WO2006083379A2

WO2006083379A2 - Nanoenergetic materials based on aluminum and bismuth oxide

Info

Publication number: WO2006083379A2
Application number: PCT/US2005/043249
Authority: WO
Inventors: Jan A. Puszynski; Jacek J. Swiatkiewicz
Original assignee: South Dakota School Of Mines And Technology
Priority date: 2004-11-30
Filing date: 2005-11-30
Publication date: 2006-08-10
Also published as: US20060113014A1; US7670446B2; WO2006083379A3

Abstract

This invention generally relates to the field of energetic materials, and more particularly to relatively environmentally benign, lead-free energetic material compositions based on aluminum and at least one oxidant, preferably bismuth trioxide. In a preferred embodiment, a composition of the invention comprises from about 95 percent by weight to 70 percent by weight of an oxidant, such as bismuth trioxide, having particle sizes of about 10 nanometers to about 5 micrometers, and, from about 5 percent by weight to about 30 percent by weight of a solid-powdered fuel, wherein the solid-powered fuel comprises aluminum having particle sizes of about 30 nanometers to about 5 micrometers. The composition may also comprise a surface modifier. The compositions of this invention are useful in percussion primers, ignition devices, propellants, explosives, pyrotechnic formulations and similar applications.

Description

NANOENERGETIC MATERIALS BASED ON ALUMINUM AND BISMUTH OXIDE

FIELD OF THE INVENTION

5 This invention generally relates to the field of energetic materials, and more particularly to relatively environmentally benign, lead-free energetic material compositions based on aluminum and at least one oxidant, preferably bismuth trioxide.

BACKGROUND OF THE INVENTION

10 During the past several years, the Department of Defense (DOD) and the

Department of Energy (DOE) have made a significant effort to find a replacement for currently used lead styphnate-based primers due to their toxicity. Both the energetic material itself and the resulting combustion products can be harmful to the environment. For example, approximately one billion rounds ignited by lead

15 styphnate based primers may release about ten to twenty tons of lead. Examples of relatively non-toxic alternatives that function comparable to lead-based primer compositions can be found in U.S. Pat. Nos. 5,993,577; 5,610,367; 5,538,569; 5,684,268;and 5,353,707, among others. These patents generally disclosure compositions that replace lead styphnate as the primary explosive material with

20 alternatives, such as dinitrobenzofuroxan, diazodinitrophenol or copper azide.

A significant effort has been made to investigate a new class of materials known as metastable intermolecular composites (MIC) for use as energetic materials, such a percussion primers. These composites are made from very small particles of reactive materials, including nanosize aluminum and an oxidizer.

2.5 Primarily this effort has focused on molybdenum trioxide, copper oxide, and tungsten trioxide as oxidants for nanosize aluminum. The above-mentioned MIC compositions have similar combustion characteristics, but each of them involves metal oxides as an oxidant. Although some metal oxides are believed to be less toxic compared to the lead-based energetic materials and of the resulting combustion products, their environmentally benign characteristics are questionable.

Additionally, some of the reported metal oxides have a relatively strong affinity to moisture, which can result in accelerated aging of the MIC material and altering its performance. For example, molybdenum and tungsten trioxides react with water forming molybdic and tungstic acids. These acids may potentially reduce active aluminum content and generate less energy due to water retention. Existing alternatives to lead-based energetic materials have other performance problems. For example, a percussion primer must generate a sufficient energy and quantity of hot gas and particles to ignite the main charge of propellant at a specific time. The aluminum molybdenum trioxide mixture identified above generally has difficulty meeting such requirements. As such, gas producing agents, such as PETN (pentaerythrite-tetranitrate), GAP (glacidyl azide polymer), or high nitrogen energetic compounds typically are added to the energetic MIC formulations.

Further, the use of nanosize or larger particles of aluminum for such applications presents processing and handling problems. Essentially pure aluminum with particle sizes of approximately 20 nanometers to approximately 500 nanometers is black and fluffy. If exposed to the air, it can immediately ignite and form aluminum oxide. To make such aluminum particles more processable in the presence of air, one can passivate the surface of the aluminum particles to reduce its reactivity with oxygen. In an existing process, the aluminum particles are placed in a restricted chamber. Air is introduced very slowly into the chamber, thereby forming a very thin layer of aluminum oxide on the outer surface of the aluminum particles. In addition to the processing complexities, time and expense, such a passivation process consumes a portion of the aluminum itself, rendering that portion unavailable for its intended use as energetic material. The amount of aluminum metal that is available as fuel for reaction is defined as active aluminum. If the active aluminum content decreases below 50 weight percent, the

MIC will not generate a sufficient amount of energy for the intended application. Based upon the problems described above, a need exists for an energetic material, such as a primer composition to replace lead-based primers, that is relatively environmentally benign, while also providing comparable or improved performance, cost and stability to existing energetic materials. Relatedly, a need exists for improved MIC compositions and methods of protecting passivated aluminum from decreasing active metal content, particularly in the case of very small particles.

