WO2020147205A1 - 一种金属材料或金属复合材料的制备方法 - Google Patents

一种金属材料或金属复合材料的制备方法 Download PDF

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Publication number
WO2020147205A1
WO2020147205A1 PCT/CN2019/081420 CN2019081420W WO2020147205A1 WO 2020147205 A1 WO2020147205 A1 WO 2020147205A1 CN 2019081420 W CN2019081420 W CN 2019081420W WO 2020147205 A1 WO2020147205 A1 WO 2020147205A1
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metal
powder
carbon
composite material
preparing
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French (fr)
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肖鹏
方华婵
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Central South University
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Central South University
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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
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/12—Metallic powder containing non-metallic particles
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/05—Mixtures of metal powder with non-metallic powder
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C47/00—Making alloys containing metallic or non-metallic fibres or filaments
    • C22C47/14—Making alloys containing metallic or non-metallic fibres or filaments by powder metallurgy, i.e. by processing mixtures of metal powder and fibres or filaments

Definitions

  • the present invention relates to a method for preparing a metal material or a metal composite material, in particular to a method for preparing a metal material or a metal composite material by adding phenolic resin powder.
  • Carbon particles (carbon fiber, graphite, etc.) reinforced metal matrix composite materials combine the high electrical and thermal conductivity of metal, good strength and toughness, corrosion resistance, high strength and toughness of carbon fiber, and the lubricating properties of graphite. They are widely used in thermal conductive materials, Conductive materials, friction materials and other fields.
  • Cide patent CN104388847B discloses a method for preparing a carbon fiber reinforced copper-based composite material, including the following steps: Step 1. Weigh the ingredients for ball milling and mixing, and the mixing time is 3 hours; the mixture is obtained; the carbon fiber The surface is covered with a nickel layer; the particle size of the graphite powder is 5 (Vm), and the graphite powder is treated with electroless plating technology and the surface is plated with a copper layer; step two, the mixture prepared in step one is heated at 700 MPa Pressing under pressure; obtaining a blank; step three, subjecting the blank prepared in step two to the second-stage sintering to obtain a sintered alloy block; step four, subjecting the alloy block treated in step three to heat treatment; obtaining the present invention The carbon fiber reinforced copper-based composite material.
  • the copper-based composite material prepared by the present invention not only has excellent self-lubricating properties, but also has excellent wear resistance and mechanical properties.
  • the present invention combines carbon fiber and nickel powder, iron powder and copper powder, etc. Ball milling and mixing will cause serious damage to the carbon fiber.
  • the use of pressing and high-temperature sintering to prepare the material will cause uneven distribution of the carbon fiber, and obvious interface incompatibility between the carbon fiber and copper, which further affects the material performance.
  • Chinese invention patent CN108441791 A discloses a carbon fiber reinforced cermet composite material, which is composed of a carbon fiber preform, an interface layer, a ceramic matrix and a metal matrix.
  • the metal is aluminum alloy, magnesium alloy, One of copper alloys and tin alloys, the ceramic is SiC, and the composite material has a density of 1.8 to 3.8 g/cm 3.
  • the patent also discloses methods for preparing ceramic composite materials of different alloys.
  • This composite material has the advantages of short preparation cycle and adjustable density, overcomes the brittleness and low density of ceramics, and can meet the needs of ceramic matrix composites in many fields.
  • this invention adopts the first preparation of ceramic matrix in the carbon fiber preform and then the preparation of the metal matrix.
  • the precursor immersion cracking method is used to prepare the ceramic matrix in the carbon fiber preform with the prepared interface layer. It will cause damage to the carbon fiber, and the resulting ceramic interface layer is brittle, which has a negative impact on performance.
  • Chinese invention patent CN108018506A discloses a short carbon fiber modified high friction composite material.
  • the raw materials used in the short carbon fiber modified high friction composite material include the following components: resin coating-curing treatment of short carbon fiber 1 ⁇ 3wt% ; nano Oxide dispersion strengthened copper powder is greater than or equal to 15wt% ; in the nanometer oxide dispersion strengthened copper powder, nanometer oxide is generated in situ.
  • the short carbon fiber and metal copper powder are ball milled to prepare the pre-alloyed powder by resin coating-curing treatment, and then mixed with other component powders, and pressed and sintered to prepare a short carbon fiber modified high friction composite material.
  • the possible problem with this method is that a small amount of carbon fibers are exposed to the outside of the copper particles, which will hinder the diffusion of sintering between the copper particles, resulting in possible non-density of sintering. If the carbon surface is plated with transition metal or metal carbide is formed through oxidation or impregnation-cracking compound, it will affect the performance of carbon particles or carbon fiber itself.
  • the present invention adopts the ultrasonic treatment combined with the low-temperature heating-chilling process to effectively remove the carbon embedded on the surface of the metal powder, combined with the highly reducing atmosphere formed when the phenolic resin powder is cracked at high temperature, while promoting the sintering between the metal powder particles, It effectively protects the structure of the carbon itself and maximizes its characteristics.
  • the present invention provides a method for preparing metal materials or metal composite materials, which aims to obtain a density of 99%. % Or more, metal materials or metal composite materials with excellent properties such as strength and toughness, especially to provide a carbon/metal composite material that can ensure a density of more than 99% and excellent properties such as strength and toughness.
  • the present invention is a method for preparing a metal material or a metal composite material; the preparation method includes two sets of solutions
  • the first solution is: mixing the raw materials uniformly, pressing-sintering to obtain a metal material;
  • the raw materials include metal powder and phenolic resin powder;
  • the second solution is: ball mill the reinforcement and the base metal A to obtain the metal powder with the reinforcement embedded on the surface and inside [0011] At the end; the metal powder embedded with the reinforcement is subjected to ultrasonic treatment combined with a low-temperature heating-chilling process, The reinforcing particles on the surface are removed to obtain a spare material; the spare material is mixed with phenolic resin powder and then pressed-sintered, or the spare material is mixed with phenolic resin powder and particle phase B and then pressed-sintered to obtain a carbon/metal composite Material
  • the present invention is a method for preparing a metal material or a metal composite material; in the second solution, the phenolic resin
  • the particle size of the powder is less than or equal to 100 ⁇ m, preferably 10-80 ⁇ m.
  • a method for preparing a metal material or a metal composite material of the present invention is selected from carbon materials
  • the use of carbon materials can enhance the performance of the metal matrix composite material, but there are often interface barriers between the carbon material and the metal phase, and it is difficult to give full play to the reinforcing effect of the carbon material.
  • the carbon material and the base metal are combined in advance to obtain the carbon embedded metal powder. Direct pressing-sintering or mixing with other hard second phases-pressing-sintering can improve the performance of the obtained carbon-reinforced metal, but the degree of improvement is limited.
  • the inventor found for the first time that the main reason is that the inevitably exposed carbon material on the surface of the carbon-embedded metal powder hinders the sintering diffusion of the sintering process, resulting in less dense sintering.
  • the present invention innovatively proposes a method of ultrasonic treatment combined with low-temperature heating-chilling process to remove the carbon material on the surface of the carbon metal powder, adding phenolic resin powder when combining and mixing, and sintering
  • the carbon material is at least one of zero-dimensional, one-dimensional, two-dimensional, and three-dimensional carbon materials. Further preferably, the carbon material is One or more of granular graphite, carbon fiber, and carbon particles after the carbon fiber is broken are mixed in any ratio.
  • the carbon material is a short carbon fiber after degumming; the method for preparing the short carbon fiber after degumming is: in a protective atmosphere; heating the short carbon fiber bundle to 650 ⁇ 800°C for 20 ⁇ 90min; Obtain the short carbon fiber after degumming.
  • the length of the short carbon fiber after degumming is preferably The diameter is preferably 6 ⁇ 8 [ xm.
  • a method for preparing a metal material or a metal composite material according to the present invention is
  • the carbon material is a short carbon fiber coated with a phenolic resin; the preparation method of the phenolic resin coating is: dissolving the prepared phenolic resin in an organic solvent to obtain a phenolic resin alcohol saturated solution; Then the short carbon fiber is immersed in a saturated solution of phenolic resin alcohol at 60 ⁇ 80°C for 1 ⁇ 2 h; and then dried at 80 ⁇ 150°C for 1 ⁇ 3h; short carbon fiber coated with phenolic resin is obtained.
  • the short carbon fiber is preferably a short carbon fiber after degumming.
  • the length of the short carbon fiber after degumming is preferably 1 ⁇ 5mm; the diameter is preferably 6 ⁇ 8 [ xm.
  • the oxide of A is difficult to use and/or can be reduced with one or more of H2 and CO in a reducing atmosphere; preferably, the base metal A is selected from said base metal A being aluminum, titanium, zirconium At least one of copper, iron, nickel, chromium, manganese, and silver; more preferably at least one of copper, aluminum, titanium, and nickel.
  • a method for preparing a metal material or a metal composite material of the present invention includes the following steps:
  • step 2 After the oversize material C obtained in step 1 is heat-treated at 150 ⁇ 300° C. for 30 to 60 minutes under vacuum conditions, it is then placed in liquid nitrogen for thermal insulation treatment for 5 to 10 minutes, and the processed oversize material C is added Obtain the slurry in alcohol, ultrasonically treat it for 10-30 min, dry the slurry in vacuum to obtain dry powder N, pass the dry powder N through a 400 600 mesh sieve to obtain an oversize D, and the oversize D is only internally inlaid Metal powder with reinforcement.
  • the 400-600 mesh screening in step 1) and step 2) is selected from any one of ultrasonic stainless steel vibrating screen, ultra-fine powder separation ultrasonic rotary vibrating screen, and ordinary vibrating screen.
  • the vacuum drying temperature in step 1) and step 2) is 60 to 80°C.
  • the solvent is preferably an aqueous ethanol solution.
  • the frequency of the ultrasound is preferably 20-50KHz.
  • the particle phase B is iron, chromium, tungsten, silicon carbide, granular graphite, flake graphite, iron-chromium alloy, alumina,
  • silicon carbide, titanium carbide, hard ceramics, and tungsten carbide are mixed in any ratio.
  • a method for preparing a metal material or a metal composite material of the present invention when the raw material contains particle phase B; the mass ratio of spare material, phenolic resin powder and particle phase B is 20-99.5: 0.5-2 : 0.5-78
  • a method for preparing a metal material or a metal composite material of the present invention cold press the mixed material to obtain a compact, and then sinter it in a protective atmosphere or a vacuum or a protective atmosphere.
  • the pressing pressure of the cold forming process is 200 ⁇ 600MPa, the holding time is 20 ⁇ 30 s; the temperature of the green compact sintering process is 60% ⁇ 80% of the melting point of the base metal, and the holding time is 0.5 ⁇ 3 h, pressure 0 ⁇ l MPa;
  • the unit pressure of the hot pressing process is 200 to 600 MPa, the temperature is 60% to 80% of the melting point of the base metal, and the heat preservation and pressure holding time is 2 to 90 min.
  • the density of the obtained carbon/metal composite material is greater than or equal to 99%.
  • the carbon material is ball-milled and embedded in the base metal in advance, and then the carbon embedded in the metal powder exposed to the outside of the metal is removed by the innovative use of ultrasonic treatment and low-temperature heating-chilling process, thereby effectively Improve its sintering diffusion in the base metal, and significantly enhance the sintering compactness.
  • phenolic resin powder is added during the mixing process, and the reducing atmosphere formed by the high temperature cracking of micron and submicron phenolic resins during sintering is used to achieve near-to-full compactness Sintering.
  • the preparation method provided by the invention obtains a metal matrix composite material with high strength, high toughness, high temperature resistance, and good wear resistance on the premise that the metal powder is compacted by sintering, and has a simple preparation process and low cost.
  • the base metal A can be anything known to those skilled in the alloy industry that can be used
  • the base metal material of the carbon reinforced composite material is prepared.
  • the oxide of the base metal A is unavailable or difficult to be reduced by one or more reducing atmospheres of H2 and CO;
  • the base metal A is, for example, at least one of aluminum, titanium, and zirconium .
  • the oxide of the base metal A can be reduced with one or more reducing atmospheres of H2 and CO
  • the base metal A is, for example, one of copper, iron, nickel, chromium, manganese, and silver.
  • the base metal A is at least one of aluminum, titanium, zirconium, copper, iron, nickel, chromium, manganese, and silver.
  • This method is particularly suitable for the use of surface pre-oxidation-reduction process is difficult to remove the carbon material on the surface of the carbon metal powder.
  • the base metal A is at least one of aluminum, titanium, and zirconium.
  • the carbon material and the base metal A are ball-milled, and the carbon material is embedded in the base metal in advance, so that a uniformly distributed metal powder of the carbon material can be obtained to improve the performance of the composite material;
  • innovative ultrasonic treatment can further significantly improve the performance of the composite material.
  • the volume ratio of the carbon material and the base metal A is 5 to 95 :
  • the present invention innovatively uses an ultrasonic method to remove the residual carbon material on the surface of the carbon embedded metal powder, which can not only effectively remove the residual carbon material on the surface, but also is particularly suitable for the surface of the base metal that is difficult to be pre-oxidized-reduced Decarburization.
  • the oversize material D or the particle phase B is passed through a conventional mixing and a conventional sintering process to prepare the carbon-reinforced metal composite material.
  • the particulate phase B is one of iron, chromium, tungsten, silicon carbide, granular graphite, flake graphite, iron-chromium alloy, alumina, silicon carbide, titanium carbide, hard ceramics, tungsten carbide, or Multiple mixed in any proportion
  • the particle size of the particle phase B is preferably 10 ⁇ 400:1.
  • the raw material contains the particle phase B; the mass ratio of the spare material, the phenolic resin powder and the particle phase B is 20-99.5:0.5-2:0.5-78.
  • the mixed material after mixing is used according to the characteristics of the base metal, and the existing method can be used for sintering to obtain the composite material.
  • the mixed material is cold pressed to obtain a compact, which is then sintered under a protective atmosphere or a vacuum or protective atmosphere to obtain a carbon/metal composite material; or the mixed powder is directly hot pressed A carbon/metal composite material is obtained.
  • the temperature of the cold press forming process is, for example, room temperature, preferably 15 to 35°C.
  • the pressing pressure of the cold forming process is 200 ⁇ 600MPa, and the holding time is 20 ⁇ 30 s; the temperature of the green compact sintering process is 60% ⁇ 80% of the melting point of the base metal, and the holding time is 0.5 ⁇ 3 h, pressure It is 0 ⁇ l MPa.
