WO2020056535A1 - Method for preparing tungsten particle-reinforced metal-based composite material on basis of 3d printing technology - Google Patents

Method for preparing tungsten particle-reinforced metal-based composite material on basis of 3d printing technology Download PDF

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WO2020056535A1
WO2020056535A1 PCT/CN2018/000359 CN2018000359W WO2020056535A1 WO 2020056535 A1 WO2020056535 A1 WO 2020056535A1 CN 2018000359 W CN2018000359 W CN 2018000359W WO 2020056535 A1 WO2020056535 A1 WO 2020056535A1
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alloy
powder
tungsten
composite material
reinforced metal
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PCT/CN2018/000359
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French (fr)
Chinese (zh)
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薛云飞
周上程
王本鹏
王富耻
王鲁
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北京理工大学
薛云飞
周上程
王本鹏
王富耻
王鲁
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Publication of WO2020056535A1 publication Critical patent/WO2020056535A1/en

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    • 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
    • B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
    • 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
    • B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
    • B22F10/30—Process control
    • B22F10/36—Process control of energy beam parameters
    • B22F1/0003—
    • 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
    • B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
    • B22F10/30—Process control
    • B22F10/32—Process control of the atmosphere, e.g. composition or pressure in a building chamber
    • 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
    • B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
    • B22F10/30—Process control
    • B22F10/34—Process control of powder characteristics, e.g. density, oxidation or flowability
    • 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
    • B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
    • B22F10/80—Data acquisition or data processing
    • 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
    • B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
    • B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
    • B22F9/082—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y10/00—Processes of additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/25—Process efficiency

Definitions

  • the invention relates to a method for preparing tungsten particle-reinforced metal-based composite materials based on 3D printing technology, and belongs to the technical field of particle-reinforced metal-based composite materials and 3D printing.
  • Tungsten particle reinforced metal matrix composite is a composite material with metal tungsten as the reinforcing phase and NiFe, Cu or other low melting point elements as the matrix phase.
  • the tungsten content is higher than 80% by mass, it is also a high specific gravity alloy.
  • Tungsten particle-reinforced metal-based composite materials that have been developed so far include W-Ni-Cu, W-Ni-Fe, W-Ni-Mn, W-Cu, and W-Ni series.
  • the mechanical properties of the bonding phases such as Ni-Cu, Ni-Fe, Ni-Mn and the morphology of tungsten particles have a decisive effect on the mechanical properties of tungsten particle reinforced metal matrix composites.
  • the main preparation methods of tungsten particle reinforced metal matrix composites include liquid phase sintering, solid phase sintering, and melt infiltration.
  • the liquid phase sintering method is the most common method for preparing high specific gravity tungsten particle reinforced metal matrix composites, and has the advantages of high density, high strength, large plasticity and uniform microstructure.
  • this method has the following disadvantages: when the tungsten content is small, the tungsten particle-reinforced metal matrix composite material will have serious deformation and uneven structure; the hydrogen atmosphere in the liquid phase sintering will cause hydrogen embrittlement, and a dehydrogenation is required after sintering The process greatly increases the production cost; the prepared tungsten particle reinforced metal matrix composite has relatively coarse grains.
  • the solid-phase sintering method is generally used to prepare metal matrix composites with low tungsten content and fine-grained tungsten particle reinforcement, but this method results in low density and poor mechanical properties of the alloy.
  • extremely complicated and complicated processes are often introduced in the solid phase sintering method, or unconventional sintering methods such as high voltage and discharge are introduced.
  • Preparation of tungsten particle reinforced metal matrix composites by the melt infiltration method has the advantages of tungsten content, morphology controllability, controllable cooling rate, and high density.
  • it has the disadvantages of limited sample size and high cost.
  • the existing conventional preparation methods have disadvantages that cannot be ignored, such as difficult molding, high subsequent processing costs, complex preparation processes, and high porosity of the finished product, which limit the development of tungsten particle-reinforced metal matrix composites.
  • the present invention provides a method for preparing tungsten particle-reinforced metal-based composites based on 3D printing technology, which can regulate the bonding phase and The ratio of the reinforcing phase, the prepared composite material has excellent mechanical properties, and the method has the advantages of short preparation cycle, simple process, low cost and the like.
  • the tungsten particle reinforced metal matrix composite material is composed of a tungsten reinforcement phase and a matrix phase, and the matrix phase is Ni, Cu, Al, NiFe alloy, NiCu alloy, CuZn alloy, NiMn alloy, NiCo alloy, or AlCrFeNiVM high entropy alloy; where the matrix phase is Ni, Cu, Al, NiFe alloy, NiCu alloy, CuZn alloy, NiMn alloy, NiCo alloy, and the mass percentage of the tungsten phase is 5% to 90%. %, The mass percentage of the tungsten phase when the matrix phase is AlCrFeNiVM high entropy alloy is 5% to 80%;
  • the mass ratio of the first element to the second element is independently 1 to 4, and the first element and the second element in the NiMn alloy (that is, The mass ratio of Ni element to Mn element is 0.5 to 3;
  • the molar ratio of each element in AlCrFeNiVM high entropy alloy is (0.3 to 1.0): (0.2 to 1.0): (0.6 to 1.2): (1.5 to 3.5): (0.1 to 0.5): (0 to 0.3), preferably (0.5 to 1.0): (0.9 to 1.0): (0.8 to 1.0): (1.5 to 3.0): (0.1 to 0.3): 0,
  • M is Cu, One or more of Ti, Mo, W;
  • the mixed powder is a mixed powder of tungsten powder and Ni simple powder, Cu simple powder, Al simple powder, NiFe alloy powder, NiCu alloy powder, CuZn alloy powder, NiMn alloy powder, NiCo alloy powder or AlCrFeNiVM high-entropy alloy powder.
  • the AlCrFeNiVM high-entropy alloy powder is prepared by the following method: Al, Cr, Fe, Ni, V, and M metals are first smelted into an alloy liquid and cast into an alloy ingot, and then performed in a gas atomizing furnace. Atomizing powder to obtain AlCrFeNiVM high entropy alloy powder; among them, the process parameters of gas atomizing powder are as follows: superheat degree 50 °C ⁇ 400 °C, atomizing gas pressure 2MPa ⁇ 8MPa, diversion tube diameter 3mm ⁇ 10mm, atomization The medium was argon.
  • the process parameters of 3D printing are as follows: the laser spot diameter is 0.5mm ⁇ 6mm, the scanning speed is below 30mm / s, the spot path interval is set so that the overlap rate is 5% ⁇ 70%, the laser power is 200W ⁇ 5000W, and the powder feed rate is 0.1kg / h ⁇ 5kg / h, energy area density 30J / mm 2 ⁇ 260J / mm 2 , energy mass density 1000J / g ⁇ 20,000J / g, single-layer deposition thickness is greater than 0mm and less than or equal to 4mm.
  • the particle diameter of the tungsten powder is less than 25 ⁇ m, and the particle diameters of the elemental powder, the alloy powder, and the AlCrFeNiVM high-entropy alloy powder are all less than 250 ⁇ m.
  • the present invention uses 3D printing technology to prepare tungsten particle-reinforced metal-based composite materials, which can regulate the ratio of tungsten-reinforced phase and matrix phase in the composite material within a relatively large range, and can be designed strong, the process is simple, and the preparation cycle is short And low cost;
  • tungsten reinforcement phase particles are uniformly distributed on the matrix phase, tungsten reinforcement phase particles are fine, grains are not significantly grown, and mechanical properties are excellent.
  • FIG. 1 is a scanning electron microscope (SEM) image of a tungsten / AlCrFeNiV high-entropy alloy composite material prepared in Example 1.
  • SEM scanning electron microscope
  • FIG. 2 is a SEM image of the tungsten / AlCrFeNiV high-entropy alloy composite material prepared in Example 2.
  • FIG. 2 is a SEM image of the tungsten / AlCrFeNiV high-entropy alloy composite material prepared in Example 2.
  • Example 3 is a SEM image of a tungsten / AlCrFeNiV high-entropy alloy composite material prepared in Example 3.
  • FIG. 4 is a SEM image of the tungsten / nickel composite prepared in Example 4.
  • FIG. 4 is a SEM image of the tungsten / nickel composite prepared in Example 4.
  • FIG. 5 is a SEM image of the tungsten / nickel-iron composite material prepared in Example 5.
  • FIG. 6 is a SEM image of the tungsten / nickel copper composite material prepared in Example 6.
  • FIG. 7 is a SEM image of the tungsten / AlCrFeNiVCu composite material prepared in Example 7.
  • FIG. 7 is a SEM image of the tungsten / AlCrFeNiVCu composite material prepared in Example 7.
  • FIG. 8 is a comparison graph of quasi-static tensile mechanical properties of the tungsten / AlCrFeNiV high-entropy alloy composite material prepared in Example 3 and the tungsten / nickel-iron composite material prepared in Example 5.
  • FIG. 8 is a comparison graph of quasi-static tensile mechanical properties of the tungsten / AlCrFeNiV high-entropy alloy composite material prepared in Example 3 and the tungsten / nickel-iron composite material prepared in Example 5.
