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EP1211335B1 - Superlegierung auf Nickelbasis mit sehr hoher Beständigkeit gegen Heisskorrosion für Einkristallturbinenschaufeln von industriellen Turbinen - Google Patents

Superlegierung auf Nickelbasis mit sehr hoher Beständigkeit gegen Heisskorrosion für Einkristallturbinenschaufeln von industriellen Turbinen Download PDF

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Publication number
EP1211335B1
EP1211335B1 EP00403361A EP00403361A EP1211335B1 EP 1211335 B1 EP1211335 B1 EP 1211335B1 EP 00403361 A EP00403361 A EP 00403361A EP 00403361 A EP00403361 A EP 00403361A EP 1211335 B1 EP1211335 B1 EP 1211335B1
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EP
European Patent Office
Prior art keywords
alloy
resistance
hot corrosion
phase
single crystal
Prior art date
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.)
Expired - Lifetime
Application number
EP00403361A
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English (en)
French (fr)
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EP1211335A1 (de
Inventor
Pierre Caron
Michael Blackler
Gordon Malcolm Mccolvin
Rajeshwar Prasad Wahi
André Marcel Escale
Laurent Lelait
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.)
Hahn Meitner Institut Berlin GmbH
Electricite de France SA
Office National dEtudes et de Recherches Aerospatiales ONERA
Safran Helicopter Engines SAS
Howmet Ltd
Alstom NV
Original Assignee
Hahn Meitner Institut Berlin GmbH
Electricite de France SA
Office National dEtudes et de Recherches Aerospatiales ONERA
Turbomeca SA
Howmet Ltd
ABB Alstom Power NV
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.)
Filing date
Publication date
Application filed by Hahn Meitner Institut Berlin GmbH, Electricite de France SA, Office National dEtudes et de Recherches Aerospatiales ONERA, Turbomeca SA, Howmet Ltd, ABB Alstom Power NV filed Critical Hahn Meitner Institut Berlin GmbH
Priority to DE60034797T priority Critical patent/DE60034797T2/de
Priority to EP00403361A priority patent/EP1211335B1/de
Priority to US09/999,167 priority patent/US20030047251A1/en
Priority to JP2001365809A priority patent/JP2002235135A/ja
Publication of EP1211335A1 publication Critical patent/EP1211335A1/de
Priority to US10/460,860 priority patent/US20040033156A1/en
Priority to US11/068,085 priority patent/US20050194068A1/en
Application granted granted Critical
Publication of EP1211335B1 publication Critical patent/EP1211335B1/de
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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
    • C22C19/056—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%

