WO2020249115A1 - 一种复合强化型耐蚀高温合金及其制备工艺 - Google Patents

一种复合强化型耐蚀高温合金及其制备工艺 Download PDF

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WO2020249115A1
WO2020249115A1 PCT/CN2020/095963 CN2020095963W WO2020249115A1 WO 2020249115 A1 WO2020249115 A1 WO 2020249115A1 CN 2020095963 W CN2020095963 W CN 2020095963W WO 2020249115 A1 WO2020249115 A1 WO 2020249115A1
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alloy
temperature
ingot
room temperature
hours
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French (fr)
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严靖博
谷月峰
袁勇
杨征
张醒兴
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Xian Thermal Power Research Institute Co Ltd
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Xian Thermal Power Research Institute Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • 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
    • 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
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • 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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  • the invention belongs to the field of high-temperature alloy materials, and specifically relates to a composite reinforced corrosion-resistant high-temperature alloy and a preparation process thereof.
  • Thermal power generation has been the most important power generation technology in my country for a long time, and improving the steam parameters of the unit is considered the most effective way to solve the above problems.
  • a large number of past practices have shown that the service performance of key component materials is the main reason that restricts the improvement of boiler unit steam parameters.
  • the super/reheater pipe has Service performance puts forward extremely high requirements. The super/reheater will withstand multiple factors such as high temperature creep, thermal fatigue, oxidation and high temperature flue gas corrosion during service.
  • the substantial improvement of the main steam parameters of thermal power units the development of superalloy materials that can meet the performance requirements of the over/reheater tubes of high-parameter units has become an urgent issue in the thermal power industry.
  • the superheater/reheater puts forward extremely high requirements on the durable strength and corrosion resistance of its candidate materials.
  • Excellent durability is an important guarantee for long-term service under high temperature conditions, and precipitation strengthening is currently the main strengthening method for candidate alloys.
  • precipitation strengthening is currently the main strengthening method for candidate alloys.
  • the coarsening and growth of the precipitated phase of the alloy during high temperature service will have a significant impact on its endurance life.
  • oxidation resistance and corrosion resistance also have an important impact on the service performance of the alloy, and the higher content of Cr in the alloy will cause problems such as unstable structure and decreased mechanical properties.
  • the Cr element content of the commonly used precipitation-strengthened nickel-based high temperature alloys is often controlled in a lower range, but at the same time, its corrosion resistance is greatly affected.
  • the purpose of the present invention is to provide a composite reinforced corrosion-resistant high-temperature alloy and its preparation process.
  • the alloy By promoting the precipitation of a large number of uniformly dispersed secondary strengthening phases in the alloy, the alloy obtains good strength performance and at the same time ensures the stability of the alloy structure.
  • a high content of Al is added to the alloy, and the ratio of Cr, Al, Ti, W and other elements is adjusted reasonably to obtain an alloy composition range with good structural stability.
  • a composite reinforced corrosion-resistant high-temperature alloy characterized in that the composition of the alloy meets the following range requirements in terms of mass percentage: Cr: 20-24%, Co: 10-15%, Ti: 1.5-2.5%, Al: 2.5- 3.5%, W: 3 ⁇ 7%, Si: ⁇ 0.5%, Mn: ⁇ 0.5%, Nb: 0.5 ⁇ 1.5%, C: 0.03 ⁇ 0.08%, Fe: 0.5 ⁇ 1.0%, the balance is Ni, of which, 1.5 ⁇ Al/Ti and W+Cr ⁇ 27%.
  • a preparation process of a composite reinforced corrosion-resistant high-temperature alloy includes the following steps:
  • Formulated alloy The alloy composition meets the following range requirements in terms of mass percentage: Cr: 20-24%, Co: 10-15%, Ti: 1.5-2.5%, Al: 2.5-3.5%, W: 3-7%, Si: ⁇ 0.5%, Mn: ⁇ 0.5%, Nb: 0.5 ⁇ 1.5%, C: 0.03 ⁇ 0.08%, Fe: 0.5 ⁇ 1.0%, the balance is Ni, where 1.5 ⁇ Al/Ti and W+Cr ⁇ 27%;
  • Hot rolling rolling the ingot with a total deformation of 50% to 70%, the deformation of each pass is controlled within the range of 15% to 25%, and the deformation temperature is 1100 to 1150°C;
  • a further improvement of the present invention is that the smelting in step 2) is carried out in a vacuum smelting furnace, and the vacuum degree during smelting is not higher than 1.0 ⁇ 10 -4 MPa.
