EP0362661B1 - Pièce creuse en alliage à base de nickel coulé comportant une structure de grains colonaire, alliage et procédé de sa fabrication - Google Patents

Pièce creuse en alliage à base de nickel coulé comportant une structure de grains colonaire, alliage et procédé de sa fabrication Download PDF

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EP0362661B1
EP0362661B1 EP89117666A EP89117666A EP0362661B1 EP 0362661 B1 EP0362661 B1 EP 0362661B1 EP 89117666 A EP89117666 A EP 89117666A EP 89117666 A EP89117666 A EP 89117666A EP 0362661 B1 EP0362661 B1 EP 0362661B1
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article
alloy
cast
temperature
range
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EP89117666A
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German (de)
English (en)
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EP0362661A1 (fr
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Earl Warren Ross
Kevin Swayne O'hara
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General Electric Co
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General Electric Co
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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%
    • 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

  • This invention relates to cast directionally solidified columnar grain nickel base alloy articles and, more particularly, to such an article of outstanding elevated temperature surface stability as represented by oxidation resistance, particularly in thin walled hollow articles, and to the alloy and neat treatment for making such article.
  • such structures have been generated by the well known precision casting techniques of solidifying a molten metal directionally (directional solidification) to cause the solidifying crystals or grains to be elongated. If only one grain is allowed to grow in the article during solidification, for example, through choking out others or using a seed crystal, an article of a single crystal and substantially no grain boundaries results.
  • the grain boundaries in such an article are substantially all longitudinal grain boundaries, it is important in an article casting that longitudinal mechanical properties, such as stress rupture life and ductility, be very good, along with good transverse mechanical properties and good alloy surface stability. With this property balance in the article, the article alloy must be capable of being cast and directionally solidified in complex shapes and generally with complex internal cavities and relatively thin walls without cracking. So called “thin-wall” hollow castings have presented difficult quality problems to article casters using the well known "lost wax" type of precision casting methods with alloys designed for improved properties: though the alloy properties are good and within desired limits, thin wall castings, for example with a wall less than about 0.889mm (0.035 inch) thick, generally cracked during multicolumnar grain directional solidification.
  • the present invention provides a nickel base superalloy consisting of in weight percent 0.12% carbon, 1.5% hafnium, 12% cobalt, 6.35% tantalum, 6.8% chromium, 1.5% molybdenum, 4.9% tungsten, 6.15% aluminum, 2.8% rhenium, 0.015% boron, the substantial absence of zirconium, the substantial absence of titanium, the substantial absence of vanadium and the balance of nickel and incidental impurities.
  • Articles may be formed from the above alloy and are characterized by outstanding elevated temperature surface stability for a directionally solidified article, resulting from an alloy specification enhanced, in one form, by heat treatment and by an improved combination and balance between longitudinal and transverse stress rupture properties.
  • the article has at least one internal cavity and includes an integral cast wall substantially free of a major crack, the wall having a thickness of less than about 0.889mm (0.035 inch).
  • Such heat treatment comprises a combination of at least three progressive heating steps including a solutioning step, a preliminary, first aging step and a second aging step, to improve stress rupture properties of the article.
  • the present invention also provides a method of heat treating a cast nickel base alloy article made of an alloy consisting of, in weight percent, 0.1-0.15 C, 0.3-2 Hf, 11-14 Co, 5-9 Ta, less than 0.05 Zr, no more than 1 of V, no more than 1 of Ti, 5-10 Cr, 0.5-3 Mo, 4-7 W, 5-7 Al, 1.5-4 Re, 0.005-0.03 B, up to 1.5 Nb, up to 0.5 Y and the balance Ni and incidental impurities comprising the steps of :
  • the solutioning temperature is in the range of 1246-1293°C (2275-2360°F) and the heating time is at least about 30 minutes.
  • the drawing is a graphical comparison of oxidation resistance of the alloy associated with the present invention with other alloys.