Definitions

  • the invention relates to a nickel-based superalloy suitable for the controlled solidification production of stationary and mobile monocrystalline blades of industrial gas turbines.
  • Nickel-based superalloys are the most efficient materials used today for the manufacture of stationary and mobile blades for industrial gas turbines. The two main features required so far for these alloys for these specific applications are good creep resistance at temperatures up to 850 ° C and very good resistance to hot corrosion. Reference alloys commonly used in this field are those known as IN738, IN939 and IN792.
  • the blades made with these reference alloys are prepared by conventional lost-wax casting and have a polycrystalline structure, that is to say that they consist of the juxtaposition of randomly oriented crystals with respect to one another. and called grains. These grains are themselves constituted by a nickel-based austenitic gamma ( ⁇ ) matrix in which gamma prime ( ⁇ ') phase hardening particles whose base is the Ni 3 Al intermetallic compound are dispersed. These grains give these alloys high creep resistance up to temperatures close to 850 ° C., which guarantees the longevity of the blades for which life times of between 50 000 and 100 000 hours are generally sought.
  • the chemical composition of the IN939, IN738 and IN792 alloys has been defined in order to give them an excellent resistance to the environment of the combustion gases, in particular with respect to hot corrosion, a particularly aggressive phenomenon in the case of gas turbines industrial.
  • Important additions of chromium, typically between 12 and 22% by weight, are thus necessary to give these alloys the hot corrosion resistance required for the applications concerned.
  • the classification of these alloys is: IN939 ⁇ IN738 ⁇ IN792. From the point of view of resistance to hot corrosion, the classification is reversed, ie: IN792 ⁇ IN738 ⁇ IN939.
  • These monocrystalline blades are manufactured by solidification directed in lost-wax foundry.
  • the elimination of grain boundaries, which are preferred locations for creep deformation at high temperatures, has dramatically increased the performance of nickel-based superalloys.
  • the monocrystalline solidification process makes it possible to select the preferential orientation of growth of the monocrystalline part and thus to choose the ⁇ 001> orientation which is optimal from the point of view of resistance to creep and to thermal fatigue, these two mechanical stressing modes being the most harmful for turbine blades.
  • the superalloy chemical compositions developed for monocrystalline turbine blades for aeronautical applications are not suitable for blades for terrestrial or marine applications, so-called industrial applications. These alloys are indeed defined so as to favor their mechanical strength up to temperatures above 1100 ° C, and this to the detriment of their resistance to hot corrosion.
  • the chromium concentration of the superalloys for single-crystal blades of aeronautical turbines is generally less than 8% by weight, which makes it possible to reach ⁇ 'phase volume fractions of the order of 70%, favorable to resistance to high creep. temperature.
  • a chromium-rich nickel-based superalloy capable of monocrystalline solidification of industrial gas turbine parts is known under the name SC16 and described in FR 2 643 085 A. Its chromium concentration is equal to 16% by weight.
  • the creep resistance characteristics of the SC16 alloy are such that this alloy provides, relative to the reference polycrystalline alloy IN738, an operating temperature gain of approximately 30 ° C. (830 ° C. instead of 800 ° C.). at about 50 ° C (950 ° C instead of 900 ° C). Comparative tests for cyclic corrosion at 850 ° C in air at atmospheric pressure with Na 2 SO 4 contamination showed that the hot-corrosion resistance of the SC16 alloy was at least equivalent to that of the alloy polycrystalline reference IN738.
  • the object of the invention is to provide a nickel-based superalloy having a resistance to hot corrosion, in the aggressive environment of the combustion gases of industrial gas turbines, at least equivalent to that of the reference polycristalline superalloy IN738 , with a creep resistance greater than or equal to that of the IN792 reference alloy in a temperature range of up to 950 ° C.
  • This superalloy must in particular be suitable for the production by directed solidification of fixed and mobile monocrystalline blades of large dimensions (up to several tens of centimeters in height) of industrial gas turbines.
  • This superalloy must also show good microstructural stability with respect to the precipitation of chromium-rich brittle intermetallic phases during long-term high temperature holdings.
