EP1211335A1 - Superalliage à base de nickel à résistance très élevée à la corrosion à chaud pour aubes monocristallines de turbines industrielles - Google Patents
Superalliage à base de nickel à résistance très élevée à la corrosion à chaud pour aubes monocristallines de turbines industrielles Download PDFInfo
- Publication number
- EP1211335A1 EP1211335A1 EP00403361A EP00403361A EP1211335A1 EP 1211335 A1 EP1211335 A1 EP 1211335A1 EP 00403361 A EP00403361 A EP 00403361A EP 00403361 A EP00403361 A EP 00403361A EP 1211335 A1 EP1211335 A1 EP 1211335A1
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- European Patent Office
- Prior art keywords
- alloy
- resistance
- phase
- hot corrosion
- monocrystalline
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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
- C22C19/056—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 in the manufacture by direct solidification of monocrystalline blades stationary and mobile industrial gas turbines.
- Nickel-based superalloys are the most common materials most efficient used today for the manufacture of stationary and movable blades of industrial gas turbines. The two main features requested so far to these alloys for these specific applications are good creep resistance at temperatures up to go up to 850 ° C and very good corrosion resistance hot. Reference alloys commonly used in this area are those known under the designations IN738, IN939 and IN792.
- the blades produced with these reference alloys are produced by conventional lost wax casting and have a polycrystalline structure, that is to say that they consist of the juxtaposition of crystals randomly oriented with respect to each other. and called grains. These grains are themselves made up of an austenitic gamma ( ⁇ ) matrix based on nickel in which are hardened particles of gamma prime phase ( ⁇ '), the base of which is the intermetallic compound Ni 3 Al. This particular structure of Grain gives these alloys a high creep resistance up to temperatures around 850 ° C, which guarantees the longevity of the blades for which we generally seek lifetimes between 50,000 and 100,000 hours.
- the chemical composition of the alloys IN939, IN738 and IN792 has also been defined so as to give them excellent resistance to the environment of combustion gases, in particular with respect to hot corrosion, a particularly aggressive phenomenon in the industrial gas turbines.
- 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 produced by solidification directed in lost wax foundry. Elimination of grain boundaries, which are preferred locations for creep deformation at high temperature, increased dramatically the performance of superalloys based on nickel.
- the solidification process monocrystalline allows to select the preferential orientation growth of the monocrystalline part and thus choose the orientation ⁇ 001> which is optimal from the point of the resistance to creep and to thermal fatigue, these two modes of mechanical stress being the most harmful to turbine blades.
- a nickel-based superalloy rich in chromium and capable of solidifying monocrystalline parts of industrial gas turbines 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, compared to the reference polycrystalline alloy IN738, a gain in operating temperature ranging from approximately 30 ° C. (830 ° C. instead of 800 ° C.) at around 50 ° C (950 ° C instead of 900 ° C). Comparative tests of cyclic corrosion at 850 ° C. in air at atmospheric pressure with contamination by Na 2 SO 4 have shown that the resistance to hot corrosion of the alloy SC16 was at least equivalent to that of the alloy polycrystalline reference IN738.
- the object of the invention is to propose a superalloy based on nickel having resistance to hot corrosion, in the aggressive environment of the combustion gases of industrial gas turbines, at least equivalent to that of polycrystalline reference superalloy IN738, with a creep resistance greater than or equal to that of the alloy IN792 reference in a temperature range from up to 950 ° C.
- This superalloy must in particular be suitable for manufacturing by directed solidification of fixed monocrystalline vanes and large-scale mobiles (up to several tens of centimeters in height) of industrial gas turbines.
- This superalloy must also show good stability. microstructural with respect to phase precipitation fragile intermetallics rich in chromium during long-term maintenance at high temperature.
- the alloy according to the invention presents an excellent compromise between creep resistance and corrosion resistance hot. It is suitable for the manufacture of monocrystalline parts, that is to say made up of a single metallurgical grain. This particular structure is obtained for example using a conventional directed solidification process in a thermal gradient, using a device selection of grain with propeller or baffles or a germ Monocrystalline.
- the invention also relates to a turbine blade industrial carried out by monocrystalline solidification of above superalloy.
- Figures 1 to 4 are graphs illustrating the properties of different superalloys.
- SCA425 An alloy according to the invention called SCA425 was developed by targeting the nominal composition presented in Table I. In this table are also reported the nominal concentrations of major elements of the reference alloys IN939, IN738, IN792 and SC16. Concentrations by weight of 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 predominant effect on the hold to hot corrosion of nickel-based superalloys.
