DE2335317A1 - EXPLOSIVE SUBSTANCES - Google Patents

Description

The invention relates to new mixtures of substances and, more particularly, to new explosive mixtures of substances.

Explosive mixtures in pulpy form which contain oxidizing salts, fuel, sensitizers and water as well as, if necessary, conventional additives are known. While these mixtures are predominantly satisfactory as explosives, the disadvantage was that their sensitivity to detonation tends to vary from batch to batch of production. In particular, the detonation sensitivity of such mixtures tends to decrease from the original value during the mixture, prolonged storage or after pumping into boreholes.

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Among the materials proposed so far for use in pulpy explosives are alloys, certain non-metallic elements or metals, especially in finely divided form, which give the explosive its energy. So far, the use of various substances with a high thermal energy content has been proposed, including aluminum, silicon, ferrosilicon, ferrophosphorus, magnesium, titanium, boron and their mixtures, eg mixtures of aluminum and ferrosilicon. These metals have been suggested as fuels and as sensitizers. In general, these substances were mainly used as fuels. However, if these substances are in very finely divided form, for example in the form of a powder with particles below 0.053 now or with a high specific surface area of up to 2.5 and even 10 or more m / g, certain such metals in the explosive mixture act both as detonation sensitizers as well as fuels. A typical example of a finely divided metal] is fine aluminum powder. While these finely divided metals are extremely suitable as sensitizers, their sensitizing effect decreases increasingly in certain aqueous pulpy explosives when these are standing, pumped, mixed or otherwise exposed to shear stress. It is also known that such pulpy explosives tend to become less sensitive to detonation when in a wet place

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Borehole exposed to water. It was assumed, that such aqueous mixtures with very finely divided metal lose their sensitivity over time, because the metal surface becomes increasingly wet. In order to reduce wetting, it has been proposed to use the finely divided Treat metals with various coating materials or surfactants, which the Making metals hydrophobic. Such materials were, for example, paraffin, stearic acid, calcium stearate or Sebum amine. While these substances are effective for a short time, they become ineffective after longer periods. In particular, it was also found that such-hydrophobized metals be wetted in pulpy explosive mixtures if a common additive such as guar flour is present.

It is an object of the present invention to reduce the detonation sensitivity of pulpy explosives Mixtures improve, and in particular the speed with which these mixtures are insensitive to storage will be to belittle. Furthermore, a pulpy explosive mixture with increased compared to known mixtures Resistance to water can be created.

In Australian patent application PA 9654/72 a new mixture of substances was proposed that

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Reaction product of resin, resin acids or their derivatives with certain metals or alloys. It has now been found that certain of the mixtures proposed there used with advantage for pulpy explosives can be, whereby this compared to known pulpy explosive misehings an increased sensitivity obtain.

The new pulpy explosive mixture of substances consists of at least one oxygen-releasing salt, water, at least one fuel and at least one finely divided detonation sensitizer, which is used as a metallic Component aluminum and / or aluminum series alloys contains, and according to the invention is characterized in that on the surface of at least part of the metallic Component a material selected from the group consisting of resin, resin acids and / or their derivatives in an amount of 0.01 to 2% by weight, preferably from 0.01 to 0.2% by weight? of the detonation sensitizer is bound. As an an example of such a detection sensitizer can be named the product obtained by reacting aluminum powder with Sodium abietate is created and excellent water-repellent Has properties.

The amount of metallic detonation sensitizer

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in the mixtures can be varied within a wide range and depends to some extent on the nature and proportions of the other ingredients in the mixture and the desired level of detonation sensitivity .Mix from. For many purposes, a satisfactory detonation sensitivity can be achieved if the metallic detonation sensitizer up to 10 weight * of the mix. However, larger amounts, for example up to 15 or 20%, can be used if desired will.

The degree of fragmentation of the metallic detonation sensitizer can vary within a wide range. Particles that vary in size from coarse, if, for example, about 20% of the particles on a DIN number lh sieve and about 50% of the particles on a DIN number 2 ^} i sieve, to fine, if, for example, almost all the particles are smaller than about Q. , O ^ mm are sufficient, can be used in a satisfactory manner.

