US3785876A - Treating nickel base alloys - Google Patents

Treating nickel base alloys Download PDF

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US3785876A
US3785876A US00291858A US3785876DA US3785876A US 3785876 A US3785876 A US 3785876A US 00291858 A US00291858 A US 00291858A US 3785876D A US3785876D A US 3785876DA US 3785876 A US3785876 A US 3785876A
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percent
nickel
metal
base alloy
group
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R Bailey
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ALLEGHENY INTERNATIONAL ACCEPTANCE Corp
TABERT Inc
Special Metals Corp
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Special Metals Corp
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Assigned to AL-INDUSTRIAL PRODUCTS, INC. reassignment AL-INDUSTRIAL PRODUCTS, INC. SECURITY INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: SPECIAL METALS CORPORATION A DE CORP
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Assigned to TABERT INC reassignment TABERT INC CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). EFFECTIVE AUG. 22, 1985 Assignors: CIP INC
Assigned to HELLER FINANCIAL, INC. reassignment HELLER FINANCIAL, INC. SECURITY INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: SPECIAL METALS CORPORATION
Assigned to SPECIAL METALS CORPORATION reassignment SPECIAL METALS CORPORATION RELEASED BY SECURED PARTY (SEE DOCUMENT FOR DETAILS). Assignors: CITICORP INDUSTRIAL CREDIT, INC.
Assigned to SPECIAL METALS CORPORATION reassignment SPECIAL METALS CORPORATION RELEASED BY SECURED PARTY (SEE DOCUMENT FOR DETAILS). Assignors: AL-INDUSTRIAL PRODUCTS, INC., A CORP. OF PA, ALLEGHENY INTERNATIONAL, INC., A CORP. OF PA
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/10—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of nickel or cobalt or alloys based thereon

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  • ABSTRACT A method of treating a nickel base alloy so as to produce an alloy having a structure characterized by dispersed discrete fine spherical carbides.
  • the method comprises the steps of casting an ingot of nickel base alloy, homogenizing the ingot at a temperature of from 2,200 to 2,400 F so as to dissolve primary carbides present in the alloy and increase the chemical homogeneity thereof; cooling the ingot at least to a temperature of from l,750 to 2,l85 F at a rate whichsubstantially precludes the precipitation of coarse and film-like carbides; and hot working the ingot with the primary carbides in solution with sufficient intensity to cause dispersed discrete fine spherical carbides to precipitate.
  • the present invention provides a sophisticated heat treatment which decreases dendritic segregation and minimizes the formation of carbide stringers. Instead of coarse and/or film-like carbides, it produces a structure characterized by dispersed discrete fine spherical carbides and an alloy with a high degree of chemical homogeneity. As a result the alloy has improved tensile strength and/or tensile ductility and/or stress rupture properties, and particularly in the direction transverse to metal solidification and/or metal flow. More specifically, the invention involves a high homogenization temperature and critically controlled cooling and hot working, as well as casting. Moreover, it is in part based upon processing which was previously considered detrimetal. Previous technical reports have indicated that so called high" homogenization temperatures cause a subsequent formation of carbide films and thereby decrease ductility.
  • FIG. 1 is a photomicrograph at 50X of a billet processed in accordance with the present invention.
  • FIG. 2 is aphotomicrograph at 50X of a billet processed in'accordance with prior art techniques.
  • Nickel base alloys having a structure characterized by dispersed discrete fine spherical carbides, are proucked, in accordance with the present invention, by a method which comprises the steps of: casting an ingot of nickel base alloy; homogenizing the ingot at a temperature of from 2,200 to 2,400" F and preferably at a temperature of from 2,250 to 2,400 F, thereby dissolving primary carbides present in the alloy and increasing the chemical homogeneity thereof; cooling the ingot at least to a temperature of from l,750 to 2,185 F at a rate which substantially precludes the precipitation of coarse and film-like carbides; and hot working the ingot with the primary carbides in solution with sufficient intensity to cause dispersed discrete fine spherical carbides to precipitate.
  • the primary carbides are generally MC or M C carbides.
  • MC carbides are comprised of titanium with optional amounts of molybdenum, nickel, chromium and zirconium
  • M C carbides are comprised of molybdenum with optional amounts of tungsten, chromium, iron and cobalt. It is essential to dissolve the primary carbides in order for the desired dispersed discrete fine spherical carbides to form during hot working, and in order to do so homogenization must be at a temperature of at least 2,200 F. A maximum homogenization temperature of 2,400 F is, however, imporsed as carbides melt at higher temperatures.
