CZ306594B6 - A millisecond delay pyrotechnic composition for industrial detonators with explosion delay time of 25-1000 ms from the initiation, the method of manufacturing the delay composition and an electric and non-electric detonator - Google Patents

Abstract

The pyrotechnic delay composition contains FeSiZr as a flammable material and Bi.sub.2.n.O.sub.3 .n. as an oxidizing agent in the ratio of 50 .+-. 15 % of weight FeSiZr a 50 .+-. 15 % of weight Bi.sub.2.n.O.sub.3.n.. FeSiZr is an alloy of dominant elements of Si, Zr, Fe, with the contents of Ti, and trace admixtures originating from aluminosilicates. The threshold portion of the dominant elements in FeSiZr is: Si at least 30 % of weight, Zr at least 10 % of weight, Fe maximum 25 % of weight The regulator of burning speed is an additive TiO.sub.2 .n. in the amount of up to 5 % of weight from the total weight. When producing the millisecond delay pyrotechnic composition, FeSiZr is modified by a physical process of grinding to a particle size in the range from 1 to 10 .mi.m, Bi.sub.2.n.O.sub.3 .n. to a particle size in the range from 1 to 10 .mi.m, and then the two components are mechanically homogenized and made in tablets using the pressure of 255 .+-. 100 MPa, and, subsequently, they are crushed to fraction having a grain size of 0,2 to 0,8 mm. Finally, the composition is pressed into the casing of the detonator retarder using the pressure of 280 .+-. 100 MPa with column height of 5 to 40 mm. Further, there is described the electric and non-electric detonator containing this pyrotechnic delay composition.

Description

Pyrotechnic millisecond delay composition for industrial detonators with an explosion delay time of 25 to 1000 ms from initiation, method of manufacturing the delay composition and electric and non-electric detonator

Field of the invention

The invention relates to a pyrotechnic millisecond delay composition for industrial detonators with an explosion delay time of 25 to 1000 ms from initiation. The component is intended for compaction into a retarder housing, for detonators initiated by an electric pill by an impulse generated from a detonator, and for detonators initiated by a detonation tube non-electrically by means of a shock wave or spark generated from a detonator. It applies to electric detonators in series or series parallel connection as well as non-electric detonators, where the ignition network is created by connecting detonation tubes of non-electric detonators, especially in ground destruction of rocks, quarrying, underground rock mining and tunneling.

The invention also relates to a method of manufacturing said pyrotechnic delay composition.

The invention also relates separately to an electric detonator and also as a separate invention to a non-electric detonator, for use together with a pyrotechnic delay composition.

Prior art

At present, pyrotechnic delay compositions containing flammable and oxidizing agents are used to achieve a detonation delay of up to 1,000 milliseconds. Metal powders Si, B, Zr, Ti and alloys Fe + Si + Cr, Si + Se + Fe, Zr + B, Zr + Ni and others are generally used as combustibles. Lead-lead oxide and lead dioxide are usually used here as oxidizing agents. However, such a composition contains heavy metals which enter the environment after use of the detonator. Therefore, there is a general effort to eliminate heavy metals. Solutions are known, for example, according to SE patents SE 446 180 and SE 457 380, where the oxidizing agents are designed non-toxic on the basis of tin. However, these solutions have higher production requirements and negatively affect the possibility of setting the time. A solution according to U.S. Pat. No. 5,654,520 is also known, in which bismuth oxide is used as the oxidizing agent and elemental silicon is used as the fuel. The disadvantage of the solution according to this patent is the need to add a number of different additives to achieve the desired function.

It is an object of the present invention to provide a fuel and oxidant composition and weight ratios which are inexpensive to manufacture and cost, with minimal need for additional additives for time variability and delay accuracy. In particular, however, the solution should meet the condition of the absence of heavy metals.

It is also an object of the invention to provide a method of manufacturing a delayed composition so that the resulting parameters correspond to said task while keeping production costs to a minimum.

It is also an object of the invention to provide an electric and non-electric detonator in which it will be possible to use the formed composition.

