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US20100051149A1 - Pyrotechnic Grains of Large Dimensions, and Their Production and Use - Google Patents

Pyrotechnic Grains of Large Dimensions, and Their Production and Use Download PDF

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Publication number
US20100051149A1
US20100051149A1 US12/225,812 US22581207A US2010051149A1 US 20100051149 A1 US20100051149 A1 US 20100051149A1 US 22581207 A US22581207 A US 22581207A US 2010051149 A1 US2010051149 A1 US 2010051149A1
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US
United States
Prior art keywords
pyrotechnic
grains
granules
charge
porosity
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.)
Abandoned
Application number
US12/225,812
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English (en)
Inventor
Hélène Blanchard
Vincent Bodart
Hugues Rocton
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.)
Safran Ceramics SA
Original Assignee
SNPE Materiaux Energetiques SA
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 SNPE Materiaux Energetiques SA filed Critical SNPE Materiaux Energetiques SA
Assigned to SNPE MATERIAUX ENERGETIQUES reassignment SNPE MATERIAUX ENERGETIQUES ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: BLANCHARD, HELENE, BODART, VINCENT, ROCTON, HUGUES
Publication of US20100051149A1 publication Critical patent/US20100051149A1/en
Abandoned legal-status Critical Current

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    • CCHEMISTRY; METALLURGY
    • C06EXPLOSIVES; MATCHES
    • C06BEXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B45/00Compositions or products which are defined by structure or arrangement of component of product
    • CCHEMISTRY; METALLURGY
    • C06EXPLOSIVES; MATCHES
    • C06BEXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B21/00Apparatus or methods for working-up explosives, e.g. forming, cutting, drying
    • C06B21/0033Shaping the mixture
    • C06B21/0041Shaping the mixture by compression
    • CCHEMISTRY; METALLURGY
    • C06EXPLOSIVES; MATCHES
    • C06DMEANS FOR GENERATING SMOKE OR MIST; GAS-ATTACK COMPOSITIONS; GENERATION OF GAS FOR BLASTING OR PROPULSION (CHEMICAL PART)
    • C06D5/00Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets
    • C06D5/06Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets by reaction of two or more solids

