WO2024152500A1 - 一种颗粒增强铝基复合中间合金、铝基复合材料及其制备方法 - Google Patents

一种颗粒增强铝基复合中间合金、铝基复合材料及其制备方法 Download PDF

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WO2024152500A1
WO2024152500A1 PCT/CN2023/097080 CN2023097080W WO2024152500A1 WO 2024152500 A1 WO2024152500 A1 WO 2024152500A1 CN 2023097080 W CN2023097080 W CN 2023097080W WO 2024152500 A1 WO2024152500 A1 WO 2024152500A1
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aluminum
based composite
particle
master alloy
composite master
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French (fr)
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赵玉涛
黄璐瑶
怯喜周
赵朋飞
王涛
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Jiangsu University
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Jiangsu University
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/10—Alloys containing non-metals
    • C22C1/1036—Alloys containing non-metals starting from a melt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/02—Compacting only
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only
    • B22F3/1039—Sintering only by reaction
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/0408—Light metal alloys
    • C22C1/0416—Aluminium-based 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
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/05—Mixtures of metal powder with non-metallic powder
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • C22C32/0005—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with at least one oxide and at least one of carbides, nitrides, borides or silicides as the main non-metallic constituents
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • C22C32/001—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides
    • C22C32/0015—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides with only single oxides as main non-metallic constituents
    • C22C32/0036—Matrix based on Al, Mg, Be or alloys thereof
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • C22C32/0047—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents
    • C22C32/0073—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents only borides

Definitions

  • the invention belongs to the technical field of aluminum-based alloys, and specifically relates to a particle-reinforced aluminum-based composite master alloy, an aluminum-based composite material and a preparation method thereof.
  • 7000 series aluminum alloys Al-Zn-Mg-Cu
  • Al-Zn-Mg-Cu 7000 series aluminum alloys
  • the grains will grow and the precipitation phase will coarsen, reducing the interface strength between the precipitation phase and the aluminum matrix, thereby greatly reducing the high-temperature creep resistance of the 7000 series aluminum alloys and causing cracks.
  • the high temperature creep resistance of 7000 series aluminum alloy is mainly improved by adding nanoparticles to the 7000 series aluminum alloy; the nanoparticles are mainly aluminum oxide nanoparticles and zirconium diboride nanoparticles.
  • the added nanoparticles will agglomerate, reduce the tightness of the interface, and thus affect the high temperature creep resistance of the alloy.
  • the present invention provides a particle-reinforced aluminum-based composite master alloy, an aluminum-based composite material and a preparation method thereof. Introducing the reinforcing phase provided by the present invention into the aluminum-based alloy can significantly improve the high-temperature creep resistance of the aluminum-based composite material.
  • the present invention provides a particle-reinforced aluminum-based composite master alloy, including an aluminum oxide particle-reinforced aluminum-based composite master alloy and a nano zirconium diboride particle-reinforced aluminum-based composite master alloy; the aluminum oxide particle-reinforced aluminum-based composite master alloy includes a nano aluminum oxide particle-reinforced aluminum-based composite master alloy and a micron aluminum oxide particle-reinforced aluminum-based composite master alloy.
  • the volume ratio of the nano-alumina particles, the micron-alumina particles and the nano-zirconium diboride particles is 0.5-1:0.5-1:1.
  • the preparation method of the nano-alumina particle reinforced aluminum-based composite master alloy is The medium-high temperature hot pressing method comprises the following steps:
  • Aluminum hydroxide powder and aluminum powder are placed in a ball mill in a mass ratio of 2:5 in an argon atmosphere for ball milling, and the ball-milled mixture is dried and pressed to obtain a prefabricated block;
  • the prefabricated block is sintered under vacuum conditions to obtain the nano-alumina particle reinforced aluminum-based composite master alloy.
  • the preparation method of the micron alumina particle reinforced aluminum-based composite master alloy is an in-situ reaction method, and the in-situ reaction method comprises the following steps:
  • the mixed powder is added into aluminum melt, and reacts under the coupling of magnetic field, ultrasound and pressure field to obtain a mixed melt;
  • the mixed melt is cooled, a refining agent is added, and then slag is removed and degassing is performed to obtain a pure melt;
  • the pure melt is cast to obtain a micron alumina particle reinforced aluminum-based composite master alloy.
  • the preparation method of the nano zirconium diboride particle reinforced aluminum-based composite master alloy is an in-situ reaction method, and the in-situ reaction method comprises the following steps:
  • Potassium fluoroborate and potassium fluorozirconate are added to aluminum melt, and react under the coupling of magnetic field, ultrasound and pressure field to obtain aluminum melt containing nano zirconium diboride particles;
  • the aluminum melt containing the nano zirconium diboride particles is cooled, and then a refining agent is added to refine the aluminum melt, and then slag removal and degassing are performed to obtain a pure melt;
  • the pure melt is cast to obtain a nano zirconium diboride particle reinforced aluminum-based composite master alloy.
  • the present invention also provides an aluminum-based composite material, comprising a reinforcement phase and a 7000 series aluminum alloy, wherein the reinforcement phase is nano-aluminum oxide particles, micron-aluminum oxide particles, and nano-zirconium diboride particles; the nano-aluminum oxide particles are partially derived from the nano-aluminum oxide particle-reinforced aluminum-based composite master alloy described in the above technical solution; in the process of preparing the aluminum-based composite material, part of the aluminum hydroxide that is not completely decomposed into aluminum oxide in the nano-aluminum oxide particle-reinforced aluminum-based composite master alloy is reacted with aluminum melt through an in-situ reaction method to generate the remaining nano-aluminum oxide particles; the micron-aluminum oxide particles and nano-zirconium diboride particles are derived from the particle-reinforced aluminum-based composite master alloy described in the above technical solution;
  • the mass ratio of the reinforcement phase to the 7000 series aluminum alloy is 1:20-500.
  • the present invention also provides a method for preparing the aluminum-based composite material described in the above technical solution, comprising the following steps:
  • particle-reinforced aluminum-based composite master alloy and 7000 series aluminum alloy raw materials are mixed and smelted, they react under the coupling of magnetic field, ultrasound and pressure field to obtain a melt;
  • the melt is heat-insulated and then cast to obtain an aluminum-based composite material.
  • the frequency of the magnetic field is 15-20 Hz
  • the power of the ultrasound is 1.5-2 kW
  • the pressure of the pressure field is 0.3-0.8 MPa.
  • the three-field coupling time is 25 to 35 minutes.
  • the temperature of the heat preservation treatment is 1000-1100K, and the time of the heat preservation treatment is 1-2h.
  • the present invention provides a particle-reinforced aluminum-based composite master alloy, including an aluminum oxide particle-reinforced aluminum-based composite master alloy and a nano zirconium diboride particle-reinforced aluminum-based composite master alloy; the aluminum oxide particle-reinforced aluminum-based composite master alloy includes a nano aluminum oxide particle-reinforced aluminum-based composite master alloy and a micron aluminum oxide particle-reinforced aluminum-based composite master alloy.
  • the particle-reinforced aluminum-based composite master alloy provided by the present invention contains binary particles of aluminum oxide and zirconium diboride.
  • the binary particles as high-temperature stable phases, can hinder dislocation movement in a high-temperature environment for a long time, play an Orowan strengthening role, and can pin grain boundaries, effectively hinder grain boundary migration and coarsening, and thus inhibit grain coarsening.
  • the particle-reinforced aluminum-based composite master alloy provided by the present invention contains particles of two different sizes, nanoparticles and micron particles, which improves the problem that single nanoparticles are easy to agglomerate.
  • the present invention introduces binary particles of different sizes into the aluminum-based alloy, which can significantly improve the high-temperature creep resistance of the aluminum-based composite material.
  • the present invention introduces reinforcing particles in the form of a master alloy to avoid the problem of unsatisfactory organizational properties caused by a large amount of impurities or incomplete slag removal during the smelting process of preparing the aluminum-based composite material.