Resin is a solid, resinous material that occurs naturally in pine balsam. It is a complex mixture of mainly resin acids and a small amount of non-acidic components. It can

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starting from the natural form by chemical treatment such as hydrogenation, dehydration, dimerization or polynization can be modified. The naturally occurring and the modified resin can be converted into carboxylic acid derivatives or their salts. the The above resin acids have the typical empirical formula CpyH ^ yü and are cyclic compounds of the general Formula R-COOII, where R is a group with one two double bonds containing ring system, usually a three-ring system. Abietic acid is typical of such Resin acids. Other resin acids worth mentioning are, for example, levopimaric acid, neoabietic acid, palustric acid, Dehydroabietic acid, dihydroabietic acid, tetrahydroabietic acid

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acid, pimaric acid, isopimaric acid, *: '-isopimaric acid, Elliotinonic acid and gandarak pimaric acid. From the typical Salts of the carboxylic acids are alkali metal or alkaline earth metal salts to mention, e.g. sodium or calcium abietate.

The amount of resin, resin acids or their derivatives in the mixtures can vary within a wide range. It depends to a certain extent on the desired detonation sensitivity and on the type and degree of distribution the metallic component on which the resin, the Harzsäux'e or their derivatives is applied. Appropriate amounts

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of resin, resin acids or their derivatives that are in the mixture bound to the metallic component are in the range of 0.0001 to 0.0 * 1 weight ;? the mix for convenience expressed as abietic acid.

The oxygen donating salts suitable for use in the mixtures are those in slurry explosive mixtures commonly used types. You can, for example, inorganic nitrates, chlorates, perchlorates and their mixtures. Preferably the oxygen-releasing Salt chosen from the nitrates of alkali and alkaline earth metals or ammonium. In particular, will Sodium nitrate and ammonium nitrate are preferred. The amount of the oxygen donating salt in the mixtures according to the invention is not strictly limited. It has been found that mixtures with 50 to 90% by weight of oxygen-releasing salts, deliver satisfactory results based on the total mixture; amounts of 65 to 85% by weight are preferred The particle size and shape of the oxygen donating salt is not essential and depends on the technique of ammonium nitrate production known. Powder and prilled particles give satisfactory results.

The proportion of water in the mixture should be sufficient to absorb at least part of the oxygen-releasing inorganic salt and at least a portion of any water-soluble fuel that may be present

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to solve. The water content should also be sufficient to hydrate at least some, preferably all of the thickening agent present. Appropriately makes the present water quantity 5 to 35 Weight-? the whole mix, however, is supposed to be the the amount present is not outside the explosion limit of the mixture. The water content is preferably 5 to 25 weight- ^, especially 12 to 17 weight-? the whole mix.

In this description, fuels are understood to mean substances that are stable in the explosive mixtures are chemically inert to the system prior to detonation and during manufacture and storage are. These substances must be flammable and their physical nature must be such that they can be incorporated into the mixtures and evenly distributed in them. Such fuels are in the art well known. They can be organic or inorganic and can be made from vegetable or animal products /

The fuels used in the mixtures according to the invention can not, for example, even be explosive fuels

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explosive carbonaceous, non-metallic and metallic fuels or mixtures of the aforementioned types of fuel. They can be extremely different. Examples of self-explosive fuels are one or more organic nitrates, nitro compounds and nitroamines a such as trinitrotoluene, cyclotrimethylene _{trinxtramine »Cyclotetramethylene tetranitramine, TetryI 3} pentaerythritol tetranitrate, explosive nitrocellulose and nitro starch»

The self-explosive fuel can for example be in any of the known flake, crystal, or pellet forms. In general, the self-explosive Fuel in an amount up to 35% by weight, preferably from 10 to 30% of the weight of the mixture are used.