  • the nickel base alloy of the present invention is particularly characterized by the relatively high C content in combination with a relatively large amount of Hf and additions of Co and Ta. This, along with the intentional control and limitation of the elements V, Zr and Ti, enabled the total alloy to have, for a DS structure, outstanding oxidation resistance and the good DS castability and resistance to grain boundary and fatigue cracking to the point at which thin walls of less than 0.889mm (0.035 inch) can be DS cast with elongated grains substantially crack free.
  • Other elements in the alloy contributing to its unique mechanical properties and surface stability, in a nickel base, are Cr, Mo, W, Al, Re and B.
  • the resultant article with an unusual, unique combination of mechanical properties and surface stability, is particularly useful in making hollow, air cooled, high temperature operating components such as blading members (blades and vanes) of the type used in the strenuous environment of the turbine section of gas turbine engines.
  • blading members blades and vanes
  • the crack free condition of thin walls associated with internal cooling passages is essential to safe, efficient engine operation.
  • a selection of nickel base superalloys sometimes used or designed for use in gas turbine engine turbine components is presented in the following Table II along with a form of the particular alloy associated with the present invention.
  • the alloy identified as Rene' N5, designed for use in making single crystal alloy articles, is described in US-A-5100484 and GB-A-2235697; the alloy identified as Rene' 150, designed for use as a DS columnar grain article, is described in the U.S. Patent 4,169,742. Also included in Table II are the castability ratings of such alloys.
  • the data of Table III show primarily the benefit and criticality of including Co at a level greater than 7.5 wt% (for example about 10 wt %) up to about 12 wt%, in combination with Hf in the range of about 0.3 - 1.6 wt%.
  • the alloy modification of Rene' N5 alloy had reduced longitudinal stress rupture strength due to dilution of the hardening elements from the addition of more Co to the Rene' N5 alloy base chemistry of Table II above, at a C level of about 0.05 wt%.
  • vanadium can detract from the surface stability, i.e., hot corrosion and oxidation resistance; Zr can increase crackability; and Ti can seriously reduce oxidation resistance. Therefore, these elements have been controlled and limited to the ranges in weight percent of less than 1 V, 0.05 Zr and 1.5 Ti, preferably less than 0.1V, 0.03 Zr and 0.02 Ti. While yttrium is helpful in improving oxidation resistance, it can cause grain boundary weakening; thus, it is limited to amounts less than 0.1% in the alloys of the invention. Cr is included primarily for its contribution to oxidation and hot corrosion resistance; Mo, W and Re primarily for matrix strengthening and B to enhance grain boundary strength.
  • Rene' 150 alloys as Rene' 150 were very good and within the acceptable range for thin wall castings, their surface stabilities were unacceptable for certain high temperature applications under strenuous environments.
  • a comparison of the elevated temperature surface stability of Rene' 150 alloy and the alloy of the present invention has shown that during 100 hours exposure to Mach 1 air, Rene' 150 alloy at 1135°C (2075°F) lost 1.27-1.65mm (50-65 mils) of metal per specimen side, whereas the alloy of the present invention, in the form shown in Table II, at a higher temperature of 1177°C (2150°F) and a longer exposure time of 150 hours lost only 0.038mm (1.5 mils) per specimen side, i.e. less than about 0.127mm (5 mils) per side according to this invention.
  • Rene' 150 alloy at 1135°C (2075°F) in Mach 1 airflow lost 1.016mm (40 mils) per specimen side after 82 hours.
  • MA754 alloy One nickel base alloy considered to have outstanding elevated temperature oxidation resistance is MA754 alloy, identified in Table II. Such alloy is a wrought rather than cast alloy but is included here for further comparison with the oxidation resistance of the present invention. After exposure of a specimen of MA 754 at Mach 1 airflow and 1177°C (2150°F) loss of 0.254mm (10 mils) per specimen side occurred after 140 hours exposure. Confirming the outstanding elevated temperature oxidation resistance of the present invention were tests conducted on specimens from a 1361 kg (3000 pound) heat of the alloy of the present invention.
  • an important characteristic of the present invention is its improved longitudinal stress rupture strength and improved balance between longitudinal and transverse stress rupture properties along with the outstanding surface stability discussed above. It exhibits, in a DS columnar grain article, the good stress rupture strength of Rene' 150 alloy and outstanding oxidation resistance of the single crystal article of the Rene' N5 composition in Table II above.
  • Table IV compares certain stress rupture properties: TABLE IV LONGITUDINAL STRESS RUPTURE DATA (uncoated, 0.160 diameter bars) TEMP °C (°F) STRESS MPa (ksi) ALLOY/RUPTURE LIFE (hours) INVENTION(DS) RENE' 150(DS) RENE' N4(a) 982 (1800) 276 (40) 40 - 70 40 - 70 60 871 (1600) 552 (80) 45 - 100 50 - 90 65 (a) Single crystal, diffusion aluminide coated.
