WO2016124073A1 - Procédé pour la préparation de poudre métallique composite sphérique micrométrique et nanométrique ayant une structure cœur-écorce - Google Patents

Procédé pour la préparation de poudre métallique composite sphérique micrométrique et nanométrique ayant une structure cœur-écorce Download PDF

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WO2016124073A1
WO2016124073A1 PCT/CN2016/071175 CN2016071175W WO2016124073A1 WO 2016124073 A1 WO2016124073 A1 WO 2016124073A1 CN 2016071175 W CN2016071175 W CN 2016071175W WO 2016124073 A1 WO2016124073 A1 WO 2016124073A1
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powder
composite metal
metal
core
copper
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PCT/CN2016/071175
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Chinese (zh)
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唐少龙
黄海富
雷成龙
程振之
都有为
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南京大学
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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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites

Definitions

  • the invention relates to a wide range of applications suitable for use in the fields of powder metallurgy, conductive paste, cemented carbide, magnetic materials, sensing, optics, catalysis, and the like.
  • Core-shell structured metal particles are composite particles composed of two or more metals of different nature, generally consisting of a central core body and a shell layer coated on the outside. Compared with a single metal particle, the core-shell structure metal particle has unique structural characteristics. It integrates the properties of the inner and outer materials and complements each other's deficiencies. It is an important research direction of the shape determining properties in recent years. Since the structure and composition of core-shell composite particles can be designed and tailored, it has many unique physical and chemical properties such as light, electricity, magnetism, force, and catalysis, which are different from single-component particles, and is important for constructing new functional materials. Component. Core-shell composite particles can be prepared by chemical or physical methods.
  • Both methods can synthesize bimetallic nanoparticles with core-shell structure.
  • Chemical preparation of metal core-shell structures is generally carried out in liquids. Liquid phase chemical reduction is a complex reaction system involving many factors (temperature, pH, solvent, metal precursor, reducing agent, complexing agent/protective agent). Types and impurity ions, etc., any change in factors affect the product to a certain extent, such as the average size, morphology, dispersion of the particles, etc., large-scale production control is difficult; in addition, the inherent properties of the metal itself will affect the metal core Shell structure composite particle formation (especially microstructure), for example, the relative height of the two metal electrode potentials, the relative relationship of the two metals in the phase diagram, and so on.
  • pre-nucleation and post-coating shells corresponding to the above synthetic strategy (eg, high-low temperature disperse core-shell particles created by solid-state reactions; Nature Materials, 10, 710 (2011) )) and one-time formation of core-shell structure (eg, atomization method, Farmation of Immiscible Alloy poders with egg-type microstructure, Science) 297,990 (2002)).
  • the high-low temperature two-step heat treatment solid state reaction method is to form a core by high-temperature heat treatment, and a shell is grown on the core precipitated at a high temperature during low-temperature heat treatment. This core-shell structure particle is distributed in the metal matrix.
  • Patent No. 201210395540.5 provides a method for preparing a core-shell composite particle powder of a silver-based copper-nickel-based alloy by an atomization method, the step of which is to place copper, nickel, and silver metals into a vacuum induction furnace.
  • Patent No. 200810070976.0 provides a method for preparing a copper-based alloy-coated stainless steel core-shell composite particle powder by an atomization method, the step of which is to melt copper, iron and chromium into a vacuum induction furnace.
  • the device is melted; the molten alloy liquid is poured into the liquid receiving hopper, and the inert gas is sprayed at the moment when the liquid flows into the atomizing chamber, and after cooling, a copper/stainless steel composite spherical powder having a core-shell structure can be obtained.
  • the core-shell composite metal prepared by the above patents 1) There are specific restrictions on the series of composite metal materials, and it is required that the composite metal is dissolved at a high temperature in the liquid phase, and the phase separation in the cooling process is two incompatible.
  • Patent application No. CN201410462791.X discloses a method for producing a micron and nano metal spherical powder, and proposes to prepare micron and nano metal spheres by a method of metal droplet/carbon material or ceramic material interface (ie, liquid/solid interface).
  • the principle is to use a carbon material powder or a ceramic material powder to sufficiently separate the metal particles to provide a fluffy dispersion environment, using metal droplets to be non-wetting or low-wetting, non-diffusion or less diffusion at the carbon material or at the solid interface of the ceramic material.
