A ceramic / high entropy alloy composite particle reinforced aluminum-based composite material and laser additive manufacturing method thereof

Abstract

The present invention discloses a ceramic / high-entropy alloy composite particle-reinforced aluminum-based composite material and a laser additive manufacturing method thereof. Ceramic / high-entropy alloy composite powder and aluminum alloy powder are first mixed by ball milling to obtain a ceramic / high-entropy alloy composite particle-reinforced aluminum alloy composite powder. The three-component composite powder is then spread on a powder bed. Laser scanning is then used to melt and solidify the powder, adjusting the laser power, scanning speed, and scanning spacing, to form a ceramic / high-entropy alloy composite particle-reinforced aluminum-based composite material. The composite material of the present invention is highly dense, so the ceramic / high-entropy alloy composite particles can effectively improve the mechanical properties of the aluminum-based composite material and can be used in the manufacture of high-performance, complex parts for aerospace, automotive, and rail transportation applications.

Description

Technical Field

[0001] The present invention belongs to the field of metal materials, and in particular relates to an aluminum-based composite material reinforced with ceramic / high-entropy alloy composite particles and a laser additive manufacturing method thereof. Background Art

[0002] Aluminum-based composites combine the advantages of aluminum alloys (low density, high ductility) and reinforcement materials (high strength, high elastic modulus), exhibiting superior specific strength, high specific stiffness, low thermal expansion coefficient, and excellent wear resistance. Selective laser melting (SLM), an additive manufacturing technology, features rapid heating and cooling, high precision, and a high degree of design freedom. When preparing aluminum-based composites, the unique Marangoni effect within the molten pool allows the reinforcement phase to be evenly distributed within the aluminum matrix. However, currently, single ceramic particles used as reinforcements often produce sharp interfaces, resulting in high internal stress within the aluminum matrix. Furthermore, the interfacial bonding between the ceramic particles and the aluminum matrix is ​​poor, and harmful reactions are prone to occur at the interface, leading to a significant decrease in the plasticity of the composite material.

[0003] High-entropy alloys (HEAs) possess excellent mechanical properties. Compared to ceramics, HEAs exhibit better wettability with aluminum substrates and higher interfacial bonding strength, making them promising reinforcement materials. However, HEAs are composed of multiple elements, and during the SLM process, some of these elements may react with the aluminum matrix to form brittle intermetallic compounds. This reaction can also create pores within the aluminum matrix.

[0004] Ceramic / high-entropy alloy composite particles combine the advantages of both ceramic and high-entropy alloy particles. They possess excellent mechanical properties while maintaining good wettability and interfacial bonding with aluminum, making them less susceptible to reaction or decomposition. While there have been reports of directly using ceramic / high-entropy alloy composite particles to prepare ceramic-reinforced high-entropy alloy composites through techniques such as spark plasma sintering, hot pressing, and SLM, there have been no reports of using ceramic / high-entropy alloy composite particles as a reinforcement phase to prepare aluminum-based composites. Therefore, to further improve the mechanical properties and application scope of aluminum alloys, exploring high-performance ceramic / high-entropy alloy composite particle-reinforced aluminum-based composites and their laser additive manufacturing methods has important research significance and application value. Summary of the Invention

[0005] In order to overcome the shortcomings and deficiencies in the design theory of particle-reinforced aluminum-based composite materials and the preparation and forming process of industrial complex-shaped composite materials in the prior art, the primary purpose of the present invention is to provide a laser selective melting preparation process for ceramic / high-entropy alloy composite particle-reinforced aluminum-based composite materials.

[0006] Another object of the present invention is to provide a composite powder of ceramic / high entropy alloy composite particles reinforced aluminum alloy required for the above-mentioned preparation process.

[0007] Another object of the present invention is to provide an aluminum-based composite material reinforced with ceramic / high entropy alloy composite particles obtained by using the above-mentioned preparation process and composite powder.

[0008] The purpose of the present invention is achieved through the following technical solutions:

[0009] A ceramic / high-entropy alloy composite particle-reinforced aluminum-based composite material and a laser additive manufacturing method thereof. The material composition is characterized by a matrix comprising various aluminum alloys, including cast aluminum alloys such as Al-Si, Al-Cu, Al-Mg, and Al-Zn; and also wrought aluminum alloys such as 1xxx, 2xxx, 4xxx, 5xxx, 6xxx, 7xxx alloys, and Al-Li alloys. The reinforcing phase comprises ceramic / high-entropy composite powder particles, wherein the ceramic particles include TiB2, TiC, TiN, SiC, ZrO2, and the like; and the high-entropy alloy particles include high-entropy alloys such as FeCoCrNi, FeCoCrNiMn, FeCoCrNiMo, AlCoCrFeNi, AlTiCrNiCu, WTaMoNbV, and TiNbZrTa.

