CN108441741B - High-strength corrosion-resistant nickel-based high-temperature alloy for aerospace and manufacturing method thereof - Google Patents

High-strength corrosion-resistant nickel-based high-temperature alloy for aerospace and manufacturing method thereof Download PDF

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CN108441741B
CN108441741B CN201810322530.6A CN201810322530A CN108441741B CN 108441741 B CN108441741 B CN 108441741B CN 201810322530 A CN201810322530 A CN 201810322530A CN 108441741 B CN108441741 B CN 108441741B
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CN108441741A (en
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张文久
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LINYI XINHAI NEW MATERIAL 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
    • 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
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
    • C22B9/16—Remelting metals
    • C22B9/18—Electroslag remelting
    • 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
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • C22C1/03—Making non-ferrous alloys by melting using master alloys
    • 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
    • C22C1/06—Making non-ferrous alloys with the use of special agents for refining or deoxidising
    • 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
    • C22C19/056—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 10% but less than 20%
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/25—Process efficiency

Abstract

The high-strength corrosion-resistant nickel-based high-temperature alloy for aerospace is characterized in that the reasonable proportion of Co, Cr, Mo, W, Ta, Al, Ti, Ni and other elements is controlled and a specific preparation method is combined, the lasting life of the product is more than or equal to 130h at 1100 ℃ and 200MPa, and the lasting life of the product is more than or equal to 100h at 1200 ℃ and 150 MPa; the instantaneous tensile property yield strength of the nickel-based high-temperature alloy at 800 ℃ is more than or equal to 1050MPa, the tensile strength is more than or equal to 1350MPa, the yield strength at 1000 ℃ is more than or equal to 700MPa, and the tensile strength is more than or equal to 950 MPa.

Description

High-strength corrosion-resistant nickel-based high-temperature alloy for aerospace and manufacturing method thereof
Technical Field
The invention relates to the technical field of nickel-based high-temperature alloys, in particular to a high-strength corrosion-resistant nickel-based high-temperature alloy which is suitable for manufacturing high-temperature parts used in the fields of aviation, aerospace, energy sources and the like.
Background
The high-temperature alloy is a material which takes iron, nickel and cobalt as the base, can bear certain mechanical stress in a high-temperature environment and has excellent surface stability. High temperature alloys generally have high room temperature and high temperature strength, excellent creep and fatigue resistance, good oxidation resistance, hot corrosion resistance, structural stability and reliability in use. Therefore, the high-temperature alloy is not only a key material for high-temperature components of aviation and aerospace engines, but also an indispensable important material in the industrial fields of ships, energy sources, petrochemical industry and the like. The material design and process level of the high-temperature alloy become one of the important marks for measuring the material development level of a country. The nickel element has a unique atomic structure and a stable crystal structure, the crystal structure of the nickel element is kept unchanged from room temperature to a melting point temperature range, and meanwhile, a plurality of alloy elements can be dissolved into the nickel-based material for sufficient alloying, so that the nickel has an excellent property as a high-temperature alloy matrix element, and meanwhile, the nickel-based high-temperature alloy can precipitate L12The gamma' phase of the structure is the most effective strengthening mode in the nickel-based high-temperature alloy, so that the nickel-based high-temperature alloy has excellent comprehensive performance. Therefore, nickel-based superalloys have an important position in the entire field of superalloys. Compared with iron-based and cobalt-based superalloys, the nickel-based superalloy has higher high-temperature strength and structural stability, and is widely applied to hot end component materials of aircraft engines and industrial gas turbines. On the current advanced engines, the usage amount of the nickel-based high-temperature alloy accounts for more than half of the total weight of the engine.
With the gradual development of the aero-engine towards large thrust-weight ratio and long service life, the thrust-weight ratio of the current domestic and foreign advanced aero-engine reaches more than 12. The improvement of the turbine inlet temperature is one of the ways to realize high thrust, the higher the temperature is, the higher the requirements on the performance, especially the high-temperature performance, of hot end parts such as a turbine disc of an engine are, and the traditional deformed high-temperature alloy cannot meet the use requirements. Therefore, the nickel-based superalloy with higher high temperature resistance and high strength, excellent creep resistance and good oxidation resistance and corrosion resistance is always the focus of research.
Disclosure of Invention
The present invention has been made in view of such circumstances, and an object thereof is to provide a nickel-base superalloy having higher high-temperature and high-strength resistance, superior creep resistance, and good oxidation and corrosion resistance.
The high-strength corrosion-resistant nickel-based high-temperature alloy for aerospace is characterized by comprising the following components in percentage by mass: 20.5-20.8 of Co, 16.2-16.8 of Cr, 7.3-7.8 of Mo, 4.6-4.8 of W, 2.2-2.8 of Ta2, 3.3-3.8 of Al, 1.6-2.4 of Ti, 1.1-1.9 of Re, 1.3-1.6 of Nb, 0.1-0.2 of Mn, 0.1-0.15 of Si, 0.04-0.08 of C, 0.01-0.02 of Zr, 0.0005-0.0015 of B, 0.005-0.05 of Y, 6-7 of Fe, 0.10-0.20 of Hf0.01-0.1 of Mg, and the balance of Ni and inevitable impurities; the structure of the nickel-based high-temperature alloy consists of a matrix gamma, a main strengthening phase is gamma ', the grain diameter of the gamma ' phase is 50-600 nm, the precipitation amount of the gamma ' phase is preferably 70-88 vol% relative to the whole alloy, and the rest precipitates consist of a small amount of MC carbide and M3B2 boride, wherein the lasting life of the nickel-based high-temperature alloy under the conditions of 1100 ℃ and 200MPa is not less than 130h, and the lasting life of the nickel-based high-temperature alloy under the conditions of 1200 ℃ and 150MPa is not less than 100 h; the instantaneous tensile property of the nickel-based high-temperature alloy at 800 ℃ is that the yield strength is more than or equal to 1050MPa, the tensile strength is more than or equal to 1350MPa, the yield strength is more than or equal to 700MPa at 1000 ℃, and the tensile strength is more than or equal to 950 MPa.
The high-strength corrosion-resistant nickel-based high-temperature alloy for aerospace is characterized by comprising the following components in percentage by mass: co20.5-20.7, Cr 16.2-16.7, Mo 7.3-7.7, W4.6-4.7, Ta2.2-2.7, Al 3.3-3.7, Ti1.6-2.3, Re 1.1-1.8, Nb 1.3-1.5, Mn 0.1-0.18, Si 0.1-0.14, C0.04-0.07, Zr 0.01-0.018, B0.0005-0.0014, Y0.005-0.04, Fe 6-6.8, Hf0.10-0.18, Mg 0.01-0.09, and the balance of Ni and inevitable impurities.
The high-strength corrosion-resistant nickel-based high-temperature alloy for aerospace is characterized by comprising the following components in percentage by mass: co20.5, Cr 16.2, Mo 7.3, W4.6, Ta2.2, Al 3.3, Ti1.6, Re 1.1, Nb1.3, Mn0.1, Si0.1, C0.04, Zr 0.01, B0.0005, Y0.005, Fe 6, Hf0.10, Mg 0.01, and the balance of Ni and unavoidable impurities.
The high-strength corrosion-resistant nickel-based high-temperature alloy for aerospace is characterized by comprising the following components in percentage by mass: co20.7, Cr 16.7, Mo 7.7, W4.7, Ta2.7, Al 3.7, Ti 2.3, Re 1.8, Nb1.5, Mn0.18, Si 0.14, C0.07, Zr 0.018, B0.0014, Y0.04, Fe 6.8, Hf 0.18, Mg 0.09, and the balance of Ni and unavoidable impurities.
The high-strength corrosion-resistant nickel-based high-temperature alloy for aerospace is characterized by comprising the following components in percentage by mass: co20.8, Cr 16.8, Mo 7.8, W4.8, Ta2.8, Al 3.8, Ti2.4, Re 1.9, Nb1.6, Mn 0.2, Si 0.15, C0.08, Zr 0.02, B0.0015, Y0.05, Fe 7, Hf0.20 and Mg 0.1, and the balance of Ni and inevitable impurities.
