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EP0767155B1 - Charges hétérogènes génératrices de gaz - Google Patents

Charges hétérogènes génératrices de gaz Download PDF

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Publication number
EP0767155B1
EP0767155B1 EP96307233A EP96307233A EP0767155B1 EP 0767155 B1 EP0767155 B1 EP 0767155B1 EP 96307233 A EP96307233 A EP 96307233A EP 96307233 A EP96307233 A EP 96307233A EP 0767155 B1 EP0767155 B1 EP 0767155B1
Authority
EP
European Patent Office
Prior art keywords
gas generant
fuel
accordance
charge
composition
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
EP96307233A
Other languages
German (de)
English (en)
Other versions
EP0767155A1 (fr
Inventor
Michael W. Barnes
Christopher Hock
Matthew A. Cox
Robert D. Taylor
Michael P. Jordan
Alan J. Ward
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.)
Autoliv ASP Inc
Original Assignee
Autoliv ASP 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
Priority claimed from US08/540,379 external-priority patent/US5670740A/en
Application filed by Autoliv ASP Inc filed Critical Autoliv ASP Inc
Publication of EP0767155A1 publication Critical patent/EP0767155A1/fr
Application granted granted Critical
Publication of EP0767155B1 publication Critical patent/EP0767155B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B45/00—Compositions or products which are defined by structure or arrangement of component of product

