WO2023226166A1 - 一种形状记忆陶瓷增强铝基复合材料及可调控奥氏体含量的制备方法 - Google Patents

一种形状记忆陶瓷增强铝基复合材料及可调控奥氏体含量的制备方法 Download PDF

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WO2023226166A1
WO2023226166A1 PCT/CN2022/104280 CN2022104280W WO2023226166A1 WO 2023226166 A1 WO2023226166 A1 WO 2023226166A1 CN 2022104280 W CN2022104280 W CN 2022104280W WO 2023226166 A1 WO2023226166 A1 WO 2023226166A1
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shape memory
memory ceramic
composite material
aluminum
powder
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French (fr)
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郭强
郑王树
时岩
韩一帆
倪梓鸿
贾双悦
张荻
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Shanghai Jiao Tong University
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    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
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    • 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
    • B22F3/12—Both compacting and sintering
    • B22F3/14—Both compacting and sintering simultaneously
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
    • B22F3/12—Both compacting and sintering
    • B22F3/14—Both compacting and sintering simultaneously
    • B22F3/15—Hot isostatic pressing
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    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • 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
    • 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
    • C22C1/051—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/005—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides comprising a particular metallic binder
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/12—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on oxides
    • 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
    • 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
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
    • 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 present invention relates to the technical field of metal matrix composite materials. Specifically, it relates to a shape memory ceramic reinforced aluminum matrix composite material and a preparation method with controllable austenite content.
  • zirconium oxide (ZrO 2 )-based shape memory ceramics can generate martensite
  • phase transition temperature and stress threshold of shape memory ceramics have controlled the phase transition temperature and stress threshold of shape memory ceramics by changing element doping (such as cerium, yttrium, magnesium, etc.), giving this type of material continuously adjustable phase transition characteristics.
  • element doping such as cerium, yttrium, magnesium, etc.
  • the preparation process of this method is simple, The disadvantage is that the preparation temperature is too high, and there may be serious interface reactions (3Al+[Zr]-Al 3 Zr); the second is solid-state methods, such as external field-assisted sintering (flash sintering, discharge plasma sintering, ultra-fast sintering methods). Disadvantages This is due to the poor degree of densification and difficulty in designing composite configurations. For example, Abdizadeh et al. (Ceramics International, 2013, 39(2):2045-2050) prepared 15vol% 3YSZ particle-reinforced A356 aluminum composites through stir casting and achieved a tensile strength of 232MPa, but the article did not further study it.
  • the purpose of the present invention is to provide a shape memory ceramic reinforced Aluminum-based composite materials and preparation methods with controllable austenite content.
  • the preparation method of the present invention can evenly disperse the shape memory ceramic in the composite material, thereby achieving controllable preparation of the austenite phase content of the shape memory ceramic in the composite material at room temperature.
  • the invention provides a shape memory ceramic reinforced aluminum-based composite material.
  • the raw materials of the composite material include shape memory ceramics and aluminum powder; in the raw materials of the composite material, the mass content of the shape memory ceramic is 1 to 90%, and the remainder is The amount is aluminum powder;
  • the shape memory ceramic used is single crystal particles based on cerium-containing zirconium dioxide; its composition includes: 3 to 12 mol% CeO 2 and the balance ZrO 2 .
  • CeO 2 content in the shape memory ceramic used is less than 3 mol%, a composite material with both high density and high austenite content cannot be obtained.
  • the particle size D50 of the shape memory ceramic used is 0.2 to 2 ⁇ m, and the austenite phase proportion at room temperature is 0 to 12.3 wt%.
  • the components of the shape memory ceramic used in the raw materials of the composite material include: 6 to 12 mol% CeO 2 and the balance ZrO 2 .
  • the aluminum powder is pure aluminum powder or aluminum alloy powder, and the particle size D50 of the aluminum powder is 10 to 100 ⁇ m.
  • the shape memory ceramic in the composite material has an austenite phase proportion of 3.8 to 100 wt% at room temperature.
  • the shape memory ceramic in the composite material has an austenite phase proportion of 60 to 100 wt% at room temperature.
  • the invention also provides a preparation method of shape memory ceramic reinforced aluminum matrix composite material, which includes the following steps:
  • A1 Mix and disperse the shape memory ceramic and aluminum powder, the raw materials of the composite material, to obtain the shape memory ceramic/aluminum composite powder;
  • the mixing and dispersing step is to use a ball mill to perform uniform speed ball milling or variable speed ball milling, the speed of the ball mill is 200 to 500 rpm, and the ball milling time is not less than 3 hours.
  • the temperature range of the heat preservation is 300-600°C, and the heat preservation time is 1-2 hours.
  • the temperature range for heat preservation is 500-600°C; the CeO 2 content of the shape memory ceramic is greater than 6 mol% and less than When the CeO 2 content of the shape memory ceramic is greater than 9 mol% and less than or equal to 12 mol%, the temperature range is 300-400°C.
  • the inventor found that if the insulation temperature used is too high, the higher the cerium content, the easier it is for interfacial reactions to affect the performance of the shape memory ceramic; if the insulation temperature is too low, the shape memory ceramic cannot austenitize.
  • the present invention further optimizes the insulation temperature ranges used by shape memory ceramics with different CeO 2 contents, thereby preparing a shape memory ceramic reinforced aluminum matrix composite material with both high density and high austenite content.
  • the temperature of the heat preservation is higher than the austenite starting temperature of the shape memory ceramic.
  • the densification process adopts a sintering process
  • the pressure range used in the sintering process is 300-1000MPa. If the pressure used is too high, the mold will easily fail; if the pressure is too low, it will be difficult to retain the austenite phase due to matrix constraints.
  • the present invention can significantly increase the austenite content of the composite shape memory ceramic through heat preservation and densification processing.
  • the shape memory ceramic raw material with a CeO 2 content of 6-12 mol% can be used to make the composite after the preparation method of the present invention.
  • the austenite content reaches more than 60wt%; after adopting the optimized holding temperature, the austenite content after composite can reach 100%.
  • the sintering process is selected from any one of atmosphere sintering, vacuum hot pressing sintering, discharge ion beam sintering, and hot isostatic pressing sintering.
  • the sintering temperature used in the vacuum hot pressing sintering is consistent with the heat preservation temperature, and the sintering time is 1 to 2 hours.
  • the present invention adopts the above preparation method, can uniformly disperse reinforcement particles (shape memory ceramics) on the microstructure, and can regulate the austenite phase content of the shape memory ceramics in the composite material at room temperature.
  • the austenite phase content is The titanium content has increased.
  • the shape memory ceramics can be austenitized to a certain extent, which can avoid the interface reaction between the shape memory ceramics and aluminum and retain the structural-functional integrity of the shape memory ceramics.
  • Appropriate pressure is used in the sintering process, which can produce enough matrix restraint so that the shape memory ceramics still maintain the austenite phase after cooling, which can fully exert the stress-induced phase change effect of shape memory ceramics in composite materials and broaden the scope of shape memory ceramics.
  • the application range of the superelastic effect at room temperature saves energy and time, and is suitable for batch preparation and production.
  • the present invention has the following beneficial effects:
  • the shape memory ceramic is evenly dispersed, has high density, and maintains good structural integrity, and no brittle phase Al 3 Zr is generated.
