EP4299776A1 - Tial-legierung zum schmieden, tial-legierungsmaterial sowie verfahren zur herstellung von tial-legierungsmaterial - Google Patents

Tial-legierung zum schmieden, tial-legierungsmaterial sowie verfahren zur herstellung von tial-legierungsmaterial Download PDF

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Publication number
EP4299776A1
EP4299776A1 EP22787917.8A EP22787917A EP4299776A1 EP 4299776 A1 EP4299776 A1 EP 4299776A1 EP 22787917 A EP22787917 A EP 22787917A EP 4299776 A1 EP4299776 A1 EP 4299776A1
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EP
European Patent Office
Prior art keywords
tial alloy
atomic
forging
phase
heat treatment
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.)
Pending
Application number
EP22787917.8A
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English (en)
French (fr)
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EP4299776A4 (de
Inventor
Takeo Miyamura
Masao Takeyama
Hirotoyo Nakashima
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kobe Steel Ltd
Tokyo Institute of Technology NUC
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Kobe Steel Ltd
Tokyo Institute of Technology NUC
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Priority claimed from JP2022008171A external-priority patent/JP2022164557A/ja
Application filed by Kobe Steel Ltd, Tokyo Institute of Technology NUC filed Critical Kobe Steel Ltd
Publication of EP4299776A1 publication Critical patent/EP4299776A1/de
Publication of EP4299776A4 publication Critical patent/EP4299776A4/de
Pending legal-status Critical Current

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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
    • C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
    • C22F1/18—High-melting or refractory metals or alloys based thereon
    • C22F1/183—High-melting or refractory metals or alloys based thereon of titanium or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C14/00—Alloys based on titanium

