JP2011046972A - Nickel based superalloy for unidirectional solidification having excellent strength and oxidation resistance characteristic - Google Patents
Nickel based superalloy for unidirectional solidification having excellent strength and oxidation resistance characteristic Download PDFInfo
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本発明は、強度及び耐酸化特性に優れた一方向凝固用ニッケル基超合金に関する。 The present invention relates to a nickel-base superalloy for unidirectional solidification excellent in strength and oxidation resistance.
近年、ジェットエンジンやガスタービンなどの動力機関においては、その高性能化および高効率化などのために、タービン入口温度の高温化が必要不可欠となっており、このような高温化に耐えうるタービン動翼材料の開発が重要課題とされている。 In recent years, in a power engine such as a jet engine or a gas turbine, it is indispensable to increase the turbine inlet temperature in order to improve the performance and efficiency of the engine, and a turbine that can withstand such a high temperature. Development of rotor blade materials is considered as an important issue.
このタービン動翼材料に要求される主な特性は、高温での遠心力に耐えるための優れたクリープ破断強度、靭性および高温燃焼ガス雰囲気に対する優れた耐酸化性、及び耐食性である。そして、この要求を満たすために、現在ではＮｉ基超合金の一方向凝固材や単結晶材が使用されている。 The main properties required for this turbine blade material are excellent creep rupture strength, toughness to withstand high temperature centrifugal force, excellent oxidation resistance to high temperature combustion gas atmosphere, and corrosion resistance. In order to satisfy this requirement, a unidirectional solidified material or a single crystal material of a Ni-base superalloy is currently used.
Ｎｉ基超合金の単結晶合金は、従来の普通鋳造合金（等軸晶）や一方向凝固合金と異なり、粒界がないために融点直下で溶体化処理することが可能であり、固溶強化度の高いＷやＴａを多量に添加し、凝固偏析を完全に除去した均質組織を得ることができる。このため、従来の合金に比べてクリープ破断強度と靭性が著しく高いという特徴を有している。一方、一方向凝固合金は、単結晶材ほどクリープ破断強度は高くないが、普通鋳造合金よりはクリープ破断強度と靭性が著しく高く、また鋳造も単結晶材に比べると非常に容易であり、コスト的にも安くなることから、単結晶材ほどの強度を必要としない部分には数多く使用されている。 Ni-base superalloy single crystal alloys, unlike conventional ordinary cast alloys (equiaxial crystals) and unidirectionally solidified alloys, have no grain boundaries and can be solution-treated just below the melting point. By adding a large amount of high-grade W or Ta, a homogeneous structure in which solidification segregation is completely removed can be obtained. For this reason, it has the characteristic that creep rupture strength and toughness are remarkably high compared with the conventional alloy. On the other hand, unidirectionally solidified alloys are not as high in creep rupture strength as single crystal materials, but are significantly higher in creep rupture strength and toughness than ordinary cast alloys, and casting is much easier than single crystal materials, and costs are low. Since it becomes cheaper, it is used in many parts that do not require the strength of a single crystal material.
上述したように単結晶合金は優れた特徴を有しているが、単結晶翼の鋳造が難しくコストが高いことが大きな課題となっている。特に発電用の大型ガスタービンの動翼を単結晶化することは非常に困難であり、この点が各種特性に優れた単結晶翼が普及しない大きな要因となっている。 As described above, single crystal alloys have excellent characteristics, but it is a major problem that single crystal blades are difficult to cast and costly. In particular, it is very difficult to make a moving blade of a large gas turbine for power generation into a single crystal, and this is a major factor that prevents a single crystal blade having excellent characteristics from spreading.
これに対し、一方向凝固合金は鋳造が容易であり、発電用大型ガスタービンの動翼の鋳造も容易であり、現有の発電用大型ガスタービンの動翼として数多く使用されている。しかしながら、現在の発電用大型ガスタービンの動翼に使用されている一方向凝固合金は、クリープ破断強度が弱く、ガスタービンの燃焼温度を高温化し熱効率の向上を図るには、もはや限界に達しているのが実情である。 On the other hand, the unidirectionally solidified alloy is easy to cast, and it is easy to cast a moving blade of a large-sized gas turbine for power generation. However, the unidirectionally solidified alloy used in the blades of current large-scale gas turbines for power generation has low creep rupture strength, and the limit is no longer reached to increase the combustion temperature of the gas turbine and improve thermal efficiency. The fact is.
すなわち、燃焼ガス温度の上昇による発電ガスタービンの更なる熱効率向上を図るためには、クリープ強度に優れた一方向凝固用合金が強く求められている。 That is, in order to further improve the thermal efficiency of the power generation gas turbine by increasing the combustion gas temperature, there is a strong demand for a unidirectional solidification alloy having excellent creep strength.
本発明は、上述した従来の実情に鑑みてなされたものであり、高温でのクリープ破断強度に優れ、更には高温での耐酸化性に優れ、高温ガスタービンに最適な一方向凝固用Ｎｉ基合金を提供することを目的としている。 The present invention has been made in view of the above-described conventional situation, and is excellent in creep rupture strength at high temperature, and further excellent in oxidation resistance at high temperature, and is suitable for a high-temperature gas turbine. The aim is to provide alloys.
本発明のニッケル基超合金は、質量基準でＣｒ：５．８〜１１．０％、Ｃｏ：６．０〜１８．０％、Ｗ：３．８〜１１．０％、Ｒｅ：３．３％以下、Ｔａ：２．０〜１０．０％、Ｔｉ：０．６〜２．４％、Ａｌ：４．５〜６．５％、Ｈｆ：０．１〜２．０％、Ｃ：０．０５〜０．１５％、Ｂ：０．００１〜０．０５％、Ｚｒ：０．００１〜０．０５％、Ｍｏ：１．０％未満、Ｒｕ：４．０％以下、Ｎｂ：０．１％未満、Ｐ：０．０１％以下、Ｓ：０．００５％以下、Ｏ：０．００５％以下、Ｎ：０．００５％以下を含み、残部がＮｉ及び不可避不純物よりなることを特徴とする。 The nickel-base superalloy of the present invention has Cr: 5.8 to 11.0%, Co: 6.0 to 18.0%, W: 3.8 to 11.0%, Re: 3.3 on a mass basis. % Or less, Ta: 2.0 to 10.0%, Ti: 0.6 to 2.4%, Al: 4.5 to 6.5%, Hf: 0.1 to 2.0%, C: 0 0.05 to 0.15%, B: 0.001 to 0.05%, Zr: 0.001 to 0.05%, Mo: less than 1.0%, Ru: 4.0% or less, Nb: 0.0. Less than 1%, P: 0.01% or less, S: 0.005% or less, O: 0.005% or less, N: 0.005% or less, with the balance being made of Ni and inevitable impurities To do.
ここで、質量基準でＣｒ：５．８〜１１．０％とは、本発明のニッケル基超合金の質量を基準として、その合金中に合金の一成分であるＣｒが５．８〜１１．０％、すなわち５．８％以上かつ１１．０％以下の範囲で含まれることをいう。すなわち、５．８〜１１．０質量％又は５．８〜１１．０ｍａｓｓ％と表記してもよい。この場合に、５．８％及び１１．０％はそれぞれ下限値及び上限値であり、これらの下限値及び上限値も本発明の範囲に含まれるものとする。他の成分についても同様である。 Here, Cr: 5.8 to 11.0% on a mass basis is based on the mass of the nickel-base superalloy of the present invention, and Cr as a component of the alloy is 5.8 to 11. 0%, that is, contained in the range of 5.8% or more and 11.0% or less. That is, it may be expressed as 5.8 to 11.0 mass% or 5.8 to 11.0 mass%. In this case, 5.8% and 11.0% are a lower limit value and an upper limit value, respectively, and these lower limit value and upper limit value are also included in the scope of the present invention. The same applies to the other components.