The essence of the invention

This task is fulfilled by a pyrotechnic millisecond delay composition for electric and non-electric industrial detonators with an explosion delay time of 25 to 1000 ms from initiation, in the composition according to the invention, which consists in containing ferrosilicon zirconium (FeSiZr) as flammable and bismuth oxide (hereinafter only Bi ₂ O ₃ ) as an oxidizing agent in a ratio of 50 ± 15 wt. FeSiZr and 50 ± 15 wt. Bi ₂ O ₃ , where FeSiZr is an alloy of dominant elements Si, Zr, Fe, with content

- 1 CZ 306594 B6

Ti and trace impurities originating from aluminosilicates, input substances in the production of alloys, where the limit representation of dominant elements in FeSiZr is: Si at least 30% by weight, Zr at least 10% by weight, Fe at most 25% by weight, Ti content is at least 1% by weight, where Ti is the combustion rate regulator. TiO ₂ with a purity of at least 95% by weight. the composition may contain up to 5% by weight. of the total weight of the pyrotechnic delay composition.

In the pyrotechnic millisecond delay composition, Bi ₂ O ₃ is a substance with a purity of at least 90%.

In one preferred embodiment of the pyrotechnic millisecond delay composition, the FeSiZr alloy has a composition of Si 52.1% by weight, Zr 27.4% by weight, Fe 12.7% by weight. Ti 5.8 wt. and a purity of 2% by weight, wherein with Bi ₂ O _{3 the} purity is 99.8% by weight. in a ratio of 52.8 wt.%, Bi ₂ O ₃ , and 47.2 wt.%. FeSiZr.

In another embodiment, depending on the required properties, the FeSiZr alloy has a composition of Si 52.1% by weight, Zr 27.4% by weight, Fe 12.7% by weight, Ti 5.8% by weight, impurities 2% by weight, wherein is with Bi ₂ O ₃ of 99.8% purity by weight. in a ratio of 60.0% by weight. Bi ₂ O ₃ and 40.0 wt. FeSiZr.

In another preferred embodiment proving the variability of the final properties, the FeSiZr alloy has a composition of Si 63.5 wt.%, Zr 21.3 wt.%, Fe 11.7 wt.%, Ti 1.1 wt.%, Impurities 2.4 wt.%. ., with Bi ₂ O _{3 of} purity 99.8% by weight. in a ratio of 60.0% by weight. Bi ₂ O ₃ and 40.0% by weight, FeSiZr.

In another preferred embodiment, the FeSiZr alloy has a composition of Si 63.5% by weight, Zr 21.3% by weight, Fe 11.7% by weight, Ti 1.1% by weight, impurities 2.4% by weight, Bi ₂ O ₃ of purity 99.8 wt.% in a ratio of 50.0 wt. Bi ₂ O ₃ and 50.0 wt. FeSiZr or FeSiZr alloy has a composition of Si 63.5% by weight, Zr 21.3% by weight, Fe 11.7% by weight, Ti 1.1% by weight, impurities 2.4% by weight, with s Bi ₂ O ₃ purity 99.8 wt. in a ratio of 55.0 wt. Bi ₂ O ₃ and 45.0 wt. FeSiZr.

In the embodiment with the TiO ₂ additive optionally added, the FeSiZr alloy may have a composition of Si 63.5% by weight, Zr 21.3% by weight, Fe 11.7% by weight, Ti 1.1% by weight, impurities 2.4% by weight. ., with Bi ₂ O _{3 of} purity 99.8% by weight. and TiO _{2 of} purity 99.8 wt. in a ratio of 53.9 wt. Bi ₂ O ₃ , 44.1 wt. FeSiZr and 2.0 wt. TiO ₂ .

In another preferred embodiment with optionally added TiO ₂ additive, the FeSiZr alloy has a composition of Si 63.5% by weight, Zr 21.3% by weight, Fe 11.7% by weight, Ti 1.1% by weight, impurities 2.4 wt., with a Bi ₂ O _{3 of} purity of 99.8 wt. and TiO ₂ purity 98% wt. in a ratio of 52.3 wt. Bi ₂ O ₃ , 42.7 wt. FeSiZr and 5.0 wt. TiO ₂ .

