High energy blast explosives for confined spaces

Abstract

The invention disclosed herein relates to an explosive capable of enhanced combustion efficiently capable of sustaining a high pressure over a period of time in a confined environment, such as an air tight room or a cave, where oxygen may be in limited supply. An embodiment of the present invention is a metal composite that combines a binder, a nano-sized reactive metal and an oxidizer. The nano-sized reactive metal has an average particle size of approximately 20 nano-meters

Description

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT

The invention described herein may be manufactured and used by or for the government of the United States of America for governmental purposes without the payment of any royalties thereon or therefor.

FIELD OF THE INVENTION

The invention disclosed herein relates to explosive formulations with improved combustion efficiency. More particularly, the explosive formulations of the invention are capable of maintaining a relatively high blast pressure in an oxygen poor environment, such as a tunnel or other confined spaces.

BACKGROUND OF THE INVENTION

There is a long history of studying blast explosives, reactive metals and associated metal combustion technologies. The success of the development of Solid Fuel-Air-Explosive (SFAE) has been demonstrated providing 30-40% increased internal blast over a conventional explosive. SFAE is a singular event with combined mixing and initiation of the reaction. In confined spaces, transition to full detonation is not required for enhanced blast, if the solid fuel is ignited early in the dispersion process. A series of reflective shock waves generated by the detonation mixes the hot detonation gases with metal particles and compresses the metal particles at the same time. These actions provide the chemical kinetic support to maintain a hot environment, causing more metal to ignite and burn. This late time metal combustion process produces a significant pressure rise over a longer time duration (10-50 msec). This is a phase generally referred to as after burning or late-time impulse which can occur outside of where the detonation occurred, resulting in more widespread damage.

Aluminum has been used as the metal of choice, due to high heat of combustion, cost and availability. Billets of SFAE made with Al, provide savings in volume with increased fuel mass for blast performance. However, combustion efficiency has been an issue, especially in the event that the fuel content (35-60 wt %) is high with respect to the total weight of explosive composition. Poor combustion efficiency is often observed in many of the thermobaric warhead tests, which causes the severe ineffectiveness of the weapon. This is due to the high ignition temperature, 2200 K, typically required for proper combustion of AL. During the burning of Al, heat is produced and aluminum oxide is formed. However, the burning of all the metal to completion requires maintaining the hot environment. This environment can be best maintained if it is supported chemically by the combustion of other oxidizer species (i.e. AP or nitrate ester liquid, IPN (isopropyl nitrate)) that are much easier to ignite (AP has an ignition temperature of 250 C and IPN has a low flash point of 22 C). The combustion of these additives produce the hot gases to support the burning of metal, thus 100% combustion efficiency can be obtained. Metal composites, metal and oxidizer combined granules, produced from coating of particles with a binder, can be made easily with techniques well known in the art.

Another combined approach to further improve the metal combustion efficiency is to use a more reactive metal as part of or as the entire metal fuel component. New reactive metal materials such as nano-sized aluminum to increase the reactivity, titanium and boron alloy to increase the thermal output, and magnesium/aluminum alloy to lower the ignition temperature are among the most promising approaches to increase the metal combustion efficiency. More powerful explosives such as CL-20 that are capable of raising the detonation pressure and temperature are also extremely beneficial.

There exists a need in the art for new explosive formulations with new reactive metal and metal composites to have 50-100% higher blast energy than those by the baseline composition such as Tritonal or PBX N109. Further, the new formulations coupled with new warhead designs will have the potential to form one of the most powerful thermobaric warheads, when compared to the weapon systems that currently exist.

SUMMARY OF THE INVENTION

The present invention relates to a metal composite that combines a binder, a reactive metal and an oxidizer. In an embodiment of the present invention, a plasticizer and a catalyst are also included. In yet another embodiment of the present invention, the binder includes polymers capable of coating the reactive metal and oxidizer powder. Two embodiments include methods to produce the compositions of the present invention:

• • (1) The coated powder forms the fuel charge through pressing, combining this fuel charge with a high explosive charge (HMX, RDX or CL-20 based PBX's) in an annular design to make up the fill for the warhead.
  • (2) Using metal or metal/oxidizer powders in a mixing, casting and curing process to combine with high explosive to form castable PBX's. The reactive metal contains ingredients that are intrinsically reactive with the reaction products of high explosive and oxidizer with or without the presence of high concentration of oxygen.