The manufacturing method of the high-strength corrosion-resistant nickel-based high-temperature alloy for aerospace comprises the following preparation steps:
(1) the vacuum induction smelting is carried out according to the proportion of the chemical components of the alloy, and the alloy is added into a vacuum induction smelting furnace for smelting, wherein the smelting process is distributed for smelting, refining, cooling, alloying and pouring; in the melting step, selecting a Ni-Co intermediate alloy with the Co mass ratio of 80%, selecting a Ni-Cr intermediate alloy with the Cr mass ratio of 51%, selecting a Ni-Mo intermediate alloy with the Mo mass ratio of 64%, selecting a Fe-Mo intermediate alloy with the Fe mass ratio of 35%, selecting a proper intermediate alloy from W, Ta, Re, Nb, Zr and Hf, and selecting a proper intermediate alloy or a simple substance from Al, Ti, Mn, Si, C, B and Y; respectively loading the raw materials into a crucible, completely melting the raw materials, refining for 30-50 min, adding a refining agent in the refining process, wherein the refining agent is a Ba-Al-Ca ternary alloy, the mass ratio of Ba to Al to Ca is 6: 3: 1, the adding amount of the refining agent accounts for 2-2.5% of the total mass of the alloy in the crucible, adding CaO powder with the mass fraction of 2-3% in the later period of the refining period for desulfurization, and after the refining is finished, using a composite stirring mode of electromagnetic stirring and mechanical stirring, wherein the electromagnetic stirring is performed for 5-8min in one period, the mechanical stirring is stopped for 3-5min, the mechanical stirring is performed for 5-8min and the mechanical stirring is stopped for 3-5min, and the stirring can be performed for 1-3 periods according; controlling the carbon-oxygen content ratio in the smelting process of the vacuum induction smelting furnace to ensure that the carbon-oxygen content ratio is 1: 1.2-1.3, adding Ni-Mg intermediate alloy with the Mg mass fraction of 10-13% when pouring out the alloy solution, wherein the adding amount is 0.2-0.25%; stirring and slagging off, pouring when the temperature of the alloy liquid melt reaches 1500-1800 ℃, and pouring the alloy liquid melt into an ingot mold preheated at 250 ℃ under 200-plus-one conditions to prepare an electrode rod with the diameter of 350mm under 300-plus-one conditions;
(2) the mass ratio of the electroslag remelting electroslag amount is CaF2∶Al2O3∶CaO∶TiO2∶SiO2Adding an electrode bar, installing a crystallizer, adding an arc striking agent, starting voltage of 50-60V, stabilizing current of 2600-plus-3000A, adding the electroslag after arc striking, melting slag in an electric furnace, stabilizing the current after the slag is melted, entering a melting state, melting the electrode bar, stopping power supply after crystallizer alloy liquid reaches a set area, cooling for 10-12 minutes, and cooling and solidifying to form a bar material with the diameter of 250-plus-300 mm;
(3) the heat treatment heats the bar with the diameter of 250-: firstly heating to 1000-1100 ℃ at a heating speed of 200-; then preserving the heat at 1080-1100 ℃ for 5-5.5h, and then air-cooling to room temperature; and then preserving the heat at 900-930 ℃ for 12-20 h, and then cooling the air to room temperature.
The further manufacturing method of the high-strength corrosion-resistant nickel-based high-temperature alloy for aerospace comprises the following steps of mixing the amounts of electroslag slag according to the mass ratio of CaF2 to Al2O3 to CaO to TiO2 to SiO 2: 55: 25: 12: 4.
The method for manufacturing the high-strength corrosion-resistant nickel-based high-temperature alloy for aerospace comprises the following steps: firstly, heating to 1050 ℃ at a heating speed of 220 ℃/min, then preserving heat for 2.5h, then heating to 1310 ℃ at a heating speed of 130 ℃/min, preserving heat for 7h, and then air-cooling to room temperature; then preserving the heat at 1100 ℃ for 5.5h, and then cooling the mixture to room temperature in air; then, the temperature is kept at 920 ℃ for 16h, and then the temperature is cooled to room temperature in an air cooling mode.
The effects of the alloying elements in the present invention and their preferred content ranges are as follows:
co is dissolved in the austenite matrix to improve the high-temperature strength. Further, the γ ' phase [ Ni3(Al, Ti, Nb, Ta) ] is also dissolved in a solid state, and this has the effect of strengthening the γ ' phase and increasing the amount of γ ' phase precipitated. However, if the content of Co exceeds 20.8%, intermetallic compound phases are formed, which lower the mechanical strength and also cause an increase in the alloy cost. On the other hand, if the content of Co is less than 20.5%, the mechanical strength is lowered. Therefore, the content of Co is set to 20.5 to 20.8%, more preferably 20.5 to 20.7%.
Cr is solid-dissolved in the austenite matrix, and is an element that is not only solid-solution strengthened but also essential for improving oxidation resistance and corrosion resistance. Moreover, the M23C6 type carbide is indispensable as a constituent element, and particularly, the creep strength of the alloy can be maintained by precipitating the M23C6 type carbide during the operation of the steam turbine in a high temperature environment of 700 ℃. In addition, Cr can also improve oxidation resistance in high temperature environments. When the Cr content is less than 16.2%, the oxidation resistance is lowered. On the other hand, if the Cr content exceeds 16.8%, precipitation of M23C6 type carbide is significantly promoted to increase the tendency to coarsen, and the strength and ductility are reduced when the alloy is held at high temperature for a long time. Since Cr increases the thermal expansion coefficient of the alloy, it is preferable to add Cr in a small amount in designing a high-temperature device. Therefore, the content of Cr is 16.2 to 16.8%, more preferably 16.2 to 16.7%.
Mo is also a strong solid solution strengthening element, and can increase the mismatching degree of gamma/gamma', so that a mismatching dislocation network is dense, dislocation motion is effectively hindered, and the alloy performance is improved. Mo and W are respectively enriched in interdendritic dendrites and dendrite trunks, and the addition of Mo and W is beneficial to the comprehensive reinforcement of the alloy. However, excessive addition of Mo also causes precipitation of harmful phases, and adversely affects the hot corrosion performance of the alloy, so that the content of Mo is controlled to be 7.3-7.8%, preferably 7.3-7.7%.
The solid solution strengthening effect of W in the nickel-based high-temperature alloy is strong, the interatomic bonding force and the diffusion activation energy can be improved, and the strengthening effect at high temperature is also remarkable. W is also greatly dissolved in the gamma 'strengthening phase, so that the thermal stability of the gamma' phase is improved. When the element Re is not added, the W strengthening effect is sufficiently exhibited. However, excessive addition of W can cause supersaturation of gamma phase, so that the microstructure is unstable, TCP harmful phases such as sigma phase and mu phase are easy to form, and the alloy performance is reduced. Excessive addition of W also affects the castability of the alloy, and equiaxed grains and other defects appear in the growth of single crystals. Therefore, the content of W is controlled to be W4.6-4.8%, preferably W4.6-4.7%.
Ta is also one of main forming elements of a gamma 'phase in the nickel-based single crystal superalloy, and has the effect of inhibiting the aggregation and growth of the gamma' phase, so that the heat strength of the alloy can be improved, the casting performance of the alloy can be improved, the structural stability of the alloy is not reduced, and a high Ta content can be added into the alloy. However, too high a Ta increases the eutectic content in the alloy, increasing the complexity of the heat treatment. Therefore, the amount of Ta added in the present alloy is controlled to Ta2.2 to 2.8%, preferably Ta2.2 to 2.7%.