Definitions

  • the present invention relates to a TiAl alloy for forging, a TiAl alloy material, and a method for manufacturing a TiAl alloy material, and particularly to a TiAl alloy material having excellent oxidation resistance and creep strength, a TiAl alloy for forging with which such a TiAl alloy material can be obtained and which has excellent hot forgeability and can be subjected to die forging, and a method for manufacturing a TiAl alloy material.
  • Turbochargers for obtaining high combustion energy are employed in engines for transportation machines, industrial machines, and the like.
  • the use of a TiAl alloy which has excellent high-temperature resistance and is light weight, has been put to practical use as turbocharger members.
  • a related-art TiAl alloy such as a casting TiAl alloy is composed of a ⁇ phase having a face centered cubic lattice (FCC) structure as a crystal structure and an ⁇ phase having a hexagonal close-packed lattice (HCP) structure as a crystal structure.
  • the material structure of such a TiAl alloy is characterized in that a thin plate-like ⁇ phase precipitates in the ⁇ phase during a cooling process after a heat treatment, and a lamellar phase is formed.
  • the TiAl alloy for hot forging is added with a component that stabilizes a ⁇ phase having a body centered cubic lattice (BCC) structure that is easily deformed at a high temperature, and the ⁇ phase is responsible for most of the deformation, so that hot forging is possible.
  • BCC body centered cubic lattice
  • Patent Literature 1 discloses a forging TiAl alloy in which Nb, V, and B are added to Ti and Al and a grain size of a boride is specified.
  • Patent Literature 2 discloses a TiAl-based alloy containing Al and Nb in which relative amounts of additive components are adjusted, and a TiAl-based alloy in which Nb, V, Cr, and Mo are co-added to Ti and Al.
  • Patent Literature 3 discloses a titanium-aluminum-based alloy material containing Ti, Al, Nb, Mo and/or Mn, and B and/or C and/or Si and having a specified ⁇ /B2-Ti phase ratio.
  • Patent Literature 4 discloses a titanium aluminide alloy composed of titanium, aluminum, and niobium and having a predetermined lamellar structure.
  • Nb is an important element for improving oxidation resistance of the TiAl alloy, and Nb is added to many TiAl alloys for hot forging.
  • Nb is added alone to a material set to a high concentration of Al
  • the ⁇ phase cannot be sufficiently stabilized in a practical forging heating temperature range of lower than 1300°C. Therefore, in most of the related art, either “isothermal forging", which is a low-manufacturability working process, or "co-addition" of Nb and other ⁇ -stabilizing elements is used to form a sufficient ⁇ phase in the forging heating temperature range, and to ensure good hot forgeability.
  • the TiAl alloy for forging requires a heat treatment for adjusting the material structure after forging.
  • a heat treatment include two heat treatments including a high-temperature heat treatment for recrystallizing an ⁇ phase of a forged material and promoting an ⁇ single phase, and thereafter, a lower-temperature heat treatment for precipitating a ⁇ plate in the ⁇ phase and introducing a lamellar structure. Then, the material structure after the second heat treatment becomes the material structure of a TiAl product.
  • the ⁇ phase maintains the ⁇ phase at a high temperature, but becomes more ordered at around room temperature, and is sometimes referred to as a " ⁇ 2 phase".
  • the ⁇ phase becomes a "B2 structure" at around room temperature.
  • the description of the ⁇ phase and the ⁇ phase in the description of the present application does not particularly limit the temperature.
  • Examples of the hot forging for the TiAl alloy include general die forging in which a die is preheated to room temperature or several hundred Celsius degrees, and isothermal forging in which a die is heated to a temperature same as that of a forging material, such as 1200°C, and forged over time under conditions where a strain rate is slow, such as 10 -3 /sec.
  • a strain rate is slow, such as 10 -3 /sec.
  • Nb which is a ⁇ -stabilizing element and contributes to improving the oxidation resistance
  • the present invention has been made in view of such problems, and an object thereof is to provide a TiAl alloy for forging which has excellent hot forgeability and can be subjected to die forging, a TiAl alloy material obtained using the TiAl alloy for forging and having excellent oxidation resistance and high-temperature creep strength due to addition of Nb, and a method for manufacturing a TiAl alloy material for obtaining the TiAl alloy material.
  • a TiAl alloy for forging which has excellent hot forgeability and can be subjected to die forging, a TiAl alloy material obtained by forging the TiAl alloy for forging and having excellent oxidation resistance and high-temperature creep strength, and a method for manufacturing a TiAl alloy material for obtaining the TiAl alloy material.
  • the present embodiment will be described in detail.
  • the present invention is not limited to the embodiments described below, and can be optionally modified and implemented without departing from the scope of the present invention.
  • the inventors of the present invention have found that by co-adding Nb and Cu at a specified concentration, deformability of an ⁇ phase during hot forging can be improved, and the amount of a ⁇ phase after a heat treatment can be reduced while sufficiently ensuring the ⁇ phase during forging.
  • Al is an element that promotes the formation of an Al 2 O 3 protective film on the surface of the TiAl alloy.
  • base oxidation resistance is improved, a ⁇ phase is stabilized, and a large amount of ⁇ plate is formed in the ⁇ phase to form a lamellar structure. Accordingly, creep strength of the TiAl alloy can be improved.
  • the concentration of Al in the TiAl alloy is 42.0 atomic% or more, and preferably 42.5 atomic% or more.
  • the concentration of Al in the TiAl alloy is more than 43.6 atomic%, the ⁇ phase is excessively stabilized and ⁇ grains are formed, making it impossible to obtain the desired creep strength, and decreasing the hot forgeability. Therefore, the concentration of Al is 43.6 atomic% or less, and preferably 43.5 atomic% or less.
  • Cu is an element that has an effect of stabilizing the ⁇ phase at a high temperature, and appropriately controlling a content of Cu in the TiAl alloy is the most important requirement in the present embodiment.
  • Cu is an element that has an effect of improving the deformability of the ⁇ phase during hot forging and forming the ⁇ phase only at a hot forging temperature.