An embodiment of the present invention discloses a metal composite comprising about 60 to about 96 weight % of at least one reactive metal, about 4 to about 10 weight % of at least one binder and about 0 to about 36 weight % of an oxidizer. The reactive metal includes, but not limited to at least one of nano-sized metal particles, metastable mechanical alloy and any combination thereof. More specifically, the reactive metal includes, but not limited to at least one of nano-sized aluminum, nano-sized boron and nano-sized titanium, nano-sized magnesium, and nano-sized Al—Mg, Al—Mg—H, B—Mg, Al—B and Ti—B mixtures. The binder includes, but not limited to at least one of copolymer of vinylidine fluoride hexafluoropropylene, nitrocellulose, GAP and Zeon.

Embodiments of the present invention relating to castable compositions disclose an explosive having an annular construction. The explosive includes a cylindrical shell of solid fuel air explosive surrounding a cylindrically shaped high explosive. In other embodiments the solid fuel air explosive includes at least one of reactive metal and metal composite. The metal composite including about 60 to about 80 weight % of at least one reactive metal, about 4 to about 8 weight % of at least one binder and about 0 to about 36 weight % of an oxidizer. The reactive metal includes, but is not limited to at least one of nano-sized metal particles, metastable mechanical alloy and any combination thereof. More specifically, the reactive metal includes at least one of nano-sized aluminum, nano-sized boron and nano-sized titanium, nano-sized magnesium, and nano-sized Al—Mg, Al—Mg—H, B—Mg, Al—B and Ti—B mixtures, H-2 (2 μm spherical aluminum) and H-5 (5 μm spherical aluminum). The oxidizer includes, but is not limited to at least one of ammonium perchlorate, ammonium dinitramide and ammonium nitrate.

The present invention is to provide an explosive with enhanced combustion efficiently capable of sustaining a high pressure over a period of time in a confined environment with a limited oxygen supply.

The present invention is to provide an explosive capable of maintaining a relatively high pressure (30-60 psi) for up to 50 msec in an environment characterized with high rate of thermal quenching (cold air), this environment has a profound adverse effect for metal combustion, which is the main cause for combustion efficiency.

Further, when very small metal particles in the order of twenty nano-meters are utilized as the reactive metal in an explosive device made in accordance with the present invention blast effectiveness is increased by a factor of two over more conventional explosive devices and

Additionally, embodiments the present invention -is to provide an explosive with increased reactivity, increased thermal output and lower ignition temperatures.

Embodiments the present invention are also to provide thermobaric explosive formulations with reactive metals and metal composites which have a 100% higher blast energy than compositions such as Tritonal and PBX N109.

It is to be understood that the foregoing general description and the following detailed description are exemplary and explanatory only and are not to be viewed as being restrictive of the present invention, as claimed. These and other objects, features and advantages of the present invention will become apparent after a review of the following detailed description of the disclosed embodiments and the appended claims.

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 is a sectional view of a typical explosive having an annular construction; and

FIG. 2 is a plot illustrating the blast effectiveness of an explosive which includes a reactive metal of nano-meter sized metal particles.

DETAILED DESCRIPTION OF THE INVENTION

The invention disclosed herein relates to an explosive capable of enhanced combustion efficiently capable of sustaining a high pressure over a period of time in a confined environment, such as an air tight room or a cave, where oxygen may be in limited supply.