  • FIG1 is a schematic diagram of the three-field coupling effect of the embodiment, wherein the left side is a schematic diagram of the device structure, and the right side is a schematic diagram of the principle of the three-field coupling effect;
  • FIG2 is a TEM image of the aluminum-based composite material prepared in Example 1;
  • FIG3 is a comparison diagram of tensile curves of aluminum-based materials of Example 1 and Comparative Examples 1 to 2;
  • FIG4 is a comparison diagram of high temperature creep curves of the aluminum-based materials of Example 1 and Comparative Examples 1-2.
  • the present invention provides a particle-reinforced aluminum-based composite master alloy, including an aluminum oxide particle-reinforced aluminum-based composite master alloy and a nano zirconium diboride particle-reinforced aluminum-based composite master alloy;
  • the aluminum oxide particle-reinforced aluminum-based composite master alloy includes a nano aluminum oxide particle-reinforced aluminum-based composite master alloy and a micron aluminum oxide particle-reinforced aluminum-based composite master alloy.
  • the volume ratio of the nano aluminum oxide particles, the micron aluminum oxide particles and the nano zirconium diboride particles is preferably 0.5 to 1:0.5 to 1:1, more preferably 0.5:0.5:1 or 1:1:1.
  • the preparation method of the nano aluminum oxide particle-reinforced aluminum-based composite master alloy is preferably a medium-high temperature hot pressing method, and the medium-high temperature hot pressing method preferably includes the following steps:
  • Aluminum hydroxide powder and aluminum powder are placed in a ball mill in a mass ratio of 2:5 in an argon atmosphere for ball milling, and the ball-milled mixture is dried and pressed to obtain a prefabricated block;
  • the prefabricated block is sintered under vacuum conditions to obtain the nano-alumina particle reinforced aluminum-based composite master alloy.
  • the average particle size of the aluminum hydroxide powder is preferably 2 to 5 ⁇ m, more preferably 3 to 4 ⁇ m.
  • the average particle size of the aluminum powder is preferably 10 to 20 ⁇ m, more preferably 13 to 15 ⁇ m.
  • the rotation speed of the ball mill is preferably 200-500 r/min, more preferably 300-400 r/min; the time of the ball mill is preferably 5-20 h, more preferably 10-15 h.
  • the drying is preferably vacuum drying, the temperature of the vacuum drying is preferably 470-480 K, more preferably 473-475 K; the drying time is preferably 1.8-2.2 h, more preferably 2 h.
  • the pressing is preferably performed in a mold, and the compactness of the pressing is preferably above 75%, more preferably 78-85%.
  • the shape of the mold is preferably a cube, and the side length of the cube is preferably 70 mm.
  • the present invention sintered the prefabricated block under vacuum conditions to obtain the nano-alumina particle reinforced aluminum-based composite intermediate alloy.
  • the vacuum degree of the vacuum condition is preferably 8-12Pa, and more preferably 10Pa.
  • the sintering preferably includes low-temperature sintering and high-temperature sintering performed in sequence; the temperature of the low-temperature sintering is preferably 720-730K, and more preferably 723-728K; the holding time of the low-temperature sintering is preferably 1.8-2.2h, and more preferably 2h.
  • the heating rate to the low-temperature sintering temperature is preferably 8 to 12 K/s, more preferably 10 K/s.
  • the temperature of the high temperature sintering is preferably 820-830K, more preferably 823-828K; the holding time of the high temperature sintering is preferably 0.8-1.2h, more preferably 1h.
  • the temperature of the high temperature sintering is preferably increased from the low temperature sintering temperature to the high temperature sintering temperature.
  • the process preferably further comprises: cooling the system after sintering, and the temperature after cooling is preferably 293-308 K, more preferably 298-303 K.
  • the cooling is preferably carried out with the furnace.
  • the cooling is preferably carried out under a pressure of 250 MPa.
  • the preparation method of the micron alumina particle reinforced aluminum-based composite master alloy is preferably an in-situ reaction method, and the in-situ reaction method preferably includes the following steps:
  • the mixed powder is added into aluminum melt, and reacts under the coupling of magnetic field, ultrasound and pressure field to obtain a mixed melt;
  • the mixed melt is cooled, a refining agent is added, and then slag is removed and degassing is performed to obtain a pure melt;
  • the pure melt is cast to obtain a micron alumina particle reinforced aluminum-based composite master alloy.
  • the average particle size of the zirconium oxide powder is preferably 300-400 nm, more preferably 330-380 nm.
  • the average particle size of the aluminum powder is preferably 10-20 ⁇ m, more preferably 13-18 ⁇ m.
  • the mass ratio of the zirconium oxide powder to the aluminum powder is preferably 0.8-1.2:3, more preferably 1:3.
  • the mixing is preferably ball milling the zirconium oxide powder and the aluminum powder under a protective atmosphere.
  • the protective atmosphere is preferably nitrogen or argon, more preferably argon.
  • the rotation speed of the ball mill is preferably 200-500 r/min, more preferably 300-400 r/min; the ball milling time is preferably 4-16 h, more preferably 6-12 h.
  • the drying is preferably vacuum drying, the vacuum drying temperature is preferably 470-480K, more preferably 473-475K; the drying time is preferably 1.8-2.2h, more preferably 2h.
  • the present invention adds the mixed powder to the aluminum melt, reacts under the coupling of the magnetic field, ultrasound and pressure field, and obtains a mixed melt.
  • the present invention preferably melts aluminum to obtain an aluminum melt.
  • the temperature of the aluminum melt is preferably 923-933K, more preferably 925-930K.
  • the present invention preferably adds the mixed powder to the aluminum melt accompanied by stirring, and the stirring is preferably electromagnetic stirring; the electromagnetic stirring is preferably clockwise electromagnetic stirring.
  • the present invention preferably adds the mixed powder to the aluminum melt in batches; the number of batches is preferably 5-10 times, more preferably 6-8 times.
  • the present invention preferably provides a magnetic field by electromagnetic stirring, and the electromagnetic stirring is preferably alternating clockwise stirring and counterclockwise stirring, and the alternating time is preferably 4 to 6 minutes, more preferably 5 minutes.
  • the frequency of the magnetic field is preferably 15 to 20 Hz.
  • the electromagnetic stirring is turned on in the embodiment of the present invention, it is preferably kept at a magnetic field frequency of 15 Hz for 20 seconds and then the magnetic field frequency is increased to 20 Hz.
  • the power of the ultrasound is preferably 1.5 to 2 kW.
  • the power is increased to 2 kW after being kept at a power of 1.5 kW for 20 seconds;
  • the pressure of the pressure field is preferably 0.3 to 0.8 MPa, more preferably 0.5 MPa.
  • the three-field coupling is preferably carried out under a protective atmosphere, and the protective atmosphere is preferably nitrogen or argon, more preferably argon.
  • the temperature of the three-field coupling is preferably 1073 to 1573 K, more preferably 1173 to 1473 K.
  • the time of the three-field coupling is preferably 25 to 35 minutes, more preferably 30 minutes.
  • the present invention has no special limitation on the device for performing three-field coupling, as long as it can provide magnetic field, ultrasound and pressure at the same time.
  • a schematic diagram of the structure of the device for performing three-field coupling is shown in Figure 1, wherein the left side is a schematic diagram of the device structure, and the right side is a schematic diagram of the principle of three-field coupling.
  • the device for three-field coupling used in the embodiment of the present invention includes a container, an electromagnetic field is arranged on the surface of the container wall, an ultrasonic amplitude transformer is arranged in the container, and a feed port and a vent pipe are arranged at the top of the container.
  • the protective atmosphere can enter the container through the vent pipe to provide a pressure field.
  • the present invention cools the mixed melt, adds a refining agent, refines it, and then performs slag removal to obtain a pure melt.
  • the refining agent is preferably C 2 Cl 6 .
  • the mass percentage of the refining agent in the mixed melt is preferably 3-6%, more preferably 4-5%.
