EP1087919B1 - Chargements pyrotechniques solides generateurs de gaz a base de composition contenant de l'eau - Google Patents

Chargements pyrotechniques solides generateurs de gaz a base de composition contenant de l'eau Download PDF

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Publication number
EP1087919B1
EP1087919B1 EP99920902A EP99920902A EP1087919B1 EP 1087919 B1 EP1087919 B1 EP 1087919B1 EP 99920902 A EP99920902 A EP 99920902A EP 99920902 A EP99920902 A EP 99920902A EP 1087919 B1 EP1087919 B1 EP 1087919B1
Authority
EP
European Patent Office
Prior art keywords
composition according
composition
binder
water
nitrate
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.)
Expired - Lifetime
Application number
EP99920902A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP1087919A1 (fr
Inventor
Christian Perut
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.)
Societe Nationale des Poudres et Explosifs
Original Assignee
Societe Nationale des Poudres et Explosifs
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.)
Filing date
Publication date
Application filed by Societe Nationale des Poudres et Explosifs filed Critical Societe Nationale des Poudres et Explosifs
Publication of EP1087919A1 publication Critical patent/EP1087919A1/fr
Application granted granted Critical
Publication of EP1087919B1 publication Critical patent/EP1087919B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
    • A62D1/06—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires containing gas-producing, chemically-reactive components
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B31/00—Compositions containing an inorganic nitrogen-oxygen salt
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B47/00—Compositions in which the components are separately stored until the moment of burning or explosion, e.g. "Sprengel"-type explosives; Suspensions of solid component in a normally non-explosive liquid phase, including a thickened aqueous phase
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06D—MEANS FOR GENERATING SMOKE OR MIST; GAS-ATTACK COMPOSITIONS; GENERATION OF GAS FOR BLASTING OR PROPULSION (CHEMICAL PART)
    • C06D5/00—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets

Definitions

  • the present invention relates to the field of pyrotechnic compositions generating cold gases, non-toxic and free of solid residues. More precisely the invention relates to the field of solid composite pyrotechnic compositions at amorphous structure comprising one or more oxidants and an organic binder in the gel state.
  • the essays according to the invention are well suited to constitute loads intended to inflate cushions protection or to ensure the functioning of a pyrotechnic fire extinguisher.
  • cold, non-toxic, residue-free gases solid.
  • the term "cold" gases means gases which are products at a temperature below about 1800 ° C.
  • liquid propellants consisting of aqueous solutions of compounds such as hydroxylammonium nitrate, triethanolammonium nitrate, aminotetrazole nitrate, nitrate aminotriazole, urea nitrate, biuret nitrate, etc.
  • liquid propellants are for example described in US Patents 5,060,973 and US 5,684,269.
  • these liquid propellants require suitable gas generators, the structure of which is complex and which are of a high cost price.
  • compositions constituted by a binder such as polyvinyl alcohol and by solid eutectics to based on ammonium nitrate and guanidine nitrates or aminoguanidine in the presence of nitrate or potassium perchlorate.
  • binder such as polyvinyl alcohol
  • solid eutectics to based on ammonium nitrate and guanidine nitrates or aminoguanidine in the presence of nitrate or potassium perchlorate.
  • the object of the present invention is precisely to meet this need.
  • Polyvinyl alcohol is the preferred binder because it improves the chemical stability of the compositions according to the invention.
  • the solid compositions according to the invention thus present an amorphous structure in which the binder is in the form of a solid impregnated gel by the aqueous hydroxylammonium phase.
  • the binder is in the form of a solid impregnated gel by the aqueous hydroxylammonium phase.
  • the water content by weight of the compositions according to the invention will be between 5 and 20%.
  • the invention thus makes it possible to have compositions which contain water contents much higher than the contents in humidity of previously known compositions.
  • the weight of the nitrate of hydroxylammonium represents at least 50% of the total weight of the composition, the content of the latter in hydroxylammonium nitrate preferably being between 60% and 70%.
  • One of the advantages of the present invention resides in the fact that at the indicated contents the mixtures water / hydroxylammonium nitrate remain liquid from the as long as the temperature does not drop below zero degrees Celsius.
  • the compositions according to the invention also contain secondary oxidants which are advantageously chosen in the group consisting of ammonium nitrate, hexogen (RDX) and octogen (HMX). These oxidants allow to increase the number of gaseous molecules produced by the combustion of a given volume of composition without the temperature of combustion gas does not increase too much thanks to the water contained in the composition.
  • secondary oxidants which are advantageously chosen in the group consisting of ammonium nitrate, hexogen (RDX) and octogen (HMX).
  • compositions when the compositions are intended to constitute loads pyrotechnics for gas generators in front inflate protective cushions for occupants of a motor vehicle, avoid the use of nitrate ammonium or in any case limit the content by weight of the ammonium nitrate composition to a few percent.
  • compositions will most often contain stabilizing additives who will be chosen from bipyridine, ammonium hydrogen phosphate and ammonium acetate.
  • the weight content of these stabilizers in the composition will be close to 2%.
  • Bipyridine and ammonium hydrogen phosphate are stabilizers preferred.
  • compositions will contain thickening additives which will be chosen from the group consisting of water-soluble isocyanates, melamine-formaldehyde resins and borax which is a sodium tetraborate of formula: Na 2 B 4 O 7 , 10H 2 O.
  • the kneading and extrusion apparatus is a twin-screw extruder.
  • the binder with gelling effect is polyvinyl alcohol and the twin-screw extruder is heated to a temperature between 50 ° C. and 60 ° C., the temperature inside the oven being close to 80 ° C.
  • all the constituents other than the binder and which are soluble in water will be mixed with the liquid phase containing the water and the hydroxylammonium nitrate before introduction of the latter into the twin-screw extruder.
  • the pyrotechnic charges thus obtained can in particular be used either in pyrotechnic extinguishers to constitute the source of engine gas in these fire extinguishers, either in pyrotechnic gas generators intended to inflate protective cushions for vehicle occupants automobile.
  • the installation shown in FIG. 1 basically comprises a twin-screw extruder 1 extended by an extrusion head 2, a conveyor belt 3 passing inside an oven 4 and a cutting system 5.
  • the first device consists of a pipe 6 connected via a tap 7 to a tank 8 provided with an agitator 9.
  • a second device feed consisting of a hopper 10 and a belt carrier 11.
  • the tank 8 contains a liquid mixture A consisting with water, hydroxylammonium nitrate and, if applicable constituents other than the binder and soluble in water such as ammonium nitrate.
  • the reactive constituents with respect to water are not incorporated into this aqueous liquid phase.
  • the conveyor belt 11 feeds the hopper 10 with a mixture of granules B comprising granules of binder and, if necessary, granules of additives not soluble in water and in particular oxidizing granules not soluble in water such as hexogen or octogen.
  • Extruder 1 is temperature controlled to have an internal temperature between 50 ° C and 60 ° C when the binder is polyvinyl alcohol.
  • the liquid phase A and the granules B are mixed in the extruder 1 to form, by gelation of the binder, a composite paste with an amorphous structure which is extruded through the extrusion head 2 in the form of a profiled rod 12.
  • This rod may be a simple cylindrical strand, possibly provided with internal channels, to give, after cutting, loose grains or be a rod of larger dimensions, with, if necessary, a worked external profile, to give after cutting. solid or annular blocks.
  • This rod 12 is led through the conveyor belt 3 through a heated oven to cause hardening of the gelled binder.
  • the binder is polyvinyl alcohol
  • the temperature of the oven will be close to 80 ° C. and the residence time of the rod in the oven will be a few minutes.
  • Example 1 Example 2 water 8 15% polyvinyl alcohol 20% 15% hydroxylammonium nitrate 68.5% 66.5% ammonium nitrate 3.5% 3.5%