Definitions

  • the present invention relates to large pyrotechnic grains based on binder-free formulations, to their production, and to their use. More precisely, it relates to:
  • Gas generation has a number of applications, both in the civilian and in military fields.
  • compositions with a high combustion rate In the automotive safety sector, gas generators have been developed with a short operational duration, which use compositions with a high combustion rate. Those compositions are in the form of thin pellets (1 mm [millimeter] to 3 mm) with a small diameter (3 mm to 7 mm). This provides them with a large combustion surface, encouraging a high rate over a short period (necessary for airbag applications in automotive safety, of the driver's airbag type). The porosity of such pellets is generally less than 4%. Pelletization operations carried out to produce said pellets are well known, similar to those used in medicinal formulations. Compositions based on guanidine nitrate and basic copper nitrate have been used in that context (United States patent U.S. Pat. No. 5,608,183). An attempt has even been made to improve the combustion rate (U.S. Pat. No. 6,143,102) since said combustion rate of such compositions is rather low, compared with that of other compositions used in the same field
  • That relates to the field of slow gas generation.
  • a gas stored under pressure is generally used.
  • the use of chemical reactions or the combustion of pyrotechnic cartridges has also been mentioned.
  • the flow rate of the gas that is generated is controlled by selecting the characteristics of the propellant, the geometry of the cartridges, and/or the conditions for ejecting said generated gas, etc.
  • the present invention falls within the context of generators operation providing long duration, low flow rate, and low operating pressure.
  • the present invention proposes pyrotechnic grains that are simple in shape and that satisfy the following specifications:
  • a long combustion period 50 ms [millisecond] to 1 min [minute] due to a slow combustion rate (to ensure a long period of operation) and/or to a ratio of combustion area over burning thickness that is low, and/or to a low operating pressure (for use in low pressure generators and to encourage a low combustion rate);
  • the pyrotechnic grains of the invention are also advantageously non-aggressive for the gas generator in which they are used and for the associated system (i.e., on combustion, they generate neither particles nor corrosive species). In the same manner, the generated species are advantageously of low toxicity.
  • the pyrotechnic grain of the invention must be thick and have a small combustion area. Thus, it must be a large grain, larger than the pellets mentioned above.
  • the Applicant has obtained pyrotechnic grains, from specific oxidizing and reducing charges, which are simple in shape and that satisfy the above specifications.
  • Such pyrotechnic grains constitute the first aspect of the present invention.
  • Said pyrotechnic grains of the invention have a composition that comprises at least one (specific) oxidizing charge and at least one (specific) reducing charge, but that includes no binder.
  • they are pyrotechnic grains of the pellet type mentioned above.
  • the composition of the pyrotechnic grains of the invention generally essentially consists of at least one such (specific) oxidizing charge and at least one such (specific) reducing charge. It generally essentially consists of a (specific) oxidizing charge (an oxidizer) and a (specific) reducing charge (a reducer).
  • Said at least one specific oxidizing charge is selected from ammonium, potassium, sodium, barium, strontium, and basic copper nitrates, and ammonium, potassium, and sodium perchlorates, and mixtures thereof.
  • it comprises basic copper nitrate and/or potassium perchlorate.
  • it consists of basic copper nitrate or potassium perchlorate.
  • it consists of basic copper nitrate.
  • Said at least one specific reducing charge is selected from nitroguanidine, guanidine nitrate, and mixtures thereof. Preferably, it consists of guanidine nitrate.
  • said pyrotechnic grains of the invention are in the form of substantially cylindrical blocks:
  • Said (monolithic) blocks are large blocks, which are simple in shape and of low porosity.
  • Said blocks have a substantially cylindrical shape. Generally, but not exclusively, they are circular cylinders or near (quasi) circular cylinders.
  • the shape of the grains of the invention is the signature of the last step of the method by which they are obtained: a compacting step (see below).
  • Said blocks may in particular consist of solid (quasi) cylinders or (quasi) cylindrical sleeves.
  • the grains in question are large objects (thickness more than 5 mm, equivalent diameter (or, clearly, diameter if it is a perfect circular cylinder) of 10 mm or more), and are relatively dense (porosity in the range 1% to 8%).
  • Non-limiting dimensions of said grains are detailed below.
  • said thickness and said equivalent diameter are both 75 mm or less.
  • said thickness and said equivalent diameter are both as precised above.
  • said thickness and said equivalent diameter are both in the range 10 mm to 60 mm (values of 10 mm and 60 mm being included).
  • the porosity of the blocks is in the range 1% to 8% (it should be noted here that this parameter, expressed as a percentage, corresponds to the ratio between the actual density and the theoretical density; it is in fact the difference from the theoretical density).