  • the temperature of the system after cooling is preferably 970-980 K, more preferably 973-976 K.
  • the present invention has no special requirements for the slagging and degassing, and the conventional method in the art can be used.
  • the present invention casts the pure melt to obtain a micron alumina particle reinforced aluminum-based composite master alloy.
  • the casting is preferably carried out in a mold.
  • the mold is preferably a copper mold.
  • the mold is preferably preheated before casting; the preheating temperature is preferably 520-530K, more preferably 523-526K, and the preheating time is preferably 2-4h, more preferably 3h.
  • the present invention has no special limitation on the casting, and the conventional method in the art can be used.
  • the method for preparing the nano zirconium diboride particle reinforced aluminum-based composite master alloy preferably comprises the following steps:
  • Potassium fluoroborate and potassium fluorozirconate are added into aluminum melt, and react under the coupling of magnetic field, ultrasound and pressure field to obtain a mixed melt;
  • the mixed melt is cooled, a refining agent is added, and then slag is removed and degassing is performed to obtain a pure melt;
  • the pure melt is cast to obtain a nano zirconium diboride particle reinforced aluminum-based composite master alloy.
  • potassium fluoroborate and potassium fluorozirconate are added to aluminum melt, and reacted under the coupling of magnetic field, ultrasound and pressure field to obtain a mixed melt.
  • potassium fluoroborate (KBF 4 ) and potassium fluorozirconate (K 2 ZrF 6 ) are preferably dried before mixing.
  • the drying temperature is preferably 470-480K, more preferably 473-475K; the drying time is preferably 1.8-2.2h, more preferably 2h.
  • the drying is preferably carried out in an oven.
  • the crystal water in potassium fluoroborate and potassium fluorozirconate is removed by drying.
  • aluminum is preferably melted to obtain aluminum melt.
  • the temperature of the aluminum melt is preferably 1120-1130K, more preferably 1123-1125K.
  • the process of adding potassium fluoroborate and potassium fluorozirconate to the aluminum melt is preferably accompanied by stirring, and the stirring is preferably electromagnetic stirring; the electromagnetic stirring is preferably clockwise electromagnetic stirring.
  • potassium fluoroborate and potassium fluorozirconate are preferably added to the aluminum melt in batches; the number of batches is preferably 5 to 10 times, and more preferably 6 to 8 times.
  • the frequency of the magnetic field is preferably 15 to 20 Hz, more preferably 16 to 18 Hz.
  • the present invention preferably provides a magnetic field by electromagnetic stirring, and the electromagnetic stirring is preferably alternating clockwise stirring and counterclockwise stirring, and the alternating time is preferably 4 to 6 minutes, and more preferably 5 minutes.
  • the power of the ultrasound is preferably 1.5 to 2kW. When the ultrasound is turned on in the embodiment of the present invention, it is preferably kept at 1.5kW power for 20 seconds and then the power is increased to 2kW.
  • the pressure of the pressure field is preferably 0.3 to 0.8MPa, and more preferably 0.5MPa.
  • the three-field coupling is preferably carried out under a protective atmosphere, and the protective atmosphere is preferably nitrogen or argon, and more preferably argon.
  • the temperature of the three-field coupling is preferably 1073 to 1573K, and more preferably 1173 to 1473K.
  • the time of the three-field coupling is preferably 25 to 35min, and more preferably 30min.
  • the present invention cools the mixed melt, adds a refining agent for refining, and then performs slag removal and degassing to obtain a purified melt.
  • the refining agent is preferably C 2 Cl 6 .
  • the mass percentage of the refining agent in the mixed melt is preferably 3-6%, more preferably 4-5%.
  • the temperature of the system after cooling is preferably 970-980K, more preferably 973-976K. The present invention has no special requirements for the slag removal and can be carried out in a conventional manner in the art.
  • the present invention casts the pure melt to obtain a nano zirconium diboride particle reinforced aluminum-based composite master alloy.
  • the casting is preferably carried out in a mold.
  • the mold is preferably a copper mold.
  • the mold is preferably preheated before the casting; the preheating temperature is preferably 520-530K, more preferably 523-526K.
  • the present invention has no special limitation on the casting, and the conventional method in the art can be used.
  • the present invention also provides an aluminum-based composite material, comprising a reinforcement phase and a 7000 series aluminum alloy, wherein the reinforcement phase is nano aluminum oxide particles, micron aluminum oxide particles, and nano zirconium diboride particles, wherein the nano aluminum oxide particles are partially derived from the nano aluminum oxide particle-enhanced aluminum-based composite master alloy described in the above technical solution; during the preparation of the aluminum-based composite material, part of the aluminum hydroxide that is not completely decomposed into aluminum oxide in the nano aluminum oxide particle-enhanced aluminum-based composite master alloy is reacted with aluminum melt by an in-situ reaction method to generate the remaining nano aluminum oxide particles; the nano-micron aluminum oxide particles and nano zirconium diboride particles are respectively derived from the micron aluminum oxide particle-enhanced aluminum-based composite master alloy and the nano zirconium diboride particle-enhanced aluminum-based composite master alloy described in the above technical solution.
  • the 7000 series aluminum alloy preferably includes a 7055 aluminum alloy.
  • the mass ratio of the reinforcement phase to the 7000 series aluminum alloy is 1:20 to 500, preferably It is 1:50 ⁇ 400.
  • the aluminum-based composite material provided by the invention has excellent mechanical properties and high-temperature creep resistance.
  • the present invention also provides a method for preparing the aluminum-based composite material described in the above technical solution, comprising the following steps:
  • particle-reinforced aluminum-based composite master alloy and 7000 series aluminum alloy raw materials are mixed and smelted, they react under the coupling of magnetic field, ultrasound and pressure field to obtain a melt;
  • the melt is heat-insulated and then cast to obtain an aluminum-based composite material.
  • the present invention mixes and melts a particle-reinforced aluminum-based composite master alloy and a 7000 series aluminum alloy raw material, and reacts under the coupling of a magnetic field, an ultrasound field, and a pressure field to obtain a melt.
  • the present invention has no special restrictions on the 7000 series aluminum alloy raw material, and a conventional commercial product can be used.
  • the present invention has no special requirements for the smelting, and a conventional method in the art can be used.
  • the frequency of the magnetic field is preferably 15 to 20 Hz, more preferably 16 to 18 Hz. In the embodiment of the present invention, when the magnetic field is turned on, it is preferably kept at 15 Hz for 20 seconds and then the frequency is increased to 20 Hz.
  • the magnetic field is preferably provided by electromagnetic stirring, and the electromagnetic stirring is preferably alternating clockwise stirring and counterclockwise stirring, and the alternating time is preferably 4 to 6 minutes, more preferably 5 minutes.
  • the power of the ultrasound is preferably 1.5 to 2 kW. In the embodiment of the present invention, when the ultrasound is turned on, it is preferably kept at 1.5 kW power for 20 seconds and then the power is increased to 2 kW.
  • the pressure of the pressure field is preferably 0.3 to 0.8 MPa, more preferably 0.5 MPa.
  • the three-field coupling is preferably carried out under a protective atmosphere, and the protective atmosphere is preferably nitrogen or argon, more preferably argon.
  • the temperature of the three-field coupling is preferably 1073 to 1573 K, more preferably 1173 to 1473 K.
  • the three-field coupling time is preferably 25 to 35 minutes, more preferably 30 minutes.
  • the present invention After obtaining the melt, the present invention performs heat preservation treatment on the melt and then casts it to obtain an aluminum-based composite material.
  • the heat preservation treatment temperature is preferably 1000-1100K, more preferably 1053-1080K; the heat preservation treatment time is preferably 0.8-1.2h, more preferably 1h.
  • the step of cooling the system after the heat preservation treatment is preferably further included before casting.
  • the temperature of the melt after cooling is preferably 990-993K.
  • the casting is preferably carried out in a mold, and the mold is preferably a copper mold.