  • the properties of the droplets at the liquid-solid interface and the surface tension of the droplets at the liquid-gas interface simultaneously form spherical metal droplets, and after cooling, micro- and nano-metal spheres are obtained.
  • This method allows us to effectively control the holding time and cooling rate of the droplet alloy.
  • a high-quality core-shell metal composite spherical powder can be prepared.
  • the powder is either separated by a ceramic material powder.
  • a composite metal precursor Or a certain temperature of the melting point of more than one metal to form a metal droplet / carbon material or ceramic material interface (ie: liquid / solid interface), using metal droplets in the carbon material or at the solid interface of the ceramic material does not wet or Low wetting, non-diffusion or low diffusion property, the spherical metal droplets are formed under the action of the interfacial tension of the droplets at the solid-liquid interface and the surface tension of the liquid; at the same time, the liquid phase is incompatible after being melted by the composite metal precursor.
  • the molten metal and the unmelted solid matter are not solid solution and low solid solution, and the layered coating is realized under the simultaneous action of the surface energy and the interface energy of the two phases.
  • the core-shell micro- and nano-composite metal spheres are obtained during the process.
  • the technical scheme of the present invention is: a method for manufacturing a core-shell micro- and nano-composite metal spherical powder, comprising the following steps: (1) preparing a powder precursor of a composite metal (here, the metal is referred to as an elemental metal, an alloy or an intermetallic compound) (2) prepared composite metal powder precursor and carbon material powder or uniformly mixed powder with ceramic material powder; (3) high temperature heat treatment causes more than one metal in the composite metal precursor to melt, solidified to form core-shell structure composite a metal ball; a high temperature heat treatment temperature of at least a melting temperature of a metal in the composite metal precursor, especially a temperature in the range of 40 ° C to 100 ° C above the melting point of the metal; (4) removal of carbon material powder or ceramic material The powder obtained a spherical shell-shell micron and nanocomposite metal spherical powder.
  • a composite metal having a core-shell structured spherical powder includes: 1) a metal having two or more incompatible phase phases in a liquid temperature range, including: iron (or iron-based alloy) / copper (or copper-based alloy) , iron (or iron-based alloy) / silver (or silver-based alloy), cobalt (or cobalt-based alloy) / silver (or silver-based alloy), nickel (or nickel-based alloy) / silver (or silver-based alloy), tungsten (or tungsten-based alloy) / copper (or copper-based alloy), tungsten (or tungsten-based alloy) / silver (or silver-based alloy), tungsten carbide / copper (or copper-based alloy), tungsten carbide / silver (or silver base) Alloy), iron (or iron-based alloy) / niobium (or niobium-based alloy), cobalt (or cobalt-based alloy) / niobium (or niobium-based alloy), etc.; 2) two
  • the preparation of the composite metal powder precursor material comprises: 1) mixing two or more metal powders to obtain a uniform composite powder; 2) obtaining a composite metal by smelting, breaking into a composite metal powder, and 3) rapidly quenching After the strip is broken into composite metal powder; 4) composite alloy powder obtained by mechanical alloying; 5) by mixing different metal oxides or metal salts to obtain a uniform composite oxide or metal salt, and obtaining uniformity after reduction Composite metal powder; 6) composite metal powder coated by electrochemical reaction or other methods; 7) composite metal powder obtained by other methods.
  • the composite metal powder precursor has a size of less than 10 mm, preferably a size ranging from 50 nm to 1 mm.
  • the carbon material powder is graphite, graphene, diamond, carbon powder or coal powder and a mixture of two or more kinds thereof;
  • the ceramic material powder is a carbide ceramic, a boride ceramic, an oxide ceramic or a nitride ceramic, and both of them Or a mixture of two or more.
  • the method for preparing the composite metal powder precursor and the carbon material powder or the ceramic powder uniformly mixed powder is one of the following, i) uniformly mixing by mechanical means; ii) stirring uniformly in a liquid (such as water, ethanol, etc.); Iii) After being dispersed by the dispersant, it is mixed with the carbon material powder or the ceramic material powder, mixed and dried to obtain a uniform mixed powder of the composite metal powder precursor coated with the carbon material or the ceramic material.