SUMMARY OF THE INVENTION

An object of this invention is to provide a relatively environmentally benign, lead-free, energetic material that can be used as a substitute for lead-based energetic materials.

It is another object of the invention to provide a lead-free energetic material composition that may be used in percussion primers, ignition devices, propellants, explosives, pyrotechnic formulations, and similar applications, for both military and commercial applications.

It is a further object of the invention to provide a lead-free energetic material composition that is less susceptible to degradation and other performance problems due to reactivity to, and availability of, other reactants, such as water and oxygen. It is yet another object of the invention to provide a lead-free energetic material composition without the addition of gas producing agents.

It is a further object of the invention to provide a lead-free energetic material composition comprising a surface modifier to reduce the reactivity with moisture and to enhance mixing of the composition.

It is yet another object of the invention to provide a relatively environmentally benign, lead-free energetic material composition comprising aluminum and bismuth trioxide. In a preferred embodiment, the composition comprises bismuth trioxide in amounts of approximately 95 percent by weight to approximately 70 percent by weight and having particle sizes in the range of approximately 10 nanometers to approximately 5 micrometers, and a solid powdered fuel in amounts of approximately 5 percent by weight to approximately 30 percent by weight, wherein the solid-powdered fuel comprises aluminum having particle sizes in the range of approximately 30 nanometers to approximately 5 micrometers.

The present invention may be used for various applications including percussion primers, electric matches, fuses, propellants, explosives, pyrotechnic formulations, energetic materials in warheads and other military weapon systems, as well as an intermittent energy source. The versatility of the present invention is yet another advantage to its use as a replacement for currently used lead-based compositions.

DETAILED DESCRIPTION This invention generally relates to the field of energetic materials, and more particularly to relatively environmentally benign, lead-free energetic material compositions based on aluminum and at least one oxidant, preferably bismuth trioxide.

Such mixtures of aluminum and oxidants form energetic composites also referred to as metastable intermolecular composites (MICs) or superthermites, which are characterized by different heats of reaction, as shown in Table 1, and energy release dynamics.

Table 1. Adiabatic temperatures, heat of reactions per mass and per volume, and the amount of generated gas during the reaction for different energetic reacting s stems.

As can be seen in Table 1, an aluminum-bismuth trioxide MIC system generates far more hot gases during the reaction. The adiabatic temperature is comparable to other energetic superthermite systems. The MIC composites formed by mixtures of aluminum and bismuth trioxide are useful in percussion primers, ignition devices, propellants, explosives, pyrotechnic formulations and similar applications. The reactants and the stable products of the reaction are believed to be environmentally benign as compared to other MIC systems.

Although not wishing to be bound by any theory or reaction mechanism, it is believed that a reaction scheme of one embodiment of the invention would be as follows:

Al(Al₂O₃)(S) + Bi₂O₃(S) ► Al₂O₃₀) + Bi_(g) ^air ► A1₂O_3(S) +

In a preferred embodiment, a composition of the invention comprises bismuth trioxide in amounts from about 95 percent by weight to about 70 percent by weight and having particle sizes of about 10 nanometers to about 5 micrometers, and a solid powdered fuel from about 5 percent by weight to about 30 percent by weight, wherein the solid-powdered fuel comprises aluminum having particle sizes of about 30 nanometers to about 5 micrometers.

