WO2019143784A1 - Générateurs à base de nitrate non-ammonium - Google Patents

Générateurs à base de nitrate non-ammonium Download PDF

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Publication number
WO2019143784A1
WO2019143784A1 PCT/US2019/013955 US2019013955W WO2019143784A1 WO 2019143784 A1 WO2019143784 A1 WO 2019143784A1 US 2019013955 W US2019013955 W US 2019013955W WO 2019143784 A1 WO2019143784 A1 WO 2019143784A1
Authority
WO
WIPO (PCT)
Prior art keywords
airbag
formulation
gas generant
gas
generant formulation
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/US2019/013955
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English (en)
Inventor
James M. Rose
Timothy Wayne FRAZIER
Dan R. DENOMME
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.)
ARC Automotive Inc
Original Assignee
ARC Automotive 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 ARC Automotive Inc filed Critical ARC Automotive Inc
Priority to CN201980006212.1A priority Critical patent/CN111433172A/zh
Publication of WO2019143784A1 publication Critical patent/WO2019143784A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • C06B31/02—Compositions containing an inorganic nitrogen-oxygen salt the salt being an alkali metal or an alkaline earth metal nitrate
    • C06B31/12—Compositions containing an inorganic nitrogen-oxygen salt the salt being an alkali metal or an alkaline earth metal nitrate with a nitrated organic compound
    • 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
    • C06D5/06—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets by reaction of two or more solids

