EP1438441B1 - Verfahren zur wärmebehandlung von legierungen mit elementen zur erhöhung der korngrenzfestigkeit - Google Patents

Verfahren zur wärmebehandlung von legierungen mit elementen zur erhöhung der korngrenzfestigkeit Download PDF

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Publication number
EP1438441B1
EP1438441B1 EP02772392A EP02772392A EP1438441B1 EP 1438441 B1 EP1438441 B1 EP 1438441B1 EP 02772392 A EP02772392 A EP 02772392A EP 02772392 A EP02772392 A EP 02772392A EP 1438441 B1 EP1438441 B1 EP 1438441B1
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Prior art keywords
heat treatment
casting
alloy
temperature
degrees
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English (en)
French (fr)
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EP1438441A1 (de
Inventor
Winfried Esser
Dirk Goldschmidt
Michael Ott
Uwe Paul
Ursula Pickert
Russel G. Vogt
Christopher R. Hanslits
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Siemens AG
Siemens Corp
Howmet Corp
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Siemens AG
Siemens Corp
Howmet Research Corp
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
    • C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
    • C22C19/056—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 10% but less than 20%
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
    • C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
    • C22C19/057—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being less 10%
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/10—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of nickel or cobalt or alloys based thereon

Definitions

  • the present invention relates to a heat treatment of alloys, especially nickel base superalloy and, more particularly, to castings having a columnar grain microstructure.
  • US-PS 4 597 809 describes single crystal castings made from a nickel base superalloy having a matrix with a composition consisting essentially of, in weight %, of 9.5% to 14% Cr, 7% to 11% Co, 1% to 2.5% Mo, 3% to 6% W, 1% to 4% Ta, 3% to 4% Al, 3% to 5% Ti, 6.5% to 8% Al + Ti, 0% to 1% Nb, and balance essentially nickel with the matrix containing about 0.4 to about 1.5 volume of a phase based an tantalum carbide as a result of the inclusion in the alloy of about 0.05% to about 0.15% C and extra Ta in an amount equal to 1 to 17 times the C content.
  • the directionally solidified (DS) columnar grain castings produced were unacceptable as DS castings as a result of the castings exhibiting essentially no transverse grain boundary strength and no ductility when tested at a temperature of 750 degrees C (1382 degrees F) and stress of 660 MPa (95.7 Ksi).
  • the transverse grain boundary strength and ductility were so deficient as to render DS columnar grain castings produced from the aforementioned nickel base superalloy unsuitable for use as turbine blades of gas turbine engines.
  • WO 99/67435 discloses nickel base superalloy castings having boron added to improve transverse stress rupture strength and ductility of DS castings.
  • the castings are heat treated at 1250°C for 4h so that a fully solution of the secondary phase ( ⁇ '-phase) is performed. Due to the occurrence of grain boundary cracks after the fully solution heat treatment the producibility is so deficient as to render DS columnar grain castings produced from the aforementioned nickel base superalloy unsuitable for use as turbine blades of gas turbine engines.
  • An object of the present invention is to provide a heat treatment of alloys, especially of as-cast alloys, e.g. DS columnar grain castings based on the aforementioned single crystal nickel base superalloy, having substantially improved transverse stress rupture strength and ductility as well as producibility to an extent that the DS castings are acceptable for use as high temperature applications such as turbine blades of a gas turbine engine.
  • alloys especially of as-cast alloys, e.g. DS columnar grain castings based on the aforementioned single crystal nickel base superalloy, having substantially improved transverse stress rupture strength and ductility as well as producibility to an extent that the DS castings are acceptable for use as high temperature applications such as turbine blades of a gas turbine engine.
  • the present invention as disclosed in the claims involves a heat treatment of cast alloys, such as superalloys, having at least one addition, which improves grain boundary strength such as boron in the nickel base superalloy described here above in a manner discovered to significantly improve transverse stress rupture strength and ductility of directionally solidified (DS) columnar grain castings produced with a heat treatment, which solves a secondary phase only partly, e.g. no fully solution heat treatment is performed.
  • Boron is often added to superalloy compositions in an effective amount to substantially improve transverse stress rupture strength and ductility of directionally solidified columnar grain castings produced from the boron-modified superalloy.
  • the boron concentration preferably is controlled in the range of about 0.003% to about 0.0175% by weight of the superalloy composition to this end.
