eidg Munitionsfabrik Thun Der Gruppe Fur Rustungsdienste | Incendiary fragmentation particle, a method for its production, as well as the use thereof |
| US5852256A (en) * | 1979-03-16 | 1998-12-22 | The United States Of America As Represented By The Secretary Of The Air Force | Non-focusing active warhead |
| US20040234914A1 (en) * | 2003-05-21 | 2004-11-25 | Alexza Molecular Delivery Corporation | Percussively ignited or electrically ingnited self-contained heating unit and drug-supply unit employing same |
| US6846372B1 (en) * | 2003-03-31 | 2005-01-25 | The United States Of America As Represented By The Secretary Of The Navy | Reactively induced fragmentating explosives |
| US7402777B2 (en) | 2004-05-20 | 2008-07-22 | Alexza Pharmaceuticals, Inc. | Stable initiator compositions and igniters |
| US7581540B2 (en) | 2004-08-12 | 2009-09-01 | Alexza Pharmaceuticals, Inc. | Aerosol drug delivery device incorporating percussively activated heat packages |
| US20120067242A1 (en) * | 2010-09-17 | 2012-03-22 | Dse, Inc. | Pyrophoric projectile |
| US20120118192A1 (en) * | 1999-12-06 | 2012-05-17 | Peter Nopper | Incendiary method & apparatus |
| US8181576B1 (en) * | 2010-05-14 | 2012-05-22 | The United States Of America As Represented By The Secretary Of The Navy | Projectile for standoff destruction of explosive devices |
| US20140261041A1 (en) * | 2013-03-14 | 2014-09-18 | Firepoint Products, Inc. | Fire ignition flare system and method |
| WO2017029303A1 (en) * | 2015-08-17 | 2017-02-23 | Ruag Ammotec Ag | Composite material and corresponding production method for projectiles |
| US10408590B1 (en) * | 2018-10-24 | 2019-09-10 | The United States Of America As Represented By The Secretary Of The Army | Flash output for projectile training |
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| US2951752A (en) * | 1958-05-21 | 1960-09-06 | Stevenson Thomas | Incendiary composition |
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| US2758983A (en) * | 1953-05-11 | 1956-08-14 | Midland Chemical Corp | Coating compositions comprising metallic dust |
| US3030243A (en) * | 1958-02-24 | 1962-04-17 | Hart David | First fire and igniter composition |
| US2951752A (en) * | 1958-05-21 | 1960-09-06 | Stevenson Thomas | Incendiary composition |
| US3291665A (en) * | 1962-01-24 | 1966-12-13 | Hi Shear Corp | Zirconium composition with potassium perchlorate and graphite |
Cited By (30)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4256521A (en) * | 1973-09-05 | 1981-03-17 | Metal Sales Company (Proprietary) Limited | Porous metal agglomerates |
| US4351240A (en) * | 1975-02-28 | 1982-09-28 | The United States Of America As Represented By The Secretary Of The Navy | Incendiary fragmentary warhead |
| US4351239A (en) * | 1975-02-28 | 1982-09-28 | The United States Of America As Represented By The Secretary Of The Navy | Warhead, incendiary |
| US4015529A (en) * | 1975-06-04 | 1977-04-05 | The United States Of America As Represented By The Secretary Of The Army | Illuminative and incendiary explosive munitions |
| US4152987A (en) * | 1977-02-18 | 1979-05-08 | The United States Of America As Represented By The Secretary Of The Navy | Impermeable polymer bomb liner for use with TNT containing explosives |
| US4381692A (en) * | 1977-05-11 | 1983-05-03 | Quantic Industries, Inc. | Method of making an incendiary munition |
| US5049883A (en) * | 1978-05-30 | 1991-09-17 | The United States Of America As Represented By The Secretary Of The Navy | Combined microwave and infrared chaff |
