WO2000007846A2 - Improved gas generating composition - Google Patents
Improved gas generating composition Download PDFInfo
- Publication number
- WO2000007846A2 WO2000007846A2 PCT/US1999/016154 US9916154W WO0007846A2 WO 2000007846 A2 WO2000007846 A2 WO 2000007846A2 US 9916154 W US9916154 W US 9916154W WO 0007846 A2 WO0007846 A2 WO 0007846A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- composition
- copper
- compound
- nitrate
- catalyst
- Prior art date
Links
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
- C06B31/28—Compositions containing an inorganic nitrogen-oxygen salt the salt being ammonium nitrate
- C06B31/32—Compositions containing an inorganic nitrogen-oxygen salt the salt being ammonium 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60R—VEHICLES, VEHICLE FITTINGS, OR VEHICLE PARTS, NOT OTHERWISE PROVIDED FOR
- B60R21/00—Arrangements or fittings on vehicles for protecting or preventing injuries to occupants or pedestrians in case of accidents or other traffic risks
- B60R21/02—Occupant safety arrangements or fittings, e.g. crash pads
- B60R21/16—Inflatable occupant restraints or confinements designed to inflate upon impact or impending impact, e.g. air bags
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B23/00—Compositions characterised by non-explosive or non-thermic constituents
- C06B23/007—Ballistic modifiers, burning rate catalysts, burning rate depressing agents, e.g. for gas generating
-
- 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
- C06B45/04—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive
- C06B45/06—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive the solid solution or matrix containing an organic component
- C06B45/10—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive the solid solution or matrix containing an organic component the organic component containing a resin
-
- 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 generally to gas generating compositions and specifically to a gas generating composition with improved ballistic properties suitable for use in automatically inflating inflatable structures such as vehicle airbags and aircraft escape chutes .
- Gas generating compositions have long been used for a multitude of purposes. The requirement for vehicular, especially automotive, airbags in passive restraint systems designed to protect drivers and passengers in the event of a collision has produced a substantial amount of research for the ideal gas generating composition for this purpose.
- the ideal gas generating composition should be a thermally stable, cool burning, noncorrosive composition that generates a large volume of substantially ash or solids- free clean, nontoxic gas.
- the ideal gas generating composition should also be storage stable so that it ignites effectively and burns efficiently when needed. While the prior art has proposed gas generating compositions that approach this ideal, it has not yet been achieved for automatically inflated structures such as vehicle airbags.
- compositions typically include an ammonium nitrate oxidizer, either combined with a rubbery binder or in a pressed charge to form a pellet, which is stored until ignited to inflate the airbag or other structure.
- ammonium nitrate oxidizer typically include an ammonium nitrate oxidizer, either combined with a rubbery binder or in a pressed charge to form a pellet, which is stored until ignited to inflate the airbag or other structure.
- chemical additives for example highly oxygenated fuels such as guanidine nitrate, aminoguanidine nitrate and oxamide are combined with the ammonium nitrate to aid ignition, modify burning rates, promote smooth burning and produce acceptably low flame temperatures.
- Combustion catalysts may be included in the composition to increase burning rate, promote ignition and low pressure combustion.
- the metallic additives often used in combustion catalysts produce solids in the effluent gas that may interfere with the gas toxicity, exhaust particulates, or inflation of the airbag or
- Ammonium nitrate is the most commonly used oxidizer in these types of gas generator compositions. It is readily available, safe to handle, and inexpensive. Moreover, ammonium nitrate burns at low flame temperatures and burning rates to produce a nontoxic, noncorrosive exhaust. Primary disadvantages of using ammonium nitrate as the oxidizer in a gas generator composition are inherently low burning rates, higher pressure exponents, poor combustion at low pressures, and its tendency to undergo phase changes during temperature variations, which causes cracks and voids in the pellet. Cracked pellets are not likely to yield a reliable gas generator when needed. Crack formation can be minimized by employing a binder that is sufficiently strong and flexible to hold the composition together.
- U.S. Patent No. 5,551,725 to udwig discloses an inflator composition for a vehicle airbag that includes an oxidizer, such as ammonium nitrate, and a fuel, which may be a nitro-organic, such as guanidine nitrate.
- the Ludwig composition like the Poole et al . composition, would not avoid potentially detrimental ammonium nitrate phase changes .
- the burning rates tend to be low and the pressure exponent values tend to be high so that they are not as efficient as desired.