  • the transverse stress rupture strength at 982°C (1800°F) and 221 MPa (32,000 psi)(32 ksi) nominally was in the range of about 80 - 120 hours, as shown in Table V below.
  • a preferred form of the heat treatment of the present invention includes an additional progressive combination of aging steps: a primary, first aging to improve ductility and transverse stress rupture properties, and two additional aging treatments at temperatures consecutively lower than that of the primary age to further optimize the gamma prime precipitate.
  • the heat treatments identified as A, B, C and D, summarize the heating steps, first with a solution temperature in the range of 1260°C-1279°C (2300-2335°F) for 2 hours. This is followed by a progressive combination and series of aging steps identified in a manner widely used and understood in the metallurgical art.
  • the solution and aging steps were conducted in a non-oxidizing atmosphere: vacuum, argon or helium. Cooling below 649°C (1200°F) conducted between aging steps, need not be conducted in such an atmosphere.
  • heat treatment D involving a unique relatively slow cooling step from the first aging to the temperature at which the second aging temperature was to be conducted, resulted in the best combination of properties.
  • a substantially full solutioning step is included. This is in contrast with the partial solutioning commonly used with such DS articles made from alloys from Table II such as Rene' 150, certain properties of which are affected detrimentally by a full solution heat treatment.
  • solutioning of at least about 90% of the gamma - gamma prime eutectic and coarse secondary gamma prime and with less than about 4%incipient melting is important because the stress rupture life is increased with increased solutioning of the gamma prime eutectic and coarse secondary gamma prime.
  • Table VI compares amount of solutioning and stress rupture life for the alloy associated with the present invention. TABLE VI Effect of Solutioning on Stress Rupture Life % Unsolutioned 982°C (1800°F) Stress Rupture Life 20 x 10 - 15 2x 0 - 5 3x
  • cooling for example to a temperature in the range of 1107-1135°C (2025-2075°F) be at a rate of at least 56°C (100°F) per minute.
  • cooling for example to a temperature in the range of 1107-1135°C (2025-2075°F) be at a rate of at least 56°C (100°F) per minute.
  • more rapid cooling rates have a beneficial effect on properties such as stress rupture strength.
  • the heat treatment of the present invention is further characterized by a progressive combination of aging stops after solutioning
  • the first or primary age is conducted in a temperature range of 1107-1135°C (2025-2075°F) in a non-oxidizing atmosphere, for example for about 1 - 10 hours, to improve ductility and stress rupture strength of the article.
  • cooling for example to the range of 1066-1093°C (1950-2000°F) be at a rate of about 42°C (75°F) per hour prior to further cooling.
  • a second aging step at a temperature lower than the first aging, for example in the range of 1066-1093°C (1950-2000°F) for about 4-12 hours, generally about 4-8 hours, enables growth of the gamma prime to improve ductility, As can be seen from the data of Table V, this unique progressive combination of heating steps results in a structure of improved mechanical properties and enables heat treatment of castings having thin walls without detrimental affect on such walls.
  • a final aging step generally is beneficial, for example, in the range of 885-913°C (1625-1675°F) for about 2-10 hours, typically about 4-8 hours.
  • the heat treatment of the present invention in connection with the DS cast article utilizing the alloy associated with this invention maximizes longitudinal stress rupture strength while retaining acceptable transverse strength and ductility. This is due, at least in part, to the increased solutioning of the gamma prime at a relatively higher temperature, Introduction of a primary or first aging in the range of 1107-1135°C (2025-2075°F) followed by a relatively slow cool (for example, about 1 hour) to a temperature in the range of 1066-1093°C (1950-2000°F) before further cooling resulted in a further improvement in longitudinal stress rupture life coupled with improved transverse stress rupture properties.
  • the combination of alloy selection, casting practice, and heat treatment, according to the present invention enables provision of an improved DS columnar grain article including a thin wall of less than about 0.889mm (0.035 inch) substantially free of cracks.
  • the grain boundaries and primary dendritic orientation is approximately straight and parallel.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Turbine Rotor Nozzle Sealing (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Heat Treatment Of Nonferrous Metals Or Alloys (AREA)
  • Powder Metallurgy (AREA)