The reactive metal used in an embodiment of the present invention includes nano-sized metal particles, metastable mechanical alloys and any combination thereof. The metal fuel in these explosive formulations of the present invention incorporates nano-sized aluminum, including, for example, Alex®, boron, manganese and titanium, those having a size of about 20-500 nm. The metastable mechanical alloys include nano-sized Al—Mg, Al—Mg—H, B—Mg, Al—B, Ti—B, mixtures and H-2 and H-5 made from high energy milling. The metastable mechanical alloys include nano-crystalline metastable phases with particle sizes of about 1-50 μm. The reactive metal used also includes Ti, B or Mg. In another embodiment of the present invention, the reactive metal includes about 60-80 weight % of the total metal composite, or at about 74 weight %.

The thermobaric explosive formulations of the present invention incorporate high energy explosive material including, but not limited to hexa-nitro-hexa-aza-isowurtzitane (CL-20), cyclotrimethylenetrinitramine (RDX) and cyclotetramethylene tetranitramine (HMX). The powerful oxidizers, including ammonium perchlorate (AP), ammonium dinitramide (ADN), ammonium nitrate (AN) and barium nitrate are selected to be used in the metal composite or castable PBX's. Another embodiment of the present invention uses ammonium perchlorate (AP) particles, or about 11-100 μm in size. The oxidizer includes about 12-36 weight % of the total metal composites, or at about 20 weight %.

The binder includes polymers capable of coating the reactive metal and high explosive powder. The binder includes, but is not limited to at least one of copolymer of vinylidine fluoride hexafluoropropylene, including Viton®, nitrocellulose, glycidyl azide polymer (GAP) or an acrylic acid ester polymer, including Zeon®. In another embodiment of the present invention, the binder includes about 4-6 weight % of the total metal composites, or at about 4 weight % for the total metal composite. The binders used for castable PBX's include, for example, hydroxy-terminated polybutadienes (HTPB), hydroxy-terminated polycaprolactone (PCP), hydroxy-terminated polyesters, hydroxy-terminated polyethers (HTPE), Glycidyl azide polymer (GAP), trifluoroethyl-terminated poly(1-cyano-1-difluoramino)-polyethylene glycol (PCDE) and any combination thereof. Typically, 5 to 7 weight % is used for castable PBX embodiment.

In other embodiments, a plasticizer and a burn rate catalyst is added. The plasticizer includes bis-(2,2-ro-2-fluoroethyl) formal (FEFO). However, other plasticizers utilized, include energetic plasticizers selected from those compounds, which are liquids and contain energetic moieties or groups in their chemical structures. These moieties include, but not limited to nitro or nitrate ester groups, azido groups, or nitramino groups. Suitable plasticizers include TEGDN (triethyleneglycol dinitrate), or Butyl NENA (n-butyl-2-nitratoethyl-nitramine). Other suitable plasticizers include DEGDN (diethyleneglycol dinitrate), TMETN (trimethylolethane trinitrate), and BTTN (butanetriol trinitrate). These plasticizers are used independently or in combination. Other fluoramino groups including bis-(2,2-ro-2-fluoroethyl) formal (FEFO) and bis-[2,2-bis(difluoramino)-5, 5-dinitro-5-fluoropentoxy] methane (SYFO) could also incorporated into the formulations. In other embodiments of the present invention, the plasticizer include about 4-weight % of the formulations.

Iron oxide (Fe₂O₃), nano-sized is a suitable burn rate catalyst and is optional to exotic burn rate catalysts including superfine iron oxide, chromic oxide, catocene, or carboranes. In other embodiments aluminum oxide is also used. In embodiments of the present invention, the burn rate catalyst comprises about 1 weight % of the total metal composites. Tables I and II disclose a number of the formulations of the present invention.