- a concentration close to 16% by weight was necessary in the alloy of the invention to obtain equivalent hot corrosion resistance to that of the reference alloy IN738 in the conditions of the hot corrosion tests described below, which are representative of the environment created by gases of combustion of certain industrial turbines.
- Chrome 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 quantity of molybdenum which can be introduced into the alloy is however limited because this element has a detrimental effect on the resistance to hot corrosion of superalloys based on nickel.
- a concentration close to 1% by weight in the alloy of the invention is not penalizing for its corrosion resistance and contributes significantly to its hardening.
- Cobalt also participates in solution hardening solid of the matrix ⁇ .
- the cobalt concentration has a influence on the solution dissolution temperature of the phase hardening ⁇ '(solvent temperature ⁇ '). It is so advantageous to increase the cobalt concentration for lower the solvent temperature of the ⁇ 'phase and facilitate homogenization of the alloy by heat treatment without may cause the onset of fusion. Besides, he can also be beneficial to reduce the concentration of cobalt to increase the solvent temperature of the phase ⁇ 'and thus benefit from greater stability of the ⁇ 'phase at high temperature which is favorable for creep resistance.
- the concentration around 5% in weight of cobalt in the alloy of the invention leads to a optimal compromise between good homogenization ability and good creep resistance.
- Tungsten whose concentration is close to 4% in weight in the alloy of the invention is distributed so substantially equal between phases ⁇ and ⁇ 'and contributes thus to their respective hardening. His concentration in the alloy is however limited because this element is heavy, and has a negative effect on the resistance to hot corrosion.
- the aluminum concentration is close to 4% by weight in the alloy of the invention.
- the presence of this element causes precipitation of the hardening phase ⁇ '.
- Aluminum also promotes resistance to oxidation. Titanium and tantalum elements are added to the alloy of the invention in order to strengthen the ⁇ 'phase in which they replace the aluminum element.
- the concentrations respective of these two elements in the alloy of the invention are close to 2% by weight for titanium and 5% by weight for tantalum. Under the test conditions of hot corrosion described below, corresponding to the intended application, experience has shown that the presence of tantalum was more favorable to corrosion resistance hot than that of titanium. However tantalum is heavier than titanium which is unfavorable for of the density of the alloy.
- the sum of the concentrations in tantalum, titanium and aluminum roughly defined the volume fraction of hardening phase ⁇ '.
- the concentrations of these three items have been settled so as to optimize the volume fraction of phase ⁇ ', while retaining the ⁇ and ⁇ 'phases stable during the maintenance of long duration at high temperature, and taking into account the fact that the chromium concentration has been set at around 16% in weight so as to achieve corrosion resistance desired.
- the SCA425 alloy was developed in the form of single crystals with orientation ⁇ 001>.
- the density of this alloy was measured and found to be 8.36 g.cm -3 .
- the alloy After directed solidification, the alloy essentially consists of two phases: the austenitic matrix ⁇ , a solid solution based on nickel, and the phase ⁇ ', an intermetallic compound whose basic formula is Ni 3 Al, which mainly precipitates at within the matrix y in the form of fine particles of size less than one micrometer during cooling in the solid state. 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 an eutectic transformation of the residual liquid at the end of solidification.
- SCA425 alloy has undergone a homogenization heat treatment at a temperature of 1285 ° C for 3 hours with air cooling. This temperature is higher than the solvent temperature of phase ⁇ '(setting temperature in solution of the precipitates of phase ⁇ '), 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 whose distribution of sizes is very extensive in the raw solidification state directed and reduce related chemical heterogeneities to the dendritic solidification structure.
- the difference between the solvent temperature ⁇ 'of the SCA425 alloy and its melting start temperature is very large, which allows easy application of the homogenization treatment without risk of merger and with the certainty of obtaining a homogeneous microstructure allowing resistance to creep optimized.
- the cooling after the homogenization treatment described above was produced by air quenching. In practical, the speed of this cooling must be sufficient high so that the particle size having precipitated during this cooling to be less than 500 nm.
- the homogenization heat treatment procedure which just described is an example to obtain the expected result, i.e. a homogeneous distribution of fines ⁇ 'phase particles whose size does not exceed 500 nm. This does not exclude the possibility of obtaining a result. similar using another processing temperature provided that it falls within the interval separating the solvent temperature ⁇ 'and the start temperature of fusion.
