JPWO2006104059A1 - Cobalt-free Ni-base superalloy - Google Patents
Cobalt-free Ni-base superalloy Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D27/00—Treating the metal in the mould while it is molten or ductile ; Pressure or vacuum casting
- B22D27/04—Influencing the temperature of the metal, e.g. by heating or cooling the mould
- B22D27/045—Directionally solidified castings
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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
- C22C19/007—Alloys based on nickel or cobalt with a light metal (alkali metal Li, Na, K, Rb, Cs; earth alkali metal Be, Mg, Ca, Sr, Ba, Al Ga, Ge, Ti) or B, Si, Zr, Hf, Sc, Y, lanthanides, actinides, as the next major constituent
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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%
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C30/00—Alloys containing less than 50% by weight of each constituent
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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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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01D—NON-POSITIVE DISPLACEMENT MACHINES OR ENGINES, e.g. STEAM TURBINES
- F01D5/00—Blades; Blade-carrying members; Heating, heat-insulating, cooling or antivibration means on the blades or the members
- F01D5/12—Blades
- F01D5/28—Selecting particular materials; Particular measures relating thereto; Measures against erosion or corrosion
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F05—INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
- F05D—INDEXING SCHEME FOR ASPECTS RELATING TO NON-POSITIVE-DISPLACEMENT MACHINES OR ENGINES, GAS-TURBINES OR JET-PROPULSION PLANTS
- F05D2300/00—Materials; Properties thereof
- F05D2300/10—Metals, alloys or intermetallic compounds
- F05D2300/12—Light metals
- F05D2300/121—Aluminium
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F05—INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
- F05D—INDEXING SCHEME FOR ASPECTS RELATING TO NON-POSITIVE-DISPLACEMENT MACHINES OR ENGINES, GAS-TURBINES OR JET-PROPULSION PLANTS
- F05D2300/00—Materials; Properties thereof
- F05D2300/10—Metals, alloys or intermetallic compounds
- F05D2300/13—Refractory metals, i.e. Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, W
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F05—INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
- F05D—INDEXING SCHEME FOR ASPECTS RELATING TO NON-POSITIVE-DISPLACEMENT MACHINES OR ENGINES, GAS-TURBINES OR JET-PROPULSION PLANTS
- F05D2300/00—Materials; Properties thereof
- F05D2300/10—Metals, alloys or intermetallic compounds
- F05D2300/13—Refractory metals, i.e. Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, W
- F05D2300/131—Molybdenum
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F05—INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
- F05D—INDEXING SCHEME FOR ASPECTS RELATING TO NON-POSITIVE-DISPLACEMENT MACHINES OR ENGINES, GAS-TURBINES OR JET-PROPULSION PLANTS
- F05D2300/00—Materials; Properties thereof
- F05D2300/10—Metals, alloys or intermetallic compounds
- F05D2300/13—Refractory metals, i.e. Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, W
- F05D2300/132—Chromium
Abstract
Ｃｒ:１．０−１０ｗｔ％、Ｍｏ:０．１−３．５ｗｔ％、Ｗ:７．５−１０ｗｔ％、Ａｌ:４．０−８ｗｔ％、Ｔａ、ＮｂおよびＴｉの少なくとも１種:１２ｗｔ％以下、Ｈｆ:０−２．０ｗｔ％、Ｒｅ:０．１−５．０ｗｔ％を含有し、残部がＮｉと不可避的不純物からなる組成を有し、長時間にわたり組織安定性が高く高温におけるクリープ特性が優れ、しかも放射能汚染等に対するメンテナンスが容易な原子力発電等のタービンブレードやタービンベーンとして好適なＣｏを含まないＮｉ基超合金とする。Cr: 1.0-10 wt%, Mo: 0.1-3.5 wt%, W: 7.5-10 wt%, Al: 4.0-8 wt%, at least one of Ta, Nb and Ti: 12 wt% In the following, Hf: 0-2.0 wt%, Re: 0.1-5.0 wt%, with the balance being composed of Ni and inevitable impurities, high structure stability over a long period of time and high temperature creep A Ni-based superalloy containing no Co and suitable for turbine blades and turbine vanes for nuclear power generation and the like having excellent characteristics and easy maintenance for radioactive contamination and the like.
Description
この出願の発明は、ジェットエンジン、産業用ガスタービンなど高温機器に用いる耐熱合金であるＮｉ基超合金に関するものであり、さらに詳しくは、原子力発電等のタービンブレードやタービンベーンとして好適なＣｏ（コバルト）を含まない、いわゆるコバルトフリーのＮｉ（ニッケル）基超合金に関するものである。 The invention of this application relates to a Ni-base superalloy, which is a heat-resistant alloy used in high-temperature equipment such as jet engines and industrial gas turbines, and more specifically, Co (cobalt) suitable as a turbine blade or turbine vane for nuclear power generation or the like. ) And a so-called cobalt-free Ni (nickel) -base superalloy.