Al forms a γ ' phase [ Ni3(Al, Ti, Nb, Ta) ] together with Ni, and precipitation improves the high-temperature strength of Ni-based cast alloys, and has an effect of improving high-temperature corrosion resistance, when the content of Al is less than 3.3%, precipitation of the γ ' phase is insufficient, and thus the γ ' phase is not sufficiently strengthened, and if Ti, Nb, and Ta are present in a large amount, the γ ' phase is unstable, and η phase (Ni3Ti) and δ phase [ Ni3(Nb, Ta) ] are precipitated, and become brittle, and when a large amount of Al is added, a large amount of eutectic γ ' phase is precipitated during casting, which causes a decrease in high-temperature strength or the occurrence of casting cracks, and therefore, the content of Al is 3.3 to 3.8%, more preferably, Al 3.3 to 3.7%.
Ti is useful for designing high-temperature equipment because it forms a γ' phase [ Ni3(Al, Ti, Nb, Ta) ] together with Ni, like Al, and increases the high-temperature strength of Ni-based cast alloys by precipitation, and further has an effect of reducing the thermal expansion coefficient of the alloys, and when the content of Ti is less than 1.6%, the above effect cannot be exerted, but if the content of Ti exceeds 2.4%, precipitation of η phase (Ni3Ti) as an embrittlement phase is promoted, and the high-temperature strength is decreased and the defect sensitivity is increased, and therefore, the content of Ti is 1.6 to 2.4%, more preferably 1.6 to 2.3%.
Re rhenium obviously reduces the growth and coarsening kinetic factors of gamma' phase crystal grains, Re is partially polymerized in a gamma matrix to form atom clusters, the dislocation motion is hindered, the strengthening effect more obvious than that of a single atom can be generated, and the high temperature resistance can be improved by about 30 ℃ compared with the high temperature resistance without Re by adding 3 wt% of Re. Re can reduce the bulk diffusion coefficient of other elements and slow down all diffusion-controlled processes, thus slowing down the growth of the gamma' precipitates of the strengthening phase and also slowing down the diffusion rate controlling the creep mechanism. Thus, Re-containing alloys are highly advantageous at high temperatures, with the selected Re content being 1.1-1.9% Re, preferably 1.1-1.8% Re.
Nb and Ta are dissolved in the γ 'phase [ Ni3(Al, Ti, Nb, and Ta) ] to improve the high-temperature strength, suppress coarsening of the γ' phase, and stabilize the precipitation strength. In addition, the formation of carbide by combination with C contributes to the improvement of high-temperature strength. If the Nb content is less than 1.3%, the above-described effects cannot be exhibited, and if the Nb content exceeds 1.6%, the δ phase may increase precipitation and become brittle. Therefore, the content of Nb is specified to be 1.3 to 1.6%. More preferably 1.3 to 1.5%.
Si is useful as a deoxidizer in melt refining. It can also improve oxidation resistance. However, if the content is too high, a decrease in ductility is caused. The appropriate Si content is 0.1-0.15% Si. More preferably 0.1 to 0.14% Si.
Mn is useful as a deoxidizer in the melt refining as in Si, but if the content is too high, the high-temperature oxidation characteristics are deteriorated and the ductility is deteriorated due to the precipitation of η phase (Ni3 Ti). the Mn content is preferably 0.1 to 0.2%, more preferably 0.1 to 0.18%.
C is a constituent element of M23C6 type carbide which is a strengthening phase, and particularly, one of important factors for maintaining the creep strength of an alloy is to precipitate M23C6 type carbide in a high temperature environment of 700 ℃. In addition, coarsening of crystal grains can be prevented. In addition, the effect of ensuring the fluidity of the melt during casting is also obtained. When the content of C is less than 0.04%, a sufficient amount of precipitated carbide cannot be secured, and the fluidity of the melt during casting is significantly reduced. On the other hand, if the content of C exceeds 0.08%, the tendency of component segregation in the production of large-sized cast products is increased, and the formation of M6C type carbide as an embrittlement phase is promoted, resulting in a decrease in corrosion resistance and ductility. Therefore, the content of C is 0.04-0.08%. More preferably from 0.04 to 0.07% C.
Zr enters the grain boundary like B, and the high-temperature strength can be improved. In addition, the carbon forms carbide in combination with C, which contributes to the improvement of high-temperature strength. If the Zr content is less than 0.01%, the above-mentioned effects cannot be exhibited, and if the Zr content exceeds 0.02%, the high-temperature strength is rather lowered, and the ductility is also lowered. Therefore, the Zr content is defined to be 0.01 to 0.02%. More preferably Zr 0.01-0.018%.
The B element is used as the 'vitamin' of the alloy and can play a strong role of a modifier in the alloy. A large amount of boron is deviated and gathered in the grain boundary, so that the interface energy can be changed, the shape of a second phase on the grain boundary can be favorably changed, the second phase is easy to spheroidize, and the grain boundary strength is improved. In the aspect of high-temperature alloy, boron mainly affects grain boundary diffusion and precipitation by grain boundary segregation, and further has a strengthening effect on the durability and creep property of the alloy. Therefore, the content of B is defined as B0.0005-0.0015%. More preferably 0.0005 to 0.0014%.
The rare earth elements have obvious effect on improving the performance of the high-temperature alloy. A small amount of rare earth elements are added into the high-temperature alloy, so that the vulcanization resistance, the high-temperature strength and the thermoplasticity can be improved, the oxidation resistance and the lasting life of the high-temperature alloy can be improved, and therefore 0.005-0.05% of the rare earth element Y, preferably 0.005-0.04% of the Y, is added into the alloy.
Fe contributes to the reduction of the cost of the alloy in Ni-based superalloy castings. However, if added in a large amount, not only a decrease in high-temperature strength is caused, but also an increase in the coefficient of thermal expansion of the alloy is involved, which is disadvantageous in use under high-temperature conditions. Therefore, the Fe content is specified to be Fe 6-7%. More preferably from 6 to 6.8% Fe.
The use of grain boundary strengthening elements such as Hf is changed from limited to limited. The trace amount of Hf can obviously improve the corrosion resistance; the addition of hafnium element changes the morphology of carbide, when the weight percentage of hafnium is more than 0.2%, the skeleton carbide is converted into massive carbide, the hafnium belongs to orthosegregation element, is easy to aggregate among dendrites, and is also a main element forming gamma 'phase, so that the growth of gamma' phase in the solidification process of alloy can be prevented, the size of gamma 'phase is reduced, and the formation of gamma + gamma' eutectic can be remarkably promoted. Therefore, the content of Hf is defined as Hf0.10-0.20%. More preferably Hf0.10 to 0.18%.
The hot working plasticity of the alloy can be greatly improved by adding Mg with specific content, and the Mg has thermodynamic tendency of grain boundary equilibrium segregation. The proper amount of Mg can adjust the crystal boundary state of the alloy, and the effect of improving the bonding force of the crystal boundary is achieved, so that the hot working plasticity of the alloy is greatly improved. Therefore, the content of Mg is defined to be 0.01 to 0.1% of Mg. More preferably 0.01 to 0.09%.
The heat treatment is an indispensable process step of the nickel-based high-temperature alloy, and after the heat treatment, the segregation of each element is reduced, so that the strength of the alloy is increased. Since the as-cast structure is a structure deviating from the equilibrium state, there is composition segregation and structural heterogeneity between dendrite trunks and dendrites, although all grain boundaries have been eliminated. In order to obtain as high a high temperature proof strength and creep properties as possible, it is necessary to select an optimum heat treatment regime to improve the microstructure of the alloy. To achieve this goal, nickel-base superalloys typically employ a multi-step heat treatment: the first step of heat treatment is to eliminate eutectic and tissue homogenization and reduce the influence of element segregation on the alloy performance; a second heat treatment to obtain a suitable microstructure. The components of the gamma and gamma ' phases tend to be homogenized, the strength of the reinforcing phase gamma ' phase is increased, the volume fraction of the reinforcing phase gamma ' phase is also increased, and therefore the reinforcing effect on the alloy is better. Secondly, the gamma' phase of the as-cast alloy has irregular shape, different sizes and uneven distribution. After the alloy is deformed for a long time, the structure deformation is not uniform. After heat treatment, γ' is a regularly arranged cube, evenly distributed throughout the alloy. The alloy has uniform deformation structure after permanent fracture, thereby having better permanent strength.