Suitable water-soluble fuels are organic water-soluble substances, e.g. urea, carbohydrates such as sugar or hot liquids, water-soluble alcohols or Sylcols, glues or mixtures of these substances. Appropriately the proportion of the water-soluble fuel in the mixture is in the range from 0.8 to 8, preferably from U to 7% by weight of the total mixture.

Suitable water-insoluble or sparingly water-soluble Fuels can be inorganic substances, e.g. sulfur, aluminum, silicon, ferrosilicon, ferrophosphorus, titanium, Boron, their mixtures, such as mixtures of aluminum and ferrosilicon, or organic materials, e.g. fine

Partial charcoal, anthracite, gilsonite, asphalt, cellulose-containing substances such as sawdust, or cereal products such as flour, dextrins or starches. When the inorganic fuel is a metal, e ^r is preferably in granulated or powdered Fo: m in a particle size of coarse, for example, upper grain eimis sieve DIN No. 12, to very fine, for example undersize a sieve mesh # 325..

used. This granulated or powdered metal can be in the form of discrete regularly shaped particles. Metal powders in which the metal is in the form of irregularly shaped particles or in flakes or agglomerations particles or flakes are also useful. Preferred fuels are the metal powders, especially aluminum. The proportion of water-insoluble or sparingly water-soluble non-metallic fuel can expediently be in the range from 1 to 10% by weight, preferably U to ″% by weight of the total mixture. If metallic, water-insoluble fuels are present in the mixtures according to the invention, their Share up to 25% by weight, preferably 0.5 to 20% by weight of the total mixture.

Others common in pulpy explosives If desired, additives can be added to the explosive mixtures according to the invention are added in amounts which are subsequently given in parts by weight per 100 parts by weight of the final mixture are specified. These additives can, for example

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BATH ORIGINAL

Thickeners, such as guar flour or made from carbohydrates biopolymer substances, in amounts of e.g. 0 to 5 parts, crosslinking agents, e.g. zinc chromate, in amounts of e.g. 0> to 0.1 part, and antifoam agents, e.g. ethylhexanol, in amounts of e.g. Obis 0.1 part. If so desired can add additional sensitizers in the form of a gas or a gas mixture, such as air, to the mixtures according to the invention be admitted. They can be in the form of blown-in or ex-agitated air, as blown-in or stirred-in gas can be used. They can also be added as air or gas encapsulated or to the surface of the finely divided material is bound. Alternatively, a Gas, such as nitrogen or carbon dioxide, optionally generated in the mixture by known methods.

Our mixtures have advantages over the well-known br ei ar tiffin explosive mixtures because by the modifying reactant in shape of resin, resin acids or their derivatives "the range of aluminum powders suitable as a sensitizer component Compared to the known aluminum powders used for this purpose is expanded. So it is now possible, for example, the so-called .atomized aluminum powder as sensitizer components to use. As far as we know, these atomized aluminum powders were used in the known Mixtures are used as fuels only and have not previously been considered an effective sensitizer material. Consequently has made the use of these atomized powders cheaper

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Explosive slurries resulted in these powders being less costly than the so-called paint-fine types of aluminum powder used so far.

Our St: off mixtures can be used »for work, which are connected with: blasting »in mining as well as at the preparation of grounds prior to the construction of buildings or machine systems.

Accordingly, a blasting procedure is created »at a pulpy explosive punitive mixture according to the invention filled into a borehole and detonated therein will.

The invention will now be described with reference to the following

Examples are explained in more detail, without this being considered to be a restriction. All parts and percentages relate on the Hewichi, unless otherwise stated. the Examples 1, 2, 4 and 6 are for comparison purposes and do not fall within the scope of the invention.