  • the composite material prepared by the present invention can regulate the phase content of austenite, which is conducive to giving full play to the structure and phase change effects of shape memory ceramics.
  • the preparation method of the present invention has a wide range of applications, saves energy and time, and has a reliable and efficient process. It overcomes the problems of intrinsic brittleness and high phase transition temperature of shape memory ceramics, enables its large-scale preparation and application, and is conducive to large-scale production.
  • Figure 1 is a schematic flow chart of preparing shape memory ceramic reinforced aluminum matrix composite materials according to a preferred embodiment of the present invention
  • Figure 2 is the X-ray diffraction pattern of the sample in the embodiment of the present invention, in which: (a) is the original shape memory ceramic single crystal; (b) is the composite powder particles obtained after ball milling; (c) is the final shape memory ceramic reinforced aluminum matrix composite materials;
  • Figure 3 is a transmission electron microscope photograph of the sample in the embodiment of the present invention, wherein: Figure 3(a) is a transmission electron microscope picture of the shape memory ceramic reinforced aluminum matrix composite material, Figure 3(b) is a partial enlarged view, Figure 3 (c) is the shape memory ceramic-aluminum interface, and Figure 3(d) is the selected area electron diffraction pattern of the position indicated by the circle in Figure 3(c), indicating that the as-prepared shape memory ceramic is in the austenite phase.
  • the following embodiment also provides a preparation method of shape memory ceramic reinforced aluminum matrix composite material, including the following steps:
  • A1 Mix and disperse the shape memory ceramic and aluminum powder, the raw materials of the composite material, to obtain the shape memory ceramic/aluminum composite powder;
  • step A3 Densify the austenitized shape memory ceramic/aluminum composite powder to obtain a shape memory ceramic reinforced aluminum matrix composite material.
  • the mixing and dispersing step is to use a ball mill to perform uniform speed ball milling or variable speed ball milling, the speed of the ball milling is 200-500 rpm, and the ball milling time is not less than 3 hours.
  • step A1 among the raw materials of the composite material, the mass content of shape memory ceramics is 1 to 90%, and the balance is aluminum powder;
  • the shape memory ceramic is a single crystal particle based on cerium-containing zirconium dioxide; its composition includes: 3 to 12 mol% CeO 2 and the balance ZrO 2 ; the particle size D50 of the shape memory ceramic is 0.2 to 2 ⁇ m at room temperature.
  • the proportion of austenite phase below is 0 ⁇ 12.3wt%.
  • the aluminum powder is pure aluminum powder or aluminum alloy powder, and the particle size D50 of the aluminum powder is 10 to 100 ⁇ m.
  • step A2 the temperature range of the heat preservation is 300-600°C, and the heat preservation time is 1-2 hours.
  • step A3 the densification process adopts a sintering process, and the pressure range used in the sintering process is 300-1000MPa.
  • the sintering process is selected from any one of atmosphere sintering, vacuum hot pressing sintering, discharge ion beam sintering, and hot isostatic pressing sintering.
  • Shape memory ceramic reinforced aluminum matrix composite materials can be prepared using the above methods, and the shape memory ceramic content in the prepared composite material is 1-90wt%, and the austenite phase proportion at room temperature is 3.8-100wt%.
  • the metal powders used in the following examples are all injection molded.
  • the preparation method of shape memory ceramics refers to the method recorded in the patent number: US 2019/0039959 A1. All examples were carried out according to the process shown in Figure 1, and the room temperature mechanical properties of the materials in all examples were tested with reference to "GB/T228.1-2010".
  • This implementation provides a method for preparing a shape memory ceramic reinforced aluminum-based composite material (containing 30wt.% of shape memory ceramics, in which the cerium doping amount is 12 mol%), as shown in Figure 1, and the steps are as follows:
  • Figure 2 is the X-ray diffraction pattern (where: Figure 2(a) is the raw shape memory ceramic; Figure 2(b) is the composite powder particles obtained after ball milling; Figure 2(c) is the final shape memory ceramic reinforced aluminum matrix composite material .
  • Figure 3(a) is a transmission electron microscope image of the shape memory ceramic reinforced aluminum matrix composite
  • Figure 3(b) is a partial enlarged view
  • Figure 3(c) is the shape memory ceramic-aluminum interface
  • Figure 3(d) It is the selected area electron diffraction pattern of the position indicated by the circle in (c), indicating that the as-prepared shape memory ceramic is in the austenite phase.
  • the method of this comparative example is basically the same as that of Example 1, and the only difference is that no shape memory ceramic is added in this comparative example.
  • the components and mechanical properties of the finally obtained matrix material are listed in Table 1.
  • This embodiment provides a method for preparing a shape memory ceramic-reinforced aluminum-based composite material (containing 20 wt.% of shape memory ceramics, in which the cerium doping amount is 12 mol%).
  • the specific steps are basically the same as those in Example 1, with the only difference being The following is:
  • shape memory ceramic/aluminum composite powder take 12g, 10 ⁇ m pure aluminum powder (spherical powder) and 3g shape memory ceramic and place them in a planetary ball mill.
  • the components and properties of the final block are shown in Table 1.
  • This embodiment provides a method for preparing a shape memory ceramic-reinforced aluminum-based composite material (containing 10 wt.% of shape memory ceramics, in which the cerium doping amount is 12 mol%).
  • the specific steps are basically the same as those in Example 1, with the only difference being The following is:
  • shape memory ceramic/aluminum composite powder take 13.5g, 10 ⁇ m pure aluminum powder (spherical powder) and 1.5g shape memory ceramic and place them in a planetary ball mill.
  • the components and properties of the final block are shown in Table 1.
  • This implementation provides a method for preparing a shape memory ceramic reinforced aluminum-zinc-magnesium-copper matrix composite material (containing 30wt.% of shape memory ceramics, in which the cerium doping amount is 12 mol%).
  • the specific steps are as follows:
  • the above composite powder was kept at 400°C for 1 hour, degreased, annealed, and austenitized, and then sintered by vacuum hot pressing for 1 hour at 400°C and 1GPa to form a block with a diameter of 18 mm. Its components and properties are listed in in FIG. 1.
  • the method of this comparative example is basically the same as that of Example 4, and the only difference is that shape memory ceramics are not added in this comparative example.
  • the components and properties of the finally obtained aluminum-zinc-magnesium-copper alloy are listed in Table 1.
  • This embodiment provides a method for preparing a shape memory ceramic-reinforced aluminum-based composite material (containing 30 wt.% of shape memory ceramics, in which the cerium doping amount is 12 mol%).
  • the specific steps are basically the same as those in Embodiment 1. The differences are The only thing is: when preparing the shape memory ceramic/aluminum composite powder, a uniform ball mill is used, the rotation speed is 200 rpm, and the ball milling time is 12 hours.
  • the components and properties of the final block are shown in Table 1.
  • This embodiment provides a method for preparing a shape memory ceramic-reinforced aluminum-based composite material (containing 30 wt.% of shape memory ceramics, in which the cerium doping amount is 12 mol%).
  • the specific steps are basically the same as those in Embodiment 1. The differences are The only thing is: when preparing the shape memory ceramic/aluminum composite powder, a uniform ball mill is used, the rotation speed is 500 rpm, and the ball milling time is 3 hours.
  • the components and properties of the final block are shown in Table 1.