  • the unit pressure of the hot pressing process is 200 to 600 MPa, the temperature is 60% to 80% of the melting point of the base metal, and the heat preservation and pressure holding time is 2 to 90 min.
  • the designed composite material is a carbon/metal composite material
  • its more preferred preparation method includes the following steps:
  • the surface and internal carbon-inserted metal powder (carbon-inserted metal powder) is added to alcohol to obtain a mixed solution, ultrasonically treated for 10 to 30 minutes, the mixed solution is vacuum dried to obtain a dry powder M, and the dry powder M is over 400 ⁇ 600 mesh sieve to obtain an oversize C, where the oversize C is a metal powder from which carbon is removed from the primary surface;
  • the obtained oversize material C is heat-treated at 150 ⁇ 300° C. for 30 to 60 minutes under vacuum conditions, and then placed in liquid nitrogen for heat preservation treatment for 5 to 10 minutes, and the processed oversize material C is added to alcohol to obtain The slurry is ultrasonically treated for 10-30 min. After the slurry is vacuum dried, dry powder N is obtained. The dry powder N is passed through a 400-600 mesh sieve to obtain an oversize D. The oversize D is only internally embedded in carbon Metal powder.
  • the mixed powder obtained in step 2 is compressed and refrigerated to obtain a compact, and then sintered under one condition of a protective atmosphere, a vacuum, and a protective atmosphere to obtain a carbon/metal composite material; or the mixed powder is directly hot-pressed Obtain a carbon/metal composite material.
  • the designed composite material is a carbon/metal composite material
  • the V-shaped mixer is used to mix until it is uniform; the mixing speed of the V-shaped mixer is 45-120 r/min, mixing Time 2 ⁇ 8 h.
  • step four the pressing pressure of the cold pressing is 200 ⁇ 600MPa, and the holding time is 20 ⁇ 30 s;
  • the sintering temperature is 60% to 80% of the melting point of the base metal
  • the holding time is 0.5 to 3 h
  • the pressure is 0 to l MPa
  • the hot pressing pressure is 200-600 MPa
  • the hot pressing temperature is 60% to 80% of the melting point of the base metal
  • the heat preservation and pressure holding time is 2 to 90 min .
  • the present invention is a method for preparing a metal material or a metal composite material, and the resulting metal material or metal composite material has a density greater than or equal to 99%. After optimization, it can reach 99.8%.
  • the present invention tried for the first time, using reinforcements (including carbon) reinforced metal powder instead of metal powder as raw materials, combined with ultrasonic treatment combined with low-temperature heating-chilling process, and adding phenolic resin powder when mixing, and pressing-sintering.
  • reinforcements including carbon
  • metal powder instead of metal powder as raw materials
  • ultrasonic treatment combined with low-temperature heating-chilling process
  • phenolic resin powder when mixing, and pressing-sintering.
  • High-performance metal materials or metal composite materials including carbon/metal composite materials
  • Carbon types include artificial graphite, granular graphite, carbon fiber, carbon fiber broken carbon particles, etc.
  • carbon is easy to spontaneously agglomerate, resulting in uneven distribution in the matrix, thereby reducing the mechanics and friction of the material Wear performance. If carbon can be pre-formed into carbon-reinforced metal powder by ball milling and other processes, it will significantly increase the degree of carbon dispersion in the matrix, resulting in a significant improvement in overall performance.
  • the ultrasonic treatment combined with the low-temperature heating-chilling process can remove the carbon on the surface of the metal powder, which is beneficial to the subsequent pressing and sintering of the powder.
  • this patent proposes to replace the saturated phenolic resin solution with phenolic resin powder.
  • phenolic resin powder By adding micron or sub-micron phenolic resin powder during mixing, it is evenly distributed in the mixture. After pressing, the powder is It evenly cracks and releases reducing gases such as H2 and CO, which effectively reduces the oxide film on the metal surface and promotes metal sintering.
  • the carbon remaining after the cracking of phenolic resin powder is activated carbon, which is porous and very thin, and can easily react with H2 to generate reduction Sexual CH4 gas.
  • the preparation process is simple and low in cost.
  • the preparation of a composite material using carbon-reinforced metal powder as a raw material is realized by only ultrasonic treatment combined with a low-temperature heating-chilling process, combined with the addition of phenolic resin powder during mixing.
  • FIG. 2 The morphology of the carbon-reinforced metal powder is shown in FIG. 2.
  • the composite material prepared by directly using carbon-reinforced metal powder as raw material without any treatment is shown in Figure 3.
  • the carbon-reinforced metal powder is subjected to ultrasonic treatment and drying treatment, and the prepared composite material is shown in Figure 4.
  • Figure 2 It can be seen from Figure 2 that a large amount of carbon is exposed on the surface of the carbon-reinforced metal powder, which will hinder the subsequent sintering.
  • Fig. 3 the carbon-reinforced metal powder is directly used as the raw material without any treatment. Due to the obstacle of the carbon interface, a large number of pores exist in the composite material after mixing-pressing-sintering.
  • the ultrasonic treatment combined with the low-temperature heating-chilling process realizes the sintering and compaction of the metal particles, and obtains a metal matrix composite material with a density of more than 99%.
  • the resulting composite material has excellent and uniform properties, and has good properties. market expectation.
  • Figure 1 is a flow chart of the preparation of the carbon / metal composite material provided by the present invention.
  • FIG. 3 is a composite material prepared by using carbon-reinforced copper powder as raw material in Comparative Example 1 without any treatment;
  • FIG. 4 shows the copper-based composite material prepared in Example 1 after ultrasonic treatment and drying of carbon-reinforced copper powder, and then mixing with phenolic resin powder, and finally pressing and sintering.
  • the preparation process of the carbon/metal composite material designed in the present invention is specifically as follows: First, the surface of the carbon-reinforced metal powder is ultrasonically treated combined with low-temperature heating-chilling to remove carbon, and then combined with phenolic resin powder , Hard particles are equally mixed with conventional materials, and finally pressed-sintered to obtain a carbon/metal composite material.
  • this comparative example 1 The other conditions of this comparative example 1 are the same as those of example 1, the difference is that the granular graphite embedded in copper powder prepared by ball milling is directly subjected to room temperature compression-hydrogen pressure sintering, and the process is the same as that of example 1, without ultrasonic treatment and low temperature -Chilling treatment.
  • the prepared copper-based composite material has a porosity of up to 14%, and the metal particles are not diffused and sintered, and the bending strength is 350MPa.
  • granular graphite and electrolytic copper powder are added to the ball milling equipment for high-energy ball milling, the particle size of the electrolytic copper powder added is 150 pm, and the particle size of the granular graphite is 30 pm; electrolytic copper powder and particles
  • the volume ratio of graphite is 5:1, the ball milling speed is 280r/min, the ball milling time is 8 hours, the ball milling ball is a stainless steel ball, and the ball diameter is 3mm ⁇ 10mm (ball milling ball diameter 3mm, 4mm, 5mm, 6mm, 7mm, 8mm,
  • the mass ratio of 9mm is 4:8: 11:20: 12:8:6:1), the mass ratio of the sum of the mass of granular graphite and electrolytic copper powder to the mass ratio of the ball milling ball It is 1:6.
  • the copper powder embedded with graphite particles is mixed with alcohol, and ultrasonic treatment is applied for 120 min (ultrasonic frequency is 35 KHz), the temperature of the solution is maintained at room temperature, and the ultrasonic solution is vacuum dried at 60° C.
  • Ultrasonic rotary vibrating sieve for sieving the minimum mesh size of the sieve is 400 meshes, and the on-sieve is the metal powder removed from the primary surface carbon.
  • the powder is kept in vacuum at 150°C for 30 minutes, it is directly placed in liquid nitrogen for 10 minutes, then mixed with alcohol, and ultrasonicated for 20 minutes.
  • the ultrasonic solution is vacuum dried at 60°C and passed through ultrafine powder Separate the ultrasonic rotary vibrating sieve for sieving treatment to obtain copper powder with only graphite particles embedded inside.
  • the copper powder with only graphite particles embedded in it was directly cold pressed at room temperature, the pressing pressure was 450 MPa, and the holding time was 20 s.
  • the prepared copper-based composite compact was pressurized and sintered under the protection of a hydrogen atmosphere at 960 Sintering at °C for 2h, the pressure is 0.85 MPa, and the heating rate and cooling rate of the furnace are both 10-15°C/min, and the sample of Comparative Example 2 is obtained.
  • the density of the copper-based composite material is 98%, and the bending strength is 450MPa.
  • the copper powder embedded with graphite particles is mixed with alcohol, and ultrasonic treatment is applied for 120 min (ultrasonic frequency is 35 KHz), the temperature of the solution is maintained at room temperature, and the ultrasonic solution is vacuum dried at 60° C.
  • Ultrasonic rotary vibrating sieve for sieving the minimum mesh size of the sieve is 400 meshes, and the on-sieve is the metal powder removed from the primary surface carbon.
  • the powder is kept in vacuum at 150°C for 30 minutes, it is directly placed in liquid nitrogen for 10 minutes, then mixed with alcohol, and ultrasonicated for 20 minutes.
  • the ultrasonic solution is vacuum dried at 60°C and passed through ultrafine powder Separate the ultrasonic rotary vibrating sieve for sieving treatment to obtain copper powder with only graphite particles embedded inside.
  • the prepared copper matrix composite compacts are pressure sintered under the protection of hydrogen atmosphere, and sintered at 960 °C for 2 hours at a pressure of 0.85 MPa, the heating rate and cooling rate of the furnace are both 10-15°C/min, and 3 samples of Comparative Example are obtained.
  • the density of the copper-based composite material is 96%, and the flexural strength is 375MPa.
  • Example 1 particulate graphite and electrolytic copper powder are added to the ball milling equipment for high-energy ball milling.
  • the particle size of the electrolytic copper powder added is 150 pm, and the particle size of the particulate graphite is 30 pm; electrolytic copper powder and particles
  • the volume ratio of graphite is 5:1, the ball milling speed is 280r/min, the ball milling time is 8 hours, the ball milling ball is a stainless steel ball, and the ball diameter is 3mm ⁇ 10mm (ball milling ball diameter 3mm, 4mm, 5mm, 6mm, 7mm, 8mm,
  • the mass ratio of 9mm is 4:8:11:20:12:8:6:1), the mass ratio of the sum of the mass of granular graphite and electrolytic copper powder to the mass of the ball milling ball is 1:6.
  • the copper powder embedded with graphite particles is mixed with alcohol, and ultrasonic treatment is applied for 120 min (ultrasonic frequency is 35 KHz), the temperature of the solution is maintained at room temperature, and the ultrasonic solution is vacuum dried at 60° C.
  • Ultrasonic rotary vibrating sieve for sieving the minimum mesh size of the sieve is 400 meshes, and the on-sieve is the metal powder removed from the primary surface carbon.
  • the powder is kept in vacuum at 150°C for 30 minutes, it is directly placed in liquid nitrogen for 10 minutes, then mixed with alcohol, and ultrasonicated for 20 minutes.
  • the ultrasonic solution is vacuum dried at 60°C and passed through ultrafine powder Separate the ultrasonic rotary vibrating sieve for sieving treatment to obtain copper powder with only graphite particles embedded inside.
  • the copper powder with only graphite particles inlaid inside and the phenolic resin powder were mixed at a mass ratio of 99:1, the particle size of the phenolic resin powder was HXHon, and mixed in a V-type mixer to obtain a mixed powder. Then the mixed powder was cold pressed at room temperature, the pressing pressure was 450 MPa, and the pressure holding time was 20 s.
  • the prepared copper-based composite compact was sintered under pressure under the protection of a hydrogen atmosphere and sintered at 960 °C for 2 hours. The heating rate of the furnace The temperature and cooling rate are both 10-15°C/min, the pressure is 0.85 MPa, and the sample of Example 1 is obtained.
  • the morphology of the prepared copper-based composite material is shown in FIG. 4. The density of copper-based composite material is 99.5%, and the bending strength is 500MPa.
  • Example 5 The other conditions of this Comparative Example 5 are the same as those of Example 2, except that the carbon particles prepared by ball milling are directly embedded in the copper powder.
  • the room temperature compression-hydrogen sintering is performed, and the process is the same as that of Example 2, without ultrasonic treatment and low-temperature-chilling treatment.
  • the morphology of the prepared copper-based composite is shown in Figure 3, the porosity is as high as 10%, and the metal particles are not diffused and sintered, and the bending strength is 380MPa.
  • This comparative example 5 takes commercially available short carbon fibers as an object, and the short carbon fibers have a diameter of 7 pm and a length of 1 mm. Under vacuum conditions, heat preservation at 700°C for 60 minutes, then degumming treatment; then add electrolytic copper powder to ball milling equipment for high-energy ball milling, the particle size of added electrolytic copper powder is 150 pm; electrolytic copper powder and degummed short carbon fiber
  • the volume ratio of the ball mill is 3: 1, the ball milling speed is 250r/min, the ball milling time is 6 h, the ball milling ball is a stainless steel ball, and the ball diameter is 3mm ⁇ 10mm (ball milling ball diameter 3mm, 4mm, 5mm, 6mm, 7mm, 8mm, 9m
  • the mass ratio of m is 4:8:11:20:12:8:6:1), the mass ratio of the sum of the degummed short fiber and the electrolytic copper powder to the mass of the ball milling ball is 1:6.
  • the copper powder embedded with ultrafine carbon powder is mixed with alcohol, and ultrasonic treatment is applied for 120 min (ultrasonic frequency is 25KHz), the temperature of the solution is maintained at room temperature, and the ultrasonic solution is vacuum dried at 60°C Afterwards, the ultrasonic rotary vibrating sieve is sieved, and the minimum mesh of the sieve is 400 meshes, and the on-sieve is the metal powder removed from the primary surface carbon. After the powder is kept in vacuum at 150°C for 30 minutes, it is directly placed in liquid nitrogen for 10 minutes, then mixed with alcohol, and ultrasonicated for 20 minutes. Finally, the ultrasonic solution is vacuum dried at 60°C and passed through ultrafine powder Separate the ultrasonic rotary vibrating sieve for screening treatment to obtain copper powder with only ultrafine carbon embedded inside.
  • ultrasonic frequency is 25KHz
  • the copper powder with only ultra-fine carbon embedded inside is directly cold pressed at room temperature, the pressing pressure is 450 MPa, and the holding time is 20 s.
  • the prepared copper-based composite material compact is pressurized and sintered under the protection of a hydrogen atmosphere. Sintering at 950°C for 2 hours, the heating rate and cooling rate of the furnace are both 10 ⁇ 15°C/min, and the pressure is 0.9 MPa. Comparative Example 6 samples are obtained.