  • the present invention has no special limitation on the casting, and the conventional method in the art can be used.
  • the solidification stage of the casting is preferably carried out under a protective atmosphere, and the protective atmosphere is preferably nitrogen or argon, more preferably argon; the pressure of the protective atmosphere is preferably 0.6-0.8MPa, more preferably 0.7MPa.
  • Example 1 According to the method of Example 1, a 0.5 vol.% nano-alumina particle reinforced aluminum-based composite master alloy was prepared;
  • Example 1 According to the method of Example 1, a 0.5 vol.% micron alumina particle reinforced aluminum-based composite master alloy was prepared;
  • Nano-alumina particle reinforced aluminum-based composite master alloy, micron-alumina particle reinforced aluminum-based composite The composite master alloy and the aluminum-based composite master alloy reinforced with nano zirconium diboride particles are placed in a melting furnace, the required alloy elements of the corresponding proportion of 7055 aluminum alloy are added, the three-field coupling is turned on, the ultrasonic power is maintained at 1.5 kW for 20 seconds, and the power is increased to 2 kW; the argon gas is passed and pressurized to 0.5 MPa; the magnetic field frequency is maintained at 15 Hz for 20 seconds and then the power is increased to 20 Hz, and electromagnetic stirring is performed in a cycle of stirring clockwise for 5 minutes and then counterclockwise for 5 minutes; the three-field coupling is performed at a temperature of 1053 K for 30 minutes under the combined action of magnetic field, ultrasound and pressure field; the melt after the three-field coupling is kept at 1053 K for 1 hour, and finally cooled to 993 K, and cast in a copper mold in a pressure device to obtain an aluminum-based composite material;
  • Example 1 The 7055 aluminum alloy in Example 1 is used as a comparative example.
  • Pure aluminum is placed in a melting furnace for melting to obtain aluminum melt.
  • electromagnetic stirring is turned on for clockwise electromagnetic stirring.
  • KBF4 and K2ZrF6 are kept at 473K for 2h and then added into the aluminum melt under electromagnetic stirring in 8 portions.
  • the ultrasonic power is maintained at 1.5kW for 20s and then increased to 2kW.
  • Argon gas is passed and pressurized to 0.5MPa.
  • the magnetic field frequency is maintained at 15Hz for 20s and then increased to 20Hz.
  • Electromagnetic stirring is performed in a cycle of clockwise stirring for 5min and counterclockwise stirring for 5min.
  • Three-field coupling is performed at 1053K for 30min under the combined action of magnetic field, ultrasonic and pressure field to obtain a mixed melt.
  • the mixed melt was cooled to 973K, and C 2 Cl 6 refining agent was added to the mixed melt at a ratio of 5% by mass of the refining agent to refine the mixed melt, and slag removal was performed; the mixed melt was poured into a copper mold preheated at 523K and kept warm for 2 hours to obtain a ZrB 2 /7055 aluminum-based composite material.
  • the aluminum-based composite material prepared in Example 1 was examined by transmission electron microscopy to obtain TEM images, as shown in Figure 2, where (a) is the TEM image of nano-alumina and nano-zirconium diboride, and (b) is the TEM image of micron-alumina. It can be seen from Figure 2 that the aluminum-based composite material contains zirconium diboride particles, nano-alumina particles and micron-alumina particles; the particle size of zirconium diboride particles and nano-alumina particles is 20-80nm, and the particle size of micron-alumina particles is 4-6 ⁇ m.
