Shape Memory Ceramic Reinforced Aluminum Matrix Composite Material and Preparation Method with Controllable Austenite Content

Abstract

An object of the present invention is to provide a shape memory ceramic reinforced aluminum-based composite material and a preparation method capable of controlling the austenite content. 【Solution means】 The raw materials of the composite material include shape memory ceramics and aluminum powder. In the raw materials of the composite material, the content of shape memory ceramics is 1 to 90% by mass, and the balance is aluminum powder. The shape memory ceramics used are single crystal particles based on cerium-containing zirconium oxide, and the composition is 3 to 12 mol% of CeO 2 and the balance of ZrO 2 and. The present invention uses the steps of austenitization and densification treatment by heating in the preparation process to realize the preparation with controllable austenite content. The shape memory ceramic reinforced aluminum-based composite material prepared according to the present invention has high density, no interfacial reaction between the matrix phase and the reinforcing material, the proportion of the austenite phase in the composite material is 3.8 to 100% by mass, and the structural-functional integrity of the shape memory ceramic in the large block is realized, saving energy and time, and is suitable for mass preparation and manufacturing.

Description

Technical Field

[0001] The present invention relates to the technical field of metal matrix composites, and particularly to a shape memory ceramic reinforced aluminum matrix composite and a preparation method capable of controlling the austenite content.

Background Art

[0002] Under the action of a temperature field or a force field, zirconia (ZrO 2 )-based shape memory ceramics can undergo a reversible martensite ←→ austenite phase transformation, thereby causing a remarkable shape memory effect or superelastic effect, and having potential engineering applications such as energy dissipation and transformation strengthening. It has gradually become a hot research object of smart materials in the 21st century.

[0003] Since the 1980s, researchers have controlled the phase transformation temperature and stress threshold of shape memory ceramics by changing methods such as element doping (cerium, yttrium, magnesium, etc.), and have continuously given adjustable phase transformation characteristics to this type of material. For example, Swan et al. (Non-Patent Document 1) discovered and reported for the first time that tetragonal zirconia polycrystalline ceramics stabilized with 9.4 mol% of MgO can recover 0.5% strain at 800 °C. Lai et al. (Non-Patent Document 2) discovered that 8% CeO 2 -0.5% Y 2 O 3 -ZrO 2 micropillars can achieve 50 cycles at 7% strain. On the other hand, conventional shape memory ceramics cannot overcome the inherent contradiction of "dimension - brittleness", and their development and application prospects are greatly limited. On the other hand, due to too little doping amount, the operating temperature range of shape memory ceramics becomes high, and when the doping amount is too much, the energy consumption density decreases. It has been a great difficulty to realize the controllable preparation of the austenite content of shape memory ceramics with less doping amount and lower operating temperature.

[0004] Since the 21st century, the application and rapid development of particle-reinforced aluminum-based composites in high-tech fields such as the aerospace and defense industries have provided new ideas and methods for the research on the reversible phase transformation of large-sized shape memory ceramics. At present, there are no literature reports on shape memory ceramic-reinforced metal matrix composites. According to existing reports of similar literature, the preparation methods of ZrO 2 / metal mainly use the following two methods. The first is the liquid method such as 3D printing, stir casting, pressureless (pressure) impregnation method, etc. The preparation process of this method is simple, but because the preparation temperature is too high, there is a disadvantage that significant interfacial reactions (3Al + [Zr]--Al 3 Zr) may occur. The second is the solid method such as external electric field-assisted sintering (flash sintering, discharge plasma sintering, ultra-high speed sintering method), etc., which has the disadvantages of insufficient densification and difficulty in designing the composite structure. For example, Abdizadeh et al. (Non-Patent Document 3) prepared 15 vol% 3YSZ particle-reinforced A356 aluminum composites by stir casting and achieved a tensile strength of 232 MPa. However, in this literature, the phase transformation effect was not studied in detail. Zhang et al. (Non-Patent Document 4) prepared nano-ZrO 2 particle-reinforced AlSi10Mg composites by selective laser melting technology. Its tensile strength reached 478.6 MPa and the elongation reached 10.6%. However, the ceramic in the as-manufactured state was in the monoclinic phase and there were significant interfacial reactions.

Prior Art Documents

Non-Patent Documents

[0005]

Non-Patent Document 1

Non-Patent Document 2

Non-Patent Document 3

Non-Patent Document 4

Summary of the Invention

Problems to be Solved by the Invention

[0006] Focusing on the bottleneck in the application of reversible phase transformation of large-scale shape memory ceramics and the problems of significant interfacial reactions and difficulty in austenitization during the preparation process of shape memory ceramic-reinforced aluminum-based composites, the object of the present invention is to provide a shape memory ceramic-reinforced aluminum-based composite material and a preparation method capable of controlling the austenite content. The preparation method of the present invention can uniformly disperse shape memory ceramics in the composite material on the premise of ensuring the complete structure and performance of the shape memory ceramics, and can realize the controllable preparation of the austenite content of the used shape memory ceramics in the raw materials of the composite material at room temperature.

