EP1038982A1 - Einkristalline Superlegierungskörpern mit verminderter Rekristallisierung der Körnern - Google Patents
Einkristalline Superlegierungskörpern mit verminderter Rekristallisierung der Körnern Download PDFInfo
- Publication number
- EP1038982A1 EP1038982A1 EP00105884A EP00105884A EP1038982A1 EP 1038982 A1 EP1038982 A1 EP 1038982A1 EP 00105884 A EP00105884 A EP 00105884A EP 00105884 A EP00105884 A EP 00105884A EP 1038982 A1 EP1038982 A1 EP 1038982A1
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- EP
- European Patent Office
- Prior art keywords
- casting
- single crystal
- carbon
- weight
- heat treating
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- 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.)
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- 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%
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
- C23C8/20—Carburising
Definitions
- the present invention relates to nickel base superalloy castings and, more particularly, to a method of heat treating single crystal superalloy castings in a manner to reduce or localize deleterious extraneous grain recrystallization during heat treatment.
- U.S. Patent 4 643 782 describes single crystal castings made from a nickel base superalloy having a composition consisting essentially of, in weight %, of 6.4% to 6.8% Cr, 9.3% to 10.0% Co, 0.5% to 0.7% Mo, 6.2% to 6.6% W, 6.3% to 6.7% Ta, 5.45% to 5.75% Al, 0.8% to 1.2% Ti, 2.8% to 3.2% Re, 0.07 to 0.12% Hf and balance essentially nickel. Carbon is held to incidental impurity levels of for example 60 ppm maximum C in the alloy.
- the present invention provides a method of making of superalloy single crystal castings, such as gas turbine engine single crystal blades and vanes (airfoils), in a manner to address the problem of grain recrystallization during heat treatment of the single crystal castings.
- the invention involves the discovery that grain recrystallization can be reduced by solution heat treating the single crystal castings in the presence of gaseous species carburizing relative to the superalloy castings so as to introduce carbon into the castings in an effective amount to reduce recrystallized grains during heat treatment.
- a carburizing atmosphere can be provided by introducing a mixture of carbon monoxide and an inert gas, such as argon, into the heat treatment furnace or by heat treating in a furnace having a component, such as heating elements, that inherently provides a carburizing atmosphere during heat treatment.
- a furnace to this end typically comprises heating elements, heat shields and/or other furnace components or inserts comprising graphite or other carbon-bearing material as a source of carbon for reaction with oxygen to form a carbon-bearing gas, such as carbon monoxide, in-situ in the furnace that is carburizing relative to the castings.
- the carbon concentration of at least the outer surface region of the superalloy single crystal castings is locally increased during heat treatment as compared to the nominal carbon concentration of the bulk superalloy casting as evidenced, for example, by the presence of blocky carbides of one or more alloying elements, which carbides are not present when the superalloy casting is heat treated under vacuum or inert gas atmosphere only in the absence of a carburizing gas species in the furnace.
- the carbides form in the microstructure in a manner to pin any recrystallized grain boundaries during solution heat treatment and retard, limit and localize their growth in a manner to improve the yield of acceptable heat treated single crystal castings.
- the present invention involves heat treating nickel base superalloys formulated for single crystal casting in a manner to unexpectedly and surprisingly substantially reduce or localize grain recrystallization after heat treatment of the casting at elevated temperature, such as a high temperature solution heat treatment to dissolve or solution most of the eutectic and coarse gamma prime phases present in the as-cast microstructure. Improved yields of acceptable heat treated single crystal castings are thereby achieved.
- the present invention can be practiced on a variety of low carbon nickel base superalloys that are formulated for single crystal casting and include W, Ta, Mo, Co, Al and Cr as important alloying elements as well as optionally Ti, Re, Y, Hf, one or more rare earth elements such as La, B, and Mg as intentional alloying elements and that suffer undesirable grain recrystallization upon heat treatment.
- Such grain recrystallization prone nickel base superalloys typically have carbon concentration less than about 200 ppm by weight (about 0.02 weight % C) with some less than about 100 ppm C (about 0.01 weight % C), although the invention may be practiced with superalloys having other carbon concentrations to reduce grain recrystallization in a particular nickel base superalloy.
- Nickel base superalloys formulated for casting single crystal castings such as single crystal airfoils (blades and vanes), and heat treatable pursuant to the invention include, but are not limited to, those described in U.S. Patents 4 643 782 and 5 366 695 the teachings of which are incorporated herein by reference with respect to particular alloy compositions.