  • Example 1 The aluminum-based materials of Example 1 and Comparative Examples 1-2 were separated at room temperature (298K) and 473K. Axial force was applied to the samples to carry out tensile tests to detect their mechanical properties, and the results are listed in Table 1.
  • the tensile curve is drawn according to Table 1, as shown in FIG3 .
  • the strength of the aluminum-based composite material prepared in Example 1 is 10% higher than that of the aluminum alloy in Comparative Example 1 and 3% higher than that of the aluminum-based composite material in Comparative Example 2.
  • the aluminum-based composite material prepared in Example 1 has higher room temperature and high temperature tensile strength and elongation.
  • Example 1 and Comparative Examples 1-2 were subjected to high temperature creep performance testing by applying axial constant tensile stress at 573K and 70MPa stress to obtain creep curves as shown in FIG. 4 .
  • the aluminum-based composite material provided by the present invention has a lower steady-state creep rate, indicating that the aluminum-based composite material provided by the present invention has better creep resistance under high temperature environment.

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Abstract

本发明属于铝基合金技术领域，具体涉及一种颗粒增强铝基复合中间合金、铝基复合材料及其制备方法。本发明提供的颗粒增强铝基复合中间合金，包括氧化铝颗粒增强铝基复合中间合金和纳米二硼化锆颗粒增强铝基复合中间合金；所述氧化铝颗粒增强铝基复合中间合金包括纳米氧化铝颗粒增强铝基复合中间合金和微米氧化铝颗粒增强铝基复合中间合金。本发明提供的颗粒增强铝基复合中间合金包括纳米颗粒和微米颗粒两种不同尺度的颗粒，改善了单一纳米颗粒容易团聚的问题。本发明向铝基合金中引入不同尺度的双元颗粒能够显著提高铝基复合材料的高温抗蠕变性。

Description

一种颗粒增强铝基复合中间合金、铝基复合材料及其制备方法
本申请要求于2023年01月17日提交中国专利局、申请号为CN202310067435.7、发明名称为“一种颗粒增强铝基复合中间合金、铝基复合材料及其制备方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本发明属于铝基合金技术领域，具体涉及一种颗粒增强铝基复合中间合金、铝基复合材料及其制备方法。
背景技术
7000系铝合金(Al-Zn-Mg-Cu)广泛应用于军事国防、航空领域，但是传统的7000系铝合金在高温下长期承受载荷，晶粒会长大且析出相粗化，降低析出相与铝基体界面强度，从而导致7000系铝合金高温抗蠕变性能大幅降低，继而出现开裂的情况。
目前主要通过向7000系铝合金中添加纳米颗粒提高7000系铝合金高温抗蠕变性能；纳米颗粒主要为氧化铝纳米颗粒及二硼化锆纳米颗粒。但是添加的纳米颗粒会团聚，降低与界面结合紧密度，从而影响合金高温抗蠕变性能。
发明内容
有鉴于此，本发明提供了一种颗粒增强铝基复合中间合金、铝基复合材料及其制备方法，向铝基合金中引入本发明提供的增强相能够显著提高铝基复合材料的高温抗蠕变性能。
为了解决上述技术问题，本发明提供了一种颗粒增强铝基复合中间合金，包括氧化铝颗粒增强铝基复合中间合金和纳米二硼化锆颗粒增强铝基复合中间合金；所述氧化铝颗粒增强铝基复合中间合金包括纳米氧化铝颗粒增强铝基复合中间合金和微米氧化铝颗粒增强铝基复合中间合金。
优选的，所述纳米氧化铝颗粒、微米氧化铝颗粒和纳米二硼化锆颗粒的体积比为0.5～1:0.5～1:1。
优选的，所述纳米氧化铝颗粒增强铝基复合中间合金的制备方法为中高 温热压法，所述中高温热压法包括以下步骤：
将氢氧化铝粉和铝粉按2:5的质量比置于球磨罐中在氩气气氛中进行球磨，将球磨得到的混合物干燥后压制，得到预制块；
在真空条件下对所述预制块进行烧结，得到所述纳米氧化铝颗粒增强铝基复合中间合金。
优选的，所述微米氧化铝颗粒增强铝基复合中间合金的制备方法为原位反应法，所述原位反应法包括以下步骤：
将氧化锆粉末和铝粉混粉，得到混合粉末；
将所述混合粉末添加入至铝熔体中，在磁场、超声和压力场三场耦合作用下反应，得到混合熔体；
将所述混合熔体降温后加入精炼剂精炼后进行扒渣除气，得到纯净熔体；
将所述纯净熔体进行浇铸，得到微米氧化铝颗粒增强铝基复合中间合金。
优选的，所述纳米二硼化锆颗粒增强铝基复合中间合金的制备方法为原位反应法，所述原位反应法包括以下步骤：
将氟硼酸钾和氟锆酸钾加入铝熔体中，在磁场、超声和压力场三场耦合作用下反应，得到含有纳米二硼化锆颗粒的铝熔体；
将所述含有纳米二硼化锆颗粒的铝熔体降温后加入精炼剂精炼后进行扒渣除气，得到纯净熔体；
将所述纯净熔体进行浇铸，得到纳米二硼化锆颗粒增强铝基复合中间合金。
本发明还提供了一种铝基复合材料，包括增强相和7000系铝合金，所述增强相为纳米氧化铝颗粒、微米氧化铝颗粒、纳米二硼化锆颗粒；所述纳米氧化铝颗粒部分来自上述技术方案所述纳米氧化铝颗粒增强铝基复合中间合金；在制备铝基复合材料过程中，纳米氧化铝颗粒增强铝基复合中间合金中未完全分解成氧化铝的部分氢氧化铝通过原位反应方法与铝熔体反应生成剩余部分纳米氧化铝颗粒；所述微米氧化铝颗粒、纳米二硼化锆颗粒来自上述技术方案所述颗粒增强铝基复合中间合金；
所述增强相和7000系铝合金的质量比为1:20～500。
本发明还提供了上述技术方案所述铝基复合材料的制备方法，包括以下步骤：
将颗粒增强铝基复合中间合金和7000系铝合金原料混合熔炼后，在磁场、超声和压力场三场耦合作用下反应，得到熔体；
将所述熔体保温处理后进行浇铸，得到铝基复合材料。
优选的，所述磁场的频率为15～20Hz，所述超声的功率为1.5～2kW；所述压力场的压力为0.3～0.8MPa。
优选的，所述三场耦合作用的时间为25～35min。
优选的，所述保温处理的温度为1000～1100K，所述保温处理的时间为1～2h。
本发明提供了一种颗粒增强铝基复合中间合金，包括氧化铝颗粒增强铝基复合中间合金和纳米二硼化锆颗粒增强铝基复合中间合金；所述氧化铝颗粒增强铝基复合中间合金包括纳米氧化铝颗粒增强铝基复合中间合金和微米氧化铝颗粒增强铝基复合中间合金。本发明提供的颗粒增强铝基复合中间合金中含有氧化铝和二硼化锆双元颗粒，双元颗粒作为高温稳定相，可长期在高温环境中阻碍位错运动，起奥罗万强化作用，同时能够钉扎晶界，有效阻碍晶界迁移和粗化，进而抑制晶粒粗大。本发明提供的颗粒增强铝基复合中间合金含有纳米颗粒和微米颗粒两种不同尺度的颗粒，改善了单一纳米颗粒容易团聚的问题。本发明向铝基合金中引入不同尺度的双元颗粒能够显著提高铝基复合材料的高温抗蠕变性。本发明以中间合金的方式引入增强颗粒避免了在制备铝基复合材料的熔炼过程中出现大量杂质或除渣不彻底带来的组织性能不理想的问题。
