WO2001019757A2 - Gas generants containing silicone fuels - Google Patents

Gas generants containing silicone fuels Download PDF

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Publication number
WO2001019757A2
WO2001019757A2 PCT/US2000/025584 US0025584W WO0119757A2 WO 2001019757 A2 WO2001019757 A2 WO 2001019757A2 US 0025584 W US0025584 W US 0025584W WO 0119757 A2 WO0119757 A2 WO 0119757A2
Authority
WO
WIPO (PCT)
Prior art keywords
gas generant
silicone
generant composition
metal
group
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.)
Ceased
Application number
PCT/US2000/025584
Other languages
English (en)
French (fr)
Other versions
WO2001019757A3 (en
Inventor
Graylon K. Williams
Sean P. Burns
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.)
Automotive Systems Laboratory Inc
Original Assignee
Automotive Systems Laboratory Inc
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 Automotive Systems Laboratory Inc filed Critical Automotive Systems Laboratory Inc
Priority to JP2001523340A priority Critical patent/JP2003529515A/ja
Priority to EP00963598A priority patent/EP1377534A2/en
Publication of WO2001019757A2 publication Critical patent/WO2001019757A2/en
Anticipated expiration legal-status Critical
Publication of WO2001019757A3 publication Critical patent/WO2001019757A3/en
Ceased legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C06EXPLOSIVES; MATCHES
    • C06BEXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B33/00Compositions 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
    • C06B33/06Compositions 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 an inorganic oxygen-halogen salt
    • CCHEMISTRY; METALLURGY
    • C06EXPLOSIVES; MATCHES
    • C06BEXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B23/00Compositions characterised by non-explosive or non-thermic constituents
    • C06B23/04Compositions characterised by non-explosive or non-thermic constituents for cooling the explosion gases including antifouling and flash suppressing agents
    • 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 generally relates to gas generant compositions for inflators of occupant restraint systems.
  • High gas yield gas generants often lose large amounts of heat to the inflator body and surroundings during combustion, and thereby result in a lower generant burn rate and a reduced performance.
  • Compositions provided in accordance with the present invention exhibit a rapid and sustained burn at ambient pressure.
  • Other benefits may include a relatively lower combustion temperature and/or an increase in the moles of gas produced per gram of gas generant composition.
  • compositions or propellants containing silicone and a perchlorate oxidizer exhibit a relatively rapid burn rate and sustainable combustion at ambient pressure. Nevertheless, to sustain combustion, the combustion temperature is quite hot. As a result, these compositions are not suitable for certain applications unless an adequate heat sink is also provided. Therefore, the manufacturing cost of the inflator or combustion vessel again increases.
  • Silicone as a fuel is advantageous over other known nonazide fuels known to be useful in occupant restraint systems, for example. Because silicone does not contain nitrogen, undesirable nitrogen oxides are reduced or eliminated as combustion products. Additionally, silicone also provides elasticity to the gas generant composition thereby reducing the propensity for fracture of the gas generant over time. Finally, silicone aids in sustaining combustion at ambient pressure.
  • gas generant compositions containing silicone as a fuel an oxidizer selected from the group including metal and nonmetal perchlorates such as potassium perchlorate, lithium perchlorate, and ammonium perchlorate; and, a coolant selected from the group including metal carbonates, metal bicarbonates, metal oxalates, and metal hydroxides.
  • an oxidizer selected from the group including metal and nonmetal perchlorates such as potassium perchlorate, lithium perchlorate, and ammonium perchlorate
  • a coolant selected from the group including metal carbonates, metal bicarbonates, metal oxalates, and metal hydroxides the addition of a coolant to a composition containing a perchlorate oxidizer and a silicone fuel results in a composition that combusts at rapid and sustained burn rates at ambient pressure. Additionally, the combustion temperature is substantially lower than other state of the art compositions.
  • Preferred gas generant compositions contain coolants having more negative heats of formation. Stated another way, preferred coolants of the present invention will preferably exhibit a relatively greater negative heat of formation. Accordingly, dissociation of the coolant upon combustion of the gas generant composition results in an endothermic combustion reaction thereby resulting in a cooler combustion temperature. Furthermore, when coolants such as strontium carbonate are employed, strontium silicate is formed thereby forming an insulation around the propellant as it burns. As a result, the heat that is released upon combustion is conserved by the insulating effect of the metal silicate. Although strontium carbonate is the most preferred coolant, other metal salts also exhibit similar characteristics.
  • compositions containing at least one silicone polymer (organosiloxane polymers) as a fuel, at least one oxidizer, and at least one coolant component containing a metallic salt and/or base combust at ambient pressure at acceptable combustion temperatures.
  • Silicone is defined as any of a large group of siloxane polymers based on a structure consisting of alternate silicon and oxygen atoms with various organic radicals (or functional groups) attached to the silicon. Radicals include, but are not limited by the group including methyl, methoxy, and amino.