  • a further improvement of the present invention is that in step 2), before the temperature reaches 900°C during solidification into an ingot, the cooling rate is controlled not to exceed 15°C/min, and after the temperature reaches 900°C during solidification into an ingot, the temperature exceeds 10°C. Cool down to room temperature at a cooling rate of °C/min.
  • a further improvement of the present invention is that, in step 2), the time from the solidification of the alloy mother liquid into an ingot to cooling to room temperature does not exceed 15 minutes.
  • a further improvement of the present invention is that the specific process of step 3) is: take out the ingot, then heat the ingot to 1030 ⁇ 1070°C for half an hour, then continue to heat up to 1170 ⁇ 1200°C in the heat treatment furnace for 20 ⁇ 24 Hours, and finally cooled to room temperature.
  • a further improvement of the present invention is that in step 3), the heating rate does not exceed 10°C/min when the ingot is heated to 1030-1070°C, and the heating rate does not exceed 5°C/min when the temperature is raised to 1170°C to 1200°C.
  • a further improvement of the present invention is that in step 5), the temperature is raised from room temperature to 1110 ⁇ 1130°C at a heating rate not exceeding 10°C/min, and the temperature is raised from room temperature to 750 ⁇ 770°C at a heating rate not exceeding 10°C/min, and then Raise the temperature to 840 ⁇ 870°C at a heating rate not exceeding 10°C/min.
  • the present invention has the following beneficial effects:
  • the present invention has developed a new type of high-temperature alloy with higher Al and Ti content.
  • the higher Al and Cr element content in the alloy also ensures that it has excellent oxidation resistance and corrosion resistance. .
  • the alloy prepared according to the method of the present invention has excellent strength performance and corrosion resistance, as well as good structure stability.
  • the alloy matrix is austenite with a disordered face-centered structure.
  • the average grain size is less than 100m.
  • the fine spherical Ni3Al precipitates are uniformly dispersed in the austenite crystal, and the size is not greater than 50nm.
  • the tensile yield strength of the alloy at room temperature and 850°C is higher than 750MPa and 500MPa, respectively, and the alloy has a weight change after 500 hours of corrosion in a high temperature flue gas environment (N 2 -15% CO 2 -3.5% O 2 -0.1% SO 2 ) at 850°C Less than 0.3mg/cm 2 .
  • the alloy has excellent structural stability during heat exposure at 850°C.
  • Figure 1 shows the microstructure of the heat-treated alloy in Example 1
  • Figure 2 shows the microstructure of the alloy in the heat-exposed state (850°C/1000h) of Example 1
  • Figure 3 shows the microstructure of the heat-treated state of the comparative example
  • Figure 4 shows the alloy microstructure in the heat-exposed state (850°C/1000h) of the comparative example
  • the precipitation strengthened alloy of the present invention is a nickel-based superalloy material.
  • a composite reinforced corrosion-resistant high-temperature alloy The alloy composition meets the following requirements in terms of mass percentage: Cr: 20-24%, Co: 10-15%, Ti: 1.5-2.5%, Al: 2.5-3.5%, W: 3 ⁇ 7%, Si: ⁇ 0.5%, Mn: ⁇ 0.5%, Nb: 0.5 ⁇ 1.5%, C: 0.03 ⁇ 0.08%, Fe: 0.5 ⁇ 1.0%, the balance is Ni, where 1.5 ⁇ Al/Ti And W+Cr ⁇ 27%;
  • the preparation process of a composite reinforced corrosion-resistant high-temperature alloy includes the following steps:
  • Formulated alloy The alloy composition meets the following range requirements in terms of mass percentage: Cr: 20-24%, Co: 10-15%, Ti: 1.5-2.5%, Al: 2.5-3.5%, W: 3-7%, Si: ⁇ 0.5%, Mn: ⁇ 0.5%, Nb: 0.5 ⁇ 1.5%, C: 0.03 ⁇ 0.08%, Fe: 0.5 ⁇ 1.0%, the balance is Ni, where 1.5 ⁇ Al/Ti and W+Cr ⁇ 27%;
  • Hot rolling Rolling the ingot with a total deformation of 50% to 70%, the deformation of each pass is controlled within the range of 15% to 25%, and the deformation temperature is 1100-1150°C;
  • the heat-resistant steel material of this embodiment includes, by mass percentage, Cr: 24%, Co: 15%, Ti: 2.0%, Al: 3.0%, W: 3.0%, Si: 0.5%, Mn: 0.5%, Nb: 0.5%, C: 0.07%, Fe: 0.5%, the balance is Ni;
  • the components include: Cr: 24%, Co: 15%, Ti: 2.0%, Al: 3.0%, W: 3.0%, Si: 0.5%, Mn: 0.5%, Nb: 0.5 %, C: 0.07%, Fe: 0.5%, the balance is Ni;
  • Homogenization treatment take out the ingot, then heat the ingot to 1050°C at a rate of 10°C/min and heat it for half an hour, then continue to heat it up to 1200°C in the heat treatment furnace at a rate of 5°C/min for 24 Hours, and finally cooled to room temperature to obtain high-temperature alloy ingots;
  • Hot rolling Rolling the ingot with a total deformation of 50% to 70%, the deformation of each pass is controlled within the range of 15% to 25%, and the deformation temperature is 1100-1150°C;
  • Heat treatment heat the rolled alloy to 1120°C at a rate of 10°C/min and keep it for 4 hours for recrystallization. After air cooling, keep it at 760°C for 8 hours, then heat it up to 860°C for 2 hours. Air-cool to room temperature.