  • the purity of Al, Cr, Fe, Ni and V metals are all 99.9wt%;
  • High-vacuum non-consumable arc melting furnace DHL-400 high-vacuum non-consumable arc melting furnace, Shenyang Scientific Instrument Co., Ltd., Chinese Academy of Sciences;
  • 3D printing equipment TSC-S600 fiber laser additive manufacturing system, Xinjinghe Laser Technology Development (Beijing) Co., Ltd .;
  • Vacuum metal atomizing powder furnace The vacuum metal atomizing powder furnace developed by Shenyang Haojiduo New Material Preparation Technology Co., Ltd. can produce metal alloy powder with better sphericity;
  • V-type mixer VH5, Shanghai Tianying Machinery Equipment Co., Ltd .;
  • Vickers hardness tester Precision digital display automatic turret Vickers hardness tester, model JMHVS-10AT, Shanghai Aolong Xingdi Testing Equipment Co., Ltd. The test process uses 10kg force and the load retention time is 5 seconds;
  • HITACHI S4800 cold field emission scanning electron microscope from Hitachi, Japan was used to characterize the micromorphology, backscattered electron imaging, and the working voltage was 15kV;
  • Quasi-static tensile test CMT4305 microcomputer electronic universal testing machine is used to perform room temperature quasi-static tensile test.
  • the test specimens are made according to the relevant provisions of the national standard for room temperature tensile test methods of metal materials (GB / T 228.1-2010).
  • the strain rate is 10 -3 s -1 .
  • the atmosphere of the chamber of the 3D printing device is argon, and the mixed powder is sent to the laser heating area of the 3D printing device by a coaxial powder feeding method, and the composite material is printed layer by layer to obtain the composite material; wherein, the process of 3D printing
  • the parameters are as follows: the laser spot diameter is 4mm, the spot scanning speed is 6mm / s, the spot path interval is 2mm, the laser power is 2600W, the powder feed rate is 2.1r / min (that is, 4kg / h), and the single-layer deposition thickness is 1.8mm.
  • the composition of the light-colored particles is tungsten, the size of the tungsten particles is less than 10 ⁇ m, the composition of the dark matrix between the particles is AlCrFeNiV high-entropy alloy, and the tungsten particles are evenly distributed on the AlCrFeNiV high-entropy alloy matrix, and the two-phase interface is clear .
  • the density of the prepared composite material is 12.88 g / cm 3 and the hardness is 430 HV.
  • the volume fraction of the AlCrFeNiV high entropy alloy phase is about 62.75%.
  • the yield strength of the prepared composite material is 849 MPa
  • the tensile strength is 1308 MPa
  • the elongation is 6%.
  • the atmosphere of the chamber of the 3D printing device is argon, and the mixed powder is sent to the laser heating area of the 3D printing device by a coaxial powder feeding method, and the composite material is printed layer by layer to obtain the composite material; wherein, the process of 3D printing
  • the parameters are as follows: the laser spot diameter is 4mm, the spot scanning speed is 8mm / s, the spot path interval is 3mm, the laser power is 1800W, the powder feed rate is 1r / min (that is, 2kg / h), and the single-layer deposition thickness is 3mm. .
  • the composition of the light-colored particles is tungsten, the size of the tungsten particles is less than 1 ⁇ m, and the composition of the dark matrix between the particles is AlCrFeNiV high-entropy alloy.
  • the tungsten particles are evenly distributed on the AlCrFeNiV high-entropy alloy matrix, and the two-phase interface is clear.
  • the prepared composite has a density of 8.4 g / cm 3 , a hardness of 348 HV, and an AlCrFeNiV high entropy alloy phase volume fraction of about 95.21%.
  • the yield strength of the prepared composite material is 809 MPa
  • the tensile strength is 1027 MPa
  • the elongation is 6%.
  • the atmosphere of the chamber of the 3D printing device is argon, and the mixed powder is sent to the laser heating area of the 3D printing device by a coaxial powder feeding method, and the composite material is printed layer by layer to obtain the composite material; wherein, the process of 3D printing
  • the parameters are as follows: the laser spot diameter is 4mm, the spot scanning speed is 3mm / s, the spot path interval is 2mm, the laser power is 2800W, the powder feed rate is 1.5r / min (that is, 3kg / h), and the single-layer deposition thickness is 0.8mm.
  • the composition of the light-colored particles is tungsten, the size of the tungsten particles is less than 10 ⁇ m, the composition of the dark matrix between the particles is AlCrFeNiV high-entropy alloy, and the tungsten particles are evenly distributed on the AlCrFeNiV high-entropy alloy matrix, and the two-phase interface is clear .
  • the density of the prepared composite material is 15.02 g / cm 3
  • the hardness is 541 HV
  • the volume fraction of the AlCrFeNiV high entropy alloy phase is about 31.85%.
  • the yield strength of the prepared composite material is 1158 MPa
  • the tensile strength is 1355 MPa
  • the elongation is 1%, as shown in FIG. 8.
  • the atmosphere of the chamber of the 3D printing device is argon, and the mixed powder is sent to the laser heating area of the 3D printing device by a coaxial powder feeding method, and the composite material is printed layer by layer to obtain the composite material; wherein, the process of 3D printing
  • the parameters are as follows: the laser spot diameter is 4mm, the spot scanning speed is 12mm / s, the spot path interval is 2mm, the laser power is 1600W, the powder feed rate is 1.2r / min (that is, 2.4kg / h), and the single-layer deposition thickness is 0.6mm.
  • the composition of the light-colored particles is tungsten, the size of the tungsten particles is less than 10 ⁇ m, the composition of the dark matrix between the particles is nickel, and the tungsten particles are uniformly distributed on the nickel matrix, and the two-phase interface is clear.
  • the prepared composite material has a density of 12.44 g / cm 3 , a hardness of 392 HV, and a nickel phase volume fraction of about 57.70%.
  • the quasi-static tensile test it can be known that the tensile strength of the prepared composite material is 745 MPa, the tensile strength is 1108 MPa, and the elongation is 8%.
  • the atmosphere of the chamber of the 3D printing equipment is argon.
  • the coaxial powder feeding method is used to send the nickel-iron mixed powder and tungsten powder to the laser heating area of the 3D printing equipment according to a mass ratio of 2: 8.
  • the composite material is obtained; wherein, the process parameters of 3D printing are as follows: laser spot diameter 4mm, spot scanning speed 8mm / s, spot path interval 2mm, laser power 2400W, tungsten powder feed rate 0.42r / min (ie 1.08kg / h), the powder-feeding rate of the nickel-iron mixed powder is 0.28 r / min (that is, 0.72 kg / h), and the thickness of the single-layer deposition is 0.6 mm.
  • the composition of the light-colored particles is tungsten, the size of the tungsten particles is less than 10 ⁇ m, the composition of the dark matrix between the particles is a nickel-iron matrix, the tungsten particles are uniformly distributed on the nickel-iron matrix, and the two-phase interface is clear.
  • the density of the prepared composite material is 15.93 g / cm 3
  • the hardness is 496 HV
  • the volume fraction of the nickel-iron phase is about 31.58%.
  • the yield strength of the prepared composite material is 957 MPa, the tensile strength is 1318 MPa, and the elongation is 5.8%, as shown in FIG. 8.
  • the atmosphere of the chamber of the 3D printing device is argon.
  • the coaxial powder feeding method is used to send the nickel-copper mixed powder and tungsten powder to the laser heating area of the 3D printing device according to a mass ratio of 4: 6, and print layer by layer.
  • the composite material is obtained; wherein, the 3D printing process parameters are as follows: laser spot diameter 4mm, spot scanning speed 8mm / s, spot path interval 2mm, laser power 2500W, tungsten powder feed rate 0.42r / min (ie 1.08kg / h), the powder-feeding rate of the nickel-copper mixed powder is 0.28 r / min (ie, 0.72 kg / h), and the thickness of the single-layer deposition is 0.6 mm.
  • the composition of the light-colored particles is tungsten
  • the size of the tungsten particles is less than 10 ⁇ m
  • the composition of the dark matrix between the particles is a nickel-copper matrix
  • the tungsten particles are uniformly distributed on the nickel-copper matrix
  • the two-phase interface is clear. It can be known through measurement that the density of the prepared composite material is 12.15 g / cm 3 , the hardness is 425 HV, and the volume fraction of the nickel-copper phase is about 59.40%. It can be known from the quasi-static tensile test that the yield strength of the prepared composite material is 735 MPa, the tensile strength is 925 MPa, and the elongation is 7.3%.
  • the atmosphere of the chamber of the 3D printing device is argon, and the mixed powder is sent to the laser heating area of the 3D printing device by a coaxial powder feeding method, and the composite material is printed layer by layer to obtain the composite material; wherein, the process of 3D printing
  • the parameters are as follows: laser spot diameter 4mm, spot scanning speed 12mm / s, spot path interval 2mm, laser power 2800W, powder feed rate 1.2r / min (ie 2kg / h), single layer deposition thickness 0.8mm.
  • the composition of the light-colored particles is tungsten, the size of the tungsten particles is less than 10 ⁇ m, the composition of the dark matrix between the particles is an AlCrFeNiVCu high-entropy alloy matrix, and the tungsten particles are evenly distributed on the AlCrFeNiVCu high-entropy alloy matrix, and the two-phase interface Clear.
  • the density of the prepared composite material is 11.25 g / cm 3
  • the hardness is 465 HV
  • the volume fraction of AlCrFeNiVCu high entropy alloy phase is about 53.40%.
  • the quasi-static tensile test that the yield strength of the prepared composite material is 765 MPa, the tensile strength is 1025 MPa, and the elongation is 6.1%.