附图说明
图1为实施例进行三场耦合作用的示意图，其中左侧为装置结构示意图，右侧为三场耦合作用原理示意图；
图2为实施例1制备得到的铝基复合材料的TEM图；
图3为实施例1、对比例1～2的铝基材料的拉伸曲线对比图；
图4为实施例1、对比例1～2的铝基材料的高温蠕变曲线对比图。
具体实施方式
本发明提供了一种颗粒增强铝基复合中间合金，包括氧化铝颗粒增强铝基复合中间合金和纳米二硼化锆颗粒增强铝基复合中间合金；所述氧化铝颗粒增强铝基复合中间合金包括纳米氧化铝颗粒增强铝基复合中间合金和微米氧化铝颗粒增强铝基复合中间合金。在本发明中，所述纳米氧化铝颗粒、微米氧化铝颗粒和纳米二硼化锆颗粒的体积比优选为0.5～1:0.5～1:1，更优选为0.5:0.5:1或1:1:1。本发明对所述中间合金中铝的含量无特殊限定。在本发明中，所述纳米氧化铝颗粒增强铝基复合中间合金的制备方法优选为中高温热压法，所述中高温热压法优选包括以下步骤：
将氢氧化铝粉和铝粉按2:5的质量比置于球磨罐中在氩气气氛中进行球磨，将球磨得到的混合物干燥后压制，得到预制块；
在真空条件下对所述预制块进行烧结，得到所述纳米氧化铝颗粒增强铝基复合中间合金。
本发明将氢氧化铝粉和铝粉按2:5的质量比置于球磨罐中在氩气气氛中进行球磨，将球磨得到的混合物干燥后压制，得到预制块。在本发明中，所述氢氧化铝粉的平均粒径优选为2～5μm，更优选为3～4μm。在本发明中，所述铝粉的平均粒径优选为10～20μm，更优选为13～15μm。
在本发明中，所述球磨的转速优选为200～500r/min，更优选为300～400r/min；所述球磨的时间优选为5～20h，更优选为10～15h。在本发明中，所述干燥优选为真空干燥，所述真空干燥的温度优选为470～480K，更优选为473～475K；所述干燥的时间优选为1.8～2.2h，更优选为2h。
在本发明中，所述压制优选在模具中进行，所述压制的致密度优选为75％以上，更优选为78～85％。在本发明中，所述模具的形状优选为正方体，所述正方体的边长优选为70mm。
得到预制块后，本发明在真空条件下对所述预制块进行烧结，得到所述纳米氧化铝颗粒增强铝基复合中间合金。在本发明中，所述真空条件的真空度优选为8～12Pa，更优选为10Pa。在本发明中，所述烧结优选包括依次进行的低温烧结和高温烧结；所述低温烧结的温度优选为720～730K，更优选为723～728K；所述低温烧结的保温时间优选为1.8～2.2h，更优选为2h。在 本发明中，升温至所述低温烧结温度的升温速率优选为8～12K/s，更优选为10K/s。
在本发明中，所述高温烧结的温度优选为820～830K，更优选为823～828K；所述高温烧结的保温时间优选为0.8～1.2h，更优选为1h。在本发明中，所述高温烧结的温度优选在低温烧结温度的基础上升温至高温烧结的温度。
在本发明中，所述烧结后优选还包括：将烧结后体系降温，所述降温后温度优选为293～308K，更优选为298～303K。在本发明中，所述降温优选为随炉降温。在本发明中，所述降温优选在250MPa压力条件下进行降温。
在本发明中，氢氧化铝在烧结过程中分解为氧化铝，化学反应方程式如式1所示：
2Al(OH)3＝Al2O3+3H2O式1。
在本发明中，所述微米氧化铝颗粒增强铝基复合中间合金的制备方法优选为原位反应法，所述原位反应法优选包括以下步骤：
将氧化锆粉末和铝粉混粉，得到混合粉末；
将所述混合粉末添加至铝熔体中，在磁场、超声和压力场三场耦合作用下反应，得到混合熔体；
将所述混合熔体降温后加入精炼剂精炼后进行扒渣除气，得到纯净熔体；
将所述纯净熔体进行浇铸，得到微米氧化铝颗粒增强铝基复合中间合金。
本发明将氧化锆粉末和铝粉混粉，得到混合粉末。在本发明中，所述氧化锆粉末的平均粒径优选为300～400nm，更优选为330～380nm。在本发明中，所述铝粉的平均粒径优选为10～20μm，更优选为13～18μm。在本发明中，所述氧化锆粉末和铝粉的质量比优选为0.8～1.2:3，更优选为1:3。在本发明中，所述混合优选为将氧化锆粉末和铝粉末在保护气氛下进行球磨。在本发明中，所述保护气氛优选为氮气或氩气，更优选为氩气。在本发明中，所述球磨的转速优选为200～500r/min，更优选为300～400r/min；所述球磨的时间优选为4～16h，更优选为6～12h。在本发明中，所述混合后优选还包括：将混 合得到的混合粉末进行干燥。在本发明中，所述干燥优选为真空干燥，所述真空干燥的温度优选为470～480K，更优选为473～475K；所述干燥的时间优选为1.8～2.2h，更优选为2h。
得到混合粉末后，本发明将所述混合粉末加入至铝熔体中，在磁场、超声和压力场三场耦合作用下反应，得到混合熔体。本发明优选将铝熔融得到铝熔体。在本发明中，所述铝熔体的温度优选为923～933K，更优选为925～930K。本发明将所述混合粉末加入铝熔体过程中优选伴随搅拌，所述搅拌优选为电磁搅拌；所述电磁搅拌优选为顺时针电磁搅拌。本发明优选分批次将混合粉末加入铝熔体中；所述分批次的次数优选为5～10次，更优选为6～8次。
本发明优选通过电磁搅拌的方式提供磁场，所述电磁搅拌优选为交替进行的顺时针搅拌和逆时针搅拌，所述交替的时间优选为4～6min，更优选为5min。在本发明中，所述磁场的频率优选为15～20Hz。本发明实施例开启电磁搅拌时优选在磁场频率为15Hz条件下保持20s后升高磁场频率至20Hz。在本发明中，所述超声的功率优选为1.5～2kW。本发明实施例开启超声时在功率为1.5kW条件下保持20s后升高功率至2kW；所述压力场的压力优选为0.3～0.8MPa，更优选为0.5MPa。在本发明中，所述三场耦合作用优选在保护气氛下进行，所述保护气氛优选为氮气或氩气，更优选为氩气。在本发明中，所述三场耦合作用的温度优选为1073～1573K，更优选为1173～1473K。在本发明中，所述三场耦合作用的时间优选为25～35min，更优选为30min。
本发明对进行三场耦合作用的装置无特殊限定，只要能够同时提供磁场、超声和压力即可。在本发明的实施例中，进行三场耦合作用的装置结构示意图如图1所示，其中左侧为装置结构示意图，右侧为三场耦合作用原理示意图。本发明实施例采用的三场耦合作用的装置包括容器，所述容器器壁表面设置电磁场，所述容器内设置超声变幅杆，所述容器顶端设置入料口和通气管。在本发明中，保护气氛可以由通气管进入容器提供压力场。
得到混合熔体后，本发明将所述混合熔体降温后加入精炼剂精炼后进行扒渣除气，得到纯净熔体。在本发明中，所述精炼剂优选为C2Cl6。在本发明中，所述精炼剂占混合熔体的质量百分含量优选为3～6％，更优选为4～5％。 在本发明中，所述降温后体系的温度优选为970～980K，更优选为973～976K。本发明对所述扒渣除气无特殊要求，采用本领域常规的方式即可。
得到纯净熔体后，本发明将所述纯净熔体进行浇铸，得到微米氧化铝颗粒增强铝基复合中间合金。在本发明中，所述浇铸优选在模具中进行。在本发明中，所述模具优选为铜模。在本发明中，所述浇铸前优选对模具进行预热；所述预热的温度优选为520～530K，更优选为523～526K，所述预热的时间优选为2～4h，更优选为3h。本发明对所述浇铸无特殊限定，采用本领域常规的方式即可。
在本发明中，所述纳米二硼化锆颗粒增强铝基复合中间合金的制备方法优选包括以下步骤：
将氟硼酸钾和氟锆酸钾加入铝熔体中，在磁场、超声和压力场三场耦合作用下反应，得到混合熔体；
将所述混合熔体降温后加入精炼剂精炼后进行扒渣除气，得到纯净熔体；
将所述纯净熔体进行浇铸，得到纳米二硼化锆颗粒增强铝基复合中间合金。
本发明将氟硼酸钾和氟锆酸钾加入铝熔体后，在磁场、超声和压力场三场耦合作用下反应，得到混合熔体。本发明在混合前优选对氟硼酸钾(KBF4)和氟锆酸钾(K2ZrF6)进行干燥。在本发明中，所述干燥的温度优选为470～480K，更优选为473～475K；所述干燥的时间优选为1.8～2.2h，更优选为2h。在本发明中，所述干燥优选在烘箱中进行。本发明经过干燥将氟硼酸钾和氟锆酸钾中结晶水除去。本发明优选将铝熔融得到铝熔体。在本发明中，所述铝熔体的温度优选为1120～1130K，更优选为1123～1125K。