A prior art mixture was prepared by following the steps given below in a conventional manner Components were mixed in the specified ratio:

powdered ammonium nitrate 60.6 parts sodium nitrate 13 parts

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Vi ater 13th Parts coarse aluminum powder 2 Parts sugar 5 Parts Gilsonite Cum IHO ⁰ C emollient
Asphalt type) 2 Parts sulfur 2 Parts Guar flour 0.4 Parts

The above mixture was used as the first starting material in Examples 1 to 5, 15, 16 and 17 *

Example 1

For comparison purposes, 98 parts of the above 2 parts of atomized aluminum powder are added to the described starting material and mixed in. 99% of the aluminum powder was undersize of No. 350 BS sieve. Me resulting pulpy explosive mixture after The state of the art was cartridged in cardboard tubes. It was found that the minimum amount of pentolite (explosive from equal parts trinitrotoluene and pentaerythritol tetranitrate), which detonates a cartridge with a diameter of 76.2 mm was required with the above mixture at 23.9 ° C, was 140 g.

Example 2

For comparison purposes, the procedure was as in Example 1, but with the atomized aluminum powder

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that example by 2 parts of a metallic detonation— Sensitizer was replaced, which from the example 1

used, the same atomized aluminum consisted and its surface with 0.1% of its weight with sodium lauryl sulfate was coated. It has been found that the minimum amount of pentolite which detonates at 2 3.9 ° C a 76.2 mm cartridge with the most explosive mixture The prior art required was 35 g.

Example 3

A portion of the aluminum powder used in Example 1 was reacted with an aqueous sodium oxetate solution to provide a modified aluminum powder having water-repellent properties, on the surface of which a layer of a material derived from the matrxumabx acetate was bonded. This layer accounted for 0.1% of said modified aluminum powder. 2 parts of the Aluminaumpulvers thus prepared were added 98 parts of smaterials Ausgan ^ described above and to form the pasty explosive mixture according to the invention, eingemischrz.vDie mixture was £ n cardboard tubes patroniertν It has been found that the minimum * amount of Pentolite. " those at 23i ,, 9 ° C to detonate a cartridge of. 50> 8 mm diameter with the above mixture was required * was 25 g «'.

Example 4 .

For comparison purposes, the procedure was as in Example 1, but the atomized aluminum powder of that example was replaced by 2 parts of the same atomized aluminum, the surface of which was coated with 0.1% sodium stearate. It was not possible to detonate a cartridge with a diameter of 101.6 mm with the pulpy explosive mixture according to the state of the art ^{at .19, U 0 C using 70 ς pentolite as detonation material.}

Example 5

The procedure was as in Example 3, with but the atomized aluminum powder of that example a jrobes atomisier; it was replaced by aluminum powder. The sieve analysis of the aluminum powder was like torture: 18% the particles were oversize on a DIN No. 14 sieve; 50% of the particles were oversize on a DIN No. 24 sieve. 85% of the particles were oversize on a DIN No. sieve and 99% of the particles were oversize on a DIN sieve No. 60. The layer bound to the surface of the aluminum powder and derived from the sodium abietate made up 0.1% of the modified aluminum powder. It has been found that the minimum amount of pentolite which at 19.4 ° C to detonate a cartridge of 101.6 mm diameter with the above inventive mixture required "_

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-lie was, was 70 g.

Another prior art mixture was prepared in the usual way the components specified below in the specified Ratio were mixed together:

Ammonium nitrate 5 82 parts

Sodium nitrate 120 parts

Water 135 parts

Sugar 50 parts

^ ilsonite 6 parts

Guar flour 4 parts

Thiourea 1 part

The above mixture, referred to below as the second starting material, was used in Examples β to 12 used. These examples show the sensitivity properties of the uncrosslinked mixtures according to the invention after a certain storage time in comparison with a usual one Mixture according to the state of the art.

Example 6

For comparison purposes, 900 parts of the above-described second starting material 40 parts of a trade name "Atomised Aluminum Powder 200 / Dust"

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BATH ORIGINAL

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available, non-hydrophobic aluminum powder, in which all particles undersize a sieve mesh 150 BS ,. 3% of the particles Ü.berkorn a sieve mesh 240 RS, and 25% of the particles oversize particles a screen mesh were 300 BS, and 40 parts of a Not ^"1: -hydrophoben aluminum powder, deir 99% undersize were a sieve mesh 350 BS, added The resulting prior art explosives slurry was cartridged in cardboard tubes. After one day of storage, it was found that 70 g of pentolite was required to detonate a cartridge 76.2 mm in diameter containing the above mixture A similar result was obtained after two days of storage.