  • the concentration of Cu in the TiAl alloy is less than 0.5 atomic%, the desired hot forgeability cannot be obtained. Therefore, the concentration of Cu is 0.5 atomic% or more, and preferably 0.7 atomic% or more.
  • the concentration of Cu in the TiAl alloy is more than 2.0 atomic%, the ⁇ phase remains after the heat treatment, and the desired creep strength cannot be obtained. Therefore, the concentration of Cu is 2.0 atomic% or less, and preferably 1.2 atomic% or less.
  • Nb is an element that has an effect of improving the oxidation resistance of the TiAl alloy.
  • the concentration of Nb in the TiAl alloy is 3.0 atomic% or more, and preferably 4.5 atomic% or more.
  • the concentration of Nb in the TiAl alloy is more than 7.0 atomic%, the ⁇ phase is unstable, the formation of lamellar grains cannot be ensured, and the high-temperature creep strength decreases. Therefore, the concentration of Nb is 7.0 atomic% or less, and preferably 6.0 atomic% or less.
  • the balance of the TiAl alloy for forging according to the present embodiment, excluding the above components, is Ti and unavoidable impurities.
  • the unavoidable impurities include C, N, O, H, Cl, Fe, Si, Mg, Ca, Mn, Cr, V, Sn, Bi, Ni, Zr, Na, Be, and Zn.
  • a TiAl alloy material according to the present embodiment is obtained by forging the above [1. TiAl alloy for forging] and performing a predetermined heat treatment.
  • a composition of the TiAl alloy material is the same as the composition of the above TiAl alloy for forging.
  • ⁇ phase fraction (area ratio of ⁇ phase): 0.5% or more and 15.0% or less>
  • the TiAl alloy material according to the present invention has a ⁇ phase fraction controlled within a predetermined range.
  • the ⁇ phase fraction is less than 0.5%, grain boundary cracking occurs due to growth of the ⁇ phase. Therefore, the ⁇ phase fraction is 0.5% or more, and preferably 1.0% or more.
  • the ⁇ phase fraction is 15.0% or less, preferably 10.0% or less, and more preferably 5.0% or less.
  • the ⁇ phase fraction can be obtained, for example, by taking a backscattered electron image of a cross section of the TiAl material using a scanning electron microscope (SEM) and calculating an area ratio of a ⁇ phase region with respect to the entire field of view. It is preferable that the backscattered electron image is photographed at a plurality of any cross sections, and the area ratio of the ⁇ phase in each cross section is obtained, and as the ⁇ phase fraction, it is preferable to adopt an average area ratio obtained by averaging these area ratios.
  • SEM scanning electron microscope
  • a method for manufacturing a TiAl alloy material according to the present embodiment includes a step of forging the TiAl alloy for forging according to the present embodiment described in the above [1. TiAl alloy for forging] to obtain a forged material, and a step of subjecting the forged material to a heat treatment at a predetermined temperature.
  • the method for manufacturing a TiAl alloy material according to the present embodiment will be described in detail.
  • forging conditions for forging the TiAl alloy for forging are not particularly limited.
  • the forging step includes, for example, a step of heating an ingot of TiAl alloy for forging to a predetermined temperature and a step of applying a pressure to the heated ingot.
  • the forged material obtained by the above forging step is subjected to two heat treatments.
  • the purpose of a first heat treatment step is to bring the metal structure closer to an ⁇ single phase structure.
  • the temperature in the first heat treatment step is lower than 1200°C, the metal structure may not be brought close to a single ⁇ phase. Therefore, the temperature in the first heat treatment step is 1200°C or higher, and preferably 1250°C or higher.
  • the temperature in the first heat treatment step is 1350°C or lower, and preferably 1300°C or lower.
  • a second heat treatment step after the first heat treatment step is to form a ⁇ phase to form a lamellar structure [ ⁇ 2+ ⁇ ].
  • the temperature in the second heat treatment step is lower than 850°C, the formation of the ⁇ phase is insufficient, or the heat treatment time is longer, resulting in poor industrial productivity. Therefore, the temperature in the second heat treatment step is 850°C or higher, and preferably 875°C or higher.
  • the temperature in the second heat treatment step is 1000°C or lower, and preferably 975°C or lower.
  • TiAl Alloy Material can be obtained by forging a TiAl alloy having the composition specified in the above [1. TiAl alloy for forging] and subjecting the obtained forged material to the above first heat treatment step and second heat treatment step.
  • the TiAl alloy material according to the present embodiment can be subjected to die forging, is obtained from a TiAl alloy for forging having excellent hot forgeability, has excellent high-temperature resistance, is lightweight, and has excellent creep strength, and is thus preferably used as a member that requires such material properties. Therefore, the TiAl alloy material according to the present embodiment can be suitably used, for example, as a member for an internal combustion engine such as a turbine for transportation machines and industrial machines.
  • TiAl alloy ingots each weighing about 9 kg were prepared by a cold crucible induction melting (CCIM) method.
  • CCIM cold crucible induction melting
  • Each of the TiAl alloy ingots had a tapered cylinder shape, and had an axial diameter of 110 mm at one end face, an axial diameter of 85 mm at the other end face, and an axial length of 300 mm.
  • a cylindrical test piece having a diameter of 80 mm and an axial length of 120 mm was prepared from the obtained TiAl alloy ingot and was held at a temperature of 1250°C or higher for 0.5 hours or longer, and then uniaxial compression processing was performed with respect to the axial direction of the test piece by using a pressing machine at a rolling reduction of 70% to 80%, to prepare a disc-shaped forged material. Even when the rolling reduction is changed by about 10%, it is considered that the evaluation results for the hot forgeability and the creep strength are not greatly influenced.
  • the obtained forged material was cut at an approximate center position of the disc shape in the radial direction, and was divided into two semilunar forged materials. Then, for each member, cracks in a cross section region having a length of at least 120 mm in the radial direction were observed and the number of cracks with a depth of 2 mm or more was counted. Then, a crack number density was calculated by dividing the number of cracks by the total length (24 cm to 26 cm) in the longitudinal direction in the cross section of the two forged materials obtained by cutting.