After the alloy components and the solid solution treatment system are determined, the aging treatment plays a decisive role in the alloy structure and strength. Because single crystal superalloys have the gamma prime phase as the only strengthening phase, the degree of strengthening depends on the amount and size of the gamma prime phase. Generally, the aging process of the single crystal superalloy is carried out in two stages, and the purpose is to adjust the size of the strengthening phase so as to obtain the best matching closed alloy with strength and plasticity, after heat treatment, the gamma' phase is in a regular cubic shape and is uniformly distributed in a matrix, so that the alloy obtains a uniform deformation structure during tensile deformation, and the alloy has better strengthening effect. In addition, after the alloy is subjected to heat treatment, the distribution of each element in gamma and gamma ' phases is more uniform, the strength of the gamma ' phase is increased, and the volume fraction of the gamma ' phase is also increased, so that the strengthening effect on the alloy is improved, and the alloy has good tensile property.
The components and the heat treatment mode are strictly controlled, so that the structure of the final nickel-based high-temperature alloy consists of a matrix gamma, a main strengthening phase is gamma ', the grain diameter of the gamma ' phase is 50-600 nm, the precipitation amount of the gamma ' phase is preferably 70-88 vol% relative to the whole alloy, and the rest precipitates consist of a small amount of MC carbide and M3B2 boride, wherein the lasting life of the nickel-based high-temperature alloy under the conditions of 1100 ℃ and 200MPa is not less than 130h, and the lasting life of the nickel-based high-temperature alloy under the conditions of 1200 ℃ and 150MPa is not less than 100 h; the instantaneous tensile property of the nickel-based high-temperature alloy at 800 ℃ is that the yield strength is more than or equal to 1050MPa, the tensile strength is more than or equal to 1350MPa, the yield strength is more than or equal to 700MPa at 1000 ℃, and the tensile strength is more than or equal to 950 MPa. Provides a nickel-based high-temperature alloy with higher high-temperature resistance and high strength, excellent creep resistance and good oxidation resistance and corrosion resistance.
Detailed Description
The following describes the embodiments in detail.
Example 1
The high-strength corrosion-resistant nickel-based high-temperature alloy for aerospace is characterized by comprising the following components in percentage by mass: 20.5 of Co, 16.2 of Cr, 7.3 of Mo, 4.6 of W, 2.2 of Ta2, 3.3 of Al, 1.6 of Ti, 1.1 of Re, 1.3 of Nb1, 0.1 of Mn, 0.1 of Si, 0.04 of C, 0.01 of Zr, 0.0005 of B, 0.005 of Y, 6 of Fe, 0.10 of Hf0.01 of Mg, and the balance of Ni and inevitable impurities. The preparation steps are as follows:
(1) the vacuum induction smelting is carried out according to the proportion of the chemical components of the alloy, and the alloy is added into a vacuum induction smelting furnace for smelting, wherein the smelting process is distributed for smelting, refining, cooling, alloying and pouring; in the melting step, selecting a Ni-Co intermediate alloy with the Co mass ratio of 80%, selecting a Ni-Cr intermediate alloy with the Cr mass ratio of 51%, selecting a Ni-Mo intermediate alloy with the Mo mass ratio of 64%, selecting a Fe-Mo intermediate alloy with the Fe mass ratio of 35%, selecting a proper intermediate alloy from W, Ta, Re, Nb, Zr and Hf, and selecting a proper intermediate alloy or a simple substance from Al, Ti, Mn, Si, C, B and Y; respectively loading the raw materials into a crucible, completely melting the raw materials, refining for 30-50 min, adding a refining agent in the refining process, wherein the refining agent is a Ba-Al-Ca ternary alloy, the mass ratio of Ba to Al to Ca is 6: 3: 1, the adding amount of the refining agent accounts for 2-2.5% of the total mass of the alloy in the crucible, adding CaO powder with the mass fraction of 2-3% in the later period of the refining period for desulfurization, and after the refining is finished, using a composite stirring mode of electromagnetic stirring and mechanical stirring, wherein the electromagnetic stirring is performed for 5-8min in one period, the mechanical stirring is stopped for 3-5min, the mechanical stirring is performed for 5-8min and the mechanical stirring is stopped for 3-5min, and the stirring can be performed for 1-3 periods according; controlling the carbon-oxygen content ratio in the smelting process of the vacuum induction smelting furnace to ensure that the carbon-oxygen content ratio is 1: 1.2-1.3, adding Ni-Mg intermediate alloy with the Mg mass fraction of 10-13% when pouring out the alloy solution, wherein the adding amount is 0.2-0.25%; stirring and slagging off, pouring when the temperature of the alloy liquid melt reaches 1500-1800 ℃, and pouring the alloy liquid melt into an ingot mold preheated at 250 ℃ under 200-plus-one conditions to prepare an electrode rod with the diameter of 350mm under 300-plus-one conditions;
(2) the mass ratio of the electroslag remelting electroslag amount is CaF2∶Al2O3∶CaO∶TiO2∶SiO2Adding electrode bar, installing crystallizer and arc striking as 50-60: 20-30: 10-15: 3-5The initial voltage of the agent is 50-60V, the stable current is 2600-3000A, the electroslag is added after arc striking, the slag is melted in an electric furnace, the current is stabilized after the slag is melted, the electrode bar is melted, the power is cut off after the crystallizer alloy liquid reaches a set area, and the electrode bar is cooled for 10-12 minutes and then is cooled and solidified to form a bar material with the diameter of 250-300 mm;
(3) the heat treatment heats the bar with the diameter of 250-: firstly heating to 1000-1100 ℃ at a heating speed of 200-; then preserving the heat at 1080-1100 ℃ for 5-5.5h, and then air-cooling to room temperature; and then preserving the heat at 900-930 ℃ for 12-20 h, and then cooling the air to room temperature.
Example 2
The high-strength corrosion-resistant nickel-based high-temperature alloy for aerospace is characterized by comprising the following components in percentage by mass: 20.7 of Co, 16.7 of Cr, 7.7 of Mo, 4.7 of W, 2.7 of Ta2, 3.7 of Al, 2.3 of Ti, 1.8 of Re, 1.5 of Nb1, 0.18 of Mn, 0.14 of Si, 0.07 of C, 0.018 of Zr, 0.0014 of B, 0.04 of Y, 6.8 of Fe, 0.18 of Hf and 0.09 of Mg, and the balance of Ni and inevitable impurities. The preparation steps are as follows:
(1) the vacuum induction smelting is carried out according to the proportion of the chemical components of the alloy, and the alloy is added into a vacuum induction smelting furnace for smelting, wherein the smelting process is distributed for smelting, refining, cooling, alloying and pouring; in the melting step, selecting a Ni-Co intermediate alloy with the Co mass ratio of 80%, selecting a Ni-Cr intermediate alloy with the Cr mass ratio of 51%, selecting a Ni-Mo intermediate alloy with the Mo mass ratio of 64%, selecting a Fe-Mo intermediate alloy with the Fe mass ratio of 35%, selecting a proper intermediate alloy from W, Ta, Re, Nb, Zr and Hf, and selecting a proper intermediate alloy or a simple substance from Al, Ti, Mn, Si, C, B and Y; respectively loading the raw materials into a crucible, completely melting the raw materials, refining for 30-50 min, adding a refining agent in the refining process, wherein the refining agent is a Ba-Al-Ca ternary alloy, the mass ratio of Ba to Al to Ca is 6: 3: 1, the adding amount of the refining agent accounts for 2-2.5% of the total mass of the alloy in the crucible, adding CaO powder with the mass fraction of 2-3% in the later period of the refining period for desulfurization, and after the refining is finished, using a composite stirring mode of electromagnetic stirring and mechanical stirring, wherein the electromagnetic stirring is performed for 5-8min in one period, the mechanical stirring is stopped for 3-5min, the mechanical stirring is performed for 5-8min and the mechanical stirring is stopped for 3-5min, and the stirring can be performed for 1-3 periods according; controlling the carbon-oxygen content ratio in the smelting process of the vacuum induction smelting furnace to ensure that the carbon-oxygen content ratio is 1: 1.2-1.3, adding Ni-Mg intermediate alloy with the Mg mass fraction of 10-13% when pouring out the alloy solution, wherein the adding amount is 0.2-0.25%; stirring and slagging off, pouring when the temperature of the alloy liquid melt reaches 1500-1800 ℃, and pouring the alloy liquid melt into an ingot mold preheated at 250 ℃ under 200-plus-one conditions to prepare an electrode rod with the diameter of 350mm under 300-plus-one conditions;
(2) the mass ratio of the electroslag remelting electroslag amount is CaF2∶Al2O3∶CaO∶TiO2∶SiO2Adding an electrode bar, installing a crystallizer, adding an arc striking agent, starting voltage of 50-60V, stabilizing current of 2600-plus-3000A, adding the electroslag after arc striking, melting slag in an electric furnace, stabilizing the current after the slag is melted, entering a melting state, melting the electrode bar, stopping power supply after crystallizer alloy liquid reaches a set area, cooling for 10-12 minutes, and cooling and solidifying to form a bar material with the diameter of 250-plus-300 mm;
(3) the heat treatment heats the bar with the diameter of 250-: firstly heating to 1000-1100 ℃ at a heating speed of 200-; then preserving the heat at 1080-1100 ℃ for 5-5.5h, and then air-cooling to room temperature; and then preserving the heat at 900-930 ℃ for 12-20 h, and then cooling the air to room temperature.