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Abstract

The present invention relates to the technical fields of particle-reinforced metal-based composite materials and 3D printing, and relates to a method for preparing a tungsten particle-reinforced metal-based composite material on the basis of three-dimensional (3D) printing technology. The present invention uses 3D printing technology to prepare a tungsten particle-reinforced metal-based composite material, wherein the proportions of a tungsten-reinforced phase and a matrix phase in the composite material may be adjusted and controlled within a relatively large range. The present invention may have a strong design, a simple process, a short preparation cycle and low costs. Moreover, in the tungsten particle-reinforced metal-based composite material prepared by the described method of the present invention, tungsten-reinforced phase particles are uniformly distributed on the matrix phase, the tungsten-reinforced phase particles are fine, and the grains are not significantly grown and have excellent mechanical properties.

Description

基于3D打印技术制备钨颗粒增强金属基复合材料的方法Method for preparing tungsten particle reinforced metal matrix composite material based on 3D printing technology 技术领域Technical field
本发明涉及一种基于3D打印技术制备钨颗粒增强金属基复合材料的方法，属于颗粒增强金属基复合材料以及3D打印技术领域。The invention relates to a method for preparing tungsten particle-reinforced metal-based composite materials based on 3D printing technology, and belongs to the technical field of particle-reinforced metal-based composite materials and 3D printing.
背景技术Background technique
钨颗粒增强金属基复合材料是一种以金属钨为增强相，以NiFe、Cu或其他低熔点元素作为基体相的复合材料，在钨含量高于80％质量比时也被成为高比重合金，具有密度大、强度高等一系列优点，广泛地应用于陀螺马达转子、穿甲弹、工具振动阻尼块和砧板等。目前已经开发出的钨颗粒增强金属基复合材料有W-Ni-Cu、W-Ni-Fe、W-Ni-Mn、W-Cu、W-Ni等多个系列。Ni-Cu、Ni-Fe、Ni-Mn等粘结相的力学性能、钨颗粒的形态对钨颗粒增强金属基复合材料的力学性能具有决定性作用。Tungsten particle reinforced metal matrix composite is a composite material with metal tungsten as the reinforcing phase and NiFe, Cu or other low melting point elements as the matrix phase. When the tungsten content is higher than 80% by mass, it is also a high specific gravity alloy. With a series of advantages such as high density and high strength, it is widely used in gyro motor rotors, armor-piercing projectiles, tool vibration damping blocks and cutting boards. Tungsten particle-reinforced metal-based composite materials that have been developed so far include W-Ni-Cu, W-Ni-Fe, W-Ni-Mn, W-Cu, and W-Ni series. The mechanical properties of the bonding phases such as Ni-Cu, Ni-Fe, Ni-Mn and the morphology of tungsten particles have a decisive effect on the mechanical properties of tungsten particle reinforced metal matrix composites.
钨颗粒增强金属基复合材料的主要制备方法有液相烧结法、固相烧结法以及熔体浸渗法等。液相烧结法是制备高比重钨颗粒增强金属基复合材料最常见的手段，具有致密度高、强度高、塑性大和显微组织均匀等优点。但是此方法存在如下缺点：钨含量较少时，钨颗粒增强金属基复合材料将出现严重变形、组织不均匀的问题；液相烧结的氢气气氛会导致氢脆，需要在烧结之后增加一道脱氢工艺，大大提高生产成本；制备得到的钨颗粒增强金属基复合材料晶粒较为粗大。固相烧结法通常用于制备低钨含量、细晶钨颗粒增强金属基复合材料，但是该方法会导致合金致密度低、力学性能差。为了提升致密度，在固相烧结法中经常引入极其复杂繁琐的工艺过程，或者引入高压、放电等非常规烧结手段。熔体浸渗法制备钨颗粒增强金属基复合材料具有钨含量、形态可控，冷速可控致密度高等优点，但存在样品尺寸受限、成本高昂的缺点。现有常规制备方法都具有不可忽视的缺点，具有成型难度大、后续加工成本高、制备工艺复杂、成品孔隙率高等问题，限制了钨颗粒增强金属基复合材料的发展。The main preparation methods of tungsten particle reinforced metal matrix composites include liquid phase sintering, solid phase sintering, and melt infiltration. The liquid phase sintering method is the most common method for preparing high specific gravity tungsten particle reinforced metal matrix composites, and has the advantages of high density, high strength, large plasticity and uniform microstructure. However, this method has the following disadvantages: when the tungsten content is small, the tungsten particle-reinforced metal matrix composite material will have serious deformation and uneven structure; the hydrogen atmosphere in the liquid phase sintering will cause hydrogen embrittlement, and a dehydrogenation is required after sintering The process greatly increases the production cost; the prepared tungsten particle reinforced metal matrix composite has relatively coarse grains. The solid-phase sintering method is generally used to prepare metal matrix composites with low tungsten content and fine-grained tungsten particle reinforcement, but this method results in low density and poor mechanical properties of the alloy. In order to increase the density, extremely complicated and complicated processes are often introduced in the solid phase sintering method, or unconventional sintering methods such as high voltage and discharge are introduced. Preparation of tungsten particle reinforced metal matrix composites by the melt infiltration method has the advantages of tungsten content, morphology controllability, controllable cooling rate, and high density. However, it has the disadvantages of limited sample size and high cost. The existing conventional preparation methods have disadvantages that cannot be ignored, such as difficult molding, high subsequent processing costs, complex preparation processes, and high porosity of the finished product, which limit the development of tungsten particle-reinforced metal matrix composites.
发明内容Summary of the Invention
针对目前工艺制备钨颗粒增强金属基复合材料存在的问题，本发明提供了一种基于3D打印技术制备钨颗粒增强金属基复合材料的方法，该方法可在较大的范围内调控粘接相与增强相的比例，所制备的复合材料具有优异的力学性能，且该方法具有制备周期短、工艺简单、成本低等优点。In view of the problems existing in the preparation of tungsten particle-reinforced metal-based composites with current processes, the present invention provides a method for preparing tungsten particle-reinforced metal-based composites based on 3D printing technology, which can regulate the bonding phase and The ratio of the reinforcing phase, the prepared composite material has excellent mechanical properties, and the method has the advantages of short preparation cycle, simple process, low cost and the like.
本发明的目的是通过以下技术方案实现的。The object of the present invention is achieved by the following technical solutions.
一种基于3D打印技术制备钨颗粒增强金属基复合材料的方法，所述钨颗粒增强金属基复合材料由钨增强相和基体相组成，基体相为Ni、Cu、Al、NiFe合金、NiCu合金、CuZn合金、NiMn合金、NiCo合金或AlCrFeNiVM高熵合金；其中，基体相为Ni、Cu、Al、NiFe合金、NiCu合金、CuZn合金、NiMn合金、NiCo合金时钨相的质量百分数为5％～90％，基体相为AlCrFeNiVM高熵合金时钨相的质量百分数为5％～80％；A method for preparing a tungsten particle reinforced metal matrix composite material based on 3D printing technology. The tungsten particle reinforced metal matrix composite material is composed of a tungsten reinforcement phase and a matrix phase, and the matrix phase is Ni, Cu, Al, NiFe alloy, NiCu alloy, CuZn alloy, NiMn alloy, NiCo alloy, or AlCrFeNiVM high entropy alloy; where the matrix phase is Ni, Cu, Al, NiFe alloy, NiCu alloy, CuZn alloy, NiMn alloy, NiCo alloy, and the mass percentage of the tungsten phase is 5% to 90%. %, The mass percentage of the tungsten phase when the matrix phase is AlCrFeNiVM high entropy alloy is 5% to 80%;
所述基体相材料NiFe合金、NiCu合金、CuZn合金以及NiCo合金中第一种元素与第二种元素的质量比值分别独立为1～4，NiMn合金中第一种元素与第二种元素(即Ni元素与Mn元素)的质量比值为0.5～3；AlCrFeNiVM高熵合金中各元素的摩尔比依次为(0.3～1.0)∶(0.2～1.0)∶(0.6～1.2)∶(1.5～3.5)∶(0.1～0.5)∶(0～0.3)，优选为(0.5～1.0)∶(0.9～1.0)∶(0.8～1.0)∶(1.5～3.0)∶(0.1～0.3)∶0，M为Cu、Ti、Mo、W中的一种或几种；In the matrix phase materials NiFe alloy, NiCu alloy, CuZn alloy, and NiCo alloy, the mass ratio of the first element to the second element is independently 1 to 4, and the first element and the second element in the NiMn alloy (that is, The mass ratio of Ni element to Mn element is 0.5 to 3; the molar ratio of each element in AlCrFeNiVM high entropy alloy is (0.3 to 1.0): (0.2 to 1.0): (0.6 to 1.2): (1.5 to 3.5): (0.1 to 0.5): (0 to 0.3), preferably (0.5 to 1.0): (0.9 to 1.0): (0.8 to 1.0): (1.5 to 3.0): (0.1 to 0.3): 0, M is Cu, One or more of Ti, Mo, W;
上述钨颗粒增强金属基复合材料的制备步骤如下：The preparation steps of the above tungsten particle reinforced metal matrix composite material are as follows:
(1)在3D打印的工艺控制软件中根据输入钨颗粒增强金属基复合材料的尺寸，完成钨颗粒增强金属基复合材料的CAD三维建模，同时自动生成激光成型路径程序；(1) In the 3D printed process control software, according to the size of the input tungsten particle reinforced metal matrix composite material, complete the CAD three-dimensional modeling of the tungsten particle reinforced metal matrix composite material, and automatically generate a laser forming path program;
(2)在真空或惰性气体条件下，使用同步送粉方式将混合粉体送至3D打印设备的激光加热区域，逐层打印，得到钨颗粒增强金属基复合材料。(2) Under vacuum or inert gas conditions, use a synchronous powder feeding method to send the mixed powder to the laser heating area of the 3D printing device, and print layer by layer to obtain a tungsten particle reinforced metal matrix composite material.