Examples 7 to 9

In these examples, 900 parts of the above. described second starting material with those in table 1 specified amounts of the "Atomized Aluminum Powder 200 / Dust" of Example 1 and the modified aluminum powder of example 3 offset. The resulting explosive pulp mixes were packaged in cardboard tubes 50.8 mm in diameter Cartridges and stored for the times given in Table 1. After this time the cartridges were used for Detonated and determined the minimum amount of pentolite required for this. The results obtained are in the Table 1 given.

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Table 1

example 10 7 Example 8 Example 9 4th "Atomised Aluminum
Powder 200 / Dust " 80 parts 15th 60 parts 40 parts 4th Modified
Aluminum powder 20 parts 15th 40 parts 60 parts 4th Storage time (days) lot 15th of the pentolite used (g) 10 1 4th 2 4th 3 10 10 15th

After storage for 5 3 days, the mixture of Example 9 could not be in a cartridge of Detonated 50.8 mm in diameter. The mixture was placed in a cartridge with a diameter of 76.2 mm detonated with 70 g of Petolit.

Examples 10 to 12

The procedure was as in Examples 7 to 9, except that that used in those examples was modified Aluminum powder was replaced with another modified aluminum powder made as follows: 100 parts an aqueous 0.05% solution of a material obtained by saponification of a commercially available under the trade name "Foral AX" available, fully hydrogenated resin had been prepared with sodium hydroxide solution, 10 parts of a non-hydrophobic

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Aluminum powder was added which was 99% undersize of the sieve Mesh 350 BS. The mixture was 10 minutes at 25 ° C touched. The resulting solid product was separated from the reaction mixture by filtration and then with Dried at room temperature for two days. The dried product was in the form of fine hydrophobic particles. While After the reaction time, 0.01 part of the resin was removed from the solution.

The explosive pulp mixtures formed were cartridged in cardboard tubes with a diameter of 50.8 mm - and during the times given in Table 2. After that time, the cartridges were detonated and it the minimum amount of detonation material required for this was determined. The results are given in Table 2,

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Table 2 Example 10 Example 11 Example 12

"Atomised Aluminum

The mixture of Example 12 was made after 10 days of storage in a cartridge 2 5.4 mm diameter detonated.

Powder 200 / T-USt " 80 Parts 60 Parts 40 Parts g pentolite. 10 Ι g pentolite 4th g pentolite (only used in example 6) g pentolite Μ g pentolite 4th g pentolite Modified aluminum g pentolite 1 χ No. 8th 1 χ No. 6th powder 20th Parts HO Parts 60 Parts Al detonator Cu detonator Storage time (days) Amount of detonation material used g pentolite 1 χ No. 8th 20th g pentolite 1 10 Al detonator 2 10 g pentolite 10 χ No. 6th 1 χ No. 6th 3 4th Cu ~ detonator Cu detonator g pentolite 10 g pentolite ⁺ 10 4th 53 10 79 -

Example 13

The procedure was as in Example 11, but with the second starting material used in that example was replaced by a similar material in which 1 part of zinc chromate replaced one part of thiourea. The resulting cross-linked mixture of explosives in the form of a cartridge with a diameter of 50.8 mm, 5 g of pentolite detonated after storage for 1 and 24 days brought.

Example IH

The general procedure of Example 13 was repeated except that the modified aluminum powder of that example was replaced by 40 parts of another modified aluminum powder ?; has been replaced, the as prepared powder described 12 in the examples lObiiJ with the exception that was replaced in those examples as a starting material used non-hydrophobic Aluniumpulver dur di the "Atomised Aluminum Powder 200 / Dust" of the example. 6 The crosslinked explosive slurry thus obtained was detonated in the form of a cartridge of 50.8 mm in diameter by 50 g of pentolite after it had been stored for one day after production. After 24 days of storage, the detonation resulted using 80 g of pentolite.