Ｎｉ基超合金は、高温での組織安定性やクリープ特性が優れていることから高温機器の材料として幅広く利用されており特許出願もなされている（特許文献１および２）。 Ni-base superalloys are widely used as materials for high-temperature equipment because of their excellent structure stability and creep characteristics at high temperatures, and patent applications have been filed (Patent Documents 1 and 2).
特に、最近では原子力発電のタービンブレードやタービンベーン等の好適な材料として期待されているが、この耐熱特性に優れたＮｉ基超合金には多量のＣｏ（コバルト）が含有されている。ＣｏはＡｌ、Ｔａ等のガンマ母相に対する高温下での固溶限を大きくするとともに熱処理によって微細なガンマプライム相を分散析出して高温強度を向上するという優れた機能を有しているため高温で使用するＮｉ基超合金には不可欠な成分と考えられてきた。ところが、Ｃｏは半減期が長いためＣｏが含有されているＮｉ基超合金がもし放射能汚染された場合にはメンテナンスが大変面倒になる。したがって、Ｎｉ基超合金を原子力発電等の放射能汚染の可能性がある高温機器の部材として使用するに際し、半減期の長いＣｏを含有しなくてもＣｏを含有したものと同等あるいはそれ以上のクリープ強度特性を有するＮｉ基超合金の実現が望まれていた。
この出願の発明は以上のとおりの背景を踏まえてなされたものであって、原子力発電のタービンブレードやタービンベーン等に好適な長時間にわたり組織安定性が高く、高温におけるクリープ特性が優れたコバルトフリー（Ｃｏを含有しない）のＮｉ基超合金を提供することを課題とするものである。 The invention of this application was made on the basis of the background as described above, and is cobalt-free that has high structural stability over a long period of time suitable for nuclear power turbine blades, turbine vanes, etc., and excellent creep characteristics at high temperatures. An object of the present invention is to provide a Ni-base superalloy (containing no Co).
この出願の発明は上記の課題を解決するものとして、第１には、Ｃｒ:１．０〜１０．０ｗｔ％、Ｍｏ:０．１〜３．５ｗｔ％、Ｗ:７．５〜１０．０ｗｔ％、Ａｌ:４．０〜８．０ｗｔ％、Ｔａ、ＮｂおよびＴｉの少なくとも１種:１２．０ｗｔ％以下、Ｈｆ:０〜２．０ｗｔ％、Ｒｅ:０．１〜５．０ｗｔ％を含有し、残部がＮｉと不可避的不純物からなる組成を有するＮｉ基超合金を提供する。 The invention of this application is to solve the above problems. First, Cr: 1.0-10.0 wt%, Mo: 0.1-3.5 wt%, W: 7.5-10.0 wt% %, Al: 4.0 to 8.0 wt%, at least one of Ta, Nb and Ti: 12.0 wt% or less, Hf: 0 to 2.0 wt%, Re: 0.1 to 5.0 wt% And a Ni-base superalloy having a composition in which the balance is made of Ni and inevitable impurities.
第２には、Ｃｒ:４．０〜６．０ｗｔ％、Ｍｏ:１．０〜３．０ｗｔ％、Ｗ:７．６〜８．５ｗｔ％、Ａｌ:４．５〜６．０ｗｔ％、Ｔａ、ＮｂおよびＴｉの少なくとも１種:４．０〜１０．０ｗｔ％以下、Ｈｆ:０．１〜１．６ｗｔ％、Ｒｅ:１．５〜３．５ｗｔ％を含有し、残部がＮｉと不可避的不純物からなる組成を有するＮｉ基超合金を提供する。 Second, Cr: 4.0-6.0 wt%, Mo: 1.0-3.0 wt%, W: 7.6-8.5 wt%, Al: 4.5-6.0 wt%, Ta At least one of Nb and Ti: 4.0 to 10.0 wt% or less, Hf: 0.1 to 1.6 wt%, Re: 1.5 to 3.5 wt%, and the balance is inevitable with Ni Provided is a Ni-base superalloy having a composition comprising impurities.
