WO2000066517A1 - Ignition mixture - Google Patents

Abstract

The invention relates to an ignition mixture consisting of at least one impact-sensitive, non-metallic explosive, optionally at least one further impact-sensitive, non-metallic explosive, optionally at least one combustible and an oxidant mixture. The maximum content of the individual oxidants within the total mixture consisting of the explosive/s and optionally the combustible/s is determined by a predetermined maximum limiting concentration of the reaction product/s of the oxidants after the redox reaction and in an area surrounding the total mixture.

Description

Kindling mixture

The invention relates to an ignition mixture according to the preamble of claims 1 and 2, an explosive formulation according to claim 42 and a method for producing an ignition mixture according to claim 43.

Ignition mixtures are usually used to initiate the explosion or detonation of explosives, for example in ammunition or in various pyro-technical objects. Ignition charges of this type contain, as one of the main constituents, an oxidizing agent or an oxygen-releasing substance in order to enable a corresponding redox reaction. Such oxidizing agents should simply be available in a pure form, have a corresponding particle diameter and, in addition, be inexpensive to produce. In addition, these oxidizing agents should react neutrally in the event of moisture penetration or have non-hygroscopic properties. The oxygen contained should be released at an elevated temperature at a sufficient rate and these oxidizing agents should be thermally stable over a certain temperature range. Most oxidizing agents, which have at least some of these properties, have the disadvantage that heavy metal cations are present for charge equalization, such as lead, mercury or the like, which, because of the required concentration ratios, after firing, the ambient air and subsequently the user is also exposed to such explosive mixtures with health-endangering reaction products, such as gases, dusts or the like.

The use of such health-endangering oxidizing agents is known, for example, from US Pat. No. 3,423,259 A, from which a mixture containing, inter alia, barium nitrate and lead oxide for an initial explosive is known. The compositions for initial explosives listed in this USA contain such a high concentration of this oxidizing agent that a health hazard cannot be ruled out, especially if these materials are used over a long period of time.

An initiator composition is known from EP 0 440 873 B1, which essentially consists of diazodinitrophenol, strontium nitrate and tetrazene. Next

Diazodinitrophenol, the shock-sensitive explosive can also include potassium dinitrobenzofuroxane. For the oxidizing agent strontium nitrate, no healthy known for the matellation strontium. However, it is disadvantageous that strontium nitrate is hygroscopic and the storage of these initial igniters over a long period of time is problematic without special precautions. In addition to the formation of the tetrahydrate, the good solubility in water of approx. 41% is also disadvantageous, since the risk of melting can occur under extreme storage conditions.

The object of the invention is now to provide an ignition mixture for explosives, pyrotechnic articles or the like in which, in addition to harmless-appearing oxidizing agents, oxidizing agents can also be used which have the introductory properties and are present in a concentration which is healthy Avoid interference with the user of this primer charge.

This object is achieved by the features in the characterizing part of claim 1. It is advantageous that the composition of the primer charge is now not solely aimed at the safe detonation of the explosive, but rather the proportion of the oxidizing agents in any mixture depends on the concentration of the reaction products formed. In this way it is possible to use even those oxidizing agents that currently appear to be of concern. A safe detonation of the explosive can thus also be made possible, since the entire explosive charge can be prevented from being moistened, and mixtures defined in this way can retain their properties even under extreme storage conditions.

It is a further object of the invention to provide an ignition mixture which, when used under normal conditions, is not expected to pose a health risk due to the composition of the ignition mixture.

This object is achieved by the features in the characterizing part of claim 2. It is advantageous that the use of tungsten compounds can provide an oxidizing agent which is thermally stable up to high temperatures and which also has a high density. In addition, such connections are not hygroscopic, which, in addition to storage, can also simplify processing. Furthermore, the ignitability of the propellant powder can be improved. Further advantageous design variants are described in claims 3 to 41 and their advantages can be found in the description.

However, the object of the invention is also achieved by an explosive formulation according to claim 42. It is advantageous that by using the ignition mixture according to the invention for this explosive formulation, its properties can be adjusted according to the desired conditions, for example the time / pressure behavior, the shelf life, the hygroscopicity of the formulation, the energy content of the formulation, the gas volume and the sensitivity / Insensitivity behavior. This explosive formulation can thus be composed in such a way that it can be used in projectiles or ammunition, but on the other hand there are also civil applications, such as in airbag systems, conceivable.

The object of the invention is further achieved by the method according to the features in the characterizing part of claim 43. It is advantageous that the use of organic solvents to paste the mass for the explosive formulation or for the ignition mixture also enables hygroscopic educts to be used on the one hand, since they do not absorb any water of crystallization from the organic solvent. In addition, this can also increase the economics of the process, since those solvents are preferably used which have a lower boiling point compared to water, which makes drying easier and the drying time can be shortened.

Further advantageous design variants are described in claims 44 to 48 and their advantages can be found in the description.

For a better understanding of the invention, this will be explained in more detail with reference to the following description.

As an introduction, it should be noted that individual features or combinations of features from the different exemplary embodiments described can represent independent, inventive or inventive solutions.

Explosives, including initial explosives, fuels and guns, primers, pyrotechnic charges or the like, can be used for a wide variety of purposes, for example for military purposes and for hunting, for ammunition - -

the. In addition, such explosives are e.g. also used in airbag systems. For the respective intended use, it is decisive whether the explosive has a more pushing effect (as a gun or propellant powder) or more smashing.

A wide variety of explosives or mixtures thereof are generally used as disintegrants, e.g. nitric acid esters obtainable by nitration (glycerin trinitrate, mannitol hexanitrate), nitro compounds (TNT), nitramines (hexogen), nitrosamines, ammonium nitrate or the like. Also explosive mixtures of different substances are used, e.g. Black powder, chlorate explosives, ammonium nitrate explosives or the like

The requirements for explosives for commercial and military purposes are sometimes so different that civil explosives are sometimes not used militarily. For safety reasons, the sensitivity of commercial explosives must not be too high. Insensitivity to impact, friction and heat as well as shelf life can be achieved by desensitizing, changing the mixing ratio, specific shape, if necessary also by adding moderators or the like.

Many of these different disintegrants have in common the use of oxidizing agents in order to enable these disintegrants to react in the first place. The explosives used usually have a more or less negative oxygen balance (SB). The oxygen balance is usually used in the literature and gives information about how much oxygen is released (oxidizing agent) or consumed (reducing agent) in a reaction. The information is usually given in percent by weight.

It should be noted at this point that in addition to the SB, based on the mass of the oxidizing agent used, the density of this oxidizing agent is also important. The higher the density of the oxidizing agent for the same SB, the more active oxygen can be generated in a given volume. In order to be able to take this fact into account, a volume-specific oxygen balance (SBVol) is specified, which is calculated by multiplying the SB by the density.

Density always means the (theoretical) density of the substance and not the bulk density. WO 00/66517 - 5 - PCT / ATOO / 00109

In order to compensate for this oxygen deficit, said disintegrants are usually used in conjunction with oxidizing agents. Such oxidizing agents usually have a more or less ionic structure, i.e. they consist essentially of anions and cations.

However, as already mentioned at the beginning, the oxidizing agents which have preferably been used have the disadvantage that the cations used for charge balancing have a more or less great toxic potential. The problem that arises from this is that the increased environmental awareness means that these oxidizing agents can or can only be used in peripheral areas. For example, when using explosives equipped in this way in cartridges on shooting ranges, it is problematic to rule out a health hazard, especially in the case of insufficient air circulation or air exchange. This can result in the air being enriched with these toxic substances in closed rooms, for example in the form of smoking,

Swaths, solid particles or the like can be present. Inhalation or skin absorption may lead to cell mutations with their known consequences due to carcinogenic effects.

This is precisely where the invention comes into play. In the following, oxidizing agent mixtures are to be defined which prevent such an excessive concentration of pollutants and at the same time essentially have at least those properties which are common to the traditional oxidizing agents.

The following values can be used to assess the toxicity of the oxidizing agents.

1. The MAK value (maximum workplace concentration) refers to the TRGS 900 unless otherwise stated. In addition, the MAK value can also refer to the TRGS 402, 403, 905.

2. If no MAK values are given for individual oxidizing agents or the elements involved in their composition, corresponding limit values can be found in the OSHA list (Occupational Safety & Health, U.S. Department of Labor).

3. There is also the option of using the technical - -

reference concentration or the biological workplace tolerance value (TRGS 903).

The toxicity can be classified using the poison list (Roth, Daunderer, Poison List, 6th edition 1990, 78th supplementary delivery, status 15.1 1. 1998). In individual cases, the MAK classification of the DFG commission (Senate commission for testing harmful substances in the German Research Foundation) can also be used. Unless stated otherwise, the MAK value refers to the metal cation.

