EP1900839A1 - Procédé pour le traitement thermique de superalliages à base de Ni - Google Patents

Procédé pour le traitement thermique de superalliages à base de Ni Download PDF

Info

Publication number: EP1900839A1
Authority: EP; European Patent Office
Prior art keywords: heat treatment; nickel; annealing; fan; grain boundaries
Prior art date: 2006-09-07
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.): Granted

Application number

EP07114884A

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German (de)

English (en)

Other versions

EP1900839B1 (fr

Inventor

Mohamed Youssef Nazmy

Markus Staubli

Andreas KÜNZLER

Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)

GE Vernova GmbH

Original Assignee

Alstom Technology AG

Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)

2006-09-07

Filing date

2007-08-23

Publication date

2008-03-19

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2007-08-23 Application filed by Alstom Technology AG filed Critical Alstom Technology AG

2008-03-19 Publication of EP1900839A1 publication Critical patent/EP1900839A1/fr

2013-11-06 Application granted granted Critical

2013-11-06 Publication of EP1900839B1 publication Critical patent/EP1900839B1/fr

Status Revoked legal-status Critical Current

2027-08-23 Anticipated expiration legal-status Critical

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- 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 invention relates to the field of materials technology. It relates to a process for the heat treatment of nickel-base superalloys, which can be completely heat treated (solution annealed) per se and for the production of single crystal components (SX alloy) or directionally solidified components (DS alloy), such as Shovels for gas turbines, to be used.
SX alloy single crystal components
DS alloy directionally solidified components
the properties of the abovementioned alloys, especially at high temperatures are to be positively influenced by increasing the permissible tolerance to small angle grain boundaries and increasing the casting output and thus the effectiveness of the casting.
Nickel-based superalloys are known. Single-crystal components made of these alloys have a very good material strength at high temperatures, but also good corrosion and oxidation resistance as well as a good creep resistance. Due to these properties, when using such materials z. As in gas turbines, the inlet temperature of the gas turbine can be increased, whereby the efficiency of the gas turbine plant increases.
the first type may be completely heat treated (solution annealed) so that the entire ⁇ 'phase is in solution.
This is the case for example for the known alloy CMSX4 with the following chemical composition (in% by weight): 5.6 Al, 9.0 Co, 6.5 Cr, 0.1 Hf, 0.6 Mo, 3 Re, 6.5 Ta, 1.0 Ti, 6.0 W, Rest Ni or the alloy PWA 1484 with the following chemical composition (in% by weight): 5 Cr, 10 Co, 6 W, 2 Mo, 3 Re, 8.7 Ta, 5.6 Al, 0.1 Hf and the known alloy MC2, which unlike the abovementioned alloys, it is not alloyed with rhenium and has the following chemical composition (in% by weight): 5 Co, 8 Cr, 2 Mo, 8 W, 5 Al, 1.5 Ti, 6 Ta, balance Ni.
a typical standard heat treatment for CMSX4, for example, is the following: solution annealing at 1320 ° C / 2h / shielding gas, fan cooling
the second type of single crystal nickel base superalloys is not fully heat treatable, that is, not the entire portion of the ⁇ 'phase is solubilized in a solution anneal, but only a certain portion.
This is the case, for example, with the known superalloy CMSX186 having the following chemical composition (in% by weight): 0.07 C, 6 Cr, 9 Co, 0.5 Mo, 8 W, 3 Ta, 3 Re, 5.7 Al, 0.7 Ti, 1.4 Hf, 0.015 B, 0.005 Zr, balance Ni and the alloy CMSX486 with the following chemical composition (in% by weight): 0.07 C, 0.015 B, 5.7 Al, 9.3 Co, 5 Cr, 1.2 Hf, 0.7 Mo, 3 Re, 4.5 Ta, 0.7 Ti, 8.6 W, 0.005 Zr, balance Ni.
the nickel-base superalloys of the second type are usually subjected to a two-stage heat treatment (aging process at lower temperatures), since at higher temperatures, as typically used in the alloys of the first type for solution annealing, the melting point start temperature is achieved, and the alloy thus begins to melt undesirably.