第３には、上記のＮｉ基超合金において、その組成に、さらに、Ｓｉ：０．３ｗｔ％以下、Ｖ：３ｗｔ％以下、Ｚｒ：３ｗｔ％以下、Ｃ：０．３ｗｔ％以下、Ｂ：０．２ｗｔ％以下、Ｙ：０．２ｗｔ％以下、Ｌａ：０．２ｗｔ％以下、Ｃｅ：０．２ｗｔ％以下の１種以上を含有することを特徴とするＮｉ基超合金を提供する。 Third, in the above Ni-base superalloy, the composition further includes Si: 0.3 wt% or less, V: 3 wt% or less, Zr: 3 wt% or less, C: 0.3 wt% or less, B: 0 Provided is a Ni-base superalloy characterized by containing at least one of 2 wt% or less, Y: 0.2 wt% or less, La: 0.2 wt% or less, and Ce: 0.2 wt% or less.
第４には、上記いずれかのＮｉ基超合金を、普通鋳造法、一方向凝固法、あるいは単結晶凝固法により鋳造することを特徴とするＮｉ基超合金の製造方法。 Fourth, a method for producing a Ni-base superalloy, characterized in that any of the above-mentioned Ni-base superalloys is cast by a normal casting method, a unidirectional solidification method, or a single crystal solidification method.
第５には、鋳造後に、１２６０〜１３００℃で２０分〜２時間の予備熱処理を施し、１３００〜１３５０℃での３〜１０時間の溶体化処理、１０５０〜１１５０℃での２〜８時間の１次時効処理並びに８００〜９００℃での１０〜２４時間の２次時効処理を施すことを特徴とするＮｉ基超合金の製造方法。 Fifth, after casting, pre-heat treatment is performed at 1260 to 1300 ° C. for 20 minutes to 2 hours, solution treatment at 1300 to 1350 ° C. for 3 to 10 hours, and heat treatment at 1050 to 1150 ° C. for 2 to 8 hours. A method for producing a Ni-base superalloy characterized by performing a primary aging treatment and a secondary aging treatment at 800 to 900 ° C. for 10 to 24 hours.
第６には、上記いずれかに記載のＮｉ基超合金を少くともその構成の一部としていることを特徴とするタービンブレードあるいはタービンベーン部品。 Sixth, a turbine blade or turbine vane component characterized in that the Ni-base superalloy described in any of the above is at least a part of its configuration.
この出願の発明は、上記のとおりの特徴を持つものであるが、以下にその実施の形態について詳細に説明する。 The invention of this application has the characteristics as described above, and the embodiments thereof will be described in detail below.
ＣｏはＡｌ、Ｔａ等のガンマ母相に対する高温下での固溶限を大きくするとともに熱処理によって微細なガンマプライム相を分散析出して高温強度を向上するという機能を有しているため高温での組織安定性やクリープ特性が優れたＮｉ基超合金には不可欠な成分と考えられていた。しかしながら、この出願の発明ではこれまで高強度Ｎｉ基超合金において不可欠であると考えられてきたＣｏを添加しないでも、Ｎｉ基超合金を特定の組成にすることにより、すなわち、Ｃｒ:０〜１０．０ｗｔ％、Ｍｏ:０．１〜３．５ｗｔ％、Ｗ:７．６〜１０．０ｗｔ％、Ａｌ:４．０〜７．０ｗｔ％、Ｔａ、ＮｂおよびＴｉの少なくとも１種:１２．０ｗｔ％以下、Ｈｆ:０〜２．０ｗｔ％、Ｒｅ:０．１〜５．０ｗｔ％を含有し、残部がＮｉと不可避的不純物からなる組成にすることにより、第２世代Ｎｉ基単結晶合金として使用実績のあるＣｏを含んだＣＭＳＸ−４に比較しても高いクリープ強度を有したＮｉ基超合金を生成することが可能である。 Co has the function of increasing the solid solubility limit at high temperatures for gamma matrix phases such as Al and Ta, and dispersing and precipitating fine gamma prime phases by heat treatment to improve the high temperature strength. It was considered an indispensable component for a Ni-base superalloy having excellent structure stability and creep characteristics. However, in the invention of this application, even without adding Co, which has been considered to be indispensable in high-strength Ni-base superalloys so far, by making the Ni-base superalloy a specific composition, that is, Cr: 0 to 10 0.0 wt%, Mo: 0.1-3.5 wt%, W: 7.6-10.0 wt%, Al: 4.0-7.0 wt%, at least one of Ta, Nb and Ti: 12.0 wt %, Hf: 0 to 2.0 wt%, Re: 0.1 to 5.0 wt%, and the balance is made of Ni and inevitable impurities, thereby producing a second generation Ni-based single crystal alloy. It is possible to produce a Ni-base superalloy having a high creep strength even compared to CMSX-4 containing Co, which has been used.