[0010] Furthermore, in the plasma-spheroidized ceramic / high-entropy alloy composite particle reinforcement phase, the mass fraction of ceramic is between 0.5% and 50%, the mass fraction of high-entropy alloy is between 50% and 99.5%, and the sum of the two is equal to 1. The ceramic powder is flaky or other irregularly shaped and has a particle size of 0.05 to 1 μm, while the high-entropy alloy powder is spherical and has a particle size of 1 to 100 μm. The ceramic / high-entropy alloy composite powder is spherical, has good flowability, and has a particle size of 1 to 100 μm.

[0011] Furthermore, in the composite powder of ceramic / high entropy alloy composite particles reinforced aluminum alloy, the mass fraction of the ceramic / high entropy alloy composite particle reinforcement phase is 1% to 10%, the mass fraction of the aluminum alloy matrix is ​​90% to 99%, and the sum of the two is equal to 1, and the aluminum alloy powder is spherical and has a particle size between 1 and 100 μm.

[0012] A ceramic / high entropy alloy composite particle reinforced aluminum-based composite material and its laser additive manufacturing method, the preparation and forming process of which is characterized by: weighing ceramic / high entropy alloy composite powder and aluminum alloy powder and mixing them by ball milling; using laser selective melting technology to form the ceramic / high entropy alloy composite particle reinforced aluminum-based composite material. The preparation process of the present invention is shown in the attached figure. Figure 1 shown.

[0013] The laser additive manufacturing method of the ceramic / high entropy alloy composite particle reinforced aluminum-based composite material of the present invention specifically comprises the following steps:

[0014] (1) Preparation of composite powder: Weigh a certain mass fraction ratio of ceramic / high entropy alloy composite powder and aluminum alloy powder respectively, mix them evenly in a ball mill for 4-8 hours, and pass argon or nitrogen as protection. After sieving through a standard sieve, dry them in a vacuum environment at 70-120°C for 4-6 hours to obtain a composite powder of ceramic / high entropy alloy composite particles reinforced with aluminum alloy.

[0015] (2) SLM (Selective Laser Melting, SLM) preparation of aluminum-based composite materials: The composite powder of ceramic / high entropy alloy composite particles reinforced aluminum alloy is spread flat on the substrate of the SLM metal 3D printer forming chamber, and the aluminum alloy substrate is preheated to 150-200°C under the protection of gas; the laser power is adjusted to 270-370W and the scanning speed is 1100mm / s-1600mm / s, the powder layer thickness is 20-75μm, the scanning spacing is 110-150μm, and the scanning strategy is 67° interlayer rotation; the laser is scanned layer by layer on the powder bed to deposit and form, and the aluminum-based composite material is printed.

[0016] A ceramic / high entropy alloy composite particle reinforced aluminum-based composite material is prepared by the above laser selective melting process.

[0017] This invention proposes, for the first time, the use of a high-entropy alloy reinforced with ceramic particles as a reinforcing phase, combining the advantages of both ceramic and high-entropy alloy reinforcements. First, it effectively improves the laser absorptivity of the aluminum alloy during the laser forming process. Furthermore, the ceramic / high-entropy alloy composite particles are uniformly distributed within the aluminum alloy matrix due to the Marangoni effect in the molten pool. They exhibit good wettability with the aluminum matrix, forming a good metal-metal interface bond, resulting in a highly dense composite material. Therefore, the ceramic / high-entropy alloy composite particles can effectively improve the mechanical properties of aluminum-based composite materials and can be used in the manufacture of high-performance, complex parts for aerospace, automotive, and rail transportation applications.

[0018] Compared with the prior art, the present invention has the following advantages and beneficial effects:

[0019] (1) The ceramic / high entropy alloy composite powder of the present invention has nano-ceramics distributed inside and on the surface of the high entropy alloy, and the composite powder has high sphericity, a smooth surface, and good fluidity, meeting the requirements of SLM technology for the powder used.

[0020] (2) The composite powder of the ceramic / high entropy alloy composite particles reinforced aluminum alloy of the present invention can improve the laser absorption rate of the aluminum-based composite material during the SLM forming process, and the presence of the high melting point ceramic absorbs the energy required for the reaction between the high entropy alloy and aluminum, inhibits the adverse reaction between the high entropy alloy elements and the aluminum matrix, and reduces the porosity inside the matrix, thereby achieving high density of the composite material and effectively improving the forming quality of the aluminum alloy.