在本发明中，将氟硼酸钾和氟锆酸钾加入铝熔体过程优选伴随搅拌，所述搅拌优选为电磁搅拌；所述电磁搅拌优选为顺时针电磁搅拌。本发明优选分批次将氟硼酸钾和氟锆酸钾加入铝熔体；所述分批次的次数优选为5～10次，更优选为6～8次。
在本发明中，所述磁场的频率优选为15～20Hz，更优选为16～18Hz。本发明实施例开启磁场时优选在15Hz频率的条件下保持20s后升高频率至 20Hz。本发明优选通过电磁搅拌的方式提供磁场，所述电磁搅拌优选为交替进行的顺时针搅拌和逆时针搅拌，所述交替的时间优选为4～6min，更优选为5min。在本发明中，所述超声的功率优选为1.5～2kW。本发明实施例开启超声时优选在1.5kW功率的条件下保持20s后升高功率至2kW。在本发明中，所述压力场的压力优选为0.3～0.8MPa，更优选为0.5MPa。在本发明中，所述三场耦合作用优选在保护气氛下进行，所述保护气氛优选为氮气或氩气，更优选为氩气。在本发明中，所述三场耦合作用的温度优选为1073～1573K，更优选为1173～1473K。在本发明中，所述三场耦合作用的时间优选为25～35min，更优选为30min。
得到混合熔体后，本发明将所述混合熔体降温后加入精炼剂精炼后进行扒渣除气，得到纯化熔体。在本发明中，所述精炼剂优选为C2Cl6。在本发明中，所述精炼剂占混合熔体的质量百分含量优选为3～6％，更优选为4～5％。在本发明中，所述降温后体系的温度优选为970～980K，更优选为973～976K。本发明对所述扒渣除气无特殊要求，采用本领域常规的方式即可。
得到纯净熔体后，本发明将所述纯净熔体进行浇铸，得到纳米二硼化锆颗粒增强铝基复合中间合金。在本发明中，所述浇铸优选在模具中进行。在本发明中，所述模具优选为铜模。在本发明中，所述浇铸前优选对模具进行预热；所述预热的温度优选为520～530K，更优选为523～526K。本发明对所述浇铸无特殊限定，采用本领域常规的方式即可。
本发明还提供了一种铝基复合材料，包括增强相和7000系铝合金，所述增强相为纳米氧化铝颗粒、微米氧化铝颗粒、纳米二硼化锆颗粒，所述纳米氧化铝颗粒部分来自上述技术方案所述纳米氧化铝颗粒增强铝基复合中间合金；在制备铝基复合材料过程中，纳米氧化铝颗粒增强铝基复合中间合金中未完全分解成氧化铝的部分氢氧化铝通过原位反应方法与铝熔体反应生成剩余部分纳米氧化铝颗粒；所述纳米微米氧化铝颗粒和纳米二硼化锆颗粒分别来自上述技术方案所述微米氧化铝颗粒增强铝基复合中间合金和纳米二硼化锆颗粒增强铝基复合中间合金。在本发明中，所述7000系铝合金优选包括7055铝合金。
在本发明中，所述增强相和7000系铝合金的质量比为1:20～500，优选 为1:50～400。
本发明提供的铝基复合材料具有优异的力学性能和高温抗蠕变性能。
本发明还提供了上述技术方案所述铝基复合材料的制备方法，包括以下步骤：
将颗粒增强铝基复合中间合金和7000系铝合金原料混合熔炼后，在磁场、超声和压力场三场耦合作用下反应，得到熔体；
将所述熔体保温处理后进行浇铸，得到铝基复合材料。
本发明将颗粒增强铝基复合中间合金和7000系铝合金原料混合熔炼后，在磁场、超声和压力场三场耦合作用下反应，得到熔体。本发明对所述7000系铝合金原料无特殊限定，采用常规市售产品即可。本发明对所述熔炼无特殊要求，采用本领域常规的方式即可。
在本发明中，所述磁场的频率优选为15～20Hz，更优选为16～18Hz。本发明实施例开启磁场时优选在15Hz频率的条件下保持20s后升高频率至20Hz。本发明优选通过电磁搅拌的方式提供磁场，所述电磁搅拌优选为交替进行的顺时针搅拌和逆时针搅拌，所述交替的时间优选为4～6min，更优选为5min。在本发明中，所述超声的功率优选为1.5～2kW。本发明实施例开启超声时优选在1.5kW功率的条件下保持20s后升高功率至2kW。在本发明中，所述压力场的压力优选为0.3～0.8MPa，更优选为0.5MPa。在本发明中，所述三场耦合作用优选在保护气氛下进行，所述保护气氛优选为氮气或氩气，更优选为氩气。在本发明中，所述三场耦合作用的温度优选为1073～1573K，更优选为1173～1473K。在本发明中，所述三场耦合作用的时间优选为25～35min，更优选为30min。
在本发明中，颗粒增强铝基复合中间合金中未完全分解的氢氧化铝会与铝基体进一步生成氧化铝颗粒，反应方程式如式2所示：
2Al(OH)3+2Al＝2Al2O3+3H2O式2。
得到熔体后，本发明将所述熔体保温处理后进行浇铸，得到铝基复合材料。在本发明中，所述保温处理的温度优选为1000～1100K，更优选为1053～1080K；所述保温处理的时间优选为0.8～1.2h，更优选为1h。
在本发明中，所述浇铸前优选还包括：将保温处理后的体系降温。在本 发明中，所述降温后熔体的温度优选为990～993K。
在本发明中，所述浇铸优选在模具中进行，所述模具优选为铜模。本发明对所述浇铸无特殊限定，采用本领域常规的方式即可。在本发明中，所述浇铸的凝固阶段优选在保护气氛下进行，所述保护气氛优选为氮气或氩气，更优选为氩气；所述保护气氛的压力优选为0.6～0.8MPa，更优选为0.7MPa。
为了进一步说明本发明，下面结合实施例对本发明提供的技术方案进行详细地描述，但不能将它们理解为对本发明保护范围的限定。
实施例1
(1)将平均粒径为3μm的氢氧化铝粉末与平均粒径为13μm的纯铝粉末按照2:5的质量比放入球磨罐中，在氩气氛中以300r/min的转速球磨15h，得到混合粉末；将混合粉末于473K真空干燥2h；
(2)将干燥后的混合粉末置于边长为70mm的正方体模具中加压至致密度为85％，得到预制块；
(3)将预制块在真空度为10Pa下按照10K/s的升温速率升温至723K保温，进行低温烧结2h后继续按照10K/s的升温速率升温至823K保温，进行高温烧结1h；在压强为250MPa的环境下随炉冷却至293K，得到纳米氧化铝颗粒增强铝基复合中间合金；
(4)将平均粒径为300nm的氧化锆粉末与平均粒径为13μm的铝粉按质量比1:3放入球磨罐中在氩气氛中在转速为400r/min的条件下球磨15h，得到混合粉末，将混合粉末于473K干燥2h；
(5)将纯铝熔炼得到铝熔体，将铝熔体降温至933K，开启电磁搅拌进行顺时针电磁搅拌，将干燥后的混合粉末分8次添加至电磁搅拌的铝熔体中；开启超声，在功率为1.5kW条件下保持20s，升高功率至2kW；通氩气加压至0.5MPa；在磁场频率为15Hz的条件下保持20s后升高功率至20Hz，按照顺时针搅拌5min后逆时针搅拌5min的循环方式进行电磁搅拌；在磁场、超声和压力场的共同作用下1573K下进行三场耦合作用30min，得到混合熔体；
(6)将混合熔体降温至973k，按照精炼剂占混合熔体质量百分含量为5％的配比向降温后的混合熔体中加入C2Cl6精炼剂精炼，进行扒渣除气；浇入 预热523k保温2h的铜模中，得到微米氧化铝颗粒增强铝基复合中间合金；
(7)将纯铝置于熔炼炉中熔炼，得到铝熔体，当铝熔体温度达到1123K，开启电磁搅拌进行顺时针电磁搅拌；将KBF4与K2ZrF6在473K条件下保温2h后分8次加入电磁搅拌的铝熔体中；开启超声，在功率为1.5kW条件下保持20s，升高功率至2kW；通氩气加压至0.5MPa；在磁场频率为15Hz的条件下保持20s后升高功率至20Hz，按照顺时针搅拌5min后逆时针搅拌5min的循环方式进行电磁搅拌；在磁场、超声和压力场的共同作用下1573K下进行三场耦合作用30min，得到混合熔体；
(8)将混合熔体降温至973k，按照精炼剂占混合熔体质量百分含量为5％的配比向降温后的混合熔体中加入C2Cl6精炼剂精炼，进行扒渣除气；浇入预热523k保温2h的铜模中，得到纳米二硼化锆颗粒增强铝基复合中间合金；
(9)将纳米氧化铝颗粒增强铝基复合中间合金、微米氧化铝颗粒增强铝基复合中间合金和纳米二硼化锆颗粒增强铝基复合中间合金置于熔炼炉中，加入所需7055铝合金相应配比合金元素，开启三场耦合；开启超声，在功率为1.5kW条件下保持20s，升高功率至2kW；通氩气加压至0.5MPa；在磁场频率为15Hz的条件下保持20s后升高功率至20Hz，按照顺时针搅拌5min后逆时针搅拌5min的循环方式进行电磁搅拌；磁场、超声和压力场的共同作用下于1053K温度下进行三场耦合作用30min；将三场耦合作用后的体系在1053K下保温1h，最后降温至993K，浇铸于压力装置内的铜模中，得到铝基复合材料；其中，纳米氧化铝颗粒占比为1vol.％，微米氧化铝颗粒占比为1vol.％，纳米二硼化锆颗粒占比为1vol.％。