所述混合粉体为钨粉与Ni单质粉、Cu单质粉、Al单质粉、NiFe合金粉、NiCu合金粉、CuZn合金粉、NiMn合金粉、NiCo合金粉或AlCrFeNiVM高熵合金粉的混合粉体，或者钨粉与组成NiFe合金、NiCu合金、CuZn合金、NiMn合金、NiCo合金或AlCrFeNiVM高熵合金的相应元素单质粉的混合粉体。The mixed powder is a mixed powder of tungsten powder and Ni simple powder, Cu simple powder, Al simple powder, NiFe alloy powder, NiCu alloy powder, CuZn alloy powder, NiMn alloy powder, NiCo alloy powder or AlCrFeNiVM high-entropy alloy powder. , Or a mixed powder of tungsten powder and corresponding elemental element powders that make up NiFe alloy, NiCu alloy, CuZn alloy, NiMn alloy, NiCo alloy, or AlCrFeNiVM high entropy alloy.
进一步地，所述AlCrFeNiVM高熵合金粉是采用如下方法制备得到的：先将Al、Cr、Fe、Ni、V和M金属熔炼成合金液并浇铸成合金锭，再在气雾化炉中进行雾化制粉，得到AlCrFeNiVM高熵合金粉；其中，气雾化制粉的工艺参 数如下：过热度50℃～400℃，雾化气体气压2MPa～8MPa，导流管直径3mm～10mm，雾化介质采用氩气。Further, the AlCrFeNiVM high-entropy alloy powder is prepared by the following method: Al, Cr, Fe, Ni, V, and M metals are first smelted into an alloy liquid and cast into an alloy ingot, and then performed in a gas atomizing furnace. Atomizing powder to obtain AlCrFeNiVM high entropy alloy powder; among them, the process parameters of gas atomizing powder are as follows: superheat degree 50 ℃ ～ 400 ℃, atomizing gas pressure 2MPa ～ 8MPa, diversion tube diameter 3mm ～ 10mm, atomization The medium was argon.
3D打印的工艺参数如下：激光光斑直径0.5mm～6mm，扫描速度30mm/s以下，设置光斑路径间隔使搭接率为5％～70％，激光功率200W～5000W，送粉速率0.1kg/h～5kg/h，能量面密度30J/mm 2～260J/mm 2，能量质量密度1000J/g～20000J/g，单层沉积厚度大于0mm小于等于4mm。 The process parameters of 3D printing are as follows: the laser spot diameter is 0.5mm ~ 6mm, the scanning speed is below 30mm / s, the spot path interval is set so that the overlap rate is 5% ~ 70%, the laser power is 200W ~ 5000W, and the powder feed rate is 0.1kg / h ～ 5kg / h, energy area density 30J / mm 2 ～ 260J / mm 2 , energy mass density 1000J / g ～ 20,000J / g, single-layer deposition thickness is greater than 0mm and less than or equal to 4mm.
Figure PCTCN2018000359-appb-000001
Figure PCTCN2018000359-appb-000001
进一步地，混合粉体中，所述钨粉粒径小于25μm，所述单质粉、所述合金粉以及所述AlCrFeNiVM高熵合金粉的粒径均小于250μm。Further, in the mixed powder, the particle diameter of the tungsten powder is less than 25 μm, and the particle diameters of the elemental powder, the alloy powder, and the AlCrFeNiVM high-entropy alloy powder are all less than 250 μm.
有益效果：Beneficial effects:
(1)本发明采用3D打印技术制备钨颗粒增强金属基复合材料，可在较大的范围内调控所述复合材料中钨增强相和基体相的比例，可设计强、工艺简单、制备周期短以及成本低；(1) The present invention uses 3D printing technology to prepare tungsten particle-reinforced metal-based composite materials, which can regulate the ratio of tungsten-reinforced phase and matrix phase in the composite material within a relatively large range, and can be designed strong, the process is simple, and the preparation cycle is short And low cost;
(2)采用本发明所述方法制备钨颗粒增强金属基复合材料中，钨增强相颗粒均匀分布在基体相上，钨增强相颗粒细小、晶粒无明显长大，力学性能优异。(2) In the tungsten particle-reinforced metal matrix composite prepared by the method of the present invention, tungsten reinforcement phase particles are uniformly distributed on the matrix phase, tungsten reinforcement phase particles are fine, grains are not significantly grown, and mechanical properties are excellent.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
图1为实施例1制备的钨/AlCrFeNiV高熵合金复合材料的显微扫描电子显微镜(SEM)图。FIG. 1 is a scanning electron microscope (SEM) image of a tungsten / AlCrFeNiV high-entropy alloy composite material prepared in Example 1. FIG.
图2为实施例2制备的钨/AlCrFeNiV高熵合金复合材料的SEM图。FIG. 2 is a SEM image of the tungsten / AlCrFeNiV high-entropy alloy composite material prepared in Example 2. FIG.
图3为实施例3制备的钨/AlCrFeNiV高熵合金复合材料的SEM图。3 is a SEM image of a tungsten / AlCrFeNiV high-entropy alloy composite material prepared in Example 3.
图4为实施例4制备的钨/镍复合材料的SEM图。FIG. 4 is a SEM image of the tungsten / nickel composite prepared in Example 4. FIG.
图5为实施例5制备的钨/镍铁复合材料的SEM图。FIG. 5 is a SEM image of the tungsten / nickel-iron composite material prepared in Example 5. FIG.
图6为实施例6制备的钨/镍铜复合材料的SEM图。FIG. 6 is a SEM image of the tungsten / nickel copper composite material prepared in Example 6. FIG.
图7为实施例7制备的钨/AlCrFeNiVCu复合材料的SEM图。FIG. 7 is a SEM image of the tungsten / AlCrFeNiVCu composite material prepared in Example 7. FIG.
图8为实施例3制备的钨/AlCrFeNiV高熵合金复合材料以及实施例5制备的钨/镍铁复合材料的准静态拉伸力学性能对比曲线图。FIG. 8 is a comparison graph of quasi-static tensile mechanical properties of the tungsten / AlCrFeNiV high-entropy alloy composite material prepared in Example 3 and the tungsten / nickel-iron composite material prepared in Example 5. FIG.
具体实施方式detailed description
下面结合附图和具体实施方式对本发明作进一步阐述，其中，所述方法如 无特别说明均为常规方法，所述原材料如无特别说明均能从公开商业途径而得。The present invention will be further described below with reference to the accompanying drawings and specific embodiments, wherein the method is a conventional method unless otherwise specified, and the raw materials can be obtained from public commercial channels unless otherwise specified.
以下实施例中：In the following embodiments:
Al、Cr、Fe、Ni和V金属的纯度均为99.9wt％；The purity of Al, Cr, Fe, Ni and V metals are all 99.9wt%;
高真空非自耗电弧熔炼炉：DHL-400型高真空非自耗电弧熔炼炉，中国科学院沈阳科学仪器股份有限公司；High-vacuum non-consumable arc melting furnace: DHL-400 high-vacuum non-consumable arc melting furnace, Shenyang Scientific Instrument Co., Ltd., Chinese Academy of Sciences;
3D打印设备：TSC-S600光纤激光增材制造系统，鑫精合激光科技发展(北京)有限公司；3D printing equipment: TSC-S600 fiber laser additive manufacturing system, Xinjinghe Laser Technology Development (Beijing) Co., Ltd .;
真空金属雾化制粉炉：沈阳好智多新材料制备技术有限公司研制的真空金属雾化制粉炉，能够制备出具有较好球形度的金属合金粉末；Vacuum metal atomizing powder furnace: The vacuum metal atomizing powder furnace developed by Shenyang Haojiduo New Material Preparation Technology Co., Ltd. can produce metal alloy powder with better sphericity;
混料机：V型混合机，型号VH5，上海天阖机械设备有限公司；Mixer: V-type mixer, model VH5, Shanghai Tianying Machinery Equipment Co., Ltd .;
维氏硬度计：精密数显自动转塔维氏硬度计，型号JMHVS-10AT，上海奥龙星迪检测设备有限公司，测试过程采用10kg力，保荷时间为5秒；Vickers hardness tester: Precision digital display automatic turret Vickers hardness tester, model JMHVS-10AT, Shanghai Aolong Xingdi Testing Equipment Co., Ltd. The test process uses 10kg force and the load retention time is 5 seconds;
形貌表征：采用日本日立公司的HITACHI S4800型冷场发射扫描电子显微镜进行微观形貌表征，背散射电子成像，工作电压为15kV；Morphological characterization: HITACHI S4800 cold field emission scanning electron microscope from Hitachi, Japan was used to characterize the micromorphology, backscattered electron imaging, and the working voltage was 15kV;
准静态拉伸试验：采用CMT4305型微机电子万能试验机进行室温准静态拉伸试验，测试试样依据金属材料室温拉伸试验方法(GB/T 228.1-2010)国家标准中有关规定制成工字件试样，应变率10 -3s -1。 Quasi-static tensile test: CMT4305 microcomputer electronic universal testing machine is used to perform room temperature quasi-static tensile test. The test specimens are made according to the relevant provisions of the national standard for room temperature tensile test methods of metal materials (GB / T 228.1-2010). One sample, the strain rate is 10 -3 s -1 .