Means for Solving the Problems

[0007] To achieve the above object, the present invention presents the following technical means.

[0008] The present 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 content of shape memory ceramics is 1 to 90% by mass, and the balance is aluminum powder. In the raw materials of the composite material, the used shape memory ceramics are single crystal particles based on cerium-containing zirconium oxide, and the composition is 3 to 12 mol% of CeO 2 and the balance of ZrO 2 and contains. In the preliminary experiments of the present invention, when the CeO 2 content in the used shape memory ceramics is less than 3 mol%, it has been found that a composite material with both high density and high austenite content cannot be obtained.

[0009] Preferably, in the raw materials of the composite material, the particle size D50 of the shape memory ceramics used is 0.2 to 2 μm, and the proportion of the austenite phase at room temperature is 0 to 12.3 wt%.

[0010] Preferably, in the raw materials of the composite material, the composition of the shape memory ceramics used is 6 to 12 mol% of CeO 2 and the balance of ZrO 2 and contains. Preferably, the aluminum powder is pure aluminum powder or aluminum alloy powder, and the particle size D50 of the aluminum powder is 10 to 100 μm.

[0011] Preferably, in the raw materials of the composite material, the proportion of the austenite phase of the shape memory ceramics used at room temperature is 3.8 to 100 wt%.

[0012] Preferably, in the raw materials of the composite material, the proportion of the austenite phase of the shape memory ceramics used at room temperature is 60 to 100 wt%.

[0013] The present invention also provides a method for preparing a shape memory ceramic reinforced aluminum-based composite material including the following steps. Step A1 of mixing and dispersing the shape memory ceramics and aluminum powder, which are the raw materials of the composite material, to obtain a shape memory ceramic / aluminum composite powder, Step A2 of heating and holding the shape memory ceramic / aluminum composite powder to achieve austenitization, and Step A3 of obtaining a shape memory ceramic reinforced aluminum-based composite material by densifying the austenitized shape memory ceramic / aluminum composite powder.

[0014] Preferably, in Step A1, the mixing and dispersing step is performed by constant-speed ball milling or variable-speed ball milling with a ball mill, the rotation speed of the ball mill is 200 to 500 revolutions per minute, and the ball milling time is 3 hours or more.

[0015] Preferably, in step A2, the holding temperature range is 300 to 600 °C, and the holding time is 1 to 2 hours.

[0016] Preferably, when the CeO 2 content of the shape memory ceramics is 3 mol% or more and 6 mol% or less, the holding temperature range used is 500 to 600 °C, and the CeO 2 when the content exceeds 6 mol% and is 9 mol% or less, the temperature range is 400 to 500 °C, and the CeO 2 when the content exceeds 9 mol% and is 12 mol% or less, the temperature range is 300 to 400 °C.

[0017] The inventor has found that in the previous experiment, when the holding temperature used is too high, the higher the cerium content, the more likely an interfacial reaction occurs and the more likely it is to affect the performance of the shape memory ceramics. When the holding temperature is too low, the shape memory ceramics cannot be austenitized. The present invention further optimizes each holding temperature range used for shape memory ceramics having different CeO 2 contents, and obtains a shape memory ceramic-reinforced aluminum-based composite material with both high density and high austenite content.

[0018] Preferably, in step A2, the holding temperature is higher than the transformation start temperature of the austenite of the shape memory ceramics.

[0019] Preferably, in step A3, the densification treatment uses a sintering method, and the pressure range used in the sintering method is 300 to 1000 MPa. When the pressure used is too high, the mold is likely to be damaged. When the pressure is too low, it becomes difficult to hold the austenite phase due to the restraint of the parent phase.

[0020] The present invention can significantly increase the austenite content of the shape memory ceramics after compounding through temperature holding and densification treatment, and the CeO 2After the shape memory ceramic raw material with a content of 6 to 12 mol% undergoes the preparation method of the present invention, the austenite content after compounding can reach 60 wt% or more, and after using the optimized holding temperature, the austenite content after compounding can reach 100%.

[0021] Preferably, the sintering method is selected from any one of atmosphere sintering, vacuum hot press sintering, discharge plasma sintering, and hot isostatic pressing sintering.

[0022] Preferably, the sintering temperature used in the vacuum hot press sintering is the same as the holding temperature, and the sintering time is 1 to 2 hours.

[0023] By using the above preparation method, the present invention can uniformly disperse the strengthening particles (shape memory ceramics) in the microstructure, control the content of the austenite phase of the shape memory ceramics in the composite material at room temperature, and the content of the austenite phase is increased compared with a single shape memory ceramic. At the same time, by reasonably selecting the holding temperature, the shape memory ceramic is austenitized to a certain extent, so as to avoid the interfacial reaction between the shape memory ceramic and aluminum and maintain the structural-functional integrity of the shape memory ceramic. By using an appropriate pressure in the sintering process, sufficient matrix restraint is generated so that the shape memory ceramics can maintain the austenite phase even after cooling, maximize the stress-induced phase transformation effect of the shape memory ceramics in the composite material, expand the application range of the superelastic effect of the shape memory ceramics at room temperature, save energy and time, and is suitable for large-scale preparation and manufacturing.