The relative amounts of bismuth trioxide and aluminum in the composition can vary, as discussed herein and as shown in the examples. Active aluminum must be present in sufficient amounts for the desired reaction to proceed, and preferably is present in amounts sufficient to exceed the stoichiometric amount by approximately 10% to approximately 20%. In a preferred embodiment, a composition of the invention comprises bismuth trioxide in the range of approximately 95 percent by weight to approximately 70 percent by weight and aluminum in the range of approximately 5 percent by weight to approximately 30 percent by weight. In a more preferred embodiment, the composition comprises bismuth trioxide in the range of approximately 72 percent by weight to approximately 90 percent by weight and aluminum in the range of approximately 10 percent by weight to approximately 28 percent by weight. In an even more preferred embodiment, the composition comprises bismuth trioxide in the range of approximately 78 percent by weight to approximately 82 percent by weight and aluminum in the range of approximately 18 percent by weight to approximately 22 percent by weight. The relative amount of aluminum in compositions of the present invention is significantly less than the relative amount of aluminum present in existing energetic materials. For example, for an energetic material comprising aluminum and molybdenum trioxide, approximately 45% or more aluminum is present to achieve the desired result. By decreasing the relative amount of aluminum in the energetic material, the density of the composition of the energetic material is increased. As such, for the same volume of energetic material, the more dense composition of the present invention will provide much greater energy per unit volume. Further, since the aluminum is relatively expensive, especially relative to the oxidant, decreasing the amount of aluminum in the energetic material significantly reduces its cost. In the example of an aluminum/bismuth trioxide composition of the present invention compared to an existing aluminum/molybdenum trioxide composition, the cost savings of the present invention maybe approximately 50% or greater. The particle size of the constituents also can vary, as discussed herein and as shown in the examples. In general, reducing the particle size of the aluminum increases the rate of energy released, while increasing problems of handling and processing the aluminum. Reducing the particle size of the oxidant generally increases the problem of inadvertent reaction through electrostatic discharge. The relatively small particle sizes of both constituents also make the powder processing more difficult. Preferably, the particle sizes of the constituents are sufficiently small for optimal performance, while not so small as to unduly hamper production and use. hi a preferred embodiment, the bismuth trioxide comprises particles having a size of approximately 10 nanometers to approximately 5 micrometers and the aluminum comprises particles having a size of approximately 30 nanometers to approximately 5 micrometers, hi a more preferred embodiment, the bismuth trioxide comprises particles having a size of approximately 70 nanometers to approximately 200 nanometers and the aluminum comprises particles having a size of approximately 40 nanometers to approximately 120 nanometers, hi an even more preferred embodiment, the bismuth trioxide comprises particles having a size of approximately 80 nanometers to approximately 120 nanometers and the aluminum comprises particles having a size of approximately 50 nanometers to approximately 80 nanometers.

The size of the particles of the constituents of energetic materials can cause problems in processing and handling. For example, nanosize aluminum particles react very quickly in the presence of humid air to form aluminum hydroxide. Existing methods to "passivate" the aluminum require the carefully controlled introduction of small amounts of oxygen into a closed system. Through that process and further exposure of the powder to ambient air, a very thin protective layer comprising aluminum oxide with hydroxyl groups may be formed on the surface of the aluminum, with the intention of leaving sufficient amounts of active aluminum within the interior of the particle. That passivation process consumes aluminum, rendering that portion of the aluminum particle unavailable for use as an energetic material.

Li one embodiment of the invention, the oxide passivated aluminum particles are additionally coated with a surface modifier, such as hydrophobic organic compounds. For example, a surface modifier can be introduced to the aluminum particles to form a protective layer around the highly reactive aluminum and to inhibit undesired reactions, such as with moist air. In a preferred embodiment, a surface modifier can be utilized to chemically react on the surface of the aluminum particle with at least part of the outer aluminum oxide with hydroxyl group and thereby form an additional protective layer. Additionally, these surface modifiers can be applied to the oxidant, whether separately from the aluminum or during the mixing process. For example, the mixing process may be improved by the addition of a surface modifier, whether on the aluminum, on the oxidant, separately on both the aluminum and the oxidant, or introduced into the mixing process.

Preferred compounds suitable for use as such surface modifiers include silane compounds, such as n-octyltrimethoxysilane and phenyltrimethoxysilane, fatty acids and/or their fluorine derivatives, such as oleic acid, stearic acid, and sodium dioctylsulfosuccinate, with the most preferred being oleic acid. The organic or inorganic surface modifiers preferably are present in amounts in the range of approximately 0.1 percent by weight to approximately 20 percent by weight, and more preferably approximately 0.2 percent by weight to approximately 10 percent by weight, and even more preferably approximately 0.5 percent by weight to approximately 5 percent by weight.

In another embodiment of the invention, the constituents of the energetic material are mixed in liquid suspension containing aluminum with surface modifiers and preferably an organic solvent. This aids in more thoroughly and more safely mixing the aluminum and the bismuth trioxide. Preferred surface modifiers include sodium dioctylsulfosuccinate dissolved in organic solvents like cyclic and aliphatic hydrocarbons, ketones, ethers and alcohols.