また、この出願の発明ではＮｉ基超合金を用いる高温機器の特定の用途により、たとえば、Ｓｉ:０．３ｗｔ％以下、Ｖ：３ｗｔ％以下、Ｚｒ:３ｗｔ％以下、Ｃ：０．３ｗｔ％以下、Ｂ：０．２ｗｔ％以下、Ｙ：０．２ｗｔ％以下、Ｌａ：０．２ｗｔ％以下、Ｃｅ:０．２ｗｔ％以下の少なくとも１種以上を添加することにより、様々な用途に応じた製品の物性をさらに向上させることが可能である。 In the invention of this application, depending on the specific application of the high-temperature equipment using the Ni-base superalloy, for example, Si: 0.3 wt% or less, V: 3 wt% or less, Zr: 3 wt% or less, C: 0.3 wt% or less , B: 0.2 wt% or less, Y: 0.2 wt% or less, La: 0.2 wt% or less, Ce: 0.2 wt% or less It is possible to further improve the physical properties.
この出願の発明のコバルトフリーのＮｉ基超合金は、高温での組織安定性やクリープ特性が優れており、特にタービンブレードまたはタービンベーン部品の製造に好適である。 The cobalt-free Ni-base superalloy of the invention of this application has excellent structure stability and creep characteristics at high temperatures, and is particularly suitable for the production of turbine blades or turbine vane parts.
この出願の発明のＮｉ基超合金の成分の最適な含有範囲を下記に示す。 The optimum content range of the Ni-base superalloy components of the invention of this application is shown below.
Ｃｒ（クロム）は、耐酸化性に優れた元素であり、Ｎｉ基超合金の高温耐食性を向上させる。Ｃｒの含有量は１．０−１０．０ｗｔ％の範囲が好ましく、さらに４．０〜６．０ｗｔ％がより好ましい。 Cr (chromium) is an element excellent in oxidation resistance, and improves the high temperature corrosion resistance of the Ni-base superalloy. The Cr content is preferably in the range of 1.0-10.0 wt%, and more preferably 4.0-6.0 wt%.
Ｍｏ（モリブデン）は、素地中に固溶して高温強度を上昇させるとともに析出硬化により高温強度に寄与する。Ｍｏの含有量は０．１−３．５ｗｔ％の範囲が好ましく、さらに１．０〜３．０ｗｔ％がより好ましい。 Mo (molybdenum) dissolves in the substrate to increase the high temperature strength and contributes to the high temperature strength by precipitation hardening. The Mo content is preferably in the range of 0.1 to 3.5 wt%, more preferably 1.0 to 3.0 wt%.
Ｗ（タングステン）は、Ｍｏと同様に固溶強化と析出硬化の作用がある。Ｗの含有量は７．５−１０．０ｗｔ％の範囲が好ましく、さらに７．６〜８．５ｗｔ％がより好ましい。 W (tungsten) has the effects of solid solution strengthening and precipitation hardening, similar to Mo. The W content is preferably in the range of 7.5 to 10.0 wt%, and more preferably 7.6 to 8.5 wt%.
Ａｌ（アルミニウム）は、Ｎｉと化合してガンマ母相中に析出するガンマプライム相を構成するＮｉ3Ａｌで表される金属間化合物を体積分率で５０〜７０%の割合で形成して高温強度を向上させる。Ａｌの含有量は４．０−８．０ｗｔ％の範囲が好ましく、さらに４．５〜６．０ｗｔ％がより好ましい。Al (aluminum) forms an intermetallic compound represented by Ni 3 Al constituting a gamma prime phase that combines with Ni and precipitates in a gamma matrix phase at a volume fraction of 50 to 70%. Improve strength. The content of Al is preferably in the range of 4.0 to 8.0 wt%, and more preferably 4.5 to 6.0 wt%.
特に本発明では、Ｔａ（タンタル）、Ｎｂ（ニオブ）、Ｔｉ（チタン）は、いずれもガンマプライム相を強化してクリープ強度を向上させる。これらの1つ以上を添加することが必要であるが、好ましくは０．１ｗｔ％以上とし、また、元素の含有量の総和が１２ｗｔ％以上になると有害相の生成が助長されるので１２ｗｔ％以下とする。さらに４．０〜１０．０ｗｔ％の範囲がより好ましい。Ｈｆ（ハフニウム）は、耐酸化性を向上させる効果がある。含有量が２ｗｔ％を超えると有害相の生成を助長するのでこれ以下とする必要がある。なお、単結晶凝固法により作成するタービンブレードやタービンベーン部品ではＨｆを０ｗｔ％としても良いが、０．１〜１．６ｗｔ％がより好ましい。 Particularly in the present invention, Ta (tantalum), Nb (niobium), and Ti (titanium) all strengthen the gamma prime phase and improve the creep strength. It is necessary to add one or more of these, but preferably 0.1 wt% or more, and if the total content of elements is 12 wt% or more, the formation of harmful phases is promoted, so 12 wt% or less And Furthermore, the range of 4.0-10.0 wt% is more preferable. Hf (hafnium) has an effect of improving oxidation resistance. If the content exceeds 2 wt%, the formation of a harmful phase is promoted, so it is necessary to make it less than this. In addition, in the turbine blade and turbine vane part produced by the single crystal solidification method, Hf may be 0 wt%, but 0.1 to 1.6 wt% is more preferable.