[0021] (3) The ceramic / high entropy alloy composite particle reinforcement phase of the present invention is uniformly distributed inside the matrix, and presents an irregular shape or spherical shape under the action of the Marangoni effect in the molten pool, giving full play to the good wettability of the high entropy alloy and the aluminum matrix. No defects are observed at the interface, indicating that the metal bonding at the interface is good; a very thin transition layer is formed between the ceramic / high entropy alloy composite particle reinforcement phase and the aluminum matrix, and the load can be effectively transferred to the ceramic / high entropy composite particle reinforcement phase, reducing the residual stress in the SLM forming process and delaying the fracture of the aluminum-based composite material.

[0022] (4) The ceramic / high-entropy alloy composite particles of the present invention possess excellent strength and deformation capacity. Dispersed within the aluminum matrix, they can hinder the movement of dislocations and grain boundaries, achieving dislocation strengthening, grain boundary strengthening, and dispersion strengthening. Furthermore, some ceramics and the aluminum matrix can form strong nucleating agents, which, on the one hand, can promote heterogeneous nucleation within the aluminum alloy and refine the grains. On the other hand, the precipitation of nanoceramics at the grain boundaries can also hinder grain boundary movement and play a strengthening role. The aluminum-based composite material of the present invention has excellent mechanical properties and can be well applied in actual working conditions. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 The present invention provides a process flow chart for preparing the aluminum-based composite material reinforced with ceramic / high entropy alloy composite particles by laser selective melting.

[0024] Figure 2 This is a microscopic image of the aluminum-based composite material prepared in Example 1 of the present invention.

[0025] Figure 3 This is a microstructure morphology diagram of the aluminum-based composite material prepared in Example 1 of the present invention.

[0026] Figure 4 This is the microstructure morphology of AlSi10Mg prepared in the comparative example of the present invention. DETAILED DESCRIPTION

[0027] In order to make those skilled in the art better understand the technical solution of the present invention, the present invention is further described in detail below with reference to the accompanying drawings. The embodiments listed below are only some embodiments of the present invention, and it should be understood that the protection scope of the present invention is not limited thereto.

[0028] Example 1

[0029] Step (1) Preparation of composite powder: The selected ceramic powder is TiB2 with an average particle size of 0.8 μm, the high entropy alloy powder is FeCoCrNi with an equiatomic ratio and a particle size of 15 to 53 μm, and the aluminum alloy powder is AlSi10Mg with a particle size of 15 to 53 μm. First, FeCoCrNi high entropy powder and TiB2 ceramic powder are plasma spheroidized at a mass ratio of 95:5 to obtain ceramic / high entropy alloy composite powder; then, a certain mass ratio of ceramic / high entropy alloy composite powder and aluminum alloy powder are weighed, wherein the ceramic / high entropy alloy composite powder is 100 μm, the average particle size of the ceramic / high entropy alloy composite powder is 0.8 μm, the average particle size of the high ... and the average particle size of the high entropy alloy composite powder is 0.8 μm. The mass fraction of the porcelain / high entropy alloy composite powder is 2%, and the rest is AlSi10Mg powder. The sizes of the stainless steel balls used are 2mm, 4mm, and 6mm. The stainless steel balls are weighed at a mass ratio of 3:2:1, and the ball-to-material ratio is 5:1. They are added to a ball mill and mixed for 4 hours. Argon is filled for protection at a speed of 220rpm. After that, they are sieved through a sieve and dried at 80℃ in a vacuum drying oven for 4 hours to obtain a spherical composite powder of TiB2 / FeCoCrNi composite particles reinforced AlSi10Mg with a particle size of 15 to 53μm.

[0030] Step (2) The composite powder prepared in step (1) is spread onto the substrate of the SLM metal printer forming cylinder. In this example, the substrate is a 6061 aluminum alloy plate, which is preheated to 200°C and filled with argon for protection. Three-dimensional modeling is performed using SolidWorks software, and the model is imported into the equipment to set the printing process parameters: laser power of 330W, scanning speed of 1400mm / s, powder layer thickness of 30μm, scanning spacing of 150μm, and scanning strategy of 67° interlayer rotation.

