WO2000025959A1 - Single crystal vane segment and method of manufacture - Google Patents
Single crystal vane segment and method of manufacture Download PDFInfo
- Publication number
- WO2000025959A1 WO2000025959A1 PCT/US1999/025976 US9925976W WO0025959A1 WO 2000025959 A1 WO2000025959 A1 WO 2000025959A1 US 9925976 W US9925976 W US 9925976W WO 0025959 A1 WO0025959 A1 WO 0025959A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- directionally solidified
- component
- alloy
- solidified alloy
- single crystal
- Prior art date
Links
- 239000013078 crystal Substances 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims description 22
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 49
- 239000000956 alloy Substances 0.000 claims abstract description 49
- 238000005266 casting Methods 0.000 claims abstract description 18
- 229910052702 rhenium Inorganic materials 0.000 claims abstract description 6
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000007858 starting material Substances 0.000 claims description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 7
- 230000008018 melting Effects 0.000 claims description 5
- 238000002844 melting Methods 0.000 claims description 5
- 239000012212 insulator Substances 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 229910052735 hafnium Inorganic materials 0.000 claims description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims 6
- 229910052759 nickel Inorganic materials 0.000 claims 6
- 239000012530 fluid Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910000601 superalloy Inorganic materials 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D27/00—Treating the metal in the mould while it is molten or ductile ; Pressure or vacuum casting
- B22D27/04—Influencing the temperature of the metal, e.g. by heating or cooling the mould
- B22D27/045—Directionally solidified castings
Definitions
- the present invention relates generally to cast gas turbine engine components and their method of manufacture. More particularly, in one embodiment of the present invention, a multi-airfoil vane segment is produced as a single crystal casting from a Rhenium containing directionally solidified (DS) chemistry alloy.
- DS directionally solidified
- the performance of a gas turbine engine generally increases with an increase in the operating temperature of a high temperature working fluid flowing from a combustion chamber.
- One factor recognized by gas turbine engine designers as limiting the allowable temperature of the working fluid is the capability of the engine components to not degrade when exposed to the high temperature working fluid.
- the airfoils, such as blades and vanes, within the engine are among the components exposed to significant thermal and kinetic loading during engine operation.
- Many gas turbine engines utilize cast components formed of a nickel or cobalt alloy.
- the components can be cast as a polycrystalline, directionally solidified, or single crystal structure.
- the most desirable material properties are associated with the single crystal structure.
- the geometry of some components, such as the multi-airfoil vane segment causes difficulty during the casting process largely associated with grain or crystal defects.
- Single crystal alloys are not tolerant to these types of defects and therefore castings, which exhibit these defects, are generally not suitable for engine use. Thus, the casting yields are lower and consequently the cost to manufacture the component increases.
- a directionally solidified component has material properties between single crystal and polycrystalline and are easier to produce than single crystal components.
- Directionally solidified components are generally defined as multi-crystal structures with columnar grains and are generally cast from a directionally solidified alloy containing grain boundary strengtheners.
- the directionally solidified component is best suited for designs where the stress field is oriented along the columnar grains and the stress field transverse to the columnar grain is minimized.
- the stress fields are elevated along the airfoils and in a transverse direction associated the inner and outer shrouds which tie the airfoils together.
- One form of the present invention contemplates a product comprising a cast single crystal structure formed of a directionally solidified alloy.
- Another form of the present invention contemplates a gas turbine engine component, comprising a single cast single crystal vane segment having a plurality of airfoils, the vane segment is formed of a directionally solidified alloy.
- Yet another form of the present invention contemplates a gas turbine engine component comprising a single cast single crystal shrouded vane formed of a directionally solidified alloy.
- another form of the present invention contemplates a method for producing a single crystal article.
- the method comprising: providing a directionally solidified alloy; melting the directionally solidified alloy; pouring the molten directionally solidified alloy into a casting mold; and, solidifying the directionally solidified alloy to produce a single crystal article.
- One object of the present invention is to provide a single crystal multi- airfoil vane segment and method of manufacture.
- FIG. 1 is an illustrative view of a gas turbine engine.
- FIG. 2 is a perspective view of a multi-airfoil vane segment comprising a portion of the FIG. 1 gas turbine engine.