Definitions

  • the present Invention is directed to gas generant compositions for inflating automotive airbags and other devices in which rapid production of high volumes of gas is required. More particularly, the invention is directed a gas generant charge which is a heterogeneous mixture of two types of gas generant compositions.
  • the gas generant compositions of the heterogeneous mixture complement each other, producing combustion products which are both low in undesirable gases and low in particulate matter.
  • azole compounds including tetrazole and triazole compounds.
  • Tetrazole compounds include 5-amino tetrazole (AT), tetrazole, bitetrazole and metal salts of these compounds.
  • Triazole compounds include 1,2,4-triazole-5-one, 3-nitro 1,2,4-triazole-5-one and metal salts of these compounds.
  • Gas generant systems include, in addition to the fuel component, an oxidizer.
  • Proposed oxidizers for use in conjunction with azole fuels include alkali and alkaline earth metal salts of nitrates, chlorates and perchlorates.
  • spherical prills In order to properly feed the tablet press, one needs well formed spherical prills. Without prills, plugging or bridging in the feed system is a common occurrence. Without prills, it is difficult to achieve uniform, high speed filling of the tablet press. These prills will not form in the spray drying step without at least a portion of the generant being water soluble. Typical slurries contain up to 35% water and it is preferred that at least 15% of the solid ingredients need to be soluble in the slurry.
  • a problem encountered with gas generant compositions which utilize tetrazoles or triazoles as fuel is the production of undesirable gases, such as CO, NO x , NH 3 , and HCN.
  • U.S. Patent No. 5,467,715 to Robert Taylor et al describes a gas generant composition which uses as fuel, in addition to a tetrazole or triazole, a water-soluble fuel, such as guanidine nitrate, and as the oxidizer, a transition metal oxide, plus, preferably, an additional oxidizer, such as strontium nitrate.
  • This composition is aqueous-processable, and also minimizes levels of undesirable combustion gases. Nevertheless, the automotive industry is becoming increasingly sensitive to undesirable combustion gases and is imposing increasingly stricter standards. Thus, there is a continuing need to provide gas generant formulations producing further reduced levels of undesirable gases.
  • the gas generant composition described in above-referenced U.S. Patent No. 5,467,715 are auto-ignitable, auto-igniting, e.g., in the event of a vehicle fire, at a temperature substantially below temperatures where ignitor housings, particularly aluminum ignitor housings, weaken.
  • U.S. Patent No. 3,785,149 issued 15 January 1974 to Timmerman, describes gas generant compositions which produce combustion gases which are substantially entirely carbon dioxide and water.
  • the gas generant compositions of U.S. Patent No. 3,785,149 use as the fuel an organic compound which contains only the elements carbon, hydrogen and oxygen, the organic compound being a compound containing carboxylic acid groups or carboxylic acid salt groups and therefore being high in oxygen content.
  • the oxidizer is an alkali metal, preferably sodium or potassium, chlorate or perchlorate.
  • One problem with this type of fuel is that it produces high levels of particulate material which appear as smoke in the interior of a vehicle when the airbag deploys.
  • gas generant compositions may produce different types of undesirable effluents, either gases or particulates. Often, it is difficult to reduce one or more specific undesirable effluent below a predetermined standard.
  • Formulating a gas generant composition for any particular application requires balancing of a number of pyrotechnic parameters, such as burn rate, combustion temperature, gas volume per weight of generant composition, etc. In addition, production of undesirable effluents, including both gases and particulates, must be considered.
  • a gas generant charge suitable for inflating automotive airbags comprising a heterogeneous mixture of between 80 and 95 wt% of a first separately compounded gas generant composition (1) and between 5 and 20 wt% of a second separately compounded gas generant composition (2), based on the total weight of (1) plus (2),
  • each gas generant composition and its components are calculated relative to the active ingredients, i.e., the total of fuel and oxidizer components.
  • the weight percentages of other ingredients, such as coolants, fillers, pressing aids, etc. are calculated relative to the total active ingredients of each gas generant composition, the total of oxidizer plus fuel being 100%.
  • the major fuel component (A 1 ) of the first gas generant composition (1) may be selected from any of the tetrazole and triazole compounds listed above and mixtures thereof; from an availability and cost standpoint, 5-aminotetrazole (AT) is presently the azole compound of choice.
  • the purpose of the fuel is to produce carbon dioxide, water and nitrogen gases when burned with an appropriate oxidizer or oxidizer combination. The gases so produced are used to inflate an automobile gas bag or other such device.
  • AT is combusted to produce carbon dioxide, water and nitrogen according to the following equation: 2CH 3 N 5 + 7/2O 2 ⁇ 2CO 2 + 3H 2 O + 5N 2 .
  • a minor portion of the first (1) fuel i.e., between 15 and 50 wt% of the fuel, is a water soluble fuel (A 2 ).
  • water-soluble oxidizers such as strontium nitrate also facilitate water-processing, over-reliance on such water-soluble oxidizers tend to produce undesirably high combustion temperatures.
  • Specific desirable characteristics of water-soluble fuels are:
  • any transition metal oxide will serve as an oxidizer (B 1 ).
  • Particularly suitable transition metal oxides include ferric oxide and cupric oxide.
  • the preferred transition metal oxide is cupric oxide which, upon combustion of the gas generant, produces copper metal as a slag component.
  • the purpose of the oxidizer is to provide the oxygen necessary to oxidize the fuel; for example, CuO oxidizes AT according to the following equation: 4CH 3 N 5 + 14CuO ⁇ 14Cu + 4CO 2 + 6H 2 O + 10N 2 .
  • the transition metal oxide (B 1 ) may comprise the sole oxidizer in the first fuel or it may be used in conjunction with other oxidizers (B 2 ) including alkali and alkaline earth metal nitrates, chlorates and perchlorates and mixtures of such oxidizers. Of these, nitrates (alkali and/or alkaline earth metal salts) are preferred, and strontium nitrate is currently most preferred. Nitrate oxidizers increase gas output slightly. Alkali metal nitrates are particularly useful as ignition promoting additives.