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Business, Economics & Management (AREA)
  • Combustion & Propulsion (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Emergency Management (AREA)
  • Inorganic Chemistry (AREA)
  • Air Bags (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Feeding, Discharge, Calcimining, Fusing, And Gas-Generation Devices (AREA)
  • Treatment Of Sludge (AREA)
  • Glanulating (AREA)
EP99920902A 1998-06-05 1999-05-21 Chargements pyrotechniques solides generateurs de gaz a base de composition contenant de l'eau Expired - Lifetime EP1087919B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR9807090 1998-06-05
FR9807090A FR2779426B1 (fr) 1998-06-05 1998-06-05 Chargements pyrotechniques solides generateurs de gaz a base de compositions contenant de l'eau
PCT/FR1999/001206 WO1999064375A1 (fr) 1998-06-05 1999-05-21 Chargements pyrotechniques solides generateurs de gaz a base de composition contenant de l'eau

Publications (2)

Publication Number Publication Date
EP1087919A1 EP1087919A1 (fr) 2001-04-04
EP1087919B1 true EP1087919B1 (fr) 2002-12-04

Family

ID=9527056

Family Applications (1)

Application Number Title Priority Date Filing Date
EP99920902A Expired - Lifetime EP1087919B1 (fr) 1998-06-05 1999-05-21 Chargements pyrotechniques solides generateurs de gaz a base de composition contenant de l'eau

Country Status (6)

Country Link
EP (1) EP1087919B1 (ja)
JP (1) JP2002517376A (ja)
AT (1) ATE228984T1 (ja)
DE (1) DE69904326T2 (ja)
FR (1) FR2779426B1 (ja)
WO (1) WO1999064375A1 (ja)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100357234C (zh) * 2006-04-14 2007-12-26 安徽盾安化工集团有限公司 一种粉状铵油炸药及其制备方法
CN100357235C (zh) * 2006-04-14 2007-12-26 安徽盾安化工集团有限公司 无梯粉状改性铵油炸药及其制备方法
JP5110256B2 (ja) * 2006-12-12 2012-12-26 独立行政法人 宇宙航空研究開発機構 ガス発生剤組成物
JP2009190911A (ja) * 2008-02-13 2009-08-27 Daicel Chem Ind Ltd ガス発生剤組成物
DE102012104087A1 (de) * 2012-05-09 2013-11-14 Bayern-Chemie Gesellschaft Für Flugchemische Antriebe Mbh Gasgenerator-Treibstoff

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ZA835342B (en) * 1982-08-02 1985-01-30 Jet Research Center A stable single phase liquid explosive
GB2293820B (en) * 1988-12-20 1996-07-03 Aerojet General Co Liquid oxidizer compositions and their use in energetic formulations
US5060973A (en) * 1990-07-23 1991-10-29 General Electric Company Liquid propellant inflator for vehicle occupant restraint apparatus
US5386777A (en) * 1992-02-10 1995-02-07 Aero-Jet General Corporation Rocket motor construction from porous binder core
US5684269A (en) * 1996-03-15 1997-11-04 Morton International, Inc. Hydroxylammonium nitrate/water/self-deflagrating fuels as gas generating pyrotechnics for use in automotive passive restraint systems
US5703323A (en) * 1996-09-17 1997-12-30 Olin Corporation Pyridine and pyridone stabilizers for hydroxylammonium nitrate and hydroxylamine-containing compositions

Also Published As

Publication number Publication date
JP2002517376A (ja) 2002-06-18
WO1999064375A1 (fr) 1999-12-16
DE69904326T2 (de) 2003-08-28
DE69904326D1 (de) 2003-01-16
FR2779426A1 (fr) 1999-12-10
FR2779426B1 (fr) 2000-07-13
EP1087919A1 (fr) 2001-04-04
ATE228984T1 (de) 2002-12-15

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