  • carbide films would subsequently form following homogenization at temperatures as high as 2,200 F, and that these films would detrimentally affect the alloys ductility.
  • a sufficient period of time is preferably allowed for the primary carbides to dissolve and to permit carbon and other elements to diffuse over a distance at least approaching one half the local dendrite-arm spacing.
  • the required period for homogenization is in excess of 4 hours, although no specific time period can be set as it is dependent upon the homogenization temperature and the thickness of the ingot.
  • the ingot To obtain the desired carbide structure the ingot must hot worked with the primary carbides in solution and with an intensity which results in an overall reduction in area to the cross section of the ingot of a least 20 percent, and preferably at least 30 percent. Moreover, the hot working must occur at a temperature lower than that at which the primary carbides dissolve and within a range of from l,750 to 2,l85 F, and preferably within a range of from l,800 to 2,1 50 F. The ingot tends to excessivley crack at lower hot working temperatures and cannot be uniformly deformed without cracking at higher temperatures. Prior to hot working, the ingot must be cooled to at least its hot working temperature at a rate which substantially precludes the precipitation of coarse and film-like carbides.
  • This cooling rate is in excess of 25 F per hour, and is preferably in excess of F per hour, and moreover, can be to a temperature as low as room temperature.
  • ingots cooled to room temperature must be reheated for hot working.
  • the present invention includes forging, swaging, extrusion, rolling, drawing, pressing and'all other processes known to those skilled in the art.
  • hot working temperatures and all other temperatures referred to herein as well as rates involving temperatures are based upon furnace temperatures rather than metal temperatures, as it is more practical to talk about furnace temperatures when discussing production size ingots and billets.
  • Furnace temperatures are lower than metal temperatures during cooling, and cooling as discussed above is a critical part of the present invention. Metal temperatures do, however, reach furnace temperatures during homogenization due to the prolonged exposure at temperature.
  • the nickel base alloy being treated is most often a gamma prime strengthened alloy and generally, but not necessarily, consists essentially of, in weight percent: up to 0.2 percent carbon, up to 2.0 percent manganese, up to 2 percent silicon, from S to 25 percent chromium, up to 20 percent cobalt, up to 10 percent molybdenum, up to 10.0 percent titanium, up to 5 percent aluminum, up to 0.05 percent boron, up to 0.5 percent zirconium, up to 40.0 percent iron, up to 8.0 percent of metal from .the group consisting of columbium, tantalum and hafnium, up to 2.0 percent vanadium, up to 10 percent tungsten, up to 0.5 percent rhenium, up to 0.02 percent of metal from Group II A of the periodic table, up to 0.5 percent of rare earth metal, balance essentially nickel, said percentage of nickel being at least 40 percent silicon, 19.1 percent chromium, 13.7 percent cobalt, 4.20 percent molybdenum, 3.10 percent titanium, 1.34 percent aluminum,
  • an alloy which has proven 5 nickel. to be particularly well suited for the treatment of the A number of ingots having a composition, in weight present invention consists essentially of, in weight perpercent, of from 0.05 to 0.07 percent carbon, less than cent, up to 0.15 percent carbon, up to 1.0 pe nt 0.10 percent manganese, less than 0.10 percent silicon, manganese, up to 1.0 percent silicon, from 15-23 per- 18.7 percent to 19.7 chromium, 13.0 to 14.5 percent cent chromium, from to 18 percent cobalt, from 3 10 cobalt, 3.75 to 4.5 percent molybdenum, 2.9 to 3.2 perto 6 percent molybdenum, from 2 to 3.5 percent titacent titanium, 1.30- 1.38 percent aluminum, 0.0040 to nium, from 1 0 to 20 percent aj min n-n from 00025 0.0055 percent bOl'OIl, 0.055 to 0.075 percent Zll'CO- to 0.0125 percent boronita
  • the carbides theein are cent carbon, up to 2.0 percent manganese, up to 1.0 Concentrated m bands percent silicon, from 5.0 to 15.0 percent chromium, up Pancake property data for both the alloy treated in to 10.0 percent cobalt, from 2 to 7 percent molybdeaccordance with the present invention and for the avernum, from 1.0 to 3.75 percent titanium, up to 2 percent age of the prior art billets is set forth below in Table 1.
  • the general composition M (Al and/or Ti and It will be apparent to those skilled in the art that the possibly one or more additional metals from the group comprised of tantalum, columbium, molybdenum and- /or chromium).
  • the M portion of the gamma prime is regarded as consisting mainly of nickel with possible one or more metals from the group comprised of chromium, cobalt, molybdenum and iron.
