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EP0362661A1 - 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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Publication number
EP0362661A1
EP0362661A1 EP89117666A EP89117666A EP0362661A1 EP 0362661 A1 EP0362661 A1 EP 0362661A1 EP 89117666 A EP89117666 A EP 89117666A EP 89117666 A EP89117666 A EP 89117666A EP 0362661 A1 EP0362661 A1 EP 0362661A1
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EP
European Patent Office
Prior art keywords
article
cast
alloy
less
nickel base
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Granted
Application number
EP89117666A
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German (de)
English (en)
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EP0362661B1 (fr
Inventor
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 solumnar 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 heat 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 0.035 inch thick, generally cracked during multicolumnar grain directional solidification.
  • the present invention provides an improved cast columnar grain nickel base alloy article 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 0.035 inch.
  • the alloy includes essentially, in percentages by weight, the combination of 0.1-1.15 C, 0.3-2 Hf, 11-14 Co, 5-9 Ta, less than 0.05 Zr and the substantial absence of V and Ti at no more than about 1 each, to provide the alloy with the capability of being made into a DS multigrain article through good castability and resistance to grain boundary and fatigue cracking, along with outstanding oxidation reistance.
  • the remainder of the alloy is 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 Cb, up to 0.5 Y and the balance Ni and incidental impurities.
  • 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 nickel base alloy associated with 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 international 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 wich thin walls of less than 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, B and optional, limited amount of Cb and Y.
  • 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 strenous 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 currently pending U.S. patent application Serial No. 790,439 - Wukusick et al., filed October 15, 1985; the alloy identified as Rene' 150, designed for use as a DS columnar grain article, is described in the above incorporated U.S. Patent 4,169,742 - Wukusick, et al.
  • the disclosure of such copending application assigned to the assignee of this invention also is hereby incorporated herein by reference.
  • 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 about 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 were very good and within the acceptable range for thin wall castings, their surface stabilities were unacceptable for certain high temperature applications under strenous 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 2075°F lost 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 2150°F and a longer exposure time of 150 hours lost only 1.5 mils per specimen side, i.e. less than about 5 mils per side according to this invention.
  • Rene' 150 alloy at 2075°F in Mach 1 airflow lost 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.
  • MA754 alloy is a wrought rather than cast alloy but is included here for further comparison with the oxidation resistance of the present invention.
  • loss of 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 3000 pound heat of the alloy of the present invention. After 170 hours exposure at 2150°F and Mach 1 airflow, a specimen showed a metal loss of only 1.6 mils per side; after 176 hours at those conditions, a loss of only 2 mils of metal per side was observed.
  • 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 (°F) STRESS (ksi) ALLOY/RUPTURE LIFE (hours) RENE' N4(a) INVENTION(DS) RENE′ 150(DS) 1800 40 40 - 70 40 - 70 60 1600 80 45 - 100 50 - 90 65 (a) Single crystal, diffusion aluminide coated.
  • the transverse stress rupture strength at 1800°F and 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 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 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 course 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 course 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 1800°F Stress Rupture Life 20 x 10 - 15 2x 0 - 5 3x
  • cooling for example to a temperature in the range of about 2025 - 2075°F, be at a rate of at least 100°F per minute.
  • cooling for example to a temperature in the range of about 2025 - 2075°F, be at a rate of at least 100°F per minute.
  • the heat treatment of the present invention is further characterized by a progressive combination of aging steps after solutioning.
  • the first or primary age is conducted in a temperature range of about 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 about 1950 - 2000°F, be at a rate of about 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 about 1950 - 2000°F for about 4 - 12 hours, generally about 4 - 8 hours, enables growth of the gamma prime to improve ductility.
  • this unique progressive combination of heating steps results in a structure of improved mechanical properties and enables heat treatment of castings having this walls without detrimental affect on such walls.
  • a final aging step generally is beneficial, for example, in the range of about 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 of first aging in the range of about 2025 - 2075°F followed by a relatively slow cool (for example, about 1 hour) to a temperature in the range of about 1950 - 2000°F before further cooling resulted in a futher 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 0.035 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)
  • Mechanical Engineering (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Turbine Rotor Nozzle Sealing (AREA)
  • Powder Metallurgy (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Heat Treatment Of Nonferrous Metals Or Alloys (AREA)
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)

Application Number Priority Date Filing Date Title
US25310988A 1988-10-03 1988-10-03
US253109 1999-02-19

Publications (2)

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

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EP89117666A Expired - Lifetime EP0362661B1 (fr) 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

Country Status (8)