In addition to the toxicity, the price of the oxidizing agents can of course play a role in the economic importance of the ignition charges and the properties of these oxidizing agents, such as Stability, behavior against water etc., a selection criterion.

As already mentioned, the oxidizing agents commonly used have an ionic character, i.e. they consist of anions and cations.

As anions, e.g. Chromates, dichromates, chlorates, perchlorates, bromates, perbromates, iodates, periodates, permanganates, nitrates, oxides, peroxide compounds, carbonates, sulfates and oxalates can be considered. Of course, other anions not mentioned here can also be used if necessary.

Due to the carcinogenicity of chromium compounds - the TRK value is 0.05

3 mmgg // mm for the small amounts of chro- roomate tea and di-chromate are only added to the oxidizing agent mixture in very small amounts.

When using chlorates and perchlorates, attention must be paid to their corrosive and possibly toxic reaction products. In addition, when organic compounds are burned in the presence of chlorine in a temperature window between 300 ° C and 600 ° C, the very toxic dioxins can arise. For example,

2,3,7,8-tetrachlorodibenzopdioxin has a TRK value of 5 * 1 8 mg / m 3.

Likewise, when using bromates, perbromates, iodates or periodates, care must be taken to form corrosive and toxic combustion products. The use of permanganates is also problematic, although not excluded because manganates are usually very soluble in water, which can worsen the storage properties of formulations containing permanganates. In addition, manganese has a very low MAK value of 0.5 mg / m.

In general, it should be noted at this point that it is favorable if the MAK value of the respective metal is greater than 1 mg / m 3, preferably greater than 2 mg / m 3, in particular

3 is greater than 4 mg / m.

The use of nitrates is advantageous since, owing to the composition of nitrogen and oxygen, nitrates break down into reaction products which are usually unproblematic and also have a strongly positive oxygen balance. As a result, the toxicity of nitrates is only dependent on the respective cation.

Oxides behave in the same way. Such metal oxides are preferably used whose cation is easily reducible, i.e. can be converted to a lower oxidation state. For example, tin dioxide (SnÜ2) can be converted into SnO or Fe2 O into FeO with the release of oxygen, which is subsequently available for the reaction in the ignition mixture.

The use of peroxide compounds is also advantageous, since their toxicity is primarily dependent on the cation.

Peroxide compounds can be divided into those with a heteropolar, covalent or complex bond. With covalent properties, for example, peroxoborates, peroxo (di) sulfates, peroxo (di) phosphates and various usable organic peroxo compounds can be used.

Complex bonds have e.g. Metal complexes with peroxo ligands, the metal being predominantly transition metals, such as Titanium (Ti), chrome (Cr), molybdenum (Mo), tungsten (W) are used.

In addition, in a broader sense, peroxide compounds may also be present in the oxidizing agent mixture which, as water of hydration, do not have H ^ O but H ^ O ^ (hydrogen peroxide), ie so-called peroxy hydrates.

But the so-called hyperoxides also belong to the peroxo compounds in the broadest sense, since they contain the paramagnetic O ^ anion, which is a derivative of the very unstable len HO2 radicals can be included. As is known, only the alkali metals can form pure hyperoxides in the usual way.

In addition to these groups of compounds, it is also possible to use oxidizing agents whose oxygen balance is at least almost balanced.

As already mentioned, e.g. Cabonates also act as an oxidizing agent, with regard to the balanced oxygen balance, CO2 can be assumed as a reaction product in addition to the respective metal oxide. What is interesting about the carbonates is that the resulting CO2 is known to be in equilibrium with carbon monoxide (CO), which is known as the Boudouard equilibrium (CO2 <=> CO + 0.5 O2). This equilibrium can be shifted to the right side, ie towards free oxygen, by increasing the temperature (above 800 ° C) and oxygen deficiency. Since very high temperatures and on the other hand a lack of oxygen are usually predominant when the ignition mixture is ignited, carbonates can also have an oxidizing effect due to this equilibrium.

In addition, the use of carbonates has the advantage that, from a toxicological point of view, reaction products which are normally unproblematic, namely carbon monoxide or carbon dioxide, are formed, which are normally present anyway when the propellant powder is burned off.

The situation is quite similar for sulfates, although it should be noted that there is no equilibrium with SO2 for the sulfur trioxide (SOo) formed in addition to the metal oxides when the metal sulfates decompose. However, it is advantageous that at elevated temperatures, for example above 1200 ° C., SO3 breaks down into SO ₂ and 0 ₂ according to the equation SO ₃ -> S0 ₂ + 0.5 0 ₂ , so that again free oxygen for the reaction of the propellant is available. It is also advantageous that various metals, such as platinum, can accelerate this decay and lower the temperature of the decay. For platinum, such decay can be achieved from 430 ° C. Due to the reducing conditions (negative oxygen balance) when the propellant charge is ignited, SO can act as an oxidizing agent. However, the toxicity and the corrosiveness of the resulting exhaust gases, that is, SO or S0 ₂ , must be taken into account in the amount of sulfates to be estimated for the oxidant mixture. For sulfur trioxide

3, for example, a limit value of 1 mg / m is given (Kühn, Birett, leaflets on hazardous substances 63. Erg. Lfg. 2/93). - -

Finally, the use of oxalates is also advantageous, even under the circumstance that their SB is negative with respect to CO ₂ . However, if you take into account the Boudouard equilibrium mentioned, you again get a positive oxygen balance, similar to the carbonate anion. It is particularly advantageous that oxalates are largely harmless from a toxicological point of view, ie that the toxicity is determined by the cation.

The following metals are possible cations.

1. Alkali metals

These include lithium (Li), sodium (Na), potassium (K), rubidium (Rb) and cesium (Cs). Na and Cs are of interest here, as an advantageous MAK for the corresponding hydroxides - the most likely reaction product because the oxides hydrolyze

Value exists that relates to the toxicological properties of the

3 composition is 2 mg / m.

There is currently no MAK value for potassium, but a classification similar to NaOH is recommended.

Li and Rb can of course also be used, although no MAK value is currently specified for these metals.

2. Alkaline earth metals

Magnesium (Mg) and calcium (Ca) are of particular interest. With Ca, however, it should be noted that the MAK according to TRGS 900 is 5 mg / m ³ and according to DGF 3 1.5 mg / m. It may therefore be advantageous for the toxicological assessment of the oxidizing agent mixture to use calcium in such quantities that the value suggested by the DGF is not exceeded. However, due to the usually toxicological harmlessness of calcium, a lot is possible.

3 loaned, which leads to no more than 5 mg / m in the reaction products.

The use of strontium (Sr) also proves to be advantageous, since this element is generally classified as not very toxic and can therefore also be used in larger amounts in the oxidizing agent mixture according to the invention.

Beryllium, on the other hand, due to its carcinogenic properties, especially when inhaled, can only be added in traces of the oxidizing agent mixture. The 3 associated MAK value can be 0.02 mg / m.

For MAK, a MAK value of 6 mg / m magnesium oxide (MgO), calculated as fine dust, should not be exceeded.

3 Due to the toxicity, a MAK value of 0.5 mg / m, also based on fine dust, should not be exceeded for barium salts.

3. Transition metals These include those metals that are classified in groups 3 to 12 according to the periodic table of the elements.

Compounds with yttrium (Y), titanium (Ti), zircon (Zr), niobium (Nb), tantalum (Ta), molybdenum (Mo), tungsten (W) and iron (Fe) can be particularly advantageous with regard to the MAK values. can be used in low-emission primers. However, the lower DFG values are also possible for Ti and Ta.

Although all MAK values can be found in the relevant literature, the following table is intended to assist the person skilled in the art with these elements.

As already mentioned, not only the toxicity plays a role in the choice of the oxidizing agent mixture, but also the price situation. According to these considerations, it is therefore particularly advantageous to use compounds of the elements Ti, Zr, Mo and W in appropriate amounts. In particular, this also applies to connections of the elements Fe and Zn.

It should be noted at this point that of course those with the invention Oxidizing agent mixture produced, so-called "primers" can also contain reducing agents in the form of various metals. The corresponding limit values for these reducing agents are of course equally remarkable.

4. Earth metals

From this group it is particularly advantageous to use the elements boron (B) and aluminum

(AI) or their connections due to the favorable limit values in ignition kits

3 use. For B, based on B ₂ O-3, the MAK value is 15 mg / m (based on

Total dust) and for AI 6 mg / m (based on fine dust). With AI, however,

3 possible to reduce this limit according to the DFG to 1.5 mg / m.

For gallium (Ga), the respective amount should be tested beforehand using appropriate test methods due to the lack of MAK values.