Example 3
The high-strength corrosion-resistant nickel-based high-temperature alloy for aerospace is characterized by comprising the following components in percentage by mass: 20.8 of Co, 16.8 of Cr, 7.8 of Mo, 4.8 of W, 2.8 of Ta, 3.8 of Al, 2.4 of Ti, 1.9 of Re, 1.6 of Nb1, 0.2 of Mn, 0.15 of Si, 0.08 of C, 0.02 of Zr, 0.0015 of B, 0.05 of Y, 7 of Fe, 0.20 of Hf and 0.1 of Mg, and the balance of Ni and inevitable impurities. The preparation steps are as follows:
(1) the vacuum induction smelting is carried out according to the proportion of the chemical components of the alloy, and the alloy is added into a vacuum induction smelting furnace for smelting, wherein the smelting process is distributed for smelting, refining, cooling, alloying and pouring; in the melting step, selecting a Ni-Co intermediate alloy with the Co mass ratio of 80%, selecting a Ni-Cr intermediate alloy with the Cr mass ratio of 51%, selecting a Ni-Mo intermediate alloy with the Mo mass ratio of 64%, selecting a Fe-Mo intermediate alloy with the Fe mass ratio of 35%, selecting a proper intermediate alloy from W, Ta, Re, Nb, Zr and Hf, and selecting a proper intermediate alloy or a simple substance from Al, Ti, Mn, Si, C, B and Y; respectively loading the raw materials into a crucible, completely melting the raw materials, refining for 30-50 min, adding a refining agent in the refining process, wherein the refining agent is a Ba-Al-Ca ternary alloy, the mass ratio of Ba to Al to Ca is 6: 3: 1, the adding amount of the refining agent accounts for 2-2.5% of the total mass of the alloy in the crucible, adding CaO powder with the mass fraction of 2-3% in the later period of the refining period for desulfurization, and after the refining is finished, using a composite stirring mode of electromagnetic stirring and mechanical stirring, wherein the electromagnetic stirring is performed for 5-8min in one period, the mechanical stirring is stopped for 3-5min, the mechanical stirring is performed for 5-8min and the mechanical stirring is stopped for 3-5min, and the stirring can be performed for 1-3 periods according; controlling the carbon-oxygen content ratio in the smelting process of the vacuum induction smelting furnace to ensure that the carbon-oxygen content ratio is 1: 1.2-1.3, adding Ni-Mg intermediate alloy with the Mg mass fraction of 10-13% when pouring out the alloy solution, wherein the adding amount is 0.2-0.25%; stirring and slagging off, pouring when the temperature of the alloy liquid melt reaches 1500-1800 ℃, and pouring the alloy liquid melt into an ingot mold preheated at 250 ℃ under 200-plus-one conditions to prepare an electrode rod with the diameter of 350mm under 300-plus-one conditions;
(2) the mass ratio of the electroslag remelting electroslag amount is CaF2∶Al2O3∶CaO∶TiO2∶SiO2Adding electrode bar, installing crystallizer, adding arc-striking agent, starting voltage is 50-60V, stabilizing current is 2600-3000A, after arc striking, adding the above-mentioned electroslag, melting slag in electric furnace, after slag is melted, stabilizing the above-mentioned current, meltingMelting the electrode rod, stopping power after the crystallizer alloy liquid reaches a set area, cooling for 10-12 minutes, and cooling and solidifying to form a rod material with the diameter of 250-300 mm;
(3) the heat treatment heats the bar with the diameter of 250-: firstly heating to 1000-1100 ℃ at a heating speed of 200-; then preserving the heat at 1080-1100 ℃ for 5-5.5h, and then air-cooling to room temperature; and then preserving the heat at 900-930 ℃ for 12-20 h, and then cooling the air to room temperature.
Comparative example 1
The high-strength corrosion-resistant nickel-based high-temperature alloy for aerospace is characterized by comprising the following components in percentage by mass: co 15, Cr 12, Mo6, W4, ta2.2, Al3, Ti1.6, Re 1.1, Nb1.3, Mn0.1, si0.1, C0.04, Zr 0.01, B0.0005, Y0.005, Fe 6, hf0.10, Mg 0.01, and the balance Ni and unavoidable impurities. The preparation steps are as follows:
(1) the vacuum induction smelting is carried out according to the proportion of the chemical components of the alloy, and the alloy is added into a vacuum induction smelting furnace for smelting, wherein the smelting process is distributed for smelting, refining, cooling, alloying and pouring; in the melting step, selecting a Ni-Co intermediate alloy with the Co mass ratio of 80%, selecting a Ni-Cr intermediate alloy with the Cr mass ratio of 51%, selecting a Ni-Mo intermediate alloy with the Mo mass ratio of 64%, selecting a Fe-Mo intermediate alloy with the Fe mass ratio of 35%, selecting a proper intermediate alloy from W, Ta, Re, Nb, Zr and Hf, and selecting a proper intermediate alloy or a simple substance from Al, Ti, Mn, Si, C, B and Y; respectively loading the raw materials into a crucible, completely melting the raw materials, refining for 30-50 min, adding a refining agent in the refining process, wherein the refining agent is a Ba-Al-Ca ternary alloy, the mass ratio of Ba to Al to Ca is 6: 3: 1, the adding amount of the refining agent accounts for 2-2.5% of the total mass of the alloy in the crucible, adding CaO powder with the mass fraction of 2-3% in the later period of the refining period for desulfurization, and after the refining is finished, using a composite stirring mode of electromagnetic stirring and mechanical stirring, wherein the electromagnetic stirring is performed for 5-8min in one period, the mechanical stirring is stopped for 3-5min, the mechanical stirring is performed for 5-8min and the mechanical stirring is stopped for 3-5min, and the stirring can be performed for 1-3 periods according; controlling the carbon-oxygen content ratio in the smelting process of the vacuum induction smelting furnace to ensure that the carbon-oxygen content ratio is 1: 1.2-1.3, adding Ni-Mg intermediate alloy with the Mg mass fraction of 10-13% when pouring out the alloy solution, wherein the adding amount is 0.2-0.25%; stirring and slagging off, pouring when the temperature of the alloy liquid melt reaches 1500-1800 ℃, and pouring the alloy liquid melt into an ingot mold preheated at 250 ℃ under 200-plus-one conditions to prepare an electrode rod with the diameter of 350mm under 300-plus-one conditions;
(2) the mass ratio of the electroslag remelting electroslag amount is CaF2∶Al2O3∶CaO∶TiO2∶SiO2Adding an electrode bar, installing a crystallizer, adding an arc striking agent, starting voltage of 50-60V, stabilizing current of 2600-plus-3000A, adding the electroslag after arc striking, melting slag in an electric furnace, stabilizing the current after the slag is melted, entering a melting state, melting the electrode bar, stopping power supply after crystallizer alloy liquid reaches a set area, cooling for 10-12 minutes, and cooling and solidifying to form a bar material with the diameter of 250-plus-300 mm;
(3) the heat treatment heats the bar with the diameter of 250-: firstly heating to 1000-1100 ℃ at a heating speed of 200-; then preserving the heat at 1080-1100 ℃ for 5-5.5h, and then air-cooling to room temperature; and then preserving the heat at 900-930 ℃ for 12-20 h, and then cooling the air to room temperature.