Advantages of the Invention

[0024] Compared with the prior art, the present invention has the following advantageous effects.

[0025] (1) In the shape memory ceramic reinforced aluminum matrix composite material prepared by the present invention, the shape memory ceramics are uniformly dispersed, have high density, and well maintain the structural integrity, and the brittle phase Al3 Zr is not generated.

[0026] (2) The composite material prepared according to the present invention can control the content of the austenite phase, which helps to fully exert the structure and phase transformation effect of the shape memory ceramics.

[0027] (3) The preparation method of the present invention has a wide application range, saves energy and time, the process is highly reliable and efficient, overcomes the problems of the inherent brittleness and high phase transformation temperature of the shape memory ceramics, realizes the preparation and application of large-scale shape memory ceramics, and is also useful for large-scale manufacturing.

Brief Description of the Drawings

[0028] Other features, objects, and advantages of the present invention will become more apparent upon reading the detailed description of the non-limiting embodiments with reference to the following drawings.

[0029]

Figure 1

Figure 2

Figure 3

Modes for Carrying Out the Invention

[0030] The present invention will be described in detail with reference to specific embodiments. The following embodiments are intended to assist those skilled in the art in understanding the present invention, but are not intended to limit the present invention in any way. It should be noted that those skilled in the art can make some modifications and improvements without departing from the technical idea of the present invention. Such modifications and improvements are included in the protection scope of the present invention.

[0031] The following embodiments also provide a method for preparing a shape memory ceramic reinforced aluminum-based composite material including the following steps. Step A1 of mixing and dispersing shape memory ceramics and aluminum powder, which are raw materials of the composite material, to obtain shape memory ceramics / aluminum composite powder. Step A2 of heating and holding the shape memory ceramics / aluminum composite powder to achieve austenitization, and Step A3 of densifying the austenitized shape memory ceramics / aluminum composite powder to obtain a shape memory ceramic reinforced aluminum-based composite material.

[0032] Preferably, in step A1, the mixing and dispersing process is carried out by constant-speed ball milling or variable-speed ball milling in a ball mill, the rotation speed of the ball mill is 200 - 500 revolutions per minute, and the ball milling time is 3 hours or more.

[0033] In step A1, in the raw materials of the composite material, the content of shape memory ceramics is 1 - 90% by mass, and the balance is aluminum powder. The shape memory ceramics are single crystal particles based on cerium-containing zirconium oxide, and the composition is 3 - 12 mol% of CeO 2 and the balance of ZrO 2 and the particle size D50 of the shape memory ceramics is 0.2 - 2 μm, and the proportion of the austenite phase at room temperature is 0 - 12.3 wt%.

[0034] The aluminum powder is pure aluminum powder or aluminum alloy powder, and the particle size D50 of the aluminum powder is 10 - 100 μm.

[0035] In Project A2, the holding temperature range is 300 - 600 °C, and the holding time is 1 - 2 hours.

[0036] The densification treatment uses the sintering method, and the pressure range used in the sintering method is 300 - 1000 MPa.

[0037] The sintering method is selected from any of atmospheric sintering, vacuum hot press sintering, discharge plasma sintering, and hot isostatic pressing sintering.

[0038] Using the above method, a shape memory ceramic reinforced aluminum - based composite material can be prepared. The shape memory ceramic content in the obtained composite material is 1 - 90 wt%, and the proportion of the austenite phase at room temperature is 3.8 - 100 wt%.

[0039] The metal powders used in the following examples were uniformly injection - molded, and the preparation method of the shape memory ceramics refers to the method described in US Patent Application Publication No. 2019 / 0039959. All examples were carried out according to the process shown in Figure 1, and the mechanical properties of the materials at room temperature in all examples were uniformly tested in accordance with 《GB / T228.1 - 2010》.

[0040] (Example) (Example 1) This example provides a method for preparing a shape memory ceramic reinforced aluminum - based composite material (including 30 wt.% shape memory ceramics with a cerium doping amount of 12 mol%) as shown in Figure 1, and the steps are as follows. 10.5 g of 10 - μm pure aluminum powder (spherical powder) and 4.5 g of shape memory ceramics (the composition is 12 mol% CeO 2 and the balance ZrO 2It contains, with a particle size D50 of 0.5 μm, taken and placed in a planetary ball mill. 0.15 g of stearic acid is added as a process control agent for the ball mill. Under the protection of argon gas, zirconia balls are used as a ball milling medium with a ball-to-material ratio of 10:1. Ball milling is carried out at a rotation speed of 200 revolutions per minute for 12 hours, and then at a rotation speed of 400 revolutions per minute for 1 hour to obtain shape memory ceramic / aluminum composite powder. The obtained composite powder is held at 400 °C for 1 hour, degreased, annealed, and austenitized, and then manufactured into an 18-mm-diameter block through vacuum hot press sintering at 400 °C and 1 GPa for 1 hour. The components and properties are shown in Table 1. Figure 2 is an X-ray diffraction pattern (Figure 2(a) is the original shape memory ceramic, Figure 2(b) is the composite powder particles obtained after ball milling and pulverization, and Figure 2(c) is the final shape memory ceramic-reinforced aluminum-based composite material. Figure 3(a) is a transmission electron micrograph of the shape memory ceramic-reinforced aluminum-based composite material, Figure 3(b) is a partial enlarged view, Figure 3(c) is the interface of the shape memory ceramic-aluminum, and Figure 3(d) is the selected area electron diffraction pattern at the position surrounded by the circle in Figure (c), indicating that the shape memory ceramic in the as-manufactured state is in the austenite phase.)

