WO2023035773A1 - 用于等温锻造的大型模具坯料的制备方法 - Google Patents

用于等温锻造的大型模具坯料的制备方法 Download PDF

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WO2023035773A1
WO2023035773A1 PCT/CN2022/105931 CN2022105931W WO2023035773A1 WO 2023035773 A1 WO2023035773 A1 WO 2023035773A1 CN 2022105931 W CN2022105931 W CN 2022105931W WO 2023035773 A1 WO2023035773 A1 WO 2023035773A1
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titanium
zirconium
foil
molybdenum alloy
temperature
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PCT/CN2022/105931
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English (en)
French (fr)
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翟月雯
羊浩
周乐育
贺小毛
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北京机电研究所有限公司
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    • 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
    • C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
    • C22F1/18—High-melting or refractory metals or alloys based thereon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K20/00—Non-electric welding by applying impact or other pressure, with or without the application of heat, e.g. cladding or plating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23P—METAL-WORKING NOT OTHERWISE PROVIDED FOR; COMBINED OPERATIONS; UNIVERSAL MACHINE TOOLS
    • B23P15/00—Making specific metal objects by operations not covered by a single other subclass or a group in this subclass
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
    • C22C27/04—Alloys based on tungsten or molybdenum
    • 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
    • C22F1/02—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working in inert or controlled atmosphere or vacuum
    • 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

Definitions

  • the invention relates to a method for manufacturing metal materials, in particular to a method for preparing a large mold blank for isothermal forging, in particular to a method for preparing a titanium-zirconium-molybdenum alloy mold blank for isothermal forging.
  • Isothermal forging is especially suitable for precision forming of hard-to-deform materials with narrow forging temperature zone, poor plasticity and high deformation resistance, such as titanium alloys, nickel-based superalloys and other alloys.
  • the isothermal forging die needs to be used at high temperature and has higher flow stress than the formed part, higher requirements are placed on the high temperature performance of the die material.
  • the working temperature of the mold cavity is mostly 700°C-1200°C. In this temperature range, the mold must have high strength and hardness, good wear resistance and sufficient toughness .
  • Titanium-zirconium-molybdenum alloy for short is an alloy based on molybdenum (Mo) with a small amount of titanium (Ti), zirconium (Zr) and carbon (C) added, and has a higher recrystallization rate than metal molybdenum. Temperature (1350°C-1400°C), more excellent high temperature resistance mechanical properties and corrosion properties. Therefore, titanium-zirconium-molybdenum alloy, as an important high-temperature-resistant structural material, is very suitable for the manufacture of high-temperature-resistant molds for isothermal forging.
  • titanium-zirconium-molybdenum alloys due to the high melting point of titanium-zirconium-molybdenum alloys (about 2640°C), it is difficult to smelt or powder metallurgically prepare larger-sized titanium-zirconium-molybdenum alloys, and coarse grains and component segregation are prone to occur. Moreover, due to the high-temperature deformation resistance of titanium-zirconium-molybdenum alloys, it is more difficult to refine grains and modify large-size billets through forging, rolling and other thermal processing methods, and large-size billets are prone to uneven microstructure and chemical composition. The phenomenon that the mechanical properties of the billet also shows an obvious downward trend with the increase of the billet size.
  • the existing method proposes to stack multiple small primitives into a predetermined shape, and then package each small primitive by including electron beam welding to achieve a vacuum state between the primitives, large-scale deformation (pier thick ) and high temperature insulation to achieve interlayer diffusion of each small element to realize interlayer forging and welding, and finally forge and weld multiple elements together to form a large metal billet.
  • titanium-zirconium-molybdenum alloys it is more difficult to achieve interlayer interface diffusion of each small unit by applying pressure at high temperature, and it is more difficult to achieve a good forge-welding bond between each layer unit.
  • the welding performance of titanium-zirconium-molybdenum alloy is poor, and it is difficult to obtain a weld with better performance by electron beam welding.
  • the high temperature generated during the electron beam welding packaging process may also significantly change the structure and properties of titanium-zirconium-molybdenum alloy. Electron beam welding also increases process complexity and manufacturing costs.
  • titanium-zirconium-molybdenum alloys have high-temperature characteristics that are easy to oxidize and volatilize under high-temperature conditions, and the conventional forging welding construction process in the atmosphere is not suitable for titanium-zirconium-molybdenum alloys. Therefore, the above-mentioned forging-welding-based construction forming process is not suitable for titanium-zirconium-molybdenum alloys, and it is necessary to develop a method suitable for preparing large-scale titanium-zirconium-molybdenum alloy materials.
  • the present application provides an additive manufacturing method for isothermal forging large die blanks, which can effectively reduce the inhomogeneity in structure, composition, and performance of titanium-zirconium-molybdenum alloy blanks. It is especially suitable for the preparation of large titanium zirconium molybdenum mold blanks.
  • the present application provides a method for preparing a large die blank for isothermal forging, which includes the following steps:
  • the homogenization treatment of the primary billet is carried out for 2-24 hours, to Uniform the structure and composition of the connecting interface in the primary billet;
  • tantalum, niobium-tungsten alloy or tantalum-tungsten alloy foil material is used as the intermediate layer, the homogenization process is increased, the construction and forming process is improved, and large-scale mold blanks are prepared from titanium-zirconium-molybdenum alloys.
  • the additive manufacturing method according to the present application promotes the interdiffusion between the molybdenum element of the titanium-zirconium-molybdenum alloy plate-like element and the metal element of the foil-like intermediate layer, between the element and the intermediate A diffusion layer is formed at the connection interface of the layers, and the interconnection of multiple elementary elements is effectively realized through the foil-shaped intermediate layer, so that the preparation of a large mold blank of titanium, zirconium and molybdenum alloy can be realized by using the construction and forming process.
  • the additive manufacturing method of this application will not affect the structure and performance of titanium-zirconium-molybdenum alloy plate elements. Visibly changed.
  • the titanium-zirconium-molybdenum alloy plate-shaped element in the preparation of a plurality of titanium-zirconium-molybdenum alloy plate-shaped elements with a thickness of 30-100 mm, is mechanically processed , pre-grinding and polishing, so that the roughness Ra of the connection surface between the titanium-zirconium-molybdenum alloy plate-shaped element and the foil-shaped intermediate layer is 0.4 to 0.8, and make each of the connection surfaces and the titanium-zirconium-molybdenum alloy plate-shaped
  • the parallelism between the pressure-receiving surfaces of the basic element subjected to the axial pressure is less than 0.02 mm.
  • the tantalum is pure tantalum with a purity ⁇ 99.5%
  • the niobium-tungsten alloy or tantalum-tungsten alloy is Nb-(2-10)W or Ta-(2-10)W (wt %).
  • connection temperature is 20-60°C lower than the recrystallization temperature of titanium-zirconium-molybdenum alloy
  • the axial pressure is 7-9 MPa
  • the connection time is 3-6 Hour.
  • the homogenization temperature is a temperature 80-150° C. lower than the recrystallization temperature of the titanium-zirconium-molybdenum alloy, and the homogenization time is 5-12 hours.
  • the cooling rate in cooling the homogenized primary billet, is 2-6 °C/min from the homogenization temperature to 1000 °C, and the cooling rate is 10-15 °C/min The cooling rate is from 1000°C to 500°C.
  • the temperature in cooling the homogenized primary billet, after cooling to 500° C., the temperature is kept at 500° C. for 1 hour to remove the stress caused by cooling.
  • connection temperature by further limiting the process parameters such as connection temperature, axial connection pressure, connection time, homogenization temperature, homogenization time, cooling rate, etc., it is beneficial to further promote the molybdenum between the titanium-zirconium-molybdenum alloy element and the foil-shaped intermediate layer.