  • This embodiment provides a method for preparing a shape memory ceramic-reinforced aluminum-based composite material (containing 1 wt.% of shape memory ceramics, in which the cerium doping amount is 12 mol%).
  • the specific steps are basically the same as those in Example 1, with the only difference being that The following is:
  • shape memory ceramic/aluminum composite powder take 14.85g, 10 ⁇ m pure aluminum powder (spherical powder) and 0.15g shape memory ceramic and place them in a planetary ball mill.
  • the components and properties of the final block are shown in Table 1.
  • This implementation provides a method for preparing a shape memory ceramic reinforced aluminum-copper matrix composite material (containing 30wt.% of shape memory ceramics, in which the cerium doping amount is 12 mol%). The steps are as follows:
  • the above composite powder was kept at 400°C for 1 hour, degreased, annealed, and austenitized, and then sintered by vacuum hot pressing for 1 hour at 400°C and 1GPa to form a block with a diameter of 18 mm. Its components and properties are listed in in FIG. 1.
  • the method of this comparative example is basically the same as that of Example 8, and the only difference is that no shape memory ceramic is added in this comparative example.
  • the components and properties of the finally obtained aluminum-copper alloy are listed in Table 1.
  • This embodiment provides a method for preparing a shape memory ceramic reinforced aluminum-copper matrix composite material (containing 60wt.% of shape memory ceramics, in which the cerium doping amount is 12 mol%).
  • the specific steps are basically the same as those in Example 8, with the exception of The only difference is that when preparing shape memory ceramic/aluminum composite powder, take 6g, 10 ⁇ m aluminum-copper alloy powder and 9g shape memory ceramic and place them in a planetary ball mill.
  • the components and properties of the final block are shown in Table 1.
  • This embodiment provides a method for preparing a shape memory ceramic reinforced aluminum-copper matrix composite material (containing 90wt.% of shape memory ceramics, in which the cerium doping amount is 12 mol%).
  • the specific steps are basically the same as those in Embodiment 8, except that The only difference is: when preparing shape memory ceramic/aluminum composite powder, take 1.5g, 10 ⁇ m aluminum-copper alloy powder and 13.5g shape memory ceramic and place them in a planetary ball mill.
  • the components and properties of the final block are shown in Table 1.
  • This embodiment provides a method for preparing a shape memory ceramic-reinforced aluminum-based composite material (containing 30 wt.% of shape memory ceramics, in which the cerium doping amount is 9 mol%).
  • the specific steps are basically the same as those in Embodiment 1. The differences are The only thing is: take 10.5g, 10 ⁇ m pure aluminum powder (spherical powder) and 4.5g shape memory ceramic (composition includes: 9mol% CeO2 and the balance ZrO2 , particle size D50 is 0.5 ⁇ m) and place it in a planetary ball mill.
  • the obtained composite powder was kept at 500°C for 1 hour, degreased, annealed, and austenitized, and then sintered by vacuum hot pressing at 500°C and 300 MPa for 1 hour to form a block with a diameter of 18 mm.
  • the components and properties of the final block are shown in Table 1.
  • This embodiment provides a method for preparing a shape memory ceramic-reinforced aluminum-based composite material (containing 30 wt.% of shape memory ceramics, in which the cerium doping amount is 6 mol%).
  • the specific steps are basically the same as those in Embodiment 1. The differences are The only thing is: take 10.5g, 10 ⁇ m pure aluminum powder (spherical powder) and 4.5g shape memory ceramics (composition includes: 6mol% CeO2 and the balance ZrO2 , particle size D50 is 0.5 ⁇ m) and place it in a planetary ball mill.
  • the obtained composite powder was kept at 600°C for 1 hour, degreased, annealed, and austenitized, and then sintered by vacuum hot pressing at 600°C and 300 MPa for 1 hour to form a block with a diameter of 18 mm.
  • the components and properties of the final block are shown in Table 1.
  • This embodiment provides a method for preparing a shape memory ceramic-reinforced aluminum-based composite material (containing 30 wt.% of shape memory ceramics, in which the cerium doping amount is 6 mol%).
  • the specific steps are basically the same as those in Embodiment 1. The differences are The only thing is: take 10.5g, 10 ⁇ m pure aluminum powder (spherical powder) and 4.5g shape memory ceramics (composition includes: 6mol% CeO2 and the balance ZrO2 , particle size D50 is 0.5 ⁇ m) and place it in a planetary ball mill.
  • the obtained composite powder was kept at 500°C for 1 hour, degreased, annealed, and austenitized, and then sintered by vacuum hot pressing at 500°C and 300 MPa for 1 hour to form a block with a diameter of 18 mm.
  • the components and properties of the final block are shown in Table 1.
  • This embodiment provides a method for preparing a shape memory ceramic-reinforced aluminum-based composite material (containing 30 wt.% of shape memory ceramics, in which the cerium doping amount is 12 mol%).
  • the specific steps are basically the same as those in Embodiment 1. The differences are The only thing is: the obtained composite powder is kept at 300°C for 1 hour, degreased, annealed, and austenitized, and then sintered by vacuum hot pressing at 300°C and 1 GPa for 1 hour to form a block with a diameter of 18 mm.
  • the components and properties of the final block are shown in Table 1.
  • This embodiment provides a method for preparing a shape memory ceramic-reinforced aluminum-based composite material (containing 30 wt.% of shape memory ceramics, in which the cerium doping amount is 9 mol%).
  • the specific steps are basically the same as those in Embodiment 1. The differences are The only thing is: take 10.5g, 10 ⁇ m pure aluminum powder (spherical powder) and 4.5g shape memory ceramic (composition includes: 9mol% CeO2 and the balance ZrO2 , particle size D50 is 0.5 ⁇ m) and place it in a planetary ball mill.
  • the components and properties of the final block are shown in Table 1.
  • This embodiment provides a method for preparing a shape memory ceramic-reinforced aluminum-based composite material (containing 30 wt.% of shape memory ceramics, in which the cerium doping amount is 6 mol%).
  • the specific steps are basically the same as those in Embodiment 1. The differences are The only thing is: take 10.5g, 10 ⁇ m pure aluminum powder (spherical powder) and 4.5g shape memory ceramics (composition includes: 6mol% CeO2 and the balance ZrO2 , particle size D50 is 0.5 ⁇ m) and place it in a planetary ball mill.
  • the components and properties of the final block are shown in Table 1.
  • This embodiment provides a method for preparing a shape memory ceramic-reinforced aluminum-based composite material (containing 30 wt.% of shape memory ceramics, in which the cerium doping amount is 3 mol%).
  • the specific steps are basically the same as those in Embodiment 1. The differences are The only thing is: take 10.5g, 10 ⁇ m pure aluminum powder (spherical powder) and 4.5g shape memory ceramics (composition includes: 3mol% CeO2 and the balance ZrO2 , particle size D50 is 0.5 ⁇ m) and place them in a planetary ball mill.
  • the components and properties of the final block are shown in Table 1.
  • This embodiment provides a method for preparing a shape memory ceramic-reinforced aluminum-based composite material (containing 30 wt.% of shape memory ceramics, in which the cerium doping amount is 3 mol%).
  • the specific steps are basically the same as those in Embodiment 17. The differences are The only thing is: the obtained composite powder was kept at 600°C for 1 hour, degreased, annealed, and austenitized, and then sintered by vacuum hot pressing for 1 hour at 600°C and 600MPa to form a block with a diameter of 18 mm.