本発明によれば、高温での優れたクリープ破断強度、高温での優れた耐食性、及び耐酸化特性を有するニッケル基超合金を提供することができる。 According to the present invention, a nickel-base superalloy having excellent creep rupture strength at high temperature, excellent corrosion resistance at high temperature, and oxidation resistance can be provided.
本発明は、高温における強度、靭性・耐食性及び耐酸化特性に優れていることが要求される部品および製品の素材として利用するのに適したニッケル基超合金に関するものである。 The present invention relates to a nickel-base superalloy suitable for use as a material for parts and products that are required to have excellent strength, toughness / corrosion resistance and oxidation resistance at high temperatures.
本発明に係る強度、耐食性、耐酸化特性に優れたニッケル基超合金は、質量基準でＣｒ：５．８〜１１．０％、Ｃｏ：６．０〜１８．０％、Ｗ：３．８〜１１．０％、Ｒｅ：３．３％以下、Ｔａ：２．０〜１０．０％、Ｔｉ：０．６〜２．４％、Ａｌ：４．５〜６．５％、Ｈｆ：０．１〜２．０％、Ｃ：０．０５〜０．１５％、Ｂ：０．００１〜０．０５％、Ｚｒ：０．００１〜０．０５％、Ｍｏ：１．０％未満、Ｒｕ：４．０％以下、Ｎｂ：０．１％未満、Ｐ：０．０１％以下、Ｓ：０．００５％以下、Ｏ：０．００５％以下、Ｎ：０．００５％以下、残部Ｎｉ及び不可避不純物よりなるものである。 The nickel-base superalloy excellent in strength, corrosion resistance, and oxidation resistance according to the present invention is Cr: 5.8 to 11.0%, Co: 6.0 to 18.0%, W: 3.8 on a mass basis. -11.0%, Re: 3.3% or less, Ta: 2.0-10.0%, Ti: 0.6-2.4%, Al: 4.5-6.5%, Hf: 0 0.1-2.0%, C: 0.05-0.15%, B: 0.001-0.05%, Zr: 0.001-0.05%, Mo: less than 1.0%, Ru : 4.0% or less, Nb: less than 0.1%, P: 0.01% or less, S: 0.005% or less, O: 0.005% or less, N: 0.005% or less, balance Ni and It consists of inevitable impurities.
また、本発明に係る強度、耐食性、耐酸化特性に優れたニッケル基超合金は、質量基準でＣｒ：６．４〜１１．０％、Ｃｏ：８．０〜１３．５％、Ｗ：４．０〜１１．０％、Ｒｅ：３．３％以下、Ｔａ：３．０〜９．０％、Ｔｉ：０．６〜２．０％、Ａｌ：４．５〜６．５％、Ｈｆ：０．１〜２．０％、Ｃ：０．０５〜０．１５％、Ｂ：０．００１〜０．０５％、Ｚｒ：０．００１〜０．０５％、Ｍｏ：１．０％未満、Ｒｕ：４．０％以下、Ｎｂ：０．１％未満、Ｓｉ：０．１％以下、Ｐ：０．０１％以下、Ｓ：０．００５％以下、Ｏ：０．００５％以下、Ｎ：０．００５％以下、残部Ｎｉ及び不可避不純物よりなるものである。 Further, the nickel-base superalloy excellent in strength, corrosion resistance, and oxidation resistance according to the present invention is Cr: 6.4 to 11.0%, Co: 8.0 to 13.5%, W: 4 on a mass basis. 0.0 to 11.0%, Re: 3.3% or less, Ta: 3.0 to 9.0%, Ti: 0.6 to 2.0%, Al: 4.5 to 6.5%, Hf : 0.1-2.0%, C: 0.05-0.15%, B: 0.001-0.05%, Zr: 0.001-0.05%, Mo: less than 1.0% Ru: 4.0% or less, Nb: less than 0.1%, Si: 0.1% or less, P: 0.01% or less, S: 0.005% or less, O: 0.005% or less, N : 0.005% or less, remaining Ni and inevitable impurities.
また、本発明に係る強度、耐食性、耐酸化特性に優れたニッケル基超合金は、質量基準でＣｒ：６．４〜１１．０％、Ｃｏ：８．０〜１３．５％、Ｗ：４．０〜１１．０％、Ｒｅ：０．１〜３．３％、Ｔａ：３．０〜９．０％、Ｔｉ：０．６〜２．０％、Ａｌ：４．５〜６．５％、Ｈｆ：０．１〜２．０％、Ｃ：０．０５〜０．１５％、Ｂ：０．００１〜０．０５％、Ｚｒ：０．００１〜０．０２％、Ｍｏ：１．０％未満、Ｒｕ：４．０％以下、Ｎｂ：０．１％未満、Ｓｉ：０．１％以下、Ｐ：０．０１％以下、Ｓ：０．００５％以下、Ｏ：０．００５％以下、Ｎ：０．００５％以下、残部Ｎｉ及び不可避不純物よりなるものである。 Further, the nickel-base superalloy excellent in strength, corrosion resistance, and oxidation resistance according to the present invention is Cr: 6.4 to 11.0%, Co: 8.0 to 13.5%, W: 4 on a mass basis. 0.0-11.0%, Re: 0.1-3.3%, Ta: 3.0-9.0%, Ti: 0.6-2.0%, Al: 4.5-6.5 %, Hf: 0.1-2.0%, C: 0.05-0.15%, B: 0.001-0.05%, Zr: 0.001-0.02%, Mo: 1. Less than 0%, Ru: 4.0% or less, Nb: less than 0.1%, Si: 0.1% or less, P: 0.01% or less, S: 0.005% or less, O: 0.005% Hereinafter, N: 0.005% or less, remaining Ni and inevitable impurities.
また、本発明に係る強度、耐食性、耐酸化特性に優れたニッケル基超合金は、質量基準でＣｒ：７．０〜１１．０％、Ｃｏ：９．５〜１３．５％、Ｗ：５．０〜１１．０％、Ｒｅ：０．１〜３．３％、Ｔａ：３．０〜９．０％、Ｔｉ：０．８〜２．０％、Ａｌ：４．５〜６．５％、Ｈｆ：０．１〜２．０％、Ｃ：０．０５〜０．１５％、Ｂ：０．００１〜０．０５％、Ｚｒ：０．００１〜０．０２％、Ｍｏ：０．５％未満、Ｒｕ：４．０％以下、Ｎｂ：０．１％未満、Ｓｉ：０．１％以下、Ｐ：０．０１％以下、Ｓ：０．００５％以下、Ｏ：０．００５％以下、Ｎ：０．００５％以下、残部Ｎｉ及び不可避不純物よりなるものである。 Further, the nickel-base superalloy excellent in strength, corrosion resistance, and oxidation resistance according to the present invention is Cr: 7.0 to 11.0%, Co: 9.5 to 13.5%, W: 5 on a mass basis. 0.0-11.0%, Re: 0.1-3.3%, Ta: 3.0-9.0%, Ti: 0.8-2.0%, Al: 4.5-6.5 %, Hf: 0.1 to 2.0%, C: 0.05 to 0.15%, B: 0.001 to 0.05%, Zr: 0.001 to 0.02%, Mo: 0.0. Less than 5%, Ru: 4.0% or less, Nb: less than 0.1%, Si: 0.1% or less, P: 0.01% or less, S: 0.005% or less, O: 0.005% Hereinafter, N: 0.005% or less, remaining Ni and inevitable impurities.