  • the interdiffusion of elements and metal elements in the middle layer further increases the molybdenum content of the middle layer, thereby further improving the performance of the mold at high temperatures.
  • the homogenization and cooling processes are performed in a vacuum diffusion furnace.
  • homogenization and subsequent controlled cooling can be performed directly after the pressurized connection by adjusting the temperature of the vacuum diffusion furnace.
  • the homogenization and cooling processes are performed in a vacuum furnace or an atmosphere protection furnace.
  • the method can shorten the service time of the vacuum diffusion welding furnace and improve the production efficiency.
  • Fig. 1 is a schematic structural view of an assembly according to an embodiment of the present application
  • FIG. 2 is a schematic diagram of a diffusion connection according to an embodiment of the present application.
  • FIG. 3 is a schematic diagram of a homogenization process according to an embodiment of the present application.
  • Fig. 4 is a schematic structural view of a mold blank according to an embodiment of the present application.
  • vacuum diffusion welding furnace used in the specification and claims is a device capable of applying pressure to a workpiece while providing a vacuum environment for the workpiece.
  • vacuum heating furnace used in the specification and claims is a device capable of providing a vacuum environment for a workpiece.
  • atmosphere protection furnace as used in the specification and claims is a device capable of providing an inert gas environment for a workpiece.
  • titanium-zirconium-molybdenum alloy also known as TZM alloy, as used in the description and claims, has a composition of 0.4wt% to 0.55wt% titanium, 0.06wt% to 0.12wt% zirconium and 0.01wt% to 0.04wt% carbon .
  • the titanium and zirconium elements dissolve into the molybdenum matrix to distort the lattice and realize the solid solution strengthening of the titanium-zirconium-molybdenum alloy; on the other hand, titanium reacts with zirconium and carbon to form fine and dispersed TiC and ZrC particles, A second phase strengthening is achieved.
  • TZM alloy Due to the effect of alloying, in addition to the characteristics of high melting point, small expansion coefficient, low vapor pressure, and good electrical and thermal conductivity of molybdenum, TZM alloy has a higher recrystallization temperature (1350°C-1400°C). More excellent high temperature mechanical properties and corrosion properties.
  • diffusion bonding used in the specification and claims refers to the process of making the surfaces to be connected plastically deformed under the action of high temperature and pressure to make close contact, and inter-diffusion between atoms for a certain period of time to form a reliable joint.
  • the method is especially suitable for preparing joints with large connection areas and high requirements for dimensional accuracy and mechanical properties.
  • isothermal forging as used in the specification and claims is a forging technique in which the die and the formed part are at substantially the same temperature.
  • building forming used in the specification refers to an additive manufacturing method that uses multiple smaller metal billets as building blocks to make large metal billets.
  • axial direction refers to the direction perpendicular to the contact surface of the titanium-zirconium-molybdenum alloy plate element in contact with the foil intermediate layer.
  • FIG. 1 shows an assembly 3 with a square cross-section according to one embodiment of the present application.
  • the assembly 3 is composed of four titanium-zirconium-molybdenum alloy plate-like elements 1 and three foil-like intermediate layers 2, and the foil-like intermediate layers 2 are respectively sandwiched between the titanium-zirconium-molybdenum alloy plate-like elements 1 .
  • each titanium-zirconium-molybdenum alloy plate-like element 1 is prepared to be uniform in shape
  • each foil-like intermediate layer 2 is prepared to be uniform in shape to form an assembly 3 with such a cross-section.
  • each titanium-zirconium-molybdenum alloy plate element 1 may be prepared to be inconsistent in shape, and/or each foil-shaped intermediate layer 2 may be prepared to be inconsistent in shape, so as to form a desired shape. section to form the assembly 3 of the desired configuration.
  • each titanium-zirconium-molybdenum alloy plate-like element 1 and foil-like intermediate layer 2 can be prepared in different shapes, so that the assembly 3 has a smooth curved profile in the thickness direction from top to bottom.
  • some of the titanium-zirconium-molybdenum alloy plate-like elements 1 and the foil-like intermediate layer 2 can be prepared into a hollow shape, so that the assembly 3 has a hollow cavity, so that the mold blank as a mold can be prepared by using the hollow cavity. pieces.
  • Fig. 2 shows a schematic diagram of a diffusion connection according to an embodiment of the present application.
  • the intermediate structure 5 has a diffusion layer 7 at the connection interface and possibly a metal foil layer between the diffusion layers 7 (in some other embodiments, since the molybdenum element completely penetrates into the foil-like intermediate layer to form a solid solution, in this case It is considered that the foil-like intermediate layer 2 has partially or completely disappeared). Due to the formation of a new intermediate structure 5, from a microscopic point of view, it can be considered that the titanium-zirconium-molybdenum plate-like element 1' is thinner than the titanium-zirconium-molybdenum alloy plate-like element 1, and the metal foil layer is thinner than the foil-shaped intermediate layer 2.
  • Fig. 3 shows a schematic diagram of a homogenization process according to an embodiment of the present application.
  • Figure 4 shows a mold blank 6 according to one embodiment of the application.
  • the mold blank 6 is composed of a titanium-zirconium-molybdenum plate element 1' and a diffusion layer 7.
  • interdiffusion further occurs during the homogenization process of the primary blank 4, and the metal foil layer originally remaining in the intermediate structure 5 disappears completely with further interdiffusion. Therefore, the intermediate structure 5 is transformed into a molybdenum-titanium / niobium solid solution to form the diffusion layer 7, thereby forming the mold blank 6.
  • a certain thickness of the metal foil layer remains in the mold blank 6 .
  • tantalum foil, niobium-tungsten, and tantalum-tungsten belong to high-melting point alloys and have high high-temperature strength, the residual metal foil layer will not significantly affect the high-temperature performance of the mold blank 6, and the formed diffusion layer is sufficient to provide the mold The blank 6 is used as the mechanical properties required by the mold.
  • the element distribution of the diffusion layer 7 is not uniform, and the molybdenum element is distributed in a gradient concentration.
  • the molybdenum element can improve the high-temperature performance of the intermediate layer, the titanium element is distributed in a gradient concentration.
  • the diffusion layer 7 will not significantly affect the high-temperature performance of the mold blank 6.
  • the formed diffusion layer is sufficient to provide the mold blank 6 as the mold. mechanical properties.
  • tantalum foil, niobium-tungsten foil or tantalum-tungsten foil as an intermediate layer, the problems of titanium-zirconium-molybdenum alloy with high high-temperature yield strength, high melting point, difficult plastic deformation at the connection interface, and difficult diffusion are solved.
  • the application solves the problems of difficult preparation of titanium-zirconium-molybdenum alloy large blanks and uneven and poor performance by adding a specific intermediate layer, homogenization process and cooling process on the basis of the metal construction process.
  • the homogenization treatment of the diffusion-bonded blank in the present invention enables the interdiffusion of the intermediate layer elements and the molybdenum element of the titanium-zirconium-molybdenum alloy to fully interdiffuse, forming an obvious diffusion layer at the connection interface of the basic elements, and the bonding strength is high.
  • each connection interface of titanium, zirconium and molybdenum has high performance at room temperature and high temperature.
  • the joining temperature of this application is relatively low, 20-100°C lower than the recrystallization temperature of the titanium-zirconium-molybdenum alloy.
  • the microstructure and properties of the titanium-zirconium-molybdenum alloy plate elements do not change significantly after diffusion bonding.
  • vacuum electron beam welding and packaging are not required for each element, the process is relatively simple, and the manufacturing cost is low.
