EP1663913B1 - Verfahren zur herstellung eines funkenerzeugenden rohrs und produkt davon - Google Patents

Verfahren zur herstellung eines funkenerzeugenden rohrs und produkt davon Download PDF

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Publication number
EP1663913B1
EP1663913B1 EP04761538A EP04761538A EP1663913B1 EP 1663913 B1 EP1663913 B1 EP 1663913B1 EP 04761538 A EP04761538 A EP 04761538A EP 04761538 A EP04761538 A EP 04761538A EP 1663913 B1 EP1663913 B1 EP 1663913B1
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EP
European Patent Office
Prior art keywords
tube
mixture
pyrotechnic
shock
group
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EP04761538A
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English (en)
French (fr)
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EP1663913A1 (de
Inventor
Marco Antonio Falquete
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Britanite S/A- Ind Strias Qu Micas
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Britanite S/A- Ind Strias Qu Micas
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    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B33/00—Compositions containing particulate metal, alloy, boron, silicon, selenium or tellurium with at least one oxygen supplying material which is either a metal oxide or a salt, organic or inorganic, capable of yielding a metal oxide
    • C06B33/12—Compositions containing particulate metal, alloy, boron, silicon, selenium or tellurium with at least one oxygen supplying material which is either a metal oxide or a salt, organic or inorganic, capable of yielding a metal oxide the material being two or more oxygen-yielding compounds
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06C—DETONATING OR PRIMING DEVICES; FUSES; CHEMICAL LIGHTERS; PYROPHORIC COMPOSITIONS
    • C06C5/00—Fuses, e.g. fuse cords
    • C06C5/04—Detonating fuses