实施例1Example 1
基于3D打印技术制备尺寸为2cm×2cm×10cm长方体形状的钨/AlCrFe NiV高熵合金复合材料的具体步骤如下：The specific steps for preparing a tungsten / AlCrFeNiV high-entropy alloy composite with a size of 2cm × 2cm × 10cm based on 3D printing technology are as follows:
(1)采用砂纸和砂轮机除去Al、Cr、Fe、Ni以及V金属表面的杂质和氧化物，并用丙酮清洗金属表面，再按照0.3∶0.74∶1.0∶2.0∶0.2的摩尔比将表面处理后的Al、Cr、Fe、Ni和V金属混合；然后，将金属混合原料置于高真空非自耗电弧熔炼炉中熔炼成合金液，再将合金液浇铸成合金锭；(1) Remove the impurities and oxides on the metal surface of Al, Cr, Fe, Ni and V by using sandpaper and grinder, clean the metal surface with acetone, and then treat the surface according to a molar ratio of 0.3: 0.74: 1.0: 2.0: 0.2 Al, Cr, Fe, Ni and V metals are mixed; then, the metal mixed raw materials are placed in a high vacuum non-consumable arc melting furnace to smelt the alloy liquid, and the alloy liquid is cast into an alloy ingot;
(2)将合金锭装入真空金属雾化制粉炉中，以氩气作为雾化介质，在过热度200℃以及雾化气压4MPa下采用直径4mm的导流管将合金锭进行雾化制粉，过筛，得到粒径为150μm～75μm的AlCrFeNiV高熵合金粉；(2) Put the alloy ingot into a vacuum metal atomizing pulverizing furnace, use argon as the atomizing medium, and use an air guide tube with a diameter of 4mm to atomize the alloy ingot at a superheat degree of 200 ° C and an atomizing pressure of 4MPa. Powder, sieved to obtain AlCrFeNiV high entropy alloy powder with a particle size of 150 μm to 75 μm;
(3)将粒径25μm～13μm的钨粉与AlCrFeNiV高熵合金粉按照6∶4的质量比混合，在混料机中混粉120min后，将混合粉体置于送粉器中；(3) Mixing tungsten powder with a particle diameter of 25 μm to 13 μm and AlCrFeNiV high entropy alloy powder in a mass ratio of 6: 4, and mixing the powder in a mixer for 120 minutes, and placing the mixed powder in a powder feeder;
(4)在3D打印的工艺控制软件(沈航小机三桶20171201，下同)中根据输入所述复合材料的尺寸，完成所述复合材料的三维CAD建模，同时自动生成激光成型路径程序；(4) In the 3D printed process control software (Shen Hang Xiaoji Three Bucket 20171201, the same below) according to the size of the composite material input, complete the three-dimensional CAD modeling of the composite material, and automatically generate a laser molding path program ;
(5)3D打印设备的腔室气氛为氩气，采用同轴送粉方式将混合粉体送至3D打印设备的激光加热区域，逐层打印，得到所述复合材料；其中，3D打印的工艺参数如下：激光光斑直径4mm，光斑扫描速度6mm/s，光斑路径间隔2mm，激光功率2600W，送粉速率2.1r/min(即4kg/h)，单层沉积厚度为1.8mm。(5) The atmosphere of the chamber of the 3D printing device is argon, and the mixed powder is sent to the laser heating area of the 3D printing device by a coaxial powder feeding method, and the composite material is printed layer by layer to obtain the composite material; wherein, the process of 3D printing The parameters are as follows: the laser spot diameter is 4mm, the spot scanning speed is 6mm / s, the spot path interval is 2mm, the laser power is 2600W, the powder feed rate is 2.1r / min (that is, 4kg / h), and the single-layer deposition thickness is 1.8mm.
图1中，浅色颗粒的成分为钨，钨颗粒的尺寸在10μm以下，颗粒间深色基体的成分为AlCrFeNiV高熵合金，钨颗粒均匀分布在AlCrFeNiV高熵合金基体上，且两相界面清晰。经过测量可知，所制备的复合材料密度为12.88g/cm 3，硬度为430HV，通过金相测量可知AlCrFeNiV高熵合金相体积分数在62.75％左右。经过准静态拉伸试验测试可知，所制备的复合材料的屈服强度为849MPa，抗拉强度为1308MPa，延伸率为6％。 In Figure 1, the composition of the light-colored particles is tungsten, the size of the tungsten particles is less than 10 μm, the composition of the dark matrix between the particles is AlCrFeNiV high-entropy alloy, and the tungsten particles are evenly distributed on the AlCrFeNiV high-entropy alloy matrix, and the two-phase interface is clear . It can be known through measurement that the density of the prepared composite material is 12.88 g / cm 3 and the hardness is 430 HV. According to metallographic measurement, it is known that the volume fraction of the AlCrFeNiV high entropy alloy phase is about 62.75%. After the quasi-static tensile test, it can be known that the yield strength of the prepared composite material is 849 MPa, the tensile strength is 1308 MPa, and the elongation is 6%.
实施例2Example 2
基于3D打印技术制备尺寸为2cm×2cm×10cm长方体形状的钨/AlCrFe NiV高熵合金复合材料的具体步骤如下：The specific steps for preparing a tungsten / AlCrFeNiV high-entropy alloy composite with a size of 2cm × 2cm × 10cm based on 3D printing technology are as follows:
(1)采用砂纸和砂轮机除去Al、Cr、Fe、Ni以及V金属表面杂质和氧化物，并用丙酮清洗金属表面，再按照0.5∶0.8∶1.0∶2.5∶0.2的摩尔比将表面处理后的Al、Cr、Fe、Ni和V金属混合；然后，将金属混合原料置于高真空非自耗电弧熔炼炉中熔炼成合金液，再将合金液浇铸成合金锭；(1) Remove the impurities and oxides on the metal surface of Al, Cr, Fe, Ni, and V by using sandpaper and grinder, and clean the metal surface with acetone, and then treat the surface with a molar ratio of 0.5: 0.8: 1.0: 2.5: 0.2. Al, Cr, Fe, Ni, and V metals are mixed; then, the metal mixed raw materials are placed in a high vacuum non-consumable arc melting furnace to smelt the alloy liquid, and the alloy liquid is cast into an alloy ingot;
(2)将合金锭装入真空金属雾化制粉炉中，以氩气作为雾化介质，在过热度为200℃以及雾化气压4MPa下采用直径5mm的导流管将合金锭进行雾化制粉，过筛，得到粒径为150μm～45μm的AlCrFeNiV高熵合金粉；(2) Put the alloy ingot into a vacuum metal atomizing pulverizing furnace, use argon as the atomizing medium, and use a 5mm diameter deflector to atomize the alloy ingot at a superheat degree of 200 ° C and an atomizing pressure of 4MPa. Milling and sieving to obtain AlCrFeNiV high entropy alloy powder with a particle size of 150 μm to 45 μm;
(3)将粒径13μm～6.5μm的钨粉与AlCrFeNiV高熵合金粉按照2∶8的质量比混合，在混料机中混粉30min后，将混合粉体置于送粉器中；(3) Mix tungsten powder with a particle size of 13 μm to 6.5 μm and AlCrFeNiV high entropy alloy powder in a mass ratio of 2: 8, and mix the powder in a mixer for 30 minutes, and then place the mixed powder in a powder feeder;
(4)在3D打印的工艺控制软件中根据输入所述复合材料的尺寸，完成所述复合材料的三维CAD建模，同时自动生成激光成型路径程序；(4) 3D CAD modeling of the composite material is completed in the 3D printed process control software according to the size of the composite material input, and a laser forming path program is automatically generated at the same time;
(5)3D打印设备的腔室气氛为氩气，采用同轴送粉方式将混合粉体送至3D打印设备的激光加热区域，逐层打印，得到所述复合材料；其中，3D打印 的工艺参数如下：激光光斑直径4mm，光斑扫描速度8mm/s，光斑路径间隔3mm，激光功率1800W，送粉速率1r/min(即2kg/h)，单层沉积厚度为3mm。。(5) The atmosphere of the chamber of the 3D printing device is argon, and the mixed powder is sent to the laser heating area of the 3D printing device by a coaxial powder feeding method, and the composite material is printed layer by layer to obtain the composite material; wherein, the process of 3D printing The parameters are as follows: the laser spot diameter is 4mm, the spot scanning speed is 8mm / s, the spot path interval is 3mm, the laser power is 1800W, the powder feed rate is 1r / min (that is, 2kg / h), and the single-layer deposition thickness is 3mm. .
图2中，浅色颗粒的成分为钨，钨颗粒的尺寸在1μm以下，颗粒间深色基体的成分为AlCrFeNiV高熵合金，钨颗粒均匀分布在AlCrFeNiV高熵合金基体上，且两相界面清晰。经过测量可知，所制备的复合材料密度为8.4g/cm 3，硬度为348HV，AlCrFeNiV高熵合金相体积分数在95.21％左右。经过准静态拉伸试验测试可知，所制备的复合材料的屈服强度为809MPa，抗拉强度为1027MPa，延伸率为6％。 In Figure 2, the composition of the light-colored particles is tungsten, the size of the tungsten particles is less than 1 μm, and the composition of the dark matrix between the particles is AlCrFeNiV high-entropy alloy. The tungsten particles are evenly distributed on the AlCrFeNiV high-entropy alloy matrix, and the two-phase interface is clear. . It can be known from the measurement that the prepared composite has a density of 8.4 g / cm 3 , a hardness of 348 HV, and an AlCrFeNiV high entropy alloy phase volume fraction of about 95.21%. After the quasi-static tensile test, it can be known that the yield strength of the prepared composite material is 809 MPa, the tensile strength is 1027 MPa, and the elongation is 6%.