  • the components and properties of the final block are shown in Table 1.
  • This embodiment provides a method for preparing a shape memory ceramic-reinforced aluminum-based composite material (containing 30 wt.% of shape memory ceramics, in which the cerium doping amount is 9 mol%).
  • the specific steps are basically the same as those in Embodiment 11. The differences are The only thing is that the obtained composite powder is kept at 500°C for 1 hour, degreased, annealed, and austenitized, and then sintered by vacuum hot pressing for 1 hour at 500°C and 600MPa to form a block with a diameter of 18 mm.
  • the components and properties of the final block are shown in Table 1.
  • This embodiment provides a method for preparing a shape memory ceramic-reinforced aluminum-based composite material (containing 30 wt.% of shape memory ceramics, in which the cerium doping amount is 6 mol%).
  • the specific steps are basically the same as those in Embodiment 12. The differences are The only thing is: the obtained composite powder was kept at 650°C for 1 hour, degreased, annealed, and austenitized, and then sintered by vacuum hot pressing for 1 hour at 650°C and 300MPa to form a block with a diameter of 18 mm.
  • the components and properties of the final block are shown in Table 1.
  • This embodiment provides a method for preparing a shape memory ceramic-reinforced aluminum-based composite material (containing 30 wt.% of shape memory ceramics, in which the cerium doping amount is 6 mol%).
  • the specific steps are basically the same as those in Embodiment 12. The differences are The only thing is: the obtained composite powder was kept at 300°C for 1 hour, degreased, annealed, and austenitized, and then sintered by vacuum hot pressing for 1 hour at 300°C and 300MPa to form a block with a diameter of 18 mm.
  • the components and properties of the final block are shown in Table 1.
  • This embodiment provides a method for preparing a shape memory ceramic-reinforced aluminum-based composite material (containing 30 wt.% of shape memory ceramics, in which the cerium doping amount is 6 mol%).
  • the specific steps are basically the same as those in Embodiment 12. The differences are The only thing is: the obtained composite powder was kept at 600°C for 1 hour, degreased, annealed, and austenitized, and then sintered by vacuum hot pressing for 1 hour at 600°C and 100MPa to form a block with a diameter of 18 mm.
  • the components and properties of the final block are shown in Table 1.
  • This embodiment provides a method for preparing a shape memory ceramic-reinforced aluminum-based composite material (containing 30 wt.% of shape memory ceramics, in which the cerium doping amount is 12 mol%).
  • the specific steps are basically the same as those in Embodiment 14. The differences are The only thing is: the obtained composite powder is kept at 250°C for 1 hour, degreased, annealed, and austenitized, and then sintered by vacuum hot pressing for 1 hour at 250°C and 1GPa to form a block with a diameter of 18 mm.
  • the components and properties of the final block are shown in Table 1.
  • This embodiment provides a method for preparing a shape memory ceramic-reinforced aluminum-based composite material (containing 30 wt.% of shape memory ceramics, in which the cerium doping amount is 12 mol%).