Ｒｅ（レニウム）は、ガンマ相に固溶して固溶強化により高温強度を向上させるだけでなく耐食性を向上させる効果もある。ただ、Ｒｅを多量に含有すると、高温時にＴＣＰ相が析出して高温強度を低下させるおそれがあるので０．１−５ｗｔ％の範囲が好ましく、さらに１．５〜３．５ｗｔ％がより好ましい。 Re (rhenium) has the effect of improving the corrosion resistance as well as improving the high temperature strength by solid solution strengthening in the gamma phase. However, if a large amount of Re is contained, the TCP phase may be precipitated at high temperatures to reduce the high temperature strength, so the range of 0.1-5 wt% is preferable, and 1.5 to 3.5 wt% is more preferable.
Ｓｉ（ケイ素）は、合金表面にＳｉＯ2皮膜を生成させて保護被膜として耐酸化性を向上させる。しかしながら、Ｓｉを多量に含有すると他の元素の固溶限を低下させるため０．３ｗｔ％以下が好ましい。Si (silicon) improves the oxidation resistance as a protective film by forming a SiO 2 film on the alloy surface. However, if Si is contained in a large amount, the solid solubility limit of other elements is lowered, so 0.3 wt% or less is preferable.
Ｖ（バナジウム）は、ガンマプライム相に固溶してガンマプライム相を強化させる。しかしながら、過度の含有量はクリープ強度を低下させるため３ｗｔ％以下が好ましい。 V (vanadium) is dissolved in the gamma prime phase to strengthen the gamma prime phase. However, an excessive content of 3 wt% or less is preferable because it reduces the creep strength.
Ｚｒ（ジルコニウム）は、Ｂ（ホウ素）やＣと同様に粒界を強化する。しかしながら、過度の含有量はクリープ強度を低下させることから３ｗｔ％以下が好ましい。 Zr (zirconium) reinforces grain boundaries in the same manner as B (boron) and C. However, the excessive content is preferably 3 wt% or less because it reduces the creep strength.
Ｃ（炭素）は、粒界強化に寄与する。しかしながら、過度の含有量は延性を害するため０．３ｗｔ％以下が好ましい。 C (carbon) contributes to grain boundary strengthening. However, excessive content is preferably 0.3 wt% or less because it impairs ductility.
Ｂ（ホウ素）は、Ｃと同様に粒界強化に寄与する。しかしながら、過度の含有量は延性を害するため０．２ｗｔ％以下が好ましい。 B (boron), like C, contributes to grain boundary strengthening. However, excessive content is preferably 0.2 wt% or less because it impairs ductility.
Ｙ（イットリウム）、Ｌａ（ランタン）、Ｃｅ（セリウム）は、Ｎｉ基超合金を高温で使用中にアルミナ、クロミアなどを形成する保護酸化皮膜の密着性を向上させる。しかしながら、過度の含有量は他の元素の固溶限を低下させることになるためＹ：０．２ｗｔ％以下、Ｌａ：０．２ｗｔ％%以下、Ｃｅ:０．２ｗｔ％以下が好ましい。 Y (yttrium), La (lanthanum), and Ce (cerium) improve the adhesion of a protective oxide film that forms alumina, chromia, and the like during use of a Ni-based superalloy at high temperatures. However, since excessive content will reduce the solid solubility limit of other elements, Y: 0.2 wt% or less, La: 0.2 wt% or less, and Ce: 0.2 wt% or less are preferable.