  • the application reduces the requirements of the diffusion connection on the roughness of the connection surface of the titanium-zirconium-molybdenum alloy, the connection temperature, the connection pressure and the holding time. This application also avoids the problems of limited capacity and high investment of powder metallurgy equipment.
  • the shape of the basic element of this application can be designed according to the actual situation, and the diffusion and additive manufacturing of solid, hollow and irregular-shaped blanks can be realized, and the process is flexible and adaptable.
  • the method of the present application is more suitable for the construction and manufacture of high-melting point refractory alloys and hard-to-deform alloys, such as molybdenum alloys, tungsten alloys and nickel-based alloys.
  • This example is a titanium-zirconium-molybdenum molybdenum mold blank for isothermal forging for nickel-based superalloy blades, with a size of 200 ⁇ 200 ⁇ 60 mm (length ⁇ width ⁇ thickness).
  • the isothermal forging titanium-zirconium-molybdenum mold blank uses 3 pieces of 200 ⁇ 200 ⁇ 20 mm (length ⁇ width ⁇ thickness) titanium-zirconium-molybdenum alloy plate elements, and 2 pieces of Nb- 10W foil intermediate layer, diffusion connection additive manufacturing in vacuum diffusion furnace, and diffusion homogenization treatment in vacuum furnace. Specific steps are as follows:
  • Step 1 Machining, pre-grinding, and polishing the titanium-zirconium-molybdenum alloy plate element, so that the roughness Ra of the titanium-zirconium-molybdenum alloy connection surface is 0.4-0.8, and ensure that the titanium-zirconium-molybdenum alloy connection surface is in contact with the pressure head of the vacuum diffusion furnace
  • the parallelism of the pressure surface is less than 0.02mm.
  • Step 2 Soak the foil-shaped intermediate layer with 10wt% hydrochloric acid for 10 minutes, rinse it with clean water, put it in alcohol or acetone for ultrasonic cleaning, and then air dry it for use.
  • Step 3 Assemble the titanium-zirconium-molybdenum alloy plate-shaped element and the Nb-10W foil intermediate layer treated in steps 1 and 2 alternately, and stack them into 5 layers (3 layers of titanium-zirconium-molybdenum alloy plate, 2 layers of foil-shaped intermediate layer ) to form an assembly.
  • the niobium foil intermediate layer can be fixed on the titanium-zirconium-molybdenum alloy plate-like element by means of energy storage welding to prevent misalignment during assembly.
  • Step 4 Put the assembly into a vacuum diffusion furnace, apply 0.2MPa axial pressure to the assembly for fixation. Then start vacuuming, and when the degree of vacuum reaches 2 ⁇ 10 -3 Pa, start heating to raise the temperature.
  • the temperature is raised to 500°C at a rate of 15°C/min and held for 30 minutes to volatilize the oil in the furnace and on the surface of the workpiece; in the second stage, the temperature is raised to 1000°C at a rate of 10°C/min and held for 15 minutes to make the furnace The temperature is uniform; in the third stage, the temperature is raised to the diffusion connection temperature of 1330°C at a rate of 5 minutes/minute. After reaching the joining temperature of 1330°C, apply an axial pressure of 9 MPa to the assembly and keep it warm for 6 hours to carry out diffusion joining to obtain primary blanks.
  • Step 5 After the diffusion connection heat preservation is completed, the temperature in the furnace is lowered to 1220°C, the axial pressure is removed, and the heat preservation is carried out for 8 hours, and the homogenization treatment is carried out to eliminate the connection stress and make the composition and structure of the connection interface uniform.
  • Step 6 After completing the homogenization and heat preservation, start to cool down. In the stage of cooling from 1200°C to 1000°C, the cooling rate is 2-6°C/minute; in the stage of 1000°C to 500°C, the cooling rate is 10-15°C/minute. When the temperature reaches 500°C, it is kept at this temperature for 1 hour to perform annealing and stress relief treatment. After the stress is removed, it is cooled to room temperature with the furnace, and the titanium-zirconium-molybdenum alloy mold blank is obtained.
  • This example is a titanium-zirconium-molybdenum molybdenum die blank for isothermal forging of nickel-based superalloy blisks, with a size of 500 ⁇ 500 ⁇ 200 mm (length ⁇ width ⁇ thickness).
  • the isothermal forging titanium-zirconium-molybdenum mold blank uses 4 pieces of 500 ⁇ 500 ⁇ 50 mm (length ⁇ width ⁇ thickness) titanium-zirconium-molybdenum alloy plate-shaped primitives, and 3 pieces of 500 ⁇ 500 mm and a thickness of 60 microns Ta-2.5W foil
  • the diffusion connection additive manufacturing is carried out in the vacuum diffusion furnace, and the diffusion homogenization treatment is carried out in the vacuum furnace. Specific steps are as follows:
  • Step 1 Machining, pre-grinding, and polishing the titanium-zirconium-molybdenum alloy plate element, so that the roughness Ra of the titanium-zirconium-molybdenum alloy connection surface is 0.4-0.8, and ensure that the titanium-zirconium-molybdenum alloy connection surface is in contact with the pressure head of the vacuum diffusion furnace
  • the parallelism of the pressure surface is less than 0.02 mm.
  • Step 2 Soak the foil-shaped intermediate layer with 10wt% hydrochloric acid for 10 minutes, rinse it with clean water, put it in alcohol or acetone for ultrasonic cleaning, and then air dry it for use.
  • Step 3 Assemble the titanium-zirconium-molybdenum alloy plate-shaped element treated in steps 1 and 2 and the Ta-2.5W foil intermediate layer alternately, and stack them into 7 layers (4 layers of titanium-zirconium-molybdenum alloy plate, 3 layers of foil-shaped intermediate layer layer) to form an assembly.
  • the niobium foil intermediate layer can be fixed on the titanium-zirconium-molybdenum alloy plate-like element by means of energy storage welding to prevent misalignment during assembly.
  • Step 4 Put the assembly into a vacuum diffusion furnace, apply 0.2MPa axial pressure to the assembly for fixation. Then start vacuuming, and start heating to raise the temperature when the degree of vacuum reaches 2 ⁇ 10 -3 Pa.
  • the temperature is raised to 500°C at a rate of 15°C/min and held for 30 minutes to volatilize the oil in the furnace and on the surface of the workpiece; in the second stage, the temperature is raised to 1000°C at a rate of 10°C/min and held for 15 minutes to make the furnace The temperature is uniform; in the third stage, the temperature is raised to a diffusion connection temperature of 1300°C at a rate of 5 minutes/minute. After reaching the connection temperature of 1330°C, an axial pressure of 7 MPa was applied to the assembly and kept for 5 hours for diffusion connection. After the diffusion connection heat preservation is completed, the primary billet is taken out with the furnace air cooling to room temperature.
  • Step 5 Put the primary billet into the atmosphere furnace, pour in nitrogen protection, and heat up. Raise the temperature of the furnace to 1250°C and keep the temperature for 12 hours for homogenization.
  • Step 6 After completing the homogenization and heat preservation, start to cool down. In the stage of cooling from 1250°C to 1000°C, the cooling rate is 2-6°C/min; in the stage of 1000°C to 500°C, the cooling rate is 10-15°C/min. When the temperature reaches 500°C, it is kept at this temperature for 1 hour to perform annealing and stress relief treatment. After the stress is removed, it is cooled to room temperature with the furnace, and the titanium-zirconium-molybdenum mold blank is obtained.
  • This example is a titanium alloy compressor disc isothermally forged titanium zirconium molybdenum mold blank, the size is 400 * 400 * 160 mm (length * width * thickness).