Claims (10)

  1. Superalliage à base de nickel consistant, en pourcentage en poids, en 0,12% de carbone, 1,5% de hafnium, 12% de cobalt, 6,35% de tantale, 6,8% de chrome, 1,5% de molybdène, 4,9 % de tungstène, 6,15 % d'aluminium, 2,8% de rhénium, 0,015% de bore, une absence substantielle de zirconium, une absence substantielle de titane, une absence substantielle de vanadium, le complément étant du nickel et des impuretés accidentelles.
  2. Article en alliage selon la revendication 1 comportant une cavité interne dans la surface extérieure de l'article, la cavité comprenant une paroi venue de moulage d'une seule pièrce, sensiblement exempte de fissures, et ayant une épaisseur inférieure à environ 0,889mm (0,035 inch).
  3. Article selon la revendication 2, dans lequel la cavité interne est séparée de la surface extérieure par l'épaisseur de l'article, inférieure à environ 0,889mm (0,035 inch).
  4. Article moulé selon la revendication 2 sous la forme d'un élément d'aubage de turbine ayant un axe radial et comprenant une partie aérodynamique comprenant un bord d'attaque et un bord de fuite, dans lequel
       les joints des grains et l'orientation dendritique principale sont approximativement rectilignes et parallèles; et
       tout grain émergent qui intersecte le bord d'attaque ou le bord de fuite forme avec le bord un angle qui n'est pas supérieur à 15 degrés, et tous les autres joints de grains et dendrites principales se trouvent à l'intérieur d'un angle de 15 degrés par rapport à l'axe radial.
  5. Article selon la revendication 1, dans lequel l'article est un profil aérodynamique d'un turbomoteur.
  6. Procédé de traitement thermique d'un article moulé en alliage à base de nickel consistant, en pourcentage en poids, en 0,1-0,15 de C, 0,3-2 de Hf, 11-14 de Co, 5-9 de Ta, moins de 0,05 de Zr, pas plus qu'environ 1 de V, pas plus qu'environ 1 de Ti, 5-10 de Cr, 0,5-3 de Mo, 4-7 de W, 5-7 de Al, 1,5-4 de Re, 0,005-0,03 de B, jusqu'à 1,5 de Nb, jusqu'à 0,5 de Y, le complément étant du Ni et des impuretés accidentelles, ce procédé comprenant les étapes consistant :
    (a) à chauffer à une température de mise en solution dans une atmosphère non-oxydante pendant un temps suffisant pour mettre en solution au moins 90% de la phase eutectique gamma-gamma prime et de la phase gamma secondaire à grains grossiers et de façon qu'il n'y ait pas plus qu'environ 4% de fusion commençante, et à refroidir ensuite dans l'atmosphère jusqu'à une température comprise dans la plage de 1107-1135°C (2025-2075°F);
    (b) à chauffer à une première température de vieillissement comprise dans la plage de 1107-1135°C (2025-2075°F) dans une atmosphère non oxydante pendant 1-10 heures, et à refroidir ensuite dans l'atmosphère juqu'à une température comprise dans la plage de 1066-1093°C (1950-2000°F); et