  • a nickel base alloy ingot was cast and homogenized for 43 hours 0PT.?00Fi l rom tlie Emogenization temperature the ingot was cooled to room temperature at a rate which substantially precluded the precipitation of coarse and film-like carbides and kept the primary carbides in solution. After cooling the ingot was reheated at a temperature of2.125F and worked from a 20 inch ingot to a l4%-inch octagon billet, which was subsequently ground to a 13%-inch octagon billet. Dispersed discrete fine spherical carbides precipitated during hot working. This desirable carbide morphology and distribution is seen in FIG. 1 which is a photomicrograph of the hot worked billet.
  • composition of the ingot was, in weight percent, 0.05 percent carbon, less than 0.10 percent manganese, less than 0.10 pernovel principles of the invention disclosed herein in connection with specific examples thereof will suggest various other modifications and applications of the same. It is accordingly desired that in construing the breadth of the appended claims they shall not be limited to the specific examples of the invention described herein.
  • a method of treating a nickel base alloy so as to produce an alloy having a structure characterized by dispersed discrete fine spherical carbides which comprises the step of: casting an ingot of nickel base alloy; homogenizing said ingot at a temperature of from 2,200 to 2,400 F, thereby dissolving primary carbides present in said alloy and increasing the chemical homogeneity thereof; cooling said ingot at least to a temperature of from l,750 to 2,l85 F at a rate which substantially precludes the precipitation of coarse and film-like carbides, said cooling rate being in excess of 25 F per hour; and hot working said ingot with said primary carbides in solution with sufficient intensity to cause dispersed discrete fine spherical carbides to precipitate, said hot working occuring at a temperature lower than that at which said primary carbides dissolve and within a temperature range of from 1,750" to 2,185 F, said hot working resulting in an overall reduction in area to the cross section of the" ingot of at least 20 percent.
  • said nickel base alloy consists essentially of, in weight percent, up to 0.2 percent carbon, up to 2.0 percent manganese, up to 2.0 percent silicon, from 5.0 to 25.0 percent chromium, up to 23 percent cobalt, up to percent molybdenum, up to 10.0 percent titanium, up to 5 percent aluminum, up to 0.05 percent boron,.up to 0.5 percent zirconium, up to 40.0-percent iron, up to 8.0 percent of metal from the groupconsisting of columbium, tantalum and hafnium, up to 2.0 percent vanadium, up to 10 percent tungsten, up to 0.5 percent rhenium, up to 0.02 percent of metal from Group II A of the periodic table, up to 0.5 percent of rare earth metal, balance essentially nickel, said percentage of nickel being at least 1 40 percent.
  • nickel base alloy consists essentially of, in weight percent, up to 0.15 percent carbon, up to 1.0 percent manganese, up to 1.0 percent silicon, from -23 percent chromium, from 10 to 18 percent cobalt, from 3 to 6 per- 1 centrnolybdenum, from 2 to 3.5. percent titanium, from 4.
  • said nickel base alloy consists essentially of, in weight percent, up to 0.15 percent carbon,- up to 2.0 percent manganese, up to 1.0 percent silicon, from 5.0 to 15.0 percent chromium, up to 10.0 percent cobalt, from 2 to 7 percent molybdenum, from 1.0 to 3.75 percent titanium, up to 2 percent aluminum, up to 0.05 percent boron, from 25 to 40 percent iron, balance essentially nickel.
  • said nickel base alloy consists essentially of, in weight percent, up to 0.2 percent carbon, up to 2.0 percent manganese, up to 2.0 percent silicon, from 5.0 to 25.0 per cent chromium, up to 23 percent cobalt, up to 10 percent molybdenum, up to 10.0 percent titanium, up to 5 percent aluminum, up to 0.05 percent boron, up to 0.5 percent zirconium, up to 40.0 percent iron, up to 8,0 percent of metal from the group consisting of columbium, tantalum and hafnium, up to 2.0 percent vanadium, up to 10 percent tungsten, up to 0.5 percent rhenium, up to 0.02 percent of metal from Group 11 A of the periodic table, up to 0.5 percent of rare earth metal, balance essentially nickel, said percentage of nickel being at least 40 percent.