  • the carbon concentration preferably is controlled in the range of about 0.05% to about 0.11% by weight of the superalloy composition.
  • a preferred nickel base superalloy in accordance with an embodiment of the present invention consists essentially of, in weight %, of about 11.6% to 12.70% Cr, about 8.50% to 9.5% Co, about 1.65% to 2.15% Mo, about 3.5% to 4.10% W, about 4.80% to 5.20% Ta, about 3.40% to 3.80% Al, about 3.9% to 4.25% Ti, about 0.05% to 0.11% C, about 0.003% to 0.0175% B, and balance essentially Ni.
  • the boron modified nickel base superalloy can be cast as DS columnar grain castings pursuant to conventional DS casting techniques such as the well known Bridgman mould withdrawal technique.
  • DS castings produced in this manner typically have a plurality of columnar grains extending in the direction of the principal stress axis of the casting with the ⁇ 001> crystal axis generally parallel to the principal stress axis.
  • DS columnar grain castings pursuant to the present invention preferably exhibit a stress rupture life of at least about 100 hours and elongation of at least about 2.5% when tested at a temperature of 750 degrees C (1382 degrees F) and stress of 660 MPa (95.7 Ksi) and will find use as turbine blades, vanes, outer air seals and other components of a industrial and aero gas turbine engines.
  • a nickel base superalloy which consists essentially of, in weight %, of about 9.5% to 14% Cr, about 7% to 11% Co, about 1% to 2.5% Mo, about 3% to 6% W, about 1% to 6% Ta, about 3$ to 4% Al, about 3% to 5% Ti, about 0% to 1% Nb, and balance essentially Ni and B present in an amount effective to substantially improve transverse stress rupture strength of a DS casting as compared to a similar casting without boron present.
  • the inclusion of boron is chosen in an amount discovered effective to provide substantial transverse stress rupture strength and ductility of a DS columnar grain casting produced from the alloy as compared to a similar casting without boron present.
  • the nickel base superalloy is modified by the inclusion of boron B in the range of about 0.003% to about 0.0175%, preferably 0.010% to 0.015%, by weight of the superalloy composition to this end.
  • the carbon C concentration is controlled in a preferred range of about 0.05% to about 0.11% by weight of the superalloy composition.
  • Silizium Si, Zirkonium Zr and Hafnium Hf can be used as additon. Furthermore all combinations of B, C, Si, Zr, Hf are possible.
  • the transverse stress rupture strength and ductility as well as the producibility of DS castings produced from nickel base superalloy with the modified heat treatment are provided to an extent that the castings are rendered acceptable for use as turbine blades and other components of gas turbine engines.
  • a particularly preferred boron-modified nickel base superalloy casting composition consists essentially of, in weight %, of about 11.6% to 12.70% Cr, about 8.5% to 9.5% Co, about 1.65% to 2.15% Mo, about 3.5% to 4.10% W, about 4.80% to 5.20% Ta, about 3.40 to 3.80% Al, about 3.9% to 4.25% Ti, about 0.05% to 0.11% C, about 0.003% to 0.0175% B, and balance essentially Ni and castable to provide a DS columnar grain microstructure.
  • the DS microstructure of the columnar grain casting typically includes about 0.4 to about 1.5 volume % of a phase based an tantalum carbide.
  • boron and carbon tend to migrate to the grain boundaries in the DS microstructure to add strength and ductility to the grain boundaries at high service temperatures, for example 816 degrees C (1500 degrees F) typical of gas turbine engine blades.
  • DS columnar grain castings produced from the above boron modified nickel base superalloy typically have the ⁇ 001> crystal axis parallel to the principal stress axis of the casting and exhibit a stress rupture life of at least about 100 hours and elongation of at least about 2.5 % when tested at a temperature of 750 degrees C (1382 degrees F) and stress of 660 MPa (95.7 Ksi) applied perpendicular to the ⁇ 001> crystal axis of the casting.
  • a heat #1 having a nickel base superalloy composition in accordance with the aforementioned U.S. Patent 4 597 809 and heats #1A and #2 and #3 of boron modified nickel base superalloy were prepared with the following compositions, in weight percentages, set forth in Table I: TABLE I Heat Cr Co Mo W Ta Al Ti C B Ni #1 12.1 9.0 1.8 3.7 5.2 3.6 4.0 0.07 0.001 balance #1A 12.1 9.0 1.8 3.7 5.2 3.6 4.0 0.08 0.010 balance #2 12.1 9.0 1.8 3.7 5.2 3.6 4.0 0.09 0.011 balance #3 12.1 9.0 1.8 3.7 5.2 3.6 4.0 0.08 0.014 balance
  • each heat was cast to form DS columnar grain non-cored castings having a rectangular shape for transverse stress rupture testing pursuant to ASTM E-139 testing procedure.
  • the DS castings were produced e.g. using the conventional Bridgman mould withdrawal directional solidification technique. For example, each heat was melted in a crucible of a conventional casting furnace under a vacuum of 1 micron and superheated to 1427 degrees C (2600 degrees F). The superheated melt was poured into an investment casting mould having a face coat comprising zircon backed by additional slurry/stucco layers comprising zircon/alumina.