Comparative example 2
The high-strength corrosion-resistant nickel-based high-temperature alloy for aerospace is characterized by comprising the following components in percentage by mass: 20.7 of Co, 16.7 of Cr, 7.7 of Mo, 4.7 of W, 2.7 of Ta2, 3.7 of Al, 1 of Ti, 0.5 of Re0, 1 of Nb, 0.18 of Mn0.14 of Si, 0.07 of C, 0.018 of Zr, 0.0014 of B, 0.5 of Fe and 0.09 of Mg, and the balance of Ni and inevitable impurities. The preparation steps are as follows:
(1) the vacuum induction smelting is carried out according to the proportion of the chemical components of the alloy, and the alloy is added into a vacuum induction smelting furnace for smelting, wherein the smelting process is distributed for smelting, refining, cooling, alloying and pouring; in the melting step, selecting a Ni-Co intermediate alloy with the Co mass ratio of 80%, selecting a Ni-Cr intermediate alloy with the Cr mass ratio of 51%, selecting a Ni-Mo intermediate alloy with the Mo mass ratio of 64%, selecting a Fe-Mo intermediate alloy with the Fe mass ratio of 35%, selecting a proper intermediate alloy from W, Ta, Re, Nb and Zr, and selecting a proper intermediate alloy or a simple substance from Al, Ti, Mn, Si, C and B; respectively loading the raw materials into a crucible, completely melting the raw materials, refining for 30-50 min, adding a refining agent in the refining process, wherein the refining agent is a Ba-Al-Ca ternary alloy, the mass ratio of Ba to Al to Ca is 6: 3: 1, the adding amount of the refining agent accounts for 2-2.5% of the total mass of the alloy in the crucible, adding CaO powder with the mass fraction of 2-3% in the later period of the refining period for desulfurization, and after the refining is finished, using a composite stirring mode of electromagnetic stirring and mechanical stirring, wherein the electromagnetic stirring is performed for 5-8min in one period, the mechanical stirring is stopped for 3-5min, the mechanical stirring is performed for 5-8min and the mechanical stirring is stopped for 3-5min, and the stirring can be performed for 1-3 periods according; controlling the carbon-oxygen content ratio in the smelting process of the vacuum induction smelting furnace to ensure that the carbon-oxygen content ratio is 1: 1.2-1.3, adding Ni-Mg intermediate alloy with the Mg mass fraction of 10-13% when pouring out the alloy solution, wherein the adding amount is 0.2-0.25%; stirring and slagging off, pouring when the temperature of the alloy liquid melt reaches 1500-1800 ℃, and pouring the alloy liquid melt into an ingot mold preheated at 250 ℃ under 200-plus-one conditions to prepare an electrode rod with the diameter of 350mm under 300-plus-one conditions;
(2) the mass ratio of the electroslag remelting electroslag amount is CaF2∶Al2O3∶CaO∶TiO2∶SiO2Adding an electrode bar, installing a crystallizer, adding an arc striking agent, starting voltage of 50-60V, stabilizing current of 2600-plus-3000A, adding the electroslag after arc striking, melting slag in an electric furnace, stabilizing the current after the slag is melted, entering a melting state, melting the electrode bar, stopping power supply after crystallizer alloy liquid reaches a set area, cooling for 10-12 minutes, and cooling and solidifying to form a bar material with the diameter of 250-plus-300 mm;
(3) the heat treatment heats the bar with the diameter of 250-: firstly heating to 1000-1100 ℃ at a heating speed of 200-; then preserving the heat at 1080-1100 ℃ for 5-5.5h, and then air-cooling to room temperature; and then preserving the heat at 900-930 ℃ for 12-20 h, and then cooling the air to room temperature.
Comparative example 3
The high-strength corrosion-resistant nickel-based high-temperature alloy for aerospace is characterized by comprising the following components in percentage by mass: 20.8 of Co, 16.8 of Cr, 7.8 of Mo, 4.8 of W, 2.8 of Ta, 3.8 of Al, 2.4 of Ti, 1.9 of Re, 1.6 of Nb1, 0.2 of Mn, 0.15 of Si, 0.08 of C, 0.02 of Zr, 0.0015 of B, 0.05 of Y, 7 of Fe, 0.20 of Hf and 0.1 of Mg, and the balance of Ni and inevitable impurities. The preparation steps are as follows:
(1) the vacuum induction smelting is carried out according to the proportion of the chemical components of the alloy, and the alloy is added into a vacuum induction smelting furnace for smelting, wherein the smelting process is distributed for smelting, refining, cooling, alloying and pouring; in the melting step, selecting a Ni-Co intermediate alloy with the Co mass ratio of 80%, selecting a Ni-Cr intermediate alloy with the Cr mass ratio of 51%, selecting a Ni-Mo intermediate alloy with the Mo mass ratio of 64%, selecting a Fe-Mo intermediate alloy with the Fe mass ratio of 35%, selecting a proper intermediate alloy from W, Ta, Re, Nb, Zr and Hf, and selecting a proper intermediate alloy or a simple substance from Al, Ti, Mn, Si, C, B and Y; respectively loading the raw materials into a crucible, completely melting the raw materials, refining for 30-50 min, adding a refining agent in the refining process, wherein the refining agent is a Ba-Al-Ca ternary alloy, the mass ratio of Ba to Al to Ca is 6: 3: 1, the adding amount of the refining agent accounts for 2-2.5% of the total mass of the alloy in the crucible, adding CaO powder with the mass fraction of 2-3% in the later period of the refining period for desulfurization, and after the refining is finished, using a composite stirring mode of electromagnetic stirring and mechanical stirring, wherein the electromagnetic stirring is performed for 5-8min in one period, the mechanical stirring is stopped for 3-5min, the mechanical stirring is performed for 5-8min and the mechanical stirring is stopped for 3-5min, and the stirring can be performed for 1-3 periods according; controlling the carbon-oxygen content ratio in the smelting process of the vacuum induction smelting furnace to ensure that the carbon-oxygen content ratio is 1: 1.2-1.3, adding Ni-Mg intermediate alloy with the Mg mass fraction of 10-13% when pouring out the alloy solution, wherein the adding amount is 0.2-0.25%; stirring and slagging off, pouring when the temperature of the alloy liquid melt reaches 1500-1800 ℃, and pouring the alloy liquid melt into an ingot mold preheated at 250 ℃ under 200-plus-one conditions to prepare a bar material with the diameter of 300mm under 250-plus-one conditions;
(2) the heat treatment heats the bar with the diameter of 250-: firstly heating to 1000-1100 ℃ at a heating speed of 200-; then preserving the heat at 1080-1100 ℃ for 5-5.5h, and then air-cooling to room temperature; and then preserving the heat at 900-930 ℃ for 12-20 h, and then cooling the air to room temperature.