    (c) à chauffer à une seconde température de vieillissement inférieure à la première température de vieillissement et comprise dans la plage de 1066-1093°C (1950-2000°F) pendant 4-12 heures.
  7. Procédé selon la revendication 6 dans lequel la température de mise en solution est comprise dans la plage de 1246-1293°C (2275-2360°F) et le temps de chauffage est d'au moins environ 30 minutes.
  8. Procédé selon la revendication 6 ou la revendication 7 comprenant une troisième étape de vieillissement consistant :
    (d) à chauffer à une température comprise dans la plage de 885-913°C (1625-1675°F) pendant 2-10 heures.
  9. Procédé pour fabriquer un article moulé en superalliage à base de nickel à grains colonnaires présentant une très grande résistance à l'oxydation aux température élevées, cet article comportant une cavité interne comprenant une paroi venue de moulage d'une seule pièce et ayant une épaisseur inférieure à environ 0,889mm (0.035 inch), comprenant les étapes consistant :
    (a) à effectuer un moulage de précision de l'article à partir d'un alliage consistant, en pourcentage en poids, en 0,1-0,15 de C, 0,3-2 de Hf, 11-14 de Co, 5-9 de Ta, moins de 0,05 de Zr et pas plus de 1 de chacun deV et de Ti, 5-10 de Cr, 0,5-3 de Mo, 4-7 de W, 5-7 de Al, 1,5-4 de Re, 0,005-0,03 de B, jusqu'à 1,5 de Nb, jusqu'à 0,5 de Y, le complément étant Ni et des impuretés accidentelles, la paroi moulée faisant corps avec la pièce moulée par suite du moulage avec solidification directionnelle multigrains colonnaires;
    (b) à traiter thermiquement l'article moulé selon la revendication 6.
  10. Procédé pour fabriquer un élément moulé d'aubage de turbine de turbomoteur en superalliage à base de nickel à grains colonnaires présentant une très grande résistance à l'oxydation aux températures élevées, cet article comportant au moins une cavité interne comprenant une paroi venue de moulage d'une seule pièce, d'une épaisseur inférieure à environ 0,889mm (0,035 inch), ce procédé comprenant les étapes consistant :
    (a) à préparer un superalliage consistant , en pourcentage en poids, en 0,1-0,14 de C, 1,2-1,7 de Hf, 11,7-12,3 de Co, 6,2-6,5 de Ta, jusqu'à 0,1 de V, jusqu'à 0,03 de Zr, 6,6-7 de Cr, 1,3-1,7 de Mo, 4,7-5,1 de W, pas plus de 0,02 de Ti, 6-6,3 de Al, 2,6-3 de Re, 0,01-0,02 de B, jusqu'à 0,1 de Nb, jusqu'à 0,2 de Y, le complément étant du Ni et des impuretés accidentelles;
    (b) à effectuer un moulage de précision dudit superalliage pour obtenir un article ayant au moins une cavité interne comprenant une paroi venue de moulage d'une seule pièce, d'une épaisseur de moins de 0,889mm (0,035 inch); et
    (c) à traiter thermiquement ledit article moulé selon la revendication 7.
EP89117666A 1988-10-03 1989-09-25 Pièce creuse en alliage à base de nickel coulé comportant une structure de grains colonaire, alliage et procédé de sa fabrication Expired - Lifetime EP0362661B1 (fr)

