EP0460678A1 - Hitzebeständige Legierung auf Nickelbasis für Matrize - Google Patents

Hitzebeständige Legierung auf Nickelbasis für Matrize Download PDF

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Publication number
EP0460678A1
EP0460678A1 EP91109312A EP91109312A EP0460678A1 EP 0460678 A1 EP0460678 A1 EP 0460678A1 EP 91109312 A EP91109312 A EP 91109312A EP 91109312 A EP91109312 A EP 91109312A EP 0460678 A1 EP0460678 A1 EP 0460678A1
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EP
European Patent Office
Prior art keywords
phase
dies
alloy
nickel
volume
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP91109312A
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English (en)
French (fr)
Inventor
Mitsuru Koori
Masao Morishita
Katsuyuki Yoshikawa
Osamu Tsuda
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Kobe Steel Ltd
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Kobe Steel Ltd
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Publication of EP0460678A1 publication Critical patent/EP0460678A1/de
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • 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%

Definitions

  • This invention relates to nickel-based heat-resistant alloys for dies, and more particularly to a nickel-based heat-resistant alloy for dies which is usable, for instance, in isothermal forging of heat-resistant alloys, namely, in forging heat-resistant alloys in dies heated at high temperatures.
  • Ni-based superalloys are formed into turbine disks or the like by the superplastic working process. Dies for isothermal forging used in the process are subjected to severer conditions than are dies for ordinary hot forging.
  • the dies are always cooled in use for forging a heated work. Therefore, even if the actual forging temperature is 1000° C or above, the dies are not brought to such a high temperature.
  • the dies In isothermal forging, on the other hand, the dies must be maintained at the same temperature (constant temperature) as that for the work, and therefore cannot be cooled as in the ordinary forging. Thus, the dies are inevitably brought to exactly the same high temperature as the actual forging temperature of 1000 to 1150°C. In addition, due to the slow working rate in the isothermal forging, the dies used in the forging are kept in the high-temperature condition for a long time, which is about 10 hours per batch in actual forging cut.
  • the Mo-based alloy is poor in oxidation resistance and the Mo oxide formed on the surface of the alloy is evaporated at about 600 C, so that the dies made of the Mo-based alloy is gradually lost during isothermal forging.
  • the forging by use of Mo-based alloy dies has been carried out in a vacuum chamber or in an inert gas atmosphere.
  • general heat-resistant alloys have good oxidation resistance and can be used in the atmospheric air.
  • the general heat-resistant alloys are insufficient in high-temperature compressive strength at temperatures of 1000° C or above, so that the alloys, when adopted as a material for isothermal forging dies, must be used at temperatures below 1000° C.
  • Ni-based alloys are yet unsatisfactory in oxidation resistance and are impracticable, as will be shown by comparison of examples below.
  • these Ni-based alloys upon melting have such a high viscosity that, in the casting process for forming an ingot, the melt shows poor fluidity and low packability into the mold, resulting in high possibility of porosity produced in the ingot.
  • the presence of the porosity in the ingot of the Ni-based alloy means that the dies made from the ingot may be cracked starting from the porosity, during the use thereof. The possibility of cracking is fatal to the dies.
  • This invention contemplates overcoming the aforementioned problems associated with the heat-resistant alloys which have been proposed as a material for dies for isothermal forging to be used at high temperatures.
  • a nickel-based heat-resistant alloy for dies containing:
  • a nickel-based heat-resistant alloy for dies containing:
  • the nickel-based heat-resistant alloys for dies according to this invention have excellent strength, ductility and oxidation resistance, and are excellent in high-temperature strength at 1000°C or above. Therefore, the nickel-based heat-resistant alloys for dies exhibit high performance as a material for dies to be used for forging at high temperatures.
  • AI is an element which increases the strength of the alloy by forming the y' phase (Ni 3 Al) capable of imparting high-temperature strength and which improves greatly the oxidation resistance at high temperatures of 800 C or above by forming a dense Al 2 O 3 film on the surface of the alloy.
  • the Al 2 O 3 film for improving the oxidation resistance is little formed