また、本発明に係る強度、耐食性、耐酸化特性に優れたニッケル基超合金は、質量基準でＣｒ：７．０〜１１．０％、Ｃｏ：９．５〜１２．０％、Ｗ：５．０〜１１．０％、Ｒｅ：０．１〜３．３％、Ｔａ：３．０〜６．０％、Ｔｉ：０．８〜２．０％、Ａｌ：４．５〜６．５％、Ｈｆ：０．１〜２．０％、Ｃ：０．０５〜０．１５％、Ｂ：０．０１〜０．０２％、Ｚｒ：０．０１〜０．０２％、Ｍｏ：０．５％未満、Ｒｕ：４．０％以下、Ｎｂ：０．１％未満、Ｓｉ：０．１％以下、Ｐ：０．０１％以下、Ｓ：０．００５％以下、Ｏ：０．００５％以下、Ｎ：０．００５％以下、残部Ｎｉ及び不可避不純物よりなるものである。 Further, the nickel-base superalloy excellent in strength, corrosion resistance, and oxidation resistance according to the present invention is Cr: 7.0 to 11.0%, Co: 9.5 to 12.0%, W: 5 on a mass basis. 0.0 to 11.0%, Re: 0.1 to 3.3%, Ta: 3.0 to 6.0%, Ti: 0.8 to 2.0%, Al: 4.5 to 6.5 %, Hf: 0.1 to 2.0%, C: 0.05 to 0.15%, B: 0.01 to 0.02%, Zr: 0.01 to 0.02%, Mo: 0.0. Less than 5%, Ru: 4.0% or less, Nb: less than 0.1%, Si: 0.1% or less, P: 0.01% or less, S: 0.005% or less, O: 0.005% Hereinafter, N: 0.005% or less, remaining Ni and inevitable impurities.
また、本発明に係る強度、耐食性、耐酸化特性に優れたニッケル基超合金は、質量基準でＣｒ：８．０１〜１１．０％、Ｃｏ：９．５〜１２．０％、Ｗ：６．０〜１１．０％、Ｒｅ：０．５〜３．３％、Ｔａ：３．０〜４．５％、Ｔｉ：１．０〜２．０％、Ａｌ：４．５〜６．５％、Ｈｆ：１．０〜２．０％、Ｃ：０．０５〜０．１５％、Ｂ：０．０１〜０．０２％、Ｚｒ：０．０１〜０．０２％、Ｍｏ：０．５％未満、Ｒｕ：４．０％以下、Ｎｂ：０．１％未満、Ｓｉ：０．１％以下、Ｐ：０．０１％以下、Ｓ：０．００５％以下、Ｏ：０．００５％以下、Ｎ：０．００５％以下、残部Ｎｉ及び不可避不純物よりなるものである。 In addition, the nickel-base superalloy excellent in strength, corrosion resistance, and oxidation resistance according to the present invention is Cr: 8.01 to 11.0%, Co: 9.5 to 12.0%, W: 6 on a mass basis. 0.0-11.0%, Re: 0.5-3.3%, Ta: 3.0-4.5%, Ti: 1.0-2.0%, Al: 4.5-6.5 %, Hf: 1.0 to 2.0%, C: 0.05 to 0.15%, B: 0.01 to 0.02%, Zr: 0.01 to 0.02%, Mo: 0.0. Less than 5%, Ru: 4.0% or less, Nb: less than 0.1%, Si: 0.1% or less, P: 0.01% or less, S: 0.005% or less, O: 0.005% Hereinafter, N: 0.005% or less, remaining Ni and inevitable impurities.
また、本発明に係る強度、耐食性、耐酸化特性に優れたニッケル基超合金は、質量基準でＣｒ：８．０１〜１１．０％、Ｃｏ：９．５〜１２．０％、Ｗ：６．０〜１１．０％、Ｒｅ：０．５〜３．３％、Ｔａ：３．０〜４．５％、Ｔｉ：１．０〜２．０％、Ａｌ：４．５〜６．５％、Ｈｆ：１．０〜２．０％、Ｃ：０．０５〜０．１５％、Ｂ：０．０１〜０．０２％、Ｚｒ：０．０１〜０．０２％、Ｍｏ：０．１％未満、Ｒｕ：４．０％以下、Ｎｂ：０．１％未満、Ｓｉ：０．１％以下、Ｐ：０．０１％以下、Ｓ：０．００５％以下、Ｏ：０．００５％以下、Ｎ：０．００５％以下、残部Ｎｉ及び不可避不純物よりなるものである。 In addition, the nickel-base superalloy excellent in strength, corrosion resistance, and oxidation resistance according to the present invention is Cr: 8.01 to 11.0%, Co: 9.5 to 12.0%, W: 6 on a mass basis. 0.0-11.0%, Re: 0.5-3.3%, Ta: 3.0-4.5%, Ti: 1.0-2.0%, Al: 4.5-6.5 %, Hf: 1.0 to 2.0%, C: 0.05 to 0.15%, B: 0.01 to 0.02%, Zr: 0.01 to 0.02%, Mo: 0.0. Less than 1%, Ru: 4.0% or less, Nb: less than 0.1%, Si: 0.1% or less, P: 0.01% or less, S: 0.005% or less, O: 0.005% Hereinafter, N: 0.005% or less, remaining Ni and inevitable impurities.
また、本発明に係る強度、耐食性、耐酸化特性に優れたニッケル基超合金は、質量基準でＣｒ：８．０１〜８．４％、Ｃｏ：１０．７〜１１．５％、Ｗ：８．５〜１１．０％、Ｒｅ：０．５〜３．３％、Ｔａ：３．４〜４．０％、Ｔｉ：１．２〜１．６％、Ａｌ：４．９〜５．５％、Ｈｆ：１．２〜１．６％、Ｃ：０．０５〜０．１％、Ｂ：０．０１〜０．０１８％、Ｚｒ：０．０１〜０．０１８％、Ｍｏ：０．１％未満、Ｒｕ：４．０％以下、Ｎｂ：０．１％未満、Ｓｉ：０．１％以下、Ｐ：０．０１％以下、Ｓ：０．００５以下、Ｏ：０．００５％以下、Ｎ：０．００５％以下、残部Ｎｉ及び不可避不純物よりなるものである。 Further, the nickel-base superalloy excellent in strength, corrosion resistance, and oxidation resistance according to the present invention is Cr: 8.01 to 8.4%, Co: 10.7 to 11.5%, W: 8 on a mass basis. 0.5 to 11.0%, Re: 0.5 to 3.3%, Ta: 3.4 to 4.0%, Ti: 1.2 to 1.6%, Al: 4.9 to 5.5 %, Hf: 1.2 to 1.6%, C: 0.05 to 0.1%, B: 0.01 to 0.018%, Zr: 0.01 to 0.018%, Mo: 0.0. Less than 1%, Ru: 4.0% or less, Nb: less than 0.1%, Si: 0.1% or less, P: 0.01% or less, S: 0.005 or less, O: 0.005% or less , N: 0.005% or less, remaining Ni and inevitable impurities.
また、本発明に係る強度、耐食性、耐酸化特性に優れたニッケル基超合金は、質量基準でＣｒ：８．０１〜８．４％、Ｃｏ：１０．７〜１１．５％、Ｗ：８．５〜１１．０％、Ｒｅ：０．５〜３．３％、Ｔａ：３．４〜４．０％、Ｔｉ：１．２〜１．６％、Ａｌ：４．９〜５．５％、Ｈｆ：１．２〜１．６％、Ｃ：０．０５〜０．１％、Ｂ：０．０１〜０．０１８％、Ｚｒ：０．０１〜０．０１８％、Ｍｏ：０．１％未満、Ｒｕ：０．０１％以下、Ｎｂ：０．１％未満、Ｓｉ：０．１％以下、Ｐ：０．０１％以下、Ｓ：０．００５％以下、Ｏ：０．００５％以下、Ｎ：０．００５％以下、残部Ｎｉ及び不可避不純物よりなるものである。 Further, the nickel-base superalloy excellent in strength, corrosion resistance, and oxidation resistance according to the present invention is Cr: 8.01 to 8.4%, Co: 10.7 to 11.5%, W: 8 on a mass basis. 0.5 to 11.0%, Re: 0.5 to 3.3%, Ta: 3.4 to 4.0%, Ti: 1.2 to 1.6%, Al: 4.9 to 5.5 %, Hf: 1.2 to 1.6%, C: 0.05 to 0.1%, B: 0.01 to 0.018%, Zr: 0.01 to 0.018%, Mo: 0.0. Less than 1%, Ru: 0.01% or less, Nb: less than 0.1%, Si: 0.1% or less, P: 0.01% or less, S: 0.005% or less, O: 0.005% Hereinafter, N: 0.005% or less, remaining Ni and inevitable impurities.