The elements indium (In) and thallium (TI) should be 3 due to the low MAK values

0.1 mg / m (based on total dust) or 0.1 mg / m (based on fine dust) of

Oxidizing agent mixture can only be added in small amounts to improve their properties.

5. Carbon group

Due to the low toxicity, the elements silicon (Si) and tin (Sn) and their compounds are particularly advantageous for use in the mixture of oxidants, but germanium (Ge) and lead (Pb) can also be used, albeit in small amounts . The MAK value for silicon or SiO (as silica, amorphous) is 4 mg / m 3, based on fine dust, for tin, based on the

3 velvet dust with 2 mg / m. No MAK value is currently set for germanium. The limit for lead is due to its fruit-damaging properties

3 of lead compounds at 0.1 mg / m in total dust. This again shows the advantageous use of the oxidizing agent mixture according to the invention, since now, if the corresponding limit values are observed, lead compounds of the

Oxidizing agent mixture can be added and, as a result, the correspondingly favorable properties of these compounds, some of which are already known, can be exploited without the risk of a health hazard.

Since carbon is usually always present in the explosives formulation, no further consideration is necessary at this point. In addition to these predominantly metallic elements, the elements of the pnictogens and chalcogens must also be taken into account when assessing the overall toxicity of the respective formulation.

Since arsenic (As), antimony (Sb) and bismuth (Bi) normally have a very high toxicological hazard potential, only nitrogen (N) and phosphorus (P) come into consideration from the group of pnictogens. N can be used in the form of nitrates, but also as an ammonium cation (NH). Depending on the prevailing conditions during the combustion, molecular nitrogen, which is largely non-toxic due to the particularly stable triple bond, and nitrogen oxides can be formed as reaction product (s). Even in the latter case, the MAK values can

3 can be applied particularly carefully, for example for N0 with 9 mg / m and for NO with 30 mg / m .3 "

The usable amount of phosphorus or phosphorus compounds is due to

3 3 nes MAK value of 1 mg / m for P2θ _< r in the total dust or 0.1 mg / m for yellow or white P in the total dust relatively low.

Finally, in addition to oxygen, only sulfur (S) from the group of chalcogens is particularly advantageous for use in the oxidizing agent mixture, since it is related to S

3 on SO, 5 mg / m can be contained in the exhaust gas. For the elements selenium (Se) and 3

Tellurium (Te) the corresponding limit values are 0.1 mg / m in the total or

Fine dust, so that their use or the use of the corresponding compounds can only be useful in exceptional cases to improve the further properties of the oxidizing agent mixture or the finished explosive mixture.

Based on these considerations, it has proven to be particularly advantageous if for the oxidizing agent mixture according to the invention

1. Elements are used whose MAK value is preferably higher than

1 mg / m ³ is, which includes Na, K, Cs, Mg, Ca, Ti, Zr, Mo, W, Fe, Zn, B, Al, Si, Sn, S, NH ₄ ⁺ and Sr. (Due to the relatively high price, the elements Ta, Y, Nb are no longer considered for the following version, although there is a corresponding limit value for these elements. Their use in the oxidizing agent mixture should therefore only be used in exceptional cases.)

2. It is also particularly advantageous to use so-called non-toxic oxygen term anions, for example nitrates, oxides, peroxides, carbonates, sulfates or oxalates or the like. Although, of course, the more problematic anions, such as chromates, dichromates, chlorates, perchlorates, bromates, perbromates, iodates, periodates and permanganates, can also be used for the oxidizing agent mixture if the idea of the invention is observed, these are not to be considered further below.

As already mentioned, in addition to the toxicological point of view, the further properties of this oxidizing agent mixture or the explosives formulation are also of importance and these properties can be influenced more or less positively by using appropriate starting materials. These properties include the hydrate formation, the hygroscopicity, the solubility behavior of the various compounds and the processability or the like.

For storage conditions it is advantageous if the individual components of the oxidizing agent mixture are little or not hygroscopic. Among the less toxic elements or compounds described above, these include above all KNO and CsNO. so that these two connections are particularly suitable for use in primers.

In addition, you can also

and NaNO ₃ , which show some hygroscopicity, as well as Al (NO ₃ ) ₃ , Ca (NO ₃ ) ₂ , Cu (NO ₃ ) ₂ , Fe (NO ₃ ) ₃ , Mg (NO ₃ ) ₂ , Zn (NO ₃ ) ₂ can be used.

At this point it should be mentioned again that of course other compounds with the preferred anions are also known, such as Pb (NO) ₂ , but their use for the oxidizing agent mixture according to the invention is only possible to a limited extent due to the toxicity of the metal cation. However, this does not mean that such compounds are excluded from use in the oxidizing agent mixture.

The oxygen balance of the preferred, non-hygroscopic and no crystal water-binding compounds KN0 ₃ and CsNO is relatively high and is, for example, approximately 70% of that of strontium nitrate (Sr (N0) ₂ ). The absence of hydrates can be regarded as an advantage over Sr (NO ₃ ) ₂ , so that the ignition mixture or the primer can subsequently have the positive property of low sensitivity to moisture. What is negative, however, is that the melting points of the hydroxides formed from these nitrates (as already mentioned, the primary oxides hydrolyze) are very low at 334 ° C. and 414 ° C., so that neither Cs nor K can make an increased contribution to the formation of so-called glowing particles. (In comparison, SrO has a melting point of 2460 ° C.) Such glowing particles that are thrown out of the igniter are for a quick

Ignition of the propellant charge is advantageous, so that subsequently such compounds are used with advantage that do not melt or even evaporate up to very high temperatures. For example, the Ba (NO) known from conventional primers, i.e. the resulting BaO, a melting point of 1923 ° C. However, the use of this compound is only possible in small quantities due to the toxic properties of barium or barium oxide.

In the case of CsNO, attention should also be paid to the normally high prices, which primarily affect the economic importance of the oxidizing agent mixture according to the invention or the formulations produced therefrom, so that CsNO _{3 is} advantageously used only when the primer has certain properties, such as the one mentioned Non-hygroscopic should be conferred. With regard to the reaction products which result from the nitrates or all other compounds mentioned here, reference is made to the relevant literature, so that a discussion of these reaction equations is unnecessary.

Another positive thing about KNO and CsN0 is that due to the density and the strongly positive oxygen balance, a comparatively large amount of active oxygen can be provided per defined volume. The SB (Vol) values are 83.5 g / cm ³ and 75.5 g / cm ^3, respectively.

For metal oxides, it proves to be advantageous if they easily change from a high oxidation state to a lower one, ie that the standard potentials for electron uptake found in the literature are not too negative. From these points of view, the use of MoO, WO, Fe ₂ O ₃ and SnO 2 in the oxidizing agent mixture is advantageous. These four elements or the corresponding oxides mentioned have a positive oxygen balance, in particular 1 1, 1, 6.9%, 20% and 10.6% (in the order mentioned).

Due to the relatively high densities of these oxides, the volume-related S Saauueerrsstteoffbilanz SB (Vol) with 52.2 g / cm ³ , 50.3 g / cm ³ , 105 g / cm ³ and 72.7 g / cm ^{3 is also} advantageous . In particular, of the four oxides mentioned, the most interesting is Fe2θ and this oxide roughly reaches the value for the volume-related oxygen balance of Sr (NO ₃ ) ₂ .

Extremely favorable when using oxides is their insensitivity to water, in particular their insolubility or non-hygroscopicity. As a result, easier processing of the primer and subsequently better storage can be achieved when using these oxides, so that the properties of the mixture can also be improved, in particular when Sr (NO ₃ ) _{2 is used} as the oxidizing agent part.

The melting points of the oxides of the metal cation of a lower oxidation state formed from the oxides mentioned are in some cases significantly above 1000 ° C., so that these oxides can advantageously contribute to the formation of glowing particles. However, it should be noted that oxygen is usually only released at temperatures above 1000 ° C.

For peroxides, as already mentioned, similar to the oxides, the toxicity of the reaction products only depends on the cations involved. In principle, all peroxides formed with the aforementioned elements can be used, since the cation does not have to be reduced when oxygen is released.

Peroxides with a heteropolar bond form primarily the alkali and alkaline earth metals, as well as zinc. Especially the use of the

is due to its properties (positive oxygen balance, not hygroscopic, sparingly soluble in water) possible in the oxidizing agent mixture according to the invention.

But MgO ₂ can also be used in spite of its partially more or less negative properties (low sensitivity to moisture) due to the otherwise positive properties (insolubility in water, positive oxygen balance).

Both with ZnO ₂ and with MgO ₂ , however, it should be noted that the technical products available have a correspondingly reduced proportion of pure ZnO 2 or Mg O 2, which results from the contamination with the corresponding oxides or hydroxides.