- FIG. 3 is a Larson-Miller plot comparing three alloys.
- FIG. 4 is an illustrative view of a casting mold for forming a vane segment.
- FIG. 5 is an illustrative view of a multi -airfoil vane segment formed from the casting mold of FIG. 4.
- FIG. 1 there is illustrated a gas turbine engine 20 which includes a fan section 21, a compressor section 22, a combustor section 23, and a turbine section 24 that are integrated together to produce an aircraft flight propulsion engine.
- This type of gas turbine engine is generally referred to as a turbo-fan.
- One alternate form of a gas turbine engine includes a compressor, a combustor, and a turbine that have been integrated together to produce an aircraft flight propulsion engine without the fan section.
- aircraft is generic and includes helicopters, airplanes, missiles, unmanned space devices and any other substantially similar devices. It is important to realize that there are a multitude of ways in which the gas turbine engine components can be linked together. Additional compressors and turbines could be added with intercoolers connecting between the compressors and reheat combustion chambers could be added between the turbines.
- a gas turbine engine is equally suited to be used for an industrial application.
- industrial gas turbine engines such as pumping sets for gas and oil transmission lines, electricity generation, and naval propulsion.
- the compressor section 22 includes a rotor 25 having a plurality of compressor blades 26 coupled thereto.
- the rotor 25 is affixed to a shaft 27 that is rotatable within the gas turbine engine 20.
- a plurality of compressor vanes 28 are positioned within the compressor section 22 to direct the fluid flow relative to blades 26.
- Turbine section 24 includes a plurality of turbine blades 30 that are coupled to a rotor disk 31.
- the rotor disk 31 is affixed to the shaft 27, which is rotatable within the gas turbine engine 20.
- Energy extracted in the turbine section 24 from the hot gas exiting the combustor section 23 is transmitted through shaft 27 to drive the compressor section 22.
- a plurality of turbine vanes 32 are positioned within the turbine section 24 to direct the hot gaseous flow stream exiting the combustor section 23.
- the turbine section 24 provides power to a fan shaft 33, which drives the fan section 21.
- the fan section 21 includes a fan 34 having a plurality of fan blades 35. Air enters the gas turbine engine 20 in the direction of arrows A and passes through the fan section 21 into the compressor section 22 and a bypass duct 36. Further details related to the principles and components of a conventional gas turbine engine will not be described herein as they are believed known to one of ordinary skill in the art.
- FIG. 2 there is illustrated a vane segment 50 which forms a portion of a turbine nozzle.
- a plurality of vane segments 50 are conventionally joined together to collectively form the complete 360° turbine nozzle.
- Each of the vane segments 50 include a plurality of vanes 32 that are coupled to end wall members 51 and 52.
- the embodiment of vane segment 50, illustrated in FIG. 2 has four vanes coupled thereto, however it is contemplated herein that a vane segment may have one or more vanes per vane segment and is not limited to a vane segment having four vanes.
- the turbine nozzle includes eleven vane segments having four vanes each. However, a turbine nozzle formed from other quantities of vane segments, and vane segments having other numbers of vanes are contemplated herein.
- Vane 32 has a leading edge 32a and a trailing edge 32b and an outer surface extending therebetween.
- the term spanwise will be used herein to indicate an orientation between the first end wall member 51 and the second end wall member 52. Further, the term streamwise will be used herein to indicate an orientation between the leading edge 32a and the trailing edge 32b.
- Each vane 50 defines an airfoil with the outer surface 53 extending between the leading edge 32a and the trailing edge 32b. The leading and trailing edges of the vane extend between a first end 32c and a second opposite other end 32d.
- the outer surface 53 of the vane 50 includes a convex suction side (not illustrated) and a concave pressure side 55.
- the gas turbine engine vane 32 is a hollow single-cast single crystal structure produced by single crystal casting techniques utilizing a directionally solidified alloy composition.
- the gas turbine engine vane is a solid single-cast single crystal structure produced by single crystal casting techniques utilizing a directionally solidified alloy composition.
- the present invention contemplates gas turbine engine vanes having internal cooling passageways and apertures for the passage of a cooling media. Cast single crystal casting techniques are believed known to those of ordinary skill in the art. One process for producing a cast single crystal structure is set forth in United States Patent No. 5,295,530 to O'Connor, which is incorporated herein by reference.