また、本発明に係る強度、耐食性、耐酸化特性に優れたニッケル基超合金は、質量基準でＣｒ：８．２％、Ｃｏ：１１．０％、Ｗ：９．２％、Ｒｅ：１．０％、Ｔａ：３．６％、Ｔｉ：１．４％、Ａｌ：５．２％、Ｈｆ：１．４％、Ｃ：０．０７％、Ｂ：０．０１５％、Ｚｒ：０．０１５％を中心組成とした冶金的なばらつき範囲からなり、さらに質量基準でＭｏ：０．１％未満、Ｒｕ：０．０１％以下、Ｎｂ：０．１％未満、Ｓｉ：０．１％以下、Ｐ：０．０１％以下、Ｓ：０．００５％以下、Ｏ：０．００５％以下、Ｎ：０．００５％以下、残部Ｎｉ及び不可避不純物よりなるものである。 The nickel-base superalloy excellent in strength, corrosion resistance, and oxidation resistance according to the present invention is Cr: 8.2%, Co: 11.0%, W: 9.2%, Re: 1. 0%, Ta: 3.6%, Ti: 1.4%, Al: 5.2%, Hf: 1.4%, C: 0.07%, B: 0.015%, Zr: 0.015 % Is a metallurgical variation range having a central composition, Mo: less than 0.1%, Ru: 0.01% or less, Nb: less than 0.1%, Si: 0.1% or less, P: 0.01% or less, S: 0.005% or less, O: 0.005% or less, N: 0.005% or less, the balance Ni and inevitable impurities.
また、本発明に係る強度および耐食性に優れたニッケル基超合金は、上述のいずれかに記載の成分組成を有するニッケル基合金において、０．１質量％未満のＬｕを含むものである。 In addition, the nickel-base superalloy excellent in strength and corrosion resistance according to the present invention contains less than 0.1% by mass of Lu in the nickel-base alloy having any of the above-described component compositions.
本発明に係る強度および耐食性に優れたニッケル基合金の成分範囲及びより好ましいその他の限定条件の設定理由について説明する。 The reason for setting the component range of the nickel base alloy excellent in strength and corrosion resistance according to the present invention and other more preferable limiting conditions will be described.
（Ｃｒ：５．８〜１１．０質量％）
Ｃｒは合金の高温における耐食性を改善するのに有効な元素であり、その効果がより顕著に現れるのは５．８質量％超過からである。そして、Ｃｒ含有量の増加に伴ってその効果は大きくなるが、多くなると固溶強化元素の固溶限度を下げるとともに、脆化相であるＴＣＰ相が析出して高温強度や高温耐食性を害するため、その上限を１１．０質量％とする必要がある。この組成範囲に於いて、強度と耐食性のバランスを考慮した場合、好ましくは６．４〜１１．０質量％の範囲であり、より好ましくは７．０〜１１．０質量％の範囲であり、更に好ましいのは８．０１〜１１．０質量％の範囲であり、更により好ましいのは８．０１〜８．４質量％の範囲であり、最も好ましくは約８．２質量％のときである。
(Cr: 5.8 to 11.0% by mass)
Cr is an element effective for improving the corrosion resistance of the alloy at a high temperature, and the effect appears more remarkably from exceeding 5.8% by mass. And as the Cr content increases, the effect increases. However, when the Cr content increases, the solid solution strengthening element lowers the solid solution limit, and the TCP phase, which is an embrittlement phase, precipitates to impair the high temperature strength and the high temperature corrosion resistance. The upper limit is required to be 11.0% by mass. In this composition range, when considering the balance between strength and corrosion resistance, it is preferably in the range of 6.4 to 11.0% by mass, more preferably in the range of 7.0 to 11.0% by mass. More preferred is the range of 8.01 to 11.0% by weight, even more preferred is the range of 8.01 to 8.4% by weight, and most preferred is about 8.2% by weight. .
（Ｃｏ：６．０〜１８．０質量％）
Ｃｏは、γ’相（ＮｉとＡｌとの金属間化合物Ｎｉ３Ａｌ）の固溶温度を低下させて溶体化処理を容易にするほか、γ相を固溶強化すると共に高温耐食性を向上させる効果を有する。そのような効果が現れるのは、Ｃｏの含有量が６．０質量％以上である。一方、Ｃｏの含有量が１８．０％を越えると、γ’相の固溶温度を著しく低下させて、析出強化相であるγ’相の析出量を少なくし、高温強度を低下させてしまうため、１８．０質量％以下にする必要がある。この組成範囲に於いて、溶体化熱処理の容易性と強度とのバランスを考慮した場合、好ましくは８．０〜１３．５質量％の範囲であり、より好ましくは９．５〜１３．５質量％の範囲であり、更に好ましいのは９．５〜１２．０質量％の範囲であり、更により好ましいのは１０．７〜１１．５質量％の範囲であり、最も好ましいのは約１１．０質量％のときである。
(Co: 6.0 to 18.0 mass%)
Co reduces the solid solution temperature of the γ 'phase (intermetallic compound Ni 3 Al between Ni and Al) to facilitate solution treatment, and also enhances the solid solution strengthening of the γ phase and improves high-temperature corrosion resistance. Have Such an effect appears when the Co content is 6.0% by mass or more. On the other hand, when the Co content exceeds 18.0%, the solid solution temperature of the γ 'phase is remarkably lowered, the precipitation amount of the γ' phase, which is a precipitation strengthening phase, is reduced, and the high temperature strength is lowered. Therefore, it is necessary to make it 18.0 mass% or less. In this composition range, when considering the balance between the ease of solution heat treatment and the strength, the range is preferably 8.0 to 13.5% by mass, more preferably 9.5 to 13.5% by mass. %, More preferred is the range of 9.5 to 12.0% by weight, even more preferred is the range of 10.7 to 11.5% by weight, and most preferred is about 11. When 0% by mass.
（Ｗ：３．８〜１１．０質量％）
Ｗはマトリックスであるγ相と析出相であるγ’相に固溶し、固溶強化によりクリープ強度を高めるのに有効な元素である。そして、このような効果を十分に得るためには３．８質量％以上の含有量が必要である。しかし、Ｗは比重が大きく、合金の重量を増大するばかりでなく、合金の高温における耐食性を低下させる。また、１１．０質量％を越えると針状のα−Ｗが析出し、クリープ強度、高温耐食性および靭性を低下させるため、その上限を１１．０質量％とする必要がある。この組成範囲に於いて、高温における強度、耐食性及び高温での組織安定性のバランスを考慮した場合、好ましくは４．０〜１１．０質量％の範囲であり、より好ましくは５．０〜１１．０質量％の範囲であり、更に好ましいのは６．０〜１１．０質量％の範囲であり、更により好ましいのは８．５〜１１．０質量％の範囲であり、最も好ましいのは約９．２質量％のときである。
(W: 3.8 to 11.0% by mass)
W is an element effective for increasing the creep strength by solid solution strengthening by forming a solid solution in the matrix γ phase and the precipitated γ ′ phase. And in order to acquire such an effect sufficiently, content of 3.8 mass% or more is required. However, W has a large specific gravity, which not only increases the weight of the alloy, but also reduces the corrosion resistance of the alloy at high temperatures. On the other hand, when the amount exceeds 11.0% by mass, acicular α-W precipitates, and the creep strength, high-temperature corrosion resistance and toughness are lowered. Therefore, the upper limit thereof needs to be 11.0% by mass. In this composition range, when considering the balance between strength at high temperature, corrosion resistance and structural stability at high temperature, the range is preferably 4.0 to 11.0% by mass, more preferably 5.0 to 11%. It is in the range of 0.0% by weight, more preferably in the range of 6.0 to 11.0% by weight, even more preferably in the range of 8.5 to 11.0% by weight, most preferably It is about 9.2 mass%.