Also not ideal, but can certainly be used for the oxide WO 00/66517-17 - PCT / ATOO / 00109

is SrO ₂ - SrO ₂ is known to form and become an octahydrate

Peroxide described as sensitive to moisture. However, it is advantageous that SrO _{2 can be obtained} without the above-mentioned impurities, as a result of which the production costs for the explosive formulation can be reduced. Another advantage is the relatively high positive oxygen balance of 13.4%. The volume-related oxygen

3 balance is advantageous due to the density 59.5 g / cm.

In addition, however, Cs ₂ O ₂ and Ca O ₂ can also be used in the oxidizing agent mixture.

All of the peroxides mentioned, as well as the oxidizing agents already described or still to be described, can of course also be used as secondary oxidizing agents.

Peroxides with a covalent bond primarily include peroxoborates, peroxo (di) sulfates, peroxo (di) phosphates and organic peroxo compounds. Due to the relatively low MAK value of phosphorus, peroxophosphates and peroxodiphosphates are not described further. However, their use is not excluded, in particular to achieve special properties of the oxidizing agent mixture.

Of the available peroxosulfates, potassium hydrogen peroxosulfate is particularly advantageous because it is a commercial product, which in turn can reduce production costs accordingly. Other peroxosulfates can of course be produced by appropriate syntheses and thus used in the oxidizing agent mixture.

Of the peroxodisulfates, compounds with NH are commercially available. ^"1" , Na ⁺ or K ⁺ cations are available and can therefore be used particularly advantageously in the oxidizing agent mixture. The ammonium peroxodisulfate has an essentially balanced oxygen balance due to the high proportion of hydrogen, while the corresponding sodium or potassium analogues show a positive oxygen balance (20.2% and 17.8%). Another advantage of these compounds is that they are not hygroscopic, and that, with the exception of sodium and ammonium peroxydisulfate, the solubility in water is low and these compounds do not bind water of crystallization, which in turn has a positive effect on the storage conditions. Of the peroxoborates, especially the sodium peroxoborate (NaBO .x H ₂ O) can be used advantageously because it exists in addition to the tetrahydrate, trihydrate and the monohydrate in a water-free form.

For the organic peroxide compounds, the oxygen balance is mostly negative due to the carbon content. This is due to the fact that the oxygen balance is calculated on CO ₂ . As already mentioned, however, CO _{2 is in} equilibrium with CO via the Boudouard equilibrium, so that when calculating the oxygen balance on CO compounds with few C atoms can have a positive oxygen balance. In general, you can choose between alkyl hydroperoxides (ROOH), dialkyl hydroperoxides (R 1 -OOR 2), peroxocarboxylic acids (R-CO-

OOH), peroxocarboxylic acid esters (R ^] -CO-OOR ² ) and diacyl peroxides (R ^ CO-OO-

2 CO-R) can be distinguished. Examples of these classes are octadecyl hydroperoxide (nC ₁₈ H ₃₇ -OOH), dicumyl peroxide (PhC (CH ₃ ) ₂ -OOC (CH ₃ ) ₂ Ph), peroxododecanoic acid (Ci ι H ₂₃ -CO ₃ H), peroxobenzoic acid (Ph -CO ₃ H), tert-

Butyl monoperoximalein esters and dibenzoyl peroxide (Ph-CO-O-O-CO-Ph) are mentioned, these compounds advantageously having a reasonably high melting point with the lowest possible carbon number.

Furthermore, dibenzoyl peroxide, for example, can be used in ignition mixtures as an organic peroxide, although this compound is not an oxidizing agent in the actual sense, since the oxygen balance is very negative. However, there is the possibility that glowing soot particles can contribute to the ignition of the propellant charge powder in the event of incomplete combustion, so that use in the oxidizing agent mixture according to the invention is entirely advantageous. In addition, dibenzoyl peroxide is available as a technical commercial product at an affordable price, which means that the manufacturing costs can be reduced accordingly.

In addition, however, other peroxide compounds, such as, for example, peroxy hydrates, such as, for example, Na CO ₃ . 1.5 H ₂ O ₂ or (NH ^) ₂ CO ₃ .HO ₂ can be used. Likewise, hyperoxides, such as potassium superoxide (K0 ₂ ), can be provided in the oxidant mixture with appropriate precautions - KO2 reacts easily with water. There is also the possibility that complex peroxo compounds, ie compounds of multivalent transition metals, can be used. Because of the toxicity, however, compounds with Ti, Mo or W are predominantly used in the oxidizing agent mixture. However, this should not mean that if the corresponding limit values are observed, such transition metal complexes, which a corresponding - -

correspondingly higher hazard potential cannot be used.

With regard to the carbonates, it should be noted that very many are in the form of hydrates and are hygroscopic, so that appropriate precautions should be taken when using them.

An exception is SrCOo, for example, because it is neither hygroscopic and is only known as an anhydrous substance. In addition, it is advantageous that no limit is currently set for Sr and that, in particular, reaction products which are not very toxic also result from the carbonate ion. The oxygen balance is 10.8%,

3 counts on CO, positive, likewise the SB (Vol) value with 40.3 g / cm, again calculated on CO, shows a favorable possibility for the use of SrCO. SrCO is thermally very stable and therefore only releases oxygen at higher temperatures, so that it can be used as a moderator. Glowing SrO particles can also help ignite the explosive formulation. It is also conceivable that SrCO is mixed with Sr (NO ₃ ) 2 for the oxidizing agent mixture, which on the one hand can advantageously reduce the hygroscopicity of the entire oxidizing agent mixture - Sr (NO) 2 is hygroscopic - without being particularly dangerous due to the Clouds of smoke should be respected.

In addition to SrCOo, CaCO ₃ can also be used due to its non-hygroscopic nature. It is also advantageous that it is practically insoluble in water and organic solvents, so that the processability for the finished explosives formulation can be correspondingly facilitated. The resulting CaO in turn contributes to the formation of glowing particles which ignite the propellant powder due to its high melting point and CaCO is particularly miscible with Sr (NO) 2, which in turn has a more or less negative influence on the entire compound Can positively influence oxidizing agent mixture. The oxygen balance

3 is 1166 %% bbzzww .. ddiiee vvoolluummssbbeezzooggeennee SSaauueerrssttoofffbilanz with 46.8 g / cm (each calculated on CO), comparable to that of the SrC0 ₃ .

Finally, it is also advantageous to use an oxidizing agent mixture containing sulfate in the explosive formulation. However, it should be noted that these compounds are mostly hygroscopic and therefore easily form hydrates. In contrast, K2SO and SrSO ^ are not hygroscopic and can therefore be used particularly advantageously. However, it could have the disadvantage that the oxygen balance of the sulfates should be set rather low, the oxygen being released from the SO ₃ formed in the reaction only with relative difficulty. The consequence of this is that sulfates can advantageously only be used as oxidizing agents in oxidizing agent mixtures, for example in conjunction with Sr (NO) ₂ . The advantage here is that they can act as moderators due to this slow release of oxygen. The addition of SrSO ^ to Sr (NO) ₂ - is particularly advantageous.

However, other organic compounds, such as oxalates, can also be advantageously added to the oxidizing agent mixture. For example, there is the possibility of using oxalates with Na, Sr or Sn. Their nonhygienic copicity and their insolubility in water or alcohol are advantageous. In particular, because of the improvement in the properties of the oxidizing agent mixture, compositions of Sr (NO ₃ ) 2 with SrC2θ _{ι4 are} advantageous.

In addition, due to their oxygen balance (again calculated on CO), the oxalates mentioned are approximately 20% usable.

As already mentioned at the beginning, the toxic behavior of the explosive formulation not only counts for that of the oxidizing agent or the oxidizing agent mixture, but should also be considered in the entirety of the properties of this formulation. Since these explosive formulations usually also contain reducing agents, their toxicity, or the reaction products resulting therefrom, should be checked, in particular since they are mostly metals, and the amount to be used can thus be based on the limit value to be achieved in each case.

The use of base metals, i.e. that is, oxygen-affine metals as reducing agents. Of particular interest here are Mg, Ti, Zr, Mo, W, Fe, Zn and Al as well as B and Si due to their air stability and low toxicity. However, this does not preclude the use of metals of higher toxicity if the relevant limit values are observed.

Another advantage is that most metals passivate, that is, form a protective layer that protects against oxidation, so that these metals, in particular the powders produced therefrom, are easier to handle. If very fine powders are used, appropriate precautionary measures should be taken due to their pyrophoric properties due to the large surface area. Conversely, the surface area of these powders should of course not be too small, since this can unnecessarily worsen the reactivity of these reducing agents. Compared to very fine powder, it is advantageous that such screening lines can be used at lower prices. On the other hand, however, the proportion of reducing agent in the primer is usually around

5% is limited, so that the reference price is less important than that of the oxidizing agents.