  • the alloy according to the invention has an excellent compromise between creep resistance and hot corrosion resistance. It is suitable for the manufacture of monocrystalline parts, that is to say made of a single metallurgical grain. This particular structure is obtained for example by means of a conventional method of solidification directed in a thermal gradient, using a helical or baffled grain selection device or a monocrystalline seed.
  • the invention also relates to an industrial turbine blade made by monocrystalline solidification of the superalloy above.
  • Figures 1 to 4 are graphs illustrating the properties of different superalloys.
  • SCA425 An alloy according to the invention called SCA425 was developed by aiming at the nominal composition presented in Table I. In this table are also reported the nominal concentrations in major elements of the reference alloys IN939, IN738, IN792 and SC16. Table I: Concentrations by weight in major elements (%) Alloy Or Co Cr MB W al Ti Your Nb IN939 Based 19 22.5 - 2 1.9 3.7 1.4 1 IN738 Based 8.5 16 1.7 2.6 3.4 3.4 1.7 0.9 IN792 Based 9 12.4 1.9 3.8 3.1 4.5 3.9 - SC16 Based - 16 3 - 3.5 3.5 3.5 - SCA425 Based 5 16 1 4 4 2 5 -
  • Chromium has a beneficial and preponderant effect on the resistance to hot corrosion of nickel-based superalloys.
  • the experiment has thus shown that a concentration close to 16% by weight was necessary in the alloy of the invention to obtain a resistance to hot corrosion equivalent to that of the reference alloy IN738 under the conditions of the tests. described below, which are representative of the environment created by the combustion gases of certain industrial turbines.
  • Chromium also participates in the hardening of the ⁇ matrix in which this element is distributed preferentially.
  • Molybdenum strongly hardens the matrix y in which this element is distributed preferentially.
  • the amount of molybdenum that can be introduced into the alloy is however limited because this element has a detrimental effect on the resistance to hot corrosion of the superalloys based on nickel.
  • a concentration close to 1% by weight in the alloy of the invention is not detrimental to its resistance to corrosion and significantly contributes to its hardening.
  • Cobalt also participates in solid solution hardening of the ⁇ matrix.
  • the cobalt concentration has an influence on the solution temperature of the hardening phase ⁇ '(solvus temperature ⁇ '). It is thus advantageous to increase the cobalt concentration to lower the solvus temperature of the ⁇ 'phase and to facilitate the homogenization of the alloy by heat treatment without risk of causing a start of melting. Moreover, it may also be advantageous to reduce the cobalt concentration in order to increase the solvus temperature of the ⁇ 'phase and thus to benefit from greater stability of the ⁇ ' phase at high temperature, which is favorable to the creep resistance.
  • the concentration of 5% by weight of cobalt in the alloy of the invention leads to an optimal compromise between good homogenization ability and good creep resistance.
  • the tungsten whose concentration is around 4% by weight in the alloy of the invention is distributed substantially equally between the ⁇ and ⁇ 'phases and thus contributes to their respective hardenings. Its concentration in the alloy is however limited because this element is heavy, and has a negative effect on the resistance to hot corrosion.
  • the concentration of aluminum is around 4% by weight in the alloy of the invention.
  • the presence of this element causes the precipitation of the hardening phase ⁇ '.
  • Aluminum also promotes resistance to oxidation.
  • the titanium and tantalum elements are added to the alloy of the invention in order to reinforce the ⁇ 'phase in which they substitute for the aluminum element.
  • the respective concentrations of these two elements in the alloy of the invention are close to 2% by weight for titanium and 5% by weight for tantalum.
  • experience has shown that the presence of tantalum was more favorable to the resistance to hot corrosion than that of titanium.
  • tantalum is heavier than titanium which is unfavorable vis-à-vis the density of the alloy.
  • the sum of the concentrations of tantalum, titanium and aluminum roughly defines the hardening phase volume fraction ⁇ '.
  • the concentrations of these three elements have been adjusted in such a way as to optimize the ⁇ 'phase volume fraction, while keeping the stable ⁇ and ⁇ ' phases during the long-term hold at high temperature, and taking into account that the Chromium concentration was set at about 16% by weight so as to achieve the desired corrosion resistance.
  • the SCA425 alloy was developed as ⁇ 001> orientation single crystals. The density of this alloy was measured and found to be 8.36 g.cm -3 .