以上のような元素組成を有する本発明のＮｉ基超合金は、鋳造することができる。そして、この鋳造に際しては、たとえば、普通鋳造法、一方向凝固法、あるいは単結晶凝固法によって多結晶合金、一方向凝固合金、あるいは単結晶合金としてＮｉ基超合金を製造することができる。普通鋳造法は基本的に所望の組成に調合されたインゴットを用いて鋳造するが、鋳型温度を合金の凝固温度約１５００℃以上に加熱しておき、超合金を鋳込んだ後に、例えば加熱炉から徐々に遠ざけて温度勾配を与え多数の結晶を一方向に成長させる方法である。単結晶凝固法は一方向凝固法とほぼ同様であるが所望の品物が凝固する手前でジグザクあるいは螺旋型のセレクター部を設け、一方向で凝固してきた多数の結晶をセレクター部で一つの結晶にし、所望の品物を製造する。 The Ni-base superalloy of the present invention having the above elemental composition can be cast. In this casting, for example, a Ni-base superalloy can be manufactured as a polycrystalline alloy, a unidirectionally solidified alloy, or a single crystal alloy by a normal casting method, a unidirectional solidification method, or a single crystal solidification method. The ordinary casting method basically uses an ingot prepared to have a desired composition, but the mold temperature is heated to a solidification temperature of the alloy of about 1500 ° C. or more, and after casting the superalloy, for example, a heating furnace In this method, a large number of crystals are grown in one direction by giving a temperature gradient gradually away from the substrate. The single crystal solidification method is almost the same as the unidirectional solidification method, but a zigzag or spiral type selector unit is provided before the desired product is solidified, and many crystals that have solidified in one direction are converted into one crystal in the selector unit. To produce the desired product.
本発明のＮｉ基超合金は鋳造後に熱処理を施すことにより高クリープ強度が得られる。標準的な熱処理は、１２６０〜１３００℃で２０分〜２時間の予備熱処理を施した後に、１３００〜１３５０℃を１０５０〜１１５０℃の温度域で２〜８時間加熱、空冷を行う。この処理は耐熱・耐酸化を目的としたコーティング処理と兼ねることが可能である。空冷した後、引き続きガンマプライム相安定化を目的とした２次時効処理を８００〜９００℃で１０〜２４時間実施した後、空冷の処理を行う。それぞれの空冷を不活性ガスに置き換えてもよい。この製造方法により作成されたＮｉ基超合金によりガスタービンのタービンブレードあるいはタービンベーン等の高温部品が実現される。 The Ni-base superalloy of the present invention can have high creep strength by heat treatment after casting. In the standard heat treatment, after preliminary heat treatment at 1260 to 1300 ° C. for 20 minutes to 2 hours, 1300 to 1350 ° C. is heated in the temperature range of 1050 to 1150 ° C. for 2 to 8 hours and air-cooled. This treatment can be combined with a coating treatment for heat resistance and oxidation resistance. After air cooling, a secondary aging treatment for the purpose of stabilizing the gamma prime phase is subsequently performed at 800 to 900 ° C. for 10 to 24 hours, followed by air cooling. Each air cooling may be replaced with an inert gas. High temperature parts such as gas turbine turbine blades or turbine vanes are realized by the Ni-base superalloy produced by this manufacturing method.
表１の組成の異なる９種類の試料（Ｎｏ.１〜Ｎｏ.１２）を用いて通常の方法で、単結晶に鋳造して溶体化処理及び時効処理を行った。溶体化処理としては、１３００℃で１時間保持した後、１３３０℃まで昇温して５時間保持した。また、時効処理は１１００℃で４時間保持する１次時効と、８７０℃で２０時間保持する２次時効処理を行った。 Nine kinds of samples (No. 1 to No. 12) having different compositions shown in Table 1 were cast into a single crystal and subjected to a solution treatment and an aging treatment by an ordinary method. As a solution treatment, after holding at 1300 ° C. for 1 hour, the temperature was raised to 1330 ° C. and held for 5 hours. Moreover, the aging treatment performed the primary aging which hold | maintains at 1100 degreeC for 4 hours, and the secondary aging treatment which hold | maintains at 870 degreeC for 20 hours.
次に、溶体化処理及び時効処理を施した本実施例の試料に対してクリープ強度を測定した。クリープ試験は８００℃−７３５ＭＰa、９００℃−３９２ＭＰa、１０００℃-２４５ＭＰa 、１１００℃−１３７ＭＰaの条件で試料がクリープ破断するまでの時間を寿命とした。なお、実施例では組成の異なる９種類の試料（Ｎｏ.１〜Ｎｏ.１２）を用いて行ったが、Ｎｏ.１〜Ｎｏ.１２の試料では大きな差異はなく、図１では、この出願の発明における、Ｎｏ.５の試料を用いたクリープ試験結果とＣＭＳＸ−４とを比較した結果をクリープ寿命で整理して示したものである。 Next, the creep strength was measured for the sample of this example that had undergone solution treatment and aging treatment. In the creep test, the lifetime was defined as the time until the specimen creep ruptured under the conditions of 800 ° C.-735 MPa, 900 ° C.-392 MPa, 1000 ° C.-245 MPa, 1100 ° C.-137 MPa. In the examples, nine types of samples (No. 1 to No. 12) having different compositions were used. However, the samples No. 1 to No. 12 were not significantly different, and FIG. The result which compared the creep test result using the sample of No. 5 and CMSX-4 in invention is arranged according to the creep life.