  • the density of the copper matrix composite is 99%, and the bending strength is 480MPa.
  • This Example 2 takes commercially available short carbon fibers as an object, and the short carbon fibers have a diameter of 7 pm and a length of 1 mm. Under vacuum conditions, heat preservation at 700°C for 60 min, and degumming; then add electrolytic copper powder to ball milling equipment for high-energy ball milling, the particle size of the added electrolytic copper powder is 150 pm; electrolytic copper powder and degummed short carbon fiber
  • the volume ratio of the ball mill is 3: 1, the ball milling speed is 250r/min, the ball milling time is 6 h, the ball milling ball is a stainless steel ball, and the ball diameter is 3mm ⁇ 10mm (ball milling ball diameter 3mm, 4mm, 5mm, 6mm, 7mm, 8mm, 9m
  • the mass ratio of m is 4:8: 11:20: 12:8:6: 1), the mass sum of degummed short fiber and electrolytic copper powder and ball milling The mass ratio is 1:6.
  • the SEM morphology of the prepared carbon particles embedded in copper powder is shown
  • the copper powder embedded with ultrafine carbon powder is mixed with alcohol, and ultrasonic treatment is applied for 120 min (ultrasonic frequency is 25KHz), the temperature of the solution is maintained at room temperature, and the ultrasonic solution is vacuum dried at 60°C Afterwards, the ultrasonic rotary vibrating sieve is sieved, and the minimum mesh of the sieve is 400 meshes, and the on-sieve is the metal powder removed from the primary surface carbon. After the powder is kept in vacuum at 150°C for 30 minutes, it is directly placed in liquid nitrogen for 10 minutes, then mixed with alcohol, and ultrasonicated for 20 minutes. Finally, the ultrasonic solution is vacuum dried at 60°C and passed through ultrafine powder Separate the ultrasonic rotary vibrating sieve for screening treatment to obtain copper powder with only ultrafine carbon embedded inside.
  • ultrasonic frequency is 25KHz
  • the copper powder with only internal ultra-fine carbon and the phenolic resin powder are in a mass ratio of 99:1, and the particle size of the phenolic resin powder is 20 (Hon, mixed in a V-type mixer to obtain a mixed powder. Then the mixed powder Perform cold pressing at room temperature with a pressing pressure of 450 MPa and a holding time of 20 s.
  • the prepared copper-based composite compacts are pressure-sintered under the protection of a hydrogen atmosphere, and sintered at 950°C for 2 hours at a pressure of 0.9
  • Example 2 the sample of Example 2 is obtained.
  • the density of the copper-based composite material is 99.8%, and the bending strength is 510 MPa.
  • This Comparative Example 8 takes commercially available short carbon fibers as an object, and the short carbon fibers have a diameter of 8 pm and a length of 2 mm. Dissolve the prepared phenolic resin in an organic solvent to obtain a phenolic resin-alcohol saturated solution; then impregnate the short carbon fibers in a phenolic resin-alcohol saturated solution at 80°C for 2 hours; and then dry them at 120°C for 2 hours. Then add the electrolytic nickel powder to the ball milling equipment for high-energy ball milling.
  • the particle size of the electrolytic nickel powder added is 150 pm; the volume ratio of the electrolytic nickel powder to the degummed short carbon fiber is 4: 1, the ball milling speed is 300r/min, the ball mill The time is 3 hours, the ball milling ball is a stainless steel ball, the ball diameter is 3mm ⁇ 10mm (the mass ratio of the ball milling ball diameter 3mm, 4mm, 5mm, 6mm, 7mm, 8mm, 9mm is 4:8:11:20:12 :8:6: 1) The ratio of the sum of the mass of the short fiber coated with aldehyde resin and the mass of electrolytic nickel powder to the mass of the ball milling ball is 1:6.
  • the prepared nickel powder with short carbon fibers embedded in the inside and on the surface is mixed with alcohol, and ultrasonic treatment is applied. min (ultrasonic frequency is 30KHz), maintain the temperature of the solution at room temperature, and then vacuum dry the ultrasonic solution at 60°C, then sieve the ultrasonic vibrating sieve. The minimum mesh size of the sieve is 400 meshes.
  • Metal powder removed from surface carbon After the powder is kept in vacuum at 180°C for 30 minutes, it is directly placed in liquid nitrogen for 10 minutes, then mixed with alcohol, and ultrasonicated for 20 minutes. Finally, the ultrasonic solution is vacuum dried at 60°C and passed through ultrafine The powder is separated by an ultrasonic rotary vibrating sieve for sieving treatment to obtain nickel powder with only carbon fiber embedded inside.
  • the nickel powder with only carbon fiber embedded inside is directly cold pressed at room temperature, the pressing pressure is 500 MPa, and the holding time is 20s.
  • the prepared nickel-based composite compact is pressurized and sintered under the protection of hydrogen atmosphere. Sintering at °C for 2 hours, the pressure was 0.8 MPa, the heating rate and cooling rate of the furnace were both 10-15°C/min, and 8 samples of Comparative Example were obtained.
  • the density of the nickel-based composite material is 98.5%, and the tensile strength is 1250MPa.
  • This comparative example 9 takes commercially available short carbon fibers as an object, and the short carbon fibers have a diameter of 8 pm and a length of 2 mm. Dissolve the prepared phenolic resin in an organic solvent to obtain a phenolic resin-alcohol saturated solution; then impregnate the short carbon fibers in a phenolic resin-alcohol saturated solution at 80°C for 2 hours; and then dry them at 120°C for 2 hours. Then add the electrolytic nickel powder to the ball milling equipment for high-energy ball milling.
  • the particle size of the electrolytic nickel powder added is 150 pm; the volume ratio of the electrolytic nickel powder to the degummed short carbon fiber is 4: 1, the ball milling speed is 300r/min, the ball mill The time is 3 hours, the ball milling ball is a stainless steel ball, the ball diameter is 3mm ⁇ 10mm (the mass ratio of the ball milling ball diameter 3mm, 4mm, 5mm, 6mm, 7mm, 8mm, 9mm is 4:8:11:20:12 :8:6: 1) The ratio of the sum of the mass of the short fiber coated with aldehyde resin and the mass of electrolytic nickel powder to the mass of the ball milling ball is 1:6.
  • the prepared nickel powder with short carbon fibers embedded in the inside and on the surface was mixed with alcohol, and ultrasonic treatment was applied.
  • ultrasonic frequency is 30KHz
  • the minimum mesh size of the sieve is 400 meshes.
  • the pressure holding time is 20s
  • the prepared nickel-based composite compacts are pressurized and sintered under the protection of hydrogen atmosphere, and sintered at 1000 °C for 2 hours
  • the pressure is 0.8 MPa
  • the heating rate and cooling rate of the furnace are both 10 ⁇ 15° C/min
  • 9 samples of Comparative Example were obtained.
  • the density of the nickel-based composite material is 96.8%
  • the tensile strength is 1140MPa.
  • This Example 3 takes commercially available short carbon fibers as an object, and the short carbon fibers have a diameter of 8 pm and a length of 2 mm. Dissolve the prepared phenolic resin in an organic solvent to obtain a phenolic resin-alcohol saturated solution; then impregnate the short carbon fibers in a phenolic resin-alcohol saturated solution at 80°C for 2 hours; and then dry them at 120°C for 2 hours. Then add the electrolytic nickel powder to the ball milling equipment for high-energy ball milling.
  • the particle size of the electrolytic nickel powder added is 150 pm; the volume ratio of the electrolytic nickel powder to the degummed short carbon fiber is 4: 1, the ball milling speed is 300r/min, the ball mill The time is 3 hours, the ball milling ball is a stainless steel ball, the ball diameter is 3mm ⁇ 10mm (the mass ratio of the ball milling ball diameter 3mm, 4mm, 5mm, 6mm, 7mm, 8mm, 9mm is 4:8:11:20:12 :8:6: 1) The ratio of the sum of the mass of the short fiber coated with aldehyde resin and the mass of electrolytic nickel powder to the mass of the ball milling ball is 1:6.
  • the prepared nickel powder with short carbon fibers embedded in the inside and on the surface was mixed with alcohol, and ultrasonic treatment was applied.
  • ultrasonic frequency is 30KHz
  • the minimum mesh size of the sieve is 400 meshes.
  • the nickel powder with only carbon fiber embedded inside and the phenolic resin powder are in a mass ratio of 99:1, and the particle size of the phenolic resin powder is 20 ⁇ m, mixed in a V-type mixer to obtain a mixed powder. Then the mixed powder is at room temperature Perform cold pressing under 500 MPa pressing pressure and 20s holding time.
  • the prepared nickel-based composite compacts are pressurized and sintered under the protection of hydrogen atmosphere, sintered at 1000 °C for 2 hours, the pressure is 0.8 MPa, and the heating rate of the furnace The temperature and cooling rate are both 10-15°C/min, and the sample of Example 3 is obtained.
  • the density of the nickel-based composite material is 99.2%, and the tensile strength is 1310 MPa.
  • Comparative Example 10 [0130] The other conditions of this Comparative Example 10 are the same as those of Example 4, except that the carbon fiber embedded aluminum powder prepared by ball milling is mixed with 2% silicon carbide and mixed in a V-type mixer to obtain mixed powder. The obtained mixed powder was hot-pressed at 490 °C under the protection of a nitrogen atmosphere, the pressing pressure was 500 MPa, and the hot pressing time was 0.5 h to obtain an aluminum matrix composite material with a density of only 92% and a bending strength of 700 MPa.
  • the aluminum-based composite material prepared in Comparative Example 11 includes the following components in terms of mass percentage:
  • silicon carbide the balance being short carbon fibers embedded in aluminum alloy powder.
  • the particle size of silicon carbide is 9 (Vm), and the particle size of short carbon fiber embedded aluminum alloy powder is 100 [ xm.
  • the diameter of short carbon fiber is 8 [ xm, and the length is 2mm.
  • the prepared aluminum powder with carbon fiber embedded inside and on the surface was mixed with alcohol, and ultrasonic treatment was applied for 120 min (the ultrasonic frequency was 28KHz), and the temperature of the solution was maintained at room temperature, and then the ultrasonic solution was heated at 60°C.
  • sieving is carried out by ultrasonic rotary vibrating sieve, and the on-sieve is the metal powder removed from the primary surface carbon. After the powder is kept in vacuum at 200°C for 30 minutes, it is directly placed in liquid nitrogen for 10 minutes, then mixed with alcohol, and ultrasonicated for 20 minutes. Finally, the ultrasonic solution is vacuum dried at 60°C and passed through ultra-fine powder Separate the ultrasonic rotary vibrating sieve for sieving treatment to obtain aluminum powder with only carbon fiber embedded inside.
  • the particle size of the aluminum alloy powder with only carbon fiber remaining inside is 18 ⁇ m, and the aluminum alloy powder with only carbon fiber remaining inside is 98.0% by mass percentage, and the powder is mixed with 2% silicon carbide and mixed in a V-type mixer, A mixed powder is obtained.
  • the obtained mixed powder is hot-pressed at 490 °C under the protection of a nitrogen atmosphere, the pressing pressure is 500 MPa, and the hot pressing time is 0.5h, to obtain an aluminum-based composite material with a density of 99% and a resistance
  • the bending strength is 860MPa.
  • the aluminum-based composite material prepared in Example 4 includes the following components in terms of mass percentage:
  • silicon carbide the balance being short carbon fibers embedded in aluminum alloy powder.
  • the particle size of silicon carbide is 9 (Vm, short carbon fiber
  • the particle size of the embedded aluminum alloy powder is 100 [ xm.
  • the diameter of the short carbon fiber is 8 [ xm, and the length is 2mm.
  • the prepared aluminum powder with carbon fiber embedded inside and on the surface was mixed with alcohol, and ultrasonic treatment was applied for 120 min (the ultrasonic frequency is 28KHz), and the temperature of the solution was maintained at room temperature, and then the ultrasonic solution was heated at 60°C.
  • sieving is carried out by ultrasonic rotary vibrating sieve, and the on-sieve is the metal powder removed from the primary surface carbon.
  • the powder is kept in a vacuum at 200°C for 30 minutes, it is directly placed in liquid nitrogen for 2 minutes, then mixed with alcohol, and ultrasonicated for 20 minutes.
  • the ultrasonic solution is vacuum dried at 60°C and passed through ultrafine powder Separate the ultrasonic rotary vibrating sieve for sieving treatment to obtain aluminum powder with only carbon fiber embedded inside.
  • the aluminum alloy powder (with a particle size of 180:1) with only carbon fiber embedded inside and a phenolic resin powder (with a particle size of 25 (Hon), silicon carbide in a mass ratio of 96.5: 1.5: 2) were mixed in a V-type mixer, The mixture is obtained.
  • the mixture is hot-pressed at 490 °C under the protection of nitrogen atmosphere, the pressing pressure is 500 MPa, and the hot pressing time is 0.5h, to obtain an aluminum-based composite material with a density of 99.5% and a bending strength of 882MPa .
  • Example 12 The other conditions of this Comparative Example 12 are the same as those of Example 5. The difference is that the ultrafine carbon embedded iron powder prepared by ball milling is directly subjected to room temperature pressing-vacuum pressure sintering, and the process is the same as that of Example 5 without ultrasonic treatment and Low temperature-chilled treatment.
  • the prepared iron-based composite material has a porosity of up to 12% and a tensile strength of 610MPa.
  • This comparative example 13 uses commercially available short carbon fibers that have been degummed at 700°C for 60 min and reduced iron powder with a particle size of 120 microns as the ball mill raw materials, the volume percentage of carbon fiber is 8%, and the volume percentage of reduced iron powder is 92. %
  • the short carbon fiber has a diameter of 6pm and a length of 2mm.
  • the two are added to the ball milling equipment for high-energy ball milling.
  • the speed is 250r/min
  • the ball milling time is 6 hours
  • the ball-to-battery ratio is 6:1.
  • the ball milling ball is stainless steel and hard.
  • Quality alloy ball, the ball diameter is 3mm ⁇ 10mm (ball grinding ball diameter 3mm, 4mm, 5mm, 6mm, 7mm, 8mm, The mass ratio of 9mm is 4:8: 11:20: 12:8:6: 1).
  • the prepared iron powder with superfine carbon embedded inside and on the surface was mixed with alcohol, and ultrasonic treatment was applied for 120 min (ultrasonic frequency is 28KHz), the temperature of the solution was maintained at room temperature, and the ultrasonic solution was heated at 60°C.