Another advantage of the present invention is that the reaction mechanism involving the preferred oxidant, bismuth trioxide, generates significantly more gas than the existing aluminum-molybdenum trioxide MIC system. As a result, additional gas producing agents will be used in significantly smaller quantities and typically would not be required in connection with the present invention, thereby simplifying the manufacturing and use of the energetic material and reducing its costs. Ifgas producing agents were desired for a particular application, preferred gas producing agents include PETN, GAP and other nitrogen energetic materials applied in quantities preferably from approximately 0 to approximately 30 weight percent, more preferably from approximately 0 to 10 weight percent, and even more preferably from approximately O to less than approximately 5 weight percent.

As noted, compositions of the invention maybe used in percussion primers. One preferred embodiment of the invention for percussion primer application comprises approximately 80 percent by weight of bismuth trioxide

(B-₂0₃) powder and approximately 20 percent by weight of approximately nanosize aluminum powder. In this embodiment for this application, the bismuth trioxide particles preferably would be about 70 nanometer in size and the aluminum particles preferably would be about 42 nanometer in size. Preparation of the composition can proceed in a hexane suspension and be accomplished using normal mixing procedures that are known by those skilled in the art.

For percussion primer and other applications, a preferred embodiment of the invention that includes a surface modifier comprises bismuth trioxide in the amount of approximately 79.5 percent by weight, oxide passivated aluminum in the amount of approximately 19.9 percent by weight and the surface modifier being oleic acid, applied at the aluminum surface, in the amount of approximately 0.6 percent by weight of the dry mixture.

Another preferred embodiment of the invention that includes a surface modifier comprises bismuth trioxide in the amount of approximately 79.2 percent by weight, uncoated aluminum in the amount of approximately 19.8 percent by weight and the modifier being n-octyltrimethoxysilane, applied at the aluminum surface, in the amount of approximately 1 percent by weight of the dry mixture. Energetic material of the present invention can be loaded as a percussion primer into a primer cup using methods known by those skilled in the art.

The following examples illustrate certain preferred embodiments of the invention along with mixing procedures.

EXAMPLE 1

The following mixing procedure produced an embodiment of the present invention having the composition:

Ingredient Weight Percent Bismuth trioxide (Bi2O3) 83.3

Aluminum nanopowder 16.7

1. Dried hexane over molecular sieves to remove residual water. Decanted off dried hexane into suitable storage container.

2. Placed bismuth trioxide into the mixing vessel. Added 12 g of hexane per 1 g of bismuth trioxide with an average particle size 100 nm and allowed to soak the powder with liquid.

3. Added the aluminum powder and mixed the suspension in an ultrasonic bath for 30 minutes. The suspension appeared as uniform slurry.

4. Poured the slurry onto a conductive pan and allowed mixture to dry in an oven at 120 - 140 degree F until it reached a constant weight.

5. After drying, used a conductive spatula to carefully break the material into a free flowing powder.

6. Carefully placed the dry powder into a conductive container for further immediate processing.

EXAMPLE 2 The following composition is an example of an embodiment of the invention for a specific type of use in percussion primer applications. This composition can be prepared using different mixing and loading procedures and can be amended by those skilled in the art for the particular embodiment: Ingredient Weight Percent

Bismuth trioxide (Bi2O3) 83.3

Aluminum nanopowder 13.7

Oleic acid 3.0

1. Dried toluene over the molecular sieves for several days to remove residual water. Decanted off the dried toluene into a suitable storage container.

2. Placed bismuth trioxide into the mixing vessel. Added 12 g of toluene per 1 g of bismuth trioxide and allowed to soak the powder with liquid.

3. Added the aluminum powder and homogenize suspension in an ultrasonic bath. 4. Added oleic acid into the mixture and homogenized the suspension in the ultrasonic bath for 30 minutes. The suspension appeared as a uniform slurry.

5. Poured the slurry onto a conductive pan and allowed the mixture to dry in an oven at 120 - 140 degree F until it contained about 20 percent by weight of toluene.

6. After pre-drying, used a conductive spatula to carefully break the material.

7. Carefully placed the wet powder into a conductive container and

sealed for storage and subsequent use in a loading process of percussion primers. Described above are specific examples of many possible variations of the same invention and are not intended in a limiting sense. The claimed invention can be practiced using other variation not specifically described above.