[0041] (Comparative Example 1) This comparative example is basically the same as the method of Example 1. The only difference is that in this comparative example, shape memory ceramics are not added. The components and mechanical properties of the finally obtained matrix material are shown in Table 1.

[0042] (Example 2) This example provides a method for preparing a shape memory ceramic-reinforced aluminum-based composite material (containing 20 wt.% of shape memory ceramics with a cerium doping amount of 12 mol%). The specific process is basically the same as that of Example 1. The only difference is that when preparing the shape memory ceramic / aluminum composite powder, 12 g of 10-μm pure aluminum powder (spherical powder) and 3 g of shape memory ceramics are taken and placed in a planetary ball mill. The components and properties of the finally obtained block are shown in Table 1.

[0043] (Example 3) This example provides a method for preparing a shape memory ceramic reinforced aluminum-based composite material (containing 10 wt.% shape memory ceramics with a cerium doping amount of 12 mol%). The specific process is basically the same as that of Example 1. The only difference is that when preparing the shape memory ceramic / aluminum composite powder, 13.5 g of 10-μm pure aluminum powder (spherical powder) and 1.5 g of shape memory ceramics are taken and put into a planetary ball mill. The components and properties of the finally obtained block are shown in Table 1.

[0044] (Example 4) This example provides a method for preparing a shape memory ceramic reinforced aluminum-zinc-magnesium-copper-based composite material (containing 30 wt.% shape memory ceramics with a cerium doping amount of 12 mol%), and the process is as follows. Take 10.5 g of 10-μm aluminum-zinc-magnesium-copper alloy powder (aluminum alloy of alloy number 7075) and 4.5 g of shape memory ceramics (the composition contains 12 mol% CeO 2 and the balance ZrO 2 with a particle size D50 of 0.5 μm), put them into a planetary ball mill, add 0.15 g of stearic acid as a process control agent for the ball mill, use zirconia balls as a ball milling medium with a ball-to-material ratio of 10:1 under the protection of argon gas, perform ball milling at a rotation speed of 200 revolutions per minute for 12 hours, and then perform ball milling at a rotation speed of 400 revolutions per minute for 4 hours to obtain shape memory ceramic / aluminum composite powder. The above composite powder is held at 400 °C for 1 hour, degreased, annealed, and austenitized, and then manufactured into a block with a diameter of 18 mm through vacuum hot press sintering at 400 °C and 1 GPa for 1 hour. The components and properties are shown in Table 1.

[0045] (Comparative Example 2) This comparative example is basically the same as the method of Example 4. The only difference is that in this comparative example, no shape memory ceramics are added. The components and properties of the finally obtained aluminum-zinc-magnesium-copper alloy are shown in Table 1.

[0046] (Example 5) This example provides a method for preparing a shape memory ceramic reinforced aluminum-based composite material (containing 30 wt.% shape memory ceramics with a cerium doping amount of 12 mol%). The specific process is basically the same as that of Example 1, and the only difference is that when preparing the shape memory ceramic / aluminum composite powder, constant speed ball milling with a rotation speed of 200 revolutions per minute and a ball milling time of 12 hours was used. The components and properties of the finally obtained block are shown in Table 1.

[0047] (Example 6) This example provides a method for preparing a shape memory ceramic reinforced aluminum-based composite material (containing 30 wt.% shape memory ceramics with a cerium doping amount of 12 mol%). The specific process is basically the same as that of Example 1, and the only difference is that when preparing the shape memory ceramic / aluminum composite powder, constant speed ball milling with a rotation speed of 500 revolutions per minute and a ball milling time of 3 hours was used. The components and properties of the finally obtained block are shown in Table 1.

[0048] (Example 7) This example provides a method for preparing a shape memory ceramic reinforced aluminum-based composite material (containing 1 wt.% shape memory ceramics with a cerium doping amount of 12 mol%). The specific process is basically the same as that of Example 1, and the only difference is that when preparing the shape memory ceramic / aluminum composite powder, 14.85 g of 10 μm pure aluminum powder (spherical powder) and 0.15 g of shape memory ceramics are taken and put into a planetary ball mill. The components and properties of the finally obtained block are shown in Table 1.