Definitions

  • the present Patent refers to a process for production of a thermal shock tube and product thereof, applied as signal transmission device for connecting and initiating explosive columns, or as a flame conductor, usually complemented by a delay element or used as a delay unit, which uses a pyrotechnic mixture with low sensitivity to ignition by shock or friction, with low toxicity, which generates a spark with superior thermal performance, said process having the possibility of continuous and separated dosing of the individual non-active components, in conjunction with the formation of the plastic tube, making the process safer, and with a more accurate dosing, and said product maintaining the advantages of the current pyrotechnic shock tube relative to the shock wave propagating tube: larger transmission sensibility and sensitivity, propagation even with cuts or holes in the tubes and low risk transport classification, and presents additional advantages: use of low toxicity components, use of ordinary, low cost, low adhesiveness polymers, generation of a spark that propagates through knots, closed kinks or tube obstructions, and resistance to failure by attack of components of hot explosive emulsions.
  • non-electric detonators or “shock tubes” are broadly applied for connecting and initiating explosive charges in the mining and quarry sector.
  • Such devices marketed with brands like NONEL, EXEL, BRINEL, etc., came to substitute electric blasting caps ignited by metallic wiring, and represented a revolution in the market of detonation accessories, due to its easiness of connection and application, and to the intrinsic safety against accidental ignition by induction of spurious electric current.
  • Hot Diesel fuel is particularly aggressive to LLDPE, and prolonged contact of the tube with hot, Diesel fuel-based emulsions causes failure in signal propagation.
  • PVA protective skin is fragile and does not adhere to the LLDPE, and so a pretreatment with a cleaner (like chromic acid), with hot air or with an adhesion promoter (like Vinamul EVA copolymer) is necessary.
  • pyrotechnic shock tube A further development in the low energy transmission fuses was the invention of tubes that make use of pyrotechnic mixtures inside the tube, in substitution for high-explosive-containing powders.
  • pyrotechnic shock tube Some of the processes and products with pyrotechnic mixtures, hereinafter referred as “pyrotechnic shock tube”, are the following:
  • Signal transmission tubes are usually complemented with the insertion of a delay blasting cap in its tip, such cap made of a metal cap containing two layers of explosive powder pressed inside, the bottom layer being a secondary high explosive, and the upper layer being a primary, flame-sensitive explosive, complemented by a delay element consisting of a metallic cylinder containing in its interior a compacted column of powdery pyrotechnic delay mixture and, frequently, an additional column of pyrotechnic mixture sensitive to the heat generated by the tube's shock wave.
  • a delay blasting cap in its tip, such cap made of a metal cap containing two layers of explosive powder pressed inside, the bottom layer being a secondary high explosive, and the upper layer being a primary, flame-sensitive explosive, complemented by a delay element consisting of a metallic cylinder containing in its interior a compacted column of powdery pyrotechnic delay mixture and, frequently, an additional column of pyrotechnic mixture sensitive to the heat generated by the tube's shock wave.
  • Pyrotechnic shock tube as foreseen in the Brazilian patent PI 8104552 , from the applicant of the present patent, has the following disadvantages:
  • mixtures of powdered aluminum, whose temperature of Tammann is 193°C and ferrous-ferric oxide, Fe 3 O 4 , whose temperature of Tammann is 632°C are particularly difficult to start and propagate, while mixtures of powdered aluminum and potassium chlorate, whose temperature of Tammann is only 47,5°C, is especially dangerous.
  • One of the invention bases is to obtain enough activation energy to warranty the initiation and propagation of the pyrotechnic reaction even with the contamination of the interior of the tube by hydrocarbon fuel coming from explosive emulsion, such contamination decreasing the enthalpy pyrotechnic reaction.
  • potassium perchlorate potassium chlorate, antimony trisulfide, sulfur, potassium nitrate, ammonium perchlorate, sodium chlorate, or any substance whose temperature of Tammann is adapted to this purpose.
  • the invention is also based, without being limited to this, in the observation that a pyrotechnic reaction that generates products with high thermal conductivity and thermal convection coefficient, will allow a better propagation continuity, and will ignite delay elements with greater thermal efficiency, allowing the use of smaller, slower delay columns without additional ignition elements.
  • this gas volume cannot be excessive, otherwise there will be the dispersal of the solid and liquid products of the spark in the tip of the tube, combined with the gaseous expansion, what will provoke the loss of the thermal energy necessary for ignition of the delay element.
  • appropriate components for gas generation are antimony trisulfide, potassium perchlorate, potassium nitrate, sodium nitrate, ammonium perchlorate, sodium perchlorate, etc.
  • Another knowledge taken into account as base for the invention is that certain products present lubricating properties and superficial adherence properties, what reduces the sensibility to the friction and mechanical shock of the mixture, and provides adhesiveness even to difficult polymers like pure LLDPE. Examples of such products are: talc (magnesium and aluminum hydrosilicate) and graphite.
  • Another objective of the invention is to obtain an unpublished process in that the mixture of the oxidizers and additive is done in separate from the fuels or reduction agents, and that the final active mixture is obtained in the own plastic extruder, in an automated, continuous or semi-batch process, so that just a very small amount of pyrotechnic mixture is formed at any instant, minimizing the risks and effects of an accidental ignition of the tube during the industrial production.
  • Another aspect taken as base for the invention is that, to propagate through eventual cuts or holes accidentally done in the tube during field application, the spark should be constituted so much by products of high heat transfer, as by gaseous products, in a way to happen both the heat transfer to allow the continuity of the pyrotechnic signal transmission as to allow the mechanical impulse for releasing of the spark for the open portion of the tube.
  • the components of the pyrotechnic mixture formulation can have combined characteristics, in other words, the same substance component can have more than a function as mentioned above at the same time.
  • the characteristics of the components of the formulation can be applied to conventional shock tubes, individually or combined, with the aim of optimizing them to obtain a better performance, a higher safety in production and a decrease in the environmental and occupational health risks.
  • Additional steps of processing could include tube cooling, stretching of the tube to obtain tensile strength, thermal treatment of the tube, and other techniques conventional in the plastic processing area, without loss for the invention teachings.
  • the final product, thermal shock tube uses conventional plastic tube, such as EVA, POLYETHYLENE, LLDPE or SURLYN, with outer diameter ranging from 2.0 to 6.0 mm and inner diameter ranging from 1.0 to 5.0 mm and containing 5 to 40 mg/m of pyrotechnic mixture adhered to its internal walls; TABLE 1 - Practical Tests Results Formulation Speed of propagation Minimum gap between kinks in kink propagation test Tight knot propagation Low energy detonating cord initiation Shock Sensibility Slower Delay Sensibility all-fire air gap Initiation after exposure to the hot explosive emulsion Adherence of the mixture to the tube (% of free powder) Al 65% * Fe 3 O 4 17% KClO 4 17% Talc 1.0% 750 m / s Failure at any distance 3 f-kg 8% 9.2 N 8 cm 80 mm 25% 5% Al 50 % Fe 3 O 4 24.5% KClO 4 29.5% Talc 1.0% 1170 m / s 1

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Air Bags (AREA)
  • Lining Or Joining Of Plastics Or The Like (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Pipe Accessories (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)

Claims (3)