  • the above test material was subjected to two heat treatments under various conditions also shown in Table 1 below.
  • the purpose of the first heat treatment is to bring the structure close to an ⁇ single phase structure, and the purpose of the second heat treatment is to form a ⁇ phase to form a lamellar structure [ ⁇ 2+ ⁇ ].
  • the heat treatment was performed by changing the post-heat treatment temperature every about 30°C, the material structure was observed for all test pieces, and the lowest temperature among the test pieces that underwent the ⁇ single phase was adopted.
  • the second heat treatment was performed at conditions including a temperature of 950°C for 1 hour or at a temperature of 900°C for 3 hours to obtain a heat-treated material.
  • a flanged creep test piece having a total length of 80 mm, a parallel portion diameter of 6 mm, a length of 30 mm, and a screw portion (both ends of the test piece in the longitudinal direction) M12 was prepared from the obtained heat-treated material, and a creep rate test was performed with a single type creep tester.
  • the test conditions were a temperature of 800°C and a stress of 150 MPa, and a minimum creep rate was obtained based on test data.
  • the minimum creep rate is an index of how much deformation occurs at a high temperature, and is a value generally used as one of indices for the creep strength.
  • a creep test piece was taken from the heat-treated material obtained by the above heat treatment, and then the surface of the remaining material at the end in the longitudinal direction was mirror-finished by mechanical and chemical polishing to prepare a test piece for structure observation.
  • a backscattered electron image of the above test piece was taken using a scanning electron microscope (SEM) at a magnification of 400 times. The photographing was performed near the center of the plate thickness of the test piece, and three photographs were obtained for each test piece. Then, for each SEM photograph, the presence of the ⁇ phase was identified based on a bright contrast (Z contrast reflecting composition information) peculiar to the ⁇ phase, and the ⁇ phase region was colored separately using image processing software. Thereafter, the area ratio of the ⁇ phase in the entire field of view was obtained using image analysis software "Image Pro Plus" (manufactured by Media Cybernetics), and an average area ratio of the ⁇ phase in the three photographs was calculated.
  • SEM scanning electron microscope
  • the composition of the TiAl alloy satisfies the requirements specified in the present invention, and the area ratio of the ⁇ phase of the TiAl alloy material also satisfies the requirements specified in the present invention, so that both good hot forgeability and high-temperature creep strength can be achieved.
  • Comparative Example No. 6 the concentration of Al is more than the upper limit of the range of the present invention, so that the hot forgeability decreases.
  • Comparative Example No. 7 the concentration of Al is more than the upper limit of the range of the present invention, so that the hot forgeability is poor, and brittle fracture is exhibited at a high temperature, so that brittle rupture occurs immediately after the creep test, and the creep strength remarkably decreases.
  • Comparative Example No. 8 the concentration of Al and the concentration of Nb are less than the lower limits of the range of the present invention and the concentration of Cu is more than the upper limit of the range of the present invention, so that the creep strength decreases.
  • the concentration of Nb is less than the lower limit of the range of the present invention and the concentration of Cu is more than the upper limit of the range of the present invention, so that the creep strength decreases.
  • the concentration of Cu is more than the upper limit of the range of the present invention, so that the ⁇ phase remains after the first and second heat treatment steps, and the average area ratio of the ⁇ phase is more than the range specified in the present invention, and as a result, the creep strength decreases.
  • Fig. 1 is a graph showing a relationship between Examples and Comparative Examples, where the vertical axis represents the concentration of Cu and the horizontal axis represents the concentration of Al.
  • white one indicates good creep strength, and black one indicates poor creep strength.
  • ⁇ indicates good hot forgeability
  • 0 indicates poor hot forgeability. That is, “ ⁇ ” indicates that the hot forgeability and the creep strength are good, and represents Examples Nos. 1 to 5.
  • "•” indicates that the hot forgeability is good but the creep strength decreases, and represents Comparative Examples Nos. 8, 9 and 10.
  • "0” indicates that the creep strength is good but the hot forgeability decreases, and represents Comparative Example No. 6.
  • ⁇ indicates that the hot forgeability and the creep strength decrease, and represents Comparative Example No. 7.
  • a range indicated by the dashed line in the drawing is a region in which the concentration of Cu and the concentration of Al are within the ranges of the present invention.
  • Fig. 2 is a graph showing a relationship between Examples and Comparative Examples, where the vertical axis represents the minimum creep rate and the horizontal axis represents the ⁇ phase fraction.
  • " ⁇ ", "•”, “0” and “ ⁇ ” are the same as in Fig. 1 .
  • Comparative Example 7 indicated by “ ⁇ ” rupture occurs instantaneously immediately after the start of the test, so that " ⁇ ” is indicated in the figure, indicating that the creep rate is extremely high.
  • a range indicated by the dashed line in the figure is a region in which the ⁇ phase fraction is within the range of the present invention and the minimum creep rate is acceptable.
  • the TiAl alloy material obtained by the manufacturing method according to the present invention using the TiAl alloy for forging according to the present invention shows a tendency that the smaller the remaining ⁇ phase fraction, the better the minimum creep rate. If the ⁇ phase fraction is 5% or less, an even better minimum creep rate can be obtained in the present invention. If the ⁇ phase fraction is less than 0.5%, it is shown that the minimum creep rate increases (worsens) or the forgeability decreases.