- An illustrative nickel base superalloy casting composition heat treatable pursuant to the present invention consists essentially of, in weight % or parts per million (ppm) by weight, of about 6% to 6.8% Cr, about 8% to 10% Co, about 0.5% to 0.7% Mo, about 6.2% to 6.6% W, about 6.3% to 7% Ta, about 5.4% to 5.8% Al, about 0.6% to 1.2% Ti, about 0.10% to 0.3% Hf, up to about 200 ppm by weight B, up to about 50 ppm by weight Mg, up to about 200 ppm by weight carbon, and balance essentially Ni and castable to provide a single crystal microstructure, especially for gas turbine engine blades and vanes (i.e. airfoils).
- ppm parts per million
- An illustrative low carbon, high Re nickel base superalloy casting composition heat treatable pursuant to the present invention consists essentially of, in weight %, of about 1.5% to 5% Cr, about 1.5% to 10% Co, about 0.25% to 2% Mo, about 3.5% to 7.5% W, about 7% to 10% Ta, about 5% to 7% Al, up to about 1.2% Ti, about 5% to 7% Re, up to about 0.15% Hf, up to about 0.5% Nb, C less than about 0.02% or at incidental impurity level, and balance essentially Ni and castable to provide a single crystal microstructure, especially for gas turbine engine blades and vanes (i.e. airfoils).
- An illustrative low carbon, high Cr nickel base superalloy casting composition heat treatable pursuant to the present invention consists essentially of, in weight %, of about 11% to 16% Cr, about 2% to 8% Co, about 0.2% to 2% Mo, about 3.5% to 7.5% W, about 4% to 6% Ta, about 3% to 6% Al, about 2% to about 5% Ti, up to about 0.2% Nb, C less than about 0.02% or at incidental impurity level, and balance essentially Ni and castable to provide a single crystal microstructure, especially for gas turbine engine blades and vanes (i.e. airfoils).
- Single crystal gas turbine engine blades were conventionally cast using the Bridgeman withdrawal technique from commercially available CMSX-4 nickel base superalloy, described in US Patent 4 643 782, and were subjected in the as-cast condition after removal of a ceramic shell mold and a ceramic core to solution heat treatments in various atmospheres.
- the nominal composition, in weight %, of the single crystal blades was 6.4% Cr, 9.7% Co, 0.6% Mo, 6.4% W, 6.5% Ta, 5.6% Al, 1.0% Ti, 2.9% Re, 0.10% Hf, 30 ppm by weight C and balance essentially Ni and impurities.
- the ceramic shell mold and core were removed completely from the castings in conventional manner using a mechanical knock-out procedure and chemical leaching.
- the single crystal blade castings then were solution heat treated in various furnaces using various atmospheres. After heat treatment, the castings were examined for the presence of recrystallized grains on the casting surfaces.
- the cast single crystal blades were solution heat treated in various heat treatment furnaces.
- One type of furnace included graphite electrical resistance heating element and graphite sides or heat shield liners.
- Another type of furnace included molybdenum electrical resistance heating elements and graphite sides or heat shield liners.
- Different heat treatment atmospheres were provided for different heat treatment runs in the different types of furnaces.
- one heat treatment run involved providing a vacuum of less than 5 microns in a furnace having molybdenum heating elements and graphite heat shields or liners and then introducing a mixture of argon and 10% by volume CO at a flow rate during continued vacuum pump evacuation of the furnace to maintain 400 microns partial pressure of argon plus CO in the furnace as the atmosphere during heat treatment.
- the argon/10% by volume CO gas mixture was introduced from a conventional gas cylinder having a mixture of argon and 10% by volume CO therein. The mixture was introduced after the furnace temperature reached 1900 degrees F so as to reduce chromium vaporization from the castings.
- a total of 10 cast single crystal blades were solution heat treated in this furnace by slowly heating the castings to a solutioning temperature of 2400 degrees F plus or minus 15 degrees F over 11 hours. The solutioning temperature was held for 6 hours, and the castings were cooled to room temperature over a time of 1 hour.
- the solution heat treatment dissolved most of the eutectic and coarse gamma prime phases in the as-cast microstructure.
- the only recrystallized grains observed were initiated proximate a core print (at a blade tip) with the recrystallized grains localized to an extent that they existed outside the finished casting dimensions for the particular blade involved; i.e. such that the localized amount of recrystallized grains on the heat treated blade would be removed by subsequent finish machining of the blade.