  • the yield strength of the alloy described in Example 1 at room temperature and 850°C was 817 MPa and 473 MPa, respectively, and the weight change after 500 hours of high temperature flue gas corrosion at 850°C was 0.16 mg/cm 2 .
  • the heat-resistant steel material of this embodiment includes, by mass percentage: Cr: 20%, Co: 15%, Ti: 1.5%, Al: 3.5%, W: 7.0%, Si: 0.5%, Mn: 0.5%, Nb: 0.5%, C: 0.07%, Fe: 0.5%, the balance is Ni;
  • the ingredients include: Cr: 20%, Co: 15%, Ti: 1.5%, Al: 3.5%, W: 7.0%, Si: 0.5%, Mn: 0.5%, Nb: 0.5 in mass percentage %, C: 0.07%, Fe: 0.5%, the balance is Ni;
  • Homogenization treatment take out the ingot, then heat the ingot to 1050°C at a rate of 10°C/min and heat it for half an hour, then continue to heat it up to 1200°C in the heat treatment furnace at a rate of 5°C/min for 24 Hours, and finally cooled to room temperature to obtain high-temperature alloy ingots;
  • Hot rolling Rolling the ingot with a total deformation of 50% to 70%, the deformation of each pass is controlled within the range of 15% to 25%, and the deformation temperature is 1100 to 1150°C;
  • Heat treatment heat the rolled alloy to 1120°C at a rate of 10°C/min and keep it for 4 hours for recrystallization. After air cooling, keep it at 760°C for 8 hours, then heat it up to 860°C for 2 hours. Air-cool to room temperature.
  • the yield strength of the alloy described in Example 2 at room temperature and 850°C is 867 MPa and 506 MPa, respectively, and the weight change after 500 hours of high temperature flue gas corrosion at 850°C is 0.11 mg/cm 2 .
  • the heat-resistant steel material of this embodiment includes, by mass percentage: Cr: 25%, Co: 10%, Ti: 2.0%, Al: 3.0%, W: 5%, Mo: 0.5%, Si: 0.2%, Mn: 0.2%, Nb: 0.5%, C: 0.07%, Fe: 3.0%, the balance is Ni;
  • the ingredients include: Cr: 25%, Co: 10%, Ti: 2.0%, Al: 3.0%, W: 5%, Mo: 0.5%, Si: 0.2%, Mn: 0.2 in terms of mass percentage %, Nb: 0.5%, C: 0.07%, Fe: 3.0%, the balance is Ni;
  • Homogenization treatment take out the ingot, then heat the ingot to 1050°C at a rate of 10°C/min and heat it for half an hour, then continue to heat it up to 1200°C in the heat treatment furnace at a rate of 5°C/min for 24 Hours, and finally cooled to room temperature to obtain high-temperature alloy ingots;
  • Hot rolling Rolling the ingot with a total deformation of 50% to 70%, the deformation of each pass is controlled within the range of 15% to 25%, and the deformation temperature is 1100-1150°C;
  • Heat treatment heat the rolled alloy to 1120°C at a rate of 10°C/min and keep it for 4 hours for recrystallization. After air cooling, keep it at 760°C for 8 hours, then heat it up to 860°C for 2 hours. Air-cool to room temperature.
  • the yield strength of the alloy in the comparative example was 950 MPa and 565 MPa at room temperature and 850°C, respectively, and the weight change after 500 hours of high temperature flue gas corrosion at 850°C was 0.18 mg/cm 2 .