  • said nickel base alloy consists essentially of, in weight percent, up to 0.15 percent carbon,- up to 1.0 percent manganese, up to 1.0 percent silicon, from 15-23 percent chromium, from 10 to 18 percent cobalt, from 3 to 6 percent molybdenum, from 2 to 3.5 percent titanium, from 1.0 to 2.0 percent aluminum, from 0.0025 to 0.0125 percent boron, from 0.02 to 0.2 percent zirconium, up to 2 percent iron, up to 4.0 percent of metal from the group consisting of columbium, tantalum and hafnium, up to-0.5 percent vanadium, up to 0.02 percent of metal from Group 11 A of the periodic table, up
  • said nickel base alloy is a gamma prime strengthened alloy.
  • said nickel base alloy consists essentially of, weight percent, up to 0.2 percent carbon, up to 2.0 percent manganese, up to 2.0 percent silicon, from 5.0 to 25.0 percent chromium, up to 23 percent cobalt, up to 10 percent molybdenum, up to 10.0 percent titanium, up to 5 percent aluminum, up to 0.05 percent boron, up to 0.5 percent zirconium, up to 40.0 percent iron, up to 8.0 percent of metal from the group consisting of columbium, tantalum and hafnium, up to 2.0 percent vanadium, up to 10 percent tungsten, up to 0.5 percent rhenium, up to 0.02 percent of metal from Group 11 A of the periodic table, up to 0.5 percent of rare earth metal, balance essentially nickel, said percentage of nickel being at least 40 percent.
  • said nickel base alloy consists essentially of, in weight percent, up to 0.15 percent carbon, up to 1.0 percent manganese, up to 1.0 percent silicon, from 15-23 percent chromium, from 10 to 18 percent cobalt, from 3 to 6 percent molybdenum, from 2 to 3.5 percent titanium, from 1.0 to 2.0 percent aluminum, 'from 0.0025 to 0.0125 percent boron, from 0.02 to 0.2 percent zirconium, up to 2 percent iron, up to 4.0 percent of metal from the group consisting of columbium, tantalum and hafnium, up to 0.5 percent vanadium, up to 0.02 percent of .metal from Group 11 A of the periodic table, up

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Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2628349A1 (fr) * 1988-03-09 1989-09-15 Snecma Procede de forgeage de pieces en superalliage a base de nickel
US4908069A (en) * 1987-10-19 1990-03-13 Sps Technologies, Inc. Alloys containing gamma prime phase and process for forming same
EP0392484A1 (en) * 1989-04-14 1990-10-17 Inco Alloys International, Inc. Corrosion-resistant nickel-chromium-molybdenum alloys
EP0492517A1 (en) * 1990-12-21 1992-07-01 Nippon Steel Corporation Alloy and composite steel tube with corrosion resistance in combustion environment where vanadium sodium sulphur, and chlorine are present
US5169463A (en) * 1987-10-19 1992-12-08 Sps Technologies, Inc. Alloys containing gamma prime phase and particles and process for forming same
US5470371A (en) * 1992-03-12 1995-11-28 General Electric Company Dispersion strengthened alloy containing in-situ-formed dispersoids and articles and methods of manufacture
US5863494A (en) * 1995-11-17 1999-01-26 Asea Brown Boveri Ag Iron-nickel superalloy of the type in 706
US6132535A (en) * 1999-10-25 2000-10-17 Mitsubishi Heavy Industries, Ltd. Process for the heat treatment of a Ni-base heat-resisting alloy
US6576068B2 (en) 2001-04-24 2003-06-10 Ati Properties, Inc. Method of producing stainless steels having improved corrosion resistance
US20090257865A1 (en) * 2008-03-31 2009-10-15 Kabushiki Kaisha Toshiba Ni-base alloy for turbine rotor of steam turbine and turbine rotor of steam turbine
US20090285692A1 (en) * 2008-03-17 2009-11-19 Kabushiki Kaisha Toshiba Ni-base alloy for turbine rotor of steam turbine and turbine rotor of steam turbine
CN104278175A (zh) * 2013-07-12 2015-01-14 大同特殊钢株式会社 高温强度优异的能够热锻造的Ni基超合金
CN105463257A (zh) * 2015-12-08 2016-04-06 南通金源智能技术有限公司 一种镍基高温合金粉
CN111575535A (zh) * 2020-05-14 2020-08-25 张家港广大特材股份有限公司 一种镍基高温合金及其制备方法
US11193186B2 (en) 2017-07-28 2021-12-07 Vdm Metals International Gmbh High-temperature nickel-base alloy