- the SCA425 alloy has been tested after being subjected to a homogenization treatment as described above, then two income treatments to stabilize the size and volume fraction of ⁇ 'phase precipitates.
- a first income treatment consisted of heating the alloy at 1100 ° C for 4 hours with cooling to air which has the effect of stabilizing the size of ⁇ 'phase precipitates.
- a second income treatment at 850 ° C for 24 hours, followed by air cooling, optimizes the volume fraction of phase ⁇ '.
- This volume fraction of phase ⁇ ' is estimated at 50% in SCA425 alloy. After all the treatments most of the ⁇ 'phase has precipitated under the shape of cuboid particles whose size is included between 200 and 500 nm. A small fraction of fine particles ⁇ 'phase whose size does not exceed 50 nm is present between the big 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 with the following weight composition: 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 .
- An air mixture + 0.15% SO 2 by volume passes through the ash mixture at the speed 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 of samples of alloys 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 of figures 1 to 3 show the depths corrosion penetration averages for the different alloys at 700 ° C, 800 ° C and 850 ° C respectively, in depending on the duration of the test. Corrosion resistance the better the penetration depth is low.
- the SCA425 alloy shows a corrosion resistance equivalent to that of the alloy IN738 and better than that of SC16 alloy.
- the corrosion resistance of SCA425 alloy is comparable to those of the reference alloys IN738 and IN939.
- Creep tests in tension were carried out on test pieces machined in monocrystalline bars of orientation ⁇ 001>. The bars were previously homogenized and then returned according to the procedures described above. Break time values obtained at 750, 850 and 950 ° C for different levels of applied stress are given in Table II. Creep lifetime of SCA425 alloy Temperature (° C) Stress (MPa) Break time (h) 750 650 216 / 321.1 750 575 984 850 400 201/276 850 300 2121/2945/3220 850 250 6161 950 250 73/76 950 200 261/291 950 180 578 950 160 1098 950 140 2109 950 120 3872
- the graph in FIG. 4 makes it possible to compare the creep rupture times obtained for the alloys SCA425, IN792 and SC16.
- the applied stress is plotted on the abscissa.
- the value of the Larson-Miller parameter is plotted on the ordinate.
- T the creep temperature in Kelvin
- t the failure time in hours.
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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)
Abstract
Description
- Une résistance à la corrosion à chaud optimisée, dans tous les cas au moins égale à celle du superalliage polycristallin de référence IN738, et ce dans un environnement représentatif de celui des gaz de combustion des turbines industrielles;
- Une fraction volumique maximale de précipités durcissants de phase γ' afin de favoriser la résistance au fluage à haute température;
- Une résistance au fluage jusqu'à 950 °C au moins égale à celle de l'alliage polycristallin de référence IN792;
- Une aptitude à l'homogénéisation par remise en solution totale des particules de phase γ', y compris les phases eutectiques γ/γ';
- L'absence de précipitation de phases intermétalliques fragiles riches en chrome, à partir de la matrice γ, au cours de maintiens de longue durée à haute température;
- Une masse volumique inférieure à 8,4 g.cm-3 afin de minimiser la masse des aubes monocristallines et par conséquent de limiter la contrainte centrifuge agissant sur ces aubes et sur le disque de turbine sur lequel elles sont fixées;
- Une bonne aptitude à la solidification monocristalline d'aubes de turbines dont la hauteur peut atteindre plusieurs dizaines de centimètres et la masse plusieurs kilogrammes.
Concentrations pondérales en éléments majeurs (%) | |||||||||
Alliage | Ni | Co | Cr | Mo | W | Al | Ti | Ta | Nb |
IN939 | Base | 19 | 22,5 | - | 2 | 1,9 | 3,7 | 1,4 | 1 |
IN738 | Base | 8,5 | 16 | 1,7 | 2,6 | 3,4 | 3,4 | 1,7 | 0,9 |
IN792 | Base | 9 | 12,4 | 1,9 | 3,8 | 3,1 | 4,5 | 3,9 | - |
SC16 | Base | - | 16 | 3 | - | 3,5 | 3,5 | 3,5 | - |
SCA425 | Base | 5 | 16 | 1 | 4 | 4 | 2 | 5 | - |
Durées de vie en fluage de l'alliage SCA425 | ||
Température (°C) | Contrainte (MPa) | Temps à rupture (h) |
750 | 650 | 216/321,1 |
750 | 575 | 984 |
850 | 400 | 201/276 |
850 | 300 | 2121/2945/3220 |
850 | 250 | 6161 |
950 | 250 | 73/76 |
950 | 200 | 261/291 |
950 | 180 | 578 |
950 | 160 | 1098 |
950 | 140 | 2109 |
950 | 120 | 3872 |
Claims (2)
- Superalliage à base de nickel, apte à la solidification monocristalline, caractérisé en ce que sa composition pondérale est la suivante: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 et impuretés éventuelles: complément à 100 %.