  • the specific steps are basically the same as those in Embodiment 14. The differences are The only thing is: the obtained composite powder is kept at 550°C for 1 hour, degreased, annealed, and austenitized, and then sintered by vacuum hot pressing for 1 hour at 550°C and 1GPa to form a block with a diameter of 18 mm.
  • the components and properties of the final block are shown in Table 1.
  • Table 1 also provides the hardness results of the composite materials prepared in each embodiment. From an application perspective, it can be seen that the higher the hardness, the more conducive it is to load-bearing from a structural perspective, and from a functional perspective, it is more conducive to load transmission and inducing austenite transformation. Unleash phase change potential.
  • the interfacial bonding properties of the shape memory ceramic reinforced aluminum matrix composite materials prepared in the above examples are basically consistent.
  • the present invention describes a shape memory ceramic reinforced aluminum-based composite material and a preparation method with adjustable austenite content.
  • composite materials with different austenite contents at normal temperature are obtained by adjusting the temperature.
  • the austenite content of the material is increased, which can protect the structural-functional integrity of shape memory ceramics to the greatest extent, realize the large-scale preparation and application of shape memory ceramics, and broaden the scope of shape memory ceramics.
  • the application range of phase change at normal temperature is energy-saving, time-saving, safe and easy to implement, and has the potential for large-scale application.

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Abstract

一种形状记忆陶瓷增强铝基复合材料及可调控奥氏体含量的制备方法，复合材料的原料包括形状记忆陶瓷和铝粉；复合材料的原料中，形状记忆陶瓷的质量含量为1～90％，余量为铝粉；采用的形状记忆陶瓷是以含铈的二氧化锆为基的单晶颗粒；其成分包括：3～12mol％CeO 2和余量的ZrO 2。制备方法通过在制备过程中采用升温奥氏体化和致密化加工的步骤，实现了奥氏体含量的可调控制备。

Description

一种形状记忆陶瓷增强铝基复合材料及可调控奥氏体含量的制备方法 技术领域
本发明涉及金属基复合材料技术领域，具体地，涉及一种形状记忆陶瓷增强铝基复合材料及可调控奥氏体含量的制备方法。
背景技术
在温度场或力场作用下，氧化锆(ZrO 2)基形状记忆陶瓷能够发生马氏体
Figure PCTCN2022104280-appb-000001
奥氏体的可逆相变，进而引起显著的形状记忆效应或超弹性效应，具备能量耗散、相变增韧等潜在工程应用，逐渐成为21世纪新一代智能材料的热门研究对象。
自1980年代以来，研究者通过改变元素掺杂(如铈、钇、镁等)等方法，来调控形状记忆陶瓷的相变温度和应力阈值，赋予了这类材料连续可调的相变特性。例如，Swan等人(Nature,1986,322(6076):234-236)首次发现并报道9.4mol％MgO稳定的四方氧化锆多晶陶瓷能够在800℃下恢复0.5％的应变。Lai等人(Science,2013,341(6153):1505-8)发现8％CeO 2-0.5％Y 2O 3-ZrO 2微柱能够在7％应变下实现50次循环。一方面，传统的形状记忆陶瓷无法克服“尺寸-脆性”的本征矛盾，极大地限制了其发展和应用前景；另一方面，掺杂量过低导致形状记忆陶瓷动作温度窗口较高，过高容易导致能耗密度降低。如何在更小的掺杂量、更低的工作温度实现形状记忆陶瓷的奥氏体含量的可控制备成为了一大难点。
21世纪以来，颗粒增强铝基复合材料在航空航天、国防军工等高技术领域的应用与快速发展，为形状记忆陶瓷的大尺寸可逆相变研究提供了新思路和新方法。目前，尚未见有与形状记忆陶瓷增强金属基复合材料相关的文献报道。且从已有的相似文献报道中，ZrO 2/金属的制备法主要采用以下两种：一是液态法，如3D打印、搅拌铸造、无压(压力)浸渗法，该法制备过程简单，缺点是制备温度过高，可能存在严重的界面反应(3Al+[Zr]——Al 3Zr)；二是固态法，如外场辅助的烧结(闪烧、放电等离子烧结、超快烧结法)，缺点是致密化程度较差、难以对复合构型进行设计等原因。例如，Abdizadeh等人(Ceramics International,2013,39(2):2045-2050)通过搅拌铸造制备15vol％3YSZ颗粒增强A356铝复合材料，实现了232MPa的抗拉强度，但该文并没有进一步研究其相变 效应；Zhang等人(Materials Science and Engineering:A,2022,838:142792)通过选区激光熔融技术制备纳米ZrO 2颗粒增强AlSi10Mg复合材料，抗拉强度达到478.6MPa，延伸率达到10.6％，但制备态的陶瓷为单斜相，且存在严重的界面反应。
发明内容
针对形状记忆陶瓷大尺寸下可逆相变的应用瓶颈，与形状记忆陶瓷增强铝基复合材料制备过程中界面反应严重与难以奥氏体化的问题，本发明的目的在于提供一种形状记忆陶瓷增强铝基复合材料及可调控奥氏体含量的制备方法。本发明的制备方法在保证形状记忆陶瓷完整结构及性能的前提下，形状记忆陶瓷能够均匀分散在复合材料中，实现了常温下复合材料中形状记忆陶瓷的奥氏体相含量的可控制备。
为了实现上述发明目的，本发明提供以下技术方案：
本发明提供了一种形状记忆陶瓷增强铝基复合材料，所述复合材料的原料包括形状记忆陶瓷和铝粉；所述复合材料的原料中，形状记忆陶瓷的质量含量为1～90％，余量为铝粉；
所述复合材料的原料中，采用的形状记忆陶瓷是以含铈的二氧化锆为基的单晶颗粒；其成分包括：3～12mol％CeO 2和余量的ZrO 2。在本发明前期的实验中发现，所采用的形状记忆陶瓷中CeO 2的含量低于3mol％时，无法获得高致密性和高奥氏体含量兼顾的复合材料。