  • the isothermal forging titanium-zirconium-molybdenum mold blank uses 4 pieces of 400 ⁇ 400 ⁇ 40 mm (length ⁇ width ⁇ thickness) titanium-zirconium-molybdenum alloy plate-shaped primitives, and 3 pieces of Ta-
  • the 10W foil is the middle layer, and the diffusion connection additive manufacturing is carried out in the vacuum diffusion furnace, and the diffusion homogenization treatment is carried out in the vacuum furnace. Specific steps are as follows:
  • Step 1 Machining, pre-grinding, and polishing the titanium-zirconium-molybdenum alloy plate element, so that the roughness of the titanium-zirconium-molybdenum alloy connection surface is Ra0.4-0.8, and ensure the pressure head between the titanium-zirconium-molybdenum alloy connection surface and the vacuum diffusion furnace The parallelism of the contact pressure surface is less than 0.02mm.
  • Step 2 Soak the foil-shaped intermediate layer with 10wt% hydrochloric acid for 10 minutes, rinse it with clean water, put it in alcohol or acetone for ultrasonic cleaning, and then air dry it for use.
  • Step 3 Assemble the titanium-zirconium-molybdenum alloy plate-shaped element treated in steps 1 and 2 and the Ta-10W foil intermediate layer alternately, and stack them into 7 layers (4 layers of titanium-zirconium-molybdenum alloy plate, 3 layers of foil-shaped intermediate layer ) to form an assembly.
  • the titanium foil intermediate layer can be fixed on the titanium-zirconium-molybdenum alloy plate element by means of energy storage welding to prevent misalignment during assembly.
  • Step 4 Put the assembly into a vacuum diffusion furnace, apply 0.2MPa axial pressure to the assembly for fixation. Then start vacuuming, and start heating to raise the temperature when the degree of vacuum reaches 2 ⁇ 10 -3 Pa.
  • the temperature is raised to 500°C at a rate of 15°C/min and held for 30 minutes to volatilize the oil in the furnace and on the surface of the workpiece; in the second stage, the temperature is raised to 1000°C at a rate of 10°C/min and held for 15 minutes to make the furnace The temperature is uniform; in the third stage, the temperature is raised to a diffusion connection temperature of 1300°C at a rate of 5 minutes/minute. After reaching the connection temperature of 1300°C, an axial pressure of 6 MPa was applied to the assembly, and the temperature was kept for 3 hours to carry out diffusion connection to obtain the primary blank.
  • Step 5 After the diffusion connection heat preservation is completed, the temperature in the furnace is lowered to 1220°C, the axial pressure is removed, and the heat preservation is carried out for 10 hours, and the homogenization treatment is carried out to eliminate the connection stress, and the composition and structure of the connection interface are homogenized.
  • Step 6 After completing the homogenization and heat preservation, start to cool down. In the stage of cooling from 1220°C to 1000°C, the cooling rate is 2-6°C/minute; in the stage of 1000°C to 500°C, the cooling rate is 10-15°C/minute. When the temperature reaches 500°C, it is kept at this temperature for 1 hour to perform annealing and stress relief treatment. After the stress is removed, it is cooled to room temperature with the furnace, and the titanium-zirconium-molybdenum mold blank is obtained.
  • This example is an isothermal forging titanium-zirconium-molybdenum mold blank for a titanium alloy impeller disc, with a size of ⁇ 300 ⁇ 150 mm (length ⁇ width ⁇ thickness).
  • the isothermal forging titanium-zirconium-molybdenum mold blank uses 3 pieces of ⁇ 300 ⁇ 50 mm titanium-zirconium-molybdenum alloy plate-shaped element, and 2 pieces of tantalum foil with a diameter of ⁇ 300mm and a thickness of 40 microns are used as the middle layer.
  • Diffusion connection is added in a vacuum diffusion furnace. Fabricated and subjected to diffusion homogenization in a vacuum furnace. Specific steps are as follows:
  • Step 1 Machining, pre-grinding, and polishing the titanium-zirconium-molybdenum alloy plate element, so that the roughness of the titanium-zirconium-molybdenum alloy connection surface is Ra0.4-0.8, and ensure the pressure head between the titanium-zirconium-molybdenum alloy connection surface and the vacuum diffusion furnace The parallelism of the contact pressure surface is less than 0.02mm.
  • Step 2 Soak the foil-shaped intermediate layer with 10wt% hydrochloric acid for 10 minutes, rinse it with clean water, put it in alcohol or acetone for ultrasonic cleaning, and then air dry it for use.
  • Step 3 Assemble the titanium-zirconium-molybdenum alloy plate-like element and the tantalum foil intermediate layer treated in steps 1 and 2 alternately, and stack them into 5 layers (3 layers of titanium-zirconium-molybdenum alloy plate, 2 layers of foil-shaped intermediate layer) to form assembly.
  • the titanium foil intermediate layer can be fixed on the titanium-zirconium-molybdenum alloy plate element by means of energy storage welding to prevent misalignment during assembly.
  • Step 4 Put the assembly into a vacuum diffusion furnace, apply 0.2MPa axial pressure to the assembly for fixation. Then start vacuuming, and start heating to raise the temperature when the degree of vacuum reaches 2 ⁇ 10 -3 Pa.
  • the temperature is raised to 500°C at a rate of 15°C/min and held for 30 minutes to volatilize the oil in the furnace and on the surface of the workpiece; in the second stage, the temperature is raised to 1000°C at a rate of 10°C/min and held for 15 minutes to make the furnace The temperature is uniform; in the third stage, the temperature is raised to the diffusion connection temperature of 1320°C at a rate of 5 minutes/minute. After reaching the connection temperature of 1320°C, an axial pressure of 6 MPa was applied to the assembly and kept for 3 hours for diffusion connection to obtain the primary blank.
  • Step 5 After the diffusion connection heat preservation is completed, the temperature in the furnace is lowered to 1200°C, the axial pressure is removed, and the heat preservation is carried out for 12 hours, and the homogenization treatment is carried out to eliminate the connection stress, and the composition and structure of the connection interface are homogenized.
  • Step 6 After completing the homogenization and heat preservation, start to cool down. In the stage of cooling from 1200°C to 1000°C, the cooling rate is 2-6°C/minute; in the stage of 1000°C to 500°C, the cooling rate is 10-15°C/minute. When the temperature reaches 500°C, it is kept at this temperature for 1 hour to perform annealing and stress relief treatment. After the stress is removed, it is cooled to room temperature with the furnace, and the titanium-zirconium-molybdenum mold blank is obtained.