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Example 15

The procedure was as in Example 5, but with the modified aluminum of that example through 10 parts of a modified aluminum sensitizer made from atomized aluminum powder des Example 5 existed, on the surface of which 0.16% of a material derived from sodium abietate was bound. The resulting product was successfully exploded in the form of a 101.6 mm cartridge.

Example 16

The procedure was as in Example 3, but the modified aluminum of that example was replaced by a product from the reaction of an aluminum powder which was 99% undersize of the No. 350 mesh sieve with an aqueous one Sodium abietate solution had been replaced. A modified aluminum powder was obtained by the reaction Surface 0.012% hydrophobic substance: was bound. The modified aluminum was a little less hydrophobic than that modified aluminum used in Example 3. However, when 5 parts thereof were added 95 parts of the first starting material and mixed with this, an explosive pulp mixture was obtained which was successfully detonated became.

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Example 17

To 100 g of a 0.05% solution of abietic acid in toluene, 10.g of non-hydrophobic aluminum powder was added, which was 99% undersize of sieve mesh no. was. The mixture was stirred at 35 ° C. for one hour. The resulting solid product was from the reaction mixture separated by filtration and then dried for 5 days at room temperature. The dried product lay now in the form of hydrophobic particles. 0.012 g of abietic acid were removed from the solution during the reaction period. When 2 parts of the product thus prepared were added to 98 parts of the first starting material described above, an exx> losive mixture was obtained, which after cartridge insertion into tubes with a diameter of 76.2 mm using 70 g of pentolite were made to explode.

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Claims (9)

Claims 1. Mushy explosive mixtures of substances?, Consisting of from at least one oxygen-releasing salt, water, at least one fuel and at least one finely divided Detonation sensitizer that acts as a metallic component Contains aluminum and / or aluminum-rich alloys, characterized in that at least of a part of the metallic component at least one material consisting of resin, resin acids and / or their derivatives Group is bound in an amount of 0.01 to 2, preferably 0.01 to 0.2% by weight of the detonation sensitizer. 2. Explosive mixture of substances according to claim 1, characterized in that it releases 50 to 90% by weight of oxygen Sa] ζ, 5 to 25% by weight of hater, 0.8 to 8% by weight of water-soluble fuel and / or 1 to 10% by weight of water-insoluble or sparingly water-soluble non-metallic fuel and / or 0.5 to Contains 20% by weight of water-insoluble metallic fuel and 1 to 10% by weight of detonate xon sensitizer. 3. Explosive mixture of substances according to claim 1 or 2, characterized in that the metallic component of the detonation sensitizer consists of finely divided aluminum, which contains up to 50% by weight of oversized grain Includes sieve mesh Mr. 60 BS. 30988 L / 12 2 L. 4. Explosive mixture of substances according to claim 1 or 2, characterized in that the metallic component of the detonation sensitizer is made of finely divided aluminum consists of up to 5% by weight of the upper grain of the sieve Mesh No. 240 BS and up to 30% by weight of the upper grain of the Contains No. 300 BS sieve mesh. 5. Explosive mixture of substances according to claim 1 or 2, characterized in that the metallic component of the detonation sensitizer is finely divided aluminum which consists of at least 95% by weight undersize of the No. 350 BS sieve. 6. Explosive mixture according to one of claims 1 to 5, characterized in that the to the surface-bound material of an alkali metal or alkaline earth metal salt of a resin acid, in particular of Sodium abietate. 7. Explosive mixture of substances according to one of claims 1 to 5, characterized in that the to the surface bound material is derived from a modified resin, particularly a hydrogenated resin. 8. Explosive mixture of substances according to one of the claims 1 to 5, characterized in that the material bound to the surface is derived from abietic acid. 309884/1224 9. A method for blasting with an explosive pulpy mixture of substances according to one of claims 1 to 8, characterized in that the explosive mixture of substances is filled into a borehole and exploded therein . Dr Fe / 8 309884/122 / *