[0031] The prepared aluminum matrix composite material was subjected to microstructure characterization, hardness test and room temperature tensile mechanical property test that meets national standards, such as Figure 2 , irregularly shaped or spherical ceramic / high entropy alloy composite particle reinforcement phases are uniformly distributed inside the aluminum matrix. Figure 3 This demonstrates the good interfacial bonding between the ceramic / high-entropy alloy composite particles and the aluminum matrix. Comparing the tensile properties of Example 1 with Comparative Example 1 reveals a significant increase in the yield strength and tensile strength of the aluminum-based composite, reaching 358.42 MPa and 506.38 MPa, respectively. The plasticity remains at 4.4%, and the hardness is increased to 186.92 HV.

[0032] Example 2

[0033] Step (1) Preparation of composite powder: The selected ceramic powder is TiB2 with an average particle size of 0.5 μm, the high entropy alloy powder is AlCoCrFeNi2.1 with a particle size of 15 to 53 μm, and the aluminum alloy powder is AlSi10Mg with a particle size of 15 to 53 μm. First, AlCoCrFeNi2.1 high entropy powder and TiB2 ceramic powder are plasma spheroidized in a mass ratio of 95:5 to obtain ceramic / high entropy alloy composite powder; then, a certain mass ratio of ceramic / high entropy alloy composite powder and aluminum alloy powder are weighed, wherein the ceramic / high entropy alloy composite powder is 0.5 μm, the high entropy alloy powder is 0.5 μm, the high entropy alloy powder is 0.5 μm, and the aluminum alloy powder is 0.5 μm. The mass fraction of the porcelain / high entropy alloy composite powder is 2%, and the rest is AlSi10Mg powder. The sizes of the stainless steel balls used are 2mm, 4mm, and 6mm. The stainless steel balls are weighed at a mass ratio of 3:2:1, and the ball-to-material ratio is 5:1. They are added to a ball mill and mixed for 6 hours. Argon is filled for protection at a speed of 200 rpm. After that, they are sieved through a sieve and dried at 80°C in a vacuum drying oven for 4 hours to obtain a spherical composite powder of TiB2 / AlCoCrFeNi2.1 composite particles reinforced with AlSi10Mg with a particle size of 15 to 53 μm.

[0034] Step (2) The composite powder prepared in step (1) is spread onto the substrate of the SLM metal printer forming cylinder. In this example, the substrate is a 5083 aluminum alloy plate, which is preheated to 200°C and filled with argon for protection. Three-dimensional modeling is performed using SolidWorks software, and the model is imported into the equipment to set the printing process parameters: laser power of 330W, scanning speed of 1400mm / s, powder layer thickness of 30μm, scanning spacing of 150μm, and scanning strategy of 67° interlayer rotation.

[0035] The prepared aluminum matrix composite material was subjected to microstructure characterization, hardness test and room temperature tensile mechanical property test that meets national standards. It can be clearly found that the yield strength and tensile strength are greatly improved, increasing to 362.39MPa and 517.32MPa respectively, the plasticity is maintained at 4.1%, and the hardness is also increased to 196.92HV. The metallographic structure of the TiB2 / AlCoCrFeNi2.1 composite particle reinforced aluminum matrix composite material (compared to Figure 2 It was found that the particles were evenly distributed in the matrix and the interface was well bonded.

[0036] Example 3

[0037] Step (1) Preparation of composite powder: The selected ceramic powder is TiC with an average particle size of 0.5 μm, the high entropy alloy powder is FeCoCrNiMn with a particle size of 15 to 53 μm, and the aluminum alloy powder is AlSi10Mg with a particle size of 15 to 53 μm. First, FeCoCrNiMn high entropy powder and TiC ceramic powder are plasma spheroidized at a mass ratio of 95:5 to obtain ceramic / high entropy alloy composite powder; then, a certain mass ratio of ceramic / high entropy alloy composite powder and aluminum alloy powder are weighed, wherein the ceramic / high entropy alloy composite powder is 0.5 μm, the average particle size of the high entropy alloy powder is 0.5 μm, the average particle size of the high entropy alloy powder is 0.5 μm, and the average particle size of the high entropy alloy powder is 0.5 μm. The mass fraction of the entropy alloy composite powder is 10%, and the rest is AlSi10Mg powder. The sizes of the stainless steel balls used are 2mm, 4mm, and 6mm. The stainless steel balls are weighed at a mass ratio of 3:2:1, and the ball-to-material ratio is 10:1. They are added to a ball mill and mixed for 6 hours. Argon is filled for protection, the rotation speed is 180rpm, and then sieved through a sieve and dried at 80°C in a vacuum drying oven for 4 hours to obtain a spherical composite powder of TiC / FeCoCrNiMn composite particles reinforced with AlSi10Mg with a particle size of 15 to 53μm.