- blocky carbides rich in Ta and Ti having a lateral dimension (e.g. diameter) of less than 0.5 mil (0.0005 inch) were observed to exist throughout the airfoil and pinning the recrystallized grain boundaries as illustrated in Figure 1 by the arrow.
- the carbides were determined to include Ta in the approximate range of 71-77 weight % Ta, Ti in approximate range of 9-10 weight % Ti, Hf in approximate range of 2-7 weight % Hf, Ni in approximate range of 3-4 weight % Ni with other elements such as Co, W, Cr, Fe, also present in lesser amounts.
- the carbides were formed predominantly along cast surfaces, providing a high population of carbides in thin sections of the castings where grain growth is more likely to be a problematic.
- the carbides were attributed to the carburization of the castings, resulting in introduction of carbon into the castings during heat treatment. For example, typical carbon concentration at the airfoil surface and of the bulk airfoil was twice as high (at least 100% higher) as the as-cast carbon content at the airfoil surface.
- the as-cast carbon concentration of the bulk airfoil and bulk root were increased from about 38 ppm by weight C to 113 ppm and 89 ppm by weight carbon for the airfoil and root, respectively.
- the carbon content at the airfoil surface was even higher, being about 171 ppm by weight C after the above heat treatment.
- the present invention provides single crystal castings having carbon concentrations increased by the heat treatment in an amount discovered to form carbides in-situ in the heat treated microstructure that pin recrystallized grain boundaries and retard, limit and localize their growth to reduce recrystallized grains that are cause for rejection of the single crystal castings and increase yield of acceptable heat treated castings.
- Practice of the invention as described above produced a six times increase in yield of acceptable heat treated single crystal turbine blade castings.
- the present invention envisions use of carburizing atmospheres or gaseous carburizing species other than carbon monoxide that are effective to introduce carbon to single crystal nickel base superalloy castings during their heat treatment in amounts effective to reduce or localize recrystallized grains.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Furnace Details (AREA)
- Turbine Rotor Nozzle Sealing (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US276859 | 1988-11-25 | ||
US27685999A | 1999-03-26 | 1999-03-26 |
Publications (1)
Publication Number | Publication Date |
---|---|
EP1038982A1 true EP1038982A1 (de) | 2000-09-27 |
Family
ID=23058370
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP00105884A Withdrawn EP1038982A1 (de) | 1999-03-26 | 2000-03-20 | Einkristalline Superlegierungskörpern mit verminderter Rekristallisierung der Körnern |
Country Status (2)
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EP (1) | EP1038982A1 (de) |
JP (1) | JP2000319769A (de) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1211336A1 (de) * | 2000-11-30 | 2002-06-05 | ONERA (Office National d'Etudes et de Recherches Aérospatiales) | Superlegierung auf Nickelbasis für Einkristallturbinenschaufeln von industriellen Turbinen mit hoher Beständigkeit gegen Heisskorrosion |
EP1211335A1 (de) * | 2000-11-30 | 2002-06-05 | ONERA (Office National d'Etudes et de Recherches Aérospatiales) | Superlegierung auf Nickelbasis mit sehr hoher Beständigkeit gegen Heisskorrosion für Einkristallturbinenschaufeln von industriellen Turbinen |
US6675586B2 (en) | 2001-06-27 | 2004-01-13 | Siemens Aktiengesellschaft | Heat shield arrangement for a component carrying hot gas, in particular for structural parts of gas turbines |
US6719853B2 (en) | 2001-04-27 | 2004-04-13 | Siemens Aktiengesellschaft | Method for restoring the microstructure of a textured article and for refurbishing a gas turbine blade or vane |
GB2404924A (en) * | 2003-08-11 | 2005-02-16 | Hitachi Ltd | Nickel-based single crystal superalloy |
CN107119325A (zh) * | 2017-06-26 | 2017-09-01 | 中国科学院金属研究所 | 一种消除激光3d打印单晶高温合金再结晶倾向的方法 |