实施例3Example 3
基于3D打印技术制备尺寸为2cm×2cm×10cm长方体形状的钨/AlCrFe NiV高熵合金复合材料的具体步骤如下：The specific steps for preparing a tungsten / AlCrFeNiV high-entropy alloy composite with a size of 2cm × 2cm × 10cm based on 3D printing technology are as follows:
(1)采用砂纸和砂轮机除去Al、Cr、Fe、Ni以及V金属表面杂质和氧化物，并用丙酮清洗金属表面，再按照0.5∶0.9∶1.2∶2.5∶0.2的摩尔比将表面处理后的Al、Cr、Fe、Ni和V金属混合；然后，将金属混合原料置于高真空非自耗电弧熔炼炉中熔炼成合金液，再将合金液浇铸成合金锭；(1) Use sandpaper and grinder to remove Al, Cr, Fe, Ni, and V metal surface impurities and oxides, and clean the metal surface with acetone, and then according to the molar ratio of 0.5: 0.9: 1.2: 2.5: 0.2, the surface treated Al, Cr, Fe, Ni, and V metals are mixed; then, the metal mixed raw materials are placed in a high vacuum non-consumable arc melting furnace to smelt the alloy liquid, and the alloy liquid is cast into an alloy ingot;
(2)将合金锭装入真空金属雾化制粉炉中，以氩气作为雾化介质，在过热度为300℃以及雾化气压4MPa下采用直径5mm的导流管将合金锭进行雾化制粉，过筛，得到粒径为25μm～18μm的AlCrFeNiV高熵合金粉；(2) Put the alloy ingot into a vacuum metal atomizing pulverizing furnace, use argon as the atomizing medium, and use an air guide tube with a diameter of 5mm to atomize the alloy ingot with a superheat degree of 300 ° C and an atomizing pressure of 4MPa. Milling and sieving to obtain AlCrFeNiV high entropy alloy powder with a particle size of 25 μm to 18 μm;
(3)将粒径45μm～13μm的钨粉与AlCrFeNiV高熵合金粉按照8∶2的质量比混合，在混料机中混粉30min后，将混合粉体置于送粉器中；(3) mixing tungsten powder with a particle diameter of 45 μm to 13 μm and AlCrFeNiV high entropy alloy powder in a mass ratio of 8: 2, and mixing the powder in a mixer for 30 minutes, and placing the mixed powder in a powder feeder;
(4)在3D打印的工艺控制软件中根据输入所述复合材料的尺寸，完成所述复合材料的三维CAD建模，同时自动生成激光成型路径程序；(4) 3D CAD modeling of the composite material is completed in the 3D printed process control software according to the size of the composite material input, and a laser forming path program is automatically generated at the same time;
(5)3D打印设备的腔室气氛为氩气，采用同轴送粉方式将混合粉体送至3D打印设备的激光加热区域，逐层打印，得到所述复合材料；其中，3D打印的工艺参数如下：激光光斑直径4mm，光斑扫描速度3mm/s，光斑路径间隔2mm，激光功率2800W，送粉速率1.5r/min(即3kg/h)，单层沉积厚度为0.8mm。(5) The atmosphere of the chamber of the 3D printing device is argon, and the mixed powder is sent to the laser heating area of the 3D printing device by a coaxial powder feeding method, and the composite material is printed layer by layer to obtain the composite material; wherein, the process of 3D printing The parameters are as follows: the laser spot diameter is 4mm, the spot scanning speed is 3mm / s, the spot path interval is 2mm, the laser power is 2800W, the powder feed rate is 1.5r / min (that is, 3kg / h), and the single-layer deposition thickness is 0.8mm.
图3中，浅色颗粒的成分为钨，钨颗粒的尺寸在10μm以下，颗粒间深色基体的成分为AlCrFeNiV高熵合金，钨颗粒均匀分布在AlCrFeNiV高熵合金基体上，且两相界面清晰。经过测量可知，所制备的复合材料密度为15.02g/cm 3， 硬度为541HV，AlCrFeNiV高熵合金相体积分数在31.85％左右。经过准静态拉伸试验测试可知，所制备的复合材料的屈服强度为1158MPa，抗拉强度为1355MPa，延伸率为1％，如图8所示。 In Figure 3, the composition of the light-colored particles is tungsten, the size of the tungsten particles is less than 10 μm, the composition of the dark matrix between the particles is AlCrFeNiV high-entropy alloy, and the tungsten particles are evenly distributed on the AlCrFeNiV high-entropy alloy matrix, and the two-phase interface is clear . It can be known through measurement that the density of the prepared composite material is 15.02 g / cm 3 , the hardness is 541 HV, and the volume fraction of the AlCrFeNiV high entropy alloy phase is about 31.85%. After the quasi-static tensile test, it can be known that the yield strength of the prepared composite material is 1158 MPa, the tensile strength is 1355 MPa, and the elongation is 1%, as shown in FIG. 8.
实施例4Example 4
基于3D打印技术制备尺寸为2cm×2cm×10cm长方体形状的钨/镍复合材料的具体步骤如下：The specific steps for preparing a tungsten / nickel composite material with a size of 2cm × 2cm × 10cm rectangular parallelepiped based on 3D printing technology are as follows:
(1)将粒径25μm～13μm的钨粉与粒径为75μm～45μm的镍粉按照6∶4的质量比混合，在混料机中混粉60min后，将混合粉体置于送粉器中；(1) Mix tungsten powder with a particle size of 25 μm to 13 μm and nickel powder with a particle size of 75 μm to 45 μm in a mass ratio of 6: 4. After mixing the powder in a mixer for 60 minutes, place the mixed powder in a powder feeder. in;
(2)在3D打印的工艺控制软件中根据输入所述复合材料的尺寸，完成所述复合材料的三维CAD建模，同时自动生成激光成型路径程序；(2) 3D CAD modeling of the composite material is completed in the 3D printed process control software according to the size of the composite material input, and a laser forming path program is automatically generated at the same time;
(3)3D打印设备的腔室气氛为氩气，采用同轴送粉方式将混合粉体送至3D打印设备的激光加热区域，逐层打印，得到所述复合材料；其中，3D打印的工艺参数如下：激光光斑直径4mm，光斑扫描速度12mm/s，光斑路径间隔2mm，激光功率1600W，送粉速率1.2r/min(即2.4kg/h)，单层沉积厚度为0.6mm。(3) The atmosphere of the chamber of the 3D printing device is argon, and the mixed powder is sent to the laser heating area of the 3D printing device by a coaxial powder feeding method, and the composite material is printed layer by layer to obtain the composite material; wherein, the process of 3D printing The parameters are as follows: the laser spot diameter is 4mm, the spot scanning speed is 12mm / s, the spot path interval is 2mm, the laser power is 1600W, the powder feed rate is 1.2r / min (that is, 2.4kg / h), and the single-layer deposition thickness is 0.6mm.
图4中，浅色颗粒的成分为钨，钨颗粒的尺寸在10μm以下，颗粒间深色基体的成分为镍，钨颗粒均匀分布在镍基体上，且两相界面清晰。经过测量可知，所制备的复合材料密度为12.44g/cm 3，硬度为392HV，镍相体积分数在57.70％左右。经过准静态拉伸试验测试可知，所制备的复合材料的抗拉强度为745MPa，抗拉强度为1108MPa，延伸率为8％。 In FIG. 4, the composition of the light-colored particles is tungsten, the size of the tungsten particles is less than 10 μm, the composition of the dark matrix between the particles is nickel, and the tungsten particles are uniformly distributed on the nickel matrix, and the two-phase interface is clear. It can be known from the measurement that the prepared composite material has a density of 12.44 g / cm 3 , a hardness of 392 HV, and a nickel phase volume fraction of about 57.70%. After the quasi-static tensile test, it can be known that the tensile strength of the prepared composite material is 745 MPa, the tensile strength is 1108 MPa, and the elongation is 8%.