TABLE I
Chemical Composition of Metal Composite Coated by Various Binders
			Plasti-
Reactive Metal	Oxidizer	Binder	cizer	Catalyst
80% H-5	14% AP, 11 μm	6% Viton ®	None	None
60% H-5, 20%	14% AP, 11 μm	6% Viton ®	None	None
Al/Mg
alloy, 28 μm
80% H-5	12% AP, 11 μm	6% Viton ®	None	1% Fe2O3,
				nano-sized
74% H-5	20% AP, 11 μm	6% Viton ®	None	1% Fe2O3,
				nano-sized
37% Ti, 44 μm	21% AP, 11 μm	6%	None	None
37% B,		Nitrocellulose
0.6-7 μm
74% Ti—B,	21% AP, 11 μm	6%	None	None
20 μm		Nitrocellulose
74% Mg—B,	21% AP, 11 μm	6%	None	None
20 μm		Nitrocellulose
50% H-5 24%	20% AP, 11 μm	5%	None	1% Fe2O3,
Alex ® 0.2 μm		Nitrocellulose		nano-sized
50% H-5 24%	20% AP, 11 μm	4%	4%	1% Fe2O3,
Alex ® 0.2 μm		Nitrocellulose	FEFO	nano-sized
74% Alex ®	20% AP, 11 μm	5%	None	1% Fe2O3,
0.2 μm		Nitrocellulose		nano-sized
40% Flake Al,	36% AP, 100 μm	4% Viton ®	None	None
20% Al/Mg
alloy
Note:
Al/Mg milled in batch MA020129-01, Ti—B milled in batch MA020317-01, and Mg—B milled in batch MA020319-01 at New Jersey Institute of Technology, Newark, New Jersey.

TABLE II
Typical Composition of Castable PBX's Containing Reactive
Metal and AP Oxidizer
Reactive				Plasticizer
Metal	Oxidizer	Binder	High Explosive	& Catalyst
20-40%	15-35% AP,	10-15% HTPB	30-55% HMX	4-6%
	11-100 μm
Metal
Composite		Binder	High Explosive	Plasticizer
40-60%*	None	10-15% HTPB	30-45% HMX	None
			or 30-50% HMX
40-60%*	None	10-15% LMA	30-45% HMX	None
30-55%*	None	10-15% HTPB	35-60% CL-20	None
20-24%*	15-35% AP	10-15% HTPB	30-55% HMX	None
Note:
*metal composite contains oxidizer

The novel thermobaric explosives of the present invention are spherical particles of composite material containing high explosive, oxidizer, reactive metal and binder. Plasticizer and burn rate catalyst are added to manipulate performance. A method of making the novel thermobaric explosives described herein is disclosed in U.S. Pat. No. 5,750,921 issued to Chan et al. on May 12, 1998, hereby incorporated herein by reference.

In an embodiment of the present invention, a solid fuel-air explosive annular construction is used as shown in FIG. 1. In a typical annular construction, a cylindrical shell of solid fuel air explosive (SFAE) 22 surrounds the high explosive 21. As a matter of preference, the shapes of the high explosive charge are include, but not limited to spherically or cylindrically symmetric, to provide a uniform dispersion pattern. Solid metal casings 23 are typically pressed from reactive metal powder or metal composite (listed in Table 1) as SFAE. These solid metal casings are typically machined from stock into billets, but are also manufactured by other methods including casting or forging. The SFAE is then pressed into solid billets with a density (preferred to be 80-90% TMD) applicable to the particular use. The annular construction uses flake aluminum as the reactive metal. The SFAE billets are then placed in the warhead and the explosive is cast or pressed into place. The final SFAE fuel to explosive ratio is dependent upon the size and configuration of the warhead. PBX N112 consists of 89% HMX (high explosive) and 11% LMA (lauryl methacrylate). The PBX N112/reactive metal weight ratio includes the range of about 0.66 to about 1.45, or the ratio of about 1.

Embodiments of the compositions of the present invention are formed into a unicharge. The unicharge construct uses spherical aluminum as the reactive metal. Table II discloses ranges of ingredients for the formulations of the unicharge embodiment. As noted previously, a plasticizer and/or a burn rate catalyst are added to the formulations to tailor the formulations to particular needs. Although specific binders are listed, any of the binders previously noted are also used in the formulations. Similarly, any of the oxidizers previously noted are also substituted for AP and any of the high explosives previously noted are substituted for HMX.