  • sieving is carried out by ultrasonic rotary vibrating sieve, and the on-sieve is the metal powder removed from the primary surface carbon.
  • the powder is kept in vacuum at 200°C for 30 minutes, it is directly placed in liquid nitrogen for 10 minutes, then mixed with alcohol, and ultrasonicated for 20 minutes.
  • the ultrasonic solution is vacuum dried at 60°C and passed through the ultrafine
  • the powder is separated by ultrasonic rotary vibrating sieve for sieving treatment to obtain iron powder with only ultra-fine carbon embedded inside.
  • the iron powder with only ultra-fine carbon embedded inside was directly cold pressed at room temperature, the pressing pressure was 550 MPa, and the holding time was 20 s.
  • the prepared ferroalloy compact was pressurized and sintered under vacuum protection at 1050° C sintering for 2 h, the pressure is 0.3 MPa, the heating rate and cooling rate of the furnace are both 10-15 °C/min, and the iron-based composite material is obtained with a density of 98.5% and a tensile strength of 750 MPa.
  • Example 5 commercially available short carbon fibers with a degumming treatment at 700°C for 60 min and reduced iron powder with a particle size of 120 microns were used as the ball mill raw materials.
  • the volume percentage of carbon fiber was 8%, and the volume percentage of reduced iron powder was 92. %
  • the short carbon fiber has a diameter of 6 pm and a length of 2mm.
  • the two are added to the ball milling equipment for high-energy ball milling.
  • the speed is 250r/min
  • the ball milling time is 6 h
  • the ball-to-battery ratio is 6:1.
  • the ball milling ball is a stainless steel ball and Cemented carbide ball
  • the ball diameter is 3mm ⁇ 10mm (the mass ratio of ball milling ball diameter 3mm, 4mm, 5mm, 6mm, 7mm, 8mm, 9mm is 4:8:11:20:12:8:6:1).
  • the prepared iron powder with ultrafine carbon embedded inside and on the surface was mixed with alcohol, and ultrasonic treatment was applied for 120 min (the ultrasonic frequency was 28KHz), and the temperature of the solution was maintained at room temperature, and then the ultrasonic solution was heated at 60°C.
  • sieving is carried out by ultrasonic rotary vibrating sieve, and the on-sieve is the metal powder removed from the primary surface carbon.
  • the powder is kept in vacuum at 200°C for 30 minutes, it is directly placed in liquid nitrogen for 10 minutes, then mixed with alcohol, and ultrasonicated for 20 minutes.
  • the ultrasonic solution is vacuum dried at 60°C and passed through the ultrafine
  • the powder is separated by ultrasonic rotary vibrating sieve for sieving treatment to obtain iron powder with only ultra-fine carbon embedded inside.
  • the iron powder with only ultra-fine carbon embedded inside and the phenolic resin powder were mixed at a mass ratio of 98:2, and the phenolic resin powder had a particle size of 15 ⁇ m, and was mixed in a V-type mixer to obtain a mixed powder.
  • the resulting mixed powder Perform cold pressing at room temperature with a pressing pressure of 550 MPa and a holding time of 20 s.
  • the prepared ferroalloy compacts are pressure-sintered under vacuum protection and sintered at 1050 °C for 2 h at a pressure of 0.3 MPa, the heating rate and cooling rate of the furnace are both 10-15 °C/min, and the iron-based composite material is obtained with a density of 99.5% and a tensile strength of 860MPa.
  • Example 14 The other conditions of this Comparative Example 14 are the same as those of Example 6, the difference is that the ultrafine carbon embedded titanium powder prepared by ball milling is directly pressed at room temperature-vacuum sintered, and the process is the same as that of Example 6, without ultrasonic treatment and low temperature- Chilling treatment.
  • the prepared titanium-based composite material has a porosity of up to 11% and a tensile strength of 950MPa.
  • This comparative example 15 uses commercially available short carbon fibers degummed at 800°C for 30 min and titanium alloy powder with a particle size of 50 microns (Ti-6wt%Al-2.8wt%Sn-3.5wt%Zr-0.75wt% Nb-0.35wt%Si) is the raw material for ball milling (the volume ratio of titanium alloy powder and short carbon fiber after degumming is 5:1).
  • the short carbon fiber has a diameter of 6pm and a length of 2 mm. The two are added to the high-energy ball mill in the ball mill. The speed is 250r/min and the milling time is 12h.
  • the ball milling ball is a cemented carbide ball with a diameter of 3mm ⁇ 9mm (ball milling ball).
  • the mass ratio of diameter 3mm, 4mm, 5mm, 6mm, 7mm, 8mm, 9mm is 4:8: 11:20: 12:8:6:1), the sum of the mass of the degummed short fiber and the titanium alloy powder and the ball milling ball
  • the mass ratio is 1:8.
  • the prepared titanium alloy powder with embedded ultrafine carbon inside and on the surface was mixed with alcohol, and ultrasonic treatment was applied for 120 min (ultrasonic frequency is 28KHz), and the temperature of the solution was maintained at room temperature.
  • ultrasonic frequency is 28KHz
  • the temperature of the solution was maintained at room temperature.
  • vacuum drying at 60°C
  • the powder is sieved by an ultrasonic rotary vibrating sieve, and the on-sieve is the metal powder removed from the primary surface carbon.
  • the powder is kept in vacuum at 400°C for 30 minutes, it is directly placed in liquid nitrogen for 10 minutes, then mixed with alcohol, and ultrasonicated for 20 minutes.
  • the ultrasonic solution is vacuum dried at 60°C and separated by ultrafine powder
  • the ultrasonic rotary vibrating screen is sieved to obtain titanium alloy powder with only ultrafine carbon embedded inside.
  • the titanium alloy powder with only ultrafine carbon remaining inside was cold pressed at room temperature, the pressing pressure was 400 MPa, and the holding time was 20s.
  • the prepared titanium-based composite material compact was sintered under vacuum at 1350 °C. After sintering for 2 h, the heating rate and cooling rate of the furnace are both 15°C/min, and the titanium-based composite material is obtained with a density of 98% and a tensile strength of 1240MPa.
  • This Example 6 uses commercially available short carbon fibers with a degumming treatment at 800°C for 30 min and a titanium alloy powder with a particle size of 50 pm (Ti-6wt%Al-2.8wt%Sn-3.5wt%Zr-0.75wt%Nb -0.35wt% Si) is the raw material for ball milling (the volume ratio of titanium alloy powder and short carbon fiber after degumming is 5:1).