It follows that the powders used have such a small grain size that the surface and the reactivity are high, even if their handling is more problematic.

It is also advantageous if the energy made available as a result of this reaction assumes a very high value. The elements Zr and Ti have proven to be particularly advantageous since they have a relatively high value of -1094 kJ / mol and -944 kJ / mol (based on the metal). The calculation is based on the oxidation of Zr to ZrÜ2 or Ti to Tiθ2. In addition, Mg (-601 kJ / mol), Mo (-745 kJ / mol), W (-838 kJ / mol), Zn (-349 kJ / mol), B (-632 kJ / mol), Al also provide (-838 kJ / mol), Si (-859 kJ / mol) and C (-394 kJ / mol) usable energy gains. The data in turn relate to the metal and are calculated for Mo on the oxidation to MoO, for W to WOτ, for Si to SiO 2 and for C to CO ₂ .

Of course, metals whose formation enthalpies are lower, such as iron, can also be used.

In the above figures, however, it must also be taken into account that oxygen can be the limiting factor, so that the conditions shown can change accordingly, especially if the enthalpy is based on 1 mol of O ₂ . From this point of view, Mg, AI, Zr and Ti provide the most energy.

On the other hand, B can develop the highest energy in relation to the energy provided per unit volume.

From this point of view it becomes clear that the use of the respective element in the explosive formulation to be manufactured can depend on the particular circumstances desired, so that the most varied of metals are specifically designed for the speaking application can be particularly advantageous.

In addition to the pure metals, natural alloys, in particular the less toxic metals, can be used. For example, the use of equimolar Al-Mg alloys is advantageous. In addition, of course, various mixtures of individual metals or alloys with metal powders can also be used as reducing agents.

In addition to the substances mentioned above, intermetallic compounds can also be used. For example, it is possible to add silicides, for example calcium silicides, in particular Ca ₂ Si, CaSi or CaSi, to the explosive formulation as reducing agents.

Of course, other intermetallic compounds not listed here can serve the same purpose.

The use of metal hydrides is also possible, TiH ₂ and ZrH2 in particular having proven to be advantageous owing to their resistance and their non-hygroscopic properties. When calculating the individual components of the explosives formulation, however, it should be borne in mind that metal hydrides have an increased oxygen requirement compared to the metals due to the hydrogen content.

Finally, the possible use of metal carbides, in particular covalent carbides, as a reducing agent should also be mentioned. The advantage here is that carbides generally react inertly and are insoluble in water, organic solvents, acids or alkalis. In particular, TiC, ZrC and WC should be mentioned, because these carbides are available in various qualities due to their use in the hard metal industry at reasonable prices. The advantage of using carbides over metal powders is that they are easier to handle, but again it should be noted that at higher temperatures, as e.g. when the ignition mixture according to the invention is to be expected, these carbide powders are quickly oxidized and the oxygen requirement of the entire explosive formulation is in turn increased by the additional carbon content.

To better illustrate the invention, it will be explained in more detail below with the aid of individual examples, but it should be mentioned here that WO 00/66517-23 - PCT / ATOO / 00109

The large number of possible combinations for oxidizing agents and / or reducing agents are only given as individual examples, but this does not preclude the use of other formulations which likewise fall under the scope of protection.

In order to achieve the advantages of the invention, the oxidizing agent mixture can comprise several individual oxidizing agents, in particular 2, 3, 4 or 5. Of course, this also applies to the reducing agents or mixtures used.

An inventive, in particular low-pollution primer cap can be between 18 wt% and 35 wt%, especially between 22 wt ^<7r and 30 wt% of an explosive or a mixture of explosives included. Possible explosives that could be used would be, for example, DDNP (diazodinitrophenol) or tetrazene. Of course, usual other explosives can be contained or at least partially replace the explosives mentioned. An explosive formulation according to the invention can contain, for example, approximately 27% by weight of DDNP and 8% by weight of tetrazene.

Furthermore, the primer cap can contain at least one fuel, e.g. Ball powder, to an extent between 8 wt .-% and 20 wt .-%, in particular between 1 1.5 wt .-% and 18.7 wt .-%, have.

The proportion of the oxidizing agent mixture in the overall formulation can be between 30% by weight and 70% by weight, in particular between 43.5% by weight and 57.8% by weight. The oxidizing agent mixture can be produced from the aforementioned oxidizing agents in any mixing ratio.

In addition, the primer according to the invention or the secondary products made therewith can contain at least one reducing agent, e.g. Titanium powder, between 1% and 20% by weight, in particular 2.9% and 15.7% by weight, e.g. Contain 5.8% by weight.

Of course, so-called friction agents, e.g. Glass powder, in the range between 0.1% <7r and 7% by weight, in particular between 1.3% and 5.2% by weight, e.g. 3.9% by weight may be included.

Finally, various other processing aids and auxiliaries, such as, for example, binder materials, for example gum arabic, can be used. A possible oxidizing agent mixture can, for example, 45.7% by weight of Sr (NO) ₂ as the main oxidizing agent and in small amounts, for example 5% by weight, of at least one further oxidizing agent selected from the group consisting of SrO ₂ , SrCO, SrSO ^ or SrC ₂ O. ^ included. The last-mentioned four oxidizing agents can in total be at least approximately 4% by weight or each of these oxidizing agents can be present to the extent of at least approximately 5% by weight in addition to the main oxidizing agent. Of course, it is possible that these last-mentioned oxidizing agents at least partially substitute the main oxidizing agent Sr (NO) ₂ , so that the properties, such as shelf life, hygroscopicity, toxicity, processability etc., can be adapted to the desired requirements within wide limits. In addition, it is of course also possible for the oxidizing agent mixture to contain further oxidizing agents in addition to the five oxidizing agents mentioned, again an extent of up to 5% by weight being possible.

Another possible oxidizing agent mixture consists, for example, of 50% by weight calcium or potassium peroxodisulfate and 50% by weight of Sr NO, this oxidizing agent mixture in turn making up a total proportion of the ignition mixture of approximately 45% to 55% by weight, e.g. 50% by weight.

Furthermore, it is possible that the oxidizing agent mixture, which may be present in the entire explosive formulation to an extent between 30% by weight and 60% by weight, for example 49% by weight, consists of Sr (NO) 2, KNO and / or CsNO ₃ , where the latter nitrates can in turn be present either as additional oxidizing agents or as oxidizing agents substituting for strontium nitrate. The quantitative proportion can be in the range between 3% by weight and 10% by weight, in particular 4.5% by weight and 6.7% by weight, for example 5.3% by weight.

It is also possible that, in addition to Sr (NO) 2, various oxides, such as MoO, WO, SnO ₂ , various peroxide compounds, for example MgO ₂ , Sr0 ₂ , ZnO ₂ ,

Na ₂ S ₂ O, K ₂ S ₂ O or dibenzoyl peroxide to the extent between 2.5% by weight and 8.3% by weight, in particular 3.1% by weight and 5.6% by weight, for example 3.4% by weight, are present and these compounds can of course occur individually or in mixtures or these oxidizing agents can at least partially replace the Sr (NO) ₂ .

In addition, mixtures are also conceivable which contain about 50% by weight of Sr (N0 ₃ ) and up to 7% by weight of CaCO ₃ . Of course, it is also possible that the oxidizing agent mixture contains no strontium nitrate and that at least two, preferably several of the various oxidizing agents mentioned are involved in the explosive formulation in a total amount of approximately 55% by weight. The proportion of the respective oxidizing agent in the total oxidizing agent mixture can range between 0.5% by weight and 9

% By weight, especially between 2.3% and 7.7% by weight, e.g. 5, 1 wt. Are, of course, also possible in individual cases proportions of the oxidizing agent mixture which identify one of the oxidizing agents mentioned as the main constituent of the mixture, so that this oxidizing agent is involved in the oxidizing agent mixture, for example, to an extent of up to 99% by weight.

In addition to the effect of the low-pollutant formulation of the explosives or the achievement of the properties already mentioned, other parameters of the primer, for example the flame temperature, i.e. the temperature of the flame during combustion, the pressure / time behavior, the energy content, the gas volume, can also be selected by appropriately selecting the composition of the oxidant mixture , the sensitivity or insensitivity can be set. For example, the flame temperature and / or the pressure / time properties can be controlled by secondary oxidizing agents, for example copper oxide, zirconium oxide, zinc oxide etc., with a maximum of up to 25% by weight in addition to Sr (NO ₃ ) ₂ .

As already mentioned, the hygroscopicity of the oxidizing agents also plays an important role and, by suitable choice of the oxidizing agent mixture, those oxidizing agents which do not meet this requirement can also be used. Thus, for example, Sr (NO) _{2 can be} at least partially replaced by further oxidizing agents, so that the overall hygroscopicity of the explosive formulation can be reduced. Sr (NO) ₂ , which can be used in crystal water-free form, can form Sr (NO) ₂ .4 H ₂ O during processing at too low temperatures or during storage under contact with water, eg air humidity.