实施例5Example 5
基于3D打印技术制备尺寸为2cm×2cm×10cm长方体形状的钨/镍铁复合材料的具体步骤如下：The specific steps to prepare a tungsten / nickel-iron composite with a size of 2cm × 2cm × 10cm based on 3D printing technology are as follows:
(1)将粒径45μm～13μm的钨粉置于一个送粉器中，将粒径分别为75μm～45μm的镍粉与铁粉按照3∶2的质量比在混料机中混粉30min后转移至另一个送粉器中；(1) Put tungsten powder with a particle size of 45μm ～ 13μm in a powder feeder, and mix nickel powder and iron powder with a particle size of 75μm ～ 45μm in a mixer at a mass ratio of 3: 2 for 30min Transfer to another powder feeder;
(2)在3D打印的工艺控制软件中根据输入所述复合材料的尺寸，完成所述复合材料的三维CAD建模，同时自动生成激光成型路径程序；(2) 3D CAD modeling of the composite material is completed in the 3D printed process control software according to the size of the composite material input, and a laser forming path program is automatically generated at the same time;
(3)3D打印设备的腔室气氛为氩气，采用同轴送粉方式将镍铁混合粉体以及钨粉按照2∶8的质量比送至3D打印设备的激光加热区域，逐层打印，得到所述复合材料；其中，3D打印的工艺参数如下：激光光斑直径4mm，光斑扫描速度8mm/s，光斑路径间隔2mm，激光功率2400W，钨粉的送粉速率0.42r/min(即1.08kg/h)，镍铁混合粉体的送粉速率0.28r/min(即0.72kg/h)，单层沉积厚度为0.6mm。(3) The atmosphere of the chamber of the 3D printing equipment is argon. The coaxial powder feeding method is used to send the nickel-iron mixed powder and tungsten powder to the laser heating area of the 3D printing equipment according to a mass ratio of 2: 8. The composite material is obtained; wherein, the process parameters of 3D printing are as follows: laser spot diameter 4mm, spot scanning speed 8mm / s, spot path interval 2mm, laser power 2400W, tungsten powder feed rate 0.42r / min (ie 1.08kg / h), the powder-feeding rate of the nickel-iron mixed powder is 0.28 r / min (that is, 0.72 kg / h), and the thickness of the single-layer deposition is 0.6 mm.
图5中，浅色颗粒的成分为钨，钨颗粒的尺寸在10μm以下，颗粒间深色基体的成分为镍铁基体，钨颗粒均匀分布在镍铁基体上，且两相界面清晰。经过测量可知，所制备的复合材料密度为15.93g/cm 3，硬度为496HV，镍铁相体积分数在31.58％左右。经过准静态拉伸试验测试可知，所制备的复合材料的屈服强度为957MPa，抗拉强度为1318MPa，延伸率为5.8％，如图8所示。 In FIG. 5, the composition of the light-colored particles is tungsten, the size of the tungsten particles is less than 10 μm, the composition of the dark matrix between the particles is a nickel-iron matrix, the tungsten particles are uniformly distributed on the nickel-iron matrix, and the two-phase interface is clear. It can be known through measurement that the density of the prepared composite material is 15.93 g / cm 3 , the hardness is 496 HV, and the volume fraction of the nickel-iron phase is about 31.58%. It can be known from the quasi-static tensile test that the yield strength of the prepared composite material is 957 MPa, the tensile strength is 1318 MPa, and the elongation is 5.8%, as shown in FIG. 8.
实施例6Example 6
基于3D打印技术制备尺寸为2cm×2cm×10cm长方体形状的钨/镍铜复合材料的具体步骤如下：The specific steps of preparing a tungsten / nickel-copper composite material with a size of 2cm × 2cm × 10cm rectangular parallelepiped based on 3D printing technology are as follows:
(1)将粒径45μm～13μm的钨粉置于一个送粉器中，粒径分别为75μm～45μm的镍粉和铜粉按照5∶2的质量比在混料机中混粉30min后转移至另一个送粉器中；(1) Put tungsten powder with a particle size of 45μm ～ 13μm in a powder feeder, and nickel powder and copper powder with a particle size of 75μm ～ 45μm, respectively, and then transfer the powder in a mixer for 30min. Into another powder feeder;
(2)在3D打印的工艺控制软件中根据输入所述复合材料的尺寸，完成所述复合材料的三维CAD建模，同时自动生成激光成型路径程序；(2) 3D CAD modeling of the composite material is completed in the 3D printed process control software according to the size of the composite material input, and a laser forming path program is automatically generated at the same time;
(3)3D打印设备的腔室气氛为氩气，采用同轴送粉方式将镍铜混合粉体以及钨粉按照4∶6的质量比送至3D打印设备的激光加热区域，逐层打印，得到所述复合材料；其中，3D打印的工艺参数如下：激光光斑直径4mm，光斑扫描速度8mm/s，光斑路径间隔2mm，激光功率2500W，钨粉送粉速率0.42r/min(即1.08kg/h)，镍铜混合粉体送粉速率0.28r/min(即0.72kg/h)，单层沉积厚度为0.6mm。(3) The atmosphere of the chamber of the 3D printing device is argon. The coaxial powder feeding method is used to send the nickel-copper mixed powder and tungsten powder to the laser heating area of the 3D printing device according to a mass ratio of 4: 6, and print layer by layer. The composite material is obtained; wherein, the 3D printing process parameters are as follows: laser spot diameter 4mm, spot scanning speed 8mm / s, spot path interval 2mm, laser power 2500W, tungsten powder feed rate 0.42r / min (ie 1.08kg / h), the powder-feeding rate of the nickel-copper mixed powder is 0.28 r / min (ie, 0.72 kg / h), and the thickness of the single-layer deposition is 0.6 mm.
图6中，浅色颗粒的成分为钨，钨颗粒的尺寸在10μm以下，颗粒间深色基体的成分为镍铜基体，钨颗粒均匀分布在镍铜基体上，且两相界面清晰。经过测量可知，所制备的复合材料密度为12.15g/cm 3，硬度为425HV，镍铜相体积分数在59.40％左右。经过准静态拉伸试验测试可知，所制备的复合材料的屈 服强度为735MPa，抗拉强度为925MPa，延伸率为7.3％。 In FIG. 6, the composition of the light-colored particles is tungsten, the size of the tungsten particles is less than 10 μm, the composition of the dark matrix between the particles is a nickel-copper matrix, and the tungsten particles are uniformly distributed on the nickel-copper matrix, and the two-phase interface is clear. It can be known through measurement that the density of the prepared composite material is 12.15 g / cm 3 , the hardness is 425 HV, and the volume fraction of the nickel-copper phase is about 59.40%. It can be known from the quasi-static tensile test that the yield strength of the prepared composite material is 735 MPa, the tensile strength is 925 MPa, and the elongation is 7.3%.
实施例7Example 7
基于3D打印技术制备尺寸为2cm×2cm×10cm长方体形状的钨/AlCrFeNi VCu高熵合金复合材料的具体步骤如下：The specific steps for preparing tungsten / AlCrFeNiVCu high entropy alloy composites with a cube shape of 2cm × 2cm × 10cm based on 3D printing technology are as follows:
(1)采用砂纸和砂轮机除去Al、Cr、Fe、Ni、V以及Cu金属表面杂质和氧化物，并用丙酮清洗金属表面，再按照0.5∶0.9∶1.0∶2.5∶0.2∶0.05的摩尔比将表面处理后的Al、Cr、Fe、Ni、V和Cu金属混合；然后，将金属混合原料置于高真空非自耗电弧熔炼炉中熔炼成合金液，再将合金液浇铸成合金锭；(1) Use Aluminium Paper and Grinder to remove Al, Cr, Fe, Ni, V and Cu metal surface impurities and oxides, and clean the metal surface with acetone, and then change the molar ratio of 0.5: 0.9: 1.0: 2.5: 0.2: 0.05 After the surface treatment, Al, Cr, Fe, Ni, V, and Cu metals are mixed; then, the metal mixed raw materials are smelted in a high-vacuum non-consumable arc melting furnace into an alloy liquid, and the alloy liquid is cast into an alloy ingot;
(2)将合金锭装入真空金属雾化制粉炉中，以氩气作为雾化介质，在过热度为200℃以及雾化气压4MPa下采用直径3.5mm的导流管将合金锭进行雾化制粉，过筛，得到粒径为150μm～45μm的AlCrFeNiVCu高熵合金粉；(2) Put the alloy ingot into a vacuum metal atomizing pulverizing furnace, use argon as the atomizing medium, and use a 3.5mm diameter deflector to atomize the alloy ingot at a superheat degree of 200 ° C and an atomizing pressure of 4MPa. Powder, sieved to obtain AlCrFeNiVCu high entropy alloy powder with a particle size of 150 μm to 45 μm;
(3)将粒径13μm～6.5μm的钨粉与AlCrFeNiVCu高熵合金粉按照5∶5的质量比混合，在混料机中混粉30min后，将混合粉体置于送粉器中；(3) mixing tungsten powder with a particle diameter of 13 μm to 6.5 μm and AlCrFeNiVCu high entropy alloy powder at a mass ratio of 5: 5, and mixing the powder in a mixer for 30 minutes, and placing the mixed powder in a powder feeder;
(4)在3D打印的工艺控制软件中根据输入所述复合材料的尺寸，完成所述复合材料的三维CAD建模，同时自动生成激光成型路径程序；(4) 3D CAD modeling of the composite material is completed in the 3D printed process control software according to the size of the composite material input, and a laser forming path program is automatically generated at the same time;
(5)3D打印设备的腔室气氛为氩气，采用同轴送粉方式将混合粉体送至3D打印设备的激光加热区域，逐层打印，得到所述复合材料；其中，3D打印的工艺参数如下：激光光斑直径4mm，光斑扫描速度12mm/s，光斑路径间隔2mm，激光功率2800W，送粉速率1.2r/min(即2kg/h)，单层沉积厚度0.8mm。(5) The atmosphere of the chamber of the 3D printing device is argon, and the mixed powder is sent to the laser heating area of the 3D printing device by a coaxial powder feeding method, and the composite material is printed layer by layer to obtain the composite material; wherein, the process of 3D printing The parameters are as follows: laser spot diameter 4mm, spot scanning speed 12mm / s, spot path interval 2mm, laser power 2800W, powder feed rate 1.2r / min (ie 2kg / h), single layer deposition thickness 0.8mm.