  • the short carbon fiber has a diameter of 6pm and a length of 2mm , Add the two to the high-energy ball mill of the ball mill, the speed is 250r/min, the milling time is 12h, the ball milling ball is a cemented carbide ball, the ball diameter is 3mm ⁇ 9mm (the ball diameter is 3mm, 4mm, 5mm, 6mm, 7 The mass ratio of mm, 8mm, and 9mm is 4:8:11:20:12:8:6:1), and the mass ratio of the sum of the mass of the degummed short fiber and the titanium alloy powder to the mass of the ball milling ball is 1:8.
  • the prepared titanium alloy powder with ultrafine carbon embedded in the inside and on the surface was mixed with alcohol, and ultrasonic treatment was applied for 120 min (the ultrasonic frequency was 28KHz), and the temperature of the solution was maintained at room temperature.
  • the ultrasonic frequency was 28KHz
  • the temperature of the solution was maintained at room temperature.
  • vacuum drying at 60°C it is sieved by an ultrasonic rotary vibrating sieve, and the on-sieve is the metal powder removed from the primary surface carbon.
  • the powder is kept under vacuum at 400°C for 30 minutes, it is directly placed in liquid nitrogen for 10 minutes, then mixed with alcohol, and ultrasonicated for 20 minutes.
  • the ultrasonic solution is vacuum dried at 60°C and passed through ultrafine powder Separate the ultrasonic rotary vibrating screen for sieving treatment to obtain titanium alloy powder with only ultrafine carbon embedded inside
  • the titanium alloy with only ultra-fine carbon embedded inside and the phenolic resin powder were mixed at a mass ratio of 98:2, and the phenolic resin powder had a particle size of 15 ⁇ m, and was mixed in a V-type mixer to obtain a mixed powder.
  • the resulting mixed powder Cold pressing is carried out at room temperature, the pressing pressure is 400 MPa, and the holding time is 20s.
  • the prepared titanium-based composite compacts are sintered under vacuum and sintered at 1350 °C for 2 h. The heating rate and cooling rate of the furnace are both 15 °C/min, the resulting titanium-based composite material has a density of 98.8% and a tensile strength of 1365MPa.
  • the preparation process, mixing and pressing process of the iron powder with only ultrafine carbon embedded in the embodiment 7 is the same as that of the embodiment 5, and the difference lies in the sintering process.
  • the sintering process is pressure sintering of the compact under vacuum protection, sintering at 750 °C for 2 h, and then heating to 1100 °C for sintering 2
  • the heating rate and cooling rate of the furnace are both 10-15 °C/min, and the pressure is 0.5 MPa, resulting in an ultrafine iron carbide particle reinforced ferroalloy with a density of 99.2% and a tensile strength of 865 MPa.

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Abstract

一种金属材料或金属复合材料的制备方法，具体涉及补入酚醛树脂粉末制备金属材料或金属复合材料的方法。该方法包括两套方案；方案一为：将原料混合均匀，压制-烧结，得到金属材料；原料包括金属粉体和酚醛树脂粉末；方案二为：将增强体和基体金属A球磨得到表面和内部嵌有增强体的金属粉末；将嵌有增强体的金属粉末进行超声处理结合低温加热-激冷工艺，去除其表面的增强颗粒，得到备用料；将备用料与酚醛树脂粉末混料后压制-烧结，或，将备用料与酚醛树脂粉末、颗粒相B混料后压制-烧结，得到碳/金属复合材料。

Description

一种金属材料或金属复合材料的制备方法 技术领域
[0001] 本发明涉及一种金属材料或金属复合材料的制备方法， 具体涉及补入酚醛树脂 粉末制备金属材料或金属复合材料的方法。
背景技术
[0002] 碳颗粒 （碳纤维、 石墨等） 增强金属基复合材料兼具金属的高导电导热、 良好 强韧性、 耐腐蚀性能和碳纤维的高强韧性、 石墨的润滑特性等， 被广泛应用于 导热材料、 导电材料、 摩擦材料等领域。
[0003] 近年来， 研究人员为提高复合材料的力学性能和高温抗氧化性能， 做了大量的 研究， 主要集中于碳 /金属界面润湿性的改进、 通过碳的加入， 如碳表面镀覆金 属、 金属中加入其他合金元素降低与碳的界面润湿性， 使用人造颗粒、 碳纤维 来改善材料的抗氧化性能， 通过酚醛树脂包覆处理， 促进金属氧化物膜层的还 原， 从而促进金属的烧结扩散。
[0004] 中国发明专利 CN104388847B公开了一种碳纤维增强的铜基复合材料的制备方 法， 包括如下的步骤： 步骤一、 称取配料进行球磨混合， 混合时间为 3小时； 得 到混合料； 所述碳纤维表面包覆有镍层； 所述石墨粉粒径为 5（Vm， 并且所述的 石墨粉经过化学镀技术处理表面镀有铜层； 步骤二、 将所述步骤一制备的混合 料在 700MPa的压力下压制； 得到毛坯； 步骤三、 将所述步骤二制备的毛坯进行 二期烧结， 得到烧结后的合金块； 步骤四、 将所述步骤三处理后的合金块进行 热处理； 得到本发明所述的碳纤维增强的铜基复合材料。 本发明制备的铜基复 合材料不仅具有优良的自润滑性能， 而且耐磨性能和力学性能优异。 但是该发 明将碳纤维和镍粉、 铁粉和铜粉等球磨混合， 会对碳纤维造成严重的损伤， 同 时采用压制和高温烧结的方式制备材料会导致碳纤维分布不均， 以及碳纤维和 铜会产生明显的界面不相容现象， 进一步影响材料性能。
[0005] 中国发明专利 CN108441791 A公开了一种碳纤维增强的金属陶瓷复合材料， 由 碳纤维预制体， 界面层， 陶瓷基体和金属基体组成， 金属为铝合金， 镁合金， 铜合金， 锡合金中的一种， 陶瓷为 SiC， 该复合材料密度为 1.8 ~ 3.8g/cm3， 该专 利还公开了制备不同合金陶瓷复合材料的方法。 这种复合材料具有制备周期短 ， 密度可调的优点， 克服了陶瓷的脆性和低密度， 可满足多领域对陶瓷基复合 材料的需求。 但是该发明采用在碳纤维预制体中先制备陶瓷基体再制备金属基 体， 虽然保护碳纤维免受金属熔液的损伤， 但先驱体浸渍裂解法在制备好界面 层的碳纤维预制体中制备陶瓷基体， 势必会导致碳纤维收到损伤， 且生成的陶 瓷界面层脆性大， 对性能影响不利。
[0006] 发明人研究发现， 脱胶碳纤维或酚醛树脂包覆碳纤维与软性金属球磨， 可获得 碳颗粒或短碳纤维均匀嵌入的金属粉末。 中国发明专利 CN108018506A公开了一 种短碳纤维改性高摩复合材料， 所述短碳纤维改性高摩复合材料其所用原料包 括下述组分： 树脂包覆 -固化处理短碳纤维 1〜 3wt% ; 纳米氧化物弥散强化铜粉 大于等于 15wt% ; 所述纳米氧化物弥散强化铜粉中， 纳米氧化物通过原位生成 。 采用树脂包覆-固化处理短碳纤维与金属铜粉球磨制备预合金粉， 再与其他组 元粉末混合， 通过压制烧结， 制备一种短碳纤维改性高摩复合材料。 但该方法 可能存在的问题， 即少量碳纤维裸露于铜颗粒外部， 将阻碍铜颗粒间的烧结扩 散， 导致烧结可能存在的不致密现象。 如采用碳表面镀覆过渡性质金属或通过 氧化或浸渍-裂解化合形成金属碳化物， 都会影响碳颗粒或碳纤维本身的性能。 本发明采用本发明采用超声处理结合低温加热 -激冷工艺， 有效去除金属粉末表 面镶嵌的碳， 结合酚醛树脂粉末高温裂解时形成的高还原性气氛， 在促进金属 粉末颗粒间的烧结的同时， 有效的保护了碳本身的结构， 最大程度发挥了其特 性。
发明概述
技术问题
[0007] 为解决现有碳 /金属复合材料存在的致密性差、 各项性能不理想的技术不足， 本发明提供了一种金属材料或金属复合材料的制备方法， 旨在制得致密度达 99% 以上、 强度、 韧性等性能优异的金属材料或金属复合材料， 尤其是提供一种能 确保致密度达 99%以上、 强度、 韧性等性能优异的碳 /金属复合材料。
问题的解决方案 技术解决方案
[0008] 本发明一种金属材料或金属复合材料的制备方法； 所述制备方法包括两套方案
[0009] 方案一为： 将原料混合均匀， 压制-烧结， 得到金属材料； 所述原料包括金属 粉体和酚醛树脂粉末；
[0010] 方案二为： 将增强体和基体金属 A球磨得到表面和内部嵌有增强体的金属粉 [0011] 末； 将嵌有增强体的金属粉末进行超声处理结合低温加热 -激冷工艺， 去除其 表面的增强颗粒， 得到备用料； 将备用料与酚醛树脂粉末混料后压制 -烧结， 或 ， 将备用料与酚醛树脂粉末、 颗粒相 B混料后压制-烧结， 得到碳 /金属复合材料
[0012] 本发明一种金属材料或金属复合材料的制备方法； 方案一中， 所述酚醛树脂 [0013] 粉末的粒径小于等于 30(Vm; 所述金属粉体和酚醛树脂粉末的质量比为 98-99.5 : 0.5-2。
[0014] 本发明一种金属材料或金属复合材料的制备方法； 方案二中， 所述酚醛树脂
[0015] 粉末的粒径小于等于 100畔、 优选为 10-80畔。
[0016] 本发明一种金属材料或金属复合材料的制备方法； 所述增强体选自碳材
[0017] 料、 碳化物中的至少一种。
[0018] 采用碳材料可以增强金属基复合材料的性能， 但碳材料和金属相往往存在界面 阻碍， 难于充分发挥碳材料增强效果， 预先将碳材料和基底金属复合， 得到嵌 碳金属粉末， 随后再直接压制-烧结或和其他硬质第二相混合 -压制 -烧结可以提 升得到的碳增强金属的性能， 但改善程度有限。 本发明人通过深入研究， 首次 发现其主要原因为嵌碳金属粉末表面不可避免地裸露碳材料阻碍了烧结过程的 烧结扩散， 导致烧结不致密。 基于本发明首创性地发现的该技术问题， 本发明 创新地提出一种通过超声处理结合低温加热-激冷工艺脱除嵌碳金属粉末表面的 碳材料， 结合混料时加入酚醛树脂粉末， 烧结时高温裂解时形成的高还原性气 氛， 实现烧结时的近全致密， 改善烧结得到的复合材料性能的方法。
[0019] 作为优选， 本发明一种金属材料或金属复合材料的制备方法； 所述的碳材料为 零维、 一维、 二维、 三维碳材料中的至少一种。 进一步优选， 所述的碳材料为 颗粒石墨、 碳纤维、 碳纤维破碎后的碳颗粒的一种或多种按任意比例混合。 作 为更进一步的优选方案， 所述碳材料为脱胶后的短碳纤维； 所述脱胶后的短碳 纤维的制备方法为： 在保护气氛下； 将短碳纤维束加热至 650~800°C保温处理 20 ~90min； 得到脱胶后的短碳纤维。 脱胶后的短碳纤维的长度优选为
Figure imgf000006_0001
直 径优选为 6~8 [xm。
[0020] 作为优选， 本发明一种金属材料或金属复合材料的制备方法； 所述碳材料为
[0021] 酚醛树脂包覆的碳材料。 作为更进一步的优选方案， 所述碳材料为酚醛树脂包 覆的短碳纤维； 所述酚醛树脂包覆的制备方法为： 将配取的酚醛树脂溶于有机 溶剂中， 得到酚醛树脂酒精饱和溶液； 然后将短碳纤维经 60~80°C酚醛树脂酒精 饱和溶液浸渍 l~2 h; 再在 80~150°C下烘干 l~3h; 得到酚醛树脂包覆的短碳纤维 。 该短碳纤维优选为脱胶后的短碳纤维。 脱胶后的短碳纤维的长度优选为 l~5m m； 直径优选为 6~8 [xm。
[0022] 作为优选， 本发明一种金属材料或金属复合材料的制备方法； 所述基体金属
[0023] A的氧化物难用和 /或可用 H2、 CO中的一种或多种还原性气氛还原； 优选地， 基体金属 A选自所述的所述基体金属 A为铝、 钛、 锆、 铜、 铁、 镍、 铬、 锰、 银 中的至少一种； 进一步优选为铜、 铝、 钛、 镍中的至少一种。
[0024] 作为优选， 本发明一种金属材料或金属复合材料的制备方法； 所述超声的过程 包括如下步骤：
[0025] 1） 将将嵌有增强体的金属粉末 （包括表面和内部嵌碳金属粉末） 加入酒精中 获得混合液， 超声处理 5~60 min， 将混合液真空干燥， 获得干燥粉体 M， 将干燥 粉体 M过 400~600目筛， 获得筛上物 C， 所述筛上物 C为初级表面增强体去除的金 属粉 （包括初级表面碳去除的金属粉） ；
[0026] 2） 将步骤 1所得筛上物 C在真空条件下于 150~300°C热处理 30~60min后， 再置 于液氮中保温处理 5~10min， 将处理后的筛上物 C加入酒精中获得浆液， 超声处 理 10~30 min， 将浆液真空干燥后， 获得干燥粉体 N， 将干燥粉体 N过 400 600目 筛， 获得筛上物 D， 所得筛上物 D为仅内部镶嵌有增强体的金属粉末。
[0027] 作为进一步的优选， 所述步骤 1） 中、 步骤 2） 中的 400~600目筛选自超声波不 锈钢振动筛、 超细粉分离超声波旋振筛、 普通振动筛中的任意一种。 [0028] 作为进一步的优选， 所述步骤 1） 中、 步骤 2） 中真空干燥的温度为 60~80°C。