The invention also relates to a method of manufacturing a pyrotechnic millisecond delay composition for electric and non-electric industrial detonators with an explosion delay time of 25 to 1000 ms from initiation. The essence of the production method lies in the fact that ferrosilicon zirconium (hereinafter referred to as FeSiZr), with a limit representation of the dominant elements Si at least 30% by weight, Zr at least 10% by weight, Fe at most 25% by weight and Ti content of at least 1% by weight is adjusted to a particle size in the range of 1 to 10 μm by physical grinding, bismuth dioxide (hereinafter Bi ₂ O ₃ ) of at least 90% purity is adjusted to a particle size in the range of 1 to 10 μm. . Then the two components in a ratio of 50 ± 10% by weight. FeSiZr and 50 ± 10 wt. The Bi ₂ O _{3 are} mechanically homogenized and tableted at a pressure of 255 ± 100 MPa, and then crushed to a fraction with a grain size of 0.2 to 0.8 mm.

The component is pressed into the housing of the detonator retarder at a pressure of 280 ± 100 MPa with a column height of 5 to 40 mm.

The essence of the production method according to the invention is also that FeSiZr and Bi ₂ O ₃ are supplemented with TiO ₂ in an amount of up to 5% by weight before homogenization. composition, the purity of TiO ₂ is at least 95%, adjusted to a particle size in the range of 1 to 10 μm.

-2EN 306594 B6

The essence of a non-electric industrial detonator with a shell in the form of a tube with an inserted detonation tube is that a space is created in the shell at least for the primary explosive and for the delay composition. The cavity is closed on the underside and has a space in the lower part for a secondary explosive, which is closed from above by a retarder. A primary explosive is located in its cylindrical case and a delay composition above it. Above the retarder, a sleeve with a reinforcing composition is inserted in the cavity, closed by a cover. From the upper side, a detonation tube is inserted into the tube, provided with a seal against the shell of the tube.

The essence of an industrial electric detonator with a pyrotechnic delay composition, which has a shell in the shape of a hollow with an inserted electric pill, which is provided with supply conductors, is that a space is created in the shell for at least the primary explosive and the delay composition. The cavity is closed on the underside and has a space for a secondary explosive in the lower part, which is closed from above by a retarder, in the cylindrical housing of which the primary explosive is located. Above it is a delay component. Above the retarder, an electric pill is inserted in the socket with supply conductors provided with a seal against the shell of the socket.

The main advantage and currently highly valued higher effect is the absence of heavy metals, given that the presence of heavy metals even in foodstuffs, such as rock salt, probably due to the method of mining, is a major problem in actively industrialized areas of the world. The pyrotechnic composition is free of lead oxides or chromates and free of barium. The benefit of this solution, while maintaining the above-mentioned main advantage, is the simplicity of production and versatility of use for different intervals of the required delay, with high accuracy. Delay variability is achieved by the ratio of the basic components, it is not necessary to add other additives. From the point of view of usability, this solution seems to be very simple and practical, from the production point of view technologically and investment-intensive.

Explanation of drawings

Both electric and non-electric detonators are described on the basis of exemplary embodiments with the aid of the accompanying drawings, in which FIG. 1 shows a non-electric detonator and FIG. 2 an electric detonator.

Examples of embodiments of the invention

General information common to all embodiments:

Ferrosilicon zirconium (hereinafter FeSiZr) is a flammable composition in the retardation composition. Its definition for the purposes of describing the invention:

Alloy of dominant elements Si, Zr, Fe, with Ti content and trace impurities originating from aluminosilicates, input substances in alloy production. The limiting representation of dominant elements in FeSiZr for the purposes of the invention is:

At least 30 wt.

Zr at least 10% by weight.

Fe max. 25% by weight

and the proportion is Ti at least 1% by weight.

The FeSiZr alloy is modified by a physical milling process to a particle size in the range of 1 to 10 μm.

Bismuth dioxide (hereinafter referred to as Bi ₂ O ₃ ) is an oxidizing agent in the retardant composition. Its definition for the purposes of describing the invention:

Substance of at least 90% purity, adjusted, usually by physical grinding, to a particle size in the range of 1 to 10 μm.

-3 CZ 306594 B6

Titanium dioxide (hereinafter referred to as TiO ₂ ) is an additive in the retardant composition, it does not actively participate in the combustion process, it influences the burning rate in a desirable way. Substance of at least 95% purity, adjusted, usually by physical grinding, to a particle size in the range of 1 to 10 μm.