  • Two or more metal oxide or metal salt precursors are mixed with a carbon material powder or a ceramic material powder in the above manner, and heat-treated in a reducing atmosphere (such as hydrogen, ammonia, carbon monoxide, or a mixed gas thereof) A uniform mixed powder of the composite metal powder precursor with the carbon material powder or with the ceramic material powder is obtained.
  • a reducing atmosphere such as hydrogen, ammonia, carbon monoxide, or a mixed gas thereof
  • the mass ratio of the composite metal powder precursor to the carbon material powder or the ceramic material powder should satisfy the total surface area of the weighed composite metal powder precursor Less than the total surface area of the proportioned carbon material powder or ceramic material powder; the carbon material powder or ceramic material powder may be any size, and the range of 10 nm to 100 ⁇ m particle diameter is better; carbon material powder or ceramic material
  • the morphology of the powder can be in the form of flakes, spheres, wires, tubes or other shapes.
  • the melting temperature of the metal preferably 40 to 100 ° C above the melting point of the metal; holding time: to ensure complete melting of the metal, preferably 4 to 10 minutes, short-term insulation against metal droplets and carbon or ceramic materials Interdiffusion to ensure non-wetting or low wetting of metal droplets at the interface of carbon or ceramic materials; cooling method: 1) rapid cooling, allowing composite metal particles to maintain the shape of liquid metal spheres, while overcoming alloys Macroscopic segregation of material composition and reduction of diffusion of carbon material or ceramic material to metal particles at high temperature; 2) rapid cooling combined with slow cooling, rapid cooling to a temperature below the melting point, and then slowly cooling to obtain a core-shell structure with a good crystallinity Nano composite metal ball.
  • a vacuum or atmosphere including hydrogen, nitrogen, argon, ammonia, etc.
  • Carbon material powder or ceramic in a composite metal/carbon material or ceramic material mixed powder treated by high temperature heat treatment Porcelain material powder separation, obtaining core-shell micro- and nano-composite metal spherical powder; separation methods include: 1) after immersion in liquid (such as water or organic solvent, etc.), using composite metal and carbon material or ceramic material Density difference, ultrasonic cleaning, removal of carbon material powder or ceramic material powder, obtaining core-shell composite metal spherical powder; 2) after immersion in liquid, using centrifugal, filtration or external magnetic field method to obtain core-shell composite metal spherical powder 3) Using the core-shell structure
  • the composite metal particles are different from the carbon material or the shape and size of the ceramic material, and the two are separated by a suitable sieve.
  • the core-shell composite metal spherical powder has a diameter of less than 10 mm.
  • Preferred metal spherical powders have a diameter in the range of 50 nm to 1 mm.
  • the prepared core-shell structured micron and nanocomposite metal spherical powder particles include a core and an outer shell.
  • the core is the metal with the largest liquid surface energy at the heat treatment temperature
  • the outer shell is the metal with the smallest liquid surface energy at the heat treatment temperature
  • the liquid for the high temperature heat treatment Solid-phase coexisting composite metal:
  • the inner core is a solid phase metal at the heat treatment temperature
  • the outer shell is the metal having the smallest surface energy in the liquid phase at the heat treatment temperature.
  • the invention has the beneficial effects that the composite metal powder precursor is separated by the carbon material powder or by the ceramic material powder, and the metal droplets are not wetted or low-wet, non-diffused or less diffused at the carbon material or at the solid interface of the ceramic material.
  • the nature of the liquid-solid interface droplets at the liquid-solid interface and the surface tension of the droplets at the liquid-gas interface simultaneously form spherical metal droplets.
  • the liquid phase is incompatible by melting with the composite metal, or a part of the metal is melted by the composite metal.
  • the liquid-solid phase coexists, the liquid phase and the solid phase are mutually insoluble or low-miscible, and the layered coating is realized by the interaction of the surface energy and the liquid-solid two-phase interface energy, and the micro-shell of the core-shell structure is obtained after cooling.
  • Nano composite metal ball According to the invention, the principle of preparing the core-shell composite metal sphere is clear, the method for manufacturing the core-shell composite metal spherical powder is simple, the manufacturing cost is low, the production efficiency is high, and the method is simple, environmentally friendly, and can be mass-produced. A method for producing a core-shell micron and nano composite metal spherical powder.