[0049] (Example 8) This example provides a method for preparing a shape memory ceramic reinforced aluminum-copper-based composite material (containing 30 wt.% shape memory ceramics with a cerium doping amount of 12 mol%), and the process is as follows. 10.5 g of aluminum-copper alloy powder with a particle size of 10 μm (aluminum alloy of alloy number 2024) and 4.5 g of shape memory ceramics (composition: 12 mol% CeO 2 and the balance ZrO 2 with a particle size D50 of 0.5 μm) were taken, placed in a planetary ball mill, and 0.15 g of stearic acid was added as a process control agent for the ball mill. Under the protection of argon gas, zirconia balls were used as the ball milling medium with a ball-to-material ratio of 10:1, and ball milling was carried out at a rotational speed of 200 revolutions per minute for 12 hours, and then at a rotational speed of 400 revolutions per minute for 2 hours to obtain a composite powder. The above composite powder was held at 400 °C for 1 hour, degreased, annealed, and austenitized, and then subjected to vacuum hot press sintering at 400 °C and 1 GPa for 1 hour to produce a block with a diameter of 18 mm, and the components and properties are shown in Table 1.

[0050] (Comparative Example 3) This comparative example is basically the same as the method of Example 8, and the only difference is that no shape memory ceramics are added in this comparative example. The components and properties of the finally obtained aluminum-copper alloy are shown in Table 1.

[0051] (Example 9) This example provides a method for preparing a shape memory ceramic-reinforced aluminum-copper-based composite material (including 60 wt.% shape memory ceramics with a cerium doping amount of 12 mol%). The specific process is basically the same as that of Example 8, and the only difference is that when preparing the shape memory ceramic / aluminum composite powder, 6 g of aluminum-copper alloy powder with a particle size of 10 μm and 9 g of shape memory ceramics are taken and placed in a planetary ball mill. The components and properties of the finally obtained block are shown in Table 1.

[0052] (Example 10) This example provides a method for preparing a shape memory ceramic reinforced aluminum - copper - based composite material (containing 90 wt.% shape memory ceramics with a cerium doping amount of 12 mol%). The specific process is basically the same as that of Example 8. The only difference is that when preparing the shape memory ceramics / aluminum composite powder, 1.5 g of 10 - μm aluminum - copper alloy powder and 13.5 g of shape memory ceramics are taken and put into a planetary ball mill. The components and properties of the finally obtained block are shown in Table 1.

[0053] (Example 11) This example provides a method for preparing a shape memory ceramic reinforced aluminum - based composite material (containing 30 wt.% shape memory ceramics with a cerium doping amount of 9 mol%). The specific process is basically the same as that of Example 1. The only difference is that 10.5 g of 10 - μm pure aluminum powder (spherical powder) and 4.5 g of shape memory ceramics (the composition is 9 mol% CeO 2 and the remaining ZrO 2 are taken, put into a planetary ball mill, the obtained composite powder is held at 500 °C for 1 hour, degreased, annealed, austenitized, and then subjected to vacuum hot - press sintering at 500 °C and 300 MPa for 1 hour to produce a block with a diameter of 18 mm. The components and properties of the finally obtained block are shown in Table 1.

[0054] (Example 12) This example provides a method for preparing a shape memory ceramic reinforced aluminum - based composite material (containing 30 wt.% shape memory ceramics with a cerium doping amount of 6 mol%). The specific process is basically the same as that of Example 1. The only difference is that 10.5 g of 10 - μm pure aluminum powder (spherical powder) and 4.5 g of shape memory ceramics (the composition is 6 mol% CeO 2 and the remaining ZrO 2It contains, the particle size D50 is 0.5 μm), which was taken and put into a planetary ball mill. After the obtained composite powder was held at 600 °C for 1 hour and degreasing, annealing, and austenitizing were carried out, it was manufactured into a block with a diameter of 18 mm through vacuum hot press sintering at 600 °C and 300 MPa for 1 hour. The components and properties of the finally obtained block are shown in Table 1.

[0055] (Example 13) This example provides a method for preparing a shape memory ceramic reinforced aluminum-based composite material (containing 30 wt.% shape memory ceramics with a cerium doping amount of 6 mol%). The specific process is basically the same as that of Example 1. The only difference is that 10.5 g of 10-μm pure aluminum powder (spherical powder) and 4.5 g of shape memory ceramics (the composition is 6 mol% CeO 2 and the balance of ZrO 2 It contains, the particle size D50 is 0.5 μm), which was taken and put into a planetary ball mill. After the obtained composite powder was held at 500 °C for 1 hour and degreasing, annealing, and austenitizing were carried out, it was manufactured into a block with a diameter of 18 mm through vacuum hot press sintering at 500 °C and 300 MPa for 1 hour. The components and properties of the finally obtained block are shown in Table 1.

[0056] (Example 14) This example provides a method for preparing a shape memory ceramic reinforced aluminum-based composite material (containing 30 wt.% shape memory ceramics with a cerium doping amount of 12 mol%). The specific process is basically the same as that of Example 1. The only difference is that the obtained composite powder was held at 300 °C for 1 hour and degreasing, annealing, and austenitizing were carried out, and then it was manufactured into a block with a diameter of 18 mm through vacuum hot press sintering at 300 °C and 1 GPa for 1 hour. The components and properties of the finally obtained block are shown in Table 1.