CN112160031A (zh) * | 2020-09-10 | 2021-01-01 | 中国科学院金属研究所 | 一种提高定向凝固柱晶或单晶高温合金铸件高温持久寿命的方法 |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2014150342A1 (en) * | 2013-03-15 | 2014-09-25 | United Technologies Corporation | Cast component having corner radius to reduce recrystallization |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2075548A (en) * | 1980-05-09 | 1981-11-18 | United Technologies Corp | Corrosion Resistant Nickel Base Superalloys Containing Manganese |
US4849030A (en) * | 1986-06-09 | 1989-07-18 | General Electric Company | Dispersion strengthened single crystal alloys and method |
US5366695A (en) * | 1992-06-29 | 1994-11-22 | Cannon-Muskegon Corporation | Single crystal nickel-based superalloy |
US5556484A (en) * | 1995-04-26 | 1996-09-17 | General Electric Company | Method for reducing abnormal grain growth in Ni-base superalloys |
US5759303A (en) * | 1993-03-18 | 1998-06-02 | Howmet Research Corporation | Clean single crystal nickel base superalloy |
JPH11310839A (ja) * | 1998-04-28 | 1999-11-09 | Hitachi Ltd | 高強度Ni基超合金方向性凝固鋳物 |
-
2000
- 2000-03-20 EP EP00105884A patent/EP1038982A1/de not_active Withdrawn
- 2000-03-24 JP JP2000084435A patent/JP2000319769A/ja active Pending
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2075548A (en) * | 1980-05-09 | 1981-11-18 | United Technologies Corp | Corrosion Resistant Nickel Base Superalloys Containing Manganese |
US4849030A (en) * | 1986-06-09 | 1989-07-18 | General Electric Company | Dispersion strengthened single crystal alloys and method |
US5366695A (en) * | 1992-06-29 | 1994-11-22 | Cannon-Muskegon Corporation | Single crystal nickel-based superalloy |
US5759303A (en) * | 1993-03-18 | 1998-06-02 | Howmet Research Corporation | Clean single crystal nickel base superalloy |
US5556484A (en) * | 1995-04-26 | 1996-09-17 | General Electric Company | Method for reducing abnormal grain growth in Ni-base superalloys |
JPH11310839A (ja) * | 1998-04-28 | 1999-11-09 | Hitachi Ltd | 高強度Ni基超合金方向性凝固鋳物 |
Non-Patent Citations (2)
Title |
---|
DATABASE WPI Section Ch Week 200011, Derwent World Patents Index; Class M, Page 22, AN 2000-119276 * |
PATENT ABSTRACTS OF JAPAN vol. 2000, no. 02 29 February 2000 (2000-02-29) * |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1211336A1 (de) * | 2000-11-30 | 2002-06-05 | ONERA (Office National d'Etudes et de Recherches Aérospatiales) | Superlegierung auf Nickelbasis für Einkristallturbinenschaufeln von industriellen Turbinen mit hoher Beständigkeit gegen Heisskorrosion |
EP1211335A1 (de) * | 2000-11-30 | 2002-06-05 | ONERA (Office National d'Etudes et de Recherches Aérospatiales) | Superlegierung auf Nickelbasis mit sehr hoher Beständigkeit gegen Heisskorrosion für Einkristallturbinenschaufeln von industriellen Turbinen |
US6719853B2 (en) | 2001-04-27 | 2004-04-13 | Siemens Aktiengesellschaft | Method for restoring the microstructure of a textured article and for refurbishing a gas turbine blade or vane |
US6675586B2 (en) | 2001-06-27 | 2004-01-13 | Siemens Aktiengesellschaft | Heat shield arrangement for a component carrying hot gas, in particular for structural parts of gas turbines |
GB2404924A (en) * | 2003-08-11 | 2005-02-16 | Hitachi Ltd | Nickel-based single crystal superalloy |
GB2404924B (en) * | 2003-08-11 | 2005-07-27 | Hitachi Ltd | Single-crystal Ni-based superalloy with high temperature strength, oxidation resistance and hot corrosion resistance |
US7306682B2 (en) | 2003-08-11 | 2007-12-11 | Hitachi, Ltd. | Single-crystal Ni-based superalloy with high temperature strength, oxidation resistance and hot corrosion resistance |
CN107119325A (zh) * | 2017-06-26 | 2017-09-01 | 中国科学院金属研究所 | 一种消除激光3d打印单晶高温合金再结晶倾向的方法 |
CN107119325B (zh) * | 2017-06-26 | 2019-03-12 | 中国科学院金属研究所 | 一种消除激光3d打印单晶高温合金再结晶倾向的方法 |
CN112160031A (zh) * | 2020-09-10 | 2021-01-01 | 中国科学院金属研究所 | 一种提高定向凝固柱晶或单晶高温合金铸件高温持久寿命的方法 |
CN112160031B (zh) * | 2020-09-10 | 2022-03-22 | 中国科学院金属研究所 | 一种提高定向凝固柱晶或单晶高温合金铸件高温持久寿命的方法 |
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Publication number | Publication date |
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JP2000319769A (ja) | 2000-11-21 |
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