  • silicone organosiloxane
  • Hawley describes silicone (organosiloxane) as any of a large group of siloxane polymers based on a structure consisting of alternate silicon and oxygen atoms with various organic radicals attached to the silicon:
  • Formula 2 Silicone Example Note, "n" in the Formulas indicates a multiple of the polymeric group or portion of the molecule given within the brackets, to include the organic groups attached to the silicon.
  • Exemplary silicones include those disclosed in U.S. Patent Nos.
  • compositions of the present invention contain silicone as a fuel.
  • the fuel component is provided at 1 0-25% by weight of the gas generant composition.
  • the gas generant compositions of the present invention contain one or more primary oxidizers selected from the group including metal and nonmetal perchlorates.
  • exemplary secondary oxidizers include but are not limited to phase stabilized ammonium nitrate, ammonium nitrate, potassium nitrate, and strontium nitrate. Stated another way, secondary oxidizers may be selected from the group including metal and nonmetal chlorates, oxides, nitrates, and nitrites, or other well known oxidizers.
  • a coolant is selected from the group including metal carbonates, metal oxalates, metal bicarbonates, and metal hydroxides.
  • Metal is defined as alkali, alkaline earth, and transitional metals.
  • Exemplary coolants include but are not limited to strontium carbonate, magnesium carbonate, calcium carbonate, potassium carbonate, strontium oxalate, and magnesium hydroxide.
  • An additional benefit of the coolant is that upon combustion, the resulting metal and silicate ions formed during combustion will form metal silicates. As a result, a coating will form within the combustion chamber and insulate the propellant within the pressure vessel thereby conserving the heat of reaction and contributing to a strong and sustained burn rate at ambient pressure.
  • compositions include silicone, a metal perchlorate oxidizer, and an alkaline earth carbonate.
  • a most preferred composition contains silicone, potassium perchlorate, and strontium carbonate. This composition results in the formation of strontium silicates. The substantial negative heat of formation of strontium carbonate results in an endothermic combustion reaction. As a result the combustion temperature is reduced. counters the heat loss that generally results from high gas yield gas generants.
  • Metal silicates are formed upon combustion of the gas generant compositions containing silicone and metal salts as coolants.
  • Strontium silicates or other metal silicates
  • the gas generant composition contains 10-25% by weight of silicone, 30-85% by weight of a primary oxidizer, and 1 -30% by weight of a coolant. If desired, one or more secondary oxidizers are employed at 30-50% by weight of the gas generant composition.
  • the gas generant constituents in similarly sized granular or smaller particulates are added to a tumble blender at 100°C and homogeneously blended, preferably for at least two hours. Silicone is preferably added as a resin that is previously blended with a curing agent. In general, the order in which the constituents are added is not critical so long as they are homogeneously blended. Other known wet and dry blending methods may also be used. Once blending is complete, the gas generant constituents may be extruded or formed into specific shapes such as elongated extrusions, pellets, sheets, or granules.
  • Table 1 exemplifies the present invention. As shown in the table, compositions consisting of silicone and a perchlorate oxidizer have rapid and sustained burn rates (at 3000 psi) greater than or equal to one inch per second. These combustion properties have been observed at ambient pressure wherein the burn rate is approximately 0.4 inches per second or greater. Nevertheless, the combustion temperatures are relatively high. See Examples 2 and 3. However, when a coolant such as a metal carbonate is added, the temperatures (Celsius) in certain cases are notably reduced. See Examples 1 7, 21 , and 24, for example.
  • compositions containing ammonium nitrate and/or other metal nitrates or secondary oxidizers in amounts greater than 50% by weight of the gas generant composition did not exhibit sufficient burn rates (.4 inches per second or greater) at ambient pressure.
  • Strontium salts that are not oxidizers are preferred given the greater cooling effect.
  • certain compositions exhibit relatively higher temperatures than a preferred embodiment containing silicone, strontium carbonate and potassium perchlorate, for example, but still sustained rapid combustion at ambient pressure. As a result, these compositions are still desirable from the perspective that a less robust inflator is required.
  • Combustion properties may be tailored by adding known ballistic modifiers and catalysts if desired.
  • the gas generant constituents of the present invention are available from well-known sources such as Fisher Chemical or Aldrich.
  • the silicone polymers may be purchased, for example, from General Electric in Waterford, New York.
  • compositions of the present invention are useful in many applications requiring gas generation. These compositions have particular utility as gas generant compositions that may be combusted to inflate an airbag in a vehicle occupant protection system, for example.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Air Bags (AREA)
  • Feeding, Discharge, Calcimining, Fusing, And Gas-Generation Devices (AREA)
PCT/US2000/025584 1999-09-16 2000-09-18 Gas generants containing silicone fuels Ceased WO2001019757A2 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2001523340A JP2003529515A (ja) 1999-09-16 2000-09-18 シリコーン燃料を含むガス発生剤
EP00963598A EP1377534A2 (en) 1999-09-16 2000-09-18 Gas generants containing silicone fuels