Definitions

  • ammonium nitrate based generants With ammonium nitrate based generants becoming unacceptable for usage in automotive airbag inflator applications regardless whether they are used in pyrotechnic or hybrid type inflators, alternate or non-ammonium nitrate containing generants are highly desirable. Even in a hybrid inflator where the generant is stored in a high-pressure inert gas atmosphere making moisture intrusion nearly impossible, ammonium nitrate based generants are still considered unacceptable.
  • the gas generant may be used as an airbag gas generant formulation.
  • This document discloses a number of gas generant formulations and it is understood that "formulation" or “the formulation” unless otherwise stated, may refer to any gas generant formulation(s) or airbag gas generant formulation(s) of this document. That is any non-ammonium nitrate based generants of this disclosure.
  • the airbag gas generant formulation (see, e.g., as claimed) can be optimized for airbag inflators, specifically hybrid airbag inflators.
  • One aspect is an airbag gas generant formulation comprising the following: 40 wt% to 50 wt% strontium nitrate; 35 wt% to 45 wt%
  • nitroguanidine 3 wt% to 7 wt% potassium perchlorate; 3 wt% to 6 wt% w/w polyvinyl alcohol; and 2 wt% to 6 wt% w/w strontium oxalate.
  • the ingredients may be adjusted to reach 100 wt% without any additional ingredients.
  • a filler may be used to adjust the ingredients to 100 wt%.
  • wt% refers to "weight percent" which is the weight of one chemical relative to the weight of the total airbag gas generant formulation. Where the wt% is less than 100%, an optional filler known to one of ordinary skill in the art may be added.
  • the filler can be an inert filler such as clay, chalk, and the like.
  • Inert filler refers to a chemical or ingredient that does not react with the other ingredients in the formulation in an environment where the formulation is usually found. Such an environment may be, for example, in an airbag inflator, in a warehouse, or in a car. Each of these locations may be subjected to the conditions expected of an airbag inflator, of a car or of a warehouse which include subfreezing to very hot conditions of a car, for example, in the sun and in a desert.
  • the gas generant formulations and airbag gas generant formulations of the disclosure has many desirable properties.
  • One aspect is directed to a formulation which has at least one property selected from the group consisting of: a gas yield of greater than 1.57 grams of per cubic centimeter (g/cc); a constant volume flame temperature of 2700°K to 2800°K; and an overall oxygen balance of the formulation -2% to +2%.
  • the formulation comprises two of these properties.
  • the formulation comprises all of these properties.
  • One aspect relates to an airbag gas generant formulation wherein the formulation comprises 48.2 wt% strontium nitrate; 36.8 wt% nitroguanidine; 5 wt% potassium perchlorate; 5 wt% strontium oxalate; and 5 wt% polyvinyl alcohol.
  • the formulation further comprises lwt% to 5wt% cupric oxide as a burning rate modifier.
  • the airbag gas generant formulation may comprise 44.1 wt% strontium nitrate; 39.9 wt% nitroguanidine; 5 wt% potassium perchlorate; 4 wt% strontium oxalate; 4 wt% polyvinyl alcohol; and 3 wt% cupric oxide.
  • the airbag gas generant formulation can further comprise 2 wt% to 6wt% Kaolin.
  • the kaolin may be for slag formation and as a coolant.
  • the airbag gas generant formulation can further comprise 2 wt% to 6 wt% aluminum oxide.
  • the aluminum oxide may be for slag formation and as a coolant.
  • the airbag gas generant formulation can further comprise 2 wt% to 6 wt% silicon dioxide.
  • the silicon dioxide may be for slag formation and as a coolant.
  • the airbag gas generant formulation can further comprise 2 wt% to 6% wt% of at least one ingredient.
  • the one ingredient may be one, two, or all three of the following: kaolin; aluminum oxide; and silicon dioxide.
  • Vehicles may include a variety of airbags that can deploy during vehicle impacts to absorb energy from occupants of the vehicles during the impact.
  • the airbag may be a component of an airbag module comprising an airbag inflator in communication with the airbag for inflating the airbag from an uninflated position to an inflated position.
  • One aspect is directed to an airbag inflator comprising an airbag gas generant formulation described in this disclosure.
  • Another aspect is directed to an airbag module or airbag comprising an airbag gas generant formulation described in this disclosure.
  • Another aspect is directed to a method of inflating an airbag.
  • the method comprises the steps of igniting an airbag gas generant of any airbag gas generant formulation described in this disclosure to generate a gas; and inflating an airbag with the gas.
  • This disclosure describes non-ammonium nitrate based generants that are optimized as a replacement and improvement for ammonium nitrate based hybrid inflator generants.
  • Hybrid inflators contain both stored gas and pyrotechnic materials.