| US5852256A (en) * | 1979-03-16 | 1998-12-22 | The United States Of America As Represented By The Secretary Of The Air Force | Non-focusing active warhead |
| EP0255578A3 (en) * | 1986-05-28 | 1988-02-24 | Dynamit Nobel Aktiengesellschaft | Ammunition for producing smoke or an irritant agent |
| US5054399A (en) * | 1988-07-05 | 1991-10-08 | The United States Of America As Represented By The Secretary Of The Air Force | Bomb or ordnance with internal shock attenuation barrier |
| US5076169A (en) * | 1989-12-06 | 1991-12-31 | Schweizerische Eidgenossenschaft Vertreten Durch Die Eidg Munitionsfabrik Thun Der Gruppe Fur Rustungsdienste | Incendiary fragmentation particle, a method for its production, as well as the use thereof |
| US20120118192A1 (en) * | 1999-12-06 | 2012-05-17 | Peter Nopper | Incendiary method & apparatus |
| US6846372B1 (en) * | 2003-03-31 | 2005-01-25 | The United States Of America As Represented By The Secretary Of The Navy | Reactively induced fragmentating explosives |
| US20040234914A1 (en) * | 2003-05-21 | 2004-11-25 | Alexza Molecular Delivery Corporation | Percussively ignited or electrically ingnited self-contained heating unit and drug-supply unit employing same |
| US20040234916A1 (en) * | 2003-05-21 | 2004-11-25 | Alexza Molecular Delivery Corporation | Optically ignited or electrically ignited self-contained heating unit and drug-supply unit employing same |
| US9370629B2 (en) | 2003-05-21 | 2016-06-21 | Alexza Pharmaceuticals, Inc. | Self-contained heating unit and drug-supply unit employing same |
| US8991387B2 (en) | 2003-05-21 | 2015-03-31 | Alexza Pharmaceuticals, Inc. | Self-contained heating unit and drug-supply unit employing same |
| US20040234699A1 (en) * | 2003-05-21 | 2004-11-25 | Alexza Molecular Delivery Corporation | Methods of controlling uniformity of substrate temperature and self-contained heating unit and drug-supply unit employing same |
| US8387612B2 (en) | 2003-05-21 | 2013-03-05 | Alexza Pharmaceuticals, Inc. | Self-contained heating unit and drug-supply unit employing same |
| US7923662B2 (en) | 2004-05-20 | 2011-04-12 | Alexza Pharmaceuticals, Inc. | Stable initiator compositions and igniters |
| US7402777B2 (en) | 2004-05-20 | 2008-07-22 | Alexza Pharmaceuticals, Inc. | Stable initiator compositions and igniters |
| US7581540B2 (en) | 2004-08-12 | 2009-09-01 | Alexza Pharmaceuticals, Inc. | Aerosol drug delivery device incorporating percussively activated heat packages |
| US8181576B1 (en) * | 2010-05-14 | 2012-05-22 | The United States Of America As Represented By The Secretary Of The Navy | Projectile for standoff destruction of explosive devices |
| US20120067242A1 (en) * | 2010-09-17 | 2012-03-22 | Dse, Inc. | Pyrophoric projectile |
| US8813652B2 (en) * | 2010-09-17 | 2014-08-26 | Amtec Corporation | Pyrophoric projectile |
| US20140261041A1 (en) * | 2013-03-14 | 2014-09-18 | Firepoint Products, Inc. | Fire ignition flare system and method |
| US9360288B2 (en) * | 2013-03-14 | 2016-06-07 | Firepoint Products, Inc. | Fire ignition flare system and method |
| WO2017029303A1 (en) * | 2015-08-17 | 2017-02-23 | Ruag Ammotec Ag | Composite material and corresponding production method for projectiles |
| EP3736524A1 (en) * | 2015-08-17 | 2020-11-11 | RUAG Ammotec AG | Composite material and corresponding manufacturing method for projectiles |
| US10408590B1 (en) * | 2018-10-24 | 2019-09-10 | The United States Of America As Represented By The Secretary Of The Army | Flash output for projectile training |
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