Example 1

In this exemplary embodiment, an FeSiZr alloy having the composition:

Si 52.1 wt.

Zr 27.4 wt.

Fe 12.7 wt.

Ti 5.8 wt.

impurities 2% wt.

Furthermore, Bi ₂ O _{3 with a} purity of 99.8% by weight was used.

FeSiZr and Bi ₂ O ₃ were used in a ratio of 52.8% by weight. Bi ₂ O ₃ and 47.2 wt. FeSiZr.

The FeSiZr alloy was adjusted to a particle size of 1.86 μm and Bi ₂ O ₃ was adjusted to a particle size of 1.98 μm.

The mixture was mechanically homogenized and tableted at a pressure of 255 MPa.

It was then crushed to a fraction with a grain size of 0.2 to 0.8 mm.

The composition thus prepared is pressed into the housing of the retarder of the non-electric detonator at a pressure of 280 MPa with a column height of 20 mm.

The average delay time of the detonator explosion at this delay composition is 267.4 ms and the standard deviation is 3.3 ms.

Example 2

In this exemplary embodiment, an FeSiZr alloy having the composition:

Si 52.1 wt.

Zr 27.4 wt.

Fe 12.7 wt.

Ti 5.8 wt.

impurities 2% wt.

Furthermore, Bi ₂ O _{3 with a} purity of 99.8% by weight was used.

FeSiZr and Bi ₂ O ₃ were used in a ratio of 60.0% by weight. Bi ₂ O ₃ and 40.0 wt. FeSiZr. The FeSiZr alloy was adjusted to a particle size of 1.86 μm and Bi ₂ O ₃ was adjusted to a particle size of 1.98 μm.

The mixture was mechanically homogenized and tableted at a pressure of 255 MPa.

It was then crushed to a fraction with a grain size of 0.2 to 0.8 mm.

The composition thus prepared is pressed into the housing of the retarder of the non-electric detonator at a pressure of 280 MPa with a column height of 20 mm.

The average delay time of the detonator explosion at this delay composition is 235.8 ms and the standard deviation is 3.4 ms.

-4GB 306594 B6

Example 3

In this exemplary embodiment, an FeSiZr alloy having the composition:

Si 63.5 wt.

Zr 21.3 wt.

Fe 11.7 wt.

Ti 1.1 wt.

impurities 2.4% by weight.

Furthermore, Bi ₂ O _{3 with a} purity of 99.8% by weight was used.

FeSiZr and Bi ₂ O ₃ were used in a ratio of 60.0% by weight. Bi ₂ O ₃ and 40.0 wt. FeSiZr. The FeSiZr alloy was adjusted to a particle size of 2.09 μm and the Bi ₂ O ₃ was adjusted to a particle size of 1.98 μm.

The mixture was mechanically homogenized and tableted at a pressure of 255 MPa. It was then crushed to a fraction with a grain size of 0.2 to 0.8 mm.

The composition thus prepared is pressed into the housing of the retarder of the non-electric detonator at a pressure of 280 MPa with a column height of 20 mm.

The average delay time of the detonator explosion at this delay composition is 247.5 ms and the standard deviation is 2.8 ms.

Example 4

In this exemplary embodiment, an FeSiZr alloy having the composition:

Si 63.5 wt.

Zr 21.3 wt.

Fe 11.7 wt.

Ti 1.1 wt.

impurities 2.4% by weight.

Furthermore, Bi ₂ O _{3 with a} purity of 99.8% by weight was used.

FeSiZr and Bi ₂ O ₃ were used in a ratio of 50.0% by weight. Bi ₂ O ₃ and 50.0 wt. FeSiZr. The FeSiZr alloy was adjusted to a particle size of 2.09 μm and the Bi ₂ O ₃ was adjusted to a particle size of 1.98 μm.

The mixture was mechanically homogenized and tableted at a pressure of 255 MPa. It was then crushed to a fraction with a grain size of 0.2 to 0.8 mm.

The composition thus prepared is pressed into the housing of the retarder of the non-electric detonator at a pressure of 280 MPa with a column height of 20 mm.

