EP2548857B1 - Utilisation d'un sel de bi-tétrazolamine - Google Patents

Utilisation d'un sel de bi-tétrazolamine Download PDF

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Publication number
EP2548857B1
EP2548857B1 EP12005052.1A EP12005052A EP2548857B1 EP 2548857 B1 EP2548857 B1 EP 2548857B1 EP 12005052 A EP12005052 A EP 12005052A EP 2548857 B1 EP2548857 B1 EP 2548857B1
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EP
European Patent Office
Prior art keywords
salt
bta
mixture
use according
explosive
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Not-in-force
Application number
EP12005052.1A
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German (de)
English (en)
Other versions
EP2548857A1 (fr
Inventor
Arno Dr. Hahma
Eero Karvinen
Jörg Dr. Stierstorfer
Thomas Prof.Dr. Klapötke
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Diehl BGT Defence GmbH and Co KG
Original Assignee
Diehl BGT Defence GmbH and Co KG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
Application filed by Diehl BGT Defence GmbH and Co KG filed Critical Diehl BGT Defence GmbH and Co KG
Priority to EP13004639.4A priority Critical patent/EP2679567A3/fr
Publication of EP2548857A1 publication Critical patent/EP2548857A1/fr
Application granted granted Critical
Publication of EP2548857B1 publication Critical patent/EP2548857B1/fr
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

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    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B43/00—Compositions characterised by explosive or thermic constituents not provided for in groups C06B25/00 - C06B41/00
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06C—DETONATING OR PRIMING DEVICES; FUSES; CHEMICAL LIGHTERS; PYROPHORIC COMPOSITIONS
    • C06C7/00—Non-electric detonators; Blasting caps; Primers