  • Homogenization treatment take out the ingot, then heat the ingot to 1030°C for half an hour, then continue to heat up to 1170°C in a heat treatment furnace for 22 hours, and finally cool to room temperature to obtain a high-temperature alloy ingot;
  • Hot rolling rolling the ingot with a total deformation of 50%, the deformation of each pass is controlled at 15%, and the deformation temperature is 1150°C;
  • Heat treatment heat the rolled alloy at 1110°C for 4 hours for recrystallization treatment, after air cooling at 750°C for 7 hours, then heat up to 840°C for 2.5 hours, and then air cool to room temperature after completion.
  • Homogenization treatment take out the ingot, then heat the ingot to 1070°C for half an hour, then continue to heat up to 1180°C in a heat treatment furnace for 20 hours, and finally cool to room temperature to obtain a high-temperature alloy ingot;
  • Hot rolling rolling the ingot with a total deformation of 70%, the deformation of each pass is controlled at 25%, and the deformation temperature is 1100°C;
  • Heat treatment heat the rolled alloy at 1130°C for 4 hours for recrystallization treatment, after air cooling, heat at 770°C for 9 hours, then heat up to 870°C for 1.5 hours, and air cool to room temperature after completion.
  • the alloy matrix prepared by the invention has an FCC structure, with an average crystal grain size of about 30-70 microns, and fine-sized precipitated phases are uniformly dispersed within the crystal grains.
  • the alloy has excellent corrosion resistance and strength properties, and its high temperature yield at room temperature 850 °C is not less than 800 MPa and 450 MPa. In contrast, the weight gain of the alloy does not exceed 0.3mg/cm 2 after 100 hours in a flue gas corrosive environment at 850°C.

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Abstract

一种复合强化型耐蚀高温合金及其制备工艺，合金成分按质量百分比满足：Cr：20～24％，Co：10～15％，Ti：1.5～2.5％，Al：2.5～3.5％，W：3～7％，Si：≤0.5％，Mn：≤0.5％，Nb：0.5～1.5％，C：0.03～0.08％，Fe：0.5～1.0％，余量为Ni，其中，1.5≤Al/Ti且W+Cr≤27％；制备工艺包括：熔炼，均匀化处理，后热轧，最后热处理。通过促进合金内部析出大量均匀弥散分布的二次强化相使合金获得良好的强度性能，并同时在确保合金组织稳定性的前提下加入一定含量的固溶强化元素，保障合金优异的抗氧化、抗腐蚀性能。