With regard to Sr (NO ₃ ) ₂ , it should be mentioned at this point that processing this nitrate at over 30 ° C is advantageous because at this temperature the water of crystallization can escape or no hydrate formation takes place and thus also aqueous processing, for example the climb is possible.

With regard to the reducing agents that can be used, of which Mg, Ti, Zr, Mo, W, Fe, Zn, B, Al, Si, calcium silicide, TiH, ZrH ₂ , TiC, ZrC and advantageously WC can be used, the corresponding quantitative proportion of the formulation has already been mentioned, so that no further discussion is necessary. At this point, however, it should be expressly mentioned again that a mixture of several of these agents is also possible for the reducing agents, again taking care of the toxic properties. The proportion of the individual reducing agents in the mixture can be up to approximately 95% by weight.

By adding certain reducing agents, e.g. Metal powders, the energy content of the explosive formulation can be at least partially defined, e.g. be increased. For example, the energy content when using strontium nitrate as the oxidizing agent and Ti as the reducing agent is approx. 2.94 kJ / g. By adding e.g. Magnesium or other metal powders can increase this energy content.

However, the energy content can also be at least partially defined by the composition of the oxidizing agent mixture. Furthermore, the energy content can range between 2 kJ / kg and 6 kJ / kg.

The gas volume can also be increased by adding components which advantageously form many gaseous reaction products. On the other hand, by adding certain reducing agents and / or oxidizing agents, the oxides to be melted can react and the gas volume can be reduced.

Furthermore, the sensitivity / insensitivity behavior can at least partially be changed in a targeted manner by a suitable choice of the individual oxidizing and / or reducing agents and / or the explosive and / or the further explosive. As is known, on the one hand the primer charge should not be too sensitive, but on the other hand it must have a certain sensitivity. This sensitivity / insensitivity behavior can be controlled in addition to the purely mechanical components by changes in the composition, in particular by choosing suitable friction agents, but also by choosing the oxidizing agent mixture. For example, For a primer mixture in a primer (boxer version) with a diameter of 4.5 mm, a firing pin radius of 1 mm, a falling weight of 55 g and at a temperature of 20 ° C the sensitivity between 1 1 cm and 24 cm and insensitivity between 6 cm and 13 cm can be set.

In addition to the components already mentioned, ethylenediamine dinitrate can be used as the primary, secondary or tertiary explosive in the explosive formulation WO 00/66517-27 - PCT / ATOO / 00109

are, the hygroscopicity can in turn be controlled by appropriate choice of the oxidizing agent mixture or the reducing agent. Furthermore, hexanitrodiphenylamine, mannitol hexanitrate, octogen, picric acid or the like can be used as the explosive.

In addition, of course, other additives such as stabilizers, thickeners, combustion moderators, polymer binders, hardeners or the like can also be used and the corresponding components can be found in the prior art.

The ignition mixtures according to the invention or the products produced therefrom can be used, for example, in ammunition, e.g. in 9mm cartridges. Of course, these mixtures can also be used for various other purposes, e.g. in airbag systems. In the event that these mixtures are used in cartridges or the like, the ammunition produced with them can be tailored to the properties of the corresponding weapon. So it is e.g. possible by the composition of the ignition mixture to adapt the burning rate to the amount of powder. A change in time / pressure behavior is of course also possible due to the selected composition.

It is advantageous that these oxidizing agent mixtures or the primers according to the invention are used in cartridges, e.g. dimension 9 mm x 19, can be set so that, in addition to reducing pollutants, they are also completely trouble-free, even at extreme temperatures and after exposure to moisture, with the hygroscopicity of the individual components again coming into play, and after prolonged storage, let shoot, the shooter and functional safety and accuracy can be improved or guaranteed.

Through the appropriate choice of the oxidizing agent composition or the reducing agent, it is possible that the maximum permissible limit values for a work place for the substances released from the ignition and propellant charge charge are not exceeded with suitable and switched on or also non-existent ventilation.

It is advantageous that, due to the materials used, the shape and color of the tube interior is not, or only insignificantly, changed by corrosive gases. - -

It is also advantageous that e.g. a lower ignition safety limit does not fall below 76 mm and an upper ignition safety limit is approx. 305 mm. The test is carried out by the so-called run-down test with statistical security calculation. Testing is carried out according to the so-called drop hammer method, in which the sleeve with inserted firing cap is received in a barrel holding unit and the firing cap is loaded with a 55 g ball using a firing pin with an acute radius of 1 mm.

In addition, with the compositions according to the invention it is possible to achieve a predetermined gas pressure with only slight deviations over a wide temperature range, e.g. when using a certain type of ammunition and powder charge at 21 ° C an average gas pressure of at most 280 MPa. For individual values, the gas pressure can be set so that it does not exceed 265 MPa. It is also possible, by appropriate choice of the formulation, that the deviation of the mean gas pressure at 52 ° C or -30 ° C is at most 65 MPa.

It is also advantageously possible to achieve a predetermined bullet speed for a certain ammunition with only slight deviations, e.g. at 21 ° C between 370 m / s and 420 m / s, whereby the deviation of the average lock speed at 52 ° C or 30 ° C can be a maximum of 30 m / s. In addition, the hit accuracy can be set to 2.5 cm at 50 m shooting distance.

Of course, the ammunition according to the invention can be set to any type of weapon, for example pistols of the types P5, P6, P7, P10 and the H&K weapon system, MP5, in such a way that proper functioning can be guaranteed.

With regard to the shelf life test according to the NATO test (Climatic Storage Test, Section 11), it is possible to adjust the explosive formulation in such a way that the ballistic limit values are maintained after 30 days of storage under extreme temperatures.

The deviations from gas pressure and floor speed can be minimal.

It is also advantageous that the use of the explosive formulation according to the invention enables the 90 ° C. weight loss test and the Bergmann-Jung test and Hol- land test can be passed.

To analyze the dust, the dust can be collected using a diaphragm pump, which continuously sucks air through an open filter. The membrane filter can consist of type SM 1 1301 with a pore size of 8 μm and can

3 Suction rate between 3.5 to 4.1 m / h with a filter diameter of 4 cm and a suction speed in the range between 0.77 to 0.91 m / s.

Two URAS infrared gas analyzers connected in series can be used to measure the CO content. The analysis of the entire dust can be carried out by means of X-ray fluorescence analysis. Individual connection forms of various heavy metals can be identified by means of X-ray diffractometry and IR spectroscopy.

When using the ammunition according to the invention in the shooting operation, it was found that, taking into account a 20-fold air change in the indoor shooting range and a number of 100 shots per shooting range and hour, the pollutants determined did not exceed the MAK value or the 10th part of the respective MAK value to have.

For the production of such ignition mixtures according to the invention, it has proven to be advantageous if the individual components can possibly be pasted with water or with various organic solvents. The corresponding mixture can be prepared in a moist state and spread in a perforated plate of the required size. The mixture can usually be pushed into a tablet form from the perforated plate into the respective capsules.

It is also advantageous in the process according to the invention for producing the explosive formulation if the explosive used, for example DDNP, is cleaned before use, i.e. is recrystallized.

It is advantageous when recrystallizing the DDNP if it is dissolved in acetone and precipitated with water. It is possible that the acetone solution has a temperature of below 20 ° C before adding water. The water added advantageously has a temperature of below 3 ° C., for example 1 ° C. to 3 ° C., and the water can be added within 10 s to 30 s, in particular 20 s. It is also advantageous. when the recrystallized DDNP is washed with ethanol, so that the WO 00/66517-30 - PCT / ATOO / 00109

to remove adhering water. Due to special conditions during recrystallization, a certain crystal form of the DDNP can be achieved, e.g. thin plates with a thickness of less than 5 μm, e.g. 1 μm to 5 μm, an edge length of 30 to 100 μm with a rectangular habit, whereby the angle can vary between 85 ° and 95 °. The length to width ratio can range from 1: 2 to 1: 4. As a result, the impact sensitivity of the DDNP can advantageously be increased and, as a result, the impact sensitivity of the primer. When the primer is subsequently pressed, it is possible that the crystals of the DDNP break and the flake-like crystal form changes into a fragmented form with sharp edges, which can make the set more sensitive.

For the pasting of the mixture, it is advantageous if ethanol is used because it can be achieved that, compared to water, moisture-sensitive components, such as e.g. Strontium nitrate, can be processed more easily. Of course, other organic pasting agents can be used instead of ethanol, it being crucial that the advantage due to the lower boiling point and the improved drying compared to water is achieved.