  • the first gas generant composition may optionally contain a catalyst up to 3 wt%, typically between 1 and 2 wt%.
  • a catalyst up to 3 wt%, typically between 1 and 2 wt%.
  • Boron hydrides and iron ferricyanide are such combustion catalysts.
  • coolants may also optionally be included in the first gas generant composition at up to 10 wt%, typically between 1 and 5 wt%.
  • Suitable coolants include graphite, alumina, silica, metal carbonate salts, transition metals and mixtures thereof.
  • the coolants may be in particulate form, although if available, fiber form is preferred, e.g., graphite, alumina and alumina/silica fibers.
  • Suitable fuels C) for the second gas generant composition 2) include, but are not limited to oxalic acid, malonic acid, succinic acid, tartaric acid, mucic acid, citric acid, salts thereof and mixtures thereof.
  • a currently preferred fuel is tartaric acid.
  • Fuel compounds containing carboxylic acids are reactive with transition metal oxides; thus, the components of the first gas generant composition and second gas generant composition cannot be compounded together. Accordingly, the gas generant charges of the present invention must be heterogeneous.
  • the oxidizer D) for the second gas generant composition 2) is an alkali metal chlorate or perchlorate, particularly sodium chlorate, potassium chlorate, sodium perchlorate and potassium perchlorate.
  • slag formers As with the first gas generant composition, other ingredients known in the art, such as slag formers, processing aids, and/or burn rate catalysts may be optional or desirable in the second gas generant composition.
  • the first and second gas generant compositions are mutually beneficial when provided in a gas generant charge.
  • the second gas generant composition reduces undesirable gases produced by the first gas generant composition.
  • the first gas generant composition minimizes particulate matter produced by the second gas generant composition.
  • a heterogeneous charge may be provided in several manners. Powders of the two composition may be separately pressed into tablets or wafers and loaded into the inflator as two separate tablets or wafers.
  • a "two headed" tablet can be manufactured of the two gas generant compositions by partial compaction of powders of one of the compositions, addition of powder of the second composition and final compaction for loading into the inflator as tablet or wafers.
  • the currently preferred method is to dry blend powders of the two composition and press the dry-blended mixture into tablets or wafers.
  • the gas generant composition powders have particle sizes between 25 and 250 ⁇ m.
  • the gas generant composition It is generally desirable to pelletize the gas generant composition. If so, up to about 1 wt%, typically 0.2-0.5 wt% of a pressing aid or binder may be employed. If the two generants are separately pelletized or tableted, binders or pressing aids will be added to each gas generant composition. If powders of the two generant compositions are pelletized or tableted together, the binder or pressing aid will be added to a mixture of powders of the two gas generant compositions.
  • the binders or pressing agents may be selected from materials known to be useful for this purpose, including molybdenum disulfide, polycarbonate, graphite, Viton®, nitrocellulose, polysaccharides, polyvinylpyrrolidone, sodium silicate, calcium stearate, magnesium stearate, zinc stearate, talc, mica minerals, bentonite, montmorillonite and others known to those skilled in the art.
  • a preferred pressing aid/binder is molybdenum disulfide. If molybdenum disulfide is used, it molybdenum disulfide. If molybdenum disulfide is used, it is preferred that an alkali metal nitrate be included as a portion of the oxidizer.
  • alkali metal nitrate in the presence of molybdenum disulfide results in the formation of alkali metal sulfate, rather than toxic sulfur species. Accordingly, if molybdenum disulfide is used, alkali metal nitrate is used as a portion of the oxidizer in an amount sufficient to convert substantially all of the sulfur component of the molybdenum disulfide to alkali metal sulfate. This amount is at least the stoichiometric equivalent of the molybdenum disulfide, but is typically several times the stoichiometric equivalent. On a weight basis, an alkali metal nitrate is typically used at between 3 and 5 times the weight of molybdenum disulfide used.
  • a first gas generant composition is formulated as follows: 69.55 wt% cupric oxide, 19.45 wt% 5-aminotetrazole, 6 wt% guanidine nitrate, and 5 wt% strontium nitrate.
  • a second gas generant composition is formulated with 59.08 wt% potassium perchlorate and 40.92 wt% tartaric acid. Each of these compositions was manufactured by charging a vessel with water sufficient to yield a 30 wt% slurry, adding the solid ingredients, and mixing with a high shear mixture. Each slurry was poured into a tray and dried in an oven at 85-105°C until the material was dry enough to be pressed through a 3.36 mm (6 mesh) screen. Drying was then completed.
  • Comparative Example 1 was the first gas generant composition alone. Comparative Example 2 is the second gas generant composition alone.
  • Example 3 was a mixture 88 wt% of tablets of the first gas generant composition and 12 wt% of the second gas generant composition.
  • Example 4 was tablets of a dryblended mixture of the first and second gas generant compositions in the same weight percentages as Example 3.
  • the invention applies generally to heterogeneous mixing of a first and a at least a second gas generant compositions.
  • the pyrotechnic and effluent characteristics including gas effluent and particulate effluent, tends to be a weighted average of the heterogeneously mixed gas generant compositions.
  • the invention has been exemplified with respect to heterogenous mixtures of two gas generant compositions, heterogeneous mixing should apply as well to mixtures of three or more gas generant compositions.
  • the invention provides for relative predictability of pyrotechnic and effluent profiles when using two or more gas generant compositions. As airbag applications become more specific, e.g., driver-side, passenger-side, side-impact, and with specifics for particular vehicles, there is a need to be able to customize pyrotechnic and gas effluent profiles.
  • the invention provides the ability to so customize pyrotechnic and effluent characteristics with substantial predictability and confidence.