  • the stored gas vessel contains both high-pressure gas and pyrotechnic materials.
  • the pyrotechnic materials are used for gas generation and heating of the stored gas.
  • Ammonium nitrate based generants worked well due to their high gas yield and relatively high combustion temperature compared to that needed for a pyrotechnic inflator.
  • Ammonium nitrate based hybrid generants were formulated near stoichiometric such that they did not generant unacceptable levels of carbon monoxide or nitrogen oxide compounds; they had oxygen balances near zero. In this type of hybrid inflator the stored gas is inert.
  • Some hybrid inflator designs use a highly negative oxygen balance formulation that generate carbon monoxide (CO) and hydrogen (H 2 ) requiring oxygen to be added to the stored gas to combust the CO and H 2 to C0 2 and H 2 0, respectively.
  • CO carbon monoxide
  • H 2 hydrogen
  • Such a formulation is described in U.S. Patent 7,942,990. The formulation described here requires no oxygen to be included in the stored gas.
  • Ammonium nitrate based generants also have a high gas yield to volume of solid generant.
  • the ammonium nitrate based generants described in U.S. Patents 5,850,053 and 6,136,113 have a theoretical density of 1.66 g/cc with a gas yield of 1.57 grams of gas per cubic centimeter (cc) of solid generant.
  • These formulations have a constant pressure flame temperature of 2240K and a constant volume flame temperature of 2700°K.
  • a replacement generant to work in the same hybrid inflator, it is preferred to have the same or equivalent gas yield per solid volume and flame temperatures.
  • Table 1 lists some fuels used or proposed to be used in airbag gas generants. In order to meet the criteria of 1.57 grams of gas per cc of solid volume low-density ingredients in general like guanidine nitrate can be rejected as a candidate. Also, fuels with a high oxygen demand like 5-aminotetrazole can be rejected due to the low gas yield of such a system with a metal- containing oxidizer.
  • HMX and RDX tend to have high flame temperatures; besides HMX and RDX generants are sensitive and tend to fall under export control laws. So candidates like HMX and RDX are not considered as being viable; they also would require significant amounts of coolant (flame temperature reducing material) to be added to such a formulation.
  • coolant flame temperature reducing material
  • AZODN while being the ideal fuel is not commercially available so the preferred fuel is nitroguanidine.
  • Table 2 lists oxidizers that have been used or proposed to be used in airbag gas generant formulations.
  • Example 2 lists -1% oxygen balance two-component systems with oxidizers from Table2 combined with nitroguanidine; PSAN-GN formulations are also listed for comparison purposes. Potassium nitrate-nitroguanidine formulations have a low gas yield making them unable to meet the 1.57g/cc requirement. Potassium perchlorate and ammonium perchlorate containing formulations tend to have too high of a combustion temperature. Strontium nitrate and BCN are the remaining oxidizers to be considered.
  • Airbag generants have to be cost competitive so these formulations preferably use low- bulk-density (LBD) nitroguanidine which consists of long fibers which do not thermal cycle well.
  • LBD low- bulk-density
  • nitroguanidine which consists of long fibers which do not thermal cycle well.
  • LBD needs to be ground.
  • Patent 6,547,900 describes a method using vibratory ball-mills to break up the Nitroguanidine needles. It is preferred to have minimal grinding of the NQ to break up the needle bundles plus the addition of polyvinyl alcohol (PVA) as a binder allows NQ formulations to withstand thermal cycling and heat age environment conditioning.
  • PVA is a preferred binder because it is water soluble. Binders that require organic solvents to dissolve them can add high production costs to the generant.
  • strontium nitrate and BCN with NQ and PVA can achieve an ideal flame temperature
  • BCN and PVA do not heat age well together. Since PVA is the preferred binder, this eliminates BCN as a candidate.
  • the general replacement generant formulation for an ammonium nitrate formulation is strontium nitrate, nitroguanidine, and polyvinyl alcohol as the binder plus a coolant to reduce the combustion temperature.
  • strontium nitrate and NQ with PVA as a binder are shown. These combinations all meet the minimum gas weight per volume of solid generant and flame temperature.
  • Sr(N0 3 ) 2 - NQ formulations can have low burning rates potassium perchlorate (KP) and copper(ll) oxide (CuO) or combinations thereof can be added to increase the burning rate.
  • KP potassium perchlorate
  • CuO copper(ll) oxide
  • Examples 6 through 8 show cases where KP and CuO are included in the formulation. These cases also meet the gas yield and flame temperature requirements for a hybrid inflator application. Potassium perchlorate and CuO both act as burning rate catalysts.
  • Examples 3-8 Additional formulations and their experimental results

