JP2014074208A - HIGH STRENGTH Ni-BASED SUPERALLOY, AND GAS TURBINE USING THE SAME - Google Patents
HIGH STRENGTH Ni-BASED SUPERALLOY, AND GAS TURBINE USING THE SAME Download PDFInfo
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- 229910000601 superalloy Inorganic materials 0.000 title claims abstract description 17
- RLQJEEJISHYWON-UHFFFAOYSA-N flonicamid Chemical compound FC(F)(F)C1=CC=NC=C1C(=O)NCC#N RLQJEEJISHYWON-UHFFFAOYSA-N 0.000 title 1
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 14
- 229910052702 rhenium Inorganic materials 0.000 claims abstract description 11
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 10
- 239000012535 impurity Substances 0.000 claims abstract description 8
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 7
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 5
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 5
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 4
- 239000000956 alloy Substances 0.000 abstract description 73
- 229910045601 alloy Inorganic materials 0.000 abstract description 72
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- 150000001247 metal acetylides Chemical class 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
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- -1 and Co are added Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
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- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
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- Turbine Rotor Nozzle Sealing (AREA)
Abstract
Description
本発明は、高温強度を有するＮｉ基超合金と、それを用いたガスタービンに関する。 The present invention relates to a Ni-base superalloy having high temperature strength and a gas turbine using the same.
近年、化石燃料の節約、二酸化炭素の排出量削減、地球温暖化防止等、環境意識の高まりから、内燃機関においては熱効率の向上が図られている。ガスタービンやジェットエンジン等の熱機関は、カルノーサイクルの高温側をより高温で運転することにより、熱効率を有効に高めることが知られている。タービン入口温度の高温化に伴い、ガスタービンの高温部品、すなわち、燃焼器やタービン動翼又は静翼に使用される材料の改良・開発の重要性が高まっている。 In recent years, due to increasing environmental awareness, such as saving fossil fuels, reducing carbon dioxide emissions, and preventing global warming, internal combustion engines have been improved in thermal efficiency. It is known that heat engines such as gas turbines and jet engines effectively increase thermal efficiency by operating the high temperature side of the Carnot cycle at higher temperatures. As the turbine inlet temperature increases, the importance of improving and developing materials used for high-temperature parts of gas turbines, that is, combustors, turbine rotor blades or stationary blades, is increasing.
この高温化に対処するために、材料面ではより高温強度に優れるＮｉ基耐熱合金が適用されており、現在多くのＮｉ基合金が使用されている。Ｎｉ基合金には、等軸晶からなる普通鋳造合金、柱状晶からなる一方向凝固合金及び一つの結晶からなる単結晶合金がある。Ｎｉ基合金を高強度化するためには、固溶強化元素であるＷ、Ｍｏ、Ｔａ、Ｃｏ等を多く添加するとともに、Ａｌ、Ｔｉ等を添加して強化相であるγ´Ｎｉ3（Ａｌ、Ｔｉ）相を多く析出させることが重要である。 In order to cope with this high temperature, a Ni-based heat-resistant alloy that is superior in high-temperature strength is applied in terms of material, and many Ni-based alloys are currently used. Ni-based alloys include normal cast alloys made of equiaxed crystals, unidirectionally solidified alloys made of columnar crystals, and single crystal alloys made of one crystal. In order to increase the strength of the Ni-based alloy, a large amount of solid solution strengthening elements such as W, Mo, Ta, and Co are added, and Al, Ti, and the like are added to form a strengthening phase γ′Ni 3 (Al , Ti) phase is important to be precipitated.
近年の効率向上に伴う燃焼温度（タービン入口温度）の上昇により、Ｃｏ基合金よりも高温強度に優れるＮｉ基合金を使用することが検討されている。Ｎｉ基合金を高強度化するためには、固溶強化元素であるＷ、Ｍｏ、Ｔａ、Ｃｏ等を多く添加するとともに、Ａｌ、Ｔｉ等を添加して強化相であるγ´Ｎｉ3(Ａｌ、Ｔｉ)相の析出強化を利用することで、優れた高温強度及び熱疲労特性を有する。 Due to the increase in combustion temperature (turbine inlet temperature) accompanying efficiency improvement in recent years, the use of Ni-based alloys that are superior in high-temperature strength to Co-based alloys has been studied. In order to increase the strength of the Ni-based alloy, a large amount of solid solution strengthening elements such as W, Mo, Ta, and Co are added, and Al, Ti, and the like are added to form a strengthening phase γ′Ni 3 (Al , Ti) By using precipitation strengthening of the phase, it has excellent high temperature strength and thermal fatigue characteristics.
一方、燃料価格の高騰により、産業用ガスタービンの燃料として腐食の原因となる不純物を多く含む低品質の燃料を使用する動きがあり、高温強度と耐食性を兼ね備えた材料の開発も必要とされている。このような材料では、保護性の皮膜を形成するＣｒを多く添加することが望ましい。耐食性を重視した合金として、例えば特許文献１に開示される普通鋳造合金が挙げられる。 On the other hand, due to soaring fuel prices, there is a movement to use low-quality fuel that contains many impurities that cause corrosion as fuel for industrial gas turbines, and the development of materials that combine high-temperature strength and corrosion resistance is also required. Yes. In such a material, it is desirable to add a large amount of Cr that forms a protective film. As an alloy that places importance on corrosion resistance, for example, a normal casting alloy disclosed in Patent Document 1 can be cited.