  • the AI content exceeds 8.5 wt%, on the other hand, the y' phase is formed in excess, grains of phase (NiAl) are coarsened, and a eutectic reaction occurs, to lower the compressive deformation stress of the alloy and worsen the castability. Therefore, the AI content is set in the range from 3.0 to 8.5 wt%.
  • the y' phase can be strengthened not only by addition of AI but also by addition of Ti or Nb. It is thus possible to increase the high-temperature strength of the alloy by substituting Ti or Nb for part or the whole of AI in the alloy. In that case, Ti is added in an amount of from 1.7 to 4.8 wt.%, and Nb in an amount of from 0.87 to 2.5 wt%. When the Ti content is less than 1.7 wt% or the Nb content is less than 0.87 wt%, the effect of strengthening the ⁇ ' phase is slight.
  • the Ti content is more than 4.8 wt% or the Nb content is more than 2.5 wt%, on the other hand, there may result the problem of formation of an excess of the ⁇ ' phase or coarsening of ⁇ phase grains. Accordingly, the Ti content is from 1.7 to 4.8 wt%, and the Nb content is from 0.87 to 2.5 wt%.
  • Each of Mo and W serves for solution strengthening of the ⁇ phase of the matrix and, at the same time, for formation of an Mo- or W-enriched a phase, thereby enhancing the high-temperature strength of the alloy.
  • the y' phase is softened at a temperature of 950° C or above, and, in order to maintain the high-temperature strength of the alloy after the softening, the a phase rich in either of Mo and W (which are high-melting metals) should be dispersed in the alloy in a proportion of 2.5 to 11 % by volume.
  • the volume percentage of the a phase is less than 2.5%, the high-temperature strength will be low, whereas if the volume percentage exceeds 11%, a eutectic with coarsened a phase will crystallize to lower the compressive deformation stress of the alloy.
  • the Mo content is set in the range from 13 to 25.0 wt%, or, alternatively, part or the whole of the Mo in the alloy is replaced with 6.7 to 13 wt% of W. When both of the Mo and W contents are outside the respective ranges, it is impossible to obtain the a phase in the aforementioned volume percentage.
  • the substitutive element may be used in an amount (atom%) equal to that of the Al or Mo thus replaced, whereby the volume percentage of the y' phase or ⁇ phase can be easily controlled to within the desired range.
  • Zr is an element for improving the adhesion of the Al 2 O 3 film formed on the surface of the alloy and for attaining a remarkably enhanced oxidation resistance at high temperatures.
  • the Zr content is less than 0.01 wt%, the improving effect on oxidation resistance is slight, whereas a Zr content of more than 0.5 wt% leads to a lowered melting point.
  • the Zr content is therefore set in the range from 0.01 to 0.5 wt%.
  • Mn and Si which are characteristic elements according to this invention, improve the fluidity of the molten alloy through different actions thereof.
  • Mn is an element having a deoxidizing effect, and serves to remove solid oxides of AI or the like from the molten alloy, thereby increasing the fluidity of the molten alloy and preventing the formation of porosity in the resulting ingot.
  • Mn content is less than 0.04 wt%, this effect is weak, whereas use of more than 0.2 wt% of Mo results in poor oxidation resistance. Therefore, the Mn content is from 0.04 to 0.2 wt%.
  • Si improves the fluidity of the molten alloy by the presence of the element itself, and also has a deoxidizing effect on the molten alloy.
  • Si improves the adhesion of the Al 2 O 3 film formed on the surface of the alloy, thereby enhancing the high-temperature oxidation resistance of the alloy.
  • the Si content is less than 0.04 wt%, the above effects are produced only slightly, whereas an addition of more than 2.5 wt% of Si reduces toughness and may result in embrittlement.
  • the amount of Si to be added is from 0.04 to 2.5 wt%.
  • Hf improves markedly the high-temperature oxidation resistance of the alloy where the Al 2 O 3 film is formed on the surface of the alloy.
  • the Hf content is less than 0.03 wt%, the improving effect on the oxidation resistance is slight, whereas Hf contents of more than 2 wt% cause a lowering in the melting point of the alloy.
  • the Hf content is therefore from 0.03 to 2 wt%.
  • Ta is an element which improves high-temperature oxidation resistance.
  • the Ta content is less than 0.3 wt%, however, this effect is feeble.
  • the Ta content exceeds 3 wt% on the other hand, the alloy has a poorer high-temperature strength. Therefore, the Ta content is from 0.3 to 3 wt%.
  • Cr is an element for improving both oxidation resistance and ductility.
  • the Cr content of less than 3 wt% does not produce such an effect, whereas Cr contents of more than 10 wt% cause precipitation of the ⁇ phase with the result of a lowered ductility.
  • the Cr content is therefore from 3 to 10 wt%.