  • the alloy After directed solidification, the alloy consists essentially of two phases: the austenitic matrix ⁇ , a nickel-based solid solution, and the ⁇ 'phase, an intermetallic compound whose basic formula is Ni 3 Al, which precipitates for the most part at within the matrix y in the form of fine particles smaller than one micrometer during the solid state cooling. Contrary to what is generally encountered in monocrystalline superalloys for turbine blades, the SCA425 alloy does not contain massive interdendritic particles of ⁇ 'phase resulting from a eutectic transformation of the residual liquid at the end of solidification.
  • the SCA425 alloy underwent a homogenization heat treatment at a temperature of 1285 ° C. for 3 hours with cooling in air. This temperature is higher than the solvus temperature of the ⁇ 'phase (dissolution temperature of the ⁇ ' phase precipitates), which is equal to 1198 ° C., and lower than the melting start temperature, equal to 1300 ° C.
  • the purpose of this treatment is to dissolve all of the ⁇ 'phase precipitates, the size distribution of which is very extensive in the raw state of directed solidification and to reduce the chemical heterogeneities associated with the solidification dendritic structure.
  • the difference between the solvate temperature ⁇ 'of the SCA425 alloy and its melting start temperature is very large, which allows the easy application of the homogenization treatment without risk of melting and with the certainty of obtaining a homogeneous microstructure allowing optimized creep resistance.
  • the cooling following the homogenization treatment described above was carried out by quenching in air.
  • the speed of this cooling must be sufficiently high so that the size of the particles having precipitated during this cooling is less than 500 nm.
  • the homogenization heat treatment procedure that has just been described is an example that makes it possible to obtain the desired result, ie a homogeneous distribution of fine ⁇ 'phase particles whose size does not exceed 500 nm. This does not exclude the possibility of obtaining a similar result by using another processing temperature provided that it is in the range separating the solvate temperature ⁇ 'and the melting start temperature.
  • the SCA425 alloy was tested after having been subjected to a homogenization treatment as described above, then to two tempering treatments making it possible to stabilize the size and the volume fraction of the ⁇ 'phase precipitates.
  • a first treatment of income was to heat the alloy at 1100 ° C for 4 hours with cooling in air which has the effect of stabilizing the size of ⁇ phase precipitates.
  • a second treatment of income at 850 ° C for 24 hours, followed by cooling in the air, allows to optimize the volume fraction of phase ⁇ '.
  • This ⁇ 'phase volume fraction is estimated at 50% in the SCA425 alloy.
  • most of the ⁇ 'phase precipitated in the form of cuboidal particles whose size is between 200 and 500 nm.
  • a small fraction of ⁇ 'phase fine particles whose size does not exceed 50 nm is present between the large precipitates.
  • Hot corrosion tests were carried out at different temperatures on the SCA425 alloy using the following procedure: samples are partially immersed in a crucible containing a mixture of ash whose weight composition is as follows: 4.3% Na 2 SO 4 + 22.7% CaSO 4 + 22.3% Fe 2 O 3 + 20.6% ZnSO 4 + 10.4% K 2 SO 4 + 2.8% MgO + 6.5% Al 2 O 3 + 10.4% SiO 2 .
  • a mixture of air + 0.15% SO 2 by volume passes through the ash mixture at the rate of 6 liters per hour. The ash mixture is renewed every 500 hours.
  • This environment is representative of the very aggressive environment of the combustion gases of certain industrial turbines.
  • For comparison alloy samples IN738, IN939, IN792 and SC16 were tested simultaneously.
  • the samples were sectioned and the metal depth destroyed by the corrosion phenomenon was measured.
  • the graphs in Figures 1-3 show average corrosion penetration depths for the various alloys at 700 ° C, 800 ° C and 850 ° C respectively, depending on the test time. The corrosion resistance is better the lower the depth of penetration.
  • the alloy SCA425 shows a corrosion resistance equivalent to that of the alloy IN738 and better than that of the alloy SC16.
  • the corrosion resistance of the SCA425 alloy is comparable to that of the IN738 and IN939 reference alloys.
  • the graph in FIG. 4 makes it possible to compare the creep rupture times obtained for the SCA425, IN792 and SC16 alloys.
  • On the abscissa is the applied stress.
  • On the ordinate is the value of the Larson-Miller parameter.
  • T the creep temperature in Kelvin
  • t the break time in hours.
  • Control of microstructure of SCA425 alloy specimens after creep testing demonstrated the absence of precipitation of chromium-rich brittle intermetallic particles that may occur during long-term high temperature holdovers in superalloys based on nickel where the matrix is supersaturated with addition elements.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Turbine Rotor Nozzle Sealing (AREA)