（Ｒｅ：３．３質量％以下）
Ｒｅはマトリックスであるγ相にほとんど固溶し、固溶強化によってクリープ強度を高めるとともに、合金の耐食性を改善するのに有効な元素である。しかし、Ｒｅは高価であり、比重が大きく、合金の重量を増大する。また、３．３質量％を越えると針状のα−Ｗまたはα−Ｒｅ（Ｍｏ）が析出し、クリープ強度および靭性を低下させるため、その上限を３．３質量％とする必要がある。この組成範囲に於いて、高温における強度、耐食性及び高温での組織安定性、素材コストのバランスを考慮した場合、好ましくは０．１〜３．３質量％以下、より好ましくは０．５〜３．３質量％以下であり、最も好ましいのは約１．０質量％のときである。
(Re: 3.3% by mass or less)
Re is an element effective for improving the corrosion resistance of the alloy while at the same time increasing the creep strength by solid solution strengthening and being substantially dissolved in the matrix γ phase. However, Re is expensive, has a large specific gravity, and increases the weight of the alloy. On the other hand, when the content exceeds 3.3% by mass, acicular α-W or α-Re (Mo) precipitates and decreases the creep strength and toughness, so that the upper limit must be 3.3% by mass. In this composition range, when considering the balance between strength at high temperature, corrosion resistance and structure stability at high temperature, and material cost, it is preferably 0.1 to 3.3% by mass, more preferably 0.5 to 3%. .3% by mass or less, and most preferably about 1.0% by mass.
（Ｔａ：２．０〜１０．０質量％）
Ｔａはγ’相に〔Ｎｉ、（Ａｌ、Ｔａ）〕の形で固溶し、固溶強化する。これによりクリープ強度が向上する。この効果を十分に得るためには、２．０質量％以上の含有量が必要であり、１０．０質量％超過になると過飽和になって針状のδ相〔Ｎｉ、Ｔａ〕が析出し、クリープ強度を低下させる。したがって、その上限を１０．０質量％とする必要がある。この組成範囲に於いて、高温における強度と組織安定性のバランスを考慮した場合、好ましくは３．０〜９．０質量％の範囲であり、より好ましくは３．０〜６．０質量％の範囲であり、更に好ましいのは３．０〜４．５質量％の範囲であり、更により好ましいのは３．４〜４．０質量％の範囲であり、最も好ましいのは約３．６質量％のときである。
(Ta: 2.0-10.0 mass%)
Ta dissolves in the γ ′ phase in the form of [Ni, (Al, Ta)] and strengthens the solution. This improves the creep strength. In order to sufficiently obtain this effect, a content of 2.0% by mass or more is necessary, and when it exceeds 10.0% by mass, supersaturation occurs and acicular δ phase [Ni, Ta] precipitates, Reduce creep strength. Therefore, the upper limit needs to be 10.0 mass%. In this composition range, when considering the balance between strength and structure stability at high temperature, it is preferably in the range of 3.0 to 9.0% by mass, more preferably 3.0 to 6.0% by mass. More preferred is a range of 3.0 to 4.5% by mass, even more preferred is a range of 3.4 to 4.0% by mass, and most preferred is about 3.6% by mass. %.
（Ｔｉ：０．６〜２．４質量％）
ＴｉはＴａと同様にγ’相に〔Ｎｉ３（Ａｌ、Ｔａ、Ｔｉ）〕の形で固相し、固溶強化するが、Ｔａほどの効果はない。むしろ、Ｔｉは合金の高温における耐食性を改善する効果があるので０．６質量％以上の含有量とする。しかし、２．４質量％を越えて添加すると、Ｎｉ３（Ａｌ＋Ｔｉ）の共晶を形成し、クリープ強度を低下させ、更に耐酸化特性も劣化するため、その上限を２．４質量％とする必要がある。この組成範囲に於いて、高温における強度と耐食性、耐酸化特性のバランスを考慮した場合、好ましくは０．６〜２．０質量％の範囲であり、より好ましくは０．８〜２．０質量％の範囲であり、更に好ましいのは１．０〜２．０質量％の範囲であり、更により好ましいのは１．２〜１．６質量％の範囲であり、最も好ましいのは約１．４質量％のときである。
(Ti: 0.6-2.4% by mass)
Ti, like Ta, solidifies in the form of [Ni 3 (Al, Ta, Ti)] in the γ ′ phase and strengthens by solid solution, but is not as effective as Ta. Rather, Ti has the effect of improving the corrosion resistance of the alloy at high temperatures, so the content is 0.6% by mass or more. However, if added over 2.4% by mass, an eutectic of Ni 3 (Al + Ti) is formed, the creep strength is lowered, and the oxidation resistance is also deteriorated, so the upper limit is made 2.4% by mass. There is a need. In this composition range, when considering the balance between strength, corrosion resistance, and oxidation resistance at high temperatures, it is preferably in the range of 0.6 to 2.0 mass%, more preferably 0.8 to 2.0 mass. %, More preferred is the range of 1.0-2.0% by weight, even more preferred is the range of 1.2-1.6% by weight, and most preferred is about 1. When 4 mass%.
（Ａｌ：４．５〜６．５質量％）
Ａｌは析出強化相であるγ’相〔Ｎｉ３Ａｌ〕の構成元素であり、これによりクリープ強度が向上する。また、耐酸化特性の向上にも大きく寄与する。それらの効果が十分得るためには、４．５質量％以上の含有量が必要であるが、６．５質量％を超えると、γ’相〔Ｎｉ３Ａｌ〕が過大に析出し、かえって強度を低下させることから、４．５〜６．５質量％の範囲とすることが必要である。この組成範囲に於いて、高温における強度と耐酸化特性のバランスを考慮した場合、好ましくは４．９〜５．５質量％の範囲であり、最も好ましいのは約５．２質量％のときである。
(Al: 4.5-6.5% by mass)
Al is a constituent element of the γ ′ phase [Ni 3 Al], which is a precipitation strengthening phase, thereby improving the creep strength. It also greatly contributes to the improvement of oxidation resistance. In order to obtain these effects sufficiently, a content of 4.5% by mass or more is necessary. However, when the content exceeds 6.5% by mass, the γ ′ phase [Ni 3 Al] is excessively precipitated, and instead the strength is increased. Therefore, it is necessary to set it in the range of 4.5 to 6.5% by mass. In this composition range, when considering the balance between strength and oxidation resistance at high temperatures, the range is preferably 4.9 to 5.5% by mass, and most preferably about 5.2% by mass. is there.
（Ｒｕ：４．０質量％以下）
Ｒｕは、γ’相（ＮｉとＡｌとの金属間化合物Ｎｉ３Ａｌ）の固溶できる領域を広げて溶体化処理を容易にするほか、γ相を固溶強化すると共に高温での耐疲労特性を向上させる効果を有する。しかし、Ｒｕは高価であり、含有量を多くすると素材の価格が上昇する。また、Ｒｕの含有量が４．０質量％を越えると、析出強化相であるγ’相の析出を減少させて、高温強度を低下させてしまうため、４．０質量％以下にする必要がある。この組成範囲に於いて、高温におけるクリープ強度を多少犠牲にして、よりコストを重要視する場合は、０．０１質量％以下とし実質的に含有しないことである。
(Ru: 4.0% by mass or less)
Ru expands the solid solution area of the γ 'phase (intermetallic compound Ni 3 Al between Ni and Al) to facilitate solution treatment, and strengthens the γ phase by solid solution strengthening and fatigue resistance at high temperatures. Has the effect of improving. However, Ru is expensive, and increasing the content increases the price of the material. Further, if the Ru content exceeds 4.0% by mass, the precipitation of the γ ′ phase, which is a precipitation strengthening phase, is reduced and the high-temperature strength is lowered, so it is necessary to make it 4.0% by mass or less. is there. In this composition range, when the creep strength at high temperature is somewhat sacrificed and the cost is more important, it is 0.01 mass% or less and does not contain substantially.