  • Said porosity is advantageously 5% or less. It should be recalled that the lower said porosity, the lower the dependency of the rate of combustion on the operating temperature of the grain.
  • the pyrotechnic grains of the invention which are simple in shape, being substantially cylindrical, may in particular consist of solid cylinders or sleeves.
  • the equivalent internal diameter of said sleeves is advantageously more than 10 mm; preferably, it is in the range 12 mm to 35 mm (that implies obviously a greater equivalent diameter of the sleeve).
  • composition of the pyrotechnic grains of the invention the following non-limiting details can furthermore be given.
  • the said composition of the pyrotechnic grains of the invention advantageously includes basic copper nitrate as the oxidizing charge and guanidine nitrate as the reducing charge. Highly advantageously, it comprises basic copper nitrate as the only oxidizing charge and guanidine nitrate as the only reducing charge.
  • said basic copper nitrate/guanidine nitrate combination is known to have a combustion rate that is rather low relative to that of other compositions used in this field.
  • said composition generally comprises:
  • the additives in question are chemical compounds that are known per se as well as for their beneficial involvement in the general production of pyrotechnic grains.
  • they may be:
  • the present invention provides the production of large pyrotechnic grains, as described above.
  • the method in question comprises a series of steps that are known per se.
  • the method of producing pyrotechnic grains of the invention comprises carrying out the following steps in succession:
  • At least one of the charges used in the powder state has a median diameter that is substantially larger than that which is used in the prior art to prepare pellets (of small dimensions).
  • a median diameter that is substantially higher ( ⁇ 4, ⁇ 6) than that known to be used in the preparation of prior art pellets.
  • a reducing charge with a median diameter of 200 ⁇ m [micrometer] or more be used.
  • guanidine nitrate with a median diameter of 200 ⁇ m to 300 ⁇ m be used. Said guanidine nitrate is conventionally used for the fabrication of pellets, with a median diameter of 50 ⁇ m.
  • the granules selected are those that have a median diameter of more than 200 ⁇ m, preferably in the range 500 ⁇ m to 1000 ⁇ m. It is thus recommended, in the context of the present invention, that basic copper nitrate/guanidine nitrate granules with a median diameter in the range 500 ⁇ m to 700 ⁇ m or potassium perchlorate/guanidine nitrate granules with a median diameter in the range 500 ⁇ m to 1000 ⁇ m be selected.
  • a pressure in the range 15 ⁇ 10 6 Pa [pascal] to 35 ⁇ 10 6 Pa is applied for 0.1 s [second] to 30 s.
  • the method of the invention is very advantageously carried out with all the above advantageous embodiments, i.e.
  • the method of the invention is advantageously carried out with a combination of basic copper nitrate or potassium perchlorate/guanidine nitrate; highly advantageously, it is carried out with a basic copper nitrate/guanidine nitrate combination.
  • the combustion rate of compositions based on these two elements BCN/NG is reduced.
  • the teaching of the present invention thus goes against that of U.S. Pat. No. 6,143,102.
  • the present invention provides a method of generating gas, the method comprising, in conventional manner, the combustion of at least one pyrotechnic grain.
  • said method of the invention comprises the combustion of at least one pyrotechnic grain as described above (large pyrotechnic grain) and/or produced using the method described above.
  • Said gas generation method is carried out in a suitable device which, in particular, has a combustion chamber adapted to the dimensions of the original pyrotechnic charge, based on large pyrotechnic grains.
  • said device comprises:
  • Pyrotechnic grains of the invention were prepared from the following starting materials:
  • the intimate mixture of powders obtained was dry granulated in a Sahut Conreur® type granulator (an Alexanderwerk® type granulator would also have been suitable). Said intimate mixture of powders was forced through a screen. The granulometric distribution of the granules obtained was from 10 ⁇ m to 1000 ⁇ m.
  • the granules obtained were then sieved, and those with a mean diameter of more than 200 ⁇ m were selected.
  • Said selected granules were then compacted on a 35 (metric) tonne single action press.
  • the compacting pressure applied was 230 bars (23 ⁇ 10 6 Pa). It was applied for 10 s.
  • Pyrotechnic grains in accordance with the invention were obtained, which grains were cylindrical monoliths (shape of mold) with a thickness of 10 mm, a diameter of 24.6 mm, and porosity of 3%.
  • cylindrical grains were prepared as follows:
  • FIG. 3 With the prior art pellet, as expected, an operating peak was obtained ( FIG. 3 ). With the blocks of the invention, the desired spread over time was observed ( FIGS. 1 and 2 ).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Air Bags (AREA)
  • Feeding, Discharge, Calcimining, Fusing, And Gas-Generation Devices (AREA)
US12/225,812 2006-04-04 2007-04-03 Pyrotechnic Grains of Large Dimensions, and Their Production and Use Abandoned US20100051149A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR0651183 2006-04-04
FR0651183A FR2899227B1 (fr) 2006-04-04 2006-04-04 Objets pyrotechniques monolithes de grandes dimensions, obtention et utilisation
PCT/EP2007/053241 WO2007113299A1 (en) 2006-04-04 2007-04-03 Pyrotechnic grains of large dimensions, and their production and use