the creep resistance of the first type of nickel-base superalloys is usually higher than that of the second type, provided that the alloys belong to the same generation. This is mainly due to the fact that the dissolved ⁇ 'is the main source of recoverable strength.
Nickel-based superalloys for single crystal components as they are made US 4,643,782 .
EP 0 208 645 and US 5,270,123 contain alloying, such as Re, W, Mo, Co, Cr, and ⁇ '-phase-forming elements, such as Al, Ta, and Ti.
the content of high-melting alloy elements (W, Mo, Re) in the basic matrix ( austenitic ⁇ phase) increases continuously with the increase of the stress temperature of the alloy.
W, Mo, Re high-melting alloy elements
B common nickel-based superalloys for single crystals 6-8% W, up to 6% Re and up to 2% Mo (in% by weight).
the alloys disclosed in the above references have high creep strength, good LCF (low duty cycle fatigue) and HCF (high cycle fatigue) properties, and high oxidation resistance.
the alloy CMSX-4 US 4,643,782 when used experimentally in a gas turbine at a temperature above 1000 ° C, a strong coarsening of the ⁇ '-phase, which is associated with an increase in the creeping speed of the alloy adversely.
grain boundaries are particularly detrimental to the high temperature properties of single crystal articles. While small-angle grain boundaries have relatively little effect on the properties of small components, they are relatively small Castability and the oxidation behavior at high temperatures for large SX or DS components of high relevance.
Grain boundaries are areas of high local disorder of the crystal lattice because adjacent grains collide in these areas and thus there is a certain disorientation between the crystal lattices.
the tolerance for deviation in the small angle grain boundaries or grain boundary end orientation is generally greater for the second type of nickel base superalloys, that is, those which are not fully heat treatable.
the aim of the invention is to avoid the mentioned disadvantages of the prior art.
the invention has for its object to develop a suitable method for heat treatment of such known nickel-based superalloys, which have a chemical composition, which in itself a problem-free complete solution annealing (annealing to dissolve exuded components) allows and for the production of Single crystal components (SX alloy) or components with directionally solidified structure (DS alloy) can be used.
SX alloy Single crystal components
DS alloy directionally solidified structure
this is achieved by subjecting said nickel-base superalloy to a multi-stage heat treatment process, wherein the alloy is only partially solution-controlled in a first step at a temperature T2 ⁇ T1 and in a second step a two-stage aging treatment at respectively lower temperatures is carried out.
first step partial solution annealing
the calculated increase of the undissolved ⁇ 'phase in the Resteutikikum can be controlled depending on the height of the solution annealing temperature. Since most of the SX nickel base superalloys used in industrial gas turbines have high creep strength (creep strength), some reduction in creep strength can be tolerated to a high tolerance to achieve the disorientation of the small angle grain boundaries or the grain boundaries.
the inventive heat treatment process is particularly suitable for use in nickel-based superalloys for the production of large single-crystal components, in particular blades for gas turbines.
These alloys are nickel base superalloy for single crystal components and are used to make gas turbine components. They belong to the first type of nickel-base superalloys described above, i. they are completely heat treatable and in a solution annealing above a temperature T1, z. At about 1320 ° C for CMSX-4, the microstructure is completely solution annealed, i. the excretions are completely dissolved in the matrix. This applies to the standard heat treatments shown in FIGS. 2, 4, 6 and 8.