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Abstract

一种用于等温锻造的大型模具坯料（6）的增材制备方法，包括以下步骤：基于预定形状，分别制备多个钛锆钼合金板状基元（1）；基于预定形状，分别制备多个纯钽、铌钨合金和钽钨合金的箔状中间层（2）；基于预定构造，形成装配体（3），使得装配体（3）中箔状中间层（2）夹在钛锆钼合金板状基元（1）之间；借助于真空扩散焊炉（11），在高温真空的条件下对装配体（3）施加轴向压力，以发生扩散连接，获得初级坯料（4）；在高温、真空或惰性气体保护的条件下，对初级坯料（4）进行均匀化处理，以均匀初级坯料（4）中连接界面处的组织、成分；冷却经过均匀化处理的初级坯料（4），以获得模具坯料（6）。

Description

用于等温锻造的大型模具坯料的制备方法 技术领域
本发明涉及金属材料的制造方法，具体涉及一种用于等温锻造的大型模具坯料的制备方法，特别是一种用于等温锻造的钛锆钼合金模具坯料的制备方法。
背景技术
等温锻造特别适用于锻造温区窄，塑性较差，变形抗力大的难变形材料，如钛合金、镍基高温合金等合金的精密成形。但是，由于等温锻造模具需在高温下使用，且具有比成形件更高的流变应力，因此对模具材料的高温性能提出更高的要求。目前，镍基高温合金、钛合金在等温锻造时模具模膛的工作温度多在700℃-1200℃，在此温度区间模具须具有较高的强度和硬度、好的耐磨性和足够的韧性。钛锆钼合金(简称TZM合金)是一种以钼(Mo)为基体，添加了少量钛(Ti)、锆(Zr)和碳(C)元素的合金，具有比金属钼更高的再结晶温度(1350℃-1400℃)、更优异的耐高温力学性能和腐蚀性能。因此，钛锆钼合金作为一种重要的耐高温结构材料，十分适用于等温锻造用耐高温模具的制造。但是，由于钛锆钼合金的熔点较高(2640℃左右)，较大尺寸钛锆钼合金的冶炼或粉末冶金制备存在较大难度，易出现粗晶和成分偏析现象。并且，由于钛锆钼合金高温变形抗力较大，通过锻压、轧制等热加工手段对大尺寸坯料进行细化晶粒和改性的难度增大，大尺寸坯料易出现组织和化学成分不均匀的现象，坯料的力学性能也随着坯料尺寸的增大出现明显下降的趋势。
在制备大型金属材料时，现有方法提出将多个小型基元堆垛成预定形状，然后通过包含电子束焊接封装各小型基元以达到基元之间呈真空状态，大尺变形(墩粗)与高温保温使各小型基元实现层间扩散实现层间锻焊，最终将多个基元锻焊在一起以形成大型金属坯。如中国专利申请CN 105598327 A“分层多列堆垛金属构筑成形方法”、CN 107717341A“模块式金属构筑成形方法”、CN107876674A“金属分级构筑成形方法”、CN 105522349 A“同质金属构筑成形方法”，均是采用构筑成形的工艺对多个小型基元锻焊成大型金属件的方法。但是，钛锆钼合金作为高熔点难变形合金，在高温下变形 抗力较大，较难实现大变形量的锻压变形，即很难实现镦粗。因此，对于钛锆钼合金，通过高温下施加压力使各小型单元实现层间界面扩散的难度较大，实现各层单元之间良好锻焊结合的难度较大。同时，钛锆钼合金焊接性能较差，通过电子束焊接获得性能较好的焊缝较为困难，电子束焊接封装过程中产生高温也可能会使钛锆钼合金的组织和性能发生明显改变。电子束焊接也会增加工艺复杂性和制造成本。并且，钛锆钼合金具有在高温条件下易氧化挥发的高温特性，常规大气中锻焊构筑工艺不适用于钛锆钼合金。因此，上述基于锻焊的构筑成形工艺并不适合钛锆钼合金，需要发展适于制备大型钛锆钼合金材料的方法。
发明内容
鉴于现有技术的上述问题，本申请提供一种用于等温锻造大型模具坯料的增材制备方法，其能够有效减弱钛锆钼合金坯料中组织、成分、性能上的不均匀对大尺寸合金使用性能的影响，尤其适于制备大型钛锆钼模具坯料。
为了达到上述目的，本申请提供一种用于等温锻造的大型模具坯料的制备方法，其包括以下步骤：
-基于预定形状，分别制备多个厚度为20-100毫米的钛锆钼合金板状基元；
-基于预定形状，分别制备多个厚度为40-150微米的钽、铌钨合金或钽钨合金的箔状中间层；
-基于预定构造，依次装配所述钛锆钼合金板状基元和所述箔状中间层以形成装配体，使得所述装配体中所述箔状中间层夹在所述钛锆钼合金板状基元之间；
-借助于真空扩散焊炉，在低于钛锆钼合金再结晶温度20-100℃的连接温度、10 -3-10 -2Pa的真空度的条件下对所述装配体施加不低于3小时的连接时长的6-9MPa的轴向压力，使所述钛锆钼合金板状基元和所述箔状中间层发生扩散连接，以获得初级坯；
-在低于钛锆钼合金再结晶温度50-150℃的均匀化温度、真空或惰性气体保护的条件下，对所述初级坯进行均匀化时长为2-24小时的均匀化化处理，以均匀所述初级坯中连接界面处的组织、成分；
-冷却经过均匀化处理的初级坯料，以获得模具坯料。
通过利用扩散连接技术，采用钽、铌钨合金或钽钨合金的箔状材料作为中间层，增 加均匀化过程，改进了构筑成形的工艺，实现了用钛锆钼合金制备大型模具坯料。在不受理论束缚的情况下，相信根据本申请的增材制备方法促进了钛锆钼合金板状基元的钼元素与箔状中间层的金属元素之间的互扩散，在基元与中间层的连接界面处形成扩散层，经由箔状中间层有效实现了多个基元的相互连接，从而能够利用构筑成形的工艺实现了钛锆钼合金的大型模具坯料的制备。此外，由于本申请的扩散连接和均匀化处理的温度均低于钛锆钼合金的再结晶温度，因此本申请的增材制备方法不会对钛锆钼合金板状基元的组织和性能造成明显改变。
在本申请一种可能的实现方式中，在所述制备多个厚度为30-100毫米的钛锆钼合金板状基元中，对所述钛锆钼合金板状基元基元进行机械加工、预磨和抛光，使得所述钛锆钼合金板状基元与所述箔状中间层的连接面的粗糙度Ra为0.4至0.8，并使得各所述连接面与钛锆钼合金板状基元受到所述轴向压力的受压面之间的平行度小于0.02毫米。
在本申请一种可能的实现方式中，所述钽为纯度≥99.5％的纯钽，铌钨合金或钽钨合金为Nb-(2-10)W或Ta-(2-10)W(wt％)。
由上，通过进一步对箔状中间层的限定，有利于形成箔状中间层和钛锆钼合金板状基元之间的良好互扩散，从而进一步提高模具在高温下的性能。
在本申请一种可能的实现方式中，在制备多个厚度为60-80微米的钽、铌钨合金或钽钨合金的箔状中间层中，用10wt％盐酸浸泡所述箔状中间层10分钟，然后用酒精或丙酮超声波清洗所述箔状中间层。
由上，通过进一步对钛锆钼合金板状基元和箔状中间层的制备的限定，使得待连接面之间和连接面与受压面之间具有特定的平行度，待连接面具有特定的粗糙度和清洁度，有利于提高基元与中间层之间的连接质量，使得模具在高温下的性能更好。
在本申请一种可能的实现方式中，所述连接温度为低于钛锆钼合金再结晶温度20-60℃的温度，所述轴向压力为7-9MPa，所述连接时长为3-6小时。