  1. Funkenerzeugendes Rohr, gekennzeichnet durch eine pyrotechnische Mischung, weiche an einer Innenwand eines Kunststoffrohrs anhaftet, umfassend die folgenden festen pulvrigen Stoffe:
    a) zwischen 32% und 60% eines pulvrigen Brennstoffs oder eines Reduzierungsstoffes, der einen Hochtemperaturfunken erzeugt, ausgewählt aus der Gruppe bestehend aus Aluminium, Magnesium, Silizium, Bor und Zirkonium,
    b) 15% bis 35% eines Stoffes, der Produkte mit hoher Wärmegleitfähigkeit und/oder Konvektionseigenschaften erzeugt, ausgewählt aus der Gruppe bestehend aus Eisen(II, III)-oxid - Fe3O4, Eisen(III)-oxid - Fe2O3, Eisen(II)-oxid - FeO, Kobaltoxid CoO, Kupfer(II)-oxid - CuO oder Kupfer(I)-oxid - Cu2O;
    c) 20% bis 40% eines Stoffes, der die Aktivierungsenergie der pyrotechnischen Reaktion erniedrigt und gasförmige Produkte erzeugte die ein Volumen aufweisen, das groß genug ist, um sich durch Knickstellen, Knoten oder Rohrverengungen zu verbreiten, ausgewählt aus der Gruppe bestehend aus Kaliumperchlorat - KClO4, Kaliumchlorat oder Kaliumnitrat, Amoniumperchlorat, Natriumperchlorat, Schwefel oder Antimontrisulfid;
    d) 0,5% bis 3% eines Stoffes, der die Anhaftung fördert und die Schlag- und Reibungsempfindlichkeit der pyrotechnischen Mischung vermindert, ausgewählt aus der Gruppe bestehend aus Talk und Grafit.
  2. Rohr gemäß Anspruch 1, dadurch gekennzeichnet, dass die optimierte Rezeptur der pyrotechnischen Mischung davon umfasst:
    a. 32% bis 60% pulvriges Aluminium;
    b. 15% bis 35% pulvriges Eisen(II)-Eisen(III)-oxid - Fe3O4;
    c. 20% bis 40% Kaliumperchlorat - KClO4;
    d. 0,5% bis 3 % Talk.
  3. Verfahren zur Herstellung eines funkenerzeugenden Rohrs gemäß Anspruch 1, umfassend die Schritte:
    a) gründliche Mischen eines Stoffes ausgewählt aus der in Anspruch 1 definierten Gruppe a) und eines Stoffes aus der in Anspruch 1 definierten Gruppe b) und eines Stoffes aus der in Anspruch 1 definierten Gruppe c), dadurch Ausbilden einer Mischung (I);
    b) Einführen der Mischung (I) in ein erstes Dosierungssilo und der Stoffe a) aus Anspruch 1 in ein zweites Dosierungssilo;
    c) kontinuierliches Dosieren abgestimmter Anteile der Mischung (I) und der Stoffe a) von Anspruch 1 durch zwei parallele gewindeartige Dosierungseinrichtungen oder durch Vibrationsdosierungseinrichtungen oder beliebige andere herkömmliche Gewichts- oder Volumenmikrodosierungsmittel, die mit elektrischen Motoren mit Frequenzregler oder beliebigen anderen herkömmlichen Reglern in einem Regelkreis mit einem Kunststoffrohrextruder versehen sind, wobei die dosierten abgestimmten Anteile kontinuierlich einen Walzenhomogenisierungsmixer erreichen, der einen unteren Filter aufweist, wodurch die endgültige empfindliche pyrotechnische Mischung hergestellt wird, wobei der untere Filter an einem Extrusionsring des Kunststoffrohrextruders angeschlossen ist;
    d) gleichzeitig mit Schritt c), Extrudieren eines geschmolzenen herkömmlichen Polymers durch den Extrusionsring, wodurch ein Kunststoffrohres ausgebildet wird, in dem gleichzeitig aufgrund der Schwerkraft die endgültige pyrotechnische Mischung innerhalb des gebildeten Kunststoffrohres dosiert wird, wodurch das funkenerzeugende Rohr erhalten wird.
EP04761538A 2003-09-19 2004-09-20 Verfahren zur herstellung eines funkenerzeugenden rohrs und produkt davon Active EP1663913B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
BRPI0303546-8A BR0303546B8 (pt) 2003-09-19 2003-09-19 tubo de choque tÉrmico.
PCT/BR2004/000178 WO2005028401A1 (en) 2003-09-19 2004-09-20 Process for production of thermal shock tube, and product thereof

Publications (2)

Publication Number Publication Date
EP1663913A1 EP1663913A1 (de) 2006-06-07
EP1663913B1 true EP1663913B1 (de) 2008-09-03

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Family Applications (1)

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EP04761538A Active EP1663913B1 (de) 2003-09-19 2004-09-20 Verfahren zur herstellung eines funkenerzeugenden rohrs und produkt davon

Country Status (26)