  • the conventional nickel-based heat-resistant alloys with their microstructures composed of the ⁇ phase and the -y' phase, have the problem that the y' phase is softened at a temperature of 950 °C or above.
  • the nickel-based heat-resistant alloy for dies according to this invention has both the y' phase and the a phase formed in the ⁇ phase matrix so as to solve the problem of softening.
  • the proportions of the y phase, y' phase and ⁇ phase in the alloy are set in the ranges of from 30 to 88%, from 12 to 60%, and from 2.5 to 11 % by volume, respectively, whereby an excellent high-temperature strength is obtainable.
  • the ⁇ ' phase and the ⁇ phase require a high stress for deformation.
  • the proportion of the y' phase should be not less than 12% by volume, and the proportion of the a phase not less than 2.5% by volume.
  • the proportion of the y' phase is more than 60% by volume or the proportion of the ⁇ phase is more than 11% by volume, a coarse eutectic will crystallize to give a lowered strength.
  • the proportion of the y phase is set in the range from 30 to 80% by volume.
  • Nickel alloys having the compositions as set forth in Table 1 below were melted and cast according to the usual process.
  • the alloys thus cast were subjected to high-temperature tensile tests at temperatures of 1050 C and 1150°C.
  • the alloys were subjected to oxidation resistance tests, in which a cycle of maintaining each alloy sample at 1200°C for 1 hour and then forcibly cooling the alloy was repeated 10 times, followed by measurement of the weight loss by corrosion to evaluate the oxidation resistance.
  • the prior art material No. 1 which is a Co-containing heat-resistant steel, is insufficient in high-temperature strength.
  • the prior art material No. 2 which is an Ni-based heat-resistant alloy having a y-y' two-phase structure and being an excellent material for aircraft engines, has an unsatisfactory strength at high temperatures such as 1050 C. Because of containing neither Si nor Mn, the prior art material No. 2 shows poor fluidity upon melting, and is liable to yield an ingot with porosity therein.
  • the prior art material No. 3 which is an Mo-based alloy called "TZM"
  • ZM Mo-based alloy
  • the comparative material 6 equivalent to the prior art material according to Japanese Patent Application Laid-Open (KOKAI) No. 62-50429 (1987), has a problem concerning oxidation resistance, due to the low Si content.
  • the comparative material No. 7 has a lowered melting point of 1225°C, as a result of an excessively high Zr content.
  • the comparative material No. 8 is poor in oxidation resistance and ductility, due to a low Zr content.
  • the comparative material No. 9 has a lowered melting point of 1225°C, as a result of an excessively high Zr content.
  • the comparative material No. 10 has a lowered melting point, because of an excessively high Hf content.
  • the comparative material No. 11 has a lowered strength due to an excess of Ta.
  • the comparative material No. 12 has a lowered ductility, as a result of an excess of Cr.
  • the comparative material No. 13 is unsatisfactory in strength, due to an insufficient Mo content.
  • the comparative material No. 14 has a lowered ductility, because of an excessively high Mo content.
  • the comparative material No. 15 is unsatisfactory in strength, due to an insufficient AI content.
  • the comparative material No. 16 has a lowered ductility, because of an excess of Al.
  • the comparative material No. 17 has a lowered ductility, due to an excessively high W content.
  • the material Nos. 18 to 24 which are nickel-based heat-resistant alloys for dies according to this invention, are excellent in strength, ductility and oxidation resistance, as shown in Table 2. These excellent properties prove that the alloys according to this invention have high performance as nickel-based heat-resistant alloys for dies to be used for forging at high temperatures.
  • Test pieces were prepared from the ingots, and were each served to a high-temperature fatigue test at 1100° C. The test results are shown in Figure 1.
  • the material No. 19 according to this invention (marked with 0) is superior in high-temperature fatigue strength to the prior art material No. 2 (marked with o) and the prior art material No. 4 (marked with ⁇ ). It proves that the nickel-based alloys according to this invention is excellent in high-temperature fatigue strength and has high performance as a nickel-based heat-resistant alloys for dies to be used for forging at high temperatures.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Forging (AREA)
EP91109312A 1990-06-07 1991-06-06 Hitzebeständige Legierung auf Nickelbasis für Matrize Withdrawn EP0460678A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP149312/90 1990-06-07
JP14931290A JPH0441641A (ja) 1990-06-07 1990-06-07 金型用ニッケル基超耐熱合金