The average delay time of the detonator explosion at this delay composition is 372.4 ms and the standard deviation is 3.4 ms.

Example 5

In this exemplary embodiment, an FeSiZr alloy having the composition:

Si 63.5 wt.

Zr 21.3 wt.

Fe 11.7 wt.

Ti 1.1 wt.

-5 CZ 306594 B6 impurities 2.4% by weight ..

Furthermore, Bi ₂ O _{3 with a} purity of 99.8% by weight was used.

FeSiZr and Bi ₂ O ₃ were used in a ratio of 55.0% by weight. Bi ₂ O ₃ and 45.0 wt. FeSiZr. The FeSiZr alloy was adjusted to a particle size of 4.88 μm and Bi ₂ O ₃ was adjusted to a particle size of 1.98 μm.

The mixture was mechanically homogenized and tableted at a pressure of 255 MPa. It was then crushed to a fraction with a grain size of 0.2 to 0.8 mm.

The composition thus prepared is pressed into the housing of the retarder of the non-electric detonator at a pressure of 280 MPa with a column height of 20 mm.

The average time of the detonator explosion delay at this delay composition composition is 347.7 ms and the standard deviation is 3.7 ms.

Example 6

In this exemplary embodiment, an FeSiZr alloy having the composition:

Si 63.5 wt.

Zr 21.3 wt.

Fe 11.7 wt.

Ti 1.11 wt.

impurities 2.4% by weight.

Furthermore, Bi ₂ O _{3 with a} purity of 99.8% by weight was used. and TiO ₂ purity 98% by weight.

FeSiZr, Bi ₂ O ₃ and TiO ₂ were used in a ratio of 53.9% by weight. Bi ₂ O ₃ , 44.1 wt. FeSiZr and 2.0 wt. TiO ₂ .

The FeSiZr alloy was adjusted to a particle size of 4.88 μm and Bi ₂ O ₃ was adjusted to a particle size of 1.98 μm and TiO ₂ was adjusted to a particle size of 0.45 μm.

The mixture was mechanically homogenized and tableted at a pressure of 255 MPa. It was then crushed to a fraction with a grain size of 0.2 to 0.8 mm.

The composition thus prepared is pressed into the housing of the retarder of the non-electric detonator at a pressure of 280 MPa with a column height of 20 mm.

The average detonation time of the detonator explosion at this delay composition is 405.0 ms and a standard deviation of 3.5 ms.

Example 7

In this exemplary embodiment, an FeSiZr alloy having the composition:

Si 63.5 wt.

Zr 21.3 wt.

Fe 11.7 wt.

Ti 1.1 wt.

impurities 2.4% by weight.

Furthermore, Bi ₂ O _{3 with a} purity of 99.8% by weight was used. and TiO ₂ purity 98% by weight.

The alloy FeSiZr, Bi ₂ O ₃ and TiO ₂ were used in a ratio of 52.3% by weight. Bi ₂ O ₃ , 42.7 wt. FeSiZr and 5.0 wt. TiO ₂ .

The FeSiZr alloy was adjusted to a particle size of 4.88 μm and Bi ₂ O ₃ was adjusted to a particle size of 1.98 μm and TiO ₂ was adjusted to a particle size of 0.45 μm.

-6GB 306594 B6

The mixture was mechanically homogenized and tableted at a pressure of 255 MPa.

It was then crushed to a fraction with a grain size of 0.2 to 0.8 mm.

The composition thus prepared is pressed into the housing of a delayed non-electric detonator at a pressure of 280 MPa with a column height of 20 mm.

The average delay time of the detonator explosion at this delay composition is 640.4 ms and the standard deviation is 6.5 ms.

Example 8

This embodiment describes a non-electric industrial detonator in which a pyrotechnic delay composition according to the above embodiments is used. The detonator has a shell in the shape of a tube 1 with an inserted detonation tube 17. A space for a secondary explosive H is created in the lower part in the shell.

A non-electric industrial detonator with a pyrotechnic delay composition, which has a shell-shaped shell with an inserted detonation tube 17. On the underside, the closed cavity 1 has a lower explosive space 11 in the lower part, which is closed from above by a delay 12 in a cylindrical housing primary explosive 13 and above it a delay assembly 14. Above the retarder 12, a sleeve 15 with an amplifying assembly 16 is inserted in the cavity 1, which is closed by a flap 17. A detonation tube 19 is inserted into the cavity 1 from above. .