  • the mould was preheated to 1482 degrees C (2700 degrees F) and mounted an a chill plate to effect unidirectional heat removal from the molten alloy in the mould.
  • the melt-filled mould an the chill plate was withdrawn from the furnace into a solidification chamber of the casting furnace at a vacuum of 1 micron at a withdrawal rate of 6-16 inches per hour.
  • the DS columnar grain castings were cooled to room temperature under vacuum in the chamber, removed from the mould in conventional manner using a mechanical knock-out procedure, heat treated at a temperature and for a duration in such way, that the solution of a secondary phase in the matrix is only partly performed.
  • the nickel based superalloy has as a secondary phase the ⁇ '- phase.
  • the inventive heat treatment is performed after casting at 1213°C for at least 1h, which is not the solution temperature of a secondary phase (e.g. y' phase) for this alloy.
  • a secondary phase e.g. y' phase
  • the temperature of 1250°C which is normally used for a fully solution treatment, can be used but only as long as the secondary phase is not completely solved in the matrix.
  • the not solubilized amount of the secondary phase in the matrix is smaller than 90, 70, 50 or 30 vol% according to the geometry and producibility after the heat treatment, because grain boundary cracks are avoided, in order to increase the yield rate of specimens and desired mechanical properties of the specimen.
  • the alloy can have a single crystal structure or only having grains along one direction.
  • an ageing heat treatment can be performed for this composition at 1080°C for at least 2h after this solution heat treatment.
  • a second ageing heat treatment at 870°C for at least 12 h.
  • inventive heat treatment is used for hollow specimen, especially blades, vanes, or liners because cracks do appear more often in walls, especially in thin walls, than in massive specimens after the normally used heat treatment after casting.
  • the inventive heat treatment leads to an increased grain boundary strength during this heat treatment, so that the yield rate (components without cracks) after the heat treatment is increased. Also the transverse stress rupture of the component as final product is increased during use of the component at working conditions, because grain boundary strength is increased.
  • the inventive method yields also good results for massive components, e.g. of a gas turbine.
  • the castings were also analysed for chemistry, and machined to specimen configuration.
  • the results of stress rupture testing are set forth in TABLE II below where LIFE in hours (HRS) indicates the time to fracture of the specimen, ELONGATION is the specimen elongation to fracture, and RED OF AREA is the reduction of area of the specimens to fracture.
  • the BASELINE data corresponds to test data for Heat #1, and the #1A, #2 and #3 data corresponds to test data for Heat #1A, #2 and #3, respectively.
  • the BASELINE data represent an average of two stress rupture test specimens, while the #1A, #2 and #3 data represent a single stress rupture test specimen.
  • TABLE II reveals that DS columnar grain specimens produced from heat #1A exhibited a stress rupture life of 275 hours, an elongation of 3.1%, and a reduction of area of 4.7 and specimens from heat #2 exhibited a stress rupture life of 182 hours, an elongation of 2.6%, and a reduction of area of 6.3% when tested at a temperature of 750 degrees C (1382 degrees F) and stress of 660 MPa (95.7 Ksi).
  • These stress rupture properties of the invention represent an unexpected and surprising improvement over those of specimens produced from heat #1 and render DS columnar grain castings produced from heats #1A, #2 and #3 more suitable for use as turbine blades and other components of gas turbine engines.
  • the present invention is effective to provide DS columnar grain castings with substantial transverse stress rupture strength and ductility. These properties are achieved without adversely affecting other mechanical properties, such as tensile strength, creep strength, fatigue strength, and corrosion resistance of the DS castings.
  • the present invention is especially useful to provide large DS columnar grain industrial gas turbine (IGT) blade castings which have the alloy composition described above to impart substantial transverse stress rupture strength and ductility to the castings and which have a length of about 20 centimeters to about 60 centimeters and above, such as about 90 centimeters length, used throughout the stages of the turbine of stationary industrial gas turbine engines.
  • IGT DS columnar grain industrial gas turbine
  • the above described boron-modified nickel base superalloy casting composition can be cast as DS columnar grain or single crystal components.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
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  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
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  • Crystallography & Structural Chemistry (AREA)
  • Turbine Rotor Nozzle Sealing (AREA)