FIG. 3 shows the dependence of the high-temperature endurance (relative values) on the size of the disorientation of the small-angle grain boundaries / grain boundaries for the two heat treatment processes according to FIG. 2 for the alloy CMSX4. It can be seen that after the standard heat treatment (complete solution annealing) the creep strength has already dropped to about 80% from about 6 ° disorientation compared to a defect-free component, whereas after the heat treatment according to the invention still about 12 ° disorientation can be allowed.
the alloy SX MC2 according to the invention was heat-treated with a first step (partial solution annealing at 1210 ° C / 8h / argon rapid cooling with fan) and a second step (two-stage annealing at 1080 ° C / 6h / argon rapid cooling with fan and then 870 ° C / 16h / air cooling, and then the creep rupture strength was determined and the results were compared with the results after standard heat treatment (complete solution annealing at 1300 ° C.) The relative creep strength after the standard heat treatment even at a disorientation of more than 6 ° showed a significant decrease during this occurred after the heat treatment according to the invention only at a disorientation angle of about 12 °.
Figures 6 and 7 show a further embodiment of the invention.
Fig. 6 in a time-temperature diagram for the single-crystal alloy MK4HC the standard solution annealing (1290 ° C / 8h / argon rapid cooling with fan) followed by two-stage annealing (1140 ° C / 2.5h / argon Schnellkkühlung with Fan and 870 ° C / 22h / air cooling) of the inventive modified heat treatment (partial solution annealing at 1270 ° C / 8h / argon rapid cooling with fan, then two-stage annealing with the same parameters as in the standard heat treatment).
FIG. 7 once again shows the dependence of the high-temperature endurance (relative data) on the size of the disorientation of the small-angle grain boundaries / grain boundaries for the two heat treatment processes according to FIG. 6 for the alloy SXMK4HC. It can be seen that after the standard heat treatment (complete solution annealing) from about 12 ° disorientation creep has fallen to about 80% compared to a defect-free component, while after the heat treatment according to the invention, this drop occurs only at about 20 ° disorientation of the grain boundaries , So here can still be allowed about 20 ° disorientation.
This enhanced grain boundary hardening results on the one hand from the alloyed grain boundary consolidators C and B, on the other hand from the residual eutectic (5-10% ⁇ ') present as a result of the incomplete solution annealing process.
FIGS. 8 and 9 show this tendency for the alloy SX MD2.
FIG. 8 once again shows the standard heat treatment and the heat treatment according to the invention for the alloy SX MD2 in a time-temperature diagram, whereby the partial solution annealing treatment at 1230 ° C./8 h / argon is carried out with fan cooling, while the standard solution annealing is carried out at 1270 ° C. C / 8h / argon rapid cooling with fan takes place.
the subsequent two-stage annealing process is the same for both treatments: 1080 ° C / 6h / argon Rapid cooling with fan and 870 ° C / 16h / air cooling.
FIG. 9 once again shows the dependence of the high-temperature endurance (relative values) on the size of the disorientation of the small-angle grain boundaries / grain boundaries for the two heat treatment processes according to FIG. 8 for the alloy SXMD2.
the creep resistance has also fallen to approximately 80% here after the standard heat treatment (complete solution annealing) from about 12 ° disorientation of the grain boundaries, compared to a defect-free component, whereas after the heat treatment according to the invention, this drop is only approximately 20% ° Disorientation of grain boundaries occurs. This means that disorientations of about 20 ° can still be allowed here.
this increased grain boundary hardening results, on the one hand, from the alloyed grain boundary consolidators C and B, and, on the other hand, from the residual eutectic (5-10% ⁇ ') present as a result of the incomplete solution annealing process.