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

Claims (9)

  1. Une charge gazogène convenant au gonflage de sacs gonflables pour automobiles englobant un mélange hétérogène de 80 à 95% en poids d'une première composition gazogène composée séparément (1) et entre 5 et 20% en poids d'une seconde composition gazogène composée séparément (2), sur la base du poids total de (1) plus (2),
    ladite première composition gazogène (1) englobant entre 20 et 40% en poids de combustible (A) et entre 60 et 80% en poids d'oxydant (B),
    entre 50 et 85% en poids dudit combustible (A) étant un composé triazole ou tétrazole (A1), entre 15 et 50% en poids dudit combustible étant un combustible soluble dans l'eau (A2),
    au moins 20% en poids dudit oxydant (B), jusqu'à 100%, étant un oxyde de métal transitoire (B1) ; le reste dudit oxydant étant sélectionné parmi un groupe (B2) comportant des nitrates, chlorates ou perchlorates de métaux alcalins et/ou alcalino-terreux,
    ladite seconde composition gazogène (2) englobant entre 30 et 65% en poids d'un combustible (C) qui est un composé organique ayant des groupes acide carboxylique ou sel et ne contenant que les éléments carbone, hydrogène et oxygène, la teneur en oxygène étant entre 35 et 65% en poids dudit composé organique, et entre 35 et 70% en poids d'un oxydant (D) qui est sélectionné parmi les chlorates de métaux alcalins, les perchlorates de métaux alcalins et des mélanges de ceux-ci.
  2. Une charge gazogène selon la Revendication 1, dans laquelle ledit oxyde de métal transitoire est le CuO.
  3. Une charge gazogène selon la Revendication 1 ou la Revendication 2, dans laquelle ledit combustible soluble dans l'eau (A2) est sélectionné parmi : nitrate de guanidine, nitrate d'aminoguanidine, nitrate de diaminoguanidine, nitrate de semicarbazide, nitrate de triaminoguanidine, dinitrate d'éthylènediamine, dinitrate de tétramine hexaméthylénique, et des mélanges de ceux-ci.
  4. Une charge gazogène selon la Revendication 3, dans laquelle ledit combustible soluble dans l'eau (A2) est le nitrate de guanidine.
  5. Une charge gazogène selon l'une quelconque des revendications précédentes, dans laquelle lesdites première et seconde compositions génératrices de gaz sont bouletées en pastilles ou tranches séparées.
  6. Une charge gazogène selon l'une quelconque des Revendications 1 à 4, dans laquelle lesdites première et seconde compositions génératrices de gaz sont copastillées depuis un mélange sec desdites compositions génératrices de gaz.
  7. Une charge gazogène selon l'une quelconque des revendications précédentes, dans laquelle ledit combustible (C) de ladite seconde composition gazogène (2) est sélectionnée parmi : acide tartrique, acide oxalique, acide malonique, acide succinique, acide mucique, acide citrique et sels et mélanges de ceux-ci.
  8. Une charge gazogène selon la Revendication 7, dans laquelle le combustible (C) de la seconde composition gazogène (2) est l'acide tartrique.
  9. Une charge gazogène selon l'une quelconque des revendications précédentes, dans laquelle ledit oxydant (D) de la seconde charge gazogène (2) est le perchlorate de potassium.
EP96307233A 1995-10-06 1996-10-03 Charges hétérogènes génératrices de gaz Expired - Lifetime EP0767155B1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US540379 1995-10-06
US08/540,379 US5670740A (en) 1995-10-06 1995-10-06 Heterogeneous gas generant charges
US60451296A 1996-02-21 1996-02-21
US604512 1996-02-21