Description

一种复合强化型耐蚀高温合金及其制备工艺 技术领域
本发明属高温用合金材料领域，具体涉及一种复合强化型耐蚀高温合金及其制备工艺。
背景技术
随着我国用电需求不断增加，能源紧缺及环境污染问题日益凸显，发展高效、节能、环保发电方式的需求越发紧迫。火力发电作为我国长期以来最主要的发电技术，提高机组蒸汽参数被认为是解决上述问题最有效的途径。以往大量实践表明，关键部件材料的服役性能是制约锅炉机组蒸汽参数提高的最主要原因，而作为火电机组锅炉中服役工况最严苛的关键部件之一，过/再热器管道对材料的服役性能提出了极高的要求。过/再热器在服役期间将承受高温蠕变、热疲劳、氧化及高温烟气腐蚀等多重因素的影响。随着火电机组主蒸汽参数的大幅提高，开发出可以满足高参数机组过/再热器管使用性能需求的高温合金材料已成为火力发电行业亟待解决的课题。
过/再热器作为火电机组锅炉中服役工况最严苛的部件，对其候选材料的持久强度及抗腐蚀性能提出了极高的要求。优异的持久性能是合金在高温条件下长时间服役的重要保障，而析出强化是目前候选合金的主要强化方式。然而，合金在高温服役期间析出相的粗化长大将对其持久寿命带来显著影响。另一方面，抗氧化、抗腐蚀性能同样对合金的服役性能具有重要影响，而合金中较高的Cr元素含量会造成组织不稳定及力学性能下降等问题。针对高参数锅炉再热器管对材料使用性能的需求，目前国外已开发出了一系列镍基变形高温合金材料，如美国特殊金属公司开发的Inconel 740H、美国哈氏公司开发的Haynes 282、德国蒂森克虏伯公司开发的CCA 617、英国Rolls-Royce公司开发的Nimonic 263、日本日立公司开发的FENIX700、日本东芝公司开发的TOS1X、日本三菱公司开发的LTESR700等镍基变形高温合金。由于较高的Cr含量会降低合金强度并恶化组织稳定性，目前常用的析出强化型镍基高 温合金中Cr元素含量往往控制在较低的范围，但同时导致其抗腐蚀性能受到较大影响。
发明内容
本发明的目的是提供一种复合强化型耐蚀高温合金及其制备工艺，通过促进合金内部析出大量均匀弥散分布的二次强化相使合金获得良好的强度性能，并同时在确保合金组织稳定性的前提下加入一定含量的固溶强化元素。同时为保障合金优异的抗氧化、抗腐蚀性能，合金中加入了较高的Al元素含量，并通过合理调整Cr、Al、Ti、W等元素比例，获得具有良好组织稳定性的合金成分范围。
为了实现以上发明目的，本发明所采用的技术方案为：
一种复合强化型耐蚀高温合金，其特征在于：该合金成分按质量百分比满足如下范围要求：Cr：20～24％，Co：10～15％，Ti：1.5～2.5％，Al：2.5～3.5％，W：3～7％，Si：≤0.5％，Mn：≤0.5％，Nb：0.5～1.5％，C：0.03～0.08％，Fe：0.5～1.0％，余量为Ni，其中，1.5≤Al/Ti且W+Cr≤27％。
一种复合强化型耐蚀高温合金的制备工艺，包括以下步骤：
1)配制合金：合金成分按质量百分比满足如下范围要求：Cr：20～24％，Co：10～15％，Ti：1.5～2.5％，Al：2.5～3.5％，W：3～7％，Si：≤0.5％，Mn：≤0.5％，Nb：0.5～1.5％，C：0.03～0.08％，Fe：0.5～1.0％，余量为Ni，其中，1.5≤Al/Ti且W+Cr≤27％；
2)熔炼：将配制的合金熔炼成合金母液，然后采用电渣重熔工艺精炼，冷却，合金母液凝固成铸锭；
3)均匀化处理，得到高温合金铸锭；
4)热轧：将铸锭进行轧制，总变形量为50～70％，每道次变形量控制在15～25％范围内，变形温度为1100～1150℃；
5)热处理：将轧制后的合金在1110～1130℃保温4小时进行再结晶处理，空冷至室温后 在750～770℃保温7～9小时，随后升温至840～870℃保温1.5～2.5小时，然后空冷至室温。
本发明进一步的改进在于，步骤2)中熔炼在真空熔炼炉内进行，熔炼时真空度不高于1.0×10 -4MPa。
本发明进一步的改进在于，步骤2)中在凝固成铸锭过程中温度达到900℃前，控制冷却速率不超过15℃/min，在凝固成铸锭过程中温度达到900℃后，以超过10℃/min的冷却速度冷却至室温。
本发明进一步的改进在于，步骤2)中从合金母液凝固成铸锭开始至冷却至室温所用时间不超过15min。
本发明进一步的改进在于，步骤3)的具体过程为：将铸锭取出，随后将铸锭加热至1030～1070℃保温半小时后，继续升温至1170～1200℃的热处理炉内保温20～24小时，最后冷却至室温。