CN116145005A (zh) * 2023-02-09 2023-05-23 华能国际电力股份有限公司 一种高铬铁的镍铁基高温合金及其制备方法
US11753701B2 (en) 2018-12-27 2023-09-12 Siemens Energy Global GmbH & Co. KG Nickel-based alloy for additive manufacturing and method

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2641537C2 (de) * 1976-09-15 1983-06-23 Galina Vasiljevna Šurkina Verwendung einer Legierung auf der Grundlage von Nickel
JPS59166364A (ja) * 1983-03-14 1984-09-19 Japan Steel Works Ltd:The 厚肉超合金鋳塊の製造法
DE3737361A1 (de) * 1987-11-04 1989-05-24 Deutsche Forsch Luft Raumfahrt Nickel enthaltende legierungen, verfahren zu ihrer herstellung und ihre verwendung
US4877461A (en) * 1988-09-09 1989-10-31 Inco Alloys International, Inc. Nickel-base alloy
GB2307483B (en) * 1993-11-10 1998-07-08 United Technologies Corp Crack-resistant high strength super alloy articles
US5679180A (en) * 1995-06-22 1997-10-21 United Technologies Corporation γ strengthened single crystal turbine blade alloy for hydrogen fueled propulsion systems

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4908069A (en) * 1987-10-19 1990-03-13 Sps Technologies, Inc. Alloys containing gamma prime phase and process for forming same
US5169463A (en) * 1987-10-19 1992-12-08 Sps Technologies, Inc. Alloys containing gamma prime phase and particles and process for forming same
FR2628349A1 (fr) * 1988-03-09 1989-09-15 Snecma Procede de forgeage de pieces en superalliage a base de nickel
EP0392484A1 (en) * 1989-04-14 1990-10-17 Inco Alloys International, Inc. Corrosion-resistant nickel-chromium-molybdenum alloys
EP0492517A1 (en) * 1990-12-21 1992-07-01 Nippon Steel Corporation Alloy and composite steel tube with corrosion resistance in combustion environment where vanadium sodium sulphur, and chlorine are present
US5470371A (en) * 1992-03-12 1995-11-28 General Electric Company Dispersion strengthened alloy containing in-situ-formed dispersoids and articles and methods of manufacture
US5863494A (en) * 1995-11-17 1999-01-26 Asea Brown Boveri Ag Iron-nickel superalloy of the type in 706
US6132535A (en) * 1999-10-25 2000-10-17 Mitsubishi Heavy Industries, Ltd. Process for the heat treatment of a Ni-base heat-resisting alloy
US6576068B2 (en) 2001-04-24 2003-06-10 Ati Properties, Inc. Method of producing stainless steels having improved corrosion resistance
US20090285692A1 (en) * 2008-03-17 2009-11-19 Kabushiki Kaisha Toshiba Ni-base alloy for turbine rotor of steam turbine and turbine rotor of steam turbine
US8828313B2 (en) 2008-03-17 2014-09-09 Kabushiki Kaisha Toshiba Ni-base alloy for turbine rotor of steam turbine and turbine rotor of steam turbine
US20090257865A1 (en) * 2008-03-31 2009-10-15 Kabushiki Kaisha Toshiba Ni-base alloy for turbine rotor of steam turbine and turbine rotor of steam turbine
CN104278175A (zh) * 2013-07-12 2015-01-14 大同特殊钢株式会社 高温强度优异的能够热锻造的Ni基超合金
US20150284823A1 (en) * 2013-07-12 2015-10-08 Daido Steel Co., Ltd. Hot-forgeable ni-based superalloy excellent in high temperature strength
US9738953B2 (en) * 2013-07-12 2017-08-22 Daido Steel Co., Ltd. Hot-forgeable Ni-based superalloy excellent in high temperature strength
CN105463257A (zh) * 2015-12-08 2016-04-06 南通金源智能技术有限公司 一种镍基高温合金粉
US11193186B2 (en) 2017-07-28 2021-12-07 Vdm Metals International Gmbh High-temperature nickel-base alloy
US11753701B2 (en) 2018-12-27 2023-09-12 Siemens Energy Global GmbH & Co. KG Nickel-based alloy for additive manufacturing and method
CN111575535A (zh) * 2020-05-14 2020-08-25 张家港广大特材股份有限公司 一种镍基高温合金及其制备方法
CN116145005A (zh) * 2023-02-09 2023-05-23 华能国际电力股份有限公司 一种高铬铁的镍铁基高温合金及其制备方法

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FR2200368A1 (enrdf_load_html_response) 1974-04-19
GB1404539A (en) 1975-09-03
DE2348248A1 (de) 1974-04-04
CA992852A (en) 1976-07-13
JPS559943B2 (enrdf_load_html_response) 1980-03-13
FR2200368B1 (enrdf_load_html_response) 1978-10-20
IT994765B (it) 1975-10-20

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