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

EP07114884.5A 2006-09-07 2007-08-23 Procédé pour le traitement thermique de superalliages à base de Ni Revoked EP1900839B1 (fr)

Applications Claiming Priority (1)

Application Number	Priority Date	Filing Date	Title
CH14342006		2006-09-07

Publications (2)

Publication Number	Publication Date
EP1900839A1 true EP1900839A1 (fr)	2008-03-19
EP1900839B1 EP1900839B1 (fr)	2013-11-06

Family

ID=37546664

Family Applications (1)

Application Number	Title	Priority Date	Filing Date
EP07114884.5A Revoked EP1900839B1 (fr)	2006-09-07	2007-08-23	Procédé pour le traitement thermique de superalliages à base de Ni

Country Status (4)

Country	Link
US (1)	US7938919B2 (fr)
EP (1)	EP1900839B1 (fr)
JP (1)	JP5393011B2 (fr)
ES (1)	ES2444407T3 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
WO2011003804A1 (fr) *	2009-07-09	2011-01-13	Alstom Technology Ltd.	Superalliage à base de nickel
CN111349766A (zh) *	2020-02-24	2020-06-30	辽宁工业大学	一种用于耐高温合金材料的热处理方法

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
EP2465957B1 (fr) *	2009-08-10	2018-11-07	IHI Corporation	SUPERALLIAGE MONOCRISTALLIN À BASE DE Ni ET PALE DE TURBINE
US20110076182A1 (en) *	2009-09-30	2011-03-31	General Electric Company	Nickel-Based Superalloys and Articles
CH703386A1 (de) *	2010-06-30	2011-12-30	Alstom Technology Ltd	Verfahren zur Herstellung einer aus einer Nickel-Basis-Superlegierung bestehenden Einkristallkomponente.
US20130142637A1 (en) *	2011-12-06	2013-06-06	Kenneth Harris	Low rhenium single crystal superalloy for turbine blades and vane applications
WO2013167513A1 (fr)	2012-05-07	2013-11-14	Alstom Technology Ltd	Procédé de fabrication d'éléments en superalliages monocristallins (sx) ou solidifiés de manière directionnelle (ds)
US10668571B2 (en)	2017-12-14	2020-06-02	General Electric Company	Nanoparticle powders, methods for forming braze pastes, and methods for modifying articles
CN117568728B (zh) *	2023-11-21	2026-01-02	常州钢研极光增材制造有限公司	Gh4099合金的时效处理方法及热处理方法

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EP0155827A2 (fr) *	1984-03-19	1985-09-25	Cannon-Muskegon Corporation	Alliage pour la technologie des monocristaux
GB2234521A (en) *	1986-03-27	1991-02-06	Gen Electric	Nickel-base superalloys for producing single crystal articles having improved tolerance to low angle grain boundaries
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DE19617093A1 (de) *	1996-04-29	1997-10-30	Abb Research Ltd	Wärmebehandlungsverfahren für Werkstoffkörper aus Nickel-Basis-Superlegierungen
US20040055669A1 (en) *	2002-06-26	2004-03-25	Siemens Westinghouse Power Corporation	Cast single crystal alloy component with improved low angle boundary tolerance
WO2004038056A1 (fr) *	2002-10-23	2004-05-06	Siemens Aktiengesellschaft	Traitement thermique d'alliages comprenant des elements permettant d'ameliorer la resistance des joints de grains

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2007
- 2007-08-23 EP EP07114884.5A patent/EP1900839B1/fr not_active Revoked
- 2007-08-23 ES ES07114884.5T patent/ES2444407T3/es active Active
- 2007-09-07 US US11/851,749 patent/US7938919B2/en not_active Expired - Fee Related
- 2007-09-07 JP JP2007233005A patent/JP5393011B2/ja not_active Expired - Fee Related

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US20040055669A1 (en) *	2002-06-26	2004-03-25	Siemens Westinghouse Power Corporation	Cast single crystal alloy component with improved low angle boundary tolerance
WO2004038056A1 (fr) *	2002-10-23	2004-05-06	Siemens Aktiengesellschaft	Traitement thermique d'alliages comprenant des elements permettant d'ameliorer la resistance des joints de grains

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
WO2011003804A1 (fr) *	2009-07-09	2011-01-13	Alstom Technology Ltd.	Superalliage à base de nickel
CH701415A1 (de) *	2009-07-09	2011-01-14	Alstom Technology Ltd	Nickel-Basis-Superlegierung.
US9017605B2 (en)	2009-07-09	2015-04-28	Alstom Technology Ltd.	Nickel-based superalloy
EP2451986B2 (fr) †	2009-07-09	2017-10-18	Ansaldo Energia Switzerland AG	Superalliage a base de nickel
CN111349766A (zh) *	2020-02-24	2020-06-30	辽宁工业大学	一种用于耐高温合金材料的热处理方法
CN111349766B (zh) *	2020-02-24	2021-07-20	辽宁工业大学	一种用于耐高温合金材料的热处理方法

Also Published As

Publication number	Publication date
ES2444407T3 (es)	2014-02-24
EP1900839B1 (fr)	2013-11-06
US20080112814A1 (en)	2008-05-15
US7938919B2 (en)	2011-05-10
JP5393011B2 (ja)	2014-01-22
JP2008063661A (ja)	2008-03-21

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