Publications (2)

Publication Number Publication Date
EP0767155A1 EP0767155A1 (fr) 1997-04-09
EP0767155B1 true EP0767155B1 (fr) 2000-08-16

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP96307233A Expired - Lifetime EP0767155B1 (fr) 1995-10-06 1996-10-03 Charges hétérogènes génératrices de gaz

Country Status (3)

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EP (1) EP0767155B1 (fr)
JP (1) JPH09118582A (fr)
DE (1) DE69609793T2 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7758709B2 (en) 2006-06-21 2010-07-20 Autoliv Asp, Inc. Monolithic gas generant grains
US8057611B2 (en) 2007-08-13 2011-11-15 Autoliv Asp, Inc. Multi-composition pyrotechnic grain
US8808476B2 (en) 2008-11-12 2014-08-19 Autoliv Asp, Inc. Gas generating compositions having glass fibers
US8815029B2 (en) 2008-04-10 2014-08-26 Autoliv Asp, Inc. High performance gas generating compositions
US9051223B2 (en) 2013-03-15 2015-06-09 Autoliv Asp, Inc. Generant grain assembly formed of multiple symmetric pieces
US9193639B2 (en) 2007-03-27 2015-11-24 Autoliv Asp, Inc. Methods of manufacturing monolithic generant grains

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FR2761982B1 (fr) * 1997-04-11 1999-05-07 Livbag Snc Procede pour assurer un deploiement progressif d'un coussin de protection et chargement pyrotechnique pour sa mise en oeuvre
DE29722912U1 (de) * 1997-12-29 1998-02-19 TRW Airbag Systems GmbH & Co. KG, 84544 Aschau Azidfreie gaserzeugende Zusammensetzung
DE29806504U1 (de) * 1998-04-08 1998-08-06 TRW Airbag Systems GmbH & Co. KG, 84544 Aschau Azidfreie, gaserzeugende Zusammensetzung
JP2000086375A (ja) * 1998-09-09 2000-03-28 Daicel Chem Ind Ltd ガス発生剤組成物
JP2000086376A (ja) 1998-09-14 2000-03-28 Daicel Chem Ind Ltd ガス発生剤組成物
RU2250800C2 (ru) * 1999-09-30 2005-04-27 Тно Принс Мауритс Лаборатори Способ генерирования газов, предпочтительно азота, с низкой температурой и газогенератор для его осуществления
US6430920B1 (en) 1999-11-23 2002-08-13 Technanogy, Llc Nozzleless rocket motor
US6503350B2 (en) 1999-11-23 2003-01-07 Technanogy, Llc Variable burn-rate propellant
US6454886B1 (en) 1999-11-23 2002-09-24 Technanogy, Llc Composition and method for preparing oxidizer matrix containing dispersed metal particles
EP1151976A1 (fr) * 2000-05-02 2001-11-07 Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno Procédé pour le gonflage d'un objet
EP1151977A1 (fr) * 2000-05-02 2001-11-07 Nederlandse Organisatie voor toegepast-natuurwetenschappelijk Onderzoek TNO Procédé pour la génération de gaz pour fournir de l'énergie
EP1151978A1 (fr) * 2000-05-02 2001-11-07 Nederlandse Organisatie voor toegepast-natuurwetenschappelijk Onderzoek TNO Procédé pour la génération de gaz
JP5156627B2 (ja) * 2005-07-29 2013-03-06 オートモーティブ システムズ ラボラトリィ、 インク． 自己発火／ブースター組成物
US8057612B2 (en) 2007-08-13 2011-11-15 Autoliv Asp, Inc. Methods of forming a multi-composition pyrotechnic grain
JP5641934B2 (ja) * 2007-08-13 2014-12-17 オートリブ エーエスピー，インコーポレイティド 多組成物着火塊と関連する形成方法
WO2010137933A1 (fr) * 2009-05-26 2010-12-02 Boris Jankovski Charges générant un gaz pour des dispositifs de suppression d'incendie en aérosol et technologie de production correspondante
US8221565B2 (en) * 2009-08-03 2012-07-17 Autoliv Asp, Inc. Combustion inhibitor coating for gas generants
JP2012111682A (ja) * 2010-11-02 2012-06-14 Nippon Kayaku Co Ltd ガス発生剤成型体