图7中，浅色颗粒的成分为钨，钨颗粒的尺寸在10μm以下，颗粒间深色基体的成分为AlCrFeNiVCu高熵合金基体，钨颗粒均匀分布在AlCrFeNiVCu高熵合金基体上，且两相界面清晰。经过测量可知，所制备的复合材料密度为11.25g/cm 3，硬度为465HV，AlCrFeNiVCu高熵合金相体积分数在53.40％左右。经过准静态拉伸试验测试可知，所制备的复合材料的屈服强度为765MPa，抗拉强度为1025MPa，延伸率为6.1％。 In Figure 7, the composition of the light-colored particles is tungsten, the size of the tungsten particles is less than 10 μm, the composition of the dark matrix between the particles is an AlCrFeNiVCu high-entropy alloy matrix, and the tungsten particles are evenly distributed on the AlCrFeNiVCu high-entropy alloy matrix, and the two-phase interface Clear. It can be known from the measurement that the density of the prepared composite material is 11.25 g / cm 3 , the hardness is 465 HV, and the volume fraction of AlCrFeNiVCu high entropy alloy phase is about 53.40%. It can be known from the quasi-static tensile test that the yield strength of the prepared composite material is 765 MPa, the tensile strength is 1025 MPa, and the elongation is 6.1%.
综上所述，以上仅为本发明的较佳实施例而已，并非用于限定本发明的保护范围。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。In summary, the above are only preferred embodiments of the present invention, and are not intended to limit the protection scope of the present invention. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims (6)

  1. 一种基于3D打印技术制备钨颗粒增强金属基复合材料的方法，所述钨颗粒增强金属基复合材料由钨相和基体相组成，其特征在于：基体相为Ni、Cu、Al、NiFe合金、NiCu合金、CuZn合金、NiMn合金、NiCo合金或AlCrFeNiVM高熵合金，M为Cu、Ti、Mo和W中一种以上；其中，基体相为Ni、Cu、Al、NiFe合金、NiCu合金、CuZn合金、NiMn合金或NiCo合金时钨相的质量百分数为5％～90％，基体相为AlCrFeNiVM高熵合金时钨相的质量百分数为5％～80％；A method for preparing a tungsten particle reinforced metal matrix composite material based on 3D printing technology. The tungsten particle reinforced metal matrix composite material is composed of a tungsten phase and a matrix phase, and is characterized in that the matrix phase is Ni, Cu, Al, NiFe alloy, NiCu alloy, CuZn alloy, NiMn alloy, NiCo alloy, or AlCrFeNiVM high entropy alloy, M is one or more of Cu, Ti, Mo, and W; where the matrix phase is Ni, Cu, Al, NiFe alloy, NiCu alloy, CuZn alloy The mass percentage of tungsten phase when NiMn alloy or NiCo alloy is 5% ~ 90%, and the mass percentage of tungsten phase when matrix phase is AlCrFeNiVM high entropy alloy is 5% ~ 80%;
    所述钨颗粒增强金属基复合材料的制备步骤如下：The preparation steps of the tungsten particle reinforced metal-based composite material are as follows:
    (1)在3D打印的工艺控制软件中，根据输入钨颗粒增强金属基复合材料的尺寸，完成钨颗粒增强金属基复合材料的CAD三维建模，同时自动生成激光成型路径程序；(1) In the 3D printed process control software, according to the size of the input tungsten particle reinforced metal matrix composite material, complete the CAD three-dimensional modeling of the tungsten particle reinforced metal matrix composite material, and automatically generate a laser forming path program;
    (2)在真空或惰性气体条件下，使用同轴送粉方式将混合粉体送至3D打印设备的激光加热区域，逐层打印，得到钨颗粒增强金属基复合材料；(2) Under vacuum or inert gas conditions, use a coaxial powder feeding method to send the mixed powder to the laser heating area of the 3D printing device, and print layer by layer to obtain a tungsten particle reinforced metal matrix composite material;
    其中，所述混合粉体为钨粉与Ni单质粉、Cu单质粉、Al单质粉、NiFe合金粉、NiCu合金粉、CuZn合金粉、NiMn合金粉、NiCo合金粉或AlCrFeNiVM高熵合金粉的混合粉体，或者钨粉与组成NiFe合金、NiCu合金、CuZn合金、NiMn合金、NiCo合金或AlCrFeNiVM高熵合金的相应元素单质粉的混合粉体；3D打印的工艺参数如下：激光光斑直径0.5mm～6mm，扫描速度30mm/s以下，设置光斑路径间隔使搭接率为5％～70％，激光功率200W～5000W，送粉速率0.1kg/h～5kg/h，能量面密度30J/mm 2～260J/mm 2，能量质量密度1000J/g～20000J/g，单层沉积厚度大于0mm小于等于4mm。 Wherein, the mixed powder is a mixture of tungsten powder and Ni simple powder, Cu simple powder, Al simple powder, NiFe alloy powder, NiCu alloy powder, CuZn alloy powder, NiMn alloy powder, NiCo alloy powder or AlCrFeNiVM high-entropy alloy powder. Powder or tungsten powder mixed with elemental element powders of NiFe alloy, NiCu alloy, CuZn alloy, NiMn alloy, NiCo alloy or AlCrFeNiVM high entropy alloy; 3D printing process parameters are as follows: laser spot diameter 0.5mm ～ 6mm, scanning speed below 30mm / s, set the spot path interval so that the overlap rate is 5% to 70%, laser power 200W to 5000W, powder feed rate 0.1kg / h to 5kg / h, energy surface density 30J / mm 2 to 260J / mm 2 , energy mass density 1000J / g ～ 20,000J / g, single-layer deposition thickness is greater than 0mm and less than or equal to 4mm.
  2. 根据权利要求1所述的一种基于3D打印技术制备钨颗粒增强金属基复合材料的方法，其特征在于：NiFe合金、NiCu合金、CuZn合金以及NiCo合金中第一种元素与第二种元素的质量比值分别独立为1～4，NiMn合金中Ni元素与Mn元素的质量比值为0.5～3。The method for preparing tungsten particle-reinforced metal matrix composite materials based on 3D printing technology according to claim 1, characterized in that: the first element and the second element in NiFe alloy, NiCu alloy, CuZn alloy, and NiCo alloy The mass ratio is independently 1 to 4, and the mass ratio of Ni element to Mn element in NiMn alloy is 0.5 to 3.
  3. 根据权利要求1所述的一种基于3D打印技术制备钨颗粒增强金属基复合材料的方法，其特征在于：AlCrFeNiVM高熵合金中各元素的摩尔比依次为(0.3～1.0)∶(0.2～1.0)∶(0.6～1.2)∶(1.5～3.5)∶(0.1～0.5)∶(0～0.3)。The method for preparing a tungsten particle reinforced metal matrix composite material based on 3D printing technology according to claim 1, characterized in that the molar ratio of each element in the AlCrFeNiVM high entropy alloy is (0.3 to 1.0): (0.2 to 1.0) ): (0.6 to 1.2): (1.5 to 3.5): (0.1 to 0.5): (0 to 0.3).
  4. 根据权利要求1所述的一种基于3D打印技术制备钨颗粒增强金属基复合材料的方法，其特征在于：AlCrFeNiVM高熵合金中各元素的摩尔比依次为 (0.5～1.0)∶(0.9～1.0)∶(0.8～1.0)∶(1.5～3.0)∶(0.1～0.3)∶0。The method for preparing a tungsten particle-reinforced metal matrix composite material based on 3D printing technology according to claim 1, characterized in that the molar ratio of each element in the AlCrFeNiVM high entropy alloy is (0.5 to 1.0): (0.9 to 1.0) ): (0.8 to 1.0): (1.5 to 3.0): (0.1 to 0.3): 0.
  5. 根据权利要求1所述的一种基于3D打印技术制备钨颗粒增强金属基复合材料的方法，其特征在于：混合粉体中，所述钨粉粒径小于25μm，所述单质粉、所述合金粉以及所述AlCrFeNiVM高熵合金粉的粒径均小于250μm。The method for preparing tungsten particle-reinforced metal-based composite materials based on 3D printing technology according to claim 1, characterized in that in the mixed powder, the particle diameter of the tungsten powder is less than 25 μm, the elemental powder, the alloy The particle size of the powder and the AlCrFeNiVM high-entropy alloy powder are both less than 250 μm.
  6. 根据权利要求1所述的一种基于3D打印技术制备钨颗粒增强金属基复合材料的方法，其特征在于：所述AlCrFeNiVM高熵合金粉是采用如下方法制备得到的：先将Al、Cr、Fe、Ni、V和M金属熔炼成合金液并浇铸成合金锭，再在气雾化炉中进行雾化制粉，得到AlCrFeNiVM高熵合金粉；其中，气雾化制粉的工艺参数如下：过热度50℃～400℃，雾化气体气压2MPa～8MPa，导流管直径3mm～10mm，雾化介质采用氩气。The method for preparing tungsten particle-reinforced metal-based composite materials based on 3D printing technology according to claim 1, wherein the AlCrFeNiVM high-entropy alloy powder is prepared by the following method: Al, Cr, Fe , Ni, V, and M metals are smelted into alloy liquid and cast into alloy ingots, and then atomized and pulverized in a gas atomizing furnace to obtain AlCrFeNiVM high entropy alloy powder. Among them, the process parameters of gas atomized pulverization are as follows: The temperature is 50 ℃ ～ 400 ℃, the atomizing gas pressure is 2MPa ～ 8MPa, the diameter of the deflector is 3mm ～ 10mm, and the atomizing medium is argon.
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