しかし、従来の合金では、高温強度を追求するために、固溶強化元素Ｗ、Ｔａを多く含むほど材料組織の安定性が低下し、長時間の使用に際してσ相等の硬質で脆いＴＣＰ有害相が析出しやすい。すなわち、優れた高温クリープ強度と、耐酸化性及び耐食性とを併せ持つ合金材料を開発することは困難であった。 However, in the conventional alloy, in order to pursue high temperature strength, the more the solid solution strengthening elements W and Ta are contained, the lower the stability of the material structure, and the hard and brittle TCP harmful phase such as σ phase is used for a long time use. Easy to precipitate. That is, it has been difficult to develop an alloy material having both excellent high-temperature creep strength, oxidation resistance, and corrosion resistance.
本発明の目的は、普通鋳造材おいて、高価な元素Ｔａ、Ｒｅを添加せず、従来の合金と同等以上の腐食性を有し、高温でのクリープ強度及び耐酸化性を向上したＮｉ基超合金を提供することにある。 The object of the present invention is to add a Ni-based alloy that has the same or better corrosiveness as a conventional alloy without adding the expensive elements Ta and Re in ordinary casting materials, and has improved creep strength and oxidation resistance at high temperatures. To provide a superalloy.
Ｎｉ基超合金は、質量で、Ｃｒ：１１．０％〜１５．０％、Ｍｏ：０．１％〜０．５％、Ｔｉ：０．５％〜２．１％、Ａｌ：４．５％〜７．０％、Ｃｏ：９．５％〜２０．０％、Ｗ：１０．１〜１５．０％、Ｈｆ：０．５％以下、Ｎｂ：０．００５％〜０．６０％、Ｂ：０．０２％以下、Ｃ：０．２％以下を含み、Ｔａ，Ｒｅを含まず、残部がＮｉと不可避不純物であることを特徴とする。 Ni-base superalloy is, by mass, Cr: 11.0% to 15.0%, Mo: 0.1% to 0.5%, Ti: 0.5% to 2.1%, Al: 4.5 % To 7.0%, Co: 9.5% to 20.0%, W: 10.1 to 15.0%, Hf: 0.5% or less, Nb: 0.005% to 0.60%, B: 0.02% or less, C: 0.2% or less, Ta and Re are not included, and the balance is Ni and inevitable impurities.
本発明によれば、従来の合金と同等以上の腐食性を有し、高温でのクリープ強度及び耐酸化性を向上した安価なＮｉ基超合金を提供することができる。 According to the present invention, it is possible to provide an inexpensive Ni-base superalloy having a corrosivity equivalent to or higher than that of a conventional alloy and having improved creep strength and oxidation resistance at high temperatures.
以下、本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
まず、図４に、産業用ガスタービン用のタービン動翼の一例を示す。 First, FIG. 4 shows an example of a turbine rotor blade for an industrial gas turbine.
タービン動翼１は、翼部１１０とシャンク部１１１とルート部（ダブティル部）１１２から構成され、大きさは１０〜１００cm、重量は１〜１０kg程度である。また、プラットホーム部１１３と、ラジアルフィン１１４を備えている。タービン動翼は、内部に複雑な冷却構造を持つ回転部品であり、回転中の遠心力及び起動停止に伴う熱応力の負荷が繰り返し加わる厳しい環境に曝される。基本的な材料特性として、優れた高温クリープ強度、高温燃焼ガス雰囲気に対する耐酸化、耐食性が要求される。
本発明者らは、普通鋳造用合金であって、耐食性を維持しながら、従来材より更なる優れた高温クリープ強度及び耐酸化性を得る合金を検討した結果、本発明を見出すに至ったものである。
The turbine rotor blade 1 includes a blade portion 110, a shank portion 111, and a root portion (dovetil portion) 112, and has a size of 10 to 100 cm and a weight of about 1 to 10 kg. Moreover, the platform part 113 and the radial fin 114 are provided. The turbine rotor blade is a rotating part having a complicated cooling structure inside, and is exposed to a severe environment in which a centrifugal force during rotation and a load of thermal stress accompanying start and stop are repeatedly applied. As basic material properties, excellent high temperature creep strength, oxidation resistance to high temperature combustion gas atmosphere, and corrosion resistance are required.
The inventors of the present invention have found the present invention as a result of investigating an alloy that is an ordinary casting alloy and obtains a higher temperature creep strength and oxidation resistance than conventional materials while maintaining corrosion resistance. It is.
一般的なガスタービンの翼の作製手段としては、普通鋳造、一方向凝固鋳造及び単結晶鋳造による手法が挙げられる。一方向凝固合金や単結晶合金は、主に小型で軽量なジェットエンジン（航空用ガスタービン）の動翼に使用されている。しかし、一方向凝固合金や単結晶合金を用いた翼は、鋳造プロセスが複雑であるため、翼を鋳造した時の鋳造歩留りが悪くなる。特に、産業用ガスタービンの翼では形状が大きく、形も複雑であることから、鋳造歩留りが低く、そのため高価になりやすい。 General means for producing the blades of a gas turbine include a technique using ordinary casting, unidirectional solidification casting, and single crystal casting. Unidirectionally solidified alloys and single crystal alloys are mainly used in the moving blades of small and lightweight jet engines (aviation gas turbines). However, a wing using a unidirectionally solidified alloy or a single crystal alloy has a complicated casting process, so that the casting yield when the wing is cast deteriorates. In particular, the blades of industrial gas turbines are large in shape and complex in shape, so that the casting yield is low, and therefore they are likely to be expensive.