図１からも明らかなようにこの出願の発明のＮｉ基超合金はＣｏを含まなくても第２世代Ｎｉ基単結晶合金として使用実績のあるＣｏが含有されているＣＭＳＸ−４に比較しても同等以上の高いクリープ強度を有していることがわかる。 As is clear from FIG. 1, the Ni-base superalloy of the invention of this application is compared with CMSX-4, which does not contain Co and contains Co, which has been used as a second-generation Ni-base single crystal alloy. As can be seen from FIG.
この出願の発明で得られたコバルトフリーのＮｉ基超合金として（表１のＮｏ.５の組成のもの）を金属の成形において一般的に使用されている普通凝固法、単結晶凝固法および一方向凝固法を用いて、タービンブレードとタービンベーンを製造して、それぞれの物性を測定した。成形されたタービンブレードやタービンベーンは、いずれも長時間の高熱下でも組織安定性が高く、高温におけるクリープ特性が優れていることが確認された。 As the cobalt-free Ni-base superalloy obtained in the invention of this application (with the composition of No. 5 in Table 1), the normal solidification method, the single crystal solidification method, and the Turbine blades and turbine vanes were manufactured using the directional solidification method, and their physical properties were measured. It was confirmed that the molded turbine blades and turbine vanes had high structure stability even under high heat for a long time and excellent creep characteristics at high temperatures.
上記第１のＮｉ基超合金の発明によれば、ジェットエンジンや発電用ガスタービンなどのタービンブレードやタービンベーンとして好適な中温部から高温部までバランスの良い合金を提供することが可能であり、特に半減期の長いＣｏを含まないことから原子力発電などの材料としての実用化が可能となる。すなわち、原子力発電等のタービンブレードやタービンベーンとして好適な長時間にわたり組織安定性が高く、高温におけるクリープ特性が優れたコバルトフリーのＮｉ基超合金を製造することが可能となる。 According to the invention of the first Ni-base superalloy, it is possible to provide a well-balanced alloy from an intermediate temperature part to a high temperature part suitable as a turbine blade or turbine vane such as a jet engine or a power generation gas turbine, In particular, since it does not contain Co with a long half-life, it can be put to practical use as a material for nuclear power generation. That is, it becomes possible to produce a cobalt-free Ni-base superalloy having high structural stability over a long period of time suitable as a turbine blade or turbine vane for nuclear power generation and the like, and excellent creep characteristics at high temperatures.
上記第２のＮｉ基超合金の発明によれば、上記効果に加えて、さらに組成を限定することにより、タービンブレードやタービンベーンとして、より好適な中温部から高温部までバランスの良い合金を提供することが可能となる。
上記第３〜第８のタービンブレードやタービンベーンの発明によれば、請求の範囲１または２で製造されるコバルトフリーのＮｉ基超合金を普通凝固法、単結晶凝固法および一方向凝固法を用いて成形することにより、長時間にわたり組織安定性が高く、高温におけるクリープ特性が優れたタービンブレードまたはタービンベーン部品を製造することが可能となる。According to the invention of the second Ni-base superalloy, in addition to the above effects, by further limiting the composition, an alloy having a good balance from the middle temperature part to the high temperature part more suitable as a turbine blade or turbine vane is provided. It becomes possible to do.
According to the above third to eighth turbine blades and turbine vanes, the cobalt-free Ni-base superalloy produced in claim 1 or 2 is subjected to a normal solidification method, a single crystal solidification method and a unidirectional solidification method. By using and molding, it becomes possible to produce a turbine blade or turbine vane component having high structure stability over a long period of time and excellent creep characteristics at high temperatures.