优选地，所述复合材料的原料中，采用的形状记忆陶瓷的粒径D50为0.2～2μm，常温下的奥氏体相占比为0～12.3wt％。
优选地，所述复合材料的原料中，采用的形状记忆陶瓷的成分包括：6～12mol％CeO 2和余量的ZrO 2。优选地，所述铝粉为纯铝粉或铝合金粉，铝粉的粒径D50为10～100μm。
优选地，所述复合材料中的形状记忆陶瓷常温下奥氏体相占比为3.8～100wt％。
优选地，所述复合材料中的形状记忆陶瓷常温下奥氏体相占比为60～100wt％。
本发明还提供了一种形状记忆陶瓷增强铝基复合材料的制备方法，包括以下步骤：
A1、将复合材料的原料形状记忆陶瓷和铝粉进行混合分散，得到形状记忆陶瓷/铝复合粉末；
A2、将形状记忆陶瓷/铝复合粉末进行升温后保温，实现奥氏体化；
A3、将奥氏体化的形状记忆陶瓷/铝复合粉末进行致密化加工，即得到形状记忆陶瓷增强铝基复合材料。
优选地，步骤A1中，所述混合分散的步骤为采用球磨机进行匀速球磨或变速球磨， 所述球磨的转速为200～500转/分钟，球磨的时间不少于3小时。
优选地，步骤A2中，所述保温的温度范围为300～600℃，保温时间为1～2小时。
优选地，所述形状记忆陶瓷的CeO 2含量为大于等于3mol％且小于等于6mol％时，采用保温的温度范围为500～600℃；所述形状记忆陶瓷的CeO 2含量为大于6mol％且小于等于9mol％时，温度范围为400～500℃；所述形状记忆陶瓷的CeO 2含量为大于9mol％且小于等于12mol％时，温度范围为300～400℃。
在发明人前期的实验中发现，若采用的保温温度过高，铈含量越高，越容易发生界面反应影响形状记忆陶瓷性能；保温温度过低，则形状记忆陶瓷无法奥氏体化。本发明进一步通过优化不同CeO 2含量的形状记忆陶瓷采用的各保温温度范围，由此制备得到了兼顾高致密度和高奥氏体含量的形状记忆陶瓷增强铝基复合材料。
优选地，步骤A2中，所述保温的温度高于所述形状记忆陶瓷的奥氏体开始温度。
优选地，步骤A3中，所述致密化加工采用烧结工艺，烧结工艺中采用的压力范围为300～1000MPa。若采用的压力过大，会导致模具容易失效；而压力过小，则会导致基体束缚难以保留奥氏体相。
本发明通过保温和致密化加工处理，可使复合后形状记忆陶瓷的奥氏体含量显著提高，采用CeO 2含量为6-12mol％的形状记忆陶瓷原料经过本发明制备方法后均可使复合后奥氏体含量达到60wt％以上；采用优化的保温温度后，均可使复合后奥氏体含量达到100％。
优选地，所述烧结工艺选自气氛烧结、真空热压烧结、放电离子束烧结、热等静压烧结中的任一种。
优选地，所述真空热压烧结采用的烧结温度与保温温度一致，烧结时间为1～2小时。
本发明采用上述制备方法，能够在微观结构上均匀分散增强体颗粒(形状记忆陶瓷)，且可调控复合材料中形状记忆陶瓷常温下奥氏体相含量，相比于单体形状记忆陶瓷，奥氏体含量均有所提高。同时，通过合理选择保温温度，使形状记忆陶瓷进行一定程度的奥氏体化，能够避免形状记忆陶瓷与铝发生界面反应，保留形状记忆陶瓷结构-功能的完整性。烧结过程采用合适的压力，能够产生足够的基体束缚，使得形状记忆陶瓷在冷却后仍然保持奥氏体相，能够充分发挥形状记忆陶瓷在复合材料中的应力诱发相变效应，拓宽了形状记忆陶瓷在常温下超弹性效应的应用范围，节能省时，适于批量制备生产。
与现有技术相比，本发明具有如下的有益效果：
(1)本发明制备的形状记忆陶瓷增强铝基复合材料中，形状记忆陶瓷分散均匀，致密度高，且结构完整性保持较好，无脆性相Al 3Zr生成。
(2)本发明制备的复合材料能够调控奥氏体的相含量，有利于充分发挥形状记忆陶瓷的结构与相变效应。
(3)本发明制备方法适用范围广，节能省时，工艺可靠高效，克服了形状记忆陶瓷本征脆性、相变温度高的问题，实现其大尺寸的制备与应用，利于规模化生产。
附图说明
通过阅读参照以下附图对非限制性实施例所作的详细描述，本发明的其它特征、目的和优点将会变得更明显：
图1为本发明一较佳实施例制备形状记忆陶瓷增强铝基复合材料的流程示意图；
图2为本发明实施例中样品的X射线衍射图谱，其中：(a)为原始形状记忆陶瓷单晶；(b)为球磨后所得复合粉末颗粒；(c)为最终的形状记忆陶瓷增强铝基复合材料；
图3为本发明实施例中样品的透射电子显微镜照片，其中：图3(a)为形状记忆陶瓷增强的铝基复合材料的透射电子显微镜图，图3(b)为局部放大图，图3(c)为形状记忆陶瓷-铝界面，图3(d)为图3(c)中圆圈所示位置的选区电子衍射图，表明制备态的形状记忆陶瓷为奥氏体相。
具体实施方式
下面结合具体实施例对本发明进行详细说明。以下实施例将有助于本领域的技术人员进一步理解本发明，但不以任何形式限制本发明。应当指出的是，对本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进。这些都属于本发明的保护范围。
以下实施例还提供了一种形状记忆陶瓷增强铝基复合材料的制备方法，包括以下步骤：
A1、将复合材料的原料形状记忆陶瓷和铝粉进行混合分散，得到形状记忆陶瓷/铝复合粉末；
A2、将形状记忆陶瓷/铝复合粉末进行升温后保温，实现奥氏体化；
A3、将奥氏体化的形状记忆陶瓷/铝复合粉末进行致密化加工，即得到形状记忆陶瓷增强铝基复合材料。优选地，步骤A1中，所述混合分散的步骤为采用球磨机进行匀速球磨或变速球磨，所述球磨的转速为200～500转/分钟，球磨的时间不少于3小时。
步骤A1中，所述复合材料的原料中，形状记忆陶瓷的质量含量为1～90％，余量为铝粉；
所述形状记忆陶瓷是以含铈的二氧化锆为基的单晶颗粒；其成分包括：3～12mol％CeO 2和余量的ZrO 2；形状记忆陶瓷的粒径D50为0.2～2μm，常温下的奥氏体相占比为0～12.3wt％。
所述铝粉为纯铝粉或铝合金粉，铝粉的粒径D50为10～100μm。
步骤A2中，所述保温的温度范围为300～600℃，保温时间为1～2小时。
步骤A3中，所述致密化加工采用烧结工艺，烧结工艺中采用的压力范围为300～1000MPa。
所述烧结工艺选自气氛烧结、真空热压烧结、放电离子束烧结、热等静压烧结中的任一种。
采用上述方法均能制备得到形状记忆陶瓷增强铝基复合材料，且制得的复合材料中的形状记忆陶瓷含量为1-90wt％，常温下奥氏体相占比为3.8～100wt％。
以下实施例中所用的金属粉末均为喷射成形，形状记忆陶瓷的制备方法引用专利号：US 2019/0039959 A1中记载的方法。所有实施例均按照图1所示的工艺进行，所有实施例中材料的室温力学性能均参照《GB/T228.1-2010》进行测试。
实施例1
本实施提供了一种形状记忆陶瓷增强的铝基复合材料(含形状记忆陶瓷30wt.％，其中铈掺杂量为12mol％)的制备方法，如图1所示，步骤如下：
取10.5g、10μm纯铝粉(球形粉末)和4.5g形状记忆陶瓷(成分包括：12mol％CeO 2和余量的ZrO 2，粒径D50为0.5μm)置于行星式球磨机中，加入0.15g硬脂酸作为球磨过程控制剂，在氩气保护下，以氧化锆球为球磨介质，球料比为10:1，以200转/min的转速球磨12h后，再以400转/min的转速球磨1h，获得形状记忆陶瓷/铝复合粉末。将所得的复合粉末在400℃下保温1h，进行脱脂、退火、奥氏体化，随后在400℃、1GPa条件下经过1h真空热压烧结制成直径18mm的块体，其组分及性能列于表1中。图2为X射线衍射图(其中：图2(a)为原料形状记忆陶瓷；图2(b)为球磨后所得复合粉末颗粒；图2(c)为最终的形状记忆陶瓷增强铝基复合材料。图3(a)为形状记忆陶瓷增强的铝基复合材料的透射电子显微镜图，图3(b)为局部放大图，图3(c)为形状记忆陶瓷-铝界面，图3(d)为(c)中圆圈所示位置的选区电子衍射图，表明制备态的形状 记忆陶瓷为奥氏体相。
比较例1
本比较例与实施例1的方法基本相同，不同之处仅在于：本比较例中不加入形状记忆陶瓷。最终得到的基体材料的组分及力学性能列于表1中。
实施例2