Claims (20)

  1. Verfahren zum Wärmebehandeln von auf Gußnickel oder -kobalt basierenden Superlegierungen mit mindestens einer Zugabe, welches die Korngrenzenfestigkeit verbessert, wobei die Legierung eine sekundäre Phase nach dem Gießen aufweist, die vollständig in der Matrix der Legierung bei einer Voll-Lösungs-Temperatur für eine bestimmte Voll-Lösungs-Dauer gelöst werden kann,
    dadurch gekennzeichnet, dass
    die Parameter Temperatur und Dauer der Wärmebehandlung in einer Weise verändert werden, dass die nicht solubilisierte Menge der sekundären Phase in der Matrix kleiner als 90, 70, 50 oder 30 Vol.-% ist, wobei die Temperatur der Wärmebehandlung kleiner als die Voll-Lösungs-Temperatur ist und die Dauer der Wärmebehandlung so gewählt ist, dass die sekundäre Phase nicht vollständig gelöst wird, oder wobei die Temperatur der Wärmebehandlung die Voll-Lösungs-Temperatur ist,
    doch die Dauer nur solange ist wie die sekundäre Phase nicht vollständig in der Matrix gelöst ist.
  2. Verfahren nach Anspruch 1,
    wobei mindestens eine Alterungsbehandlung nach der Wärmebehandlung durchgeführt wird.
  3. Verfahren nach Anspruch 1,
    wobei die Wärmebehandlung mit hohlen Komponenten durchgeführt wird.
  4. Verfahren nach Anspruch 3,
    wobei die Wärmebehandlung mit Komponenten mit einer Länge von mindestens 200 mm durchgeführt wird.
  5. Verfahren nach Anspruch 3,
    wobei die Wärmebehandlung mit hohlen Komponenten mit der Dicke einer Außenwand von kleiner als 8 mm durchgeführt wird.
  6. Verfahren nach Anspruch 1,
    wobei die sekundäre Phase die γ'-Phase ist.
  7. Verfahren nach Anspruch 1,
    wobei die Wärmebehandlung mit einer Legierung mit Bor als eine Zugabe durchgeführt wird.
  8. Verfahren nach Anspruch 1,
    wobei die Wärmebehandlung mit einer Legierung mit Kohlenstoff als eine Zugabe durchgeführt wird.
  9. Verfahren nach Anspruch 1,
    wobei die Wärmebehandlung mit einer Legierung mit einer gerichteten Erstarrung unterworfenen säulenförmigen Körnern durchgeführt wird.
  10. Verfahren nach Anspruch 1,
    wobei die Wärmebehandlung mit einer Legierung mit einer Einkristallstruktur durchgeführt wird.
  11. Verfahren nach Anspruch 1,
    wobei die Wärmebehandlung mit einer auf Nickel basierenden Gusslegierung aus einer gerichteten Erstarrung unterworfenen säulenförmigen Körnern durchgeführt wird,
    bestehend im Wesentlichen aus, in Gew.-%,
    etwa 9,5 % bis 14 % Cr,
    etwa 7 % bis 11 % Co,
    etwa 1 % bis 2,5 % Mo,
    etwa 3 % bis 6 % W,
    etwa 1 % bis 6 % Ta,
    etwa 3 % bis 4 % Al,
    etwa 3 % bis 5 % Ti,
    etwa 0 % bis 1 % Nb,
    und dem Rest von im Wesentlichen Ni,
    und B, das in einer Menge vorliegt, die eine beträchtliche Verbesserung der Querspannungs-Zeitstandbruchfestigkeit des Gussstücks im Vergleich mit einem ähnlichen Gussstück ohne vorhandenes Bor bewirkt.
  12. Verfahren nach Anspruch 11,
    wobei die Wärmebehandlung mit einer Legierung durchgeführt wird, wobei B im Bereich von etwa 0,003 bis etwa 0,018 Gew.-% vorliegt.