Definitions

  • the invention relates to the use of a salt of bistetrazolylamine (BTA) or a mixture containing such a salt.
  • BTA bistetrazolylamine
  • BTA is also referred to as di (1H-tetrazol-5-yl) amine.
  • BTA salts have the potential to be used as additives in pyrotechnics and fuels.
  • ammonium perchlorate is the common oxidant in compound solid propellants and the thermal decomposition characteristics of ammonium perchlorate directly affect the combustion behavior of solid fuels.
  • the paper describes the investigation of the effect of the lead (II) salt of BTA on the thermal decomposition of ammonium perchlorate.
  • the object of the present invention is to provide an alternative use of a BTA salt. Furthermore, an igniter is to be provided.
  • the use of a salt of BTA or of a mixture containing such a salt is provided as initial explosive.
  • BTA salts can be ignited by introducing a small amount of energy, for example by irradiation with a laser beam having a power of less than 350, in particular less than 300, in particular less than 250 milliwatts.
  • BTA salts have high thermal stability and are insensitive to mechanical stress could be characterized as secondary explosive by the sensitivity. When ignited with a laser beam, focusing of the laser beam is not required.
  • the salts are very high in energy and thus able to enable a single stage construction of a detonator and / or a miniaturization of a detonator.
  • the energy of a conventional initial explosive is not always enough to ignite a secondary explosive directly.
  • an initiating explosive is first ignited which subsequently ignites a secondary explosive compressed in direct contact with the initiating explosive in the same detonator.
  • a three- or more stages of construction is chosen, especially if it is a detonator with small dimensions.
  • the initial explosive initially ignites a mixture of the initial and secondary explosives and this mixture then further secondary explosive in the igniter.
  • an igniter By being able to build a single-stage detonator, by means of the use of BTA salt according to the invention as an initial explosive, an igniter can be manufactured much more favorably than with an initiating explosive which requires a two-stage or multi-stage structure.
  • a multi-stage structure can be omitted because BTA salts have a sufficient energy density to ignite a secondary explosive directly.
  • the ignition of a BTA salt can also be done electrically. Due to the low ignition power required for ignition, a very thin ignition wire can be used. Both by a laser beam as well as by such a thin ignition wire can be a milliseconds to microseconds accurate ignition. At the same time, the high thermal stability and the insensitivity to mechanical influences in comparison to conventional lnitialsprengstoffe to be ignited by laser beams ensure a high level of safety against accidental ignition. The higher the thermal stability of an initial explosive, the greater its shelf life. In combination with the avoidance of corrosive perchlorate can be provided with BTA salt as initial explosive very storable igniter.
  • initial explosives to be ignited with laser radiation require a power of the laser in the range of at least several hundred milliwatts.
  • ignition of such initial explosive for example tetrammine bis (5-nitro-2H-tetrazolato-N 2 ) cobalt (III) perchlorate, causes only one deflagration and no detonation favorable for the ignition of a secondary explosive.
  • the salt is a metal salt.
  • Metal salts of BTA absorb laser radiation particularly well, so that their ignition a laser beam of relatively low power is sufficient.
  • the salt can be a salt of silver, cobalt, chromium, iron or nickel or CuBTA, in particular Ag 2 BTA, CoBTA, Cr 2 BTA 3 , FeBTA, Fe 2 BTA 3 or NiBTA.
  • These metal salts can be prepared relatively easily and have a high sensitivity to laser radiation.
  • the initial explosive preferably does not comprise any ions of lead or any other toxic element.
  • the salt is not a salt of lead or other toxic element.
  • the initial explosive preferably comprises no nitrate, no halogenate, in particular no chlorate, and / or no perchlorate. Nitrate, halogenate or perchlorate containing initial explosives are often thermally unstable and react with other explosives over time. They are therefore not storage stable and cause strong corrosion of metals. With the use according to the invention, these disadvantages can be avoided.
  • the mixture comprises at least two different of the salts specified above.
  • the sensitivity of the initial explosive can be adjusted.
  • the initial explosive may comprise only the said mixture of different salts.
  • a mixture consisting exclusively of said salts has the great advantage that only ion exchange reactions can take place in the mixture which do not alter the overall composition of the mixture. Such a mixture allows the adjustment of a desired sensitivity by the mixing ratio and is at the same time extremely storage-stable.
  • the initial explosive may additionally comprise a 5,5-azotetrazolate.
  • the 5,5-azotetrazolate the initial explosive can be made more sensitive to mechanical influences, for example if ignition by impact or friction is desired.
  • the salt is selected or the mixture is composed such that it is thermally stable up to 270.degree. C., in particular 305.degree. C., in particular 345.degree. C., in particular 355.degree. C., in particular 360.degree.
  • the ignition of the initial explosive can be done electrically or by means of at least one laser beam. Because of its high energy density, a salt from BTA can directly ignite a secondary explosive. An initiator containing the initial explosive can therefore be constructed in one stage. Such an igniter is cheaper and easier to manufacture than a multistage igniter.
  • an igniter containing an above-specified salt or mixture is provided.
  • Fig. 1 shows the structural formula of Bistetrazolylamin (Di (1 H -tetrazol-5-yl) amine), a salt thereof according to the invention is used as the initiating explosive.
  • BTA salts used according to the invention can be prepared, for example, as follows:
  • Bistetrazolylamine is prepared from sodium dicyanamide and sodium azide using hydrochloric acid as catalyst as in Klapötke, TM et al., J. Mater. Chem., 2008, 18, 5248-5258 described prepared. 15.3 g (0.10 mol) of bistetrazolylamine are dissolved in 50 ml of distilled water. To this is added 8.0 g (0.2 mol) of sodium hydroxide as a solid. The solution is stirred until fully dissolved. To ensure that no free hydroxide ions which would precipitate with metal ions as insoluble hydroxides are present in the solution, 100 mg of bistetrazolylamine are added. The solution is then filtered to remove free bistetrazolylamine. The solution is diluted to 100 ml with distilled water so that the sodium bistetrazolylamine concentration in the solution is 1 molar. The solution obtained is referred to below as the basic solution.
  • 1 ml of the base solution is placed in a 25 ml beaker on a 75 ° C hot plate of a magnetic stirrer with a 15 mm stirrer at 350 revolutions per Minute stirred.
  • 2.5 ml of 1 molar silver nitrate solution is added dropwise.
  • the silver nitrate is used in excess to reliably precipitate the BTA salt.
  • the beaker is placed after a minute on a second magnetic stirrer with a non-heated hot plate and allowed to cool with stirring. This forms a white precipitate, which is filtered and washed with 5 ml of ice-cold water and then with 5 ml of cold ethanol. Subsequently, the precipitate is dried in an oven at 40 ° C overnight.
  • Example 2 The procedure is as described in Example 1, wherein instead of 2.5 ml of 1 molar silver nitrate solution, 1.5 ml of 1-molar cobalt (II) chloride solution are used. The resulting pink precipitate is separated as described in Example 1 and dried.
  • II 1-molar cobalt
  • Example 2 The procedure is as described in Example 1, wherein instead of 2.5 ml of 1 molar silver nitrate solution 1 ml of 1 molar chromium (III) chloride solution is used. The resulting pink precipitate is separated as described in Example 1 and dried.
  • Example 2 The procedure is as described in Example 1, wherein instead of 2.5 ml of 1 molar silver nitrate solution, 1.5 ml of 1 molar copper sulfate solution are used. The resulting dark green precipitate is separated as described in Example 1 and dried.
  • the friction sensitivity was determined by means of a standardized friction apparatus of the Federal Institute for Materials Testing (BAM), small version.
  • BAM Federal Institute for Materials Testing
  • the values each indicate the force exerted by a pin contained in the friction apparatus on a friction surface contained in the friction apparatus, on which a sample of the substance to be examined is applied.
  • the impact sensitivity was determined by means of a falling on a sample of the substance to be examined standard hammer of the Federal Institute for Materials Testing, small version, determined. In each case, the drop height and the weight of the drop hammer were varied.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Medicines Containing Antibodies Or Antigens For Use As Internal Diagnostic Agents (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Claims (9)