[0029] 作为优选， 所述的溶剂优选为乙醇的水溶液。
[0030] 作为优选， 超声的频率优选为 20~50KHz。
[0031] 作为优选， 本发明一种金属材料或金属复合材料的制备方法； 所述颗粒相 B为 铁、 铬、 钨、 碳化硅、 颗粒状石墨、 鳞片状石墨、 铁铬合金、 氧化铝、 碳化硅 、 碳化钛、 硬质陶瓷、 碳化钨中的一种或多种按任意比例混合。
[0032] 作为优选， 本发明一种金属材料或金属复合材料的制备方法； 备用料与酚醛树 脂粉末的质量比为 20~99.5: 0.5-2=
[0033] 作为优选， 本发明一种金属材料或金属复合材料的制备方法； 当原料中含有颗 粒相 B时； 备用料、 酚醛树脂粉末与颗粒相 B的质量比为 20~99.5: 0.5-2： 0.5-78
[0034] 作为优选， 本发明一种金属材料或金属复合材料的制备方法； 将混料后的混合 料冷压成型后得到压坯， 再在保护气氛或真空或保护气氛加压条件下烧结， 得 到碳 /金属复合材料； 或将混合粉直接热压得到碳 /金属复合材料；
[0035] 冷压成型过程的压制压力为 200~600MPa， 保压时间为 20~30 s; 压坯烧结过程 的温度为基体金属熔点的 60%~80%， 保温时间为 0.5~3 h， 压力为 0~l MPa;
[0036] 热压过程的单位压力为 200~600MPa， 温度为基体金属熔点的 60%~80%， 保温 保压时间为 2~90 min。
[0037] 作为优选， 本发明一种金属材料或金属复合材料的制备方法； 所得碳 /金属复 合材料的致密度大于等于 99%。
[0038] 本发明优选方案中， 创新地预先将碳材料球磨嵌入至基底金属中， 随后再创新 地利用超声处理结合低温加热-激冷工艺去除嵌碳金属粉末裸露于金属外部的碳 ， 从而有效改善其在基底金属中的烧结扩散， 明显提升烧结致密性， 最后在混 料过程中加入酚醛树脂粉末， 利用微米和亚微米级的酚醛树脂烧结时高温裂解 形成的还原性气氛， 实现近全致密的烧结。 本发明提供的制备方法， 在实现了 金属粉末在烧结致密的前提下， 获得了高强、 高韧、 耐高温， 且耐磨性良好的 金属基复合材料， 制备工艺简单， 成本低。
[0039] 本发明中， 基体金属 A可以为合金领域行业技术人员所能获知的任何可以用来 制备碳增强复合材料的基底金属材料。
[0040] 作为优选， 所述基体金属 A的氧化物不可用或难以用 H2、 CO中的一种或多种 还原性气氛还原； 该基体金属 A例如为铝、 钛、 锆中的至少一种。
[0041] 和 /或， 所述基体金属 A的氧化物可用 H2、 CO中的一种或多种还原性气氛还原
; 该基体金属 A例如为铜、 铁、 镍、 铬、 锰、 银中的一种。
[0042] 优选地， 所述的所述基体金属 A为铝、 钛、 锆、 铜、 铁、 镍、 铬、 锰、 银中的 至少一种。
[0043] 本方法特别适用于采用表面预氧化-还原工艺难于脱除嵌碳金属粉末表面碳材 料的金属材料。
[0044] 进一步优选， 所述的所述基体金属 A为铝、 钛、 锆中的至少一种。
[0045] 作为优选， 将碳材料和基底金属 A球磨， 预先将碳材料嵌入基底金属中， 如此 可以获得碳材料均匀分布的金属粉末， 以改善制得的复合材料的性能； 再协同 配合本发明创新地超声处理， 可以进一步明显改善制得的复合材料的性能。
[0046] 作为优选， 嵌碳金属粉末制备过程中， 碳材料和基体金属 A的体积比为 5~95:
95-5= 控制在该比例下， 可以进一步提升制得的复合材料的性能， 特别是力学 性能、 耐磨性能提升明显。
[0047] 本发明创新地采用超声方法脱除嵌碳金属粉末表面残留的碳材料， 其不仅能有 效脱除表面残留的碳材料， 还特别适用于难于通过预氧化-还原处理的基底金属 的表面脱碳。
[0048] 将筛上物 D或与颗粒相 B通过常规的混料以及常规的烧结工艺， 制得所述的碳 增强金属复合材料。
[0049] 所述颗粒相 B为铁、 铬、 钨、 碳化硅、 颗粒状石墨、 鳞片状石墨、 铁铬合金、 氧化铝、 碳化硅、 碳化钛、 硬质陶瓷、 碳化钨中的一种或多种按任意比例混合
[0050] 所述颗粒相 B的粒径优选为 10~400 1。
[0051] 作为优选方案， 备用料与酚醛树脂粉末的质量比为 20~99.5: 0.5-2=
[0052] 作为优选方案， 当原料中含有颗粒相 B时； 备用料、 酚醛树脂粉末与颗粒相 B 的质量比为 20~99.5: 0.5-2： 0.5~78。 [0053] 将混料后的混合料采用根据基底金属的特性， 可采用现有方法进行烧结， 制得 所述的复合材料。
[0054] 作为优选， 将混料后的混合料冷压成型后得到压坯， 再在保护气氛或真空或保 护气氛加压条件下烧结， 得到碳 /金属复合材料； 或将混合粉直接热压得到碳 /金 属复合材料。 冷压成型过程的温度例如为室温， 优选为 15~35°C。
[0055] 冷压成型过程的压制压力为 200~600MPa， 保压时间为 20~30 s; 压坯烧结过程 的温度为基体金属熔点的 60%~80%， 保温时间为 0.5~3 h， 压力为 0~l MPa。
[0056] 热压过程的单位压力为 200~600MPa， 温度为基体金属熔点的 60%~80%， 保温 保压时间为 2~90 min。
[0057] 当所设计的复合材料为碳 /金属复合材料时， 其更为优选的制备方法， 包括下 述步骤：
[0058] 步骤一
[0059] 碳嵌入的金属粉末的超声处理；
[0060] 所述碳嵌入的金属粉末 （嵌碳金属粉末） 的超声处理工艺为：
[0061] 将表面和内部嵌碳金属粉末 （嵌碳金属粉末） 加入酒精中获得混合液， 超声处 理 10~30 min， 将混合液真空干燥， 获得干燥粉体 M， 将干燥粉体 M过 400~600目 筛， 获得筛上物 C， 所述筛上物 C为初级表面碳去除的金属粉；
[0062] 再将所得筛上物 C在真空条件下于 150~300°C热处理 30~60min后， 再置于液氮 中保温处理 5~10min， 将处理后的筛上物 C加入酒精中获得浆液， 超声处理 10~30 min, 将浆液真空干燥后， 获得干燥粉体 N， 将干燥粉体 N过 400~600目筛， 获得 筛上物 D， 所得筛上物 D为仅内部镶嵌于碳的金属粉末。
[0063] 步骤二
[0064] 按设计组分配步骤一得到的超声处理后的嵌碳金属粉末、 酚醛树脂粉末和颗粒 相 B组分粉末， 混合均匀后， 得到混合粉末；
[0065] 步骤三
[0066] 将步骤二得到的混合粉压制冷成型得到压坯， 再在保护气氛、 真空、 保护气氛 加压的一种条件下烧结， 得到碳 /金属复合材料； 或是将混合粉直接热压得到碳 / 金属复合材料。 [0067] 当所设计的复合材料为碳 /金属复合材料时， 步骤二中， 混料时， 通过 V型混料 机搅拌至均匀； V型混料机的搅拌速度为 45-120r/min， 混合时间 2~8 h。
[0068] 当所设计的复合材料为碳 /金属复合材料时， 步骤四中， 所述冷压的压制压力 为 200~600MPa， 保压时间为 20~30 s ;
[0069] 当所设计的复合材料为碳 /金属复合材料时， 所述烧结温度为基体金属熔点的 60%~80% , 保温时间为 0.5~3 h， 压力为 0~l MPa;
[0070] 当所设计的复合材料为碳 /金属复合材料时， 所述热压的压力为 200~600MPa， 热压温度为基体金属熔点的 60%~80% , 保温保压时间为 2~90 min。
[0071] 本发明一种金属材料或金属复合材料的制备方法， 所得金属材料或金属复合材 料的致密度大于等于 99%。 优化后可以达到 99.8%。
[0072] 本发明首次尝试了， 采用增强体 （包括碳） 增强金属粉末替代金属粉末为原料 ， 结合超声处理结合低温加热 -激冷工艺， 以及混料时加入酚醛树脂粉末， 经压 制-烧结即可得到高性能的金属材料或金属复合材料 （包括碳 /金属复合材料） 。
[0073] 本发明原理和优势：
[0074] 原料选择而言， 以碳增强金属粉末替代金属粉， 显著提高了碳在基体中的分散 。 碳种类包括人造石墨、 颗粒状石墨、 碳纤维、 碳纤维破碎的碳颗粒等等， 传 统混料过程中， 碳易自发团聚， 导致在基体中的分布及其不均匀， 从而降低了 材料的力学和摩擦磨损性能。 若碳能通过球磨等工艺预先形成碳增强金属粉原 料加入， 将明显提高碳在基体中的分散程度， 使得整体性能的显著提高。
[0075] 表面去碳工艺的选择。 粉末的烧结致密， 主要依靠颗粒间的原子扩散进行， 金 属颗粒表面的氧化膜和异质相将成为烧结的阻碍界面， 降低粉末颗粒间的烧结 致密化。 虽然以碳颗粒增强金属粉末替代金属粉可实现碳在基体中的均匀分散 ， 但在金属粉外部裸露的碳也阻碍了金属颗粒之间的烧结扩散。 虽然有氧环境 下氧化可去除表面碳， 但同样会造成金属的氧化， 如铝粉形成的氧化铝就无法 被氢气还原， 也很难被 CO还原， 针对这一类金属粉， 则不能采用氧化表面去碳 和还原的工艺， 因此选择超声处理结合低温加热 -激冷工艺， 可去除金属粉表面 的碳， 利于粉末后续的压制烧结。
[0076] 混料时酚醛树脂粉末的加入。 发明人在中国发明专利 CN108018506A中提出酚 醛树脂与酒精混合形成的饱和溶液， 用来浸渍石墨、 碳纤维等物质， 能有效去 除其表面的官能团， 且润湿速度特别快， 通过低温固化后形成的树脂包覆层修 饰了石墨表面， 保护了碳纤维结构。 但固化后的包覆层厚度达到几百微米甚至 几毫米， 虽然烧结时高温会裂解生成气体， 但裂解残留的碳尺寸较粗 （达到亚 微米级） ， 导致材料孔隙度提高。 为此， 本专利提出以酚醛树脂粉末替代酚醛 树脂饱和溶液， 通过在混料时加入微米或亚微米级酚醛树脂粉末， 使其在混合 料中均匀分布， 压制后高温烧结时， 该粉末在材料中均匀裂解且释放 H2、 CO等 还原性气体， 有效还原金属表面氧化膜， 促进金属烧结， 此外， 酚醛树脂粉末 裂解残留的碳为活性炭， 呈多孔状， 很薄， 极易与 H2反应生成还原性的 CH4气 体。 此时， 加入的酚醛树脂粉末大部分裂解成气体， 同时其余部分分解成纳米 级别厚的碳膜； 利用碳、 金属原子的扩散， 当碳膜较薄时， 形成金属原子贯穿 碳膜的铆接结构； 从而为实现了金属近全致密烧结提供必要条件。
[0077] 该制备工艺简单， 成本低， 仅通过超声处理结合低温加热 -激冷工艺， 结合混 料时酚醛树脂粉末的加入， 实现了以碳增强金属粉为原料的复合材料的制备。
[0078] 碳增强金属粉的形貌如图 2所示。 直接以碳增强金属粉为原料， 不做任何处理 制备的复合材料如图 3所示。 将碳增强金属粉进行超声处理和干燥处理， 制备的 复合材料如图 4所示。 由图 2可知， 碳增强金属粉的表面有大量碳的裸露， 这将 阻碍于后续烧结的进行。 由图 3可知， 直接以碳增强金属粉为原料， 不做任何处 理， 经混料 -压制 -烧结的复合材料中由于碳界面的阻碍， 导致存在大量孔隙。 由 图 4可知， 采用超声处理结合低温加热 -激冷工艺， 实现了金属颗粒间的烧结致密 ， 获得了致密度达到 99%以上的金属基复合材料， 所得复合材料性能优良且均匀 ， 具有良好的市场前景。
发明的有益效果
有益效果
对附图的简要说明
附图说明
[0079] 附图 1为本发明提供的碳 /金属复合材料的制备流程图;
[0080] 附图 2为碳增强铜粉末 SEM形貌； [0081] 附图 3为对比例 1直接以碳增强铜粉为原料， 不做任何处理制备的复合材料；
[0082] 附图 4为实施例 1将碳增强铜粉超声处理-干燥后， 再通过与酚醛树脂粉末混料 ， 最后压制-烧结制备的铜基复合材料。
[0083] 从图 1中可以看出本发明设计的碳 /金属复合材料的制备流程， 具体为： 首先， 碳增强金属粉末表面超声处理结合低温加热 -激冷去碳， 之后再与酚醛树脂粉末 、 硬质颗粒相等进行常规混料， 最后压制 -烧结处理， 获得碳 /金属复合材料。
[0084] 由图 2和图 3可知， 碳增强金属粉的表面有大量碳的裸露， 直接以其为原料， 不 做任何处理， 无法实现金属粉末颗粒间的烧结致密化。
[0085] 由图 4可知， 采用超声处理结合低温加热-激冷工艺实现了金属颗粒间的烧结致 密， 结合混料时酚醛树脂粉末的加入， 获得了低孔隙度的金属基复合材料。 发明实施例
本发明的实施方式
[0086] 下面结合本发明的附图， 对本发明的技术方案进行清楚、 完整地描述， 显然， 所描述的实施例仅仅是本发明所记载技术方案中的一部分实施例， 而不是全部 的实施例。 基于本发明的实施例， 本领域普通技术人员在没有做出创造性劳动 前提下所获得的所有其他实施例， 都属于本发明的保护范围。
[0087]
[0088] 对比例 1
[0089] 本对比例 1其他条件与实施例 1相同， 区别在于球磨制备的颗粒石墨嵌入铜粉直 接进行室温压制-氢气加压烧结， 其工艺与实施例 1相同， 而不进行超声处理和低 温 -激冷处理。 制备的铜基复合材料孔隙度高达 14%， 且金属颗粒间未扩散烧结 ， 抗弯强度为 350MPa。
[0090] 对比例 2
[0091] 本对比例 2以颗粒石墨与电解铜粉一起加入至球磨设备中进行高能球磨， 所加 入电解铜粉的粒径为 150 pm， 颗粒石墨的粒径为 30 pm; 电解铜粉与颗粒石墨的 体积比为 5: 1， 球磨转速为 280r/min， 球磨时间为 8 h， 球磨球为不锈钢球， 球径 为 3mm~10mm （球磨球直径 3mm、 4mm、 5mm、 6mm、 7mm、 8mm、 9mm的质 量比为 4:8: 11:20: 12:8:6:1） ， 颗粒石墨与电解铜粉的质量之和与球磨球的质量比 为 1:6。
[0092] 球磨完后， 将嵌入颗粒石墨的铜粉与酒精混合， 外加超声处理 120 min （超声 频率为 35KHz） ， 维持溶液温度为室温， 再将超声后的溶液在 60°C真空干燥后， 超声波旋振筛进行筛分， 筛网最小目数 400目， 保留筛上物即初级表面碳去除的 金属粉。 再将粉末经 150°C真空保温 30min后， 直接置于液氮中保温 lOmin， 之后 与酒精混合， 外加超声处理 20 min， 最后将超声后的溶液在 60°C真空干燥后， 通 过超细粉分离超声波旋振筛进行筛分处理， 得到仅内部镶嵌颗粒石墨的铜粉。
[0093] 将仅内部镶嵌颗粒石墨的铜粉直接在室温下进行冷压， 压制压力为 450MPa， 保压时间为 20s， 制备的铜基复合材料压坯在氢气气氛保护下加压烧结， 在 960 °C烧结 2h， 压力为 0.85 MPa， 炉子的升温速率与降温速率均为 10~15°C/min， 得 到对比例 2样件。 铜基复合材料的致密度为 98%， 抗弯强度为 450MPa。
[0094] 对比例 3
[0095] 本对比例 3以颗粒石墨与电解铜粉一起加入至球磨设备中进行高能球磨， 所加 入电解铜粉的粒径为 150 pm， 颗粒石墨的粒径为 30 pm; 电解铜粉与颗粒石墨的 体积比为 5: 1， 球磨转速为 280r/min， 球磨时间为 8 h， 球磨球为不锈钢球， 球径 为 3mm~10mm （球磨球直径 3mm、 4mm、 5mm、 6mm、 7mm、 8mm、 9mm的质 量比为 4:8: 11:20: 12:8:6:1） ， 颗粒石墨与电解铜粉的质量之和与球磨球的质量比 为 1:6。
[0096] 球磨完后， 将嵌入颗粒石墨的铜粉与酒精混合， 外加超声处理 120 min （超声 频率为 35KHz） ， 维持溶液温度为室温， 再将超声后的溶液在 60°C真空干燥后， 超声波旋振筛进行筛分， 筛网最小目数 400目， 保留筛上物即初级表面碳去除的 金属粉。 再将粉末经 150°C真空保温 30min后， 直接置于液氮中保温 lOmin， 之后 与酒精混合， 外加超声处理 20 min， 最后将超声后的溶液在 60°C真空干燥后， 通 过超细粉分离超声波旋振筛进行筛分处理， 得到仅内部镶嵌颗粒石墨的铜粉。