在本申请一种可能的实现方式中，所述均匀化温度为低于钛锆钼合金再结晶温度80-150℃的温度，所述均匀化时长为5-12小时。
在本申请一种可能的实现方式中，在冷却经过均匀化处理的初级坯料中，以2-6℃/分钟的冷却速率从所述均匀化温度冷却至1000℃，以10-15℃/分钟的冷却速率从1000℃冷却至500℃。
在本申请一种可能的实现方式中，在冷却经过均匀化处理的初级坯料中，在冷却至500℃后，在温度为500℃的条件下保持1小时，以去除由冷却引起的应力。
由上，通过进一步限定连接温度、轴向连接压力、连接时长、均匀化温度、均匀化时长、冷却速率等工艺参数，有利于进一步促进钛锆钼合金基元和箔状中间层之间的钼元素与中间层金属元素的互扩散，进一步提升中间层的钼含量，从而进一步提高模具在高温下的性能。
在本申请一种可能的实现方式中，均匀化和冷却过程是在真空扩散炉中进行。换句话说，可以通过调整真空扩散炉的温度来在加压连接后直接进行均匀化和随后的受控冷却。
在本申请一种可能的实现方式中，均匀化和冷却过程是在真空炉或气氛保护炉中进行。换句话说，需要等待真空扩散炉冷却以取出接头后，在真空炉或气氛保护炉中完成后续的均匀化和受控冷却过程。该方法可缩短真空扩散焊炉使用时间，提高生产效率。
本申请的上述内容在以下参照附图的多个实施例的描述中会更加简明易懂。
附图说明
以下将提供本申请的附图，这些附图仅为了以更直观的形式体现本申请，它们是示例性的，并不意图限制本申请的范围。
图1是根据本申请一个实施方式的装配体的构造示意图；
图2是根据本申请一个实施方式的扩散连接的示意图；
图3是根据本申请一个实施方式的均匀化处理的示意图；
图4是根据本申请一个实施方式的模具坯料的构造示意图。
具体实施方式
为使本申请更加容易理解，下面结合具体实施例，进一步阐述本申请。本申请所述的实验方法，若无特殊说明，均为常规方法；所述的材料，若无特殊说明，均可从商业途径获得。除非另有定义，本文所使用的所有的技术和科学术语与属于本申请的技术领域的技术人员通常理解的含义相同。如有不一致，以本说明书中所说明的含义或者根据本说明书中记载的内容得出的含义为准。另外，本文中所使用的术语只是为了 描述本申请实施方式的目的，不是意图限制本申请。
为了准确地对本申请中的技术内容进行叙述，以及为了准确地理解本发明，在对具体实施方式进行说明之前先对本说明书中所使用的词语和术语给出如下的解释说明或定义。
本说明书中使用的词语“一个实施方式”或“实施方式”意味着与该实施方式结合描述的特定特征、步骤或特性包括在本发明的至少一个实施方式中。因此，在本说明书各处出现的用语“在一个实施方式中”或“在实施方式中”并不一定都指同一实施方式，但可以指同一实施方式。此外，在一个或多个实施方式中，能够以任何适当的方式组合各特定特征、步骤或特性，如从本申请对本领域的普通技术人员显而易见的那样。
说明书和权利要求书中使用的术语“真空扩散焊炉”是能够为工件提供真空环境的同时对工件施加压力的设备。
说明书和权利要求书中使用的术语“真空加热炉”是能够为工件提供真空环境的设备。说明书和权利要求书中使用的术语“气氛保护炉”是能够为工件提供惰性气体环境的设备。
说明书和权利要求书中使用的术语“钛锆钼合金”，又称TZM合金，其成分为0.4wt％～0.55wt％钛、0.06wt％～0.12wt％锆和0.01wt％～0.04wt％碳。一方面，钛和锆元素溶解入钼基体使晶格发生畸变，实现钛锆钼合金的固溶强化；另一方面，钛分别和锆元素碳元素反应形成细小而弥散分布的TiC和ZrC颗粒，实现第二相强化。由于合金化的作用，TZM合金除具有金属钼所具有的熔点高、膨胀系数小、蒸汽压低、导电导热性能好的特点外，TZM合金具有更高的再结晶温度(1350℃-1400℃)，更优异的耐高温力学性能和腐蚀性能。
说明书和权利要求书中使用的术语“扩散连接”是在高温和压力的作用下，使被连接表面发生塑性变形而紧密接触，并且经一定时间的原子间互扩散从而形成可靠接头的工艺方法。该方法特别适用于制备连接面积较大，尺寸精度和力学性能要求较高的接头。
说明书和权利要求书中使用的术语“等温锻造”是使模具与成形件处于基本相同温度的一种锻造技术。
说明书中使用的术语“构筑成形”是一种采用多块体积较小的金属坯作为构筑基元制成大型金属坯的增材制造方法。
说明书和权利要求书中涉及的词语“轴向”是垂直于钛锆钼合金板状基元与箔中间层接触的接触面的方向。
将结合图1-4详细说明本申请的技术方案。
图1示出了根据本申请一个实施方式的截面为正方形的装配体3。如图1所示，装配体3由四个钛锆钼合金板状基元1和三个箔状中间层2构成，箔状中间层2分别夹在钛锆钼合金板状基元1之间。在该实施方式中，将各钛锆钼合金板状基元1制备为形状一致，并且将各箔状中间层2制备为形状一致，以形成如此截面的装配体3。应当理解，在本申请的其他实施方式中，可以将各钛锆钼合金板状基元1制备为形状不一致，和/或将各箔状中间层2制备为形状不一致，以形成所需形状的截面，从而形成所需构造的装配体3。例如，可以将各钛锆钼合金板状基元1和箔状中间层2制备成不同的形状，使得装配3在从上到下的厚度方向上具有平滑的曲线轮廓。例如，可以将其中一些钛锆钼合金板状基元1和箔状中间层2制备成中空的形状，使得装配体3具有中空腔体，从而使得作为模具的模具坯料能够利用中空腔体制备成型件。
图2示出了根据本申请一个实施方式的扩散连接的示意图。在将装配体3放入真空扩散炉11后，启动真空扩散炉11，使得真空扩散炉11内的温度达到低于钛锆钼合金再结晶温度20-100℃的连接温度并且真空度达到10 -3-10 -2Pa。然后，使真空扩散炉11对装配体3沿着箭头示出的轴向方向对装配体3施加6-9MPa的压力，在该压力下保持不少于3小时。然后从真空扩散炉11中取出制得的初级坯4。
应当理解，在初级坯4形成时，钛锆钼合金板状基元1和箔状中间层2之间已经发生扩散连接，钛锆钼合金板状基元1中的钼元素已经扩散进入箔状中间层2，而箔状中间层2中的金属元素已经扩散进入钛锆钼合金板状基元1，从而在钛锆钼板状基元1’之间形成新的中间结构5(参见图3)。中间结构5在连接界面处具有扩散层7和可能在扩散层7之间存在的金属箔层(在其他一些实施例中，由于钼元素完全渗透进入箔状中间层形成固溶体，在这种情况下认为箔状中间层2部分或完全消失)。由于形成新的中间结构5，在微观的角度，可以认为钛锆钼板状基元1’比钛锆钼合金板状基元1薄，而金属箔层则比箔状中间层2薄。
图3示出了根据本申请一个实施方式的均匀化处理的示意图。在将初级坯4放入真空炉12或气氛保护炉13后，启动真空炉12或气氛保护炉13，使得真空度达到10 -3-10 -2Pa或者使得炉内充满惰性气体，并且使得炉温达到低于钛锆钼合金再结晶温 度50-150℃的均匀化温度。在达到该均匀化温度后，在该温度下保持2-24小时，以使得初级坯4中连接界面处的组织和成分均匀化，以形成模具坯料6(参见图4)。