Referring to FIG. 2, there is shown a plot illustrating the blast effectiveness of an explosive which includes a reactive metal of nano-meter sized metal particles. The metal particles used in the explosive have sizes of twenty nano-meters and two hundred nano-meters. For the first few micro-seconds the plot represented by the reference numeral 25 is virtually identical for the twenty nano-meter and two hundred nano-meter metal particles. After about 5-10 msec., the plots vary substantially. The plot for the twenty nano-meter metal particles (represented by the reference numeral 28) represents a blast effectiveness which is two times that of the two hundred nano-meter metal particles (represented by the reference numeral 26). As shown in FIG. 2, the time required for a complete release of energy can be reduced by substantially more than 50 msec and can be as much as 100 msec. Further, by using twenty nano-meter sized metal particles in the explosive device, the time required for total energy release is reduced to approximately 20 msec. which is generally the maximum time during which total energy release by the explosive device should occur.

It should be understood that the examples and embodiments described herein are for illustrative purposes only and that various modifications or changes in light thereof will be suggested to persons skilled in the art and are to be included within the spirit and purview of this application and the scope of the appended claims.

Claims

1. An explosive composition comprising: (a) about 20 to about 70 weight % of at least one metal composite, said metal composite including about 60 to about 80 weight % of a reactive metal and about 14 to about 36 weight % of an oxidizer, said reactive metal being selected from a group of reactive metals comprising nano-sized aluminum, nano-sized boron, nano-sized titanium, and nano-sized magnesium, wherein said nano-sized aluminum, said nano-sized boron, said nano-sized titanium, and said nano-sized magnesium each have an average particle size of 20 nano-meters; (b) about 10 to about 15 weight % of at least one binder; and (c) about 20 to about 60 weight % of high explosive.

2. The explosive composition of claim 1, wherein said binder includes hydroxy-terminated polybutadienes (HTPB) and said high explosive includes cyclotetramethylene tetranitramine (HMX).

3. The explosive composition of claim 1, wherein said binder comprises at least one of a copolymer of vinylidine fluoride hexafluoropropylene, nitrocellulose, glycidyl azide polymer (GAP) and Zeon.

4. The explosive composition of claim 1, wherein said high explosive comprises at least one of hexa-nitro-hexa-aza-isowurtzitane (CL-20), cyclotrimethylenetrinitramine (RDX) and cyclotetramethylene tetranitramine (HMX).

5. The explosive composition of claim 1, wherein said oxidizer comprises at least one of ammonium perchlorate (AP), ammonium dinitramide (ADN), ammonium nitrate (AN) and barium nitrate.

6. The explosive composition of claim 1, wherein said oxidizer includes about 15 to about 35 weight %, said binder includes hydroxy-terminated polybutadienes (HTPB), and said metal composite includes about 20 to about 40 weight %.

7. The explosive composition of claim 1, wherein said binder comprises at least one of hydroxy-terminated polybutadienes (HTPB), hydroxy-terminated polycaprolactone (PCP), hydroxy-terminated polyesters, hydroxy-terminated polyethers (HTPE), glycidyl azide polymer (GAP), lauryl methacrylate (LMA) and trifluoroethyl-terminated poly(1-cyano-1-difluoramino)-polyethylene glycol (PCDE).

8. An explosive composition comprising: (a) about 20 to about 70 weight % of at least one metal composite, said metal composite including about 60 to about 80 weight % of a reactive metal and about 14 to about 36 weight % of an oxidizer, said reactive metal being selected from a group of reactive metals comprising nano-sized aluminum, nano-sized boron, nano-sized titanium, and nano-sized magnesium, wherein said nano-sized aluminum, said nano-sized boron, said nano-sized titanium, and said nano-sized magnesium each have an average particle size of approximately 20 nano-meters; (b) about 10 to about 15 weight % of at least one binder; (c) about 20 to about 60 weight % of high explosive; and (d) said explosive composition providing for an explosiveness which maintains a relatively high pressure of approximately 30 to 60 psi for a time period of up to 50 msec, wherein the time required for a complete release of energy is reduced by at least 50 msec by using said reactive metal having said average particle size of approximately 20 nano-meters in said explosive composition when compared to another explosive having 200 nano-meter sized metal particles contained therein.