Comparative example 4
The high-strength corrosion-resistant nickel-based high-temperature alloy for aerospace is characterized by comprising the following components in percentage by mass: 20.8 of Co, 16.8 of Cr, 7.8 of Mo, 4.8 of W, 2.8 of Ta, 3.8 of Al, 2.4 of Ti, 1.9 of Re, 1.6 of Nb1, 0.2 of Mn, 0.15 of Si, 0.08 of C, 0.02 of Zr, 0.0015 of B, 0.05 of Y, 7 of Fe, 0.20 of Hf and 0.1 of Mg, and the balance of Ni and inevitable impurities. The preparation steps are as follows:
(1) the vacuum induction smelting is carried out according to the proportion of the chemical components of the alloy, and the alloy is added into a vacuum induction smelting furnace for smelting, wherein the smelting process is distributed for smelting, refining, cooling, alloying and pouring; in the melting step, selecting a Ni-Co intermediate alloy with the Co mass ratio of 80%, selecting a Ni-Cr intermediate alloy with the Cr mass ratio of 51%, selecting a Ni-Mo intermediate alloy with the Mo mass ratio of 64%, selecting a Fe-Mo intermediate alloy with the Fe mass ratio of 35%, selecting a proper intermediate alloy from W, Ta, Re, Nb, Zr and Hf, and selecting a proper intermediate alloy or a simple substance from Al, Ti, Mn, Si, C, B and Y; respectively loading the raw materials into a crucible, completely melting the raw materials, refining for 30-50 min, adding a refining agent in the refining process, wherein the refining agent is a Ba-Al-Ca ternary alloy, the mass ratio of Ba to Al to Ca is 6: 3: 1, the adding amount of the refining agent accounts for 2-2.5% of the total mass of the alloy in the crucible, adding CaO powder with the mass fraction of 2-3% in the later period of the refining period for desulfurization, and after the refining is finished, using a composite stirring mode of electromagnetic stirring and mechanical stirring, wherein the electromagnetic stirring is performed for 5-8min in one period, the mechanical stirring is stopped for 3-5min, the mechanical stirring is performed for 5-8min and the mechanical stirring is stopped for 3-5min, and the stirring can be performed for 1-3 periods according; controlling the carbon-oxygen content ratio in the smelting process of the vacuum induction smelting furnace to ensure that the carbon-oxygen content ratio is 1: 1.2-1.3, adding Ni-Mg intermediate alloy with the Mg mass fraction of 10-13% when pouring out the alloy solution, wherein the adding amount is 0.2-0.25%; stirring and slagging off, pouring when the temperature of the alloy liquid melt reaches 1500-1800 ℃, and pouring the alloy liquid melt into an ingot mold preheated at 250 ℃ under 200-plus-one conditions to prepare an electrode rod with the diameter of 350mm under 300-plus-one conditions;
(2) the mass ratio of the electroslag remelting electroslag amount is CaF2∶CaO∶SiO2When the alloy liquid of the crystallizer reaches a set area, the power is cut off, and after cooling for 10-12 minutes, the electrode bar is cooled and solidified to form a bar material with the diameter of 250-300 mm;
(3) the heat treatment heats the bar with the diameter of 250-: firstly heating to 1000-1100 ℃ at a heating speed of 200-; then preserving the heat at 1080-1100 ℃ for 5-5.5h, and then air-cooling to room temperature; and then preserving the heat at 900-930 ℃ for 12-20 h, and then cooling the air to room temperature.
Comparative example 5
The high-strength corrosion-resistant nickel-based high-temperature alloy for aerospace is characterized by comprising the following components in percentage by mass: 20.8 of Co, 16.8 of Cr, 7.8 of Mo, 4.8 of W, 2.8 of Ta, 3.8 of Al, 2.4 of Ti, 1.9 of Re, 1.6 of Nb1, 0.2 of Mn, 0.15 of Si, 0.08 of C, 0.02 of Zr, 0.0015 of B, 0.05 of Y, 7 of Fe, 0.20 of Hf and 0.1 of Mg, and the balance of Ni and inevitable impurities. The preparation steps are as follows:
(1) the vacuum induction smelting is carried out according to the proportion of the chemical components of the alloy, and the alloy is added into a vacuum induction smelting furnace for smelting, wherein the smelting process is distributed for smelting, refining, cooling, alloying and pouring; in the melting step, selecting a Ni-Co intermediate alloy with the Co mass ratio of 80%, selecting a Ni-Cr intermediate alloy with the Cr mass ratio of 51%, selecting a Ni-Mo intermediate alloy with the Mo mass ratio of 64%, selecting a Fe-Mo intermediate alloy with the Fe mass ratio of 35%, selecting a proper intermediate alloy from W, Ta, Re, Nb, Zr and Hf, and selecting a proper intermediate alloy or a simple substance from Al, Ti, Mn, Si, C, B and Y; respectively loading the raw materials into a crucible, completely melting the raw materials, refining for 30-50 min, adding a refining agent in the refining process, wherein the refining agent is a Ba-Al-Ca ternary alloy, the mass ratio of Ba to Al to Ca is 6: 3: 1, the adding amount of the refining agent accounts for 2-2.5% of the total mass of the alloy in the crucible, adding CaO powder with the mass fraction of 2-3% in the later period of the refining period for desulfurization, and after the refining is finished, using a composite stirring mode of electromagnetic stirring and mechanical stirring, wherein the electromagnetic stirring is performed for 5-8min in one period, the mechanical stirring is stopped for 3-5min, the mechanical stirring is performed for 5-8min and the mechanical stirring is stopped for 3-5min, and the stirring can be performed for 1-3 periods according; controlling the carbon-oxygen content ratio in the smelting process of the vacuum induction smelting furnace to ensure that the carbon-oxygen content ratio is 1: 1.2-1.3, adding Ni-Mg intermediate alloy with the Mg mass fraction of 10-13% when pouring out the alloy solution, wherein the adding amount is 0.2-0.25%; stirring and slagging off, pouring when the temperature of the alloy liquid melt reaches 1500-1800 ℃, and pouring the alloy liquid melt into an ingot mold preheated at 250 ℃ under 200-plus-one conditions to prepare an electrode rod with the diameter of 350mm under 300-plus-one conditions;
(2) the mass ratio of the electroslag remelting electroslag amount is CaF2∶Al2O3∶CaO∶TiO2∶SiO2Adding electrode bar, installing crystallizer, adding arc-striking agent, starting voltage is 50-60V, stabilizing current is 2600-3000A, adding electroslag after arc striking, melting slag in electric furnace, stabilizing current after slag is melted, entering melting state, melting electrode bar, stopping power supply after crystallizer alloy liquid reaches set area, cooling, and coolingCooling for 10-12 minutes, and cooling and solidifying to form a bar with the diameter of 250-300 mm;
(3) the heat treatment heats the bar with the diameter of 250-: firstly heating to 1000-1100 ℃ at a heating speed of 200-; and then preserving the heat at 900-930 ℃ for 12-20 h, and then cooling the air to room temperature.