Country Link
US (1) US20050109230A1 (de)
EP (1) EP1663913B1 (de)
JP (1) JP2007505807A (de)
KR (1) KR100848214B1 (de)
CN (1) CN100506758C (de)
AP (1) AP1838A (de)
AR (1) AR045772A1 (de)
AT (1) ATE407105T1 (de)
AU (1) AU2004274048B2 (de)
BR (1) BR0303546B8 (de)
CA (1) CA2538734A1 (de)
CO (1) CO5630033A1 (de)
DE (1) DE602004016355D1 (de)
EA (1) EA009360B1 (de)
EC (1) ECSP045304A (de)
ES (1) ES2313045T3 (de)
MX (1) MXPA06001056A (de)
NO (1) NO20061632L (de)
NZ (1) NZ580211A (de)
PA (1) PA8612701A1 (de)
PE (1) PE20050272A1 (de)
PT (1) PT1663913E (de)
RS (1) RS20060181A (de)
UA (1) UA83253C2 (de)
WO (1) WO2005028401A1 (de)
ZA (1) ZA200601486B (de)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006008706A2 (en) * 2004-07-14 2006-01-26 University Of Pretoria An alternate oxidant for a delay composition
CN100348554C (zh) * 2006-03-31 2007-11-14 谢新佑 一种用于烟花爆竹的复合氧化剂
CZ306750B6 (cs) * 2006-10-27 2017-06-14 Austin Detonator S.R.O. Detonační trubice průmyslové neelektrické rozbušky pro zlepšení separovatelnosti od zpracovávané rubaniny
BR102014024720A2 (pt) * 2014-10-03 2016-05-24 Pari Sa tubo condutor de fagulha térmica com uso de partículas nanométricas
CN104439756B (zh) * 2014-12-29 2016-03-30 湖南天佑科技有限公司 一种无源自滋生高热自动焊接碳钢类金属的膏体及其制备方法与使用方法
US11592269B2 (en) 2015-09-17 2023-02-28 I P Creations Limited Flash directed reactive target and method of manufacture
US10288390B2 (en) 2015-09-17 2019-05-14 I P Creations Limited Concealed amalgamated explosive neutralizer and method of manufacture
US12000681B2 (en) 2015-09-17 2024-06-04 I P Creations Limited Biodegradable reactive shooting target and method of manufacture
FR3076830B1 (fr) * 2018-01-17 2022-01-28 Nexter Munitions Composition retard pyrotechnique
MX2020005672A (es) * 2018-02-21 2022-09-06 Enaex S A Cápsula detonante de mezcla metálica.

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JPS57140394A (en) * 1981-02-20 1982-08-30 Nissan Motor Time delay line
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US4522665A (en) 1984-03-08 1985-06-11 Geo Vann, Inc. Primer mix, percussion primer and method for initiating combustion
US4757764A (en) * 1985-12-20 1988-07-19 The Ensign-Bickford Company Nonelectric blasting initiation signal control system, method and transmission device therefor
GB2242010B (en) * 1990-03-15 1993-10-13 Ici Plc Low energy fuse
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US5212341A (en) * 1991-08-15 1993-05-18 Osborne Alfred M Co-extruded shock tube
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JPH09328387A (ja) * 1996-06-03 1997-12-22 Daicel Chem Ind Ltd ガス発生剤組成物
US5827994A (en) 1996-07-11 1998-10-27 The Ensign-Bickford Company Fissile shock tube and method of making the same
US5866842A (en) * 1996-07-18 1999-02-02 Primex Technologies, Inc. Low temperature autoigniting propellant composition

Also Published As

Publication number Publication date
CA2538734A1 (en) 2005-03-31
PA8612701A1 (es) 2005-03-28
WO2005028401A1 (en) 2005-03-31
US20050109230A1 (en) 2005-05-26
BR0303546A (pt) 2005-05-10
JP2007505807A (ja) 2007-03-15
AP1838A (en) 2008-04-07
ECSP045304A (es) 2004-11-26
NZ580211A (en) 2010-12-24
CN1852875A (zh) 2006-10-25
ES2313045T3 (es) 2009-03-01
KR20060035800A (ko) 2006-04-26
AU2004274048B2 (en) 2008-10-23
BR0303546B1 (pt) 2013-01-08
AU2004274048A1 (en) 2005-03-31
PT1663913E (pt) 2008-12-16
RS20060181A (en) 2007-12-31
PE20050272A1 (es) 2005-04-28
EA200600583A1 (ru) 2006-08-25
BR0303546B8 (pt) 2013-02-19
EP1663913A1 (de) 2006-06-07
ZA200601486B (en) 2007-05-30
NO20061632L (no) 2006-06-16
KR100848214B1 (ko) 2008-07-24
EA009360B1 (ru) 2007-12-28
CO5630033A1 (es) 2006-04-28
AR045772A1 (es) 2005-11-09
CN100506758C (zh) 2009-07-01
DE602004016355D1 (de) 2008-10-16
AP2006003526A0 (en) 2006-02-28
ATE407105T1 (de) 2008-09-15
UA83253C2 (ru) 2008-06-25
MXPA06001056A (es) 2006-03-17

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