- a catalyst for a gas generating composition with improved ballistic properties that includes a solid solution or eutectic mixture of ammonium nitrate, at least one highly oxygenated fuel, preferably guanidine nitrate (GN) and/or aminoguanidine nitrate (AGN) , and an optional phase stabilizer.
- a gas generating composition with improved ballistic properties comprising a solid solution or eutectic mixture of ammonium nitrate, GN and/or AGN, a phase stabilizer, a binder, and an effective amount of a catalyst selected from copper or copper compounds.
- a first preferred improved gas generating composition in accordance with the present invention comprises a solid solution or eutectic mixture of ammonium nitrate, guanidine nitrate and/or aminoguanidine nitrate, potassium or cesium nitrate, polyvinyl alcohol, and copper phthalocyanine .
- a second preferred improved gas generating compound comprises a eutectic mixture or solid solution of ammonium nitrate, guanidine nitrate and/or aminoguanidine nitrate, potassium perchlorate, polyvinyl alcohol and copper phthalocyanine.
- the second preferred compound can be obtained by replacing the potassium perchlorate with ammonium perchlorate and potassium nitrate in ratios which provide the same ion concentration of K + , C10 4 " in the remaining mixture of AN/GN and/or AGN/PVA.
- the burning rate of the gas generating composition is increased and the pressure exponent of the gas generating composition is simultaneously lowered without adversely affecting other propellant properties by the addition of an effective amount of copper or a selected copper compound to a solid solution or eutectic mixture of the components of the gas generating composition, which is adjusted to maintain the oxygen to fuel ratio in the desired range of .88 to 1.0.
- This entails an increase in AN and decrease in GN and/or AGN.
- Figure 1 illustrates in graphic form the burning rate at 1000 psi of a preferred gas generating composition in accordance with the present invention
- Figure 2 illustrates in graphic form the pressure exponent at 1-2 ksi of the gas generating composition of Figure 1 ;
- Figure 3 presents a graphic comparison of burning rate and pressure for a eutectic gas generating composition and for a gas generating composition containing a catalyst in accordance with the present invention.
- This type of gas generating composition is formed as a solid solution or a eutectic mixture and generally also contains low levels of a phase stabilizer, particularly potassium nitrate or potassium perchlorate, and a water soluble binder, such as polyvinyl alcohol .
- a phase stabilizer particularly potassium nitrate or potassium perchlorate
- a water soluble binder such as polyvinyl alcohol .
- Gas generating compositions comprising solid solutions or eutectic mixtures of ammonium nitrate and guanidine nitrate and/or aminoguanidine nitrate with potassium nitrate or potassium perchlorate do not exhibit the adverse ammonium nitrate phase changes or pellet cracking caused by temperature cycling characteristic of prior art ammonium nitrate gas generating compositions.
- a gas generation composition that is a eutectic mixture of ammonium nitrate (AN) , guanidine nitrate (GN) or aminoguanidine nitrate (AGN) , potassium nitrate (KN) , and, optionally, a binder.
- AN ammonium nitrate
- GN guanidine nitrate
- AGN aminoguanidine nitrate
- KN potassium nitrate
- 08/663,012 filed June 7, 1996 also owned by the assignee of the present invention, discloses a gas generation composition that is a eutectic solution of ammonium nitrate (AN) , guanidine nitrate (GN) or aminoguanidine nitrate (AGN) , and potassium perchlorate (KP) with a polyvinyl alcohol (PVA) binder.
- AN ammonium nitrate
- GN guanidine nitrate
- AGN aminoguanidine nitrate
- KP potassium perchlorate
- PVA polyvinyl alcohol
- the copper phthalocyanine family of compounds suitable for use in accordance with the present invention are referred to herein as Monarch Blue. This term is intended to encompass all chemically and structurally similar copper phthalocyanine compounds with catalytic activity in the kinds of gas generating compositions described herein.
- the gas generating compositions of the present invention are typically formed by dissolving all of the compounds in water and mixing them down to dryness, preferably to form a lower melting point eutectic mixture or solid solution. The resulting crumb is then granulated and compacted into pellets, tablets or other convenient forms. Copper or copper compounds are easily dispersed in the aqueous hot melt mixtures used in this method of forming gas generating compositions. At the addition levels employed, the copper or selected copper compound such as Monarch Blue disperses readily with the other composition components in eutectic ammonium nitrate/guanidine nitrate gas generators.