- Aube de turbine industrielle réalisée par solidification monocristalline d'un superalliage selon la revendication 1.
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP00403361A EP1211335B1 (fr) | 2000-11-30 | 2000-11-30 | Superalliage à base de nickel à résistance très élevée à la corrosion à chaud pour aubes monocristallines de turbines industrielles |
DE60034797T DE60034797T2 (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 (fr) | 2000-11-30 | 2000-11-30 | Superalliage à base de nickel à résistance très élevée à la corrosion à chaud pour aubes monocristallines de turbines industrielles |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1211335A1 true EP1211335A1 (fr) | 2002-06-05 |
EP1211335B1 EP1211335B1 (fr) | 2007-05-09 |
Family
ID=8173963
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP00403361A Expired - Lifetime EP1211335B1 (fr) | 2000-11-30 | 2000-11-30 | Superalliage à base de nickel à résistance très élevée à la corrosion à chaud pour aubes monocristallines de turbines industrielles |
Country Status (4)
Country | Link |
---|---|
US (3) | US20030047251A1 (fr) |
EP (1) | EP1211335B1 (fr) |
JP (1) | JP2002235135A (fr) |
DE (1) | DE60034797T2 (fr) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102011195A (zh) * | 2010-11-23 | 2011-04-13 | 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 |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1715068B1 (fr) | 2003-12-26 | 2012-08-01 | Kawasaki Jukogyo Kabushiki Kaisha | Alliage a base de nickel a haute resistance thermique et constituant de turbine a gaz l'utilisant |
US20060182649A1 (en) * | 2005-02-16 | 2006-08-17 | Siemens Westinghouse Power Corp. | High strength oxidation resistant superalloy with enhanced coating compatibility |
EP1914327A1 (fr) * | 2006-10-17 | 2008-04-23 | Siemens Aktiengesellschaft | Superalliage à base de nickel |
EP2431489A1 (fr) | 2010-09-20 | 2012-03-21 | Siemens Aktiengesellschaft | Superalliages à base de nickel |
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 (fr) | 2015-01-07 | 2017-08-16 | Rolls-Royce plc | Alliage de nickel |
GB2539957B (en) | 2015-07-03 | 2017-12-27 | Rolls Royce Plc | A nickel-base superalloy |
EP3604571A1 (fr) | 2018-08-02 | 2020-02-05 | Siemens Aktiengesellschaft | Composition de métal |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1038982A1 (fr) * | 1999-03-26 | 2000-09-27 | Howmet Research Corporation | Articles monocristallins en superalliage ayant une récrystallisation des grains reduite |
Family Cites Families (4)
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 |
-
2000
- 2000-11-30 DE DE60034797T patent/DE60034797T2/de not_active Expired - Lifetime
- 2000-11-30 EP EP00403361A patent/EP1211335B1/fr not_active Expired - Lifetime
-
2001
- 2001-11-29 US US09/999,167 patent/US20030047251A1/en not_active Abandoned
- 2001-11-30 JP JP2001365809A patent/JP2002235135A/ja active Pending
-
2003
- 2003-06-12 US US10/460,860 patent/US20040033156A1/en not_active Abandoned
-
2005
- 2005-02-28 US US11/068,085 patent/US20050194068A1/en not_active Abandoned
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1038982A1 (fr) * | 1999-03-26 | 2000-09-27 | Howmet Research Corporation | Articles monocristallins en superalliage ayant une récrystallisation des grains reduite |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102011195A (zh) * | 2010-11-23 | 2011-04-13 | 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 |
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 |
Also Published As
Publication number | Publication date |
---|---|
EP1211335B1 (fr) | 2007-05-09 |
JP2002235135A (ja) | 2002-08-23 |
DE60034797T2 (de) | 2008-01-17 |
US20050194068A1 (en) | 2005-09-08 |
DE60034797D1 (de) | 2007-06-21 |
US20040033156A1 (en) | 2004-02-19 |
US20030047251A1 (en) | 2003-03-13 |
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