Applications Claiming Priority (2)

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US25310988A 1988-10-03 1988-10-03
US253109 1988-10-03

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EP0362661A1 EP0362661A1 (fr) 1990-04-11
EP0362661B1 true EP0362661B1 (fr) 1995-03-08

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EP (1) EP0362661B1 (fr)
JP (1) JP3148211B2 (fr)
AU (1) AU630623B2 (fr)
DE (1) DE68921530T2 (fr)
ES (1) ES2070155T3 (fr)
GR (1) GR3015341T3 (fr)
IL (1) IL91793A (fr)
NO (1) NO175875C (fr)

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US5316866A (en) * 1991-09-09 1994-05-31 General Electric Company Strengthened protective coatings for superalloys
US5443789A (en) * 1992-09-14 1995-08-22 Cannon-Muskegon Corporation Low yttrium, high temperature alloy
US5783318A (en) * 1994-06-22 1998-07-21 United Technologies Corporation Repaired nickel based superalloy
JP2905473B1 (ja) 1998-03-02 1999-06-14 科学技術庁金属材料技術研究所長 Ｎｉ基一方向凝固合金の製造方法
EP1053804A1 (fr) * 1999-05-20 2000-11-22 Asea Brown Boveri AG Support de noyau
KR20040008381A (ko) * 2002-07-18 2004-01-31 한국기계연구원 고온크립특성이 향상된 단결정 초내열합금
JP4449337B2 (ja) * 2003-05-09 2010-04-14 株式会社日立製作所 高耐酸化性Ｎｉ基超合金鋳造物及びガスタービン部品
JP4885530B2 (ja) 2005-12-09 2012-02-29 株式会社日立製作所 高強度高延性Ｎｉ基超合金と、それを用いた部材及び製造方法
ES2444407T3 (es) 2006-09-07 2014-02-24 Alstom Technology Ltd Procedimiento para el tratamiento térmico de súper-aleaciones a base de níquel
US20100135846A1 (en) * 2008-12-01 2010-06-03 United Technologies Corporation Lower cost high strength single crystal superalloys with reduced re and ru content
EP2876176B1 (fr) 2013-11-25 2017-06-21 Mitsubishi Hitachi Power Systems, Ltd. Superalliage de coulée à base de Ni et article moulé à partir de celui-ci

Family Cites Families (8)

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Publication number Priority date Publication date Assignee Title
GB1417474A (en) * 1973-09-06 1975-12-10 Int Nickel Ltd Heat-treatment of nickel-chromium-cobalt base alloys
US4169742A (en) * 1976-12-16 1979-10-02 General Electric Company Cast nickel-base alloy article
FR2374427A1 (fr) * 1976-12-16 1978-07-13 Gen Electric Alliage a base de nickel perfectionne et piece coulee obtenue a partir de cet alliage
GB1562082A (en) * 1977-10-17 1980-03-05 Gen Electric Nickel-base olloys
JPS56108852A (en) * 1980-01-17 1981-08-28 Cannon Muskegon Corp Directional cast alloy for high temperature operation
US4643782A (en) * 1984-03-19 1987-02-17 Cannon Muskegon Corporation Single crystal alloy technology
FR2578554B1 (fr) * 1985-03-06 1987-05-22 Snecma Alliage monocristallin a matrice a base de nickel
CA1315572C (fr) * 1986-05-13 1993-04-06 Xuan Nguyen-Dinh Materiaux monocristallins a phase stable

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AU4170089A (en) 1990-04-05
NO893913D0 (no) 1989-10-02
DE68921530T2 (de) 1995-10-26
NO893913L (no) 1990-04-04
DE68921530D1 (de) 1995-04-13
JPH02153037A (ja) 1990-06-12
NO175875B (fr) 1994-09-12
AU630623B2 (en) 1992-11-05
GR3015341T3 (en) 1995-06-30
ES2070155T3 (es) 1995-06-01
NO175875C (no) 1994-12-21
IL91793A (en) 1994-07-31
JP3148211B2 (ja) 2001-03-19
IL91793A0 (en) 1990-06-10
EP0362661A1 (fr) 1990-04-11

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