- AN ammonium nitrate
- GN guanidine nitrate
- KP potassium perchlorate
- KN potassium nitrate
- PVA polyvinyl alcohol
- MB copper phthalocyanines .
- Copper phthalocyanines were added to both dry and aqueous (aq) gas generator compositions as indicated.
- the weight percent of each ingredient in the formulation was as indicated.
- the burning rates and pressure exponent values are compared to Table I, and the pellet strength and durability are compared in Table II.
- FIG. 1 and 2 illustrate, in graphic form, the burning rate and pressure exponent, respectively, of gas generator compositions containing varying percentages of Monarch Blue.
- the formulations of the gas generator compositions represented in Figures 1 and 2 contain ammonium nitrate, guanidine nitrate, potassium perchlorate, polyvinyl alcohol and Monarch Blue (AN/GN/KP/PVA/MB) .
- the burning rate at 1000 psi for amounts of Monarch Blue in this formulation from 0% to 5.0% is shown in Figure 1.
- FIG. 1 shows the effect of Monarch Blue on the pressure exponent at 1 to 2 ksi.
- the highest pressure exponent was obtained when the gas generator formulation contained no Monarch Blue, while the addition levels of 1% to 5% Monarch Blue to this formulation significantly lowered the pressure exponent.
- Pellet burning rate data have shown an increase in burning rate of approximately 50%, while the pressure exponent has decreased approximately 20%.
- Figure 3 compares the effects of 2% Monarch Blue in a gas generator composition having the formulation AN/GN/KP/PVA/MB with a gas generator composition having the formulation AN/GN/KP/PVA.
- Table III sets forth the burning rate increases in a gas generator composition having the formulation AN/GN/KP/PVA with the addition of other copper compounds as catalysts.
- the tested formulations were all solid solutions .
- gas generator formulations of the present invention will find their primary utility in gas generating devices, such as that illustrated in Figure 6 of U.S. Patent No. 5,726,382, that are used in connection with vehicle airbags and aircraft escape chutes.
- gas generating devices such as that illustrated in Figure 6 of U.S. Patent No. 5,726,382
- any application requiring the generation of a clean nontoxic gas will find the improved gas generating composition useful.
- These could range, for example, from delivering gas to inflatable structures such as life rafts and life vests or jackets to delivering gas to fire suppression apparatus and the like .
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT99939652T ATE304993T1 (en) | 1998-08-07 | 1999-07-16 | IMPROVED GAS GENERATING COMPOSITION |
CA002338496A CA2338496A1 (en) | 1998-08-07 | 1999-07-16 | Improved gas generating composition |
EP99939652A EP1121335B1 (en) | 1998-08-07 | 1999-07-16 | Improved gas generating composition |
JP2000563496A JP4067766B2 (en) | 1998-08-07 | 1999-07-16 | Improved gas generating composition |
DE69927397T DE69927397T2 (en) | 1998-08-07 | 1999-07-16 | IMPROVED GAS-PRODUCING COMPOSITION |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/130,455 | 1998-08-07 | ||
US09/130,455 US6136113A (en) | 1998-08-07 | 1998-08-07 | Gas generating composition |
Publications (2)
Publication Number | Publication Date |
---|---|
WO2000007846A2 true WO2000007846A2 (en) | 2000-02-17 |
WO2000007846A3 WO2000007846A3 (en) | 2000-05-11 |
Family
ID=22444773
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1999/016154 WO2000007846A2 (en) | 1998-08-07 | 1999-07-16 | Improved gas generating composition |
Country Status (9)
Country | Link |
---|---|
US (2) | US6136113A (en) |
EP (1) | EP1121335B1 (en) |
JP (1) | JP4067766B2 (en) |
KR (1) | KR100656293B1 (en) |
AT (1) | ATE304993T1 (en) |
CA (1) | CA2338496A1 (en) |
DE (1) | DE69927397T2 (en) |
ES (1) | ES2249909T3 (en) |
WO (1) | WO2000007846A2 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1597200A2 (en) * | 2003-01-30 | 2005-11-23 | Autoliv Asp, Inc. | Phase-stabilized ammonium nitrate |