本实施提供了一种形状记忆陶瓷增强的铝基复合材料(含形状记忆陶瓷20wt.％，其中铈掺杂量为12mol％)的制备方法，具体步骤与实施例1基本相同，不同之处仅在于：制备形状记忆陶瓷/铝复合粉末时，取12g、10μm纯铝粉(球形粉末)和3g形状记忆陶瓷置于行星式球磨机中。制得最终的块材的组分及性能如表1所示。
实施例3
本实施提供了一种形状记忆陶瓷增强的铝基复合材料(含形状记忆陶瓷10wt.％，其中铈掺杂量为12mol％)的制备方法，具体步骤与实施例1基本相同，不同之处仅在于：制备形状记忆陶瓷/铝复合粉末时，取13.5g、10μm纯铝粉(球形粉末)和1.5g形状记忆陶瓷置于行星式球磨机中。制得最终的块材的组分及性能如表1所示。
实施例4
本实施提供了一种形状记忆陶瓷增强的铝-锌-镁-铜基复合材料(含形状记忆陶瓷30wt.％，其中铈掺杂量为12mol％)的制备方法，具体步骤如下：
取10.5g、10μm的铝-锌-镁-铜合金粉末(牌号7075铝合金)和4.5g形状记忆陶瓷(成分包括：12mol％CeO 2和余量的ZrO 2，粒径D50为0.5μm)置于行星式球磨机中，加入0.15g硬脂酸作为球磨过程控制剂，在氩气保护下，以氧化锆球为球磨介质，球料比为10:1，以200转/min的转速球磨12h后，再以400转/min的转速球磨4h，获得形状记忆陶瓷/铝复合粉末。将上述复合粉末在400℃下保温1h，进行脱脂、退火、奥氏体化，随后在400℃、1GPa条件下经过1h真空热压烧结制成直径18mm的块体，其组分及性能列于表1中。
比较例2
本比较例与实施例4的方法基本相同，不同之处仅在于：本比较例中不加入形状记 忆陶瓷。最终得到的铝-锌-镁-铜合金的组分及性能列于表1中。
实施例5
本实施例提供了一种形状记忆陶瓷增强的铝基复合材料(含形状记忆陶瓷30wt.％，其中铈掺杂量为12mol％)的制备方法，具体步骤与实施例1基本相同，不同之处仅在于：制备形状记忆陶瓷/铝复合粉末时，采用匀速球磨，转速为200转/min、球磨时间为12h。制得的最终的块材的组分及性能如表1所示。
实施例6
本实施例提供了一种形状记忆陶瓷增强的铝基复合材料(含形状记忆陶瓷30wt.％，其中铈掺杂量为12mol％)的制备方法，具体步骤与实施例1基本相同，不同之处仅在于：制备形状记忆陶瓷/铝复合粉末时，采用匀速球磨，转速为500转/min、球磨时间为3h。制得的最终的块材的组分及性能如表1所示。
实施例7
本实施提供了一种形状记忆陶瓷增强的铝基复合材料(含形状记忆陶瓷1wt.％，其中铈掺杂量为12mol％)的制备方法，具体步骤与实施例1基本相同，不同之处仅在于：制备形状记忆陶瓷/铝复合粉末时，取14.85g、10μm纯铝粉(球形粉末)和0.15g形状记忆陶瓷置于行星式球磨机中。制得的最终的块材的组分及性能如表1所示。
实施例8
本实施提供了一种形状记忆陶瓷增强的铝-铜基复合材料(含形状记忆陶瓷30wt.％，其中铈掺杂量为12mol％)的制备方法，步骤如下：
取10.5g、10μm的铝-铜合金粉末(牌号2024铝合金)和4.5g形状记忆陶瓷(成分包括：12mol％CeO 2和余量的ZrO 2，粒径D50为0.5μm，)置于行星式球磨机中，加入0.15g硬脂酸作为球磨过程控制剂，在氩气保护下，以氧化锆球为球磨介质，球料比为10:1，以200转/min的转速球磨12h后，再以400转/min的转速球磨2h，获得复合粉末。将上述复合粉末在400℃下保温1h，进行脱脂、退火、奥氏体化，随后在400℃、1GPa条件下经过1h真空热压烧结制成直径18mm的块体，其组分及性能列于表1中。
比较例3
本比较例与实施例8的方法基本相同，不同之处仅在于：本比较例中不加入形状记忆陶瓷。最终得到的铝-铜合金的组分及性能列于表1中。
实施例9
本实施提供了一种形状记忆陶瓷增强的铝-铜基复合材料(含形状记忆陶瓷60wt.％，其中铈掺杂量为12mol％)的制备方法，具体步骤与实施例8基本相同，不同之处仅在于：制备形状记忆陶瓷/铝复合粉末时，取6g、10μm的铝-铜合金粉末和9g形状记忆陶瓷置于行星式球磨机中。制得的最终的块材的组分及性能如表1所示。
实施例10
本实施提供了一种形状记忆陶瓷增强的铝-铜基复合材料(含形状记忆陶瓷90wt.％，其中铈掺杂量为12mol％)的制备方法，具体步骤与实施例8基本相同，不同之处仅在于：制备形状记忆陶瓷/铝复合粉末时，取1.5g、10μm的铝-铜合金粉末和13.5g形状记忆陶瓷置于行星式球磨机中。制得的最终的块材的组分及性能如表1所示。
实施例11
本实施例提供了一种形状记忆陶瓷增强的铝基复合材料(含形状记忆陶瓷30wt.％，其中铈掺杂量为9mol％)的制备方法，具体步骤与实施例1基本相同，不同之处仅在于：取10.5g、10μm纯铝粉(球形粉末)和4.5g形状记忆陶瓷(成分包括：9mol％CeO 2和余量的ZrO 2，粒径D50为0.5μm)置于行星式球磨机中。将所得的复合粉末在500℃下保温1h，进行脱脂、退火、奥氏体化，随后在500℃、300MPa条件下经过1h真空热压烧结制成直径18mm的块体。制得的最终的块材的组分及性能如表1所示。
实施例12
本实施例提供了一种形状记忆陶瓷增强的铝基复合材料(含形状记忆陶瓷30wt.％，其中铈掺杂量为6mol％)的制备方法，具体步骤与实施例1基本相同，不同之处仅在于：取10.5g、10μm纯铝粉(球形粉末)和4.5g形状记忆陶瓷(成分包括：6mol％CeO 2和余量的ZrO 2，粒径D50为0.5μm)置于行星式球磨机中。将所得的复合粉末在600℃下保温1h，进行脱脂、退火、奥氏体化，随后在600℃、300MPa条件下经过1h真空热压烧结制成直径18mm的块体。制得的最终的块材的组分及性能如表1所示。
实施例13
本实施例提供了一种形状记忆陶瓷增强的铝基复合材料(含形状记忆陶瓷30wt.％，其中铈掺杂量为6mol％)的制备方法，具体步骤与实施例1基本相同，不同之处仅在于：取10.5g、10μm纯铝粉(球形粉末)和4.5g形状记忆陶瓷(成分包括：6mol％CeO 2和余量的ZrO 2，粒径D50为0.5μm)置于行星式球磨机中。将所得的复合粉末在500℃下保温1h，进行脱脂、退火、奥氏体化，随后在500℃、300MPa条件下经过1h真空热压烧结制成直径18mm的块体。制得的最终的块材的组分及性能如表1所示。
实施例14
本实施例提供了一种形状记忆陶瓷增强的铝基复合材料(含形状记忆陶瓷30wt.％，其中铈掺杂量为12mol％)的制备方法，具体步骤与实施例1基本相同，不同之处仅在于：将所得的复合粉末在300℃下保温1h，进行脱脂、退火、奥氏体化，随后在300℃、1GPa条件下经过1h真空热压烧结制成直径18mm的块体。制得的最终的块材的组分及性能如表1所示。
实施例15
本实施例提供了一种形状记忆陶瓷增强的铝基复合材料(含形状记忆陶瓷30wt.％，其中铈掺杂量为9mol％)的制备方法，具体步骤与实施例1基本相同，不同之处仅在于：取10.5g、10μm纯铝粉(球形粉末)和4.5g形状记忆陶瓷(成分包括：9mol％CeO 2和余量的ZrO 2，粒径D50为0.5μm)置于行星式球磨机中。制得的最终的块材的组分及性能如表1所示。
实施例16
本实施例提供了一种形状记忆陶瓷增强的铝基复合材料(含形状记忆陶瓷30wt.％，其中铈掺杂量为6mol％)的制备方法，具体步骤与实施例1基本相同，不同之处仅在于：取10.5g、10μm纯铝粉(球形粉末)和4.5g形状记忆陶瓷(成分包括：6mol％CeO 2和余量的ZrO 2，粒径D50为0.5μm)置于行星式球磨机中。制得的最终的块材的组分及性能如表1所示。
实施例17
本实施例提供了一种形状记忆陶瓷增强的铝基复合材料(含形状记忆陶瓷30wt.％， 其中铈掺杂量为3mol％)的制备方法，具体步骤与实施例1基本相同，不同之处仅在于：取10.5g、10μm纯铝粉(球形粉末)和4.5g形状记忆陶瓷(成分包括：3mol％CeO 2和余量的ZrO 2，粒径D50为0.5μm)置于行星式球磨机中。制得的最终的块材的组分及性能如表1所示。