[0038] Step (2) The composite powder prepared in step (1) is spread onto the substrate of the SLM metal printer forming cylinder. In this example, the substrate is a 6061 aluminum alloy plate, which is preheated to 200°C and filled with argon for protection. Three-dimensional modeling is performed using SolidWorks software, and the model is imported into the equipment to set the printing process parameters: laser power of 330W, scanning speed of 1300mm / s, powder layer thickness of 30μm, scanning spacing of 150μm, and scanning strategy of 67° interlayer rotation.

[0039] The prepared aluminum matrix composite material was subjected to microstructure characterization, hardness test and room temperature tensile mechanical property test that meets national standards. It can be clearly found that the yield strength and tensile strength are greatly improved, increasing to 370.63MPa and 540.68MPa respectively, the plasticity is maintained at 3.3%, and the hardness is also increased to 200.34HV. Figure 2 Similar) found that there were no obvious defects within the organization.

[0040] Example 4

[0041] Step (1) Preparation of composite powder: The selected ceramic powder is TiC with an average particle size of 0.5 μm, the high entropy alloy powder is FeCoCrNiMo with a particle size of 15 to 53 μm, and the aluminum alloy powder is AlSi10Mg with a particle size of 15 to 53 μm. First, FeCoCrNiMo high entropy powder and TiC ceramic powder are plasma spheroidized in a mass ratio of 90:10 to obtain ceramic / high entropy alloy composite powder; then, a certain mass ratio of ceramic / high entropy alloy composite powder and aluminum alloy powder are weighed, wherein the ceramic / The mass fraction of the high-entropy alloy composite powder is 3%, and the rest is AlSi10Mg powder. The sizes of the stainless steel balls used are 2mm, 4mm, and 6mm. The stainless steel balls are weighed at a mass ratio of 3:2:1, and the ball-to-material ratio is 5:1. They are added to a ball mill and mixed for 6 hours. Argon is filled for protection, the rotation speed is 160rpm, and then sieved through a sieve and dried at 80°C in a vacuum drying oven for 4 hours to obtain a spherical composite powder of TiC / FeCoCrNiMo composite particles reinforced with AlSi10Mg with a particle size of 15 to 53μm.

[0042] Step (2) The composite powder prepared in step (1) is spread onto the substrate of the SLM metal printer forming cylinder. In this example, the substrate is a 5083 aluminum alloy plate, which is preheated to 200°C and filled with argon for protection. Three-dimensional modeling is performed using SolidWorks software, and the model is imported into the equipment to set the printing process parameters: laser power of 330W, scanning speed of 1500mm / s, powder layer thickness of 30μm, scanning spacing of 150μm, and scanning strategy of 67° interlayer rotation.

[0043] The prepared aluminum matrix composite material was characterized by microstructure and tested for room temperature tensile mechanical properties that meet national standards. It was found that the yield strength and tensile strength were significantly improved, reaching 361.42MPa and 512.68MPa respectively. The plasticity was maintained at 3.8% and the hardness was also increased to 192.6HV. Figure 2 It was found that the interface between the reinforcement phase and the matrix was smooth and clean.

[0044] Example 5

[0045] Step (1) Preparation of composite powder: The selected ceramic powder is ZrO2 with an average particle size of 0.5 μm, the high entropy alloy powder is TiNbZrTa with a particle size of 1 to 25 μm, and the aluminum alloy powder is 2024 series aluminum alloy with a particle size of 15 to 53 μm. First, TiNbZrTa high entropy powder and ZrO2 ceramic powder are plasma spheroidized in a mass ratio of 95:5 to obtain ceramic / high entropy alloy composite powder; then, a certain mass ratio of ceramic / high entropy alloy composite powder and aluminum alloy powder are weighed, wherein the ceramic / The mass fraction of the high entropy alloy composite powder is 2%, and the rest is 2024 aluminum alloy powder. The sizes of the stainless steel balls used are 2mm, 4mm, and 6mm. The stainless steel balls are weighed at a mass ratio of 3:2:1, and the ball-to-material ratio is 5:1. They are added to a ball mill and mixed for 4 hours. Argon is filled for protection, the rotation speed is 140rpm, and then sieved through a sieve and dried at 80°C in a vacuum drying oven for 4 hours to obtain a spherical composite powder of ZrO2 / TiNbZrTa composite particles reinforced with 2024 aluminum alloy with a particle size of 15 to 53μm.