Families Citing this family (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6136113A (en) * | 1998-08-07 | 2000-10-24 | Atlantic Research Corporation | Gas generating composition |
US6758922B2 (en) | 2001-10-05 | 2004-07-06 | Autoliv Asp, Inc. | Low firing energy initiator pyrotechnic mixture |
US6709537B2 (en) | 2001-10-05 | 2004-03-23 | Autoliv Asp, Inc, | Low firing energy initiator pyrotechnic mixture |
US20060054257A1 (en) * | 2003-04-11 | 2006-03-16 | Mendenhall Ivan V | Gas generant materials |
US8101033B2 (en) | 2004-07-26 | 2012-01-24 | Autoliv Asp, Inc. | Alkali metal perchlorate-containing gas generants |
US20050016646A1 (en) * | 2003-07-25 | 2005-01-27 | Barnes Michael W. | Chlorine-containing gas generant compositions including a copper-containing chlorine scavenger |
US20060289096A1 (en) * | 2003-07-25 | 2006-12-28 | Mendenhall Ivan V | Extrudable gas generant |
US7887650B2 (en) | 2006-03-02 | 2011-02-15 | Daicel Chemical Industries, Ltd. | Gas generating composition |
US8372223B1 (en) * | 2008-06-18 | 2013-02-12 | Tk Holdings, Inc. | Gas generant with autoignition function |
JP5481723B2 (en) | 2009-11-27 | 2014-04-23 | 国立大学法人 東京大学 | Gas generant composition |
RU2444505C1 (en) * | 2010-08-03 | 2012-03-10 | Государственное образовательное учреждение высшего профессионального образования "Алтайский государственный технический университет им. И.И. Ползунова" (АлтГТУ) | Ammonium nitrate based gas-generating composition |
CN108238836A (en) * | 2016-12-27 | 2018-07-03 | 比亚迪股份有限公司 | It is a kind of for automatic ignition medicine of air bag and preparation method thereof and a kind of gas generator for automobile safety gas bag |
US20190218155A1 (en) | 2018-01-17 | 2019-07-18 | Arc Automotive Inc. | Non-ammonium nitrate based generants |
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US4128443A (en) * | 1975-07-24 | 1978-12-05 | Pawlak Daniel E | Deflagrating propellant compositions |
US4158583A (en) * | 1977-12-16 | 1979-06-19 | Nasa | High performance ammonium nitrate propellant |
US4971640A (en) * | 1989-08-04 | 1990-11-20 | Thiokol Corporation | Composite propellants containing copper compounds as ballistic modifiers |
US5531941A (en) * | 1993-08-04 | 1996-07-02 | Automotive Systems Laboratory, Inc | Process for preparing azide-free gas generant composition |
US5589661A (en) * | 1994-10-05 | 1996-12-31 | Fraunhofer-Gesselschaft Zur Forderung Der Angewandten Forschung E.V. | Solid propellant based on phase-stabilized ammonium nitrate |
US5596168A (en) * | 1994-10-05 | 1997-01-21 | Fraunhofer-Gesellschaft Zur Forderung Der Angewandten Forschung E.V. | Solid propellant based on phase-stabilized ammonium nitrate |
US5726382A (en) * | 1995-03-31 | 1998-03-10 | Atlantic Research Corporation | Eutectic mixtures of ammonium nitrate and amino guanidine nitrate |
US5747730A (en) * | 1995-03-31 | 1998-05-05 | Atlantic Research Corporation | Pyrotechnic method of generating a particulate-free, non-toxic odorless and colorless gas |
US5783773A (en) * | 1992-04-13 | 1998-07-21 | Automotive Systems Laboratory Inc. | Low-residue azide-free gas generant composition |
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GB805113A (en) * | 1956-08-13 | 1958-11-26 | Ici Ltd | Improvements in or relating to gas producing compositions |
US3960946A (en) * | 1972-03-10 | 1976-06-01 | Thiokol Corporation | Process for the manufacture of oxalyl dihydrazide and the use of same as a coolant in gas generating compositions |
US4263071A (en) * | 1974-07-19 | 1981-04-21 | United Technologies Corporation | Additive for reducing combustion instability in composite solid propellants |
US4525225A (en) * | 1984-03-05 | 1985-06-25 | Atlas Powder Company | Solid water-in-oil emulsion explosives compositions and processes |
US4597811A (en) * | 1985-07-03 | 1986-07-01 | The United States Of America As Represented By The Secretary Of The Army | Prevention of unwanted cure catalysis in isocyanate cured binders |