[0057] (Example 15) This example provides a method for preparing a shape memory ceramic reinforced aluminum-based composite material (containing 30 wt.% shape memory ceramics with a cerium doping amount of 9 mol%). The specific process is basically the same as that of Example 1. The only difference is that 10.5 g of 10-μm pure aluminum powder (spherical powder) and 4.5 g of shape memory ceramics (the composition is 9 mol% CeO 2 and the balance ZrO 2 , with a particle size D50 of 0.5 μm) were taken and put into a planetary ball mill. The components and properties of the finally obtained block are shown in Table 1.

[0058] (Example 16) This example provides a method for preparing a shape memory ceramic reinforced aluminum-based composite material (containing 30 wt.% shape memory ceramics with a cerium doping amount of 6 mol%). The specific process is basically the same as that of Example 1. The only difference is that 10.5 g of 10-μm pure aluminum powder (spherical powder) and 4.5 g of shape memory ceramics (the composition is 6 mol% CeO 2 and the balance ZrO 2 , with a particle size D50 of 0.5 μm) were taken and put into a planetary ball mill. The components and properties of the finally obtained block are shown in Table 1.

[0059] (Example 17) This example provides a method for preparing a shape memory ceramic reinforced aluminum-based composite material (containing 30 wt.% shape memory ceramics with a cerium doping amount of 3 mol%). The specific process is basically the same as that of Example 1. The only difference is that 10.5 g of 10-μm pure aluminum powder (spherical powder) and 4.5 g of shape memory ceramics (the composition is 3 mol% CeO 2 and the balance ZrO 2 , with a particle size D50 of 0.5 μm) were taken and put into a planetary ball mill. The components and properties of the finally obtained block are shown in Table 1.

[0060] (Example 18) This example provides a method for preparing a shape memory ceramic reinforced aluminum-based composite material (containing 30 wt.% shape memory ceramics with a cerium doping amount of 3 mol%). The specific process is basically the same as that of Example 17. The only difference is that the obtained composite powder is held at 600 °C for 1 hour, and after degreasing, annealing, and austenitizing, it is manufactured into a block with a diameter of 18 mm through vacuum hot press sintering at 600 °C and 600 MPa for 1 hour. The components and properties of the finally obtained block are shown in Table 1.

[0061] (Example 19) This example provides a method for preparing a shape memory ceramic reinforced aluminum-based composite material (containing 30 wt.% shape memory ceramics with a cerium doping amount of 9 mol%). The specific process is basically the same as that of Example 11. The only difference is that the obtained composite powder is held at 500 °C for 1 hour, and after degreasing, annealing, and austenitizing, it is manufactured into a block with a diameter of 18 mm through vacuum hot press sintering at 500 °C and 600 MPa for 1 hour. The components and properties of the finally obtained block are shown in Table 1.

[0062] (Example 20) This example provides a method for preparing a shape memory ceramic reinforced aluminum-based composite material (containing 30 wt.% shape memory ceramics with a cerium doping amount of 6 mol%). The specific process is basically the same as that of Example 12. The only difference is that the obtained composite powder is held at 650 °C for 1 hour, and after degreasing, annealing, and austenitizing, it is manufactured into a block with a diameter of 18 mm through vacuum hot press sintering at 650 °C and 300 MPa for 1 hour. The components and properties of the finally obtained block are shown in Table 1.

[0063] (Example 21) This example provides a method for preparing a shape memory ceramic reinforced aluminum-based composite material (containing 30 wt.% shape memory ceramics with a cerium doping amount of 6 mol%). The specific process is basically the same as that of Example 12. The only difference is that the obtained composite powder is held at 300 °C for 1 hour, and after degreasing, annealing, and austenitizing, it is manufactured into a block with a diameter of 18 mm through vacuum hot press sintering at 300 °C and 300 MPa for 1 hour. The components and properties of the finally obtained block are shown in Table 1.

[0064] (Example 22) This example provides a method for preparing a shape memory ceramic reinforced aluminum-based composite material (containing 30 wt.% shape memory ceramics with a cerium doping amount of 6 mol%). The specific process is basically the same as that of Example 12. The only difference is that the obtained composite powder is held at 600 °C for 1 hour, and after degreasing, annealing, and austenitizing, it is manufactured into a block with a diameter of 18 mm through vacuum hot press sintering at 600 °C and 100 MPa for 1 hour. The components and properties of the finally obtained block are shown in Table 1.

[0065] (Example 23) This example provides a method for preparing a shape memory ceramic reinforced aluminum-based composite material (containing 30 wt.% shape memory ceramics with a cerium doping amount of 12 mol%). The specific process is basically the same as that of Example 14. The only difference is that the obtained composite powder is held at 250 °C for 1 hour, and after degreasing, annealing, and austenitizing, it is manufactured into a block with a diameter of 18 mm through vacuum hot press sintering at 250 °C and 1 GPa for 1 hour. The components and properties of the finally obtained block are shown in Table 1.