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| PCT/JP2006/306022 WO2006104059A1 (en) | 2005-03-28 | 2006-03-24 | COBALT-FREE Ni BASE SUPERALLOY |
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| JP5636639B2 (en) * | 2009-06-18 | 2014-12-10 | 独立行政法人物質・材料研究機構 | Ni-base superalloy |
| IT1394975B1 (en) * | 2009-07-29 | 2012-08-07 | Nuovo Pignone Spa | NICKEL-BASED SUPERLEGA, MECHANICAL COMPONENT MADE WITH SUCH A SUPERLEGA, TURBOMACCHINA INCLUDING SUCH COMPONENT AND RELATIVE METHODS |
| JP6016016B2 (en) * | 2012-08-09 | 2016-10-26 | 国立研究開発法人物質・材料研究機構 | Ni-based single crystal superalloy |
| US20160214350A1 (en) | 2012-08-20 | 2016-07-28 | Pratt & Whitney Canada Corp. | Oxidation-Resistant Coated Superalloy |
| JP6048805B2 (en) * | 2012-09-28 | 2016-12-21 | 国立研究開発法人物質・材料研究機構 | Direct recycling method for Ni-based single crystal superalloy parts |
| WO2017154809A1 (en) * | 2016-03-07 | 2017-09-14 | 国立研究開発法人物質・材料研究機構 | Ni-BASED UNIDIRECTIONALLY SOLIDIFIED ALLOY |
| FR3057880B1 (en) * | 2016-10-25 | 2018-11-23 | Safran | SUPERALLIAGE BASED ON NICKEL, MONOCRYSTALLINE AUBE AND TURBOMACHINE |
| FR3097879B1 (en) * | 2019-06-28 | 2021-05-28 | Safran Aircraft Engines | PROCESS FOR MANUFACTURING A PART IN MONOCRISTALLINE SUPERALLY |
| CN110396624B (en) * | 2019-08-13 | 2021-04-09 | 上海大学 | Boron-rich nickel-tungsten-based alloy material for nuclear shielding and preparation method thereof |
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| US4116723A (en) * | 1976-11-17 | 1978-09-26 | United Technologies Corporation | Heat treated superalloy single crystal article and process |
| EP0207874B1 (en) * | 1985-05-09 | 1991-12-27 | United Technologies Corporation | Substrate tailored coatings for superalloys |
| US4719080A (en) * | 1985-06-10 | 1988-01-12 | United Technologies Corporation | Advanced high strength single crystal superalloy compositions |
| JP3164972B2 (en) * | 1993-08-06 | 2001-05-14 | 株式会社日立製作所 | Moving blade for gas turbine, method of manufacturing the same, and gas turbine using the same |
| DE69423061T2 (en) * | 1993-08-06 | 2000-10-12 | Hitachi Ltd | Gas turbine blade, method for producing the same and gas turbine with this blade |
| US5725692A (en) * | 1995-10-02 | 1998-03-10 | United Technologies Corporation | Nickel base superalloy articles with improved resistance to crack propagation |
| EP0789087B1 (en) * | 1996-02-09 | 2000-05-10 | Hitachi, Ltd. | High strength Ni-base superalloy for directionally solidified castings |
| JP3559670B2 (en) * | 1996-02-09 | 2004-09-02 | 株式会社日立製作所 | High-strength Ni-base superalloy for directional solidification |
| GB9718972D0 (en) * | 1996-09-25 | 1997-11-12 | Zeneca Ltd | Chemical compounds |
| JP3820430B2 (en) * | 1998-03-04 | 2006-09-13 | 独立行政法人物質・材料研究機構 | Ni-based single crystal superalloy, manufacturing method thereof, and gas turbine component |
| FR2780982B1 (en) * | 1998-07-07 | 2000-09-08 | Onera (Off Nat Aerospatiale) | HIGH SOLVUS NICKEL-BASED MONOCRYSTALLINE SUPERALLOY |
| JP2000063969A (en) * | 1998-08-13 | 2000-02-29 | Toshiba Corp | Nickel base superalloy, its production and gas turbine part |
| US6673308B2 (en) * | 2000-08-30 | 2004-01-06 | Kabushiki Kaisha Toshiba | Nickel-base single-crystal superalloys, method of manufacturing same and gas turbine high temperature parts made thereof |
| JP4222540B2 (en) * | 2000-08-30 | 2009-02-12 | 独立行政法人物質・材料研究機構 | Nickel-based single crystal superalloy, manufacturing method thereof, and gas turbine high-temperature component |
| JP2002167636A (en) * | 2000-10-30 | 2002-06-11 | United Technol Corp <Utc> | Low density oxidation resistant superalloy material capable of thermal barrier coating retention without bond coat |
| US6966956B2 (en) * | 2001-05-30 | 2005-11-22 | National Institute For Materials Science | Ni-based single crystal super alloy |
| WO2003080882A1 (en) * | 2002-03-27 | 2003-10-02 | National Institute For Materials Science | Ni-BASE DIRECTIONALLY SOLIDIFIED SUPERALLOY AND Ni-BASE SINGLE CRYSTAL SUPERALLOY |
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