As already mentioned, when using strontium nitrate tetrahydrate as part of the oxidizing agent mixture, the processing temperatures can be in the range above 30 ° C and advantageously not below 30 ° C, in order to expel the adhering crystal water from the strontium nitrate or the water absorption of strontium nitrate at the same time as the processing to prevent. At this temperature it is advantageous that the strontium nitrate still has a processable hardness. Below 30 ° C, the strontium nitrate absorbs water to form the tetrahydrate. This allows water to be removed from the mixture so that it can dry out and possibly become hard. It is advantageous to use strontium nitrate with little or no water, e.g. up to a maximum of 0.1%.

The oxidizing agent mixture can be composed of potassium and / or sodium peroxodisulfate and at least one additional oxidizing agent, selected from a group comprising tin oxalate, tungsten trioxide, magnesium peroxide and calcium carbonate. The proportion of potassium and / or sodium peroxodisulfate in the total mixture can be between 45% and 50% by weight.

Furthermore, the proportion of the additional oxidizing agent in the oxidizing agent mixture can be between 5% by weight and 50% by weight. Furthermore, at least one oxidizing agent can be selected from a group comprising sodium perchlorate, potassium perchlorate, ammonium perchlorate, copper perchlorate, sodium chlorate, potassium chlorate, ammonium chlorate, barium chromate, lead chromate and mercury chromate.

At least one reducing agent can be selected from a group containing hydrides and / or carbides.

The use of tungsten and / or tungsten compounds in the ignition mixtures according to the invention was also recognized as advantageous, not least because most of these compounds, like the element itself, are largely non-hygroscopic. For example, metallic tungsten and / or tungsten carbide, for example in powder form, can be used both as a reducing agent and as a friction agent.

In particular, the use of tungsten trioxide as an oxidizing agent or part of the oxidizing agent mixture according to the invention has proven to be advantageous. When using W and WO3, the following reactions are known to occur at approx. 1000 ° C and under inert gas:

2 WO3 + W -> 3 WO2

As recognized by the inventor, this reaction also occurs under the conditions when the ignition mixture according to the invention is ignited, at least to a comparable extent, in particular also when elementary W is at least partially caused by metals which are still significantly more oxygen-affinitive, such as e.g. Ti, Zr or the like is replaced. Possible reactions include:

2 WO3 + Ti -> 2 WO2 + TiO2

2 WO3 + Zr -> 2 WO2 + ZrO2

3 WO3 + 2 AI -> 3 WO2 + A12O3

In the presence of other oxygen carriers, it is also possible to add more metals accordingly. The reaction to WO2 can also be used directly as an energy source for the primer.

When using WC, its extremely high hardness is particularly advantageous, so that it can act as a friction agent and thus the sensitivity can be increased. In contrast to glass, WC is much harder and also has the advantage that it oxidizes from approx. 600 ° C (WC + 3/2 02 -> WO2 + CO). On the one hand, it contributes to energy turnover. On the other hand, no hard particles can get into the barrel after the oxidation, so that a shortening of the life of the weapon, as is the case when using glass, can be excluded.

The formation of WO2 is also particularly advantageous because it has a high density (10.8 g / cm ³ ) and is stable up to relatively high temperatures. At temperatures above approx. 1500 ° C, WO2 even disproportionates to W and WO2.72. W itself has an extremely high density (19.3 g / cm ³ ) and the highest melting point of all metals (3400 ° C). Due to the high oxygen content of WO2.72, this in turn can act as an oxidizing agent, whereby WO2 is formed again.

The main advantage of using tungsten and / or tungsten compounds is the formation of hot particles that have a very high density and a very high melting point. As a result, the ignition of the propellant charge powder is markedly improved compared to igniting charges without the addition of tungsten and / or tungsten compounds.

A further advantage of tungsten and / or tungsten compounds can be stated that the most important representatives (metal, oxides, carbides) are not hygroscopic. This simplifies storage and processing and is more economical. WO3, W and WC are also an intermediate product in the production of hard metals in different grain sizes. This means that these fabrics can be purchased directly at relatively low prices.

The most likely reaction products when using tungsten and / or tungsten compounds are various tungsten oxides (WO2.90, WO2.72, WO2), all of which are water-insoluble and thus have a MAK value or OSHA value of 5 mg / m ³ . A health hazard from firing such ammunition is not expected. The use of MoO3 is also advantageous since it shows reactions which are essentially comparable to WO3.

In the following, some non-limiting examples of compositions are given, with which the above advantages can be achieved. DDNPs in the range between 5% by weight and 50% by weight, in particular between 15% by weight and 40% by weight, tetrazene in the range between 1% by weight and 15% by weight, in particular between 1 , 5% by weight and 10% by weight, spherical powder to the extent between 2% by weight and 20% by weight, in particular between 3% by weight and 15% by weight, cesium nitrate and / or potassium nitrate to the extent between 5% by weight and 70% by weight, in particular between 10% by weight and 40% by weight, titanium to the extent between 1% by weight and 20% by weight, in particular between 1% by weight and 14% by weight, tungsten in the range between 1% by weight and 40% by weight, in particular in the range from 1% by weight and 30% by weight, tungsten carbide in the range between 2% by weight and 25% by weight, in particular between 3% by weight and 24% by weight, calcium silicide in an amount between 1% by weight and 25% by weight, in particular between 1% by weight and 14% by weight and tungsten trioxide in an amount between 1% by weight % and 30% by weight, in particular between 1.5% by weight and 25% by weight. The respective composition is of course to be understood in such a way that a total of 100% by weight is present. This also applies to all of the compositions mentioned

Example 1

DDNP 20-30

Tetrazen 3 - 6

Ball powder 5 - 10

Cesium nitrate 30-60

Titan 2 - 10

Tungsten carbide 5 - 15 further oxidizing agents 1 - 25

(WO3, ZnC2O4, Fe2O3,

Sr (NO3) 2)

Example 2 Share in mass%

DDNP 20-30

Tetrazen 3 - 6

Ball powder 5 - 10

Potassium nitrate 15-30 Cesium nitrate 15-30

Titan 2-10

Tungsten 5-25

Example 3 Share in mass%

DDNP 20-30

Tetrazen 3 - 6

Ball powder 5-10

Potassium nitrate 15-30 cesium nitrate 15-30

Titan 2-10

Calcium Silicide 2-10

Tungsten 5-25

Example 4 Share in mass%

DDNP 20-30

Tetrazen 3-6

Ball powder 5 - 10

Potassium nitrate 15-30 cesium nitrate 15-30

Titan 2-10

Tungsten carbide 5-15

Example 5 Share in mass% DDNP 20-30

Tetrazen 3 - 6

Ball powder 5 - 10

Potassium nitrate 15-30

Cesium nitrate 15-30 titanium 2-10

Tungsten 5-25

Example 6 Share in mass%

DDNP 20-30 tetrazen 3-6

Ball powder 5 - 10

Potassium nitrate 15-30 Cesium nitrate 15-30 titanium 2-10

Calcium Silicide 2-10 Tungsten 5-25

Example 7 Share in mass% DDNP 20-30 tetrazene 3-6 ball powder 5-10 potassium nitrate 15-30 cesium nitrate 15-30 titanium 2-10 calcium silicide 5-15

Example 8% by mass% DDNP 20-30 tetrazene 3-6 ball powder 5-10 cesium nitrate 30-60 tungsten trioxide 2-20 titanium 2-10 tungsten carbide 5-15

Example 9% by mass% DDNP 20-30 tetrazene 3-6 ball powder 5-10 cesium nitrate 30-60 tungsten trioxide 2-20 titanium 2-10

Tungsten 5-15

Example 10 Share in mass% DDNP 20-30 tetrazen 3-6

Ball powder 5 - 10 cesium nitrate 30 - 60 Tungsten trioxide 2 - 20

Titan 2-10

Calcium Silicide 5-15

Example 11 Share in mass%

DDNP 20-30

Tetrazen 3-6

Ball powder 5 - 10

Cesium nitrate 30 - 60 tungsten trioxide 2 - 20

Titan 2-10

Calcium silicide 5-15

Example 12 Share in% by weight of DDNP 20-30

Tetrazen 3 - 6

Ball powder 5 - 10

Tungsten trioxide 2 - 60

Titan 2-10 tungsten carbide 5-15

Example 13 Percentage by Weight

DDNP 20-30

Tetrazen 3-6 ball powder 5 - 10

Tungsten trioxide 20-60

Tungsten 5-25

Tungsten carbide 5-15

Finally, it should be mentioned that not only non-metallic explosives can be used as described above, but rather is

Use of, for example, heavy metal compounds, for example azides such as, for example, lead azide, mercury fullminate, lead nitro-resorcinate or the like, is possible since no health hazard is to be expected on the basis of the formulation of the ignition mixture according to the invention. The individual versions described can form the subject of independent solutions according to the invention. The relevant tasks and solutions according to the invention can be found in the description.