  13. Verfahren nach Anspruch 11,
    wobei die Legierung nach der Wärmebehandlung eine Spannungsdauerfestigkeit von mindestens etwa 100 Stunden und eine Bruchdehnung von mindestens etwa 2,5 % besitzt wenn bei einer Temperatur von 750 Grad C (1382 Grad F) und einer in senkrechter Richtung zu einer <001>-Kristallachse des Gussstücks angewandten Spannung von 660 MPa (95,7 Ksi) getestet wird.
  14. Verfahren nach Anspruch 1,
    wobei die Wärmebehandlung mit einer auf Nickel basierenden Gusslegierung aus einer gerichteten Erstarrung unterworfenen säulenförmigen Körnern durchgeführt wird, bestehend im Wesentlichen aus, in Gew.-%,
    etwa 11,6 % bis 12,70 % Cr,
    etwa 8,5 % bis 9,5 % Co,
    etwa 1,65 % bis 2,15 % Mo,
    etwa 3,5 % bis 4,10 % W,
    etwa 4,8 % bis 5,20 % Ta,
    etwa 3,4 % bis 3,80 % Al,
    etwa 3,9 % bis 4,25 % Ti,
    etwa 0,05 % bis 0,11 % C,
    etwa 0,003 % bis 0,0175 % B,
    dem Rest von im Wesentlichen Ni, und
    mit einer wesentlich verbesserten Querspannungs-Zeitstandbruchfestigkeit im Vergleich mit einem ähnlichen Gussstück ohne vorhandenes Bor.
  15. Verfahren nach Anspruch 14,
    wobei die Legierung nach der Wärmebehandlung eine Spannungsdauerfestigkeit von mindestens etwa 120 Stunden und eine Dehnung von mindestens etwa 2,5 % besitzt, wenn bei einer Temperatur von 750 Grad C (1382 Grad F) und einer in senkrechter Richtung zu einer <001>-Kristallachse des Gussstücks angewandten Spannung von 660 MPa (95,7 Ksi) getestet wird.
  16. Verfahren nach Anspruch 1,
    wobei die Wärmebehandlung mit einer auf Nickel basierenden Gusslegierung aus einer gerichteten Erstarrung unterworfenen säulenförmigen Körnern durchgeführt wird, bestehend im Wesentlichen aus, in Gew.-%,
    etwa 12,00 % Cr,
    etwa 9,00 % Co,
    etwa 1,85 % Mo,
    etwa 3,70 % W,
    etwa 5,10 % Ta,
    etwa 3,60 % Al,
    etwa 4,00 % Ti,
    etwa 0,0125 % B,
    etwa 0,09 % C, dem Rest von im Wesentlichen Ni, und
    mit einer Spannungsdauerfestigkeit von mindestens etwa 100 Stunden und einer Bruchdehnung von mindestens etwa 2,5 %, wenn bei einer Temperatur von 750 Grad C (1382 Grad F) und einer in senkrechter Richtung zu einer <001>-Kristallachse des Gussstücks angewandten Spannung von 660 MPa (95,7 Ksi) getestet wird.
  17. Verfahren nach Anspruch 1,
    wobei die Wärmebehandlung nach dem Gießen durchgeführt wird.
  18. Verfahren nach Anspruch 5,
    wobei die hohlen Komponenten aus der Gruppe bestehend aus Platten, Blättern und Auskleidungen gewählt sind.
  19. Verfahren nach Anspruch 1,
    wobei die Wärmebehandlung mit Massivkomponenten durchgeführt wird.
  20. Verfahren nach Anspruch 1,
    wobei die Wärmebehandlung mit einer Legierung mit einer Zugabe, gewählt aus der Gruppe bestehend aus Zirkon, Silizium und Hafnium, durchgeführt wird.
EP02772392A 2002-10-23 2002-10-23 Verfahren zur wärmebehandlung von legierungen mit elementen zur erhöhung der korngrenzfestigkeit Expired - Lifetime EP1438441B1 (de)