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US15429399P 1999-09-16 1999-09-16
US15424299P 1999-09-16 1999-09-16
US60/154,293 1999-09-16
US60/154,242 1999-09-16

Publications (2)

Publication Number Publication Date
WO2001019757A2 true WO2001019757A2 (en) 2001-03-22
WO2001019757A3 WO2001019757A3 (en) 2003-10-23

Family

ID=26851277

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2000/025584 Ceased WO2001019757A2 (en) 1999-09-16 2000-09-18 Gas generants containing silicone fuels

Country Status (3)

Country Link
EP (1) EP1377534A2 (enExample)
JP (1) JP2003529515A (enExample)
WO (1) WO2001019757A2 (enExample)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2077258A1 (en) * 2007-12-11 2009-07-08 Daicel Chemical Industries, Ltd. Gelatinous enhancer for inflator
EP1633688A4 (en) * 2003-05-23 2011-12-28 Autoliv Asp Inc SOFT SOFTENER CONTAINING CO-EXTRUDED PROPULSION GAS AND HUMIDITY BARRIER AND PROPULSION GAS COMPOSITIONS USED THEREWITH
WO2012108764A1 (en) * 2011-02-07 2012-08-16 Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno Chemical carbon dioxide gas generator
DE102012217718A1 (de) 2011-09-30 2013-04-04 Diehl Bgt Defence Gmbh & Co. Kg Pyrotechnische Kaltgasgeneratoren
CN111433172A (zh) * 2018-01-17 2020-07-17 Arc汽车有限公司 非硝酸铵基推进剂

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4672974B2 (ja) * 2003-10-22 2011-04-20 ダイセル化学工業株式会社 ガス発生剤組成物

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL121978C (enExample) * 1964-03-23
DE2150465C3 (de) * 1971-10-09 1978-05-24 Bayern-Chemie Gesellschaft Fuer Flugchemische Antriebe Mbh, 8261 Aschau Feststoffgasgenerator eines Aufprallschutzsystems für die Insassen eines Kraftfahrzeuges
FR2190776B1 (enExample) * 1972-07-05 1976-10-29 Poudres & Explosifs Ste Nale
FR2213254B1 (enExample) * 1972-10-17 1977-08-05 Poudres & Explosifs Ste Nale
US4309229A (en) * 1975-12-31 1982-01-05 Allied Chemical Corporation Method of generating water vapor free gas
US5656793A (en) * 1994-05-09 1997-08-12 Eiwa Chemical Ind. Co., Ltd. Gas generator compositions
US5486248A (en) * 1994-05-31 1996-01-23 Morton International, Inc. Extrudable gas generant for hybrid air bag inflation system
FR2728562B1 (fr) * 1994-12-22 1997-01-24 Poudres & Explosifs Ste Nale Procede de fabrication en continu de chargements pyrotechniques a liant silicone et compositions susceptibles d'etre mises en oeuvre par ce procede
FR2730965B1 (fr) * 1995-02-23 1997-04-04 Livbag Snc Generateur pyrotechnique de gaz pour coussin gonflable d'un vehicule automobile
US5847311A (en) * 1996-10-22 1998-12-08 Trw Vehicle Safety Systems Inc. Hybrid inflator with crystalline and amorphous block copolymer

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1633688A4 (en) * 2003-05-23 2011-12-28 Autoliv Asp Inc SOFT SOFTENER CONTAINING CO-EXTRUDED PROPULSION GAS AND HUMIDITY BARRIER AND PROPULSION GAS COMPOSITIONS USED THEREWITH
EP2077258A1 (en) * 2007-12-11 2009-07-08 Daicel Chemical Industries, Ltd. Gelatinous enhancer for inflator
WO2012108764A1 (en) * 2011-02-07 2012-08-16 Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno Chemical carbon dioxide gas generator
US9744509B2 (en) 2011-02-07 2017-08-29 Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno Chemical carbon dioxide gas generator
DE102012217718A1 (de) 2011-09-30 2013-04-04 Diehl Bgt Defence Gmbh & Co. Kg Pyrotechnische Kaltgasgeneratoren
CN111433172A (zh) * 2018-01-17 2020-07-17 Arc汽车有限公司 非硝酸铵基推进剂

Also Published As

Publication number Publication date
WO2001019757A3 (en) 2003-10-23
JP2003529515A (ja) 2003-10-07
EP1377534A2 (en) 2004-01-07

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