Publications (1)

Publication Number Publication Date
US20100051149A1 true US20100051149A1 (en) 2010-03-04

Family

ID=37806959

Family Applications (1)

Application Number Title Priority Date Filing Date
US12/225,812 Abandoned US20100051149A1 (en) 2006-04-04 2007-04-03 Pyrotechnic Grains of Large Dimensions, and Their Production and Use

Country Status (8)

Country Link
US (1) US20100051149A1 (ru)
EP (1) EP2001822B1 (ru)
CN (1) CN101415659A (ru)
CA (1) CA2648108C (ru)
FR (1) FR2899227B1 (ru)
NO (1) NO20084308L (ru)
RU (1) RU2437867C2 (ru)
WO (1) WO2007113299A1 (ru)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103739416A (zh) * 2013-12-17 2014-04-23 江西省李渡烟花集团有限公司 一种新型烟花银柳药
CN105237315A (zh) * 2015-08-18 2016-01-13 帅银飞 一种烟花亮珠自动造粒机
US10358393B2 (en) 2016-05-23 2019-07-23 Joyson Safety Systems Acquisition Llc Gas generating compositions and methods of making and using thereof
RU2722031C1 (ru) * 2019-08-29 2020-05-26 Акционерное общество "Федеральный научно-производственный центр "Научно-исследовательский институт прикладной химии" Пиротехнический состав красного огня

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9193639B2 (en) 2007-03-27 2015-11-24 Autoliv Asp, Inc. Methods of manufacturing monolithic generant grains
FR2926545B1 (fr) * 2008-01-21 2010-09-17 Snpe Materiaux Energetiques Composition generatrice de gaz azote, comprenant de l'azodicarbonamide et procede de generation de gaz azote par decomposition de ladite composition
DE102008020087B4 (de) * 2008-04-22 2019-10-10 GM Global Technology Operations LLC (n. d. Ges. d. Staates Delaware) Pyrotechnischer Aktuator mit Filter
FR2964656B1 (fr) * 2010-09-15 2012-10-12 Snpe Materiaux Energetiques Composes pyrotechniques generateurs de gaz
US9051223B2 (en) 2013-03-15 2015-06-09 Autoliv Asp, Inc. Generant grain assembly formed of multiple symmetric pieces
CN103214322A (zh) * 2013-05-15 2013-07-24 浏阳市合力高科发展有限公司 无硫烟火药组合物及其制造方法
FR3007659B1 (fr) 2013-06-28 2017-03-24 Herakles Procede de delivrance d'un liquide pressurise par les gaz de combustion d'au moins un chargement pyrotechnique
FR3022906B1 (fr) 2014-06-30 2016-07-15 Herakles Blocs monolithiques pyrotechniques generateurs de gaz
FR3037812B1 (fr) 2015-06-29 2017-08-04 Herakles Extincteur d'incendie
CN107698415A (zh) * 2017-10-24 2018-02-16 湖北航鹏化学动力科技有限责任公司 一种气体发生剂组合物、制备方法、应用及气体发生器
FR3077989B1 (fr) 2018-02-20 2021-11-19 Arianegroup Sas Extincteur d'incendie
CN109160868A (zh) * 2018-10-31 2019-01-08 湖北航天化学技术研究所 一种气囊用气体发生剂
CN111675589B (zh) * 2020-05-15 2021-08-06 湖北航鹏化学动力科技有限责任公司 一种气体发生剂组合物、制备方法及其应用
CN111548242B (zh) * 2020-05-15 2021-09-03 湖北航鹏化学动力科技有限责任公司 气体发生器

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4998751A (en) * 1990-03-26 1991-03-12 Morton International, Inc. Two-stage automotive gas bag inflator using igniter material to delay second stage ignition
US5500059A (en) * 1993-08-02 1996-03-19 Thiokol Corporation Anhydrous 5-aminotetrazole gas generant compositions and methods of preparation
US5608183A (en) * 1996-03-15 1997-03-04 Morton International, Inc. Gas generant compositions containing amine nitrates plus basic copper (II) nitrate and/or cobalt(III) triammine trinitrate
US5641938A (en) * 1995-03-03 1997-06-24 Primex Technologies, Inc. Thermally stable gas generating composition
US5682013A (en) * 1992-08-24 1997-10-28 Morton International, Inc. Gas generant body having pressed-on burn inhibitor layer
US6143102A (en) * 1999-05-06 2000-11-07 Autoliv Asp, Inc. Burn rate-enhanced basic copper nitrate-containing gas generant compositions and methods
US20040173922A1 (en) * 2003-03-04 2004-09-09 Barnes Michael W. Method for preparing pyrotechnics oxidized by basic metal nitrate
US20040216819A1 (en) * 1999-10-06 2004-11-04 Kazuya Serizawa Gas generating composition and method
US6814694B1 (en) * 1999-06-25 2004-11-09 Paul Scherrer Institut Device for carrying out proton therapy
US20060219340A1 (en) * 2005-03-31 2006-10-05 Dunham Steven M Gas generating system