本发明进一步的改进在于，步骤3)中将铸锭加热至1030～1070℃时升温速率不超过10℃/min，升温至1170℃～1200℃时升温速率不高于5℃/min。
本发明进一步的改进在于，步骤5)中自室温以不超过10℃/min的升温速率升温至1110～1130℃，自室温以不超过10℃/min的升温速率升温至750～770℃，再以不超过10℃/min的升温速率升温至840～870℃。
与现有技术相比，本发明具有的有益效果：
本发明基于析出强化的合金设计理念，开发出了一种具有较高Al、Ti含量的新型高温合金，合金中较高的Al、Cr元素含量也保障了其具备优异的抗氧化、抗腐蚀能力。
按本发明所述方法制备的合金具备优异的强度性能与抗腐蚀性能，同时具备良好的组织稳定性。合金基体是无序面心结构的奥氏体，平均晶粒尺寸小于100m，奥氏体晶界存在呈不连续分布的碳化物(NbC与Cr23C6)，奥氏体体积分数约占5-20％，奥氏体晶内均匀弥散 分布细小球状的Ni3Al析出相，其尺寸不大于50nm。合金室温及850℃拉伸屈服强度分别高于750MPa与500MPa，并且合金经850℃高温烟气环境(N 2-15％CO 2-3.5％O 2-0.1％SO 2)腐蚀500小时后重量变化小于0.3mg/cm 2。此外，合金在850℃热暴露期间具备优异的组织稳定性。
附图说明
图1为实施例1热处理态合金显微组织
图2为实施例1热暴露态(850℃/1000h)合金显微组织
图3为对比例热处理态显微组织
图4为对比例热暴露态(850℃/1000h)合金显微组织
具体实施方式
下面结合实施例对本发明作进一步详细说明。
本发明的析出强化型合金为镍基高温合金材料。
一种复合强化型耐蚀高温合金，合金成分按质量百分比满足如下范围要求：Cr：20～24％，Co：10～15％，Ti：1.5～2.5％，Al：2.5～3.5％，W：3～7％，Si：≤0.5％，Mn：≤0.5％，Nb：0.5～1.5％，C：0.03～0.08％，Fe：0.5～1.0％，余量为Ni，其中，1.5≤Al/Ti且W+Cr≤27％；
一种复合强化型耐蚀高温合金的其制备工艺，包括以下步骤：
1)配制合金：合金成分按质量百分比满足如下范围要求：Cr：20～24％，Co：10～15％，Ti：1.5～2.5％，Al：2.5～3.5％，W：3～7％，Si：≤0.5％，Mn：≤0.5％，Nb：0.5～1.5％，C：0.03～0.08％，Fe：0.5～1.0％，余量为Ni，其中，1.5≤Al/Ti且W+Cr≤27％；
2)熔炼：将配制的合金在熔炼成合金母液，然后采用电渣重熔工艺精炼，冷却，合金母液凝固成铸锭后且在凝固成铸锭过程中温度达到900℃前，控制冷却速率不超过15℃/min，在在凝固成铸锭过程中温度达到900℃后以超过10℃/min的冷却速度冷却至室温；从合金母液凝固成铸锭开始至冷却至室温所用时间不超过15min。
3)均匀化处理：将铸锭取出，随后将铸锭加热至1030～1070℃保温半小时后，继续升温至1170～1200℃的热处理炉内保温20～24小时，最后冷却至室温，得到高温合金铸锭；
4)热轧：将铸锭进行轧制，其总变形量为50～70％，每道次变形量控制在15～25％范围内，变形温度为1100-1150℃；
5)热处理：将轧制后的合金在1110～1130℃保温4小时进行再结晶处理，空冷后在750～770℃保温7～9小时，随后升温至840～870℃保温1.5～2.5小时，完成后空冷至室温。
实施例1
本实施例的耐热钢材料，按质量百分比计包括：Cr：24％，Co：15％，Ti：2.0％，Al：3.0％，W：3.0％，Si：0.5％，Mn：0.5％，Nb：0.5％，C：0.07％，Fe：0.5％，余量为Ni；
本实施例的制备方法包括以下步骤：
1)原料配制：成分按质量百分比计包括：Cr：24％，Co：15％，Ti：2.0％，Al：3.0％，W：3.0％，Si：0.5％，Mn：0.5％，Nb：0.5％，C：0.07％，Fe：0.5％，余量为Ni；
2)熔炼步骤：将陶瓷坩埚与配制的原料同时置于真空熔炼炉内，采用真空感应炉在真空度不高于1.0×10 -4MPa下，将配制的合金熔炼成合金母液，当合金母液凝固的同时利用电弧在低功率下对陶瓷坩埚进行预热。合金完全凝固成为铸锭后，将其移至预热后的陶瓷坩埚内，避免合金锭与铜坩埚接触而导致其冷却速率过高。
3)均匀化处理：将铸锭取出，随后将铸锭以10℃/min的速率加热至1050℃并保温半小时后，继续以5℃/min的速率升温至1200℃的热处理炉内保温24小时，最后冷却至室温，得到高温合金铸锭；
4)热轧：将铸锭进行轧制，其总变形量为50～70％，每道次变形量控制在15～25％范围内，变形温度为1100-1150℃；