实施例2
按照实施例1的方法制备0.5vol.％纳米氧化铝颗粒增强铝基复合中间合金；
按照实施例1的方法制备0.5vol.％微米氧化铝颗粒增强铝基复合中间合金；
按照实施例1的方法制备1vol.％纳米二硼化锆颗粒增强铝基复合中间合金；
将纳米氧化铝颗粒增强铝基复合中间合金、微米氧化铝颗粒增强铝基复 合中间合金和纳米二硼化锆颗粒增强铝基复合中间合金置于熔炼炉中，加入所需7055铝合金相应配比合金元素，开启三场耦合，在超声功率为1.5kW条件下保持20s，升高功率至2kW；通氩气加压至0.5MPa；在磁场频率为15Hz的条件下保持20s后升高功率至20Hz，按照顺时针搅拌5min后逆时针搅拌5min的循环方式进行电磁搅拌；磁场、超声和压力场的共同作用下于1053K温度下进行三场耦合作用30min；将三场耦合作用后的熔体在1053K下保温1h，最后降温至993K，浇铸于压力装置内的铜模中，得到铝基复合材料；其中，纳米氧化铝颗粒占比为0.5vol.％，微米氧化铝颗粒占比为0.5vol.％，纳米二硼化锆颗粒占比为1vol.％。
对比例1
以实施例1中7055铝合金作为对比例。
对比例2
将纯铝置于熔炼炉中熔炼，得到铝熔体，当铝熔体温度达到1123K，开启电磁搅拌进行顺时针电磁搅拌；将KBF4与K2ZrF6在473K条件下保温2h后分8次加入电磁搅拌的铝熔体中；在超声功率为1.5kW条件下保持20s，升高功率至2kW；通氩气加压至0.5MPa；在磁场频率为15Hz的条件下保持20s后升高功率至20Hz，按照顺时针搅拌5min后逆时针搅拌5min的循环方式进行电磁搅拌，在磁场、超声和压力场的共同作用下于1053K温度下进行三场耦合作用30min，得到混合熔体；
将混合熔体降温至973k，按照精炼剂占混合熔体的质量百分含量为5％的配比向降温后的混合熔体中加入C2Cl6精炼剂精炼，进行扒渣除气；浇入预热523k保温2h的铜模中，得到ZrB2/7055铝基复合材料。
对实施例1制备得到的铝基复合材料进行透射电镜检测，得到TEM图，如图2所示，其中(a)为纳米氧化铝和纳米二硼化锆的TEM图，(b)为微米氧化铝的TEM图。由图2可以看出铝基复合材料中含有二硼化锆颗粒、纳米氧化铝颗粒和微米氧化铝颗粒；二硼化锆颗粒和纳米氧化铝颗粒的粒径为20～80nm，微米氧化铝颗粒粒径为4～6μm。
对实施例1、对比例1～2的铝基材料在室温(298K)和473K温度下分 别施加轴向力对样品进行拉伸实验检测其力学性能，其结果列于表1中。
表1实施例1、对比例1～2的铝基材料的力学性能
根据表1绘制拉伸曲线，如图3所示。
结合表1和图3可以看出，实施例1制备得到的铝基复合材料的强度比对比例1铝合金高出10％，比对比例2的铝基复合材料高出3％。实施例1制备得到的铝基复合材料具有较高的室温和高温抗拉强度和伸长率。
对实施例1、对比例1～2的铝基材料在573K和70MPa应力作用下施加轴向恒定拉应力进行高温蠕变性能检测，得到蠕变曲线，如图4所示。
由图4可以看出本发明提供的铝基复合材料具有更低的稳态蠕变速率，说明本发明提供的铝基复合材料在高温环境下具有更好的蠕变抗力。
尽管上述实施例对本发明做出了详尽的描述，但它仅仅是本发明一部分实施例，而不是全部实施例，人们还可以根据本实施例在不经创造性前提下获得其他实施例，这些实施例都属于本发明保护范围。

Claims (16)

  1. 一种颗粒增强铝基复合中间合金，包括氧化铝颗粒增强铝基复合中间合金和纳米二硼化锆颗粒增强铝基复合中间合金；所述氧化铝颗粒增强铝基复合中间合金包括纳米氧化铝颗粒增强铝基复合中间合金和微米氧化铝颗粒增强铝基复合中间合金。
  2. 根据权利要求1所述颗粒增强铝基复合中间合金，其特征在于，所述纳米氧化铝颗粒、微米氧化铝颗粒和纳米二硼化锆颗粒的体积比为0.5～1:0.5～1:1。
  3. 根据权利要求1所述颗粒增强铝基复合中间合金，其特征在于，所述纳米氧化铝颗粒增强铝基复合中间合金的制备方法为中高温热压法，所述中高温热压法包括以下步骤：
    将氢氧化铝粉和铝粉按2:5的质量比置于球磨罐中在氩气气氛中进行球磨，将球磨得到的混合物干燥后压制，得到预制块；
    在真空条件下对所述预制块进行烧结，得到所述纳米氧化铝颗粒增强铝基复合中间合金。
  4. 根据权利要求3所述颗粒增强铝基复合中间合金，其特征在于，所述氢氧化铝粉的平均粒径为2～5μm，所述铝粉的平均粒径为10～20μm。
  5. 根据权利要求3所述颗粒增强铝基复合中间合金，其特征在于，所述压制的致密度为75％以上。
  6. 据权利要求3所述颗粒增强铝基复合中间合金，其特征在于，所述烧结包括依次进行的低温烧结和高温烧结；
    所述低温烧结的温度为720～730K，所述低温烧结的保温时间为1.8～2.2h，升温至所述低温烧结温度的升温速率为8～12K/s；
    所述高温烧结的温度为820～830K，所述高温烧结的保温时间为0.8～1.2h。
  7. 根据权利要求1所述颗粒增强铝基复合中间合金，其特征在于，所述微米氧化铝颗粒增强铝基复合中间合金的制备方法为原位反应法，所述原位反应法包括以下步骤：
    将氧化锆粉末和铝粉混粉，得到混合粉末；
    将所述混合粉末添加入至铝熔体中，在磁场、超声和压力场三场耦合作用下反应，得到混合熔体；
    将所述混合熔体降温后加入精炼剂精炼后进行扒渣除气，得到纯净熔体；
    将所述纯净熔体进行浇铸，得到微米氧化铝颗粒增强铝基复合中间合金。
  8. 根据权利要求7所述颗粒增强铝基复合中间合金，其特征在于，所述氧化锆粉末的平均粒径为300～400nm，所述铝粉的平均粒径为10～20μm；
    所述氧化锆粉末和铝粉的质量比为0.8～1.2:3。
  9. 根据权利要求7所述颗粒增强铝基复合中间合金，其特征在于，所述磁场的频率为15～20Hz，所述超声的功率为1.5～2kW，所述压力场的压力为0.3～0.8MPa；
    所述三场耦合作用的温度为1073～1573K，所述三场耦合作用的时间为25～35min。
  10. 根据权利要求1所述颗粒增强铝基复合中间合金，其特征在于，所述纳米二硼化锆颗粒增强铝基复合中间合金的制备方法为原位反应法，所述原位反应法包括以下步骤：
    将氟硼酸钾和氟锆酸钾加入铝熔体中，在磁场、超声和压力场三场耦合作用下反应，得到含有纳米二硼化锆颗粒的铝熔体；
    将所述含有纳米二硼化锆颗粒的铝熔体降温后加入精炼剂精炼后进行扒渣除气，得到纯净熔体；
    将所述纯净熔体进行浇铸，得到纳米二硼化锆颗粒增强铝基复合中间合金。
  11. 根据权利要求10所述颗粒增强铝基复合中间合金，其特征在于，所述磁场的频率为15～20Hz，所述超声的功率为1.5～2kW，所述压力场的压力为0.3～0.8MPa；
    所述三场耦合作用的温度为1073～1573K，所述三场耦合作用的时间为25～35min。
  12. 一种铝基复合材料，其特征在于，包括增强相和7000系铝合金， 所述增强相为纳米氧化铝颗粒、微米氧化铝颗粒、纳米二硼化锆颗粒；所述纳米氧化铝颗粒部分来自权利要求1～11任一项所述纳米氧化铝颗粒增强铝基复合中间合金；在制备铝基复合材料过程中，纳米氧化铝颗粒增强铝基复合中间合金中未完全分解成氧化铝的部分氢氧化铝通过原位反应方法与铝熔体反应生成剩余部分纳米氧化铝颗粒；所述微米氧化铝颗粒、纳米二硼化锆颗粒来自权利要求1～11任一项所述颗粒增强铝基复合中间合金；
    所述增强相和7000系铝合金的质量比为1:20～500。
  13. 权利要求12所述铝基复合材料的制备方法，包括以下步骤：
    将颗粒增强铝基复合中间合金和7000系铝合金原料混合熔炼后，在磁场、超声和压力场三场耦合作用下反应，得到熔体；
    将所述熔体保温处理后进行浇铸，得到铝基复合材料。
  14. 根据权利要求13所述制备方法，其特征在于，所述磁场的频率为15～20Hz，所述超声的功率为1.5～2kW；所述压力场的压力为0.3～0.8MPa。
  15. 根据权利要求13或14所述制备方法，其特征在于，所述三场耦合作用的温度为1073～1573K，所述三场耦合作用的时间为25～35min。
  16. 根据权利要求13所述制备方法，其特征在于，所述保温处理的温度为1000～1100K，所述保温处理的时间为1～2h。
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