  1. Utilisation d'un sel de bi-tétrazolamine (BTA) ou d'un mélange, qui contient un tel sel, comme explosif d'amorçage, dans laquelle le sel comprend un sel d'argent, de cobalt, de chrome, de fer ou de nickel ou du CuBTA.
  2. Utilisation selon la revendication 1, dans laquelle le sel comprend Ag2BTA, CoBTA, Cr2BTA3, FeBTA, Fe2BTA3 ou NiBTA.
  3. Utilisation selon l'une quelconque des revendications précédentes, dans laquelle le sel n'est pas un sel de plomb ou d'un quelconque autre élément toxique, et/ou l'explosif d'amorçage ne comprend aucun nitrate, aucun halogénate, en particulier aucun chlorate et/ou aucun perchlorate.
  4. Utilisation selon l'une quelconque des revendications précédentes, dans laquelle le mélange comprend au moins deux sels différents parmi les sels spécifiés selon l'une quelconque des revendications précédentes.
  5. Utilisation selon l'une quelconque des revendications précédentes, dans laquelle l'explosif d'amorçage comprend exclusivement le mélange selon la revendication 4 ou en outre un 5,5'-azotétrazolate.
  6. Utilisation selon l'une quelconque des revendications précédentes, dans laquelle le sel est choisi de telle manière ou le mélange est composé de telle manière qu'il soit thermiquement stable jusque 270°C, en particulier 305°C, en particulier encore 345°C, en particulier encore 355°C et en particulier encore 360°C.
  7. Utilisation selon l'une quelconque des revendications précédentes, dans laquelle l'allumage de l'explosif d'amorçage est effectué de façon électrique ou au moyen d'au moins un faisceau laser.
  8. Utilisation selon l'une quelconque des revendications précédentes, dans laquelle une amorce contenant l'explosif d'amorçage est constituée à un étage.
  9. Amorce, contenant un sel ou un mélange spécifié selon l'une quelconque des revendications 1 à 6.
EP12005052.1A 2011-07-20 2012-07-07 Utilisation d'un sel de bi-tétrazolamine Not-in-force EP2548857B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP13004639.4A EP2679567A3 (fr) 2011-07-20 2012-07-07 Utilisation d'un sel de bi-tétrazolamine

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE102011108146.5A DE102011108146B4 (de) 2011-07-20 2011-07-20 Verwendung eines Salzes von Bistetrazolylamin und Zünder

Related Child Applications (2)

Application Number Title Priority Date Filing Date
EP13004639.4A Division EP2679567A3 (fr) 2011-07-20 2012-07-07 Utilisation d'un sel de bi-tétrazolamine
EP13004639.4 Division-Into 2013-09-25

Publications (2)

Publication Number Publication Date
EP2548857A1 EP2548857A1 (fr) 2013-01-23
EP2548857B1 true EP2548857B1 (fr) 2014-01-01

Family

ID=46514069

Family Applications (2)

Application Number Title Priority Date Filing Date
EP13004639.4A Withdrawn EP2679567A3 (fr) 2011-07-20 2012-07-07 Utilisation d'un sel de bi-tétrazolamine
EP12005052.1A Not-in-force EP2548857B1 (fr) 2011-07-20 2012-07-07 Utilisation d'un sel de bi-tétrazolamine

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP13004639.4A Withdrawn EP2679567A3 (fr) 2011-07-20 2012-07-07 Utilisation d'un sel de bi-tétrazolamine

Country Status (5)

Country Link
EP (2) EP2679567A3 (fr)
DE (1) DE102011108146B4 (fr)
ES (1) ES2453897T3 (fr)
IL (1) IL220783A (fr)
ZA (1) ZA201205358B (fr)

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL9775C (fr) * 1921-02-01
GB185555A (en) * 1921-06-27 1922-09-14 Hans Rathsburg Initial primers and a process for their manufacture
US1511771A (en) * 1921-08-22 1924-10-14 Rathsburg Hans Explosive compound for primers and detonators
US5682014A (en) * 1993-08-02 1997-10-28 Thiokol Corporation Bitetrazoleamine gas generant compositions
DE19616627A1 (de) * 1996-04-26 1997-11-06 Dynamit Nobel Ag Anzündmischungen
US6453816B2 (en) * 1996-07-20 2002-09-24 Dynamit Nobel Gmbh Explosivstoff-Und Systemtechnik Temperature fuse with lower detonation point
US20100261912A1 (en) * 2009-02-17 2010-10-14 Toshiyuki Toda Bis-(1(2)h-tetrazol-5-yl)amine and production method therefor

Also Published As

Publication number Publication date
DE102011108146A1 (de) 2013-01-24
ZA201205358B (en) 2013-05-29
ES2453897T3 (es) 2014-04-08
EP2679567A2 (fr) 2014-01-01
IL220783A (en) 2015-01-29
EP2679567A3 (fr) 2017-10-04
EP2548857A1 (fr) 2013-01-23
DE102011108146B4 (de) 2014-03-20

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