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EP0460678A1 true EP0460678A1 (de) 1991-12-11

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1176222A2 (de) * 2000-06-30 2002-01-30 General Electric Company Wärmebehandlung von Matrizeeinsätzen bestehend aus Superlegierungen auf Nickel-Basis
CN103074523A (zh) * 2013-01-31 2013-05-01 安徽工业大学 一种用于高温疲劳性能检测的模具材料及其制备方法
CN111163876A (zh) * 2017-09-29 2020-05-15 日立金属株式会社 热锻材的制造方法
EP3719152A1 (de) * 2017-11-29 2020-10-07 Hitachi Metals, Ltd. Ni-basierte legierung für warmumformungsmatrize und warmschmiedegesenk mit verwendung davon
EP3719153A4 (de) * 2017-11-29 2021-04-07 Hitachi Metals, Ltd. Heissgepresste legierung auf nickelbasis, warmschmiedewerkzeug damit und herstellungsverfahren für geschmiedetes produkt
US11358209B2 (en) 2017-09-29 2022-06-14 Hitachi Metals, Ltd. Method for producing hot forged material

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6194802A (ja) * 1984-10-17 1986-05-13 Yokohama Rubber Co Ltd:The 乗用車用空気入りラジアルタイヤ
EP3543369B8 (de) * 2016-11-16 2022-08-03 Mitsubishi Heavy Industries, Ltd. Verfahren zur herstellung eines hochtemperaturstoffes aus einer legierung auf nickelbasis
JP6931112B2 (ja) * 2016-11-16 2021-09-01 三菱パワー株式会社 ニッケル基合金金型および該金型の補修方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3933483A (en) * 1972-07-14 1976-01-20 Kabushiki Kaisha Toyota Chuo Kenkyusho Silicon-containing nickel-aluminum-molybdenum heat resisting alloy
WO1987001395A1 (en) * 1985-08-30 1987-03-12 Hitachi Metals, Ltd. Nickel-base cast alloy for high-temperature forging die
US4740354A (en) * 1985-04-17 1988-04-26 Hitachi, Metals Ltd. Nickel-base alloys for high-temperature forging dies usable in atmosphere

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5635737A (en) * 1979-08-30 1981-04-08 Sumitomo Metal Ind Ltd Heat resistant nickel-base alloy
JPS60221542A (ja) * 1984-04-17 1985-11-06 Hitachi Metals Ltd 大気中で使用可能な高温鍛造金型用ニツケル基鋳造合金

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3933483A (en) * 1972-07-14 1976-01-20 Kabushiki Kaisha Toyota Chuo Kenkyusho Silicon-containing nickel-aluminum-molybdenum heat resisting alloy
US4740354A (en) * 1985-04-17 1988-04-26 Hitachi, Metals Ltd. Nickel-base alloys for high-temperature forging dies usable in atmosphere
WO1987001395A1 (en) * 1985-08-30 1987-03-12 Hitachi Metals, Ltd. Nickel-base cast alloy for high-temperature forging die

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
'METALS HANDBOOK' 1980 , AMERICAN SOCIETY FOR METALS , OHIO, US PAGE 532 J.M.MARDER "TOOLS FOR ISOTHERMAL FORGING" *

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1176222A2 (de) * 2000-06-30 2002-01-30 General Electric Company Wärmebehandlung von Matrizeeinsätzen bestehend aus Superlegierungen auf Nickel-Basis
EP1176222A3 (de) * 2000-06-30 2002-03-06 General Electric Company Wärmebehandlung von Matrizeeinsätzen bestehend aus Superlegierungen auf Nickel-Basis
CN103074523A (zh) * 2013-01-31 2013-05-01 安徽工业大学 一种用于高温疲劳性能检测的模具材料及其制备方法
CN111163876A (zh) * 2017-09-29 2020-05-15 日立金属株式会社 热锻材的制造方法
US11278953B2 (en) 2017-09-29 2022-03-22 Hitachi Metals, Ltd. Method for producing hot forged material
CN111163876B (zh) * 2017-09-29 2022-04-01 日立金属株式会社 热锻材的制造方法
US11358209B2 (en) 2017-09-29 2022-06-14 Hitachi Metals, Ltd. Method for producing hot forged material
EP3719152A1 (de) * 2017-11-29 2020-10-07 Hitachi Metals, Ltd. Ni-basierte legierung für warmumformungsmatrize und warmschmiedegesenk mit verwendung davon
EP3719152A4 (de) * 2017-11-29 2021-03-31 Hitachi Metals, Ltd. Ni-basierte legierung für warmumformungsmatrize und warmschmiedegesenk mit verwendung davon
EP3719153A4 (de) * 2017-11-29 2021-04-07 Hitachi Metals, Ltd. Heissgepresste legierung auf nickelbasis, warmschmiedewerkzeug damit und herstellungsverfahren für geschmiedetes produkt
US11326231B2 (en) 2017-11-29 2022-05-10 Hitachi Metals, Ltd. Ni-based alloy for hot-working die, and hot-forging die using same
US11692246B2 (en) 2017-11-29 2023-07-04 Proterial, Ltd. Ni-based alloy for hot-working die, and hot-forging die using same

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Publication number Publication date
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