[0066] (Example 24) This example provides a method for preparing a shape memory ceramic reinforced aluminum-based composite material (containing 30 wt.% shape memory ceramics with a cerium doping amount of 12 mol%). The specific process is basically the same as that of Example 14. The only difference is that the obtained composite powder is held at 550 °C for 1 hour, and after degreasing, annealing, and austenitizing, it is manufactured into a block with a diameter of 18 mm through vacuum hot press sintering at 550 °C and 1 GPa for 1 hour. The components and properties of the finally obtained block are shown in Table 1.

[0067]

Table 1

[0068] As can be seen from the comparison of the results of Example 12 in Table 1 with those of Examples 13, 20, and 21, when the cerium doping amount in the shape memory ceramics is 6 mol%, and the holding temperature and hot press sintering temperature used are 600 °C, the austenite content after compounding is the highest and can reach 100%. When the temperature is 500 °C, the austenite content after compounding can reach 63.7%. When the temperature is 650 °C or 300 °C, no austenite is obtained due to significant interfacial reactions and low driving force for phase transformation, respectively.

[0069] As can be seen from the comparison of the results of Example 12 with those of Example 22, in Example 21, when the pressure of hot press sintering used is 100 MPa, the austenite content after compounding is only 28.7%, which is significantly lower than that of Example 12.

[0070] As can be seen from the comparison of the results of Example 11 with those of Examples 15 and 19, when the cerium doping amount in the shape memory ceramics is 9 mol%, and the holding temperature and hot press sintering temperature used are 500 °C, the austenite content after compounding further increases and reaches 100%.

[0071] Table 1 also shows the hardness results of the composite materials prepared in each example. From the perspective of application, it can be seen that the higher the hardness, the more useful it is to withstand loads from a structural perspective, and from a functional perspective, it helps to induce the phase transformation of austenite through load transfer and exert the potential ability of phase transformation.

[0072] The interfacial bonding of the shape memory ceramic-reinforced aluminum-based composite materials prepared in the above-mentioned examples is basically the same. The shape memory ceramic-reinforced aluminum-based composite material of the present invention and the preparation method capable of controlling the austenite content can obtain composite materials with different austenite contents at room temperature by adjusting the temperature on the premise of uniformly dispersing the shape memory ceramics. Compared with a single shape memory ceramic, the austenite content increases, the structural-functional integrity of the shape memory ceramics is maximally protected, the preparation and application of large-sized shape memory ceramics can be realized, the application range of the phase transformation of shape memory ceramics at room temperature is expanded, energy and time are saved, it is safe and easy to implement, and it has the potential for large-scale application.

[0073] The description of the above embodiments is for those skilled in the art to understand and use the present invention. It is obvious that those skilled in the art can easily make various modifications to these embodiments without creative activities and apply the general principles described herein to other embodiments. Therefore, the present invention is not limited to the above embodiments, and the improvements and modifications made by those skilled in the art without departing from the scope of the present invention based on the disclosure of the present invention should be included within the protection scope of the present invention.

[0074] (Supplementary Note) (Supplementary Note 1) A shape memory ceramic-reinforced aluminum-based composite material, wherein the raw materials of the composite material include shape memory ceramics and aluminum powder. In the raw materials of the composite material, the content of shape memory ceramics is 1 to 90% by mass, and the balance is aluminum powder. In the raw materials of the composite material, the shape memory ceramics used are single crystal particles based on cerium-containing zirconium oxide, and the composition is 3 to 12 mol% of CeO 2 and the balance of ZrO 2 and, A shape memory ceramic-reinforced aluminum-based composite material, characterized in that.

[0075] (Appendix 2) In the raw materials of the composite material, the particle size D50 of the shape memory ceramics used is 0.2 to 2 μm, and the ratio of the austenite phase at room temperature is 0 to 12.3 wt%, A shape memory ceramic-reinforced aluminum-based composite material according to Appendix 1, characterized in that.

[0076] (Appendix 3) The aluminum powder is pure aluminum powder or aluminum alloy powder, and the particle size D50 of the aluminum powder is 10 to 100 μm, A shape memory ceramic-reinforced aluminum-based composite material according to Appendix 1, characterized in that.

[0077] (Appendix 4) The ratio of the austenite phase of the shape memory ceramics at room temperature in the raw materials of the composite material is 3.8 to 100 wt%, A shape memory ceramic-reinforced aluminum-based composite material according to Appendix 1, characterized in that.

[0078] (Appendix 5) A method for preparing a shape memory ceramic-reinforced aluminum-based composite material according to any one of Appendices 1 to 4, Step A1 of mixing and dispersing the shape memory ceramics and aluminum powder, which are the raw materials of the composite material, to obtain a shape memory ceramic / aluminum composite powder; Step A2 of heating and holding the shape memory ceramic / aluminum composite powder to achieve austenitization; Step A3 of obtaining a shape memory ceramic-reinforced aluminum-based composite material by densifying the austenitized shape memory ceramic / aluminum composite powder is included. A method for preparing a shape memory ceramic-reinforced aluminum-based composite material, characterized by the above.