5)热处理：将轧制后的合金以10℃/min的速率加热至1120℃并保温4小时进行再结晶处 理，空冷后在760℃保温8小时，随后升温至860℃保温2小时，完成后空冷至室温。
实施例1所述合金室温及850℃屈服强度分别为817MPa与473MPa，850℃高温烟气腐蚀500小时后重量变化为0.16mg/cm 2。
实施例2
本实施例的耐热钢材料，按质量百分比计包括：Cr：20％，Co：15％，Ti：1.5％，Al：3.5％，W：7.0％，Si：0.5％，Mn：0.5％，Nb：0.5％，C：0.07％，Fe：0.5％，余量为Ni；
本实施例的制备方法包括以下步骤：
1)原料配制：成分按质量百分比计包括：Cr：20％，Co：15％，Ti：1.5％，Al：3.5％，W：7.0％，Si：0.5％，Mn：0.5％，Nb：0.5％，C：0.07％，Fe：0.5％，余量为Ni；
2)熔炼步骤：将陶瓷坩埚与配制的原料同时置于真空熔炼炉内，采用真空感应炉在真空度不高于1.0×10 -4MPa下，将配制的合金熔炼成合金母液，当合金母液凝固的同时利用电弧在低功率下对陶瓷坩埚进行预热。合金完全凝固成为铸锭后，将其移至预热后的陶瓷坩埚内，避免合金锭与铜坩埚接触而导致其冷却速率过高。
3)均匀化处理：将铸锭取出，随后将铸锭以10℃/min的速率加热至1050℃并保温半小时后，继续以5℃/min的速率升温至1200℃的热处理炉内保温24小时，最后冷却至室温，得到高温合金铸锭；
4)热轧：将铸锭进行轧制，其总变形量为50～70％，每道次变形量控制在15～25％范围内，变形温度为1100～1150℃；
5)热处理：将轧制后的合金以10℃/min的速率加热至1120℃并保温4小时进行再结晶处理，空冷后在760℃保温8小时，随后升温至860℃保温2小时，完成后空冷至室温。
实施例2所述合金室温及850℃屈服强度分别为867MPa与506MPa，850℃高温烟气腐蚀500小时后重量变化为0.11mg/cm 2。
对比例
本实施例的耐热钢材料，按质量百分比计包括：Cr：25％，Co：10％，Ti：2.0％，Al：3.0％，W：5％，Mo：0.5％，Si：0.2％，Mn：0.2％，Nb：0.5％，C：0.07％，Fe：3.0％，余量为Ni；
本实施例的制备方法包括以下步骤：
1)原料配制：成分按质量百分比计包括：Cr：25％，Co：10％，Ti：2.0％，Al：3.0％，W：5％，Mo：0.5％，Si：0.2％，Mn：0.2％，Nb：0.5％，C：0.07％，Fe：3.0％，余量为Ni；
2)熔炼步骤：将陶瓷坩埚与配制的原料同时置于真空熔炼炉内，采用真空感应炉在真空度不高于1.0×10 -4MPa下，将配制的合金熔炼成合金母液，当合金母液凝固的同时利用电弧在低功率下对陶瓷坩埚进行预热。合金完全凝固成为铸锭后，将其移至预热后的陶瓷坩埚内，避免合金锭与铜坩埚接触而导致其冷却速率过高。
3)均匀化处理：将铸锭取出，随后将铸锭以10℃/min的速率加热至1050℃并保温半小时后，继续以5℃/min的速率升温至1200℃的热处理炉内保温24小时，最后冷却至室温，得到高温合金铸锭；
4)热轧：将铸锭进行轧制，其总变形量为50～70％，每道次变形量控制在15～25％范围内，变形温度为1100-1150℃；
5)热处理：将轧制后的合金以10℃/min的速率加热至1120℃并保温4小时进行再结晶处理，空冷后在760℃保温8小时，随后升温至860℃保温2小时，完成后空冷至室温。
对比例所述合金室温及850℃屈服强度分别为950MPa与565MPa，850℃高温烟气腐蚀500小时后重量变化为0.18mg/cm 2。
参见图1、图2、图3和图4，由实施例1与对比例两种合金的对比可以看出，本发明所述合金在850℃具备优异的组织稳定性，在高温热暴露期间无TCP相析出。
实施例3
1)配制合金：合金成分按质量百分比满足如下范围要求：Cr：22％，Co：10％，Ti：2.5％，Al：2.5％，W：4％，Si：≤0.5％，Mn：≤0.5％，Nb：1％，C：0.03％，Fe：0.8％，余量为Ni，其中，1.5≤Al/Ti且W+Cr≤27％；
2)熔炼：将配制的合金在熔炼成合金母液，然后采用电渣重熔工艺精炼，冷却，合金母液凝固成铸锭后且在凝固成铸锭过程中温度达到900℃前，控制冷却速率不超过15℃/min，在在凝固成铸锭过程中温度达到900℃后以超过10℃/min的冷却速度冷却至室温；
3)均匀化处理：将铸锭取出，随后将铸锭加热至1030℃保温半小时后，继续升温至1170℃的热处理炉内保温22小时，最后冷却至室温，得到高温合金铸锭；
4)热轧：将铸锭进行轧制，其总变形量为50％，每道次变形量控制在15％，变形温度为1150℃；