そこで、本発明者らは、各合金添加元素のバランスをとり、特に普通鋳造用の合金として、耐食性を維持しながら、従来材より高い高温強度及び耐酸化性を有する合金を検討した。
以下、本発明のＮｉ基合金に含まれる各成分の働き、好ましい組成範囲について説明する。
Therefore, the present inventors have examined the alloys having higher high-temperature strength and oxidation resistance than conventional materials while maintaining the corrosion resistance by balancing each additive element of the alloy and maintaining the corrosion resistance.
Hereinafter, the function of each component contained in the Ni-based alloy of the present invention and the preferred composition range will be described.
Ｃｒ：１１.００〜１５.００質量％
Ｃｒは、固溶強化元素として働くと共に緻密な酸化皮膜を形成し高温における腐食雰囲気下で耐酸化、耐高温腐蝕性に寄与する。特に、溶融塩腐食に対する耐食性を向上させるためには、Ｃｒ含有量をより増加させるほど効果は大きくなる。そして、その効果がより著に現れるのは１１.００質量％を超えてからである。しかし、本発明の合金では、固溶強化元素Ｗが多く添加されているため、Ｃｒ量が多くなりすぎると、脆いＴＣＰ相が析出して高温強度が低下する。そのため、他の合金元素とのバランスをとって、その上限を１５.０質量％とすることが望ましい。この組成範囲に於いて、高強度と高耐食性が得られる。好ましくは１１.５０〜１４.５０質量％の範囲である。
Cr: 11.00 to 15.00 mass%
Cr acts as a solid solution strengthening element and forms a dense oxide film, contributing to oxidation resistance and high temperature corrosion resistance in a corrosive atmosphere at high temperatures. In particular, in order to improve the corrosion resistance against molten salt corrosion, the effect increases as the Cr content increases. And the effect appears more markedly after exceeding 11.00% by mass. However, in the alloy of the present invention, since a large amount of the solid solution strengthening element W is added, if the amount of Cr is excessively large, a brittle TCP phase is precipitated and the high temperature strength is lowered. Therefore, it is desirable to balance with other alloy elements and to set the upper limit to 15.0% by mass. In this composition range, high strength and high corrosion resistance can be obtained. Preferably it is the range of 11.50-14.50 mass%.
Ｃｏ：９．５０〜２０.００質量％
Ｃｏはγ´相の固溶温度を低下させ、溶体化熱処理を容易にする効果があり、特に本発明合金のように、部分溶体化で使用される場合には低い熱処理温度でも溶体化率を大きくすることが可能となる。その効果を得るためには、９．５０％以上の添加が必要である。
しかし、Ｃｏの過度の添加は、γ´相を不安定化し、強度低下につながる。従って、Ｃｏは最大でも２０.００％にする必要がある。この組成範囲に於いて、高い高温強度が得られる。好ましくは１０.００〜１８.００質量％の範囲である。
Co: 9.50 to 20.00% by mass
Co has the effect of lowering the solid solution temperature of the γ ′ phase and facilitating solution heat treatment. Especially when used in partial solution formation, as in the case of the present invention alloy, the solution rate is reduced even at a low heat treatment temperature. It becomes possible to enlarge. In order to obtain the effect, it is necessary to add 9.50% or more.
However, excessive addition of Co destabilizes the γ ′ phase and leads to a decrease in strength. Therefore, Co needs to be 20.00% at the maximum. In this composition range, high high-temperature strength can be obtained. Preferably it is the range of 10.00 to 18.00 mass%.
Ａｌ：４.５０〜７.００質量％
Ａｌはγ´相（Ｎｉ3Ａｌ）を形成するために必須の元素であり、６０％分率γ´を形成するために、最低でも４.５０％以上の添加が必要である。ＡｌはＡｌ2Ｏ3保護皮膜を形成することで、耐酸化性及び耐食性を向上させる。しかし、過度に添加するとγ´相の固溶強化度が低下し、高温強度が低下することから、添加量は最大でも７.００％にする必要がある。この組成範囲において、高温における強度と耐酸化特性、耐食性のバランスを考慮した場合、好ましくは４.８０〜６．５０質量％の範囲である。
Al: 4.50 to 7.00 mass%
Al is an essential element for forming the γ ′ phase (Ni 3 Al), and in order to form the 60% fraction γ ′, it is necessary to add at least 4.50% or more. Al improves the oxidation resistance and corrosion resistance by forming an Al 2 O 3 protective film. However, if added excessively, the solid solution strengthening degree of the γ ′ phase is lowered and the high-temperature strength is lowered. Therefore, the addition amount needs to be 7.00% at the maximum. In this composition range, when considering the balance between strength at high temperature, oxidation resistance, and corrosion resistance, the range is preferably 4.80 to 6.50 mass%.
Ｔｉ：０.５０〜２.１０質量％
ＴｉはＣｒとＡｌの複合酸化物の形成を防止し、合金の耐食性を向上させる効果がある。然し、Ｔｉの添加ではγ´相の固相線温度を下げるから、高温強度を低下させるため、溶融塩腐食に対する耐食性を維持するためには、０.５０質量％以上の含有量が必要である。しかし、２.１０質量％を越えて添加すると、更に脆化相のη相が析出してくるため、また、γ´相の形成元素としてγ´相の析出量はＴｉの添加量とともに増加し、γ´相の析出量を制御するために、その上限を２.１０質量％とする必要がある。本発明合金のようにＣｒを１１.０〜１５.０質量％含む合金において、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０.８０〜１.７０質量である。
Ti: 0.50 to 2.10% by mass
Ti has the effect of preventing the formation of a complex oxide of Cr and Al and improving the corrosion resistance of the alloy. However, the addition of Ti lowers the solidus temperature of the γ 'phase, so that the high-temperature strength is lowered. Therefore, in order to maintain the corrosion resistance against molten salt corrosion, a content of 0.50% by mass or more is necessary. . However, if added over 2.10% by mass, the η phase of the embrittlement phase is further precipitated, and the amount of precipitation of the γ ′ phase as the γ ′ phase forming element increases with the amount of Ti added. In order to control the precipitation amount of the γ ′ phase, the upper limit thereof needs to be 2.10% by mass. In an alloy containing 11.0 to 15.0% by mass of Cr as in the case of the present invention alloy, the balance between strength, corrosion resistance and oxidation resistance at high temperature is preferably 0.80 to 1.70 mass.
Ｗ：１０.１０〜１５.００質量％
Ｗは、高価元素Ｒｅを除いて、最も固溶強化の効果がある元素であり、主にγ相を固溶強化する。従って、優れた高温強度を求めるために、本発明には組織の安定性を維持する限り、Ｗを多めに添加する。なお、Ｗは、Ｍｏと同様固溶強化元素であって剛性率の向上と拡散係数の低減に寄与するが、Ｍｏと比較しμ相中への経年的な移行は少なく、長期間安定して強化に寄与する。γ相とγ´相の格子定数ミスマッチをより少なくすると、γとγ´の相の界面強度を向上させ、高温クリープ強度を向上させる。Ｗはγ相側に入る元素で、反対にＴａは析出相であるγ´相側にお主に入る元素である。Ｗ量が多い合金はγ相側の格子定数が大きくなり、一般に（γ´相の格子定数−γ相の格子定数）／（両相の格子定数平均）で定義される格子定数ミスマッチが小さくなる。従って、γ相とγ´相の格子定数ミスマッチを小さくするためには、Ｗ量は最低１０．１０％以上である。しかし、Ｗの過度の添加は、合金の相安定を悪化させＴＣＰ相等の析出につながり、耐食性を低下させるため、最大でも１５.００％にする必要がある。更に高温での長時間使用により、α−Ｃｒを析出させ、高温強度と延性が低下する。好ましくは１０.５０〜１４.５０質量％の範囲である。
W: 10.10-15.00 mass%
W is an element having the most solid solution strengthening effect except for the expensive element Re, and mainly strengthens the γ phase by solid solution strengthening. Therefore, in order to obtain an excellent high temperature strength, a large amount of W is added to the present invention as long as the stability of the structure is maintained. W is a solid solution strengthening element similar to Mo and contributes to the improvement of the rigidity and the reduction of the diffusion coefficient. Contributes to strengthening. If the lattice constant mismatch between the γ phase and the γ ′ phase is reduced, the interface strength between the γ and γ ′ phases is improved, and the high temperature creep strength is improved. W is an element that enters the γ phase side, and conversely Ta is an element that mainly enters the γ ′ phase side, which is a precipitated phase. An alloy having a large amount of W has a large lattice constant on the γ phase side, and generally has a small lattice constant mismatch defined by (lattice constant of γ ′ phase−lattice constant of γ phase) / (average of lattice constants of both phases). . Therefore, in order to reduce the lattice constant mismatch between the γ phase and the γ ′ phase, the amount of W is at least 10.10%. However, excessive addition of W deteriorates the phase stability of the alloy and leads to precipitation of the TCP phase and the like, and lowers the corrosion resistance. Therefore, it is necessary to make it at most 15.00%. Furthermore, α-Cr is precipitated by long-term use at a high temperature, and the high-temperature strength and ductility are reduced. Preferably it is the range of 10.50-14.50 mass%.
Ｍｏ：０.１０〜０.５０質量％
ＭｏはＷと同様の効果を有するため、必要に応じてＷの一部と代替えすることが可能である。また、γ´相の固溶温度をあげるため、Ｗと同様にクリープ強度を向上させる効果がある。そして、このような効果を得るためには０.１質量％以上の含有量が必要であり、Ｍｏの含有量が増えるにつれてクリープ強度も向上する。
Mo: 0.10 to 0.50 mass%
Since Mo has the same effect as W, it can be replaced with a part of W if necessary. In addition, since the solid solution temperature of the γ ′ phase is increased, the effect of improving the creep strength as in the case of W is obtained. And in order to acquire such an effect, content of 0.1 mass% or more is required, and creep strength improves as Mo content increases.
一方、Ｍｏは合金の耐酸化特性および耐食性を低下させる。特にＭｏの含有量が増えるにつれて耐酸化特性が大幅に悪くなることから、その上限を０.５０質量％とする必要がある。また、μ相析出によるマトリックス劣化の要因となっているＭｏを少なくし、その代りにマトリックス強化に役立つＷを多く添加する。従って、耐食性や高温での耐酸化特性は従来合金とほぼ同等とし、クリープ強度を重要視する場合は、好ましくは０.１０〜０.４０質量％の範囲である On the other hand, Mo reduces the oxidation resistance and corrosion resistance of the alloy. In particular, as the content of Mo increases, the oxidation resistance is greatly deteriorated, so the upper limit thereof needs to be 0.50% by mass. Further, Mo which is a factor of matrix deterioration due to μ phase precipitation is reduced, and instead, a large amount of W useful for matrix strengthening is added. Accordingly, the corrosion resistance and oxidation resistance at high temperature are almost the same as those of conventional alloys, and when the creep strength is important, it is preferably in the range of 0.10 to 0.40% by mass.
Ｎｂ：０.００５〜０.６０質量％
Ｎｂは、ＣｒとＡｌの複合酸化物の形成を防止し、合金の耐食性を改善する効果がある。γ´相を固溶強化する効果はＴｉより高い。従って、Ｎｂは高温強度を落とさずに耐食性を改善できる有効な元素であり、０.００５％以上添加する必要がある。しかしながら、γ´相の相安定性を保つためには、Ｎｂの添加量は０.６０％以下とする必要がある。
耐食性を特に重視する場合は、０.１０％以上の添加が好ましい。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０.１０〜０.６０質量％の範囲である。
Nb: 0.005 to 0.60 mass%
Nb has the effect of preventing the formation of a complex oxide of Cr and Al and improving the corrosion resistance of the alloy. The effect of strengthening the γ ′ phase by solid solution is higher than Ti. Therefore, Nb is an effective element that can improve the corrosion resistance without decreasing the high temperature strength, and it is necessary to add 0.005% or more. However, in order to maintain the phase stability of the γ ′ phase, the amount of Nb added needs to be 0.60% or less.
When the corrosion resistance is particularly important, addition of 0.10% or more is preferable. In consideration of the balance between strength, corrosion resistance and oxidation resistance at high temperatures, the range is preferably from 0.10 to 0.60% by mass.
Ｃ：０.２０質量％以下
Ｃは、Ｔｉ、Ｎｂ等とＭＣ型炭化物、Ｃｒ、Ｗ、Ｍｏ等とＭ23Ｃ6及びＭ6Ｃ型炭化物を形成し、高温で結晶粒界が移動するのを阻止することで結晶粒界を強化する効果があり、本発明において特に重要な役割を果たす元素である。普通鋳造材で、この効果を発揮させるためには最低でも０.０５％以上添加する必要がある。また、強度と延性をいずれも増大させたい場合には、０.１０％以上添加することが好ましい。しかし、Ｃ量を多くしすぎると、γ相及びγ´相の固溶強化に有効な元素が炭化物にとられることで、かえって高温強度が低下するようになる。また、過剰の炭化物は疲労強度を低下させる。従って、Ｃの上限は０.２０％に規制する必要がある。単結晶材では、粒界強化が不要となり、Ｃの添加が０または０．００２以下である。
C: 0.20% by mass or less C forms MC type carbides with Ti, Nb, etc., and M 23 C 6 and M 6 C type carbides with Cr, W, Mo, etc., and the grain boundaries move at high temperatures. Is an element that plays an especially important role in the present invention. It is necessary to add 0.05% or more at least in order to exhibit this effect with ordinary cast material. Further, when it is desired to increase both strength and ductility, it is preferable to add 0.10% or more. However, if the amount of C is excessively increased, elements effective for solid solution strengthening of the γ phase and the γ ′ phase are taken into the carbide, so that the high temperature strength is lowered. Excess carbides also reduce fatigue strength. Therefore, the upper limit of C needs to be regulated to 0.20%. In the single crystal material, grain boundary strengthening is unnecessary, and the addition of C is 0 or 0.002 or less.
Ｂ：０.０２質量％以下
Ｂは結晶粒界の非整合部を埋め、結晶粒界の結合力を増加させる効果がある。本発明の合金においては、最低でも０.００５％のＢの添加が必要である。普通鋳造材として、より高い粒界強度が要求される場合には０.０１０％以上添加することが望ましい。しかし、ＢはＮｉ基超合金の融点を著しく低下させるため、最大でも０.０２％とする必要がある。
B: 0.02 mass% or less B has an effect of filling non-matching portions of crystal grain boundaries and increasing the bonding strength of crystal grain boundaries. In the alloy of the present invention, at least 0.005% of B needs to be added. When higher grain boundary strength is required as a normal cast material, it is desirable to add 0.010% or more. However, since B significantly lowers the melting point of the Ni-base superalloy, it is necessary to be 0.02% at the maximum.
Ｈｆ：０〜２.００質量％、Ｚｒ：０〜０.０５質量％
Ｈｆ、及びＺｒは、結晶粒界に偏析して結晶粒界の強度を若干向上させる。しかし、大部分はＮｉとの金属間化合物すなわちＮｉ3Ｚｒ等を結晶粒界に形成する。この金属間化合物は合金の延性を低下させ、また低融点であるため、合金の溶融温度が低下し、溶体化処理温度範囲が狭くなる等、有効な作用が少ない。したがって、その上限はそれぞれ２.００質量％、０.５０質量％、及び０.０５質量％とした。好ましくは、Ｈｆが０〜０.１０質量％、Ｚｒが０〜０.０３質量％である。
Hf: 0 to 2.00% by mass, Zr: 0 to 0.05% by mass
Hf and Zr are segregated at the grain boundaries to slightly improve the strength of the grain boundaries. However, most of them form an intermetallic compound with Ni, that is, Ni 3 Zr or the like, at the grain boundaries. Since this intermetallic compound lowers the ductility of the alloy and has a low melting point, it has little effective action such as a reduction in the melting temperature of the alloy and a narrowing of the solution treatment temperature range. Therefore, the upper limit was made 2.00 mass%, 0.50 mass%, and 0.05 mass%, respectively. Preferably, Hf is 0 to 0.10% by mass and Zr is 0 to 0.03% by mass.
Ｏ：０〜０.００５質量％、Ｎ：０〜０.００５質量％
酸素と窒素は不純物であり、いずれ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あるいはＡｌＮ）として塊状に存在する。鋳物中にこれらが存在すると、クリープ変形中のクラックの起点となり、クリープ破断寿命を低下させたり、疲労亀裂発生の起点となって疲労寿命が低下したりする。特に酸素は、鋳物表面に酸化物として現れることで、鋳物の表面欠陥となり、鋳造品の歩留まりを低下させる原因となる。そのため、これら元素の含有量は少ないほど良いが、実際のインゴットを製造する場合に、無酸素、無窒素にはできないことから、特性を大きく劣化させない範囲として、両元素はいずれも０.００５質量％以下であることが望ましい。
O: 0 to 0.005 mass%, N: 0 to 0.005 mass%
Oxygen and nitrogen are impurities, both of which are often brought from alloy raw materials, O also enters from the crucible, and exists in the alloy as oxides (Al 2 O 3 ) and nitrides (TiN or AlN). To do. If these are present in the casting, it becomes the starting point of cracks during creep deformation, and the creep rupture life is reduced, or the fatigue life is reduced by starting fatigue crack generation. In particular, oxygen appears as an oxide on the surface of the casting, thereby causing a surface defect of the casting and reducing the yield of the casting. Therefore, the lower the content of these elements, the better. However, when manufacturing an actual ingot, it is impossible to make oxygen-free and nitrogen-free. % Or less is desirable.
Ｒｅ，Ｔａは添加しない。不純物として不可避にＲｅは０．５質量％以下、Ｔａは１．０質量％以下混入する場合はある。ＲｅとＴａによるマトリックスの固溶強化とγ´生成元素としてのγ´相強化の影響によるのもで、時効硬さの上昇と相関が認められる。しかし、延性についてはＲｅとＴａの添加の影響は劣化傾向が認められ、合金の加工性が低下しやすい。更に、ＲｅとＴａは高価な元素であるため、本発明は特性バランスとコストの面から、ＴａとＲｅを添加しない。 Re and Ta are not added. As an impurity, Re is inevitably mixed by 0.5 mass% or less and Ta is mixed by 1.0 mass% or less. This is due to the effect of solid solution strengthening of the matrix by Re and Ta and the strengthening of the γ ′ phase as the γ′-forming element, and a correlation is observed with the increase in age hardness. However, with respect to ductility, the effects of the addition of Re and Ta tend to deteriorate, and the workability of the alloy tends to decrease. Furthermore, since Re and Ta are expensive elements, the present invention does not add Ta and Re from the viewpoint of the balance of characteristics and cost.
上記の各成分と、不可避不純物及び残部のＮｉよりなるＮｉ基合金は、従来材より優れた高温強度と耐酸化・腐食性を得られる合金である。
The Ni-based alloy composed of the above components, inevitable impurities, and the balance Ni is an alloy capable of obtaining high-temperature strength and oxidation / corrosion resistance superior to those of conventional materials.
以下に、本実施例で試験に供したＮｉ基合金を示す。Ｎｉ基合金の組成（質量％）を表１に示す。 The Ni-based alloy used for the test in this example is shown below. Table 1 shows the composition (% by mass) of the Ni-based alloy.
合金Ｎo.Ａ１〜Ａ５が、本発明を示す合金組成であり、合金Ｎo.Ｂ１〜Ｂ２が従来材を示す合金組成である。試験片は、マスターインゴットと秤量した合金元素とをアルミナ坩堝で溶解し、厚さ１４mmの平板に鋳造した。鋳造後、試験片は溶体化熱処理及び時効熱処理を行った。 Alloys No. A1 to A5 are alloy compositions showing the present invention, and alloys No. B1 to B2 are alloy compositions showing conventional materials. For the test piece, the master ingot and the weighed alloy element were melted in an alumina crucible and cast into a flat plate having a thickness of 14 mm. After casting, the test piece was subjected to solution heat treatment and aging heat treatment.
表２に、合金試験片に対して行った熱処理の条件を示す。 Table 2 shows the conditions of the heat treatment performed on the alloy specimen.
合金組成を均一化するために１５０５Ｋで２ｈ溶体化熱処理を行った。溶体化熱処理後は空冷とし、これに続く時効熱処理の条件は、全ての合金で１３９４Ｋ／４時間／空冷＋１３５２Ｋ／４時間／空冷＋１１４８Ｋ／１６時間／空冷とした。その後、試験片加工を行い、クリープ破断試験、腐食、及び酸化試験を実施した。 In order to make the alloy composition uniform, solution heat treatment was performed at 1505 K for 2 h. After the solution heat treatment, air cooling was performed, and the subsequent aging heat treatment conditions were 1394 K / 4 hours / air cooling + 1352 K / 4 hours / air cooling + 1148 K / 16 hours / air cooling for all alloys. Thereafter, test piece processing was performed, and a creep rupture test, corrosion, and oxidation test were performed.
熱処理した試験片から、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、及び１５mm×１５mm×１５mmの立方体形状の高温腐食試験片を切り出すとともに、走査型電子顕微鏡でミクロ組織を調査し、合金の組織安定性を評価した。 From the heat-treated test piece, a creep test piece having a parallel part diameter of 6.0 mm and a parallel part length of 30 mm, a high temperature oxidation test piece having a length of 25 mm, a width of 10 mm, and a thickness of 1.5 mm, and 15 mm × 15 mm × by machining. A 15 mm cube-shaped hot corrosion test piece was cut out and the microstructure was examined with a scanning electron microscope to evaluate the structural stability of the alloy.
表３に、合金試験片に対して行った特性評価試験の条件を示す。 Table 3 shows the conditions of the characteristic evaluation test performed on the alloy specimen.
クリープ破断試験は、１２５５Ｋ−１３７ＭＰａ/１１２３Ｋ−３１４ＭＰａの条件で行った。高温酸化試験は、１３１３Ｋ−２０時間保持の酸化試験を１５回繰返し、それぞれ質量の変化を測定した。また、高温腐食試験は、１１２３Ｋの溶融塩（組成は、Ｎａ2ＳＯ4：７５％、ＮａＣｌ：２５％）中に２５時間浸漬する試験を４回（計１００時間）行い、質量の変化を測定した。 The creep rupture test was conducted under the conditions of 1255K-137MPa / 1123K-314MPa. In the high-temperature oxidation test, the oxidation test held at 1313 K-20 hours was repeated 15 times, and the change in mass was measured. The high temperature corrosion test was conducted by immersing in a molten salt of 1123K (composition: Na 2 SO 4 : 75%, NaCl: 25%) for 25 hours 4 times (100 hours in total), and measuring the change in mass. did.
これらの試験結果を表４にまとめて示す。 These test results are summarized in Table 4.
図１〜図３に、各合金の特性評価試験結果を示す。図１は１２５５Ｋ−１３７ＭＰａでのクリープ破断時間、図２は高温酸化試験での酸化減量、図３は溶融塩浸漬腐食試験での腐食減量の測定結果を示している。 1 to 3 show the results of property evaluation tests of the respective alloys. FIG. 1 shows the creep rupture time at 1255K-137 MPa, FIG. 2 shows the results of measurement of the weight loss in the high temperature oxidation test, and FIG. 3 shows the results of the measurement of the corrosion weight loss in the molten salt immersion corrosion test.
表４に示す結果から明らかなように、本実施例の合金Ａ１〜Ａ５では、既存合金Ｂ１（ＩＮ７３８ＬＣ）と比較すると、耐食性は少し低下しているが、耐酸化性とクリープ破断時間は約３倍以上になっている。本実施例の合金では、Ｂ１に対して、Ｗ、Ａｌの添加量を多くすることで高温でのクリープ強度向上を図っている。 As is apparent from the results shown in Table 4, in the alloys A1 to A5 of this example, the corrosion resistance is slightly lowered as compared with the existing alloy B1 (IN738LC), but the oxidation resistance and creep rupture time are about 3 It is more than doubled. In the alloy of this example, the creep strength is improved at a high temperature by increasing the amount of W and Al added to B1.
別の既存合金Ｂ２（ＧＴＤ１１１）と比較すると、耐酸化性と高温クリープ破断強度が大幅に改善され、耐食性も改善されていることが分かる。特にクリープ破断強度は向上が著しい。従来材Ｂ２に対して、ＷとＡｌ量を大幅に増加して、組織安定性の確保のために、他の添加元素のバランスを重視し、高温強度の向上を図っている。 When compared with another existing alloy B2 (GTD111), it can be seen that the oxidation resistance and the high temperature creep rupture strength are greatly improved and the corrosion resistance is also improved. In particular, the creep rupture strength is significantly improved. Compared to the conventional material B2, the amount of W and Al is significantly increased, and in order to ensure the structural stability, the balance of other additive elements is emphasized and the high temperature strength is improved.
すなわち、本発明により、高温での耐食性を維持しつつ、耐酸化特性とクリープ破断寿命を大幅に向上し、優れた高温強度を有するＮｉ基超合金が得られることが認められた。 That is, according to the present invention, it was confirmed that a Ni-base superalloy having excellent high-temperature strength can be obtained while maintaining the corrosion resistance at high temperatures while greatly improving the oxidation resistance and creep rupture life.
以上の実施例においては、普通鋳造材としての効果を説明した。さらに本発明の合金を一方向凝固させた一方向凝固翼として使用することも有効である。一方向凝固させることにより、耐食性、耐酸化特性を維持しながら、クリープ破断強度を大幅に向上できることは周知の事実である。特に、本発明の合金は結晶粒界強化に効果のあるＣ、Ｂを含み、さらに必要に応じて、鋳造時の結晶粒界割れの抑制に効果のあるＨｆを添加することが可能であることから、一方向凝固材として使用する場合も適した合金組成となっている。更に、単結晶合金も適用可能である。 In the above embodiment, the effect as a normal casting material has been described. It is also effective to use the unidirectionally solidified blade obtained by unidirectionally solidifying the alloy of the present invention. It is a well-known fact that the creep rupture strength can be greatly improved by maintaining the corrosion resistance and the oxidation resistance by unidirectional solidification. In particular, the alloy of the present invention contains C and B effective for strengthening grain boundaries, and it is possible to add Hf effective for suppressing grain boundary cracking during casting if necessary. Therefore, the alloy composition is also suitable for use as a unidirectionally solidified material. Furthermore, a single crystal alloy is also applicable.
以上述べたように、本発明によれば、優れた高温強度と耐酸化・腐食性を併せ持つ、普通鋳造可能なＮｉ基超合金を得ることができる。 As described above, according to the present invention, it is possible to obtain a Ni-based superalloy capable of ordinary casting having both excellent high temperature strength and oxidation / corrosion resistance.
図５はガスタービンを示す図である。
本実施例におけるガスタービンは、クリープ破断強度の高い、高温強度に優れたＮｉ基超合金をガスタービンブレード３と、ガスタービンノズル２０に適用することにより、タービン入口の燃焼ガス温度を従来のものに比べて高くでき、熱効率が高い高温発電用ガスタービンを提供することができる。
本発明におけるＮｉ基超合金は、高いクリープ強度と耐酸化・腐食を併せもつため、普通鋳造材としてガスタービンの３又は４段動翼３に用いることが望ましい。また、本発明の合金は、結晶粒界の強化に効果のあるＣ、Ｂ、鋳造時の結晶粒界割れの抑制に効果のあるＨｆを含むため、一方向鋳造材又は単結晶材としてガスタービンの１、２段タービンブレード動翼３にも用いることができる。たま、本発明合金の一方向鋳造材又は単結晶材はＴａ、Ｒｅなど高価な合金元素を含まない為、材料単価は従来材並みの安価である。しかもその耐用温度は従来以上に優れているので、寿命を従来より大きく向上させることができる。尚、本発明には、特にガスタービンに限定されるものではない、他の高温熱機関の高温部品も対応可能である。
FIG. 5 is a diagram showing a gas turbine.
The gas turbine in the present embodiment applies a Ni-base superalloy having a high creep rupture strength and an excellent high-temperature strength to the gas turbine blade 3 and the gas turbine nozzle 20 so that the combustion gas temperature at the turbine inlet is the conventional one. It is possible to provide a gas turbine for high-temperature power generation that can be made higher than the above and has high thermal efficiency.
Since the Ni-base superalloy according to the present invention has both high creep strength and oxidation / corrosion resistance, it is desirable to use it as a normal casting material for the 3- or 4-stage rotor blade 3 of a gas turbine. Further, since the alloy of the present invention contains C and B which are effective in strengthening grain boundaries, and Hf which is effective in suppressing grain boundary cracking at the time of casting, the gas turbine is used as a unidirectional cast material or a single crystal material. Can be used for the first and second stage turbine blades 3. Occasionally, the unidirectional cast material or single crystal material of the alloy of the present invention does not contain expensive alloy elements such as Ta and Re, so the material unit price is as low as that of conventional materials. In addition, since the service temperature is superior to that of the prior art, the lifetime can be greatly improved. It should be noted that the present invention is not limited to gas turbines, and can be applied to high-temperature parts of other high-temperature heat engines.
３…タービンブレード、４…タービンディスク、６…コンプレッサディスク、７…コンプレッサブレード、８…コンプレッサスタッキングボルド、９…コンプレッサスタブシャフト、１０…タービンスタブシャフト、１１…穴、１３…タービンスタッキングボルト、１５…燃焼器、１６…コンプレッサノズル、１８…タービンスペーサ、１９…デイスタントピース、２０…初段ノズル、１１０…翼部、１１１…シャンク部、１１２…ルート部（ダブティル部）、１１３…プラットホーム部、１１４…ラジアルフィン。 3 ... turbine blade, 4 ... turbine disk, 6 ... compressor disk, 7 ... compressor blade, 8 ... compressor stacking bould, 9 ... compressor stub shaft, 10 ... turbine stub shaft, 11 ... hole, 13 ... turbine stacking bolt, 15 ... Combustor, 16 ... Compressor nozzle, 18 ... Turbine spacer, 19 ... Distant piece, 20 ... First stage nozzle, 110 ... Wing part, 111 ... Shank part, 112 ... Root part (Dubtil part), 113 ... Platform part, 114 ... Radial fin.
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| CN114561563A (en) * | 2022-02-28 | 2022-05-31 | 兰州大学 | Method for improving structure stability by optimizing high-temperature alloy structure |
| CN114934211A (en) * | 2022-07-21 | 2022-08-23 | 北京钢研高纳科技股份有限公司 | Nickel-base superalloy, nickel-base superalloy powder, and nickel-base superalloy component |
| CN115198144A (en) * | 2021-04-06 | 2022-10-18 | 大同特殊钢株式会社 | Heat-resistant alloy member, material used therefor, and method for producing same |
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