实施例18
本实施例提供了一种形状记忆陶瓷增强的铝基复合材料(含形状记忆陶瓷30wt.％，其中铈掺杂量为3mol％)的制备方法，具体步骤与实施例17基本相同，不同之处仅在于：所得复合粉末在600℃下保温1h，进行脱脂、退火、奥氏体化，随后在600℃、600MPa条件下经过1h真空热压烧结制成直径18mm的块体。制得的最终的块材的组分及性能如表1所示。
实施例19
本实施例提供了一种形状记忆陶瓷增强的铝基复合材料(含形状记忆陶瓷30wt.％，其中铈掺杂量为9mol％)的制备方法，具体步骤与实施例11基本相同，不同之处仅在于：所得复合粉末在500℃下保温1h，进行脱脂、退火、奥氏体化，随后在500℃、600MPa条件下经过1h真空热压烧结制成直径18mm的块体。制得的最终的块材的组分及性能如表1所示。
实施例20
本实施例提供了一种形状记忆陶瓷增强的铝基复合材料(含形状记忆陶瓷30wt.％，其中铈掺杂量为6mol％)的制备方法，具体步骤与实施例12基本相同，不同之处仅在于：所得复合粉末在650℃下保温1h，进行脱脂、退火、奥氏体化，随后在650℃、300MPa条件下经过1h真空热压烧结制成直径18mm的块体。制得的最终的块材的组分及性能如表1所示。
实施例21
本实施例提供了一种形状记忆陶瓷增强的铝基复合材料(含形状记忆陶瓷30wt.％，其中铈掺杂量为6mol％)的制备方法，具体步骤与实施例12基本相同，不同之处仅在于：所得复合粉末在300℃下保温1h，进行脱脂、退火、奥氏体化，随后在300℃、300MPa条件下经过1h真空热压烧结制成直径18mm的块体。制得的最终的块材的组分及性能 如表1所示。
实施例22
本实施例提供了一种形状记忆陶瓷增强的铝基复合材料(含形状记忆陶瓷30wt.％，其中铈掺杂量为6mol％)的制备方法，具体步骤与实施例12基本相同，不同之处仅在于：所得复合粉末在600℃下保温1h，进行脱脂、退火、奥氏体化，随后在600℃、100MPa条件下经过1h真空热压烧结制成直径18mm的块体。制得的最终的块材的组分及性能如表1所示。
实施例23
本实施例提供了一种形状记忆陶瓷增强的铝基复合材料(含形状记忆陶瓷30wt.％，其中铈掺杂量为12mol％)的制备方法，具体步骤与实施例14基本相同，不同之处仅在于：将所得的复合粉末在250℃下保温1h，进行脱脂、退火、奥氏体化，随后在250℃、1GPa条件下经过1h真空热压烧结制成直径18mm的块体。制得的最终的块材的组分及性能如表1所示。
实施例24
本实施例提供了一种形状记忆陶瓷增强的铝基复合材料(含形状记忆陶瓷30wt.％，其中铈掺杂量为12mol％)的制备方法，具体步骤与实施例14基本相同，不同之处仅在于：将所得的复合粉末在550℃下保温1h，进行脱脂、退火、奥氏体化，随后在550℃、1GPa条件下经过1h真空热压烧结制成直径18mm的块体。制得的最终的块材的组分及性能如表1所示。
表1复合材料的组分、室温力学性能及奥氏体含量
Figure PCTCN2022104280-appb-000002
Figure PCTCN2022104280-appb-000003
由表1的实施例12与13、20、21的结果对比可见，当形状记忆陶瓷中铈掺杂量为6mol％时，采用保温和热压烧结的温度为600℃时，可使复合后奥氏体含量最高，达到100％；温度在500℃时，可使复合后奥氏体含量达到63.7％；而温度在650℃或300℃时，分别由于界面反应严重与相变驱动力低，无法获得奥氏体。
实施例12与22的结果对比可见，实施例21中采用热压烧结的压力为100MPa时，其复合后奥氏体含量仅为28.7％，相比实施例12的奥氏体含量显著下降。
实施例11与15、19的结果对比可见，当形状记忆陶瓷中铈掺杂量为9mol％时，采用保温和热压烧结的温度为500℃时，可使复合后奥氏体含量进一步提高，达到100％。
表1中还提供了各实施例制备的复合材料的硬度结果，从应用角度可知，硬度越高，从结构角度越有利于承载，从功能角度越利于通过载荷传递，诱发奥氏体相变，发挥相变潜力。
以上列举的实施例所制备的形状记忆陶瓷增强铝基复合材料的界面结合性基本一致。本发明所述的一种形状记忆陶瓷增强铝基复合材料及可调控奥氏体含量的制备方法，在均匀分散形状记忆陶瓷的前提下，通过调控温度获得了常温下不同奥氏体含量的复合材料，相比于单体形状记忆陶瓷，奥氏体含量均有所提高，可最大限度保护形状记 忆陶瓷的结构-功能完整性，实现形状记忆陶瓷的大尺寸制备与应用，拓宽了形状记忆陶瓷在常温下相变的应用范围，节能省时，安全易行，具有规模化应用的潜力。
上述的对实施例的描述是为便于该技术领域的普通技术人员能理解和使用发明。熟悉本领域技术的人员显然可以容易地对这些实施例做出各种修改，并把在此说明的一般原理应用到其他实施例中而不必经过创造性的劳动。因此，本发明不限于上述实施例，本领域技术人员根据本发明的揭示，不脱离本发明范畴所做出的改进和修改都应该在本发明的保护范围之内。

Claims (10)

  1. 一种形状记忆陶瓷增强铝基复合材料，其特征在于，所述复合材料的原料包括形状记忆陶瓷和铝粉；所述复合材料的原料中，形状记忆陶瓷的质量含量为1～90％，余量为铝粉；
    所述复合材料的原料中，采用的形状记忆陶瓷是以含铈的二氧化锆为基的单晶颗粒；其成分包括：3～12mol％CeO 2和余量的ZrO 2。
  2. 根据权利要求1所述的形状记忆陶瓷增强铝基复合材料，其特征在于，所述复合材料的原料中，采用的形状记忆陶瓷的粒径D50为0.2～2μm，常温下的奥氏体相占比为0～12.3wt％。
  3. 根据权利要求1所述的形状记忆陶瓷增强铝基复合材料，其特征在于，所述铝粉为纯铝粉或铝合金粉，铝粉的粒径D50为10～100μm。
  4. 根据权利要求1所述的形状记忆陶瓷增强铝基复合材料，其特征在于，所述复合材料中的形状记忆陶瓷常温下奥氏体相占比为3.8～100wt％。
  5. 一种根据权利要求1-4任一项所述的形状记忆陶瓷增强铝基复合材料的制备方法，其特征在于，包括以下步骤：
    A1、将复合材料的原料形状记忆陶瓷和铝粉进行混合分散，得到形状记忆陶瓷/铝复合粉末；
    A2、将形状记忆陶瓷/铝复合粉末进行升温后保温，实现奥氏体化；
    A3、将奥氏体化的形状记忆陶瓷/铝复合粉末进行致密化加工，即得到形状记忆陶瓷增强铝基复合材料。
  6. 根据权利要求5所述的形状记忆陶瓷增强铝基复合材料的制备方法，其特征在于，步骤A1中，所述混合分散的步骤为采用球磨机进行匀速球磨或变速球磨，所述球磨的转速为200～500转/分钟，球磨的时间不少于3小时。
  7. 根据权利要求5所述的形状记忆陶瓷增强铝基复合材料的制备方法，其特征在于，步骤A2中，所述保温的温度范围为300～600℃，保温时间为1～2小时。
  8. 根据权利要求7所述的形状记忆陶瓷增强铝基复合材料的制备方法，其特征在于，所述形状记忆陶瓷的CeO 2含量为大于等于3mol％且小于等于6mol％时，采用保温的温度范围为500～600℃；所述形状记忆陶瓷的CeO 2含量为大于6mol％且小于等于9mol％时，温度范围为400～500℃；所述形状记忆陶瓷的CeO 2含量为大于9mol％且小 于等于12mol％时，温度范围为300～400℃。
  9. 根据权利要求5所述的形状记忆陶瓷增强铝基复合材料的制备方法，其特征在于，步骤A3中，所述致密化加工采用烧结工艺，烧结工艺中采用的压力范围为300～1000MPa。
  10. 根据权利要求9所述的形状记忆陶瓷增强铝基复合材料的制备方法，其特征在于，所述烧结工艺选自气氛烧结、真空热压烧结、放电离子束烧结、热等静压烧结中的任一种。
PCT/CN2022/104280 2022-05-23 2022-07-07 一种形状记忆陶瓷增强铝基复合材料及可调控奥氏体含量的制备方法 Ceased WO2023226166A1 (zh)

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