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Air Bags (AREA)

Abstract

La présente invention concerne une formulation de générateur de gaz d'airbag optimisée pour des gonfleurs d'airbag hybrides, et un dispositif de gonflage d'airbag, un airbag, un module d'airbag le comprenant, et un procédé de gonflage d'un airbag à l'aide du générateur de gaz d'airbag.
PCT/US2019/013955 2018-01-17 2019-01-17 Générateurs à base de nitrate non-ammonium Ceased WO2019143784A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201980006212.1A CN111433172A (zh) 2018-01-17 2019-01-17 非硝酸铵基推进剂

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201862618269P 2018-01-17 2018-01-17
US62/618,269 2018-01-17

Publications (1)

Publication Number Publication Date
WO2019143784A1 true WO2019143784A1 (fr) 2019-07-25

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Family Applications (1)

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PCT/US2019/013955 Ceased WO2019143784A1 (fr) 2018-01-17 2019-01-17 Générateurs à base de nitrate non-ammonium

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US (1) US20190218155A1 (fr)
CN (1) CN111433172A (fr)
WO (1) WO2019143784A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113087582A (zh) * 2021-03-31 2021-07-09 陕西庆华汽车安全系统有限公司 一种含有硝基胍的安全气囊用产气药的生产方法

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5850053A (en) 1995-03-31 1998-12-15 Atlantic Research Corporation Eutectic mixtures of ammonium nitrate, guanidine nitrate and potassium perchlorate
US6136113A (en) 1998-08-07 2000-10-24 Atlantic Research Corporation Gas generating composition
US20030001369A1 (en) * 2001-04-04 2003-01-02 Yasunori Iwai Method of reducing nitrogen oxide in hybrid inflator
US6527886B1 (en) * 1996-07-22 2003-03-04 Daicel Chemical Industries, Ltd. Gas generant for air bag
US6547900B2 (en) 2001-01-24 2003-04-15 Breed Automotive Technology, Inc. Method of stabilizing the density of gas generant pellets containing nitroguanidine
US20040025991A1 (en) * 2002-08-07 2004-02-12 Canterberry Jb Nitroguanidine based gas generant containing mica
EP1538137A1 (fr) * 2002-09-12 2005-06-08 Daicel Chemical Industries, Ltd. Composition de generation de gaz
US7942990B2 (en) 2006-12-18 2011-05-17 Daicel Chemical Industries, Ltd. Hybrid inflator

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5486248A (en) * 1994-05-31 1996-01-23 Morton International, Inc. Extrudable gas generant for hybrid air bag inflation system
EP0867347B1 (fr) * 1997-03-24 2004-07-07 Daicel Chemical Industries, Ltd. Pastilles génératrices de gaz et générateur de gaz
JP2000086376A (ja) * 1998-09-14 2000-03-28 Daicel Chem Ind Ltd ガス発生剤組成物
EP1377534A2 (fr) * 1999-09-16 2004-01-07 Automotive Systems Laboratory Inc. Generateur de gaz renfermant des combustibles au silicones
EP1932817A1 (fr) * 2006-12-12 2008-06-18 Nitrochemie Wimmis AG Propergol constitué de nitratoéthyle nitramine pour systèmes de sécurité pour automobiles
CN101823927B (zh) * 2010-04-16 2012-03-28 陕西庆华汽车安全系统有限公司 一种汽车安全带预紧器的产气组合物及其制备方法
JP6443882B2 (ja) * 2015-03-13 2018-12-26 株式会社ダイセル エアロゾル消火剤組成物。

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5850053A (en) 1995-03-31 1998-12-15 Atlantic Research Corporation Eutectic mixtures of ammonium nitrate, guanidine nitrate and potassium perchlorate
US6527886B1 (en) * 1996-07-22 2003-03-04 Daicel Chemical Industries, Ltd. Gas generant for air bag
US6136113A (en) 1998-08-07 2000-10-24 Atlantic Research Corporation Gas generating composition
US6547900B2 (en) 2001-01-24 2003-04-15 Breed Automotive Technology, Inc. Method of stabilizing the density of gas generant pellets containing nitroguanidine
US20030001369A1 (en) * 2001-04-04 2003-01-02 Yasunori Iwai Method of reducing nitrogen oxide in hybrid inflator
US20040025991A1 (en) * 2002-08-07 2004-02-12 Canterberry Jb Nitroguanidine based gas generant containing mica
EP1538137A1 (fr) * 2002-09-12 2005-06-08 Daicel Chemical Industries, Ltd. Composition de generation de gaz
US7942990B2 (en) 2006-12-18 2011-05-17 Daicel Chemical Industries, Ltd. Hybrid inflator

Also Published As

Publication number Publication date
CN111433172A (zh) 2020-07-17
US20190218155A1 (en) 2019-07-18

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