The foregoing discussion of the invention has been presented for purposes of illustration and description. The foregoing is not intended to limit the invention to the form or forms disclosed herein. In the foregoing Detailed Description for example, various features of the invention are grouped together in one or more embodiments for the purpose of streamlining the disclosure. This method of disclosure is not to be interpreted as reflecting an intention that the claimed invention requires more features than are expressly recited in each claim.

Rather, as the following claims reflect, inventive aspects lie in less than all features of a single foregoing disclosed embodiment. Thus, the following claims are hereby incorporated into this Detailed Description, with each claim standing on its own as a separate preferred embodiment of the invention. Moreover though the description of the invention has included description of one or more embodiments and certain variations and modifications, other variations and modifications are within the scope of the invention, e.g. as may be within the skill and knowledge of those in the art, after understanding the present disclosure. It is intended to obtain rights which include alternative embodiments to the extent permitted, including alternate, interchangeable and/or equivalent structures, functions, ranges or steps to those claimed, whether or not such alternate, interchangeable and/or equivalent structures, functions, ranges or steps are disclosed herein, and without intending to publicly dedicate any patentable subject matter.

Claims

We claim:

1. An energetic material composition, comprising: an oxidant comprising bismuth trioxide having particle sizes in the range of approximately 10 nanometers to approximately 5 micrometers; and a solid-powdered fuel comprising aluminum having particle sizes in the range of approximately 30 nanometers to approximately 5 micrometers; the bismuth trioxide comprising approximately 95 percent by weight to about 70 percent by weight of the energetic material composition, and the aluminum comprising approximately 5 percent by weight to approximately 30 percent by weight of the energetic material composition.

2. The composition of Claim 1 , wherein the particle sizes of the bismuth trioxide are in the range of approximately 70 nanometers to approximately 200 nanometers.

3. The composition of Claim 1, wherein the particle sizes of the bismuth trioxide are in the range of approximately 80 nanometers to approximately

120 nanometers.

4. The composition of Claim 1, wherein the particle sizes of the aluminum are in the range of approximately 40 nanometers to approximately 120 nanometers.

5. The composition of Claim 1, wherein the particle sizes of the aluminum are in the range of approximately 50 nanometers to approximately 80 nanometers.

6. The composition of Claim 1, wherein the particle sizes of the bismuth trioxide are in the range of approximately 70 nanometers to approximately 200 nanometers and the particle sizes of the aluminum are in the range of approximately 40 nanometers to approximately 120 nanometers.

7. The composition of Claim 1, wherein the particle sizes of the bismuth trioxide are in the range of approximately 80 nanometers to approximately 120 nanometers and the particle sizes of the aluminum are in the range of approximately 50 nanometers to approximately 80 nanometers.

8. The composition of Claim 1, wherein the bismuth trioxide comprises approximately 90 percent by weight to about 72 percent by weight of the energetic material composition, and the aluminum comprises approximately 10 percent by weight to approximately 28 percent by weight of the energetic material composition.

9. The composition of Claim 8, wherein the particle sizes of the bismuth trioxide are in the range of approximately 70 nanometers to approximately 200 nanometers.

10. The composition of Claim 8, wherein the particle sizes of the bismuth trioxide are in the range of approximately 80 nanometers to approximately 120 nanometers.

11. The composition of Claim 8, wherein the particle sizes of the particle sizes of the aluminum are in the range of approximately 40 nanometers to approximately 120 nanometers.

12. The composition of Claim 8, wherein the particle sizes of the aluminum are in the range of approximately 50 nanometers to approximately 80 nanometers.

13. The composition of Claim 8, wherein the particle sizes of the bismuth trioxide are in the range of approximately 70 nanometers to approximately 200 nanometers and the particle sizes of the aluminum are in the range of approximately 40 nanometers to approximately 120 nanometers.

14. The composition of Claim 8, wherein the particle sizes of the bismuth trioxide are in the range of approximately 80 nanometers to approximately 120 nanometers and the particle sizes of the aluminum are in the range of approximately 50 nanometers to approximately 80 nanometers.

15. The composition of Claim 1, wherein the bismuth trioxide comprises approximately 82 percent by weight to approximately 78 percent by weight of the energetic material composition, and the aluminum comprises approximately 18 percent by weight to approximately 22 percent by weight of the energetic material composition.