5)热处理：将轧制后的合金在1110℃保温4小时进行再结晶处理，空冷后在750℃保温7小时，随后升温至840℃保温2.5小时，完成后空冷至室温。
实施例4
1)配制合金：合金成分按质量百分比满足如下范围要求：Cr：23％，Co：12％，Ti：2％，Al：3％，W：5％，Si：≤0.5％，Mn：≤0.5％，Nb：1.5％，C：0.08％，Fe：1％，余量为Ni，其中，1.5≤Al/Ti且W+Cr≤27％；
2)熔炼：将配制的合金在熔炼成合金母液，然后采用电渣重熔工艺精炼，冷却，合金母液凝固成铸锭后且在凝固成铸锭过程中温度达到900℃前，控制冷却速率不超过15℃/min，在在凝固成铸锭过程中温度达到900℃后以超过10℃/min的冷却速度冷却至室温；
3)均匀化处理：将铸锭取出，随后将铸锭加热至1070℃保温半小时后，继续升温至1180℃的热处理炉内保温20小时，最后冷却至室温，得到高温合金铸锭；
4)热轧：将铸锭进行轧制，其总变形量为70％，每道次变形量控制在25％，变形温度为1100℃；
5)热处理：将轧制后的合金在1130℃保温4小时进行再结晶处理，空冷后在770℃保温9小时，随后升温至870℃保温1.5小时，完成后空冷至室温。
本发明制备的合金基体具有FCC结构，平均晶粒尺寸约30-70微米，并有尺寸细小的析出相在晶粒内部均匀弥散分布。合金具备优良的抗腐蚀性能及强度性能，其室温850℃高温屈服不低于800MPa与450MPa。比外，合金在850℃烟气腐蚀环境下100小时后增重不超过0.3mg/cm 2。

Claims (8)

  1. 一种复合强化型耐蚀高温合金，其特征在于：该合金成分按质量百分比满足如下范围要求：Cr：20～24％，Co：10～15％，Ti：1.5～2.5％，Al：2.5～3.5％，W：3～7％，Si：≤0.5％，Mn：≤0.5％，Nb：0.5～1.5％，C：0.03～0.08％，Fe：0.5～1.0％，余量为Ni，其中，1.5≤Al/Ti且W+Cr≤27％。
  2. 一种复合强化型耐蚀高温合金的制备工艺，其特征在于，包括以下步骤：
    1)配制合金：合金成分按质量百分比满足如下范围要求：Cr：20～24％，Co：10～15％，Ti：1.5～2.5％，Al：2.5～3.5％，W：3～7％，Si：≤0.5％，Mn：≤0.5％，Nb：0.5～1.5％，C：0.03～0.08％，Fe：0.5～1.0％，余量为Ni，其中，1.5≤Al/Ti且W+Cr≤27％；
    2)熔炼：将配制的合金熔炼成合金母液，然后采用电渣重熔工艺精炼，冷却，合金母液凝固成铸锭；
    3)均匀化处理，得到高温合金铸锭；
    4)热轧：将铸锭进行轧制，总变形量为50～70％，每道次变形量控制在15～25％范围内，变形温度为1100～1150℃；
    5)热处理：将轧制后的合金在1110～1130℃保温4小时进行再结晶处理，空冷至室温后在750～770℃保温7～9小时，随后升温至840～870℃保温1.5～2.5小时，然后空冷至室温。
  3. 根据权利要求2所述的一种复合强化型耐蚀高温合金的制备工艺，其特征在于，步骤2)中熔炼在真空熔炼炉内进行，熔炼时真空度不高于1.0×10 -4MPa。
  4. 根据权利要求2所述的一种复合强化型耐蚀高温合金的制备工艺，其特征在于，步骤2)中在凝固成铸锭过程中温度达到900℃前，控制冷却速率不超过15℃/min，在凝固成铸锭过程中温度达到900℃后，以超过10℃/min的冷却速度冷却至室温。
  5. 根据权利要求4所述的一种复合强化型耐蚀高温合金的制备工艺，其特征在于，步骤2)中从合金母液凝固成铸锭开始至冷却至室温所用时间不超过15min。
  6. 根据权利要求2所述的一种复合强化型耐蚀高温合金的制备工艺，其特征在于，步骤3)的具体过程为：将铸锭取出，随后将铸锭加热至1030～1070℃保温半小时后，继续升温至1170～1200℃的热处理炉内保温20～24小时，最后冷却至室温。
  7. 根据权利要求6所述的一种复合强化型耐蚀高温合金的制备工艺，其特征在于，步骤3)中将铸锭加热至1030～1070℃时升温速率不超过10℃/min，升温至1170℃～1200℃时升温速率不高于5℃/min。
  8. 根据权利要求2所述的一种复合强化型耐蚀高温合金的制备工艺，其特征在于，步骤5)中自室温以不超过10℃/min的升温速率升温至1110～1130℃，自室温以不超过10℃/min的升温速率升温至750～770℃，再以不超过10℃/min的升温速率升温至840～870℃。
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