（Ｎｂ：０．１質量％未満）
Ｎｂは、Ｔｉに近い特性を有する元素であり、Ｔｉほどではないが合金の耐食性を向上させるのに効果のある元素である。また、一部は、合金中のＡｌと置換し、強化相であるγ’相〔Ｎｉ３（Ａｌ＋Ｔｉ）〕を形成する。しかしながら、本発明合金のようにＴｉ、及びＡｌを多く合金では、Ｎｂを添加すると合金の耐食性及び高温強度をかえって低下させることからＮｂの添加は不要であり、０．１質量％以下にする必要がある。本発明の組成範囲に於いて、より好ましくは実質的に含有しないことである。
(Nb: less than 0.1% by mass)
Nb is an element having characteristics close to that of Ti, and is an element that is not as effective as Ti but is effective in improving the corrosion resistance of the alloy. Moreover, a part is substituted with Al in the alloy to form a γ ′ phase [Ni 3 (Al + Ti)] which is a strengthening phase. However, in the case of an alloy having a large amount of Ti and Al as in the present invention alloy, if Nb is added, the corrosion resistance and high-temperature strength of the alloy are reduced, so the addition of Nb is unnecessary, and it is necessary to make it 0.1% by mass or less. There is. In the composition range of this invention, it is more preferable not to contain substantially.
（Ｈｆ：０．１〜２．０質量％）
Ｈｆは合金表面に形成される保護皮膜（例えば、Ｃｒ２Ｏ３、Ａｌ２Ｏ３）の密着性を向上させ、高温での耐食・耐酸化性を向上させることが可能である。また、結晶粒界に共晶のＮｉ３Ｈｆを形成し、結晶粒界の強度を向上させる。保護皮膜の密着性を向上させるためには、０．１質量％以上の添加が必要である。Ｈｆの添加量が多くなると保護皮膜の密着性は著しく向上し、更に結晶粒界強度も向上するが、２．０質量％を越えるとＮｉ基耐超熱合金の融点を著しく下げて、溶体化処理温度を不可能とし、更に鋳造時に雰囲気中の酸素と反応してＨｆＯ２を形成し、鋳造品の表面欠陥となって鋳造歩留りを低下させることから、２．０質量％以下にすることが必要である。この組成範囲に於いて、耐食性、耐酸化特性、及び結晶粒界強度と合金の熱処理温度範囲のバランスを考慮した場合、好ましくは１．０〜２．０質量％の範囲であり、より好ましくは１．２〜１．６質量％の範囲であり、最も好ましいのは約１．４質量％のときである。
(Hf: 0.1 to 2.0% by mass)
Hf can improve the adhesion of a protective film (for example, Cr 2 O 3 , Al 2 O 3 ) formed on the alloy surface, and can improve corrosion resistance and oxidation resistance at high temperatures. In addition, eutectic Ni 3 Hf is formed at the crystal grain boundary to improve the strength of the crystal grain boundary. In order to improve the adhesion of the protective film, it is necessary to add 0.1% by mass or more. Increasing the amount of Hf significantly improves the adhesion of the protective film and further improves the grain boundary strength. However, if it exceeds 2.0% by mass, the melting point of the Ni-base superheat resistant alloy is remarkably lowered to form a solution. The treatment temperature is not possible, and further reacts with oxygen in the atmosphere at the time of casting to form HfO 2 , which becomes a surface defect of the cast product and lowers the casting yield. is necessary. In this composition range, in consideration of the corrosion resistance, oxidation resistance, and the balance between the grain boundary strength and the heat treatment temperature range of the alloy, the range is preferably 1.0 to 2.0% by mass, more preferably The range is 1.2 to 1.6% by mass, and the most preferable is about 1.4% by mass.
（Ｍｏ：１．０質量％未満）
ＭｏはＷと同様の効果を有するため、必要に応じてＷの一部と代替することが可能である。また、ＭｏはＷに比べて比重が小さいため合金の軽量化が図れ、γ’相の固溶温度をあげるため、クリープ強度を向上させる効果がある。しかし、クリープ強度向上にはＷほどの効果はないため、クリープ強度を向上させるためには、ＭｏよりもむしろＷを多く添加するほうが効果は大きい。更にＭｏは合金の耐酸化特性および耐食性を低下させるため、添加するとしてもその上限を１．０質量％未満とする必要がある。この組成範囲に於いて、高温における強度、耐食性及び高温での耐酸化特性のバランスを考慮した場合、好ましくは０．５質量％以下とし、最も好ましいのは０．１質量％以下として実質的に含有しないことである。
(Mo: less than 1.0% by mass)
Since Mo has the same effect as W, it can be replaced with a part of W if necessary. Further, Mo has a smaller specific gravity than W, so that the weight of the alloy can be reduced and the solid solution temperature of the γ ′ phase can be increased, so that the creep strength is improved. However, since the creep strength is not as effective as W, it is more effective to add more W than Mo to improve the creep strength. Furthermore, since Mo lowers the oxidation resistance and corrosion resistance of the alloy, even if it is added, the upper limit thereof needs to be less than 1.0% by mass. In this composition range, when considering the balance between strength at high temperature, corrosion resistance and oxidation resistance at high temperature, it is preferably 0.5% by mass or less, and most preferably 0.1% by mass or less. It does not contain.
（Ｃ：０．０５〜０．１５質量％）
Ｃは従来の普通鋳造合金および一方向凝固柱状晶合金においては、強化元素として必要不可欠の元素である。Ｃは合金中に一部固溶するが、大部分は結晶粒界にＴｉＣ、ＴａＣ等の炭化物を形成し、塊状に析出することで、結晶粒界の強度を向上させる。ＴｉＣ、ＴａＣ等の炭化物を形成し、結晶粒界の強度を向上させるためには０．０５質量％以上の添加が必要であるが、添加量が０．１５質量％を超えると、固溶強化元素であるＴａと炭化物を形成することにより、固溶強化Ｔａのみかけの含有量が少なくなり、高温でのクリープ強度を低下させる。そこで、Ｃの上限を０．１５質量％とした。この組成範囲に於いて、結晶粒界強度と高温でのクリープ強度とのバランスを考慮した場合、より好ましくは０．０５〜０．１質量％の範囲であり、最も好ましいのは約０．０７質量％のときである。
(C: 0.05-0.15 mass%)
C is an indispensable element as a strengthening element in conventional ordinary cast alloys and unidirectionally solidified columnar crystal alloys. C partially dissolves in the alloy, but most forms carbides such as TiC and TaC at the crystal grain boundaries and precipitates in a lump shape, thereby improving the strength of the crystal grain boundaries. In order to form carbides such as TiC and TaC and improve the strength of the grain boundaries, addition of 0.05% by mass or more is necessary, but if the addition amount exceeds 0.15% by mass, solid solution strengthening By forming carbide with Ta, which is an element, the apparent content of solid solution strengthened Ta is reduced, and the creep strength at high temperature is reduced. Therefore, the upper limit of C is set to 0.15% by mass. In this composition range, when considering the balance between the grain boundary strength and the creep strength at high temperature, the range is more preferably 0.05 to 0.1% by mass, and most preferably about 0.07. When mass%.