16. The composition of Claim 15, wherein the particle sizes of the bismuth trioxide are in the range of approximately 70 nanometers to approximately 200 nanometers.

17. The composition of Claim 15, wherein the particle sizes of the bismuth trioxide are in the range of approximately 80 nanometers to approximately 120 nanometers.

18. The composition of Claim 15, wherein the particle sizes of the particle sizes of the aluminum are in the range of approximately 40 nanometers to approximately 120 nanometers.

19. The composition of Claim 15, wherein the particle sizes of the aluminum are in the range of approximately 50 nanometers to approximately 80 nanometers.

20. The composition of Claim 15, wherein the particle sizes of the bismuth trioxide are in the range of approximately 70 nanometers to approximately 200 nanometers and the particle sizes of the aluminum are in the range of approximately 40 nanometers to approximately 120 nanometers.

21. The composition of Claim 15, wherein the particle sizes of the bismuth trioxide are in the range of approximately 80 nanometers to approximately

120 nanometers and the particle sizes of the aluminum are in the range of approximately 50 nanometers to approximately 80 nanometers.

22. The composition of Claim 1, wherein the solid-powdered fuel further comprises a modifier.

23. The composition of Claim 1, wherein the solid-powdered fuel- further comprises a modifier in amounts from approximately 0.2 percent by weight to approximately 20 percent by weight.

24. The composition of Claim 1, wherein the solid-powdered fuel further comprises a modifier comprising at least one gas producing agent.

25. The composition of Claim 1, wherein the solid powdered fuel further comprises an inorganic modifier.

26. The composition of Claim 1 , wherein the solid powdered fuel further comprises an inorganic modifier selected from the group consisting of aluminum oxide and bismuth metal.

27. The composition of Claim 1, further comprising a surface coating material.

28. The composition of Claim 27, wherein the surface coating material is present in amounts in the range of approximately 0.1 percent by weight to approximately 20 percent by weight.

29. The composition of Claim 27, wherein the surface coating material is present in amounts in the range of approximately 0.2 percent by weight to approximately 10 percent by weight.

30. The composition of Claim 27, wherein the surface coating material is present in amounts in the range of approximately 0.5 percent by weight to approximately 5 percent by weight.

31. The composition of Claim 27, wherein the surface coating material comprises at least one silane compound.

32. The composition of Claim 27, wherein the surface coating material comprises at least one silane compound selected from the group consisting of n-octyltrimethoxysilane, phenyltrimethoxysilane, fatty acids, and fluorine derivatives thereof.

33. The composition of Claim 27, wherein the surface coating material is selected from the group consisting of oleic acid, stearic acid, and sodium dioctylsulfosuccinate

34. The composition of Claim 1, wherein the aluminum is oxide passivated.

35. The composition of Claim 1, further comprising a gas producing agent.

36. The composition of Claim 1, further comprising a gas producing agent in amounts less than approximately 10 percent by weight.

37. An energetic material composition comprising: bismuth trioxide having particle sizes in the range of approximately 10 nanometers to approximately 5 micrometers; oxide passivated aluminum having particle sizes in the range of approximately 30 nanometers to approximately 5 micrometers; and a surface modifier.

38. The composition of Claim 37, wherein the bismuth trioxide comprises approximately 95 percent by weight to approximately 70 percent by weight, the aluminum comprises approximately 5 percent by weight to approximately 30 percent by weight, and the surface modifier comprises approximately 0.1 percent by weight to approximately 20 percent by weight of the composition.

39. The composition of Claim 37, wherein the bismuth trioxide comprises approximately 90 percent by weight to approximately 72 percent by weight, the aluminum approximately 10 percent by weight to approximately 28 percent by weight and the surface modifier approximately 0.2 percent by weight to approximately 10 percent by weight of the composition.

40. The composition of Claim 37, wherein the bismuth trioxide comprises approximately 82 percent by weight to approximately 78 percent by weight, the aluminum approximately 18 percent by weight to approximately 22 percent by weight and the surface modifier approximately 0.5 percent by weight to approximately 5 percent by weight of the composition.

41. The composition of Claim 37, wherein the surface modifier is selected from the group consisting of silane compounds, fatty acids, and their fluorine derivatives.

42. The composition of Claim 37, wherein the surface modifier is selected from the group consisting of n-octyltrimethoxysilane, phenyltrimethoxysilane, oleic acid, stearic acid, sodium dioctylsulfosuccinate.

43. A percussion primer comprising the composition of Claim 1.