[0046] Step (2): The composite powder from step (1) was spread onto the substrate of the SLM metal printer's forming cylinder. In this example, the substrate was a 2024 aluminum alloy plate, preheated to 200°C, and filled with argon for protection. Three-dimensional modeling was performed using SolidWorks software, and the model was imported into the device to set the printing process parameters: laser power of 350W, scanning speed of 1600mm / s, powder layer thickness of 30μm, scanning spacing of 150μm, and scanning strategy of 67° interlayer rotation.

[0047] The prepared aluminum matrix composite material was characterized by microstructure and tested for room temperature tensile mechanical properties that meet national standards. It was found that the yield strength and tensile strength were significantly improved, reaching 261.28 MPa and 414.39 MPa respectively. The plasticity remained at 9.3% and the hardness was also increased to 143.68 HV. Figure 2 It was found that the reinforcement phase was evenly distributed inside the matrix and the grains were refined.

[0048] Example 6

[0049] Step (1) Preparation of ceramic / high entropy alloy composite particle reinforced aluminum alloy composite powder: The selected ceramic powder is TiB2 with an average particle size of 0.1 μm, the high entropy alloy powder is AlCoCrFeNi2.1 with a particle size of 15 to 53 μm, and the aluminum alloy powder is 2024 series aluminum alloy with a particle size of 15 to 53 μm. First, AlCoCrFeNi2.1 high entropy powder and TiB2 ceramic powder are prepared by plasma spheroidization at a mass ratio of 50:50 to obtain ceramic / high entropy alloy composite powder; then a certain mass ratio of ceramic / high entropy alloy composite powder is weighed. and aluminum alloy powder, of which the mass fraction of ceramic / high entropy alloy composite powder is 2%, and the rest is 2024 aluminum alloy powder. The sizes of stainless steel balls used are 2mm, 4mm, and 6mm. The stainless steel balls are weighed at a mass ratio of 3:2:1, the ball-to-material ratio is 5:1, and added to a ball mill and mixed for 8h. Argon is filled for protection at a speed of 200rpm. After that, it is sieved through a sieve and dried at 80℃ in a vacuum drying oven for 4h to obtain a spherical composite powder of TiB2 / AlCoCrFeNi2.1 composite particles reinforced with 2024 aluminum alloy with a particle size of 15 to 53μm.

[0050] Step (2) The composite powder prepared in step (1) is spread onto the substrate of the SLM metal printer forming cylinder. In this example, the substrate is a 2024 aluminum alloy plate, which is preheated to 200°C and filled with argon for protection. Three-dimensional modeling is performed using SolidWorks software, and the model is imported into the equipment to set the printing process parameters: laser power of 330W, scanning speed of 1400mm / s, powder layer thickness of 30μm, scanning spacing of 150μm, and scanning strategy of 67° interlayer rotation.

[0051] The prepared aluminum matrix composite material was characterized by microstructure and tested for room temperature tensile mechanical properties that meet national standards. It was found that the yield strength and tensile strength were significantly improved, reaching 270.3MPa and 425.65MPa respectively, while the plasticity remained at 7.3% and the hardness was also increased to 148.7HV. Figure 2 It was found that the particles were evenly distributed in the matrix without obvious defects.

[0052] Example 7

[0053] Step (1) Preparation of composite powder: The selected ceramic powder is TiB2 with an average particle size of 0.5 μm, the high entropy alloy powder is AlTiCrNiCu with a particle size of 15 to 53 μm, and the aluminum alloy powder is 2024 series aluminum alloy with a particle size of 15 to 53 μm. First, AlCoCrFeNi2.1 high entropy powder and TiB2 ceramic powder are prepared by plasma spheroidization in a mass ratio of 80:20 to obtain ceramic / high entropy alloy composite powder; then, a certain mass ratio of ceramic / high entropy alloy composite powder and aluminum alloy powder are weighed, wherein The mass fraction of the ceramic / high entropy alloy composite powder is 4%, and the rest is 2024 aluminum alloy powder. The sizes of the stainless steel balls used are 2mm, 4mm, and 6mm. The stainless steel balls are weighed at a mass ratio of 3:2:1, and the ball-to-material ratio is 5:1. They are added to a ball mill and mixed for 8 hours. Argon is filled for protection at a speed of 200 rpm. After that, they are sieved through a sieve and dried at 80°C in a vacuum drying oven for 4 hours to obtain a spherical composite powder of TiB2 / AlTiCrNiCu composite particles reinforced with 2024 aluminum alloy with a particle size of 15 to 53 μm.