图4示出了根据本申请一个实施方式的模具坯料6。模具坯料6由钛锆钼板状基元1’和扩散层7构成。在本实施例中，初级坯4在均匀化的过程中进一步发生互扩散，原本残余在于中间结构5中的金属箔层随着进一步互扩散消失完全，因此，中间结构5转变成由钼-钛/铌固溶体构成的扩散层7，从而形成模具坯料6。
在本申请一些实施方式中，尤其是以较厚钽箔、铌钨合金箔或钽钨箔作为中间层的实施方式中，模具坯料6中残余一定厚度的金属箔层。然而由于钽箔、铌-钨和钽-钨属于高熔点合金，并且具有较高的高温强度，残余的金属箔层不会显著影响模具坯料6的高温性能，同时已经形成的扩散层足够提供模具坯料6作为模具所需的力学性能。此外，在尤其是以较厚钽箔、铌-钨箔或钽-钨箔作为中间层的实施例方式中，扩散层7的元素分布不是均匀的，钼元素以梯度浓度分布。然而，由于钼元素能够改善中间层的高温性能，其中钛元素呈梯度浓度分布扩散层7不会显著影响模具坯料6的高温性能，同时已经形成的扩散层足够提供模具坯料6作为模具所需的力学性能。
总而言之，本申请具有以下优点。
本申请通过添加钽箔、铌-钨箔或钽-钨箔作为中间层，解决了钛锆钼合金高温屈服强度较高、熔点较高、连接界面塑性变形难度大、扩散难以进行的问题。
本申请通过在金属构筑工艺的基础上增加特定的中间层、均匀化过程和冷却过程，解决了钛锆钼合金大型坯料难以制备，且性能不均匀与性能较差的问题。并且，本发明中扩散连接后的坯料通过均匀化处理，使中间层元素与钛锆钼合金的钼元素充分互扩散，基元连接界面处形成明显的扩散层，结合强度较高。此外，由于中间层自身具有较高的常温与耐高温强度，并与钛锆钼合金元素充分的互扩散，每个钛锆钼基元连接界面处具有较高的常温和高温性能。
本申请的连接温度较低，低于钛锆钼合金再结晶温度20-100℃。钛锆钼合金板状基元经扩散连接后，组织和性能不发生明显改变。
本申请不需要对各基元进行真空电子束焊接封装，工艺相对简单，制造成本较低。
本申请降低了扩散连接对钛锆钼合金连接面粗糙度、连接温度、连接压力和保温时间的要求。本申请也回避粉末冶金设备能力有限，投入较高的问题。
本申请基元形状可以根据实际情况进行设计，可以实现实心、中空和不规则形状坯 料的扩散增材制造，工艺灵活适应性强。
相对于目前金属构筑方法，本申请的方法更适于高熔点难熔合金、难变形合金，如钼合金、钨合金和镍基合金的构筑制造。
为便于实施，以下描述了本申请的示例性实施例。
<实施例1>
该实例为镍基高温合金叶片用等温锻造钛锆钼模具坯料，尺寸为200×200×60毫米(长×宽×厚)。该等温锻造钛锆钼模具坯料采用3件200×200×20毫米(长×宽×厚)钛锆钼合金板状基元，2件长宽为200×200毫米、厚度为80微米的Nb-10W箔中间层，在真空扩散炉中进行扩散连接增材制造，并在真空炉中进行扩散均匀化处理。具体步骤如下：
步骤1：机械加工、预磨、抛光钛锆钼合金板状基元，使钛锆钼合金连接面粗糙度Ra为0.4-0.8，并且保证钛锆钼合金连接面与真空扩散炉的压头接触的受压面平行度小于0.02毫米。
步骤2：采用10wt％盐酸浸泡箔状中间层10分钟，用清水冲洗干净后放入酒精或丙酮中进行超声波清洗，然后风干待用。
步骤3：将步骤1和2中处理后的钛锆钼合金板状基元和Nb-10W箔中间层交错装配，堆垛成5层(钛锆钼合金板3层，箔状中间层2层)形成装配体。可通过储能焊接的方式将铌箔中间层固定在钛锆钼合金板状基元上，以防止装配时发生错位。
步骤4：将装配体放入真空扩散炉中，对装配体施加0.2MPa轴向压力以进行固定。然后开始抽真空，当真空度达到2×10 -3Pa时，开始加热升温。第一阶段以15℃/分钟的速率升温至500℃并保温30分钟，使炉内及工件表面油污挥发；第二阶段以10℃/分钟的速率升温至1000℃并保温15分钟，使炉内温度均匀；第三阶段以5分钟/分钟的速率升温至扩散连接温度1330℃。达到1330℃的连接温度后，对装配体施加9MPa轴向压力，保温6小时，以进行扩散连接，从而获得初级坯料。
步骤5：扩散连接保温结束后，将炉内温度降至1220℃，卸去轴向压力，保温8小时，进行均匀化处理，以消除连接应力，并使得连接界面处的成分及组织均匀化。
步骤6：完成均匀化保温后，开始冷却降温。在1200℃温度降温至1000℃阶段中，降温速率为2-6℃/分钟；在1000℃至500℃阶段中，降温速率为10-15℃/分钟。在温度达到500℃时，在该温度下保温1小时，以进行退火去应力处理。在去应力后随炉 冷却至室温，即获得钛锆钼合金模具坯料。
<实施例2>
该实例为镍基高温合金叶盘用等温锻造钛锆钼模具坯料，尺寸为500×500×200毫米(长×宽×厚)。该等温锻造钛锆钼模具坯料采用4件500×500×50毫米(长×宽×厚)钛锆钼合金板状基元，3件500×500毫米、厚度为60微米的Ta-2.5W箔中间层，在真空扩散炉中进行扩散连接增材制造，并在真空炉中进行扩散均匀化处理。具体步骤如下：
步骤1：机械加工、预磨、抛光钛锆钼合金板状基元，使钛锆钼合金连接面粗糙度Ra为0.4-0.8，并且保证钛锆钼合金连接面与真空扩散炉的压头接触的受压面平行度小于0.02毫米。
步骤2：采用10wt％盐酸浸泡箔状中间层10分钟，用清水冲洗干净后放入酒精或丙酮中进行超声波清洗，然后风干待用。
步骤3：将步骤1和2中处理后的钛锆钼合金板状基元和Ta-2.5W箔中间层交错装配，堆垛成7层(钛锆钼合金板4层，箔状中间层3层)形成装配体。可通过储能焊接的方式将铌箔中间层固定在钛锆钼合金板状基元上，以防止装配时发生错位。
步骤4：将装配体放入真空扩散炉中，对装配体施加0.2MPa轴向压力以进行固定。然后开始抽真空，当真空度达到2×10 -3Pa时开始加热升温。第一阶段以15℃/分钟的速率升温至500℃并保温30分钟，使炉内及工件表面油污挥发；第二阶段以10℃/分钟的速率升温至1000℃并保温15分钟，使炉内温度均匀；第三阶段以5分钟/分钟的速率升温至扩散连接温度1300℃。达到1330℃的连接温度后，对装配体施加7MPa轴向压力，保温5小时，进行扩散连接。扩散连接保温结束后，随炉空冷至室温取出初级坯料。
步骤5：将初级坯料放入气氛炉中，冲入氮气保护后，加热升温。将炉温升至1250℃，保温12小时，以进行均匀化处理。
步骤6：完成均匀化保温后，开始冷却降温。在1250℃温度降温至1000℃阶段中，降温速率为2-6℃/分钟；在1000℃至500℃阶段中，降温速率为10-15℃/分钟。在温度达到500℃时，在该温度下保温1小时，以进行退火去应力处理。去应力后随炉冷却至室温，即获得钛锆钼模具坯料。
<实施例3>
该实例为钛合金压气机盘用等温锻造钛锆钼模具坯料，尺寸为400×400×160毫米(长 ×宽×厚)。该等温锻造钛锆钼模具坯料采用4件400×400×40毫米(长×宽×厚)钛锆钼合金板状基元，3件长宽为400×400毫米、厚度为60微米的Ta-10W箔为中间层，在真空扩散炉中进行扩散连接增材制造，并在真空炉中进行扩散均匀化处理。具体步骤如下：