（Ｂ：０．００１〜０．０５質量％）
ＢはＣと同じく従来の普通鋳造合金および一方向凝固柱状晶合金においては、強化元素として必要不可欠の元素で有る。Ｂは合金中に殆んど固溶せず、結晶粒界に偏析することで結晶粒界の強度を向上させる。結晶粒界に偏析して、結晶粒界の強度を向上させるためには０．００１質量％以上の添加が必要であるが、添加量が０．０５質量％を超えると、結晶粒界でホウ化物〔（Ｃｒ、Ｎｉ、Ｔｉ、Ｍｏ）３Ｂ２〕を形成する。ホウ化物は、合金の融点に比べ著しく低融点であるため、合金の溶体化処理温度を不可能とすることから、上限を０．０５質量％とした。この組成範囲に於いて、結晶粒界強度と溶体化熱処理のバランスを考慮した場合、好ましくは０．０１〜０．０２質量％の範囲であり、より好ましくは０．０１〜０．０１８質量％の範囲であり、最も好ましいのは約０．０１５質量％のときである。
(B: 0.001 to 0.05 mass%)
B, like C, is an indispensable element as a strengthening element in conventional ordinary cast alloys and unidirectionally solidified columnar crystal alloys. B hardly dissolves in the alloy and segregates at the grain boundaries to improve the strength of the grain boundaries. In order to improve the strength of the grain boundary by segregating at the grain boundary, addition of 0.001% by mass or more is necessary. However, if the addition amount exceeds 0.05% by mass, boron is added at the grain boundary. The compound [(Cr, Ni, Ti, Mo) 3 B 2 ] is formed. Since the boride has a remarkably lower melting point than the melting point of the alloy, the solution treatment temperature of the alloy is impossible, so the upper limit was made 0.05 mass%. In this composition range, when considering the balance between grain boundary strength and solution heat treatment, it is preferably in the range of 0.01 to 0.02% by mass, more preferably 0.01 to 0.018% by mass. The most preferable case is about 0.015% by mass.
（Ｚｒ：０．００１〜０．０５質量％）
ＺｒはＢと同じく従来の普通鋳造合金および一方向凝固柱状晶合金においては、強化元素として必要不可欠の元素で有る。Ｚｒは一部合金中に固溶するが、殆んど固溶せず結晶粒界に偏析することで結晶粒界の強度を向上させる。結晶粒界に偏析して結晶粒界の強度を向上させるためには０．００１質量％以上の添加が必要であるが、添加量が０．０５質量％を超えると、結晶粒界でＮｉ３Ｚｒに代表されるＮｉとの金属間化合物を形成する。ＮｉとＺｒとの金属間化合物は、合金の融点に比べ著しく低融点であるため、合金の溶体化処理温度を不可能とすることから、上限を０．０５質量％とした。この組成範囲に於いて、結晶粒界強度と溶体化熱処理のバランスを考慮した場合、好ましくは０．０１〜０．０２質量％の範囲であり、より好ましくは０．０１〜０．０１８質量％の範囲であり、最も好ましいのは約０．０１５質量％のときである。
(Zr: 0.001 to 0.05 mass%)
Zr, like B, is an indispensable element as a strengthening element in conventional ordinary cast alloys and unidirectionally solidified columnar crystal alloys. Zr partially dissolves in the alloy, but hardly dissolves and segregates at the grain boundaries to improve the strength of the grain boundaries. In order to improve the strength of the crystal grain boundary by segregating at the crystal grain boundary, addition of 0.001% by mass or more is necessary. However, if the addition amount exceeds 0.05% by mass, Ni 3 is added at the crystal grain boundary. An intermetallic compound with Ni typified by Zr is formed. Since the intermetallic compound of Ni and Zr has a remarkably low melting point compared to the melting point of the alloy, the solution treatment temperature of the alloy is impossible, so the upper limit was made 0.05 mass%. In this composition range, when considering the balance between grain boundary strength and solution heat treatment, it is preferably in the range of 0.01 to 0.02% by mass, more preferably 0.01 to 0.018% by mass. The most preferable case is about 0.015% by mass.
（Ｌｕ：０．１質量％未満）
Ｌｕは希土類元素の一つであり、従来、希土類元素は、ＹやＣｅ等に代表されるように、合金表面に形成される保護皮膜（例えば、Ｃｒ２Ｏ３、Ａｌ２Ｏ３）の密着性を向上させ、高温での耐食、耐酸化性を向上させるために添加されてきた。今回の発明により、Ｌｕの別な効果として結晶粒界にＨｆと共に析出し、結晶粒界の強度を向上させることで、ＤＳ材のクリープ強度を向上させる働きがあることが明らかとなった。Ｌｕは、Ｈｆと共に析出することから、Ｈｆ程の添加は必要なく、結晶粒界の強度を向上させるためには、０．１質量％未満の添加で十分である。
(Lu: less than 0.1% by mass)
Lu is one of rare earth elements. Conventionally, rare earth elements are typically adhered to a protective film (eg, Cr 2 O 3 , Al 2 O 3 ) formed on the alloy surface, as represented by Y, Ce, and the like. Has been added to improve the corrosion resistance and oxidation resistance at high temperatures. According to the present invention, as another effect of Lu, it has been clarified that it precipitates together with Hf at the crystal grain boundary and improves the creep strength of the DS material by improving the strength of the crystal grain boundary. Since Lu precipitates together with Hf, addition as much as Hf is not necessary, and addition of less than 0.1% by mass is sufficient to improve the strength of the grain boundaries.
（Ｓｉ：０．１質量％以下）
Ｓｉは合金原料から持ち込まれ、不純物として存在する。Ｓｉは耐酸化特性向上の効化が認められるが、Ｈｆ程の効化はなく、過剰に存在するとＭｏやＷ等の耐火合金元素と金属間化合物を形成する。これらの金属間化合物が合金中に存在すると、クリープ変形中にクラックの起点となり、クリープ破断寿命が低下することから、上限を０．１質量％とした。この組成範囲に於いて、クリープ強度を低下させないためには、実質的に含有しないことである。
(Si: 0.1% by mass or less)
Si is brought from the alloy raw material and exists as an impurity. Si has an effect of improving the oxidation resistance, but is not as effective as Hf. When it is excessive, it forms an intermetallic compound with a refractory alloy element such as Mo or W. If these intermetallic compounds are present in the alloy, they become crack starting points during creep deformation and the creep rupture life is reduced, so the upper limit was made 0.1 mass%. In this composition range, in order not to lower the creep strength, it is not substantially contained.
（Ｐ：０．０１質量％以下、Ｓ：０．００５質量％以下）
これらの元素はいずれも合金原料から持ち込まれ、不純物として存在する。これらの元素は合金の耐食性を低下させることから、可能な限り少ないことが望まれるが、これらの元素の少ない減量は素材コストが高くなることから、素材コストとのバランスで実質的な実害が生じない含有量として、Ｐが０．０１質量％以下、Ｓが：０．００５質量％以下とした。
(P: 0.01% by mass or less, S: 0.005% by mass or less)
All of these elements are brought from the alloy raw material and exist as impurities. Since these elements reduce the corrosion resistance of the alloy, it is desirable that the amount be as small as possible. However, a small weight loss of these elements increases the material cost, so there is substantial actual harm in balance with the material cost. The content of P was 0.01% by mass or less, and S was 0.005% by mass or less.
（Ｏ：０．００５質量％以下、Ｎ：０．００５質量％以下）
これらのいずれの元素も、合金原料から持ち込まれることが多く、Ｏはるつぼからも入り、合金中には酸化物（Ａｌ２Ｏ３）や窒化物（ＴｉＮ或いはＡｌＮ）として塊状に存在する。合金中にこれらが存在すると、クリープ変形中にこれらがクラックの起点となり、クリープ破断寿命が低下する。そこで両元素の上限をいずれも０．００５質量％とした。
(O: 0.005 mass% or less, N: 0.005 mass% or less)
Any of these elements are often brought in from the alloy raw material, O enters also from the crucible, and exists in the alloy as an oxide (Al 2 O 3 ) or nitride (TiN or AlN). If they are present in the alloy, they become the starting point of cracks during creep deformation and the creep rupture life is reduced. Therefore, the upper limit of both elements was set to 0.005% by mass.
表１に、本発明実施例合金（Ｎｏ．Ａ１〜Ａ２５）、及び既存合金（Ｎｏ．Ｂ１〜Ｂ３）の化学組成を示す。 Table 1 shows the chemical compositions of the inventive alloys (No. A1 to A25) and the existing alloys (No. B1 to B3).