Country Link
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)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
WO1995035396A1 (fr) * 1994-06-22 1995-12-28 United Technologies Corporation Alliage a base de nickel pour la reparation de substrats
EP0940473A1 (fr) * 1998-03-02 1999-09-08 National Research Institute For Metals, Science and Technology Agency Procédé de fabrication par coulage d'un alliage à base de nickel solidifié directionellement
EP1053804A1 (fr) * 1999-05-20 2000-11-22 Asea Brown Boveri AG Support de noyau
EP1795621A1 (fr) 2005-12-09 2007-06-13 Hitachi, Ltd. Superalliage à haute résistance et ductilite à base de nickel, pieces et procédé de fabrication
US7938919B2 (en) 2006-09-07 2011-05-10 Alstom Technology Ltd Method for the heat treatment of nickel-based superalloys
EP2218798A3 (fr) * 2008-12-01 2011-11-23 United Technologies Corporation Superalliages monocristallins hautement résistants et peu onéreux avec une teneur réduite en Re et en Ru

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
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

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2243270A1 (fr) * 1973-09-06 1975-04-04 Int Nickel Ltd
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
FR2406001A1 (fr) * 1977-10-17 1979-05-11 Gen Electric Alliage perfectionne a base de nickel et piece coulee obtenue a partir de cet alliage
EP0032812A1 (fr) * 1980-01-17 1981-07-29 Cannon-Muskegon Corporation Alliage à base de nickel et ailette de turbine obtenue par coulée dudit alliage
EP0155827A2 (fr) * 1984-03-19 1985-09-25 Cannon-Muskegon Corporation Alliage pour la technologie des monocristaux
EP0194925A1 (fr) * 1985-03-06 1986-09-17 Association Pour La Recherche Et Le Developpement Des Methodes Et Processus Industriels (Armines) Alliage monocristallin à matrice à base de nickel
EP0246082A1 (fr) * 1986-05-13 1987-11-19 AlliedSignal Inc. Matériaux en monocristal de superalliage

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4169742A (en) * 1976-12-16 1979-10-02 General Electric Company Cast nickel-base alloy article

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2243270A1 (fr) * 1973-09-06 1975-04-04 Int Nickel Ltd
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
FR2406001A1 (fr) * 1977-10-17 1979-05-11 Gen Electric Alliage perfectionne a base de nickel et piece coulee obtenue a partir de cet alliage
EP0032812A1 (fr) * 1980-01-17 1981-07-29 Cannon-Muskegon Corporation Alliage à base de nickel et ailette de turbine obtenue par coulée dudit alliage
EP0155827A2 (fr) * 1984-03-19 1985-09-25 Cannon-Muskegon Corporation Alliage pour la technologie des monocristaux
EP0194925A1 (fr) * 1985-03-06 1986-09-17 Association Pour La Recherche Et Le Developpement Des Methodes Et Processus Industriels (Armines) Alliage monocristallin à matrice à base de nickel
EP0246082A1 (fr) * 1986-05-13 1987-11-19 AlliedSignal Inc. Matériaux en monocristal de superalliage

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
WO1995035396A1 (fr) * 1994-06-22 1995-12-28 United Technologies Corporation Alliage a base de nickel pour la reparation de substrats
US5783318A (en) * 1994-06-22 1998-07-21 United Technologies Corporation Repaired nickel based superalloy
EP0940473A1 (fr) * 1998-03-02 1999-09-08 National Research Institute For Metals, Science and Technology Agency Procédé de fabrication par coulage d'un alliage à base de nickel solidifié directionellement
US6224695B1 (en) 1998-03-02 2001-05-01 National Research Institute For Metals, Science And Technology Agency Ni-base directionally solidified alloy casting manufacturing method
EP1053804A1 (fr) * 1999-05-20 2000-11-22 Asea Brown Boveri AG Support de noyau
EP1795621A1 (fr) 2005-12-09 2007-06-13 Hitachi, Ltd. Superalliage à haute résistance et ductilite à base de nickel, pieces et procédé de fabrication
US7938919B2 (en) 2006-09-07 2011-05-10 Alstom Technology Ltd Method for the heat treatment of nickel-based superalloys
EP2218798A3 (fr) * 2008-12-01 2011-11-23 United Technologies Corporation Superalliages monocristallins hautement résistants et peu onéreux avec une teneur réduite en Re et en Ru
EP2218798B1 (fr) 2008-12-01 2016-09-14 United Technologies Corporation Superalliages monocristallins hautement résistants et peu onéreux avec une teneur réduite en Re et en Ru
EP3141623A1 (fr) * 2008-12-01 2017-03-15 United Technologies Corporation Superalliages monocristallins hautement résistants et à teneur réduite en re et en ru

Also Published As

Publication number Publication date
IL91793A0 (en) 1990-06-10
AU630623B2 (en) 1992-11-05
NO175875C (no) 1994-12-21
JP3148211B2 (ja) 2001-03-19
JPH02153037A (ja) 1990-06-12
EP0362661B1 (fr) 1995-03-08
GR3015341T3 (en) 1995-06-30
ES2070155T3 (es) 1995-06-01
IL91793A (en) 1994-07-31
NO175875B (fr) 1994-09-12
AU4170089A (en) 1990-04-05
NO893913L (no) 1990-04-04
NO893913D0 (no) 1989-10-02
DE68921530D1 (de) 1995-04-13
DE68921530T2 (de) 1995-10-26

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