步骤1：机械加工、预磨、抛光钛锆钼合金板状基元，使钛锆钼合金连接面粗糙度为Ra0.4-0.8，并且保证钛锆钼合金连接面与真空扩散炉的压头接触的受压面平行度小于0.02毫米。
步骤2：采用10wt％盐酸浸泡箔状中间层10分钟，用清水冲洗干净后放入酒精或丙酮中进行超声波清洗，然后风干待用。
步骤3：将步骤1和2中处理后的钛锆钼合金板状基元和Ta-10W箔中间层交错装配，堆垛成7层(钛锆钼合金板4层，箔状中间层3层)形成装配体。可通过储能焊接的方式将钛箔中间层固定在钛锆钼合金板状基元上，以防止装配时发生错位。
步骤4：将装配体放入真空扩散炉中，对装配体施加0.2MPa轴向压力以进行固定。然后开始抽真空，当真空度达到2×10 -3Pa时开始加热升温。第一阶段以15℃/分钟的速率升温至500℃并保温30分钟，使炉内及工件表面油污挥发；第二阶段以10℃/分钟的速率升温至1000℃并保温15分钟，使炉内温度均匀；第三阶段以5分钟/分钟的速率升温至扩散连接温度1300℃。达到1300℃的连接温度后，对装配体施加6MPa轴向压力，保温3小时，进行扩散连接，从而获得初级坯料。
步骤5：扩散连接保温结束后，炉内温度降至1220℃，卸去轴向压力，保温10小时，进行均匀化处理，消除连接应力，进行连接界面处的成分及组织均匀化处理。
步骤6：完成均匀化保温后，开始降温。在1220℃温度降温至1000℃阶段中，降温速率为2-6℃/分钟；在1000℃至500℃阶段中，降温速率为10-15℃/分钟。在温度达到500℃时，在该温度下保温1小时，以进行退火去应力处理。去应力后随炉冷却至室温，即获得钛锆钼模具坯料。
<实施例4>
该实例为钛合金叶轮盘用等温锻造钛锆钼模具坯料，尺寸为φ300×150毫米(长×宽×厚)。该等温锻造钛锆钼模具坯料采用3件φ300×50毫米钛锆钼合金板状基元，2件直径为φ300mm，厚度40微米的钽箔为中间层，在真空扩散炉中进行扩散连接增材制造，并在真空炉中进行扩散均匀化处理。具体步骤如下：
步骤1：机械加工、预磨、抛光钛锆钼合金板状基元，使钛锆钼合金连接面粗糙度为Ra0.4-0.8，并且保证钛锆钼合金连接面与真空扩散炉的压头接触的受压面平行度小于0.02毫米。
步骤2：采用10wt％盐酸浸泡箔状中间层10分钟，用清水冲洗干净后放入酒精或丙酮中进行超声波清洗，然后风干待用。
步骤3：将步骤1和2中处理后的钛锆钼合金板状基元和钽箔中间层交错装配，堆垛成5层(钛锆钼合金板3层，箔状中间层2层)形成装配体。可通过储能焊接的方式将钛箔中间层固定在钛锆钼合金板状基元上，以防止装配时发生错位。
步骤4：将装配体放入真空扩散炉中，对装配体施加0.2MPa轴向压力以进行固定。然后开始抽真空，当真空度达到2×10 -3Pa时开始加热升温。第一阶段以15℃/分钟的速率升温至500℃并保温30分钟，使炉内及工件表面油污挥发；第二阶段以10℃/分钟的速率升温至1000℃并保温15分钟，使炉内温度均匀；第三阶段以5分钟/分钟的速率升温至扩散连接温度1320℃。达到1320℃的连接温度后，对装配体施加6MPa轴向压力，保温3小时，进行扩散连接，从而获得初级坯料。
步骤5：扩散连接保温结束后，炉内温度降至1200℃，卸去轴向压力，保温12小时，进行均匀化处理，消除连接应力，进行连接界面处的成分及组织均匀化处理。
步骤6：完成均匀化保温后，开始降温。在1200℃温度降温至1000℃阶段中，降温速率为2-6℃/分钟；在1000℃至500℃阶段中，降温速率为10-15℃/分钟。在温度达到500℃时，在该温度下保温1小时，以进行退火去应力处理。去应力后随炉冷却至室温，即获得钛锆钼模具坯料。
上述仅为本申请的较佳实施例及所运用技术原理。本领域技术人员会理解，本申请不限于这里所述的特定实施例，对本领域技术人员来说能够进行各种明显的变化、重新调整和替代而不会脱离本申请的保护范围。因此，虽然通过以上实施例对本申请进行了较为详细的说明，但是本申请不仅仅限于以上实施例，在不脱离本申请构思的情况下，还可以包括更多其他等效实施例，均属于本申请保护范畴。

Claims (8)

  1. 一种用于等温锻造的大型模具坯料的制备方法，其特征在于，包括以下步骤：
    基于预定形状，分别制备多个厚度为20-100毫米的钛锆钼合金板状基元；
    基于预定形状，分别制备多个厚度为40-150微米的金属铌钨合金或钽钨合金的箔状中间层；
    基于预定构造，依次装配所述钛锆钼合金板状基元和所述箔状中间层以形成装配体，使得所述装配体中所述箔状中间层夹在所述钛锆钼合金板状基元之间；
    借助于真空扩散焊炉，在低于钛锆钼合金再结晶温度20-100℃的连接温度、10 -3-10 -2Pa的真空度的条件下对所述装配体施加连接时长为不低于3小时的连接时长的6-9MPa的轴向压力，使所述钛锆钼合金板状基元和所述箔状中间层发生扩散连接，以获得初级坯；
    在低于钛锆钼合金再结晶温度50-150℃的均化温度、真空或惰性气体保护的条件下，对所述初级坯进行均匀化时长为2-24小时的均匀化处理，以均匀所述初级坯中连接界面处的组织、成分；
    冷却经过均匀化处理的初级坯料，以获得模具坯料。
  2. 根据权利要求1所述的制备方法，其特征在于，在所述制备多个厚度为20-100毫米的钛锆钼合金板状基元中，对所述钛锆钼合金板状基元进行机械加工、预磨和抛光，使得所述钛锆钼合金板状基元与所述箔状中间层的连接面的粗糙度Ra为0.4至0.8，并使得各所述连接面与钛锆钼合金板状基元受到所述轴向压力的受压面之间的平行度小于0.02毫米。
  3. 根据权利要求1所述的制备方法，其特征在于，所述钽为纯度≥99.5％的纯钽，铌钨合金或钽钨合金为Nb-(2-10)W或Ta-(2-10)W(wt％)。
  4. 根据权利要求1所述的制备方法，其特征在于，在制备多个厚度为60-80微米的纯钽、铌钨合金或钽钨合金的箔状中间层中，用10wt％盐酸浸泡所述箔状中间层10分钟，然后用酒精或丙酮超声波清洗所述箔状中间层。
  5. 根据权利要求1所述的制备方法，其特征在于，所述连接温度为低于钛锆钼合金再结晶温度20-60℃的温度，所述轴向压力为7-9MPa，所述连接时长为3-6小时。
  6. 根据权利要求1所述的制备方法，其特征在于，所述均匀化温度为低于钛锆钼合金再结晶温度80-150℃的温度，所述均匀化时长为5-12小时。
  7. 根据权利要求1所述的制备方法，其特征在于，在冷却经过均匀化处理的初级坯料中，以2-6℃/分钟的冷却速率从所述均匀化温度冷却至1000℃，以10-15℃/分钟的冷却速率从1000℃冷却至500℃。
  8. 根据权利要求7所述的制备方法，其特征在于，在冷却经过均匀化处理的初级坯料中，在冷却至500℃后，在温度为500℃的条件下保持1小时，以去除由冷却引起的应力。
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