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FR2234246B1 (fr) * 1973-06-19 1976-09-17 Poudres & Explosifs Ste Nale
DE3346287A1 (de) * 1983-12-21 1985-07-04 WNC-Nitrochemie GmbH, 8261 Aschau Treibladung fuer rohrwaffen und verfahren zu ihrer herstellung
JPS63176387A (ja) * 1987-01-16 1988-07-20 ダイセル化学工業株式会社 ガス発生器
DE3933555C1 (en) * 1989-10-07 1991-02-21 Bayern-Chemie Gesellschaft Fuer Flugchemische Antriebe Mbh, 8261 Aschau, De Vehicle safety bag inflation change - is flat with slow-burning outer section ignited first and surrounding fast-burning central section
US5034070A (en) * 1990-06-28 1991-07-23 Trw Vehicle Safety Systems Inc. Gas generating material
JPH0648880A (ja) * 1992-06-05 1994-02-22 Trw Inc ガス発生器用の多層型ガス発生ディスク
US5386775A (en) * 1993-06-22 1995-02-07 Automotive Systems Laboratory, Inc. Azide-free gas generant compositions and processes
US5431103A (en) * 1993-12-10 1995-07-11 Morton International, Inc. Gas generant compositions
US5467715A (en) * 1993-12-10 1995-11-21 Morton International, Inc. Gas generant compositions

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7758709B2 (en) 2006-06-21 2010-07-20 Autoliv Asp, Inc. Monolithic gas generant grains
US8057610B2 (en) 2006-06-21 2011-11-15 Autoliv Asp, Inc. Monolithic gas generant grains
US9193639B2 (en) 2007-03-27 2015-11-24 Autoliv Asp, Inc. Methods of manufacturing monolithic generant grains
US8057611B2 (en) 2007-08-13 2011-11-15 Autoliv Asp, Inc. Multi-composition pyrotechnic grain
US8815029B2 (en) 2008-04-10 2014-08-26 Autoliv Asp, Inc. High performance gas generating compositions
US8808476B2 (en) 2008-11-12 2014-08-19 Autoliv Asp, Inc. Gas generating compositions having glass fibers
US9051223B2 (en) 2013-03-15 2015-06-09 Autoliv Asp, Inc. Generant grain assembly formed of multiple symmetric pieces

Also Published As

Publication number Publication date
JPH09118582A (ja) 1997-05-06
DE69609793T2 (de) 2000-12-28
EP0767155A1 (fr) 1997-04-09
DE69609793D1 (de) 2000-09-21

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