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EP22787917.8A 2021-04-16 2022-03-14 Tial-legierung zum schmieden, tial-legierungsmaterial sowie verfahren zur herstellung von tial-legierungsmaterial Pending EP4299776A4 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2021070003 2021-04-16
JP2022008171A JP2022164557A (ja) 2021-04-16 2022-01-21 鍛造用ＴｉＡｌ合金、ＴｉＡｌ合金材及びＴｉＡｌ合金材の製造方法
PCT/JP2022/011450 WO2022219991A1 (ja) 2021-04-16 2022-03-14 鍛造用ＴｉＡｌ合金、ＴｉＡｌ合金材及びＴｉＡｌ合金材の製造方法

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EP4299776A1 true EP4299776A1 (de) 2024-01-03
EP4299776A4 EP4299776A4 (de) 2024-08-21

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JP2024126296A (ja) * 2023-03-07 2024-09-20 三菱重工航空エンジン株式会社 ＴｉＡｌ基合金およびその製造方法

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JP2952924B2 (ja) * 1990-01-30 1999-09-27 日本鋼管株式会社 ＴｉＡｌ基耐熱合金及びその製造方法
JP2817427B2 (ja) * 1991-01-08 1998-10-30 三菱マテリアル株式会社 強度および延性に優れたＴｉＡｌ金属間化合物系Ｔｉ合金の製造法
DE102007051499A1 (de) 2007-10-27 2009-04-30 Mtu Aero Engines Gmbh Werkstoff für ein Gasturbinenbauteil, Verfahren zur Herstellung eines Gasturbinenbauteils sowie Gasturbinenbauteil
DE102007060587B4 (de) 2007-12-13 2013-01-31 Helmholtz-Zentrum Geesthacht Zentrum für Material- und Küstenforschung GmbH Titanaluminidlegierungen
JP2009215631A (ja) * 2008-03-12 2009-09-24 Mitsubishi Heavy Ind Ltd ＴｉＡｌ基合金及びその製造方法並びにそれを用いた動翼
DE102015103422B3 (de) * 2015-03-09 2016-07-14 LEISTRITZ Turbinentechnik GmbH Verfahren zur Herstellung eines hochbelastbaren Bauteils aus einer Alpha+Gamma-Titanaluminid-Legierung für Kolbenmaschinen und Gasturbinen, insbesondere Flugtriebwerke
EP3508594B8 (de) 2016-09-02 2021-06-16 IHI Corporation Tial-legierung und verfahren zur herstellung davon
JP2021070003A (ja) 2019-11-01 2021-05-06 Ｗｅｆ技術開発株式会社 イオン水生成具
CN113843947B (zh) 2020-06-25 2023-07-28 株式会社大镐技术 透镜及模具移送系统

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