- the material utilized to produce the cast single crystal structure is a directionally solidified alloy, which often is referred to as a DS alloy. More preferably, the alloy is a second-generation directionally solidified superalloy. Second-generation directionally solidified superalloys have creep rupture strengths similar to first generation single crystal superalloys, such as CMSX-2 ® and CMSX-3® at up to 1000 degrees centigrade. For example in Fig. 3, there is illustrated a Larson-Miller Plot showing the strength of CM 186 LC in comparison to CMSX 2/3 and CM247LC.
- Examples of the second-generation superalloys include, but are not intended to be limited herein to: PWA 1426 (a Pratt & Whitney product); Rene 142 (a General Electric product); and, CM 186 LC (a Cannon -Muskegon product).
- Other directionally solidified alloys are contemplated herein for use in producing a cast single crystal structure.
- Each of the directionally solidified alloys include grain boundary strengtheners that are designed to increase grain boundary strength.
- the alloys PWA 1426, Rene 142 and CM 186 LC each include boron, carbon, hafnium, and zirconium as their grain boundary strengtheners.
- Other directionally solidified alloys containing grain boundary strengtheners are contemplated herein.
- a grain boundary is generally defined as a region in the cast component of non-oriented structure having a width of only a few atomic diameters which serves to accommodate the crystallographic orientation difference or mismatch between adjacent grains. It will be appreciated by those skilled in the art that neither low angle grain boundaries nor high angle grain boundaries will be present in a theoretical "single crystal". However, it will be further appreciated that although there may be one or more grain boundaries present in commercial single crystal structures, they are still characterized as a single crystal structure. Further, manufacturing processes more tolerant of these crystal anomalies are inherently less expensive.
- Rhenium containing alloys PWA 1426, Rene 142 and CM186 LC are disclosed in Table I.
- FIG. 4 there is illustrated a casting mold 200 with a molten metal receiving cavity for receiving molten metal therein and forming the multi-airfoil vane segment.
- FIG. 5 there is illustrated the multi-airfoil vane segment 50 and metallic starter seed 62 with the walls of a casting mold 200 removed to aid the reader. A portion of the metallic starter seed 62 extends into the molten metal receiving cavity of the mold. The molten directionally solidified alloy contacts the starter seed 62 and causes the partial melt back thereof.
- the starter seed 62 is not in contact with a chill 65. More preferably an insulator 90 is disposed between the starter seed 62 and the chill 65. The insulator 90 functions to thermally insulate the starter seed 62 from the cooling chill 65 and thus promote melting of a portion of the starter seed.
- the directionally solidified alloy is solidified by a thermal gradient moving vertically through the casting mold. More particularly, the directionally solidified alloy is solidified epitaxially from the unmelted portion of the starter seed 62 to form the single crystal product.
- the thermal gradient for solidifying the directionally solidified alloy is produced by a combination of mold heating and mold cooling.
- One system for effectuating the thermal gradient in the mold comprises a mold heater, a mold cooling cone, a chill and the withdrawal of the structure being cast. Further details related to the growing of single crystal alloy structures are believed known to those of ordinary skill in the art and therefore have not been provided.
- the cast single crystal alloy product has been described in terms of a vane segment, however other cast single crystal product configurations formed of a directionally solidified alloy, such as blades seals, shrouds, blade tracks, nozzle liners and other components subjected to high temperature and stress are contemplated herein.
- the starter seed 62 is formed and/or oriented such that the seeds ⁇ 001> (primary orientation) crystal direction is substantially parallel with a tangent A, and the seeds ⁇ 010> (secondary orientation) crystal direction is substantially parallel with the average airfoil stacking axis B.
- the average airfoil stacking axis B is generally defined by the average of each airfoil stacking axis B, B 2 B 3 andB 4 .
- FIG. 5 is not intended herein to limit the solidification direction to that shown in the drawings.
- the solidification direction is substantially parallel to the average airfoil stacking axis B.
- other solidification directions are contemplated herein.
- the present invention is not limited to the use of a starter seed to impart the crystallographic structure to the crystal being grown.
- Single crystals can be grown by techniques generally known to one of ordinary skill in the art, such as utilizing thermal nucleation and the selection of a grain for continued growth with a pigtail sorting structure.