Comparative example 6
The high-strength corrosion-resistant nickel-based high-temperature alloy for aerospace is characterized by comprising the following components in percentage by mass: 20.8 of Co, 16.8 of Cr, 7.8 of Mo, 4.8 of W, 2.8 of Ta, 3.8 of Al, 2.4 of Ti, 1.9 of Re, 1.6 of Nb1, 0.2 of Mn, 0.15 of Si, 0.08 of C, 0.02 of Zr, 0.0015 of B, 0.05 of Y, 7 of Fe, 0.20 of Hf and 0.1 of Mg, and the balance of Ni and inevitable impurities. The preparation steps are as follows:
(1) the vacuum induction smelting is carried out according to the proportion of the chemical components of the alloy, and the alloy is added into a vacuum induction smelting furnace for smelting, wherein the smelting process is distributed for smelting, refining, cooling, alloying and pouring; in the melting step, selecting a Ni-Co intermediate alloy with the Co mass ratio of 80%, selecting a Ni-Cr intermediate alloy with the Cr mass ratio of 51%, selecting a Ni-Mo intermediate alloy with the Mo mass ratio of 64%, selecting a Fe-Mo intermediate alloy with the Fe mass ratio of 35%, selecting a proper intermediate alloy from W, Ta, Re, Nb, Zr and Hf, and selecting a proper intermediate alloy or a simple substance from Al, Ti, Mn, Si, C, B and Y; respectively loading the raw materials into a crucible, completely melting the raw materials, refining for 30-50 min, adding a refining agent in the refining process, wherein the refining agent is a Ba-Al-Ca ternary alloy, the mass ratio of Ba to Al to Ca is 6: 3: 1, the adding amount of the refining agent accounts for 2-2.5% of the total mass of the alloy in the crucible, adding CaO powder with the mass fraction of 2-3% in the later period of the refining period for desulfurization, and after the refining is finished, using a composite stirring mode of electromagnetic stirring and mechanical stirring, wherein the electromagnetic stirring is performed for 5-8min in one period, the mechanical stirring is stopped for 3-5min, the mechanical stirring is performed for 5-8min and the mechanical stirring is stopped for 3-5min, and the stirring can be performed for 1-3 periods according; controlling the carbon-oxygen content ratio in the smelting process of the vacuum induction smelting furnace to ensure that the carbon-oxygen content ratio is 1: 1.2-1.3, adding Ni-Mg intermediate alloy with the Mg mass fraction of 10-13% when pouring out the alloy solution, wherein the adding amount is 0.2-0.25%; stirring and slagging off, pouring when the temperature of the alloy liquid melt reaches 1500-1800 ℃, and pouring the alloy liquid melt into an ingot mold preheated at 250 ℃ under 200-plus-one conditions to prepare an electrode rod with the diameter of 350mm under 300-plus-one conditions;
(2) the mass ratio of the electroslag remelting electroslag amount is CaF2∶Al2O3∶CaO∶TiO2∶SiO2Adding an electrode bar, installing a crystallizer, adding an arc striking agent, starting voltage of 50-60V, stabilizing current of 2600-plus-3000A, adding the electroslag after arc striking, melting slag in an electric furnace, stabilizing the current after the slag is melted, entering a melting state, melting the electrode bar, stopping power supply after crystallizer alloy liquid reaches a set area, cooling for 10-12 minutes, and cooling and solidifying to form a bar material with the diameter of 250-plus-300 mm;
(3) the heat treatment heats the bar with the diameter of 250-: firstly, heating to 1000-1100 ℃ at a heating speed of 200-; then preserving the heat at 1050-1060 ℃ for 5-5.5h, and then cooling the air to room temperature; and then preserving the heat for 12-20 hours at 880-890 ℃, and then cooling the air to room temperature.
The nickel-base superalloys of examples 1-3 and comparative examples 1-6 were tested for their transient tensile properties and long-term durability using test methods conventional in the art, and are shown in tables 1 and 2.
TABLE 1
Figure BDA0001625678700000141
TABLE 2
Figure BDA0001625678700000142
Figure BDA0001625678700000151
The terminology used herein is for the purpose of description and illustration, rather than of limitation. As the present invention may be embodied in several forms without departing from the spirit or essential characteristics thereof, it should also be understood that the above-described embodiments are not limited by any of the details of the foregoing description, but rather should be construed broadly within its spirit and scope as defined in the appended claims, and therefore all changes and modifications that fall within the meets and bounds of the claims, or equivalences of such meets and bounds are therefore intended to be embraced by the appended claims.

Claims (1)

1. The high-strength corrosion-resistant nickel-based high-temperature alloy for aerospace is characterized by comprising the following components in percentage by mass: co20.7, Cr 16.7, Mo 7.7, W4.7, Ta2.7, Al 3.7, Ti 2.3, Re 1.8, Nb1.5, Mn0.18, Si 0.14, C0.07, Zr 0.018, B0.0014, Y0.04, Fe 6.8, Hf 0.18, Mg 0.09, and the balance of Ni and unavoidable impurities; the structure of the nickel-based high-temperature alloy consists of a matrix gamma, a main strengthening phase is gamma ', the grain diameter of the gamma ' phase is 50-600 nm, the precipitation amount of the gamma ' phase is 70-88 vol% relative to the total alloy, and the rest precipitates consist of a small amount of MC carbide and M3B2 boride, wherein the lasting life of the nickel-based high-temperature alloy under the conditions of 1100 ℃ and 200MPa is not less than 130h, and the lasting life of the nickel-based high-temperature alloy under the conditions of 1200 ℃ and 150MPa is not less than 100 h; the instantaneous tensile property of the nickel-based superalloy at 800 ℃ is that the yield strength is more than or equal to 1050MPa, the tensile strength is more than or equal to 1350MPa, the yield strength is more than or equal to 700MPa at 1000 ℃, and the tensile strength is more than or equal to 950 MP;
the manufacturing method of the high-strength corrosion-resistant nickel-based high-temperature alloy for aerospace comprises the following preparation steps:
(1) the vacuum induction smelting is carried out according to the proportion of the chemical components of the alloy, and the alloy is added into a vacuum induction smelting furnace for smelting, wherein the smelting process is distributed for smelting, refining, cooling, alloying and pouring; in the melting step, selecting a Ni-Co intermediate alloy with the Co mass ratio of 80%, selecting a Ni-Cr intermediate alloy with the Cr mass ratio of 51%, selecting a Ni-Mo intermediate alloy with the Mo mass ratio of 64%, selecting a Fe-Mo intermediate alloy with the Fe mass ratio of 35%, selecting a proper intermediate alloy from W, Ta, Re, Nb, Zr and Hf, and selecting a proper intermediate alloy or a simple substance from Al, Ti, Mn, Si, C, B and Y; respectively loading the raw materials into a crucible, completely melting the raw materials, refining for 30-50 min, adding a refining agent in the refining process, wherein the refining agent is a Ba-Al-Ca ternary alloy, the mass ratio of Ba to Al to Ca is 6: 3: 1, the adding amount of the refining agent accounts for 2-2.5% of the total mass of the alloy in the crucible, adding CaO powder with the mass fraction of 2-3% in the later period of the refining period for desulfurization, and after the refining is finished, using a composite stirring mode of electromagnetic stirring and mechanical stirring, wherein the electromagnetic stirring is performed for 5-8min in one period, the mechanical stirring is stopped for 3-5min, the mechanical stirring is performed for 5-8min and the mechanical stirring is stopped for 3-5min, and the stirring can be performed for 1-3 periods according; controlling the carbon-oxygen content ratio in the smelting process of the vacuum induction smelting furnace to ensure that the carbon-oxygen content ratio is 1: 1.2-1.3, adding Ni-Mg intermediate alloy with the Mg mass fraction of 10-13% when pouring out the alloy solution, wherein the adding amount is 0.2-0.25%; stirring and slagging off, pouring when the temperature of the alloy liquid melt reaches 1500-1800 ℃, and pouring the alloy liquid melt into an ingot mold preheated at 250 ℃ under 200-plus-one conditions to prepare an electrode rod with the diameter of 350mm under 300-plus-one conditions;
(2) the mass ratio of the electroslag remelting electroslag slag is CaF2 to Al2O3 to CaO to TiO2 to SiO2 is 50-60: 20-30: 10-15: 3-5, an electrode bar is firstly added, a crystallizer is installed, an arc striking agent is added, the starting voltage is 50-60V, the stable current is 2600-plus 3000A, the electroslag is added after arc striking, the slag is melted in an electric furnace, after the slag is melted, the current is stabilized, the electrode bar is in a melting state, the electrode bar is melted, the power is cut off after the alloy liquid of the crystallizer reaches a set area, and after the alloy liquid is cooled for 10-12 minutes, the electrode bar is cooled and solidified to form a bar material with the diameter of 250-plus 300 mm;
(3) the heat treatment heats the bar with the diameter of 250-: firstly heating to 1000-1100 ℃ at a heating speed of 200-; then keeping the temperature at 1080-1100 ℃ for 5-5.5h, and then cooling the mixture to room temperature in air; and then preserving the heat at 900-930 ℃ for 12-20 h, and then cooling the air to room temperature.
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