[0079] (Appendix 6) In the step A1, the mixing and dispersing step is carried out by constant-speed ball milling or variable-speed ball milling in a ball mill. The rotation speed of the ball mill is 200-500 revolutions per minute, and the ball milling time is 3 hours or more. A method for preparing a shape memory ceramic-reinforced aluminum-based composite material according to Appendix 5, characterized by the above.

[0080] (Appendix 7) In the step A2, the holding temperature range is 300-600°C, and the holding time is 1-2 hours. A method for preparing a shape memory ceramic-reinforced aluminum-based composite material according to Appendix 5, characterized by the above.

[0081] (Appendix 8) When the CeO content of the shape memory ceramics is 3 mol% or more and 6 mol% or less, the used holding temperature range is 500-600°C. When the CeO content of the shape memory ceramics exceeds 6 mol% and is 9 mol% or less, the temperature range is 400-500°C. When the CeO content of the shape memory ceramics exceeds 9 mol% and is 12 mol% or less, the temperature range is 300-400°C. 2 2 2 A method for preparing a shape memory ceramic-reinforced aluminum-based composite material according to Appendix 7, characterized by the above.

[0082] (Appendix 9) In the step A3, the densifying treatment uses a sintering method, and the pressure range used in the sintering method is 300-1000 MPa. A method for preparing a shape memory ceramic-reinforced aluminum-based composite material according to Appendix 5, characterized by the above.

[0083] (Appendix 10) The sintering method is selected from any one of atmosphere sintering, vacuum hot press sintering, spark plasma sintering, and hot isostatic pressing sintering, A method for preparing a shape memory ceramic reinforced aluminum-based composite material according to Appendix 9, characterized by the above.

Claims

1. A shape memory ceramic reinforced aluminum-based composite material, wherein the raw materials of the composite material include shape memory ceramics and aluminum powder. In the raw materials of the composite material, the content of shape memory ceramics is 1 to 90% by mass, and the balance is aluminum powder. In the raw materials of the composite material, the shape memory ceramics used are single crystal particles based on cerium-containing zirconium oxide, and the composition is 3 to 12 mol% of CeO ２ and the balance of ZrO ２ and contains A shape memory ceramic reinforced aluminum-based composite material, characterized by the above.

2. In the raw materials of the composite material, the particle size D50 of the shape memory ceramics used is 0.2 to 2 μm, and the ratio of the austenite phase at room temperature is 0 to 12.3 wt%. A shape memory ceramic reinforced aluminum-based composite material according to Claim 1, characterized by the above.

3. The aluminum powder is pure aluminum powder or aluminum alloy powder, and the particle size D50 of the aluminum powder is 10 to 100 μm. A shape memory ceramic reinforced aluminum-based composite material according to Claim 1, characterized by the above.

4. In the raw materials of the composite material, the ratio of the austenite phase of the shape memory ceramics at room temperature is 3.8 to 100 wt%. A shape memory ceramic reinforced aluminum-based composite material according to Claim 1, characterized by the above.

5. A method for preparing a shape memory ceramic reinforced aluminum-based composite material according to any one of Claims 1 to 4, comprising step A1 of mixing and dispersing shape memory ceramics and aluminum powder, which are raw materials of the composite material, to obtain shape memory ceramic / aluminum composite powder; step A2 of heating and holding the shape memory ceramic / aluminum composite powder to achieve austenitization; and step A3 of densifying the austenitized shape memory ceramic / aluminum composite powder to obtain a shape memory ceramic reinforced aluminum-based composite material. A method for preparing a shape memory ceramic reinforced aluminum-based composite material, characterized by the above.

6. In step A1, the mixing and dispersing step is carried out by constant-speed ball milling or variable-speed ball milling in a ball mill. The rotation speed of the ball mill is 200 to 500 revolutions per minute, and the ball milling time is 3 hours or more. A method for preparing a shape memory ceramic reinforced aluminum-based composite material according to Claim 5, characterized by the above.

7. In step A2, the holding temperature range is 300 to 600 °C, and the holding time is 1 to 2 hours. A method for preparing a shape memory ceramic reinforced aluminum-based composite material according to claim 5, characterized in that...

8. When the CeO content of the shape memory ceramics is 3 mol% or more and 6 mol% or less, the holding temperature range used is 500 to 600 °C. When the CeO content of the shape memory ceramics is ２ more than 6 mol% and 9 mol% or less, the temperature range is 400 to 500 °C. When the CeO content of the shape memory ceramics is ２ more than 9 mol% and 12 mol% or less, the temperature range is 300 to 400 °C. ２ ​ A method for preparing a shape memory ceramic reinforced aluminum-based composite material according to claim 7, characterized in that...

9. In the step A3, the densification treatment uses a sintering method, and the pressure range used in the sintering method is 300 to 1000 MPa. A method for preparing a shape memory ceramic reinforced aluminum-based composite material according to claim 5, characterized in that...

10. The sintering method is selected from any one of atmosphere sintering, vacuum hot press sintering, spark plasma sintering, and hot isostatic pressing sintering. A method for preparing a shape memory ceramic reinforced aluminum-based composite material according to claim 9, characterized in that...

Images