GB9222001D0 (en) * | 1992-10-20 | 1992-12-02 | Ici Plc | Shock tube initator |
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US5516378A (en) * | 1995-04-11 | 1996-05-14 | Olin Corporation | Explosive composition and its use in making ammunition |
NL1004618C2 (en) * | 1996-11-26 | 1998-05-27 | Tno | Gas generating preparation and application thereof in an air bag. |
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US6017404A (en) * | 1998-12-23 | 2000-01-25 | Atlantic Research Corporation | Nonazide ammonium nitrate based gas generant compositions that burn at ambient pressure |
-
1998
- 1998-08-07 US US09/130,455 patent/US6136113A/en not_active Expired - Lifetime
-
1999
- 1999-07-16 CA CA002338496A patent/CA2338496A1/en not_active Abandoned
- 1999-07-16 AT AT99939652T patent/ATE304993T1/en not_active IP Right Cessation
- 1999-07-16 ES ES99939652T patent/ES2249909T3/en not_active Expired - Lifetime
- 1999-07-16 EP EP99939652A patent/EP1121335B1/en not_active Expired - Lifetime
- 1999-07-16 JP JP2000563496A patent/JP4067766B2/en not_active Expired - Lifetime
- 1999-07-16 WO PCT/US1999/016154 patent/WO2000007846A2/en active IP Right Grant
- 1999-07-16 KR KR1020017001611A patent/KR100656293B1/en not_active IP Right Cessation
- 1999-07-16 DE DE69927397T patent/DE69927397T2/en not_active Expired - Lifetime
-
2000
- 2000-02-07 US US09/499,030 patent/US6340401B1/en not_active Expired - Lifetime
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Publication number | Priority date | Publication date | Assignee | Title |
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US4128443A (en) * | 1975-07-24 | 1978-12-05 | Pawlak Daniel E | Deflagrating propellant compositions |
US4158583A (en) * | 1977-12-16 | 1979-06-19 | Nasa | High performance ammonium nitrate propellant |
US4971640A (en) * | 1989-08-04 | 1990-11-20 | Thiokol Corporation | Composite propellants containing copper compounds as ballistic modifiers |
US5783773A (en) * | 1992-04-13 | 1998-07-21 | Automotive Systems Laboratory Inc. | Low-residue azide-free gas generant composition |
US5531941A (en) * | 1993-08-04 | 1996-07-02 | Automotive Systems Laboratory, Inc | Process for preparing azide-free gas generant composition |
US5589661A (en) * | 1994-10-05 | 1996-12-31 | Fraunhofer-Gesselschaft Zur Forderung Der Angewandten Forschung E.V. | Solid propellant based on phase-stabilized ammonium nitrate |
US5596168A (en) * | 1994-10-05 | 1997-01-21 | Fraunhofer-Gesellschaft Zur Forderung Der Angewandten Forschung E.V. | Solid propellant based on phase-stabilized ammonium nitrate |
US5726382A (en) * | 1995-03-31 | 1998-03-10 | Atlantic Research Corporation | Eutectic mixtures of ammonium nitrate and amino guanidine nitrate |
US5747730A (en) * | 1995-03-31 | 1998-05-05 | Atlantic Research Corporation | Pyrotechnic method of generating a particulate-free, non-toxic odorless and colorless gas |
Non-Patent Citations (1)
Title |
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See also references of EP1121335A2 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1597200A2 (en) * | 2003-01-30 | 2005-11-23 | Autoliv Asp, Inc. | Phase-stabilized ammonium nitrate |
EP1597200A4 (en) * | 2003-01-30 | 2009-10-21 | Autoliv Asp Inc | Phase-stabilized ammonium nitrate |
Also Published As
Publication number | Publication date |
---|---|
US6340401B1 (en) | 2002-01-22 |
JP2002522330A (en) | 2002-07-23 |
EP1121335B1 (en) | 2005-09-21 |
WO2000007846A3 (en) | 2000-05-11 |
CA2338496A1 (en) | 2000-02-17 |
ES2249909T3 (en) | 2006-04-01 |
JP4067766B2 (en) | 2008-03-26 |
EP1121335A4 (en) | 2002-10-16 |
US6136113A (en) | 2000-10-24 |
ATE304993T1 (en) | 2005-10-15 |
KR20010072311A (en) | 2001-07-31 |
KR100656293B1 (en) | 2006-12-12 |
DE69927397T2 (en) | 2006-07-06 |
DE69927397D1 (en) | 2006-02-02 |
EP1121335A2 (en) | 2001-08-08 |
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