Example 9

This exemplary embodiment describes an industrial electric detonator in which a pyrotechnic delay composition 24 according to the above exemplary embodiments is used. The industrial electric detonator with a pyrotechnic delay composition 24 has a shell in the shape of a tube 2 with an inserted electric pill 25 and is provided with supply conductors 26. A space 21 for a secondary explosive is formed in the lower part of it. The primary explosive 23 is located in the delay 22 and the delay composition 24 above it. An electric pill 25 with supply conductors 26 is inserted in the socket 2 above the delay device 22. These are provided with a seal 27 against the shell of the socket 2.

The function of both types of detonators is evident from their construction and does not differ from the function of commonly used.

Industrial applicability

The pyrotechnic delay composition according to the invention, the process for its production and the industrial detonators with the delay composition are industrially applicable. The component can be used especially for detonators in ground rock dismantling and quarrying, underground mining or tunneling, destruction and other similar special works.

Claims (15)

PATENT CLAIMS 1. Pyrotechnic millisecond delay composition for electric and non-electric industrial detonators with an explosion delay time of 25 to 1000 ms from initiation, characterized in that it contains ferrosilicon zirconium (hereinafter FeSiZr) as combustible and bismuth oxide (hereinafter Bi ₂ O ₃ ) as oxidizing reagent in a ratio of 50 ± 15 wt. FeSiZr and 50 ± 15 wt. Bi ₂ O ₃ , where FeSiZr is an alloy of dominant elements Si, Zr, Fe, with Ti content and trace impurities originating from aluminosilicates, input substances in alloy production, where the limit representation of dominant elements in FeSiZr is: Si at least 30% by weight, Zr at least 10% by weight, Fe at most 25% by weight, and the Ti content in an amount of at least 1% by weight. Pyrotechnic millisecond delay composition according to Claim 1, characterized in that it contains, as a combustion rate regulator, an additive titanium dioxide (hereinafter referred to as TiO ₂ ) in an amount of up to 5% by weight. of the total weight of the pyrotechnic delay composition and the purity of the substance at least 95% by weight. Pyrotechnic millisecond delay composition according to one of the preceding claims, characterized in that the Bi ₂ O ₃ is a substance with a purity of at least 90%. Pyrotechnic millisecond delay composition according to one of the preceding claims, characterized in that the FeSiZr alloy has a composition of Si 52.1% by weight, Zr 27.4% by weight, Fe 12.7% by weight, Ti 5.8% wt. and an impurity of 2% by weight, wherein with Bi ₂ O _{3 of} purity 99.8% by weight. in a ratio of 52.8 wt. Bi ₂ O ₃ and 47.2 wt. FeSiZr. Pyrotechnic millisecond delay composition according to one of the preceding claims, characterized in that the FeSiZr alloy has a composition of Si 52.1% by weight, Zr 27.4% by weight, Fe 12.7% by weight, Ti 5.8% wt., impurities 2 wt.%, with Bi ₂ O _{3 of} purity 99.8 wt.%. in a ratio of 60.0% by weight. Bi ₂ O ₃ and 40.0 wt. FeSiZr. Pyrotechnic millisecond delay composition according to one of the preceding claims, characterized in that the FeSiZr alloy has a composition of Si 63.5% by weight, Zr 21.3% by weight, Fe 11.7% by weight, Ti 1.1% of impurities of 2.4% by weight, with Bi ₂ O _{3 of} purity being 99.8% by weight. in a ratio of 60.0% by weight. Bi ₂ O ₃ and 40.0 wt. FeSiZr. Pyrotechnic millisecond delay composition according to one of the preceding claims, characterized in that the FeSiZr alloy has a composition of Si 63.5% by weight, Zr 21.3% by weight, Fe 11.7% by weight, Ti 1.1% of impurities of 2.4% by weight, with Bi ₂ O _{3 of} purity being 99.8% by weight. in a ratio of 50.0 wt. Bi ₂ O ₃ and 50.0 wt. FeSiZr. Pyrotechnic millisecond delay composition according to one of the preceding claims, characterized in that the FeSiZr alloy has a