[0054] Step (2) The composite powder prepared in step (1) is spread onto the substrate of the SLM metal printer forming cylinder. In this example, the substrate is a 2024 aluminum alloy plate, which is preheated to 200°C and filled with argon for protection. Three-dimensional modeling is performed using SolidWorks software, and the model is imported into the equipment to set the printing process parameters: laser power of 330W, scanning speed of 1400mm / s, powder layer thickness of 30μm, scanning spacing of 150μm, and scanning strategy of 67° interlayer rotation.

[0055] The prepared aluminum matrix composite material was characterized by microstructure and tested for room temperature tensile mechanical properties that meet national standards. It was found that the yield strength and tensile strength were significantly improved, reaching 262.78 MPa and 420.45 MPa respectively. The plasticity remained at 5.82% and the hardness was also increased to 151.23 HV. Figure 2 It was found that the interface between the particles and the matrix was well bonded, showing a smooth and clean interface.

[0056] Example 8

[0057] Step (1) Preparation of composite powder: The selected ceramic powder is TiN with an average particle size of 0.5 μm, the high entropy alloy powder is AlCoCrFeNi2.1 with a particle size of 1 to 25 μm, and the aluminum alloy powder is AlSi10Mg with a particle size of 15 to 53 μm. First, AlCoCrFeNi2.1 high entropy powder and TiN ceramic powder are prepared by plasma spheroidization at a mass ratio of 95:5 to obtain ceramic / high entropy alloy composite powder; then, a certain mass ratio of ceramic / high entropy alloy composite powder and aluminum alloy powder are weighed, wherein the ceramic / high entropy alloy composite powder is 0.5 μm, the high entropy alloy powder is 0.5 μm, the high entropy alloy powder is 0.5 μm, the high entropy alloy powder is 0.5 μm, and the aluminum alloy powder is 0.5 μm. The mass fraction of the porcelain / high entropy alloy composite powder is 1%, and the rest is AlSi10Mg. The sizes of the stainless steel balls used are 2mm, 4mm, and 6mm. The stainless steel balls are weighed at a mass ratio of 3:2:1, and the ball-to-material ratio is 5:1. They are added to a ball mill and mixed for 6 hours. Argon is filled for protection, the rotation speed is 140rpm, and then sieved through a sieve and dried at 80℃ in a vacuum drying oven for 4 hours to obtain a spherical composite powder of TiN / AlCoCrFeNi2.1 composite particles reinforced AlSi10Mg with a particle size of 15 to 53μm.

[0058] Step (2) The composite powder prepared in step (1) is spread onto the substrate of the SLM metal printer forming cylinder. In this example, the substrate is a 5083 aluminum alloy plate, which is preheated to 200°C and filled with argon for protection. Three-dimensional modeling is performed using SolidWorks software, and the model is imported into the equipment to set the printing process parameters: laser power of 330W, scanning speed of 1400mm / s, powder layer thickness of 30μm, scanning spacing of 150μm, and scanning strategy of 67° interlayer rotation.

[0059] The prepared aluminum matrix composite material was characterized by microstructure and tested for room temperature tensile mechanical properties that meet national standards. It was found that the yield strength and tensile strength were significantly improved, reaching 356.29 MPa and 499.56 MPa respectively. The plasticity remained at 4.6% and the hardness was also increased to 170.32 HV. Figure 2 It was found that the reinforcement phase was dispersed inside the aluminum matrix.

[0060] Comparative Example

[0061] In this comparative example, an AlSi10Mg alloy was prepared. The difference from Examples 1, 2, 3, 4, 5, and 8 is that no ceramic / high entropy alloy composite particle reinforcement phase was added, and the printing process was consistent.

[0062] Figure 4The microstructures perpendicular to the build direction (a) and parallel to the build direction (b) are typical of the comparative example. The perpendicular build direction shows α-Al and a network of eutectic silicon, while the parallel build direction shows columnar crystals growing perpendicular to the melt pool. The addition of ceramic / high-entropy alloy composite particle reinforcements refines the grains to a certain extent, and the columnar crystals parallel to the build direction are partially transformed into equiaxed crystals, reducing the mechanical anisotropy of the composite material, improving mechanical properties while also maintaining a certain degree of plasticity.

[0063] The mechanical properties of the ceramic / high entropy alloy composite particle reinforced aluminum matrix composite materials prepared in Examples 1, 2, 3, 4, and 8 are greatly improved compared to AlSi10Mg, while maintaining good plasticity.

[0064] The embodiments described are preferred implementations of the present invention, but the present invention is not limited to the above-mentioned implementations. Any obvious improvements, substitutions or modifications that can be made by those skilled in the art without departing from the essence of the present invention are within the scope of protection of the present invention.