Ｂ１は、航空機用ジェットエンジンの動静翼として広く使用されている合金であり、Ｂ２及びＢ３はクロムを１４質量％含み耐食性に優れていることから、発電用大型ガスタービンの動翼材として広く使用されている合金である。 B1 is an alloy widely used as a moving blade and stationary blade of an aircraft jet engine, and B2 and B3 contain 14% by mass of chromium and have excellent corrosion resistance. Therefore, B1 is widely used as a blade material for large gas turbines for power generation. Alloy.
最初に各合金の素材を配合後、容量１５ｋｇの耐火るつぼを用い、真空誘導炉で直径７０ｍｍ、長さ２００ｍｍのインゴットを溶製した。表２に溶製したインゴットの不純物量を示す。 First, after blending the materials of each alloy, an ingot having a diameter of 70 mm and a length of 200 mm was melted in a vacuum induction furnace using a refractory crucible having a capacity of 15 kg. Table 2 shows the amount of impurities in the melted ingot.
次に、上記インゴットを用いて、厚さ１５ｍｍ、幅１００ｍｍ、長さ２００ｍｍの試験片を鋳型引き出し式一方向凝固法で鋳造した。鋳造は、アルミナ質のセラミック鋳型を用い、鋳型加熱温度：１５００℃、鋳型引き出し速度：２０〜３０ｃｍ／ｈ（ｃｍ／時間）とし、全て真空中で行った。 Next, using the ingot, a test piece having a thickness of 15 mm, a width of 100 mm, and a length of 200 mm was cast by a mold drawing type unidirectional solidification method. Casting was performed in a vacuum using an alumina ceramic mold at a mold heating temperature of 1500 ° C. and a mold drawing speed of 20 to 30 cm / h (cm / hour).
鋳造した一方向凝固試験片には、表３に示す溶体化熱処理および時効熱処理を行った。これらの条件は別途予備試験を行い、マクロ組織及びミクロ組織から決定した。 The cast unidirectionally solidified test piece was subjected to solution heat treatment and aging heat treatment shown in Table 3. These conditions were determined from a macro structure and a microstructure by conducting a preliminary test separately.
本表において、１５１３Ｋ／４ｈは、１５１３Ｋ（ケルビン）で４時間保持することを意味する。本表の他の温度及び時間の条件、並びに後述の温度及び時間の条件についても同様である。また、既存合金Ｂ１の溶体化熱処理条件１５０３Ｋ／２ｈ＋１５２３Ｋ／２ｈは、１５０３Ｋで２時間保持した後、これに続けて１５２３Ｋで２時間保持することを意味する。また、ＧＦＣは、ガス強制冷却の略称である。 In this table, 1513K / 4h means holding at 1513K (Kelvin) for 4 hours. The same applies to the other temperature and time conditions in this table and the temperature and time conditions described below. Further, the solution heat treatment condition 1503K / 2h + 1523K / 2h of the existing alloy B1 means that after holding at 1503K for 2 hours, subsequently holding at 1523K for 2 hours. GFC is an abbreviation for forced gas cooling.
熱処理した一方向凝固試験片から機械加工により、平行部直径６．０ｍｍ、平行部長さ３０ｍｍのクリープ試験片と、長さ２５ｍｍ、幅１０ｍｍ、厚さ１．５ｍｍの高温酸化試験片および直径８ｍｍ、長さ４０ｍｍの高温腐食試験片を切り出した。 A creep test specimen having a parallel part diameter of 6.0 mm and a parallel part length of 30 mm, a high-temperature oxidation test specimen having a length of 25 mm, a width of 10 mm, and a thickness of 1.5 mm and a diameter of 8 mm by machining from the heat-treated unidirectional solidification test piece. A 40 mm long hot corrosion test piece was cut out.
表４に一方向凝固試験片に対して行った特性評価試験条件を示す。クリープ破断試験は、試験温度及び応力をそれぞれ、１３１３Ｋ、１３７ＭＰａ；１２５５Ｋ、２０６ＭＰａ；１１９３Ｋ、３１４ＭＰａとする３条件で行った。高温酸化試験は、温度１３１３Ｋ、６００時間の繰返し酸化試験とし、３０００時間酸化後の重量変化を測定した。また、高温腐食試験は、燃焼ガス中にＮａＣｌを８０ｐｐｍ添加し、９００℃（１１７３Ｋ）の温度条件で２５時間の燃焼ガス中腐食試験を行い、２５時間腐食試験後の重量変化を測定した。 Table 4 shows the characteristic evaluation test conditions performed on the unidirectionally solidified test piece. The creep rupture test was performed under three conditions, with the test temperature and stress being 1313K, 137 MPa; 1255K, 206 MPa; 1193K, and 314 MPa, respectively. The high temperature oxidation test was a repeated oxidation test at a temperature of 1313 K and 600 hours, and the change in weight after oxidation for 3000 hours was measured. In the high-temperature corrosion test, 80 ppm of NaCl was added to the combustion gas, and the corrosion test in the combustion gas for 25 hours was performed at a temperature of 900 ° C. (1173 K), and the weight change after the 25-hour corrosion test was measured.
表５に特性評価試験結果をまとめて示す。図１〜図３は、表５の結果を見やすく図にして示したものである。図１から明らかなように、本発明合金は、既存合金Ｂ１、Ｂ２、Ｂ３より、クリープ強度が優れていることがわかる。また、Ｔｉ量が少ないＢ１合金は、耐食性が悪くなっている。クロム量が高く耐食性に優れているＢ２、Ｂ３合金は、Ｂ２の耐酸化性は良好であるものの、Ｂ３の耐酸化性が悪く、またクリープ破断強度も低くなっている。 Table 5 summarizes the results of the characteristic evaluation test. 1 to 3 show the results of Table 5 in an easily viewable manner. As is apparent from FIG. 1, the alloy of the present invention has a higher creep strength than the existing alloys B1, B2, and B3. Further, the B1 alloy with a small amount of Ti has poor corrosion resistance. B2 and B3 alloys having a high chromium content and excellent corrosion resistance have good oxidation resistance of B2, but poor oxidation resistance of B3 and low creep rupture strength.
ガスタービンに使用される合金には、優れたクリープ強度、耐酸化性、耐食性が要求されており、これら特性のバランスが取れていることが必要不可欠である。従って、表５に示す結果より明らかなように、本発明実施例合金Ｎｏ．Ａ１〜Ａ２５では、高温クリープ強度、高温耐食性、耐酸化特性に優れたバランスの取れた合金であることが認められた。 Alloys used in gas turbines are required to have excellent creep strength, oxidation resistance, and corrosion resistance, and it is essential that these characteristics be balanced. Therefore, as is clear from the results shown in Table 5, Example Alloy No. A1 to A25 were found to be balanced alloys with excellent high-temperature creep strength, high-temperature corrosion resistance, and oxidation resistance.
これに対して、既存の合金では、高温での耐酸化特性が優れた合金は、耐食性が悪く、耐食性が良い合金は、耐酸化特性が劣っており、すべての特性に優れたバランスの取れた合金にはなっていない。 On the other hand, with existing alloys, alloys with excellent oxidation resistance at high temperatures have poor corrosion resistance, and alloys with good corrosion resistance have poor oxidation resistance, providing an excellent balance of all properties. It is not an alloy.
以上のことから、本発明合金は、クリープ破断強度、耐酸化特性及び耐食性に優れていることは明らかである。例えば、ジェットエンジンやガスタービンなどの動力機関における高性能化および高効率化のためにタービン入口温度を高める場合にも十分対応し得るものである。 From the above, it is clear that the alloy of the present invention is excellent in creep rupture strength, oxidation resistance and corrosion resistance. For example, the present invention can sufficiently cope with a case where the turbine inlet temperature is increased in order to improve performance and efficiency in a power engine such as a jet engine or a gas turbine.
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| CN115537603B (en) * | 2021-06-30 | 2023-08-11 | 宝武特种冶金有限公司 | High-temperature-resistant nickel-based alloy, manufacturing method and application thereof |
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