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PCT/EP2002/011856 WO2004038056A1 (en) 2002-10-23 2002-10-23 Heat treatment of alloys having elements for improving grain boundary strength

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EP1438441B1 true EP1438441B1 (de) 2006-09-27

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EP (1) EP1438441B1 (de)
JP (1) JP4812301B2 (de)
CN (1) CN100449031C (de)
AU (1) AU2002337170A1 (de)
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DE (1) DE60215035T2 (de)
ES (1) ES2276959T3 (de)
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2769802A1 (de) 2013-02-22 2014-08-27 Siemens Aktiengesellschaft Verbessertes Schweißmaterial bezüglich der Schweißbarkeit und Kornstabilisierung, Verfahren und Bauteil

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1849879A1 (de) * 2006-04-26 2007-10-31 Siemens Aktiengesellschaft Pendelförmiges Wärmebehandlungsverfahren für eine Superlegierung
ES2444407T3 (es) 2006-09-07 2014-02-24 Alstom Technology Ltd Procedimiento para el tratamiento térmico de súper-aleaciones a base de níquel
EP3363923A1 (de) * 2009-10-20 2018-08-22 Siemens Aktiengesellschaft Legierung zur gerichteten erstarrung und bauteil aus stängelförmigen kristallen

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WO1999067435A1 (en) * 1998-06-23 1999-12-29 Siemens Aktiengesellschaft Directionally solidified casting with improved transverse stress rupture strength

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2769802A1 (de) 2013-02-22 2014-08-27 Siemens Aktiengesellschaft Verbessertes Schweißmaterial bezüglich der Schweißbarkeit und Kornstabilisierung, Verfahren und Bauteil
WO2014127987A1 (de) 2013-02-22 2014-08-28 Siemens Aktiengesellschaft Verbessertes schweissmaterial bezüglich der schweissbarkeit und kornstabilisierung, verfahren und bauteil

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CA2503326C (en) 2011-02-08
AU2002337170A1 (en) 2004-05-13
EP1438441A1 (de) 2004-07-21
DE60215035D1 (de) 2006-11-09
CA2503326A1 (en) 2004-05-06
JP4812301B2 (ja) 2011-11-09
CN100449031C (zh) 2009-01-07
AU2002337170A8 (en) 2004-05-13
ES2276959T3 (es) 2007-07-01
JP2006503980A (ja) 2006-02-02
WO2004038056A1 (en) 2004-05-06
CN1617944A (zh) 2005-05-18

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