Claims (2)

  1. Superlegierung auf Nickelbasis, welche für eine monokristalline Erstarrung geeignet ist, dadurch gekennzeichnet, dass die Gewichtszusammensetzung die Folgende ist: Co: 4,75 à 5,25 % Cr: 15,5 à 16,5 % Mo: 0,8 à 1,2 % W: 3,75 à 4,25 % Al: 3,75 à 4,25 % Ti: 1,75 à 2,25 % Ta: 4,75 à 5,25 % C: 0,006 à 0,04 % B: ≤ 0,01 % Zr: ≤ 0,01 % Hf: ≤ 1 % Nb: ≤ 1 % Ni und mögliche Verunreinigungen: Ergänzung auf 100 %.
  2. Industrielle Turbinenschaufel erhalten durch die monokristalline Erstarrung der Superlegierung nach Anspruch 1.
EP00403361A 2000-11-30 2000-11-30 Superlegierung auf Nickelbasis mit sehr hoher Beständigkeit gegen Heisskorrosion für Einkristallturbinenschaufeln von industriellen Turbinen Expired - Lifetime EP1211335B1 (de)

Priority Applications (6)

Application Number Priority Date Filing Date Title
DE60034797T DE60034797T2 (de) 2000-11-30 2000-11-30 Superlegierung auf Nickelbasis mit sehr hoher Beständigkeit gegen Heisskorrosion für Einkristallturbinenschaufeln von industriellen Turbinen
EP00403361A EP1211335B1 (de) 2000-11-30 2000-11-30 Superlegierung auf Nickelbasis mit sehr hoher Beständigkeit gegen Heisskorrosion für Einkristallturbinenschaufeln von industriellen Turbinen
US09/999,167 US20030047251A1 (en) 2000-11-30 2001-11-29 Nickel-based superalloy having very high resistance to hot-corrosion for monocrystalline blades of industrial turbines
JP2001365809A JP2002235135A (ja) 2000-11-30 2001-11-30 産業用タービンの単結晶ブレードのための非常に高い耐高温腐食性をもつニッケル系超合金
US10/460,860 US20040033156A1 (en) 2000-11-30 2003-06-12 Nickel-based superalloy having very high resistance to hot-corrosion for monocrystalline blades of industrial turbines
US11/068,085 US20050194068A1 (en) 2000-11-30 2005-02-28 Nickel-based superalloy having very high resistance to hot-corrosion for monocrystalline blades of industrial turbines

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP00403361A EP1211335B1 (de) 2000-11-30 2000-11-30 Superlegierung auf Nickelbasis mit sehr hoher Beständigkeit gegen Heisskorrosion für Einkristallturbinenschaufeln von industriellen Turbinen

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EP1211335A1 EP1211335A1 (de) 2002-06-05
EP1211335B1 true EP1211335B1 (de) 2007-05-09

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EP00403361A Expired - Lifetime EP1211335B1 (de) 2000-11-30 2000-11-30 Superlegierung auf Nickelbasis mit sehr hoher Beständigkeit gegen Heisskorrosion für Einkristallturbinenschaufeln von industriellen Turbinen

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EP (1) EP1211335B1 (de)
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DE (1) DE60034797T2 (de)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1715068B1 (de) 2003-12-26 2012-08-01 Kawasaki Jukogyo Kabushiki Kaisha Auf nickel basierende superwärmebeständige legierung und gasturbinenbauteil damit
US20060182649A1 (en) * 2005-02-16 2006-08-17 Siemens Westinghouse Power Corp. High strength oxidation resistant superalloy with enhanced coating compatibility
EP1914327A1 (de) * 2006-10-17 2008-04-23 Siemens Aktiengesellschaft Nickel-Basis-Superlegierung
EP2431489A1 (de) 2010-09-20 2012-03-21 Siemens Aktiengesellschaft Superlegierung auf Nickelbasis
CN102011195B (zh) * 2010-11-23 2012-06-06 北京科技大学 一种定向凝固高铌钛铝合金单晶的制备方法
JP2014047371A (ja) * 2012-08-30 2014-03-17 Hitachi Ltd Ｎｉ基合金と、それを用いたガスタービン動翼兼ガスタービン
GB201400352D0 (en) 2014-01-09 2014-02-26 Rolls Royce Plc A nickel based alloy composition
EP3042973B1 (de) 2015-01-07 2017-08-16 Rolls-Royce plc Nickellegierung
GB2539957B (en) 2015-07-03 2017-12-27 Rolls Royce Plc A nickel-base superalloy
EP3604571A1 (de) 2018-08-02 2020-02-05 Siemens Aktiengesellschaft Metallzusammensetzung
DE102019201095A1 (de) * 2019-01-29 2020-07-30 Friedrich-Alexander-Universität Erlangen-Nürnberg Nickelbasislegierung für Hochtemperaturanwendungen und Verfahren

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Publication number Priority date Publication date Assignee Title
DE3109293C2 (de) * 1980-03-13 1985-08-01 Rolls-Royce Ltd., London Verwendung einer Nickellegierung für einkristalline Gußstücke
US4961818A (en) * 1985-06-21 1990-10-09 Inco Alloys International, Inc. Process for producing single crystals
US4900394A (en) * 1985-08-22 1990-02-13 Inco Alloys International, Inc. Process for producing single crystals
US5403546A (en) * 1989-02-10 1995-04-04 Office National D'etudes Et De Recherches/Aerospatiales Nickel-based superalloy for industrial turbine blades
EP1038982A1 (de) * 1999-03-26 2000-09-27 Howmet Research Corporation Einkristalline Superlegierungskörpern mit verminderter Rekristallisierung der Körnern

Non-Patent Citations (1)

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Publication number Publication date
JP2002235135A (ja) 2002-08-23
US20040033156A1 (en) 2004-02-19
DE60034797D1 (de) 2007-06-21
US20030047251A1 (en) 2003-03-13
DE60034797T2 (de) 2008-01-17
EP1211335A1 (de) 2002-06-05
US20050194068A1 (en) 2005-09-08

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