[0097] 将仅内部镶嵌颗粒石墨的铜粉浸渍于酚醛树脂酒精饱和溶液中 2 h， 再在 100°C 下烘干 2
h, 破碎后直接在室温下进行冷压， 压制压力为 450MPa， 保压时间为 20s， 制备 的铜基复合材料压坯在氢气气氛保护下加压烧结， 在 960 °C烧结 2h， 压力为 0.85 MPa, 炉子的升温速率与降温速率均为 10~15°C/min， 得到对比例 3样件。 铜基复 合材料的致密度为 96%， 抗弯强度为 375MPa。
[0098] 对比例 4
[0099] 本对比例 4其他条件与实施例 1相同， 区别在于混料时， 加入的酚醛树脂粉末的 粒度为 l~2mm， 其工艺与实施例 1相同， 。 制备的铜基复合材料孔隙度高达 15%
， 且金属颗粒间未扩散烧结， 抗弯强度为 333MPa。
[0100] 实施例 1
[0101] 本实施例 1以颗粒石墨与电解铜粉一起加入至球磨设备中进行高能球磨， 所加 入电解铜粉的粒径为 150 pm， 颗粒石墨的粒径为 30 pm; 电解铜粉与颗粒石墨的 体积比为 5: 1， 球磨转速为 280r/min， 球磨时间为 8 h， 球磨球为不锈钢球， 球径 为 3mm~10mm （球磨球直径 3mm、 4mm、 5mm、 6mm、 7mm、 8mm、 9mm的质 量比为 4:8: 11:20: 12:8:6:1） ， 颗粒石墨与电解铜粉的质量之和与球磨球的质量比 为 1:6。
[0102] 球磨完后， 将嵌入颗粒石墨的铜粉与酒精混合， 外加超声处理 120 min （超声 频率为 35KHz） ， 维持溶液温度为室温， 再将超声后的溶液在 60°C真空干燥后， 超声波旋振筛进行筛分， 筛网最小目数 400目， 保留筛上物即初级表面碳去除的 金属粉。 再将粉末经 150°C真空保温 30min后， 直接置于液氮中保温 lOmin， 之后 与酒精混合， 外加超声处理 20 min， 最后将超声后的溶液在 60°C真空干燥后， 通 过超细粉分离超声波旋振筛进行筛分处理， 得到仅内部镶嵌颗粒石墨的铜粉。
[0103] 将仅内部镶嵌颗粒石墨的铜粉与酚醛树脂粉末按质量比 99: 1， 酚醛树脂粉末的 粒度为 HXHon， 在 V型混料机混合， 得到混合粉。 再将混合粉在室温下进行冷压 ， 压制压力为 450MPa， 保压时间为 20s， 制备的铜基复合材料压坯在氢气气氛保 护下加压烧结， 在 960 °C烧结 2h， 炉子的升温速率与降温速率均为 10~15°C/min ， 压力为 0.85MPa， 得到实施例 1样件， 制备的铜基复合材料形貌如图 4所示。 铜 基复合材料的致密度为 99.5%， 抗弯强度为 500MPa。
[0104]
[0105] 对比例 5
[0106] 本对比例 5其他条件与实施例 2相同， 区别在于球磨制备的碳颗粒嵌入铜粉直接 进行室温压制 -氢气烧结， 其工艺与实施例 2相同， 而不进行超声处理和低温-激 冷处理。 制备的铜基复合材料形貌如图 3所示， 孔隙度高达 10%， 且金属颗粒间 未扩散烧结， 抗弯强度为 380MPa。
[0107] 对比例 6
[0108] 本对比例 5以市售短碳纤维为对象， 短碳纤维的直径为 7pm、 长度 1 mm。 在真 空条件下， 700°C保温 60 min， 进行脱胶处理； 然后与电解铜粉一起加入至球磨 设备中进行高能球磨， 所加入电解铜粉的粒径为 150 pm; 电解铜粉与脱胶短碳 纤维的体积比为 3: 1， 球磨转速为 250r/min， 球磨时间为 6 h， 球磨球为不锈钢球 ， 球径为 3mm~10mm （球磨球直径 3mm、 4mm、 5mm、 6mm、 7mm、 8mm、 9m m的质量比为 4:8: 11:20: 12:8:6: 1） ， 脱胶短纤维与电解铜粉的质量之和与球磨球 的质量比为 1:6。 制备的碳颗粒嵌入铜粉的 SEM形貌如图 2所示。
[0109] 球磨完后， 将嵌入超细碳粉的铜粉与酒精混合， 外加超声处理 120 min （超声 频率为 25KHz） ， 维持溶液温度为室温， 再将超声后的溶液在 60°C真空干燥后， 超声波旋振筛进行筛分， 筛网最小目数 400目， 保留筛上物即初级表面碳去除的 金属粉。 再将粉末经 150°C真空保温 30min后， 直接置于液氮中保温 lOmin， 之后 与酒精混合， 外加超声处理 20 min， 最后将超声后的溶液在 60°C真空干燥后， 通 过超细粉分离超声波旋振筛进行筛分处理， 得到仅内部镶嵌超细碳的铜粉。
[0110] 将仅内部镶嵌超细碳的铜粉直接在室温下进行冷压， 压制压力为 450MPa， 保 压时间为 20s， 制备的铜基复合材料压坯在氢气气氛保护下加压烧结， 在 950°C烧 结 2h， 炉子的升温速率与降温速率均为 10~15°C/min， 压力为 0.9 MPa， 得到对比 例 6样件， 铜基复合材料的致密度为 99%， 抗弯强度为 480MPa。
[0111] 实施例 2
[0112] 本实施例 2以市售短碳纤维为对象， 短碳纤维的直径为 7pm、 长度 1 mm。 在真 空条件下， 700°C保温 60 min， 进行脱胶处理； 然后与电解铜粉一起加入至球磨 设备中进行高能球磨， 所加入电解铜粉的粒径为 150 pm; 电解铜粉与脱胶短碳 纤维的体积比为 3: 1， 球磨转速为 250r/min， 球磨时间为 6 h， 球磨球为不锈钢球 ， 球径为 3mm~10mm （球磨球直径 3mm、 4mm、 5mm、 6mm、 7mm、 8mm、 9m m的质量比为 4:8: 11:20: 12:8:6: 1） ， 脱胶短纤维与电解铜粉的质量之和与球磨球 的质量比为 1:6。 制备的碳颗粒嵌入铜粉的 SEM形貌如图 2所示。
[0113] 球磨完后， 将嵌入超细碳粉的铜粉与酒精混合， 外加超声处理 120 min （超声 频率为 25KHz） ， 维持溶液温度为室温， 再将超声后的溶液在 60°C真空干燥后， 超声波旋振筛进行筛分， 筛网最小目数 400目， 保留筛上物即初级表面碳去除的 金属粉。 再将粉末经 150°C真空保温 30min后， 直接置于液氮中保温 lOmin， 之后 与酒精混合， 外加超声处理 20 min， 最后将超声后的溶液在 60°C真空干燥后， 通 过超细粉分离超声波旋振筛进行筛分处理， 得到仅内部镶嵌超细碳的铜粉。
[0114] 将仅内部超细碳的铜粉与酚醛树脂粉末按质量比 99: 1， ， 酚醛树脂粉末的粒度 为 20（Hon， 在 V型混料机混合， 得到混合粉。 再将混合粉在室温下进行冷压， 压 制压力为 450MPa， 保压时间为 20s， 制备的铜基复合材料压坯在氢气气氛保护下 加压烧结， 在 950°C烧结 2h， 压力为 0.9
MPa, 炉子的升温速率与降温速率均为 10~15°C/min， 得到实施例 2样件， 铜基复 合材料的致密度为 99.8%， 抗弯强度为 510MPa。
[0115] 对比例 7
[0116] 本对比例 7其他条件与实施例 3相同， 区别在于球磨制备的碳纤维嵌入镍粉直接 进行室温压制 -氢气烧结， 其工艺与实施例 3相同， 而不进行超声处理和低温-激 冷处理。 制备的镍基复合材料的孔隙度高达 10%， 抗拉强度为 750MPa。
[0117] 对比例 8
[0118] 本对比例 8以市售短碳纤维为对象， 短碳纤维的直径为 8pm， 长度 2mm。 将配 取的酚醛树脂溶于有机溶剂中， 得到酚醛树脂酒精饱和溶液； 然后将短碳纤维 经 80°C酚醛树脂酒精饱和溶液浸渍 2 h; 再在 120°C下烘干 2 h。 然后与电解镍粉一 起加入至球磨设备中进行高能球磨， 所加入电解镍粉的粒径为 150 pm; 电解镍 粉与脱胶短碳纤维的体积比为 4: 1， 球磨转速为 300r/min， 球磨时间为 3 h， 球磨 球为不绣钢球， 球径为 3mm~10mm （球磨球直径 3mm、 4mm、 5mm、 6mm、 7m m、 8mm、 9mm的质量比为 4:8:11:20: 12:8:6: 1） ， 酷醛树脂包覆的短纤维与电解 镍粉的质量之和与球磨球的质量比为 1:6。
[0119] 球磨完后， 将制备的内部和表面嵌入短碳纤维的镍粉与酒精混合， 外加超声处 理 100 min （超声频率为 30KHz） ， 维持溶液温度为室温， 再将超声后的溶液在 60°C真 空干燥后， 超声波旋振筛进行筛分， 筛网最小目数 400目， 保留筛上物即初级表 面碳去除的金属粉。 再将粉末经 180°C真空保温 30min后， 直接置于液氮中保温 1 Omin, 之后与酒精混合， 外加超声处理 20 min， 最后将超声后的溶液在 60°C真空 干燥后， 通过超细粉分离超声波旋振筛进行筛分处理， 得到仅内部嵌入碳纤维 的镍粉。
[0120] 将仅内部嵌入碳纤维的镍粉直接在室温下进行冷压， 压制压力为 500 MPa， 保 压时间为 20s， 制备的镍基复合材料压坯在氢气气氛保护下加压烧结， 在 1000 °C 烧结 2h， 压力为 0.8 MPa， 炉子的升温速率与降温速率均为 10~15°C/min， 得到对 比例 8样件。 镍基复合材料的致密度为 98.5%， 抗拉强度为 1250MPa。
[0121] 对比例 9
[0122] 本对比例 9以市售短碳纤维为对象， 短碳纤维的直径为 8pm， 长度 2mm。 将配 取的酚醛树脂溶于有机溶剂中， 得到酚醛树脂酒精饱和溶液； 然后将短碳纤维 经 80°C酚醛树脂酒精饱和溶液浸渍 2 h; 再在 120°C下烘干 2 h。 然后与电解镍粉一 起加入至球磨设备中进行高能球磨， 所加入电解镍粉的粒径为 150 pm; 电解镍 粉与脱胶短碳纤维的体积比为 4: 1， 球磨转速为 300r/min， 球磨时间为 3 h， 球磨 球为不绣钢球， 球径为 3mm~10mm （球磨球直径 3mm、 4mm、 5mm、 6mm、 7m m、 8mm、 9mm的质量比为 4:8:11:20: 12:8:6: 1） ， 酷醛树脂包覆的短纤维与电解 镍粉的质量之和与球磨球的质量比为 1:6。
[0123] 球磨完后， 将制备的内部和表面嵌入短碳纤维的镍粉与酒精混合， 外加超声处 理 100
min （超声频率为 30KHz） ， 维持溶液温度为室温， 再将超声后的溶液在 60°C真 空干燥后， 超声波旋振筛进行筛分， 筛网最小目数 400目， 保留筛上物即初级表 面碳去除的金属粉。 再将将粉末经 180°C真空保温 30min后， 直接置于液氮中保 温 lOmin， 之后与酒精混合， 外加超声处理 20 min， 最后将超声后的溶液在 60°C 真空干燥后， 通过超细粉分离超声波旋振筛进行筛分处理， 得到仅内部嵌入碳 纤维的镍粉。
[0124] 将仅内部镶嵌颗粒石墨的铜粉浸渍于酚醛树脂酒精饱和溶液中 2 h， 再在 100°C 下烘干 2 h， 破碎后直接在室温下进行冷压， 压制压力为 500
MPa, 保压时间为 20s， 制备的镍基复合材料压坯在氢气气氛保护下加压烧结， 在 1000 °C烧结 2h， 压力为 0.8 MPa， 炉子的升温速率与降温速率均为 10~15°C/min ， 得到对比例 9样件。 镍基复合材料的致密度为 96.8%， 抗拉强度为 1140MPa。
[0125] 实施例 3
[0126] 本实施例 3以市售短碳纤维为对象， 短碳纤维的直径为 8pm， 长度 2mm。 将配 取的酚醛树脂溶于有机溶剂中， 得到酚醛树脂酒精饱和溶液； 然后将短碳纤维 经 80°C酚醛树脂酒精饱和溶液浸渍 2 h; 再在 120°C下烘干 2 h。 然后与电解镍粉一 起加入至球磨设备中进行高能球磨， 所加入电解镍粉的粒径为 150 pm; 电解镍 粉与脱胶短碳纤维的体积比为 4: 1， 球磨转速为 300r/min， 球磨时间为 3 h， 球磨 球为不绣钢球， 球径为 3mm~10mm （球磨球直径 3mm、 4mm、 5mm、 6mm、 7m m、 8mm、 9mm的质量比为 4:8:11:20: 12:8:6: 1） ， 酷醛树脂包覆的短纤维与电解 镍粉的质量之和与球磨球的质量比为 1:6。
[0127] 球磨完后， 将制备的内部和表面嵌入短碳纤维的镍粉与酒精混合， 外加超声处 理 100
min （超声频率为 30KHz） ， 维持溶液温度为室温， 再将超声后的溶液在 60°C真 空干燥后， 超声波旋振筛进行筛分， 筛网最小目数 400目， 保留筛上物即初级表 面碳去除的金属粉。 再将粉末经 180°C真空保温 30min后， 直接置于液氮中保温 1 Omin, 之后与酒精混合， 外加超声处理 20 min， 最后将超声后的溶液在 60°C真空 干燥后， 通过超细粉分离超声波旋振筛进行筛分处理， 得到仅内部嵌入碳纤维 的镍粉。
[0128] 将仅内部嵌入碳纤维的镍粉与酚醛树脂粉末按质量比 99: 1， 酚醛树脂粉末的粒 度为 20（Vm， 在 V型混料机混合， 得到混合粉。 再将混合粉在室温下进行冷压， 压制压力为 500 MPa， 保压时间为 20s， 制备的镍基复合材料压坯在氢气气氛保 护下加压烧结， 在 1000 °C烧结 2h， 压力为 0.8 MPa， 炉子的升温速率与降温速率 均为 10~15°C/min， 得到实施例 3样件。 镍基复合材料的致密度为 99.2%， 抗拉强 度为 1310MPa。
[0129] 对比例 10 [0130] 本对比例 10其他条件与实施例 4相同， 区别在于球磨制备的碳纤维嵌入铝粉与 碳化硅 2%配料后， 在 V型混料机混合， 得到混合粉。 其将所得混合粉在 490 °C、 氮气气氛保护下进行热压， 压制压力为 500 MPa， 热压时间为 0.5h， 得到铝基复 合材料， 致密度仅为 92%， 抗弯强度为 700MPa。
[0131] 对比例 11
[0132] 本对比例 11中所制备的铝基复合材料， 以质量百分比计包括下述组分：
[0133] 碳化硅 2%， 余量为短碳纤维嵌入铝合金粉。 碳化硅的粒径为 9（Vm， 短碳纤维 嵌入招合金粉的粒径为 100[xm。 短碳纤维的直径为 8 [xm， 长度 2mm。
[0134] 将配取的酚醛树脂溶于有机溶剂中， 得到酚醛树脂酒精饱和溶液； 然后将短碳 纤维经 80°C酚醛树脂酒精饱和溶液浸渍 2 h; 再在 120°C下烘干 2 h。 再将固化的酚 醛树脂碳纤维和粒径 150—的雾化 Al-9.6wt%Zn-2.5wt%Mg-2.2wt%Cu-
[0135] 0.16wt%Zr合金粉进行球磨， 碳纤维体积百分比计 8%， 铝合金粉加入体积百分 比计 92%， 球磨转速为 300r/min， 球磨时间 2 h， 球料比为 6: 1， 球磨球为不锈钢 球和硬质合金球， 球径为 3mm~10mm （球磨球直径 3mm、 4mm、 5mm、 6mm、 7 mm、 8mm、 9mm的质量比为 4:8: 11:20: 12:8:6:1） 。
[0136] 球磨完后， 将制备的内部和表面嵌入碳纤维的铝粉与酒精混合， 外加超声处理 120 min （超声频率为 28KHz） ， 维持溶液温度为室温， 再将超声后的溶液在 60 °C真空干燥后， 超声波旋振筛进行筛分， 保留筛上物即初级表面碳去除的金属粉 。 再将将粉末经 200°C真空保温 30min后， 直接置于液氮中保温 lOmin， 之后与酒 精混合， 外加超声处理 20min， 最后将超声后的溶液在 60°C真空干燥后， 通过超 细粉分离超声波旋振筛进行筛分处理， 得到仅内部嵌入碳纤维的铝粉。