- the cast single crystal vane segment can be used without the long homogenization heat treat cycles commonly used to maximize properties of cast single crystal articles.
- the article in another form of the present invention, which is well suited for articles such as gas turbine blades, can be used in a fully heat treated condition.
- the fully heat treated article maximizes stress rupture and minimizes the formation of deleterious topologically close packed (TCP) phases such as sigma upon the long term exposure of the article to high temperature and stress.
- TCP topologically close packed
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Turbine Rotor Nozzle Sealing (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE69933132T DE69933132T3 (en) | 1998-11-05 | 1999-11-04 | CRYSTAL GUIDE AND METHOD FOR THE PRODUCTION THEREOF |
CA002349412A CA2349412C (en) | 1998-11-05 | 1999-11-04 | Single crystal vane segment and method of manufacture |
JP2000579385A JP2004538358A (en) | 1998-11-05 | 1999-11-04 | Single crystal vane segment and method for producing the same |
EP99969597A EP1131176B2 (en) | 1998-11-05 | 1999-11-04 | Single crystal vane segment and method of manufacture |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10714198P | 1998-11-05 | 1998-11-05 | |
US60/107,141 | 1998-11-05 | ||
US25166099A | 1999-02-17 | 1999-02-17 | |
US09/251,660 | 1999-02-17 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2000025959A1 true WO2000025959A1 (en) | 2000-05-11 |
Family
ID=26804439
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1999/025976 WO2000025959A1 (en) | 1998-11-05 | 1999-11-04 | Single crystal vane segment and method of manufacture |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP1131176B2 (en) |
JP (1) | JP2004538358A (en) |
CA (1) | CA2349412C (en) |
DE (1) | DE69933132T3 (en) |
WO (1) | WO2000025959A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2927270A1 (en) * | 2008-02-08 | 2009-08-14 | Snecma Sa | PROCESS FOR MANUFACTURING DIRECTED SOLIDIFICATION AUBES |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5232492B2 (en) * | 2008-02-13 | 2013-07-10 | 株式会社日本製鋼所 | Ni-base superalloy with excellent segregation |
EP2615243B1 (en) | 2012-01-11 | 2017-08-30 | MTU Aero Engines AG | Blade ring segment for a fluid flow engine and method for producing the same |
DE102016221470A1 (en) * | 2016-11-02 | 2018-05-03 | Siemens Aktiengesellschaft | Superalloy without titanium, powder, process and component |
KR102206061B1 (en) * | 2020-06-12 | 2021-01-21 | 터보파워텍(주) | method for manufacturing sealing segment of turbine and apparatus for manufacturing thereof |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4169742A (en) * | 1976-12-16 | 1979-10-02 | General Electric Company | Cast nickel-base alloy article |
US5611670A (en) * | 1993-08-06 | 1997-03-18 | Hitachi, Ltd. | Blade for gas turbine |
US5673745A (en) * | 1996-06-27 | 1997-10-07 | General Electric Company | Method for forming an article extension by melting of an alloy preform in a ceramic mold |
Family Cites Families (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3494709A (en) † | 1965-05-27 | 1970-02-10 | United Aircraft Corp | Single crystal metallic part |
US4180119A (en) † | 1978-09-18 | 1979-12-25 | Howmet Turbine Components Corporation | Mold for directionally solidified single crystal castings and method for preparing same |
GB2071695A (en) † | 1980-03-13 | 1981-09-23 | Rolls Royce | An alloy suitable for making single-crystal castings and a casting made thereof |
FR2724857B1 (en) * | 1980-12-30 | 1997-01-03 | Snecma | PROCESS FOR THE MANUFACTURE OF CRYSTALLINE BLADES |
US4532974A (en) † | 1981-07-03 | 1985-08-06 | Rolls-Royce Limited | Component casting |
US5399313A (en) † | 1981-10-02 | 1995-03-21 | General Electric Company | Nickel-based superalloys for producing single crystal articles having improved tolerance to low angle grain boundaries |