Claims

WO 00/66517 - 38 - PCT / ATOO / 00109P claims

1. Ignition mixture of at least one impact-sensitive, non-metallic explosive, optionally at least one further impact-sensitive, non-metallic further explosive, optionally at least one fuel, and an oxidizing agent mixture, characterized in that the maximum proportion of the individual oxidizing agents on the explosive (s) and optionally the total mixture (s) existing in a region surrounding it is determined by a predetermined maximum limit concentration of the reaction product (s) of the oxidizing agents after the redox reaction.

2. Ignition mixture of at least one impact sensitive explosive, optionally at least one further impact sensitive explosive, optionally at least one fuel, optionally at least one reducing agent and at least one oxidizing agent, characterized in that the at least one oxidizing agent is a tungsten compound, e.g. Is tungsten trioxide and / or a precursor of an oxidizing agent which is reacted, in particular at elevated temperature and / or pressure, by a reaction, e.g. Disproportionation forms the oxidizing agent.

3. Ignition mixture according to claim 1, characterized in that the limit concentration is the maximum workplace concentration.

4. Ignition mixture according to claim 1, characterized in that the limit concentration is the OSHA value.

5. Ignition mixture according to claim 2, characterized in that an oxidizing agent mixture is contained with at least one further oxidizing agent.

6. Ignition mixture according to one or more of the preceding claims, characterized in that the oxidizing agent mixture consists of at least two or three or four or five different oxidizing agents.

7. ignition mixture according to one or more of the preceding claims, characterized in that at least one oxidizing agent from a strontium nitrate, cesium nitrate, potassium nitrate, aluminum nitrate, calcium nitrate, copper (II) nitrate, iron (III) nitrate, magnesium nitrate, zinc nitrate and barium nitrate group 517 - -

is selected.

8. Ignition mixture according to one or more of the preceding claims, characterized in that at least one oxidizing agent is selected from a group comprising MoO, WO ₃ , Fe ₂ O, MnO ₂ , PbO ₂ , TiO, CuO and SnO ₂ .

9. Ignition mixture according to one or more of the preceding claims, characterized in that at least one oxidizing agent is selected from a group comprising magnesium peroxide, strontium peroxide, zinc peroxide, barium peroxide, ammonium peroxodisulfate, sodium peroxodisulfate, potassium peroxodisulfate and dibenzoyl peroxide.

10. Ignition mixture according to one or more of the preceding claims, characterized in that at least one oxidizing agent is selected from a group comprising strontium carbonate, calcium carbonate and magnesium carbonate.

11. Ignition mixture according to one or more of the preceding claims, characterized in that at least one oxidizing agent is selected from a group comprising strontium sulfate and potassium sulfate.

12. Ignition mixture according to one or more of the preceding claims, characterized in that at least one oxidizing agent is selected from a group comprising strontium oxalate, sodium oxalate and tin oxalate.

13. Ignition mixture according to one or more of the preceding claims

2 to 13, characterized in that the precursor of the oxidizing agent is a non-stoichiometric oxide of tungsten, for example WO Q, W0 _{7 72} and / or molybdenum.

14. Ignition mixture according to one or more of the preceding claims, characterized in that the oxidizing agents contained are not hygroscopic.

15. Ignition mixture according to one or more of the preceding claims, characterized in that the oxidizing agents contained have no water of hydration.

16. ignition mixture according to one or more of the preceding claims, characterized in that the proportion of a further oxidizing agent, for example strontium peroxide, strontium carbonate, strontium sulfate, strontium oxalate and magnesium oxide, in the oxidizing agent mixture is between 5% and 50% by weight.

17. Ignition mixture according to one or more of the preceding claims, characterized in that the strontium nitrate contains no water of crystallization.

18. Ignition mixture according to one or more of the preceding claims, characterized in that at least one additional reducing agent is included.

19. Ignition mixture according to one or more of the preceding claims, characterized in that the reducing agent or mixture is present in an amount between 1% by weight and 15% by weight, based on the total composition.

20. Ignition mixture according to one or more of the preceding claims, characterized in that at least one reducing agent is selected from a group containing Mg, Ti, Zr, Mo, W, Fe, Zn, B, Al and Si.

21. Ignition mixture according to one or more of the preceding claims, characterized in that at least one reducing agent is selected from a group containing Ca2Si, CaSi and CaSi2.

22. Ignition mixture according to one or more of the preceding claims, characterized in that at least one reducing agent is selected from a group containing TiH ₂ and ZrH ₂ .

23. Ignition mixture according to one or more of the preceding claims, characterized in that at least one reducing agent is selected from a group containing TiC, ZrC and WC.

24. Ignition mixture according to one or more of the preceding claims, characterized in that at least one friction agent is included.

25. Ignition mixture according to one or more of the preceding claims, characterized in that friction agents in an amount between 0.1% by weight and 5th

% By weight is present.

26. Ignition mixture according to one or more of the preceding claims, characterized in that the friction agent consists of a glass, W, tungsten carbide, e.g. Group containing WC is selected.

27. Ignition mixture according to one or more of the preceding claims, characterized in that the flame temperature is defined by the composition of the oxidizing agent mixture.

28. Ignition mixture according to one or more of the preceding claims, characterized in that the flame temperature by the selection of the or

Reducing agent is defined.

29. Ignition mixture according to one or more of the preceding claims, characterized in that the flame temperature is in the range between 1500 ° C and 4500 ° C.

30. Ignition mixture according to one or more of the preceding claims, characterized in that the time / pressure behavior of the overall mixture is defined by the composition of the oxidizing agent mixture.

31. Ignition mixture according to one or more of the preceding claims, characterized in that the time / pressure behavior of the overall mixture is defined by the selection of the reducing agent or agents.

32. Ignition mixture according to one or more of the preceding claims, characterized in that the time to rise in pressure is in the range between 0.01 ms and 2 ms, preferably 0.15 ms.

33. Ignition mixture according to one or more of the preceding claims, characterized in that the maximum pressure is reached after a time which in

Range is between 0.1 ms and 4 ms, preferably 0.35 ms.

34. Ignition mixture according to one or more of the preceding claims, characterized in that the gas volume of the total mixture is at least partially defined by the composition of the oxidizing agent mixture.

35. ignition mixture according to one or more of the preceding claims, characterized in that the gas volume of the total mixture is at least partially defined by the selection of the reducing agent (s).

36. ignition mixture according to one or more of the preceding claims,

3 characterized in that the gas volume is in the range between 150 cm / g and 3 500 cm / g.

37. Ignition mixture according to one or more of the preceding claims, characterized in that the explosive is selected from a group containing diazodinitro-phenol (DDNP) and potassium 4,6-dinitrobenzofuroxane (KDNBF).

38. Ignition mixture according to one or more of the preceding claims, characterized in that the explosive to an extent between 9% and

60% by weight, based on the total mixture, is present.

39. Ignition mixture according to one or more of the preceding claims, characterized in that the DDNP is present purified by dissolving in an organic solvent and precipitation with water.

40. Ignition mixture according to one or more of the preceding claims, characterized in that the further explosive is selected from a group containing tetrazene and nitromannite.

41. Ignition mixture according to one or more of the preceding claims, characterized in that the further explosive in an amount between 0.1 wt.

% and 15% by weight, based on the total mixture.

42. Explosive formulation from a mixture of an ignition mixture, at least one other explosive and optionally further additives, characterized in that the ignition mixture is formed according to one or more of the preceding claims.

43. A method for producing an ignition mixture consisting of at least one explosive, optionally at least one fuel, an oxidizing agent mixture of at least two oxidizing agents, at least one reducing agent and optionally at least one friction agent, in particular according to one of claims 1 to 77, characterized in that the individual Educts be pasted with an organic solvent or mixture.

44. The method according to claim 43, characterized in that between 9.0 wt .-% and 60 wt .-% of the impact sensitive explosive (s), between 0 wt% and 15 wt% of the further impact-sensitive, non-metallic explosives (s), between 5% and 30% by weight of the fuel or fuels ^), between 20% and 70% by weight of the oxidizing agent mixture, between 1% and 15% by weight of the or the reducing agent and between 0.1% and 5% by weight of the friction agent or agents are mixed together.

45. The method according to any one of claims 43 or 44, characterized in that ethanol, a higher alcohol, or the like is used as the pasting agent.

46. The method according to any one of claims 43 to 45, characterized in that DDNP is used as the explosive by recrystallization.

47. The method according to any one of claims 43 to 46, characterized in that the DDNP is dissolved in acetone and precipitated again with water.

48. The method according to any one of claims 43 to 47, characterized in that the starting materials used are free of water of crystallization.