9. The explosive composition of claim 8, wherein said binder comprises at least one of hydroxy-terminated polybutadienes (HTPB), hydroxy-terminated polycaprolactone (PCP), hydroxy-terminated polyesters, hydroxy-terminated polyethers (HTPE), glycidyl azide polymer (GAP), lauryl methacrylate (LMA) and trifluoroethyl-terminated poly(1-cyano-1-difluoramino)-polyethylene glycol (PCDE).

10. The explosive composition of claim 8, wherein said high explosive comprises at least one of hexa-nitro-hexa-aza-isowurtzitane (CL-20), cyclotrimethylenetrinitramine (RDX) and cyclotetramethylene tetranitramine (HMX).

11. The explosive composition of claim 8, wherein said binder includes hydroxy-terminated polybutadienes (HTPB) and said high explosive includes cyclotetramethylene tetranitramine (HMX).

12. The explosive composition of claim 8, wherein said oxidizer comprises at least one of ammonium perchlorate (AP), ammonium dinitramide (ADN), ammonium nitrate (AN) and barium nitrate.

13. The explosive composition of claim 8, wherein said oxidizer includes about 15 to about 35 weight %, said binder includes hydroxy-terminated polybutadienes (HTPB), and said metal composite includes about 20 to about 40 weight %.

14. The explosive composition of claim 8 wherein said binder comprises at least one of a copolymer of vinylidine fluoride hexafluoropropylene, nitrocellulose, glycidyl azide polymer (GAP) and Zeon.

15. An explosive composition comprising: (a) about 20 to about 70 weight % of at least one metal composite, said metal composite including about 60 to about 80 weight % of a reactive metal and about 14 to about 36 weight % of an oxidizer, said reactive metal being selected from a group of reactive metals consisting of nano-sized aluminum, nano-sized boron, nano-sized titanium, and nano-sized magnesium, wherein said nano-sized aluminum, said nano-sized boron, said nano-sized titanium, and said nano-sized magnesium each have an average particle size of approximately 20 nano-meters; (b) about 10 to about 15 weight % of at least one binder; (c) about 20 to about 60 weight % of high explosive; and (d) said explosive composition providing for an explosiveness which maintains a relatively high pressure of approximately 30 to 60 psi for a time period of approximately 50 msec, wherein: (i) the time required for a complete release of energy is reduced by a time period range of 50 msec to 100 msec by using said reactive metal having said average particle size of approximately 20 nano-meters contained in said explosive composition when compared to another explosive having 200 nano-meter sized metal particles contained therein; and (ii) a blast effectiveness for said explosive composition having said average particle size of approximately 20 nano-meters being approximately two times the blast effectiveness of said explosive having said 200 nano-meter sized metal particles contained therein.

16. The explosive composition of claim 15, wherein said binder comprises at least one of hydroxy-terminated polybutadienes (HTPB), hydroxy-terminated polycaprolactone (PCP), hydroxy-terminated polyesters, hydroxy-terminated polyethers (HTPE), glycidyl azide polymer (GAP), lauryl methacrylate (LMA) and trifluoroethyl-terminated poly(1-cyano-1-difluoramino)-polyethylene glycol (PCDE).

17. The explosive composition of claim 15, wherein said high explosive comprises at least one of hexa-nitro-hexa-aza-isowurtzitane (CL-20), cyclotrimethylenetrinitramine (RDX) and cyclotetramethylene tetranitramine (HMX).

18. The explosive composition of claim 15, wherein said oxidizer comprises at least one of ammonium perchlorate (AP), ammonium dinitramide (ADN), ammonium nitrate (AN) and barium nitrate.

19. The explosive composition of claim 15, wherein said oxidizer includes about 15 to about 35 weight %, said binder includes hydroxy-terminated polybutadienes (HTPB), and said metal composite includes about 20 to about 40 weight %.

20. The explosive composition of claim 15 wherein said binder comprises at least one of a copolymer of vinylidine fluoride hexafluoropropylene, nitrocellulose, glycidyl azide polymer (GAP) and Zeon.