Claims

1. A laser additive manufacturing method for aluminum-based composite materials reinforced with ceramic / high entropy alloy composite particles, characterized in that: The following steps are involved: (1) Preparation of composite powder: Ceramic powder and high entropy alloy powder are prepared by plasma spheroidization to obtain ceramic / high entropy alloy composite powder, ceramic / high entropy alloy composite powder and aluminum alloy powder are weighed respectively, uniformly mixed by ball milling, and passed with protective gas, sieved through a standard sieve and dried to obtain ceramic / high entropy alloy composite particle reinforced aluminum alloy composite powder; the mass fraction of ceramic in the ceramic / high entropy alloy composite powder is 0.5%~50%, the mass fraction of high entropy alloy is 50%~99.5%, and the sum of the two is equal to 1; the ceramic powder is flake or other irregular shape and the particle size is 0.05~1 μm, the high entropy alloy powder is spherical and the particle size is 1~100 μm, and the ceramic / high entropy alloy composite powder is spherical and the particle size is 1~100 μm; the mass fraction of the ceramic / high entropy alloy composite powder in the composite powder reinforced with the ceramic / high entropy alloy aluminum alloy is 1% to 10%, the mass fraction of the aluminum alloy is 90% to 99%, and the sum of the two is equal to 1; the aluminum alloy powder is spherical and has a particle size of 1 to 100 μm; (2) SLM preparation of aluminum-based composite materials: The composite powder of ceramic / high-entropy alloy composite particles reinforced aluminum alloy is spread flat on the substrate of the SLM metal 3D printer forming chamber, and the substrate is preheated under the protection gas. The laser power, scanning speed, scanning spacing and powder layer thickness are adjusted to allow the laser to scan and deposit layer by layer on the powder bed to print the aluminum-based composite material.

2. The laser additive manufacturing method of the ceramic / high entropy alloy composite particle reinforced aluminum-based composite material according to claim 1, characterized in that: The aluminum alloy includes a cast aluminum alloy, a deformed aluminum alloy or an Al-Li alloy; the cast aluminum alloy includes an Al-Si series, an Al-Cu series, an Al-Mg series or an Al-Zn series; the deformed aluminum alloy includes a 1xxx, 2xxx, 4xxx, 5xxx, 6xxx or 7xxx alloy; the ceramic in the ceramic / high entropy alloy composite particles includes TiB2, TiC, TiN, SiC or ZrO2; the high entropy alloy includes a FeCoCrNi series, a FeCoCrNiMn series, a FeCoCrNiMo series, an AlCoCrFeNi series, an AlTiCrNiCu series, a WTaMoNbV series or a TiNbZrTa series.

3. The laser additive manufacturing method for the ceramic / high entropy alloy composite particle reinforced aluminum matrix composite material according to claim 1, characterized in that: In step (1), the ball milling time is 4 to 8 hours, the rotation speed is 120 to 220 rpm, the grinding balls are stainless steel balls or ZrO2 grinding balls, the grinding ball size is 2 to 6 mm, and the ball-to-material ratio is 5:1 to 10:1; the protective gas is argon or nitrogen, and the drying is carried out in a vacuum environment at 70 to 120 °C for 4 to 6 hours.

4. The laser additive manufacturing method for the ceramic / high entropy alloy composite particle reinforced aluminum matrix composite material according to claim 1, characterized in that: In step (2), the substrate used in the printing process is a 1xxx, 2xxx, 4xxx, 5xxx, 6xxx or 7xxx aluminum alloy, and the substrate is preheated in a nitrogen or argon atmosphere at a temperature of 150°C to 200°C.

5. The laser additive manufacturing method for the ceramic / high entropy alloy composite particle reinforced aluminum matrix composite material according to claim 1, characterized in that: In step (2), the laser power is 270 W to 370 W, the scanning speed is 1100 mm / s to 1600 mm / s, the powder layer thickness is 20 to 75 μm, the scanning spacing is 110 to 150 μm, and the scanning strategy is an interlayer rotation of 67°.

6. The laser additive manufacturing method of the ceramic / high entropy alloy composite particle reinforced aluminum matrix composite material according to claim 1, characterized in that: The ceramic / high entropy alloy composite powder described in step (1) is characterized by ceramic particles distributed inside and on the surface of the high entropy alloy powder, and the composite powder has good sphericity, surface smoothness and powder fluidity, and is suitable for the field of additive manufacturing.

7. The laser additive manufacturing method according to any one of claims 1 to 6 produces an aluminum-based composite material reinforced with ceramic / high-entropy alloy composite particles.

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