[0137] 将仅内部残留碳纤维的铝合金粉的粒径为 18（Vm， 按质量百分比仅内部残留碳 纤维的铝合金粉 98.0%， 碳化硅 2%配取粉末， 在 V型混料机混合， 得到混合粉料 。 其将所得混合粉料在 490 °C、 氮气气氛保护下进行热压， 压制压力为 500 MPa ， 热压时间为 0.5h， 得到铝基复合材料， 致密度为 99%， 抗弯强度为 860MPa。
[0138] 实施例 4
[0139] 本实施例 4中所制备的铝基复合材料， 以质量百分比计包括下述组分：
[0140] 碳化硅 2%， 余量为短碳纤维嵌入铝合金粉。 碳化硅的粒径为 9（Vm， 短碳纤维 嵌入招合金粉的粒径为 100[xm。 短碳纤维的直径为 8 [xm， 长度 2mm。
[0141] 将配取的酚醛树脂溶于有机溶剂中， 得到酚醛树脂酒精饱和溶液； 然后将短碳 纤维经 80°C酚醛树脂酒精饱和溶液浸渍 2 h; 再在 120°C下烘干 2 h。 再将固化的酚 醛树脂碳纤维和粒径 150微米的雾化 Al-9.6wt%Zn-2.5wt%Mg-2.2wt%Cu-
[0142] 0.16wt%Zr合金粉进行球磨， 碳纤维体积百分比计 8%， 铝合金粉加入体积百分 比计 92%， 球磨转速为 300r/min， 球磨时间 10 h， 球料比为 6: 1， 球磨球为不锈钢 球和硬质合金球， 球径为 3mm~10mm （球磨球直径 3mm、 4mm、 5mm、 6mm、 7 mm、 8mm、 9mm的质量比为 4:8: 11:20: 12:8:6:1） 。
[0143] 球磨完后， 将制备的内部和表面嵌入碳纤维的铝粉与酒精混合， 外加超声处理 120 min （超声频率为 28KHz） ， 维持溶液温度为室温， 再将超声后的溶液在 60 °C真空干燥后， 超声波旋振筛进行筛分， 保留筛上物即初级表面碳去除的金属粉 。 再将将粉末经 200°C真空保温 30min后， 直接置于液氮中保温 2min， 之后与酒 精混合， 外加超声处理 20min， 最后将超声后的溶液在 60°C真空干燥后， 通过超 细粉分离超声波旋振筛进行筛分处理， 得到仅内部嵌入碳纤维的铝粉。
[0144] 将仅内部嵌入碳纤维的铝合金粉 （粒度为 180 1） 与酚醛树脂粉末 （粒度为 25 （Hon） 、 碳化硅按质量比 96.5: 1.5: 2配料， 在 V型混料机混合， 得到混合料。 其混合料在 490 °C、 氮气气氛保护下进行热压， 压制压力为 500 MPa， 热压时间 为 0.5h， 得到铝基复合材料， 致密度为 99.5%， 抗弯强度为 882MPa。
[0145] 对比例 12
[0146] 本对比例 12其他条件与实施例 5相同， 区别在于球磨制备的超细碳嵌入铁粉直 接进行室温压制-真空加压烧结， 其工艺与实施例 5相同， 而不进行超声处理和低 温 -激冷处理。 制备的铁基复合材料的孔隙度高达 12%， 抗拉强度为 610MPa。
[0147] 对比例 13
[0148] 本对比例 13采用市售、 700°C脱胶处理 60 min的短碳纤维和粒径为 120微米的还 原铁粉为球磨原料， 碳纤维体积百分比计 8%， 还原铁粉加入体积百分比计 92%
， 短碳纤维的直径为 6pm， 长度 2mm， 将两者加入到球磨设备中进行高能球磨， 转速为 250r/min， 球磨时间为 6 h， 球料比为 6: 1， 球磨球为不锈钢球和硬质合金 球， 球径为 3mm~10mm （球磨球直径 3mm、 4mm、 5mm、 6mm、 7mm、 8mm、 9mm的质量比为 4:8: 11:20: 12:8:6: 1） 。
[0149] 球磨完后， 将制备的内部和表面嵌入超细碳的铁粉与酒精混合， 外加超声处理 120 min （超声频率为 28KHz） ， 维持溶液温度为室温， 再将超声后的溶液在 60 °C真空干燥后， 超声波旋振筛进行筛分， 保留筛上物即初级表面碳去除的金属粉 。 再将将粉末经 200°C真空保温 30min后， 直接置于液氮中保温 lOmin， 之后与酒 精混合， 外加超声处理 20 min， 最后将超声后的溶液在 60°C真空干燥后， 通过超 细粉分离超声波旋振筛进行筛分处理， 得到仅内部嵌入超细碳的铁粉。
[0150] 将仅内部嵌入超细碳的铁粉直接在室温下进行冷压， 压制压力为 550 MPa， 保 压时间为 20 s， 制备的铁合金压坯在真空保护下加压烧结， 在 1050 °C烧结 2 h， 压力为 0.3 MPa， 炉子的升温速率与降温速率均为 10~15 °C/min， 得到铁基复合材 料， 致密度为 98.5%， 抗拉强度为 750MPa。
[0151] 实施例 5
[0152] 本实施例 5采用市售、 700°C脱胶处理 60 min的短碳纤维和粒径为 120微米的还 原铁粉为球磨原料， 碳纤维体积百分比计 8%， 还原铁粉加入体积百分比计 92%
， 短碳纤维的直径为 6 pm， 长度 2mm， 将两者加入到球磨设备中进行高能球磨 ， 转速为 250r/min， 球磨时间为 6 h， 球料比为 6: 1， 球磨球为不锈钢球和硬质合 金球， 球径为 3mm~10mm （球磨球直径 3mm、 4mm、 5mm、 6mm、 7mm、 8mm 、 9mm的质量比为 4:8: 11:20: 12:8:6: 1） 。
[0153] 球磨完后， 将制备的内部和表面嵌入超细碳的铁粉与酒精混合， 外加超声处理 120 min （超声频率为 28KHz） ， 维持溶液温度为室温， 再将超声后的溶液在 60 °C真空干燥后， 超声波旋振筛进行筛分， 保留筛上物即初级表面碳去除的金属粉 。 再将将粉末经 200°C真空保温 30min后， 直接置于液氮中保温 lOmin， 之后与酒 精混合， 外加超声处理 20 min， 最后将超声后的溶液在 60°C真空干燥后， 通过超 细粉分离超声波旋振筛进行筛分处理， 得到仅内部嵌入超细碳的铁粉。
[0154] 将仅内部嵌入超细碳的铁粉与酚醛树脂粉末按质量比 98: 2配料， 酚醛树脂粉 末粒度为 15（Vm， 在 V型混料机混合， 得到混合粉。 将所得混合粉在室温下进行 冷压， 压制压力为 550 MPa， 保压时间为 20 s， 制备的铁合金压坯在真空保护下 加压烧结， 在 1050 °C烧结 2 h， 压力为 0.3 MPa, 炉子的升温速率与降温速率均为 10~15 °C/min， 得到铁基复合材料， 致密 度为 99.5%， 抗拉强度为 860MPa。
[0155] 对比例 14
[0156] 本对比例 14其他条件与实施例 6相同， 区别在于球磨制备的超细碳嵌入钛粉直 接进行室温压制 -真空烧结， 其工艺与实施例 6相同， 而不进行超声处理和低温- 激冷处理。 制备的钛基复合材料的孔隙度高达 11%， 抗拉强度为 950MPa。
[0157] 对比例 15
[0158] 本对比例 15采用市售、 800°C脱胶处理 30min的短碳纤维和粒径为 50微米的钛合 金粉 （Ti-6wt%Al-2.8wt%Sn-3.5wt%Zr-0.75wt%Nb-0.35wt%Si） 为球磨原料 （钛 合金粉末和脱胶后短碳纤维的体积比为 5: 1） 。 短碳纤维的直径为 6pm， 长度 2 mm, 将两者加入到球磨设备中高能球磨， 转速为 250r/min， 球磨时间为 12h， 球 磨球为硬质合金球， 球径为 3mm~9mm （球磨球直径 3mm、 4mm、 5mm、 6mm、 7mm、 8mm、 9mm的质量比为 4:8: 11:20: 12:8:6:1） ， 脱胶短纤维与钛合金粉末的 质量之和与球磨球的质量比为 1:8。
[0159] 球磨完后， 将制备的内部和表面嵌入超细碳的钛合金粉与酒精混合， 外加超声 处理 120 min （超声频率为 28KHz） ， 维持溶液温度为室温， 再将超声后的溶液 在 60°C真空干燥后， 超声波旋振筛进行筛分， 保留筛上物即初级表面碳去除的金 属粉。 再将粉末经 400°C真空保温 30min后， 直接置于液氮中保温 lOmin， 之后与 酒精混合， 外加超声处理 20min， 最后将超声后的溶液在 60°C真空干燥后， 通过 超细粉分离超声波旋振筛进行筛分处理， 得到仅内部嵌入超细碳的钛合金粉。
[0160] 将仅内部残留超细碳的钛合金粉在室温下进行冷压， 压制压力为 400 MPa， 保 压时间为 20s， 制备的钛基复合材料压坯在真空下烧结， 在 1350 °C烧结 2 h， 炉子 的升温速率与降温速率均为 15°C/min， 得到钛基复合材料， 致密度为 98%， 抗拉 强度为 1240MPa。
[0161] 实施例 6
[0162] 本实施例 6采用市售、 800°C脱胶处理 30min的短碳纤维和粒径为 50pm的钛合金 粉 （Ti-6wt%Al-2.8wt%Sn-3.5wt%Zr-0.75wt%Nb-0.35wt%Si） 为球磨原料 （钛合 金粉末和脱胶后短碳纤维的体积比为 5: 1） 。 短碳纤维的直径为 6pm， 长度 2mm ， 将两者加入到球磨设备中高能球磨， 转速为 250r/min， 球磨时间为 12h， 球磨 球为硬质合金球， 球径为 3mm~9mm （球磨球直径 3mm、 4mm、 5mm、 6mm、 7 mm、 8mm、 9mm的质量比为 4:8: 11:20: 12:8:6:1） ， 脱胶短纤维与钛合金粉末的 质量之和与球磨球的质量比为 1:8。
[0163] 球磨完后， 将制备的内部和表面嵌入超细碳的钛合金粉与酒精混合， 外加超声 处理 120 min （超声频率为 28KHz） ， 维持溶液温度为室温， 再将超声后的溶液 在 60°C真空干燥后， 超声波旋振筛进行筛分， 保留筛上物即初级表面碳去除的金 属粉。 再将将粉末经 400°C真空保温 30min后， 直接置于液氮中保温 lOmin， 之后 与酒精混合， 外加超声处理 20min， 最后将超声后的溶液在 60°C真空干燥后， 通 过超细粉分离超声波旋振筛进行筛分处理， 得到仅内部嵌入超细碳的钛合金粉
[0164] 将仅内部嵌入超细碳的钛合金与酚醛树脂粉末按质量比 98: 2配料， 酚醛树脂 粉末粒度为 15（Vm， 在 V型混料机混合， 得到混合粉。 将所得混合粉在室温下进 行冷压， 压制压力为 400 MPa， 保压时间为 20s， 制备的钛基复合材料压坯在真 空下烧结， 在 1350 °C烧结 2 h， 炉子的升温速率与降温速率均为 15°C/min， 得到 钛基复合材料， 致密度为 98.8%， 抗拉强度为 1365MPa。
[0165] 实施例 7
[0166] 本实施例 7的将仅内部嵌入超细碳的铁粉的制备工艺以及混料、 压制工艺与实 施例 5相同， 区别在于烧结工艺不同。 烧结工艺为压坯在真空保护下加压烧结， 在 750 °C烧结 2 h， 再升温至 1100°C烧结 2
h, 炉子的升温速率与降温速率均为 10~15 °C/min， 压力为 0.5 MPa， 得到超细碳 化铁颗粒增强铁合金， 致密度为 99.2%， 抗拉强度为 865MPa。

Claims

权利要求书
[权利要求 1] 一种金属材料或金属复合材料的制备方法； 其特征在于： 所述制备方 法包括两套方案；
方案一为： 将原料混合均匀， 压制-烧结， 得到金属材料； 所述原料 包括金属粉体和酚醛树脂粉末；
方案二为： 将增强体和基体金属 A球磨得到表面和内部嵌有增强体的 金属粉末； 将嵌有增强体的金属粉末进行超声处理结合低温加热-激 冷工艺， 去除其表面的增强颗粒， 得到备用料； 将备用料与酚醛树脂 粉末混料后压制 -烧结， 或， 将备用料与酚醛树脂粉末、 颗粒相 B混料 后压制-烧结， 得到碳 /金属复合材料。
[权利要求 2] 如权利要求 1所述的一种金属材料或金属复合材料的制备方法； 其特 征在于： 方案一中， 所述酚醛树脂粉末的粒径小于等于 30(Vm; 所述 金属粉体和酚醛树脂粉末的质量比为 98-99.5 : 0.5-2。
[权利要求 3] 如权利要求 1一种金属材料或金属复合材料的制备方法， 其特征在于
: 所述增强体选自碳材料、 碳化物中的至少一种。
[权利要求 4] 如权利要求 3—种金属材料或金属复合材料的制备方法， 其特征在于
: 所述碳材料为零维、 一维、 二维、 三维碳材料中的至少一种； 优选 为颗粒石墨、 碳纤维、 碳纤维破碎后的碳颗粒的一种或多种按任意比 例混合。
[权利要求 5] 如权利要求 4所述的一种金属材料或金属复合材料的制备方法， 其特 征在于： 所述碳材料为脱胶后的短碳纤维； 所述脱胶后短碳纤维的制 备方法为： 在保护气氛下； 将短碳纤维束加热至 650~800°C保温处理 2 0~90min； 得到脱胶后的短碳纤维。
[权利要求 6] 如权利要求 4所述的一种金属材料或金属复合材料的制备方法， 其特 征在于： 所述碳材料为酚醛树脂包覆的碳材料。
[权利要求 7] 根据权利要求 1所述的一种金属材料或金属复合材料的制备方法， 其 特征在于： 所述基体金属 A的氧化物难用和 /或可用 H2、 CO中的一种 或多种还原性气氛还原； 优选地， 基体金属 A选自所述的所述基体金 属 A为铝、 钛、 锆、 铜、 铁、 镍、 铬、 锰、 银中的至少一种； 进一步 优选为铜、 铝、 钛、 镍中的至少一种。
[权利要求 8] 根据权利要求 1所述的一种金属材料或金属复合材料的制备方法， 其 特征在于：
所述超声的过程包括如下步骤：
1） 将嵌有增强体的金属粉末加入酒精中获得混合液， 超声处理 5 min
~60
min, 将混合液真空干燥， 获得干燥粉体 M， 将干燥粉体 M过 400~600 目筛， 获得筛上物 C， 所述筛上物 C为初级表面增增强体去除的金属 粉；
2） 将步骤 1所得筛上物 C在真空条件下于 150~300°C热处理 30min~60m in后， 再置于液氮中保温处理 5~10min， 将处理后的筛上物 C加入酒精 中获得浆液， 超声处理 10 min ~30 min， 将浆液真空干燥后， 获得干 燥粉体 N， 将干燥粉体 N过 400~600目筛， 获得筛上物 D， 所得筛上物 D为仅内部镶嵌有增强体的金属粉末。
[权利要求 9] 如权利要求 1所述的一种金属材料或金属复合材料的制备方法， 其特 征在于： 所述颗粒相 B为铁、 铬、 钨、 碳化硅、 颗粒状石墨、 鳞片状 石墨、 铁铬合金、 氧化铝、 碳化硅、 碳化钛、 硬质陶瓷、 碳化钨中的 一种或多种按任意比例混合。
[权利要求 10] 如权利要求 1~9任一项所述的一种金属材料或金属复合材料的制备方 法， 其特征在于： 备用料与酚醛树脂粉末的质量比为 20~99: 0.5-2=
[权利要求 11] 如权利要求 1~9任一项所述的一种金属材料或金属复合材料的制备方 法， 其特征在于： 当原料中含有颗粒相 B时； 备用料、 酚醛树脂粉末 与颗粒相 B的质量比为 20~99.5: 0.5-2： 0.5~78。
[权利要求 12] 如权利要求 1~9任一项所述所述的一种金属材料或金属复合材料的制 备方法， 其特征在于：
将混料后的混合料冷压成型后得到压坯， 再在保护气氛或真空或保护 气氛加压条件下烧结， 得到碳 /金属复合材料； 或将混合粉直接热压 得到碳 /金属复合材料；
冷压成型过程的压制压力为 200~600MPa， 保压时间为 20~30 s; 压坯 烧结过程的温度为基体金属熔点的 60%~80% , 保温时间为 0.5~3 h， 压力为 0~1 MPa；
热压过程的单位压力为 200~600MPa， 温度为基体金属熔点的 60%~80% , 保温保压时间为 2 ~ 90 min。
[权利要求 13] 如权利要求 1-9任意一项所述的一种金属材料或金属复合材料的制备 方法， 其特征在于： 所得碳 /金属复合材料的致密度大于等于 99%。
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