US4804311A (en) * | 1981-12-14 | 1989-02-14 | United Technologies Corporation | Transverse directional solidification of metal single crystal articles |
EP0100150A3 (en) † | 1982-07-28 | 1984-08-29 | Trw Inc. | Single crystal metal airfoil |
JPS60177160A (en) † | 1984-02-23 | 1985-09-11 | Natl Res Inst For Metals | Single-crystal Ni-based heat-resistant alloy and its manufacturing method |
US4637448A (en) † | 1984-08-27 | 1987-01-20 | Westinghouse Electric Corp. | Method for production of combustion turbine blade having a single crystal portion |
US4719080A (en) † | 1985-06-10 | 1988-01-12 | United Technologies Corporation | Advanced high strength single crystal superalloy compositions |
US4908183A (en) † | 1985-11-01 | 1990-03-13 | United Technologies Corporation | High strength single crystal superalloys |
US5068084A (en) † | 1986-01-02 | 1991-11-26 | United Technologies Corporation | Columnar grain superalloy articles |
US4813470A (en) † | 1987-11-05 | 1989-03-21 | Allied-Signal Inc. | Casting turbine components with integral airfoils |
US5069873A (en) † | 1989-08-14 | 1991-12-03 | Cannon-Muskegon Corporation | Low carbon directional solidification alloy |
US5706881A (en) † | 1994-05-12 | 1998-01-13 | Howmet Research Corporation | Heat treatment of superalloy casting with partial mold removal |
US5584662A (en) † | 1995-03-06 | 1996-12-17 | General Electric Company | Laser shock peening for gas turbine engine vane repair |
JPH09157777A (en) † | 1995-12-12 | 1997-06-17 | Mitsubishi Materials Corp | Nickel base alloy excellent in thermal fatigue resistance, high temperature creep resistance and high temperature corrosion resistance |
DE69701900T2 (en) † | 1996-02-09 | 2000-12-07 | Hitachi Metals, Ltd. | High-strength nickel-based superalloy for directionally solidified castings |
WO1999067435A1 (en) † | 1998-06-23 | 1999-12-29 | Siemens Aktiengesellschaft | Directionally solidified casting with improved transverse stress rupture strength |
-
1999
- 1999-11-04 JP JP2000579385A patent/JP2004538358A/en active Pending
- 1999-11-04 EP EP99969597A patent/EP1131176B2/en not_active Expired - Lifetime
- 1999-11-04 DE DE69933132T patent/DE69933132T3/en not_active Expired - Lifetime
- 1999-11-04 CA CA002349412A patent/CA2349412C/en not_active Expired - Lifetime
- 1999-11-04 WO PCT/US1999/025976 patent/WO2000025959A1/en active IP Right Grant
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4169742A (en) * | 1976-12-16 | 1979-10-02 | General Electric Company | Cast nickel-base alloy article |
US5611670A (en) * | 1993-08-06 | 1997-03-18 | Hitachi, Ltd. | Blade for gas turbine |
US5673745A (en) * | 1996-06-27 | 1997-10-07 | General Electric Company | Method for forming an article extension by melting of an alloy preform in a ceramic mold |
Non-Patent Citations (1)
Title |
---|
See also references of EP1131176A4 * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2927270A1 (en) * | 2008-02-08 | 2009-08-14 | Snecma Sa | PROCESS FOR MANUFACTURING DIRECTED SOLIDIFICATION AUBES |
EP2092999A1 (en) * | 2008-02-08 | 2009-08-26 | Snecma | Method of manufacturing vanes with directional solidification |
US8201612B2 (en) | 2008-02-08 | 2012-06-19 | Snecma | Process for manufacturing directionally solidified blades |
RU2490088C2 (en) * | 2008-02-08 | 2013-08-20 | Снекма | Method of making blades with directional crystallisation |
Also Published As
Publication number | Publication date |
---|---|
DE69933132T2 (en) | 2007-08-09 |
EP1131176B2 (en) | 2012-03-14 |
EP1131176A4 (en) | 2003-06-11 |
DE69933132T3 (en) | 2012-09-06 |
JP2004538358A (en) | 2004-12-24 |
CA2349412C (en) | 2009-09-01 |
CA2349412A1 (en) | 2000-05-11 |
DE69933132D1 (en) | 2006-10-19 |
EP1131176A1 (en) | 2001-09-12 |
EP1131176B1 (en) | 2006-09-06 |
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