composition of Si 63.5% by weight, Zr 21.3% by weight, Fe 11.7% by weight, Ti 1.1% of impurities of 2.4% by weight, with Bi ₂ O _{3 of} purity being 99.8% by weight. in a ratio of 55.0 wt. Bi ₂ O ₃ and 45.0 wt. FeSiZr. Pyrotechnic millisecond delay composition according to one of the preceding claims, characterized in that the FeSiZr alloy has a composition of Si 63.5% by weight, Zr 21.3% by weight, Fe 11.7% by weight, Ti 1.1% of impurities of 2.4% by weight, with Bi ₂ O _{3 of} purity being 99.8% by weight. and TiO ₂ purity 98% wt. in a ratio of 53.9 wt. Bi ₂ O ₃ , 44.1 wt. FeSiZr and 2.0 wt. TiO ₂ . Pyrotechnic millisecond delay composition according to one of the preceding claims, characterized in that the FeSiZr alloy has a composition of Si 63.5% by weight, Zr 21.3% by weight, Fe 11.7% by weight, Ti 1.1% wt., impurities 2.4 wt.%, with 99.8% purity _{with Bi 2} O _3. with _ wt. and TiO ₂ purity 98% wt. in a ratio of 52.3 wt. Bi ₂ O ₃ , 42.7 wt. FeSiZr and 5.0 wt. TiO ₂ . 11. Process for the production of a pyrotechnic millisecond delay composition for electric and non-electric industrial detonators with an explosion delay time of 25 to 1000 ms from initiation, characterized in that ferrosilicon zirconium (hereinafter FeSiZr), with a limit of dominant Si elements of at least 30% by weight, Zr at least 10% by weight, Fe at most 25% by weight and Ti content of at least 1% by weight is adjusted to a particle size in the range from 1 to 10 μm by physical grinding, bismuth dioxide (hereinafter referred to as Bi ₂ O ₃ ) of at least 90% purity is adjusted to a particle size in the range of 1 to 10. pm, after which the two components in a ratio of 50 ± 10 wt. FeSiZr and 50 ± 10 wt. The Bi ₂ O _{3 are} mechanically homogenized and tableted at a pressure of 255 ± 100 MPa, and then crushed to a fraction with a grain size of 0.2 to 0.8 mm. A method of manufacturing a pyrotechnic millisecond delay composition according to claim 11, characterized in that the composition is pressed into the detonator retarder housing at a pressure of 280 ± 100 MPa with a column height of 5 to 40 mm. 13. A method of manufacture of pyrotechnic millisecond delay charge according to claim 11 or 12, characterized in that FeSiZr and Bi ₂ O ₃ is completed before homogenization TiO ₂ in an amount up to 5 wt%. composition, with a purity of TiO _{2 of} at least 95%, adjusted to a particle size in the range from 1 to 10 μm. A non-electric industrial detonator with a pyrotechnic delay composition, in a composition according to any one of claims 1 to 10, having a hollow-shaped shell with an inserted detonation tube, space being provided in the shell for at least a primary explosive and a delay composition, characterized in that that the cavity (1), closed on the underside, has a space (11) for a secondary explosive formed in the lower part, which is closed from above by a delay (12), in the cylindrical housing of which the primary explosive (13) is located and above it a delay composition ( 14), where above the retarder (12) a sleeve (15) is inserted in the cavity (1) with an amplifying composition (16) closed by a cover (17), while a detonation tube (19) provided with against the shell of the sleeve (1) by a seal (18). An industrial electric detonator with a pyrotechnic delay composition, in a composition according to any one of claims 1 to 10, having a hollow-shaped shell with an inserted electric pill and provided with supply conductors, wherein a space is formed in the shell for at least a primary explosive and a delay composition. , characterized in that the cavity (2), closed on the underside, has a space (21) for a secondary explosive formed in the lower part, which is closed from above by a delay (22) in the cylindrical housing of which the primary explosive (23) is located, and above it a delay assembly (24), where above the delay (22) an electric pill (25) is inserted in the socket (2) with supply conductors (26) provided with a seal (27) against the shell of the socket (2).