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FR2772370B1 (fr) * 1997-12-12 2000-01-07 Poudres & Explosifs Ste Nale Compositions pyrotechniques generatrices de gaz non toxiques a base de perchlorate d'ammonium
JP2000086376A (ja) * 1998-09-14 2000-03-28 Daicel Chem Ind Ltd ガス発生剤組成物
JP2005538834A (ja) * 2002-09-12 2005-12-22 テクストロン システムズ コーポレーション 多段ガス発生器およびガス発生体
FR2864905B1 (fr) * 2004-01-09 2006-07-14 Airbus France Dispositif d'extinction de feu
FR2870459B1 (fr) * 2004-05-19 2006-08-25 Airbus France Sas Dispositif d'extinction de feu par injection d'un gaz genere par la combustion d'un bloc pyrotechnique
FR2887247B1 (fr) * 2005-06-15 2007-10-12 Snpe Materiaux Energetiques Procede de fabrication de pastilles generatrices de gaz comportant une etape de granulation par voie seche

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4998751A (en) * 1990-03-26 1991-03-12 Morton International, Inc. Two-stage automotive gas bag inflator using igniter material to delay second stage ignition
US5682013A (en) * 1992-08-24 1997-10-28 Morton International, Inc. Gas generant body having pressed-on burn inhibitor layer
US5500059A (en) * 1993-08-02 1996-03-19 Thiokol Corporation Anhydrous 5-aminotetrazole gas generant compositions and methods of preparation
US5641938A (en) * 1995-03-03 1997-06-24 Primex Technologies, Inc. Thermally stable gas generating composition
US5608183A (en) * 1996-03-15 1997-03-04 Morton International, Inc. Gas generant compositions containing amine nitrates plus basic copper (II) nitrate and/or cobalt(III) triammine trinitrate
US6143102A (en) * 1999-05-06 2000-11-07 Autoliv Asp, Inc. Burn rate-enhanced basic copper nitrate-containing gas generant compositions and methods
US6814694B1 (en) * 1999-06-25 2004-11-09 Paul Scherrer Institut Device for carrying out proton therapy
US20040216819A1 (en) * 1999-10-06 2004-11-04 Kazuya Serizawa Gas generating composition and method
US20040173922A1 (en) * 2003-03-04 2004-09-09 Barnes Michael W. Method for preparing pyrotechnics oxidized by basic metal nitrate
US20060219340A1 (en) * 2005-03-31 2006-10-05 Dunham Steven M Gas generating system

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103739416A (zh) * 2013-12-17 2014-04-23 江西省李渡烟花集团有限公司 一种新型烟花银柳药
CN105237315A (zh) * 2015-08-18 2016-01-13 帅银飞 一种烟花亮珠自动造粒机
US10358393B2 (en) 2016-05-23 2019-07-23 Joyson Safety Systems Acquisition Llc Gas generating compositions and methods of making and using thereof
RU2722031C1 (ru) * 2019-08-29 2020-05-26 Акционерное общество "Федеральный научно-производственный центр "Научно-исследовательский институт прикладной химии" Пиротехнический состав красного огня

Also Published As

Publication number Publication date
FR2899227A1 (fr) 2007-10-05
FR2899227B1 (fr) 2008-10-24
NO20084308L (no) 2008-10-23
EP2001822A1 (en) 2008-12-17
CA2648108C (en) 2014-04-22
WO2007113299A1 (en) 2007-10-11
CN101415659A (zh) 2009-04-22
RU2437867C2 (ru) 2011-12-27
CA2648108A1 (en) 2007-10-11
RU2008142975A (ru) 2010-05-10
EP2001822B1 (en) 2017-08-16

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Owner name: SNPE MATERIAUX ENERGETIQUES,FRANCE

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:BLANCHARD, HELENE;BODART, VINCENT;ROCTON, HUGUES;REEL/FRAME:023466/0013

Effective date: 20080925

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION