JP2022536401A - Precipitation-strengthened nickel-based high-chromium superalloy and its production method - Google Patents
Precipitation-strengthened nickel-based high-chromium superalloy and its production method Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 239000011651 chromium Substances 0.000 title claims abstract description 38
- 229910000601 superalloy Inorganic materials 0.000 title claims abstract description 34
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 20
- 229910052804 chromium Inorganic materials 0.000 title claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- 239000000956 alloy Substances 0.000 claims abstract description 92
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 91
- 239000012452 mother liquor Substances 0.000 claims abstract description 22
- 229910052742 iron Inorganic materials 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 15
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 15
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 15
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 14
- 238000005728 strengthening Methods 0.000 claims abstract description 10
- 238000000265 homogenisation Methods 0.000 claims abstract description 9
- 238000001556 precipitation Methods 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims description 24
- 238000003723 Smelting Methods 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 20
- 238000007711 solidification Methods 0.000 claims description 9
- 230000008023 solidification Effects 0.000 claims description 9
- 238000005098 hot rolling Methods 0.000 claims description 8
- 238000005096 rolling process Methods 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 5
- 238000001953 recrystallisation Methods 0.000 claims description 4
- 238000007670 refining Methods 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims 1
- 238000010792 warming Methods 0.000 claims 1
- 238000005260 corrosion Methods 0.000 abstract description 12
- 230000007797 corrosion Effects 0.000 abstract description 12
- 230000003647 oxidation Effects 0.000 abstract description 5
- 238000007254 oxidation reaction Methods 0.000 abstract description 5
- 239000000463 material Substances 0.000 description 10
- 239000000919 ceramic Substances 0.000 description 9
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000003546 flue gas Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 229910001566 austenite Inorganic materials 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000010891 electric arc Methods 0.000 description 3
- 230000006698 induction Effects 0.000 description 3
- 238000010248 power generation Methods 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910001005 Ni3Al Inorganic materials 0.000 description 1
- 241001062472 Stokellia anisodon Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910000856 hastalloy Inorganic materials 0.000 description 1
- 229910001026 inconel Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 229910001235 nimonic Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 230000004584 weight gain Effects 0.000 description 1
- 235000019786 weight gain Nutrition 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/023—Alloys based on nickel
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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
- C22C19/055—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 20% but less than 30%
-
- 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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Abstract
本発明は、析出強化型ニッケル基高クロム超合金およびその製造方法に関する。成分は、質量百分率に関して、Ｃｒ：２５％～２８％、Ｃｏ：１０％～１５％、Ｔｉ：２．５％～３．５％、Ａｌ：１．０％～１．５％、Ｗ：１．５％～５％、Ｓｉ：≦０．５％、Ｍｎ：≦０．５％、Ｎｂ：０．５％～１．５％、Ｃ：０．０３％～０．０８％、Ｆｅ：０．５％～１．０％、マージンがＮｉであることを満たす。調製された合金は、合金母液に製錬され、エレクトロスラグ再溶解プロセスを用いて精練および冷却し、合金母液はインゴットに凝固される。均質化処理した後、圧延および熱処理する。析出強化の合金設計コンセプトを採用して、合金内部に均一に分散して分布された多数の二次強化相の析出を促進することにより、合金は良好な強度性能を得ると同時に、合金構造の安定性を確保することを前提として、合金はＣｒ元素の含有量が高くなり、さらに優れた耐酸化および耐食性能が得られる。【選択図】図３The present invention relates to precipitation-strengthened nickel-based high-chromium superalloys and methods of making the same. In terms of mass percentage, the components are Cr: 25% to 28%, Co: 10% to 15%, Ti: 2.5% to 3.5%, Al: 1.0% to 1.5%, W: 1 .5% to 5%, Si: ≤0.5%, Mn: ≤0.5%, Nb: 0.5% to 1.5%, C: 0.03% to 0.08%, Fe: 0 0.5% to 1.0%, satisfying the margin of Ni. The prepared alloy is smelted into an alloy mother liquor, refined and cooled using an electroslag remelting process, and the alloy mother liquor solidified into an ingot. After homogenization, it is rolled and heat treated. By adopting the alloy design concept of precipitation strengthening to promote the precipitation of a large number of secondary strengthening phases uniformly dispersed and distributed inside the alloy, the alloy obtains good strength performance, while at the same time improving the alloy structure. On the premise of ensuring stability, the alloy has a high content of Cr element, which provides better oxidation and corrosion resistance. [Selection drawing] Fig. 3
Description
本発明は、高温用合金材料分野に属し、具体的に、析出強化型ニッケル基高クロム超合金およびその製造方法に関する。 The present invention belongs to the field of high-temperature alloy materials, and specifically relates to a precipitation-strengthened nickel-based high-chromium superalloy and a method for producing the same.
中国の電力需要が増加し続けることに従って、エネルギー不足と環境汚染問題が益々顕著になり、高効率、省エネ、環境に優しい発電方法を発展させる必要性が益々緊迫になっている。火力発電は、中国で長い間最も重要な発電技術として、ユニットの蒸気パラメータを改善することは、上記の問題を解決するための最も効果的な方法であると考えられている。従来の多くの実践により、キーコンポーネント材料のサービス性能は、ボイラユニットの蒸気パラメータの向上を制約する最も重要な原因であることが示されている。火力発電ユニットボイラの最も厳しいサービス条件のキーコンポーネントの１つとして、過熱器／再熱器パイプは材料のサーボス性能に対して非常に高い要件を提出している。過熱器／再熱器は、サービス期間に高温クリープ、熱疲労、酸化および高温煙道ガス腐食などの複数の要因の影響に耐える。火力発電ユニットの主蒸気パラメータの大幅な向上に伴い、火力発電業界では、高パラメータユニットの過熱器／再熱器パイプの使用性能の要件を満たすことができる超合金材料の開発が急務となっている。 As China's power demand continues to increase, energy shortage and environmental pollution problems become more and more prominent, and the need to develop high-efficiency, energy-saving and environmentally friendly power generation methods becomes more and more urgent. Thermal power generation, as the most important power generation technology in China for a long time, improving the steam parameters of the unit is considered to be the most effective way to solve the above problems. Many conventional practices indicate that the service performance of key component materials is the most important factor limiting the improvement of boiler unit steam parameters. As one of the most demanding service condition key components of thermal power unit boilers, superheater/reheater pipes put very high requirements on the servos performance of the material. Superheaters/reheaters withstand the effects of multiple factors during service such as high temperature creep, thermal fatigue, oxidation and hot flue gas corrosion. With the significant improvement of the main steam parameters of thermal power units, the thermal power industry urgently needs to develop superalloy materials that can meet the usage performance requirements of superheater/reheater pipes in high parameter units. there is
火力発電ユニットボイラで最も厳しいサービス条件のコンポーネントである過熱器／再熱器は、その候補材料の持続強度および耐食性に対して非常に高い要件を提出している。優れた耐久性能は、合金が高温条件下で長時間サービスする重要な保証であり、主な強化方法としての固溶体強化は、多くの場合、より大きなコストの向上および構造の不安定などの問題をもたらす。したがって、現在の候補合金は、主に合金の主な強化方法として析出強化を採用している。また、耐酸化性および耐食性も合金のサービス性能に重要な影響を及ぼし、合金中のＣｒ元素の含有量は、その耐酸化性および耐食性を決定する決定的な要素であるが、その含有量の増加に伴って、合金構造の安定性と機械的特性が著しく低下する。高パラメータボイラの再熱器パイプの材料使用性能に対する要求に応じて、現在海外で、一連のニッケル基変形超合金材料、例えば、アメリカの特殊金属会社（Ａｍｅｒｉｃａｎ Ｓｐｅｃｉａｌ Ｍｅｔａｌｓ Ｃｏｍｐａｎｙ）により開発されたＩｎｃｏｎｅｌ７４０Ｈ、アメリカハステロイ会社（Ａｍｅｒｉｃａｎ Ｈａｓｔｅｌｌｏｙ Ｃｏｍｐａｎｙ）により開発されたＨａｙｎｅｓ２８２、ドイツのティッセンクルップ会社（Ｇｅｍａｎ Ｔｈｙｓｓｅｎ Ｋｒｕｐｐ Ｃｏｍｐａｎｙ）により開発されたＣＣＡ６１７、イギリスのロールスロイス（Ｂｒｉｔｉｓｈ Ｒｏｌｌｓ－Ｒｏｙｃｅ Ｃｏｍｐａｎｙ）会社により開発されたＮｉｍｏｎｉｃ２６３、日本の日立会社により開発されたＦＥＮＩＸ７００、日本の東芝会社により開発されたＴＯＳ１Ｘ、日本の三菱会社により開発されたＬＴＥＳＲ７００などのニッケル基変形超合金などが開発されている。Ｃｒ含有量が高くなると合金強度が低下し、構造の安定性が悪化するため、現在慣用の析出強化型ニッケル基超合金中のＣｒ元素の含有量は、多くの場合、より低い範囲に制御されているが、同時にその耐食性に大きな影響を及ぼしている。 The superheater/reheater, the most demanding service component of a thermal power unit boiler, puts very high requirements on the sustained strength and corrosion resistance of its candidate materials. Good durability performance is an important guarantee that the alloy will serve for a long time under high temperature conditions, and solid solution strengthening as the main strengthening method often avoids problems such as greater cost improvement and structural instability. Bring. Therefore, current candidate alloys mainly adopt precipitation strengthening as the main strengthening method of the alloy. In addition, the oxidation resistance and corrosion resistance also have an important effect on the service performance of the alloy. As it increases, the stability and mechanical properties of the alloy structure decrease significantly. According to the requirements for the material usage performance of the reheater pipe of high parameter boilers, a series of nickel-based modified superalloy materials are currently being developed overseas, such as Inconel 740H developed by American Special Metals Company, Haynes 282 developed by American Hastelloy Company, CCA 617 developed by Geman Thyssen Krupp Company of Germany, Nimonic 263 developed by British Rolls-Royce Company, Japan Nickel-based modified superalloys such as FENIX700 developed by Hitachi, TOS1X developed by Toshiba of Japan, and LTESR700 developed by Mitsubishi of Japan have been developed. The content of elemental Cr in current precipitation-strengthened nickel-base superalloys is often controlled to a lower range, since higher Cr content reduces alloy strength and worsens structural stability. However, at the same time, it has a great influence on its corrosion resistance.
本発明の目的は、析出強化の合金設計コンセプトを採用し、合金内部に均一に分散して分布された多数の二次強化相の析出を促進することによって、合金が良好な強度性能を得ると共に、合金構造の安定性を確保することを前提として、合金に高いＣｒ元素の含有量を有させ、さらに優れた耐酸化および耐食性を実現させる、析出強化型ニッケル基高クロム超合金およびその製造方法を提供することである。 The object of the present invention is to adopt the alloy design concept of precipitation strengthening and promote the precipitation of a large number of secondary strengthening phases uniformly dispersed and distributed inside the alloy, so that the alloy can obtain good strength performance and , Precipitation-strengthened nickel-based high-chromium superalloys and a method for producing the same, in which the alloys have a high content of Cr element on the premise of ensuring the stability of the alloy structure and achieve excellent oxidation and corrosion resistance. is to provide
本発明は、上記目的を達成するために、以下のような技術案を採用する。 In order to achieve the above objects, the present invention employs the following technical solutions.
析出強化型ニッケル基高クロム超合金において、前記合金成分は、質量百分率に関して、Ｃｒ：２５％～２８％、Ｃｏ：１０％～１５％、Ｔｉ：２．５％～３．５％、Ａｌ：１．０％～１．５％、Ｗ：１．５％～５％、Ｓｉ：≦０．５％、Ｍｎ：≦０．５％、Ｎｂ：０．５～１．５％、Ｃ：０．０３％～０．０８％、Ｆｅ：０．５％～１．０％、マージンがＮｉである範囲要件を満たし、うち、Ｔｉ／Ａｌ＜２．５である。 In the precipitation-strengthened nickel-based high-chromium superalloy, the alloy components are, in terms of mass percentages, Cr: 25% to 28%, Co: 10% to 15%, Ti: 2.5% to 3.5%, Al: 1.0% to 1.5%, W: 1.5% to 5%, Si: ≤0.5%, Mn: ≤0.5%, Nb: 0.5% to 1.5%, C: 0 0.03% to 0.08%, Fe: 0.5% to 1.0%, with a margin of Ni, of which Ti/Al<2.5.
析出強化型ニッケル基高クロム超合金の製造方法は、以下のステップを含む。 A method for producing a precipitation-strengthened nickel-based high-chromium superalloy includes the following steps.
１）合金の調製ステップ：合金成分は、質量百分率に関して、Ｃｒ：２５％～２８％、Ｃｏ：１０％～１５％、Ｔｉ：２．５％～３．５％、Ａｌ：１．０％～１．５％、Ｗ：１．５％～５％、Ｓｉ：≦０．５％、Ｍｎ：≦０．５％、Ｎｂ：０．５％～１．５％、Ｃ：０．０３％～０．０８％、Ｆｅ：０．５％～１．０％、マージンがＮｉである範囲要件を満たし、うち、Ｔｉ／Ａｌ＜２．５である。 1) Alloy preparation step: The alloy components are Cr: 25% to 28%, Co: 10% to 15%, Ti: 2.5% to 3.5%, Al: 1.0% to 1.5%, W: 1.5% to 5%, Si: ≤0.5%, Mn: ≤0.5%, Nb: 0.5% to 1.5%, C: 0.03% to 0.08%, Fe: 0.5% to 1.0%, meeting the range requirements with a margin of Ni, of which Ti/Al<2.5.
２）製錬ステップ：調製された合金を合金母液に製錬し、その後エレクトロスラグ再溶解プロセスを用いて精練および冷却することによって、合金母液をインゴットに凝固する。 2) Smelting step: smelting the prepared alloy into an alloy mother liquor, followed by refining and cooling using electroslag remelting process to solidify the alloy mother liquor into an ingot.
３）超合金インゴットを得るために均質化処理ステップを行う。 3) Perform a homogenization step to obtain a superalloy ingot.
４）熱間圧延ステップ：総変形量が５０％～７０％で、各バス変形量を１５％～２５％範囲内に制御し、変形温度が１１００℃～１１７０℃の条件で、超合金インゴットを圧延する。 4) Hot rolling step: the total deformation amount is 50% to 70%, each bus deformation amount is controlled within the range of 15% to 25%, and the deformation temperature is 1100 ° C. to 1170 ° C., and the superalloy ingot is produced. to roll.
５）熱処理ステップ：圧延後の合金を１１１０℃～１１３０℃で４時間保温して再結晶処理を行い、室温まで空冷した後７５０℃～７７０℃で７～９時間保温し、その後８４０℃～８７０℃まで昇温して１．５～２．５時間保温し、その後室温まで空冷する。 5) Heat treatment step: The alloy after rolling is kept at 1110°C to 1130°C for 4 hours for recrystallization treatment, air-cooled to room temperature, then kept at 750°C to 770°C for 7 to 9 hours, and then at 840°C to 870°C. C. and maintained for 1.5-2.5 hours, then air-cooled to room temperature.
本発明のさらなる改善は、ステップ２）において、真空製錬炉の内部で製錬が行われ、製錬中の真空度が１．０×１０－４ＭＰａ以下であるという点にある。 A further improvement of the present invention is that in step 2), smelting is performed inside a vacuum smelting furnace, and the degree of vacuum during smelting is 1.0×10 −4 MPa or less.
本発明のさらなる改善は、ステップ２）において、インゴットへの凝固中に温度が９００℃に達する前に、冷却速度が１５℃／ｍｉｎを超えないように制御し、インゴットへの凝固中に温度が９００℃に達した後に、１０℃／ｍｉｎを超える冷却速度で室温まで冷却するという点にある。 A further improvement of the present invention is that in step 2), before the temperature reaches 900°C during solidification into the ingot, the cooling rate is controlled not to exceed 15°C/min, and during solidification into the ingot, the temperature reaches After reaching 900° C., it is cooled to room temperature at a cooling rate exceeding 10° C./min.
本発明のさらなる改善は、ステップ２）において、合金母液がインゴットに凝固してから室温まで冷却するまでの時間が１５ｍｉｎを超えないという点にある。 A further improvement of the present invention is that in step 2) the time from solidification of the alloy mother liquor into the ingot to cooling to room temperature does not exceed 15 min.
本発明のさらなる改善は、ステップ３）の具体的な過程において、インゴットを取出し、その後インゴットを１０３０℃～１０７０℃に加熱し３０分間保温した後、１１７０℃～１２００℃まで昇温した熱処理炉の内部で継続して２０～２４時間保温し、最後に室温まで冷却する点にある。 A further improvement of the present invention is that in the specific process of step 3), the ingot is taken out, then the ingot is heated to 1030° C. to 1070° C., held for 30 minutes, and then heated to 1170° C. to 1200° C. The point is that the temperature is kept inside continuously for 20 to 24 hours, and finally cooled to room temperature.
本発明のさらなる改善は、ステップ３）において、インゴットを１０３０℃～１０７０℃に加熱する場合、昇温速度が１０℃／ｍｉｎを超えず、１１７０℃～１２００℃まで昇温する場合、昇温速度が５℃／ｍｉｎを超えないという点にある。 A further improvement of the present invention is that in step 3), when the ingot is heated to 1030° C. to 1070° C., the temperature increase rate does not exceed 10° C./min, and when the temperature is increased to 1170° C. to 1200° C., the temperature increase rate is does not exceed 5°C/min.
本発明のさらなる改善は、ステップ５）において、１０℃／ｍｉｎを超えない昇温速度で室温から１１１０℃～１１３０℃に昇温し、１０℃／ｍｉｎを超えない昇温速度で室温から７５０℃～７７０℃に昇温し、さらに１０℃／ｍｉｎを超えない昇温速度で８４０℃～８７０℃に昇温する点にある。 A further improvement of the present invention is that in step 5), the temperature is raised from room temperature to 1110° C. to 1130° C. at a heating rate not exceeding 10° C./min, and from room temperature to 750° C. at a heating rate not exceeding 10° C./min. The temperature is raised to ~770°C, and further the temperature is raised to 840°C to 870°C at a rate not exceeding 10°C/min.
本発明は、従来技術と比較して有益な効果を有する。 The present invention has beneficial effects compared with the prior art.
本発明は、析出強化の合金設計コンセプトに基づいて、Ａｌ、Ｔｉ含有量の高い新型超合金を開発すると同時に、合金中のＣｒ元素の含有量が高いため、その優れた耐酸化および耐食性も保証される。 Based on the alloy design concept of precipitation strengthening, the present invention develops a new type of superalloy with high Al and Ti content, and at the same time, the high content of Cr element in the alloy ensures its excellent oxidation and corrosion resistance. be done.
本発明に記載の方法に従って調製された合金は、優れた強度性能および耐食性を有し、ならびに良好な溶接および加工性能を有する。合金マトリックスは、無秩序な面心構造のオーステナイトであり、平均結晶粒サイズは１００ミクロン未満である。オーステナイトの粒界には、不連続に分布された炭化物（ＮｂＣおよびＣｒ２３Ｃ６）が存在し、オーステナイトの体積分率は約５％～２０％を占め、オーステナイト結晶の内部には、サイズが５０ｎｍ以下の微細な球状のＮｉ３Ａｌ析出相が、均一に分散される。合金の室温および８５０℃の引張降伏強度は、それぞれ７５０ＭＰａおよび５００ＭＰａより高く、高温煙道ガス環境（Ｎ２－１５％ＣＯ２－３．５％Ｏ２－０．１％ＳＯ２）で５００時間腐食された後の合金の重量変化は０．３ｍｇ／ｃｍ２未満である。また、合金は８５０℃での熱暴露期間に優れた構造安定性を有する。 Alloys prepared according to the method described in this invention have excellent strength and corrosion resistance properties, as well as good welding and processing performance. The alloy matrix is austenite with a disordered face-centered structure and an average grain size of less than 100 microns. There are discontinuously distributed carbides (NbC and Cr23C6) at the grain boundaries of austenite, the volume fraction of austenite is about 5% to 20%, and inside the austenite crystals, there are A fine spherical Ni3Al precipitate phase is uniformly dispersed. The room temperature and 850° C. tensile yield strengths of the alloy are greater than 750 MPa and 500 MPa, respectively, for 500 hours in a hot flue gas environment (N 2 -15% CO 2 -3.5% O 2 -0.1% SO 2 ). The weight change of the alloy after being corroded is less than 0.3 mg/ cm2 . The alloy also has excellent structural stability during thermal exposure at 850°C.
本発明は、実施例を参照して、以下でさらに詳細に説明する。 The invention is explained in more detail below with reference to examples.
本発明の析出強化型合金は、ニッケル基超合金材料である。 The precipitation-strengthened alloy of the present invention is a nickel-based superalloy material.
析出強化型ニッケル基高クロム超合金において、合金成分は、質量百分率に関して、Ｃｒ：２５％～２８％、Ｃｏ：１０％～１５％、Ｔｉ：２．５％～３．５％、Ａｌ：１．０％～１．５％、Ｗ：１．５％～５％、Ｓｉ：≦０．５％、Ｍｎ：≦０．５％、Ｎｂ：０．５％～１．５％、Ｃ：０．０３％～０．０８％、Ｆｅ：０．５％～１．０％、マージンがＮｉである範囲要件を満たし、うち、Ｔｉ／Ａｌ＜２．５である。 In the precipitation-strengthened nickel-based high-chromium superalloy, the alloy components are Cr: 25% to 28%, Co: 10% to 15%, Ti: 2.5% to 3.5%, Al: 1 in terms of mass percentage. .0% to 1.5%, W: 1.5% to 5%, Si: ≤0.5%, Mn: ≤0.5%, Nb: 0.5% to 1.5%, C: 0 0.03% to 0.08%, Fe: 0.5% to 1.0%, with a margin of Ni, of which Ti/Al<2.5.
析出強化型ニッケル基高クロム超合金の製造方法は、以下のステップを含む。 A method for producing a precipitation-strengthened nickel-based high-chromium superalloy includes the following steps.
１）合金の調製ステップ：合金成分は、質量百分率に関して、Ｃｒ：２５％～２８％、Ｃｏ：１０％～１５％、Ｔｉ：２．５％～３．５％、Ａｌ：１．０％～１．５％、Ｗ：１．５％～５％、Ｓｉ：≦０．５％、Ｍｎ：≦０．５％、Ｎｂ：０．５％～１．５％、Ｃ：０．０３％～０．０８％、Ｆｅ：０．５％～１．０％、マージンがＮｉである範囲要件を満たし、うち、Ｔｉ／Ａｌ＜２．５である。 1) Alloy preparation step: The alloy components are Cr: 25% to 28%, Co: 10% to 15%, Ti: 2.5% to 3.5%, Al: 1.0% to 1.5%, W: 1.5% to 5%, Si: ≤0.5%, Mn: ≤0.5%, Nb: 0.5% to 1.5%, C: 0.03% to 0.08%, Fe: 0.5% to 1.0%, meeting the range requirements with a margin of Ni, of which Ti/Al<2.5.
２）製錬ステップ：調製された合金を合金母液に製錬した後、エレクトロスラグ再溶解プロセスを用いて精練および冷却することによって、合金母液をインゴットに凝固した後、インゴット温度が９００℃に達する前に、冷却速度が１５℃／ｍｉｎを超えないように制御し、インゴット温度が９００℃に達した後に、１０℃／ｍｉｎを超える冷却速度で室温まで冷却する。合金母液がインゴットに凝固してから室温まで冷却するまでの時間は１５分を超えない。 2) Smelting step: After smelting the prepared alloy into alloy mother liquor, by using electroslag remelting process to refine and cool, the alloy mother liquor is solidified into ingot, after which the ingot temperature reaches 900℃ Before, the cooling rate is controlled not to exceed 15°C/min, and after the ingot temperature reaches 900°C, it is cooled to room temperature at a cooling rate of over 10°C/min. The time from solidification of the alloy mother liquor into an ingot to cooling to room temperature does not exceed 15 minutes.
３）均質化処理ステップ：インゴットを取出し、その後１０℃／ｍｉｎを超えない昇温速度でインゴットを室温から１０３０℃～１０７０℃に加熱して３０分間保温した後、継続して５℃／ｍｉｎを超えない昇温速度で１１７０℃～１２００℃に昇温させ、熱処理炉の内部で２０～２４時間保温し、最後に室温まで冷却し、超合金インゴットを得る。 3) Homogenization step: Take out the ingot, then heat the ingot from room temperature to 1030°C to 1070°C at a rate of temperature increase not exceeding 10°C/min, keep it warm for 30 minutes, and then continue heating at 5°C/min. The temperature is raised to 1170° C.-1200° C. at a rate not to exceed, kept in a heat treatment furnace for 20-24 hours, and finally cooled to room temperature to obtain a superalloy ingot.
４）熱間圧延ステップ：総変形量が５０％～７０％で、各バス変形量を１５％～２５％範囲内に制御し、変形温度が１１００℃～１１７０℃の条件で、インゴットを圧延する。 4) Hot rolling step: The ingot is rolled under the condition that the total deformation amount is 50% to 70%, each bus deformation amount is controlled within the range of 15% to 25%, and the deformation temperature is 1100°C to 1170°C. .
５）熱処理ステップ：圧延後の合金を、１０℃／ｍｉｎを超えない昇温速度で室温から１１１０℃～１１３０℃に昇温させて４時間保温し、再結晶処理を行い、室温まで空冷した後に１０℃／ｍｉｎを超えない昇温速度で室温から７５０℃～７７０℃に昇温させ７～９時間保温し、その後１０℃／ｍｉｎを超えない昇温速度で８４０℃～８７０℃に昇温させ１．５～２．５時間保温し、完了後に室温まで空冷する。 5) Heat treatment step: The alloy after rolling is heated from room temperature to 1110° C. to 1130° C. at a heating rate not exceeding 10° C./min. The temperature is raised from room temperature to 750° C. to 770° C. at a temperature elevation rate not exceeding 10° C./min, maintained for 7 to 9 hours, and then heated to 840° C. to 870° C. at a temperature elevation rate not exceeding 10° C./min. Incubate for 1.5-2.5 hours and air cool to room temperature upon completion.
本実施例の耐熱鋼材料は、質量百分率で計算して、Ｃｒ：２８％、Ｃｏ：１５％、Ｔｉ：２．５％、Ａｌ：１．５％、Ｗ：１．５％、Ｓｉ：０．５％、Ｍｎ：０．５％、Ｎｂ：０．５％、Ｃ：０．０４％、Ｆｅ：０．５％、マージンＮｉを含む。 The heat-resistant steel material of this example is calculated in mass percentage, Cr: 28%, Co: 15%, Ti: 2.5%, Al: 1.5%, W: 1.5%, Si: 0 .5%, Mn: 0.5%, Nb: 0.5%, C: 0.04%, Fe: 0.5%, margin Ni.
本実施例の製造方法は、以下のステップを含む。 The manufacturing method of this embodiment includes the following steps.
１）原料を調製するステップ：成分は、質量百分率で計算して、Ｃｒ：２８％、Ｃｏ：１５％、Ｔｉ：２．５％、Ａｌ：１．５％、Ｗ：１．５％、Ｓｉ：０．５％、Ｍｎ：０．５％、Ｎｂ：０．５％、Ｃ：０．０４％、Ｆｅ：０．５％、マージンＮｉを含む。 1) Step of preparing raw materials: The components are calculated in terms of mass percentages, Cr: 28%, Co: 15%, Ti: 2.5%, Al: 1.5%, W: 1.5%, Si : 0.5%, Mn: 0.5%, Nb: 0.5%, C: 0.04%, Fe: 0.5%, including margin Ni.
２）製錬ステップ：セラミックるつぼと調製した原料とを同時に真空製錬炉の内部に入れ、真空誘導炉を使用して、１．０×１０－４ＭＰａ以下の真空度で、調製した合金を合金母液に製錬し、合金母液が凝固すると、同時に、電気アークを用いてセラミックるつぼを低電力で予熱する。合金が完全に凝固してインゴットになった後、それを予熱したセラミックるつぼの内部に移動させ、合金インゴットと銅るつぼとが接触しないようにすることによって、その冷却速度が高すぎることを防止する。 2) smelting step: put the ceramic crucible and the prepared raw material into a vacuum smelting furnace at the same time, and use a vacuum induction furnace to smelt the prepared alloy at a degree of vacuum of 1.0×10 −4 MPa or less; When the alloy mother liquor is smelted and the alloy mother liquor solidifies, an electric arc is used to preheat the ceramic crucible at low power at the same time. After the alloy is completely solidified into an ingot, it is moved inside a preheated ceramic crucible to avoid contact between the alloy ingot and the copper crucible, thereby preventing its cooling rate from being too high. .
３）均質化処理ステップ：インゴットを取出し、その後、インゴットを１０℃／ｍｉｎの速度で１０５０℃に加熱して３０分間保温し、５℃／ｍｉｎの速度で１２００℃まで加熱した熱処理炉の内部で継続して２４時間保温し、最後に、室温まで冷却し、超合金インゴットを得る。 3) Homogenization treatment step: take out the ingot, then heat the ingot to 1050°C at a rate of 10°C/min, keep it warm for 30 minutes, and heat it to 1200°C at a rate of 5°C/min inside the heat treatment furnace. The temperature is maintained continuously for 24 hours, and finally cooled to room temperature to obtain a superalloy ingot.
４）熱間圧延ステップ：総変形量が５０％～７０％で、各バス変形量を１５％～２５％範囲内に制御し、変形温度が１１００℃～１１７０℃の条件で、インゴットを圧延する。 4) Hot rolling step: The ingot is rolled under the condition that the total deformation amount is 50% to 70%, each bus deformation amount is controlled within the range of 15% to 25%, and the deformation temperature is 1100°C to 1170°C. .
５）熱処理ステップ：圧延後の合金を、１０℃／ｍｉｎの速度で１１２０℃に加熱して４時間保温し、再結晶処理を行い、空冷した後に７６０℃で８時間保温し、その後８６０℃に昇温させ２時間保温し、完了後に室温まで空冷する。 5) Heat treatment step: The alloy after rolling is heated to 1120°C at a rate of 10°C/min, held for 4 hours, recrystallized, air-cooled, held at 760°C for 8 hours, and then heated to 860°C. The temperature is raised and kept for 2 hours, and air-cooled to room temperature after completion.
実施例１で製造された合金の室温および８５０℃の降伏強度は、それぞれ７８５ＭＰａおよび５１０ＭＰａであり、８５０℃の高温煙道ガスで５００時間腐食した後の重量変化は０．１４ ｍｇ／ｃｍ２である。 The room temperature and 850° C. yield strengths of the alloy produced in Example 1 are 785 MPa and 510 MPa, respectively, and the weight change is 0.14 mg/cm 2 after 500 hours of corrosion in hot flue gas at 850° C. be.
本実施例の耐熱鋼材料は、質量百分率で計算して、Ｃｒ：２５％、Ｃｏ：１５％、Ｔｉ：２．５％、Ａｌ：１．５％、Ｗ：５％、Ｓｉ：０．５％、Ｍｎ：０．５％、Ｎｂ：０．５％、Ｃ：０．０７％、Ｆｅ：０．５％、マージンＮｉを含む。 The heat-resisting steel material of this example has Cr: 25%, Co: 15%, Ti: 2.5%, Al: 1.5%, W: 5%, and Si: 0.5, calculated by mass percentage. %, Mn: 0.5%, Nb: 0.5%, C: 0.07%, Fe: 0.5%, margin Ni.
本実施例の製造方法は、以下のステップを含む。 The manufacturing method of this embodiment includes the following steps.
１）原料を調製するステップ：成分は、質量百分率で計算して、Ｃｒ：２５％、Ｃｏ：１５％、Ｔｉ：２．５％、Ａｌ：１．５％、Ｗ：５％、Ｓｉ：０．５％、Ｍｎ：０．５％、Ｎｂ：０．５％、Ｃ：０．０７％、Ｆｅ：０．５％、マージンＮｉを含む。 1) Step of preparing raw materials: Components are calculated in terms of mass percentages, Cr: 25%, Co: 15%, Ti: 2.5%, Al: 1.5%, W: 5%, Si: 0 .5%, Mn: 0.5%, Nb: 0.5%, C: 0.07%, Fe: 0.5%, margin Ni.
２）製錬ステップ：セラミックるつぼと調製した原料とを同時に真空製錬炉の内部に入れ、真空誘導炉を使用して１．０×１０－４ＭＰａ以下の真空度で、調製した合金を合金母液に製錬し、合金母液が凝固すると、同時に電気アークを用いてセラミックるつぼを低電力で予熱する。合金が完全に凝固してインゴットになった後、それを予熱したセラミックるつぼの内部に移動させ、合金インゴットと銅るつぼとが接触しないようにすることによって、その冷却速度が高すぎることを防止する。 2) smelting step: put the ceramic crucible and the prepared raw material into a vacuum smelting furnace at the same time, and use a vacuum induction furnace to sinter the prepared alloy at a vacuum degree of 1.0×10 −4 MPa or less. As the mother liquor is smelted and the alloy mother liquor solidifies, an electric arc is used to simultaneously preheat the ceramic crucible at low power. After the alloy is completely solidified into an ingot, it is moved inside a preheated ceramic crucible to avoid contact between the alloy ingot and the copper crucible, thereby preventing its cooling rate from being too high. .
３）均質化処理ステップ：インゴットを取出し、その後、インゴットを１０℃／ｍｉｎの速度で１０５０℃に加熱して３０分間保温し、５℃／ｍｉｎの速度で１２００℃に加熱した熱処理炉の内部で継続して２４時間保温し、最後に室温まで冷却し、超合金インゴットを得る。 3) Homogenization treatment step: take out the ingot, then heat the ingot to 1050°C at a rate of 10°C/min, keep it warm for 30 minutes, and heat it to 1200°C at a rate of 5°C/min inside the heat treatment furnace. The temperature is maintained continuously for 24 hours, and finally cooled to room temperature to obtain a superalloy ingot.
４）熱間圧延ステップ：総変形量が５０％～７０％で、各バス変形量を１５％～２５％範囲内に制御し、変形温度が１１００℃～１１７０℃の条件で、インゴットを圧延する。 4) Hot rolling step: The ingot is rolled under the condition that the total deformation amount is 50% to 70%, each bus deformation amount is controlled within the range of 15% to 25%, and the deformation temperature is 1100°C to 1170°C. .
５）熱処理ステップ：圧延後の合金を、１０℃／ｍｉｎの速度で１１２０℃に加熱して４時間保温し、再結晶処理を行い、空冷した後に７６０℃で８時間保温し、その後８６０℃に昇温させて２時間保温し、完了後に室温まで空冷する。 5) Heat treatment step: The alloy after rolling is heated to 1120°C at a rate of 10°C/min, held for 4 hours, recrystallized, air-cooled, held at 760°C for 8 hours, and then heated to 860°C. Raise and incubate for 2 hours, and air cool to room temperature upon completion.
実施例２で製造された合金の室温および８５０℃の降伏強度は、それぞれ７６５ＭＰａおよび５２５ＭＰａであり、８５０℃の高温煙道ガスで５００時間腐食した後の重量変化は０．１６ ｍｇ／ｃｍ２である。 The room temperature and 850° C. yield strengths of the alloy produced in Example 2 are 765 MPa and 525 MPa, respectively, and the weight change is 0.16 mg/cm 2 after 500 hours of corrosion in hot flue gas at 850° C. be.
本比較例の耐熱鋼材料は、質量百分率で計算して、Ｃｒ：２８％、Ｃｏ：１５％、Ｔｉ：２．７％、Ａｌ：１．３％、Ｗ：７％、Ｓｉ：０．５％、Ｍｎ：０．５％、Ｎｂ：０．５％、Ｃ：０．０７％、Ｆｅ：０．５％、マージンＮｉを含む。 The heat-resistant steel material of this comparative example has Cr: 28%, Co: 15%, Ti: 2.7%, Al: 1.3%, W: 7%, Si: 0.5, calculated by mass percentage. %, Mn: 0.5%, Nb: 0.5%, C: 0.07%, Fe: 0.5%, margin Ni.
本実施例の製造方法は、以下のステップを含む。 The manufacturing method of this embodiment includes the following steps.
１）原料を調製するステップ：成分は、質量百分率で計算して、Ｃｒ：２８％、Ｃｏ：１５％、Ｔｉ：２．７％、Ａｌ：１．３％、Ｗ：７％、Ｓｉ：０．５％、Ｍｎ：０．５％、Ｎｂ：０．５％、Ｃ：０．０７％、Ｆｅ：０．５％、マージンＮｉを含む。 1) Step of preparing raw materials: The components are calculated in terms of mass percentages, Cr: 28%, Co: 15%, Ti: 2.7%, Al: 1.3%, W: 7%, Si: 0 .5%, Mn: 0.5%, Nb: 0.5%, C: 0.07%, Fe: 0.5%, margin Ni.
２）製錬ステップ：セラミックるつぼと調製した原料とを同時に真空製錬炉の内部に入れ、真空誘導炉を使用して１．０×１０－４ＭＰａ以下の真空度で、調製した合金を合金母液に製錬し、合金母液が凝固すると、同時に電気アークを用いてセラミックるつぼを低電力で予熱する。合金が完全に凝固してインゴットになった後、それを予熱したセラミックるつぼの内部に移動させ、合金インゴットと銅るつぼとが接触しないようにすることによって、その冷却速度が高すぎることを防止する。 2) smelting step: put the ceramic crucible and the prepared raw material into a vacuum smelting furnace at the same time, and use a vacuum induction furnace to sinter the prepared alloy at a vacuum degree of 1.0×10 −4 MPa or less. As the mother liquor is smelted and the alloy mother liquor solidifies, an electric arc is used to simultaneously preheat the ceramic crucible at low power. After the alloy is completely solidified into an ingot, it is moved inside a preheated ceramic crucible to avoid contact between the alloy ingot and the copper crucible, thereby preventing its cooling rate from being too high. .
３）均質化処理ステップ：インゴットを取出し、その後インゴットを１０℃／ｍｉｎの速度で１０５０℃に加熱して３０分間保温し、５℃／ｍｉｎの速度で１２００℃に昇温した熱処理炉の内部で継続して２４時間保温し、最後に室温まで冷却し、超合金インゴットを得る。 3) Homogenization treatment step: The ingot is taken out, then heated to 1050°C at a rate of 10°C/min, held for 30 minutes, and heated to 1200°C at a rate of 5°C/min inside the heat treatment furnace. The temperature is maintained continuously for 24 hours, and finally cooled to room temperature to obtain a superalloy ingot.
４）熱間圧延ステップ：総変形量が５０％～７０％で、各バス変形量を１５％～２５％範囲内に制御し、変形温度が１１００℃～１１７０℃の条件で、インゴットを圧延する。 4) Hot rolling step: The ingot is rolled under the condition that the total deformation amount is 50% to 70%, each bus deformation amount is controlled within the range of 15% to 25%, and the deformation temperature is 1100°C to 1170°C. .
５）熱処理ステップ：圧延後の合金を、１０℃／ｍｉｎの速度で１１２０℃に加熱して４時間保温し、再結晶処理を行い、空冷した後に７６０℃で８時間保温し、その後８６０℃に昇温させ２時間保温し、完了後に室温まで空冷する。 5) Heat treatment step: The alloy after rolling is heated to 1120°C at a rate of 10°C/min, held for 4 hours, recrystallized, air-cooled, held at 760°C for 8 hours, and then heated to 860°C. The temperature is raised and kept for 2 hours, and air-cooled to room temperature after completion.
比較例で製造された合金の室温および８５０℃の降伏強度は、それぞれ８５５ＭＰａおよび５７２ＭＰａであり、８５０℃の高温煙道ガスで５００時間腐食した後の重量変化は０．１２ ｍｇ／ｃｍ２である。 The room temperature and 850° C. yield strengths of the alloy produced in the comparative example are 855 MPa and 572 MPa, respectively, and the weight change is 0.12 mg/cm 2 after 500 hours of corrosion in hot flue gas at 850° C. .
図１、図２、図３および図４を参照すると、実施例１の２つの合金と比較例との比較から、本発明の合金は、８５０℃で優れた構造安定性を有し、高温での熱暴露期間にＴＣＰ相析出がないことが分かる。 1, 2, 3 and 4, from a comparison of the two alloys of Example 1 and the comparative example, the alloy of the present invention has excellent structural stability at 850°C and It can be seen that there is no TCP phase precipitation during the thermal exposure period of .
本発明により製造された合金マトリックスは、平均結晶粒サイズが約３０～７０ミクロンであり、微細なサイズの析出相が結晶粒の内部に均一に分散して分布されたＦＣＣ構造を備える。合金は優れた耐食性および強度性能を備え、その室温および８５０℃の高温降伏は７５０ＭＰａおよび５００ＭＰａ以上である。また、合金の重量増加は、８５０℃の煙道ガス腐食環境下で１００時間後に０．３ ｍｇ／ｃｍ２を超えない。 The alloy matrix produced according to the present invention has an average grain size of about 30-70 microns and has an FCC structure with fine-sized precipitated phases distributed uniformly dispersed within the grains. The alloy has excellent corrosion resistance and strength performance, and its high temperature yield at room temperature and 850° C. is above 750 MPa and 500 MPa. Also, the weight gain of the alloy does not exceed 0.3 mg/cm 2 after 100 hours in an 850° C. flue gas corrosive environment.
１）合金の調製：合金組成は、質量百分率に関して、Ｃｒ：２６％、Ｃｏ：１０％、Ｔｉ：３．５％、Ａｌ：１．０％、Ｗ：２％、Ｓｉ：≦０．５％、Ｍｎ：≦０．５％、Ｎｂ：１．５％、Ｃ：０．０３％、Ｆｅ：１．０％、マージンがＮｉである範囲要件を満たし、うち、Ｔｉ／Ａｌ＜２．５である。 1) Preparation of alloy: The alloy composition, in terms of mass percentage, is Cr: 26%, Co: 10%, Ti: 3.5%, Al: 1.0%, W: 2%, Si: ≤ 0.5% , Mn: ≤ 0.5%, Nb: 1.5%, C: 0.03%, Fe: 1.0%, and a margin of Ni satisfies the range requirements, of which Ti / Al < 2.5 be.
２）製錬ステップ：調製された合金を合金母液に製錬し、その後エレクトロスラグ再溶解プロセスを用いて精練および冷却することによって、合金母液をインゴットに凝固させた後、インゴット温度が９００℃に達する前に、冷却速度が１５℃／ｍｉｎを超えないように制御し、インゴット温度が９００℃に達した後に、１０℃／ｍｉｎを超える冷却速度で室温まで冷却する。合金母液がインゴットに凝固してから室温まで冷却されるまでの時間は１５分を超えない。 2) smelting step: smelting the prepared alloy into an alloy mother liquor, then using electroslag remelting process to refining and cooling to solidify the alloy mother liquor into an ingot, after which the ingot temperature reaches 900°C; Before reaching the temperature, the cooling rate is controlled not to exceed 15°C/min, and after the ingot temperature reaches 900°C, it is cooled to room temperature at a cooling rate of more than 10°C/min. The time from solidification of the alloy mother liquor into an ingot to cooling to room temperature does not exceed 15 minutes.
３）均質化処理ステップ：インゴットを取出し、その後インゴットを１０℃／ｍｉｎを超えない昇温速度で室温から１０３０℃に加熱して３０分間保温し、継続して５℃／ｍｉｎを超えない昇温速度で１１７０℃に昇温させ、熱処理炉の内部で２２時間保温し、最後に室温まで冷却し超合金インゴットを得る。 3) Homogenization treatment step: remove the ingot, then heat the ingot from room temperature to 1030°C at a rate of temperature increase not exceeding 10°C/min and keep the temperature for 30 minutes, and continuously increase the temperature not exceeding 5°C/min. The temperature is raised to 1170° C. at a high speed, kept in a heat treatment furnace for 22 hours, and finally cooled to room temperature to obtain a superalloy ingot.
４）熱間圧延ステップ：総変形量が５０％で、各バス変形量を１５％に制御し、変形温度が１１００℃の条件で、インゴットを圧延する。 4) Hot rolling step: The ingot is rolled under the condition that the total deformation amount is 50%, each bath deformation amount is controlled to 15%, and the deformation temperature is 1100°C.
５）熱処理ステップ：圧延後の合金を、１０℃／ｍｉｎを超えない昇温速度で室温から１１１０℃に昇温させ４時間保温し、再結晶処理を行い、室温まで空冷した後１０℃／ｍｉｎを超えない昇温速度で室温から７５０℃に昇温させ９時間保温し、その後１０℃／ｍｉｎを超えない昇温速度で８７０℃に昇温させ１．５時間保温し、完了後に室温まで空冷する。 5) Heat treatment step: The alloy after rolling is heated from room temperature to 1110°C at a heating rate not exceeding 10°C/min, held for 4 hours, subjected to recrystallization treatment, and air-cooled to room temperature at 10°C/min. The temperature was raised from room temperature to 750°C at a temperature elevation rate not exceeding 10°C/min, and the temperature was maintained for 9 hours, then the temperature was raised to 870°C at a temperature elevation rate not exceeding 10°C/min, and the temperature was maintained for 1.5 hours, and after completion, air cooling to room temperature. do.
１）合金の調製：合金組成は、質量百分率に関して、Ｃｒ：２７％、Ｃｏ：１２％、Ｔｉ：３％、Ａｌ：１．３％、Ｗ：３％、Ｓｉ：≦０．５％、Ｍｎ：≦０．５％、Ｎｂ：１％、Ｃ：０．０８％、Ｆｅ：０．０７％、マージンがＮｉの範囲要件を満たし、うち、Ｔｉ／Ａｌ＜２．５である。 1) Preparation of alloy: The alloy composition is, in terms of mass percentage, Cr: 27%, Co: 12%, Ti: 3%, Al: 1.3%, W: 3%, Si: ≤ 0.5%, Mn : ≤ 0.5%, Nb: 1%, C: 0.08%, Fe: 0.07%, margin meets Ni range requirements, where Ti/Al < 2.5.
２）製錬ステップ：調製された合金を合金母液に製錬し、その後エレクトロスラグ再溶解プロセスを用いて精練および冷却することによって、合金母液をインゴットに凝固した後、インゴット温度が９００℃に達する前に、冷却速度が１５℃／ｍｉｎを超えないように制御し、インゴット温度が９００℃に達した後に、１０℃／ｍｉｎを超える冷却速度で室温まで冷却する。合金母液がインゴットに凝固してから室温まで冷却するまでの時間は１５ｍｉｎ超えない。 2) Smelting step: the ingot temperature reaches 900°C after the alloy mother liquor is solidified into an ingot by smelting the prepared alloy into an alloy mother liquor, and then using the electroslag remelting process to refining and cooling; Before, the cooling rate is controlled not to exceed 15°C/min, and after the ingot temperature reaches 900°C, it is cooled to room temperature at a cooling rate of over 10°C/min. The time from solidification of the alloy mother liquor into an ingot to cooling to room temperature does not exceed 15 minutes.
３）均質化処理ステップ：インゴットを取出し、その後インゴットを１０℃／ｍｉｎを超えない昇温速度で室温から１０７０℃に加熱して３０分間保温し、継続して５℃／ｍｉｎを超えない昇温速度で１１８０℃に昇温させ、熱処理炉の内部で２０時間保温し、最後に室温まで冷却し、超合金インゴットを得る。 3) Homogenization step: remove the ingot, then heat the ingot from room temperature to 1070°C at a rate of temperature increase not exceeding 10°C/min, keep the temperature for 30 minutes, and continue to raise the temperature not exceeding 5°C/min. The temperature is raised to 1180° C. at a high speed, kept in a heat treatment furnace for 20 hours, and finally cooled to room temperature to obtain a superalloy ingot.
４）熱間圧延ステップ：総変形量が７０％で、各バス変形量を２５％に制御し、変形温度が１１７０℃の条件で、インゴットを圧延する。 4) Hot rolling step: The ingot is rolled under the condition that the total deformation amount is 70%, each bath deformation amount is controlled to 25%, and the deformation temperature is 1170°C.
５）熱処理ステップ：圧延後の合金を、１０℃／ｍｉｎを超えない昇温速度で室温から１１３０℃に昇温させて４時間保温し、再結晶処理を行い、室温まで空冷した後、１０℃／ｍｉｎを超えない昇温速度で室温から７７０℃に昇温させて７時間保温し、その後１０℃／ｍｉｎを超えない昇温速度で８４０℃に昇温させて２．５時間保温し、完了後に室温まで空冷する。 5) Heat treatment step: The alloy after rolling is heated from room temperature to 1130°C at a heating rate not exceeding 10°C/min and kept at this temperature for 4 hours, subjected to recrystallization treatment, air-cooled to room temperature, and then heated to 10°C. The temperature was raised from room temperature to 770°C at a rate not exceeding 10°C/min and maintained for 7 hours, then the temperature was raised to 840°C at a rate not exceeding 10°C/min and maintained for 2.5 hours, and completed. Then air cool to room temperature.
Claims (8)
前記合金成分は、質量百分率に関して、Ｃｒ：２５％～２８％、Ｃｏ：１０％～１５％、Ｔｉ：２．５％～３．５％、Ａｌ：１．０％～１．５％、Ｗ：１．５％～５％、Ｓｉ：≦０．５％、Ｍｎ：≦０．５％、Ｎｂ：０．５％～１．５％、Ｃ：０．０３％～０．０８％、Ｆｅ：０．５％～１．０％、マージンがＮｉである範囲要件を満たし、Ｔｉ／Ａｌ＜２．５である、ことを特徴とする析出強化型ニッケル基高クロム超合金。 A precipitation-strengthened nickel-based high-chromium superalloy comprising:
The alloy components are, in terms of mass percentage, Cr: 25% to 28%, Co: 10% to 15%, Ti: 2.5% to 3.5%, Al: 1.0% to 1.5%, W : 1.5% to 5%, Si: ≤0.5%, Mn: ≤0.5%, Nb: 0.5% to 1.5%, C: 0.03% to 0.08%, Fe : A precipitation-strengthened nickel-based high-chromium superalloy characterized in that it satisfies the range requirements of 0.5% to 1.0% with a margin of Ni and Ti/Al<2.5.
前記方法は、
１）合金成分が質量百分率に関して、Ｃｒ：２５％～２８％、Ｃｏ：１０％～１５％、Ｔｉ：２．５％～３．５％、Ａｌ：１．０％～１．５％、Ｗ：１．５％～５％、Ｓｉ：≦０．５％、Ｍｎ：≦０．５％、Ｎｂ：０．５％～１．５％、Ｃ：０．０３％～０．０８％、Ｆｅ：０．５％～１．０％、マージンがＮｉである範囲要件を満たし、Ｔｉ／Ａｌ＜２．５である合金の調製ステップ、
２）調製された合金を合金母液に製錬した後、エレクトロスラグ再溶解プロセスを用いて精練および冷却することによって、合金母液をインゴットに凝固する、製錬ステップ、
３）超合金インゴットを得るために均質化処理するステップ、
４）総変形量が５０％～７０％で、各バス変形量を１５％～２５％範囲内に制御し、変形温度が１１００℃～１１７０℃の条件で、超合金インゴットを圧延する熱間圧延ステップ、
５）圧延後の合金を１１１０℃～１１３０℃で４時間保温して再結晶処理を行い、室温まで空冷した後７５０℃～７７０℃で７～９時間保温し、その後８４０℃～８７０℃まで昇温して１．５～２．５時間保温し、その後室温まで空冷する熱処理ステップを含む、ことを特徴とする析出強化型ニッケル基高クロム超合金の製造方法。 A method for producing a precipitation-strengthened nickel-based high-chromium superalloy, comprising:
The method comprises:
1) Regarding the mass percentage of the alloy components, Cr: 25% to 28%, Co: 10% to 15%, Ti: 2.5% to 3.5%, Al: 1.0% to 1.5%, W : 1.5% to 5%, Si: ≤0.5%, Mn: ≤0.5%, Nb: 0.5% to 1.5%, C: 0.03% to 0.08%, Fe : 0.5% to 1.0%, a step of preparing an alloy that satisfies the range requirements with a margin of Ni and Ti/Al<2.5;
2) a smelting step in which the prepared alloy is smelted into an alloy mother liquor and then solidified into an ingot by refining and cooling using an electroslag remelting process;
3) homogenization to obtain a superalloy ingot;
4) Hot rolling to roll the superalloy ingot under the condition that the total deformation amount is 50% to 70%, each bus deformation amount is controlled within the range of 15% to 25%, and the deformation temperature is 1100 ° C to 1170 ° C. step,
5) The alloy after rolling is kept at 1110°C to 1130°C for 4 hours for recrystallization treatment, air-cooled to room temperature, kept at 750°C to 770°C for 7 to 9 hours, and then heated to 840°C to 870°C. A method for producing a precipitation-strengthened nickel-based high-chromium superalloy, comprising a heat treatment step of warming and holding for 1.5 to 2.5 hours, followed by air cooling to room temperature.
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| WO2020249107A1 (en) | 2020-12-17 |
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