  • the core-shell composite metal spheres produced have a diameter of less than 10 mm, preferably a sphere diameter of 50 nm to 1 mm (especially a range of 2-200 micron particle diameters).
  • the core-shell composite metal sphere has high sphericity and good surface quality, and can be widely used in powder metallurgy, conductive paste, cemented carbide, magnetic materials, sensing, optics, and catalysis.
  • Figure 1 is a scanning electron micrograph of a core-shell structure Fe/Cu microsphere powder obtained by using the copper ferrite reduced iron/copper composite powder as a precursor by the manufacturing method of the present invention
  • Figure 2 is a core shell obtained by using a copper ferrite reduced iron/copper composite powder as a precursor by the manufacturing method of the present invention.
  • Figure 3 is a scanning electron micrograph of a core-shell structure Fe/Cu microsphere powder obtained by using the copper/iron hydroxide co-reduced iron/copper composite powder as a precursor by the production method of the present invention
  • Figure 4 is a cross-sectional metallographic view of a core-shell structured Fe/Cu microsphere powder obtained by using the iron/copper composite powder in which copper hydroxide and ferric hydroxide are co-reduced as a precursor by the production method of the present invention
  • Figure 5 is a scanning electron micrograph of a core-shell structured Fe/Ag microsphere powder obtained by the manufacturing method of the present invention.
  • Figure 6 is a backscattered scanning electron micrograph of a core-shell structured Fe/Ag microsphere powder obtained by the manufacturing method of the present invention.
  • Figure 7 is a scanning electron micrograph of a core-shell structure Cu-rich alloy/Ag-rich microsphere powder obtained by using the copper/silver composite powder of micron electrolytic copper powder and nano silver powder as a precursor by the manufacturing method of the present invention
  • Fig. 8 is a core-shell structure Cu-rich alloy/Ag-rich microsphere powder obtained by using the copper/silver composite powder of micron electrolytic copper powder and nano silver powder as a precursor by the manufacturing method of the present invention (the columns a and b respectively correspond to different types) Electronic image of the ratio of Cu-rich alloy/Ag-rich and cross-sectional energy spectrum;
  • Figure 9 is a diagram showing the distribution of copper and silver elements in the core-shell structure Cu-rich alloy/Ag-rich microsphere powder obtained by using the copper/silver composite powder mixed with micron electrolytic copper powder and nano silver powder as the precursor by the manufacturing method of the present invention. ;
  • Figure 10 is a scanning electron micrograph of a core-shell structure Cu-rich alloy/Ag-rich microsphere powder obtained by using the copper/silver composite powder reduced by copper acetate and silver acetate as a precursor by the production method of the present invention
  • Fig. 11 is a scanning electron micrograph of a core-shell structure CuNi-rich alloy/Ag-rich microsphere powder obtained by using the copper/nickel/silver composite powder reduced by copper acetate, nickel acetate and silver acetate as a precursor by the production method of the present invention.
  • the present application separates the composite metal powder precursor from the carbon material powder or the ceramic material powder, and utilizes the metal droplets to be non-wetting or low-wetting, non-diffusion or less diffusion at the carbon material or at the solid interface of the ceramic material.
  • the nature of the liquid-solid interface droplets at the liquid-solid interface and the surface tension of the droplets at the liquid-gas interface simultaneously form spherical metal droplets; at the same time, the liquid phase is incompatible by melting with the composite metal, or is melted by partial metal in the composite metal.
  • the liquid-solid phase coexists, the liquid phase and the solid phase are mutually insoluble or miscible, and the layered coating is realized by the interaction of the surface energy and the liquid-solid two-phase interface energy, and the core-shell structure micron and nanometer are obtained after cooling.
  • Composite metal ball Hereinafter, a method for producing the core-shell micro- and nano-composite metal spherical powder of the present invention will be described in detail.
  • the present invention first prepares a composite metal powder precursor of the desired size.
  • Preparation of composite metal powder precursor 1) two or more metal powders are mixed to obtain a uniform composite powder; 2) obtained by smelting Metal, broken into composite metal powder, 3) metal with good toughness can be quickly quenched into strips and then broken into composite metal powder; 4) by mixing different metal oxides or metal salts to obtain a uniform composite oxide or metal The salt, after reduction, obtains a uniform composite metal powder; 5) a composite metal powder coated by an electrochemical reaction or other methods; 6)
  • the composite metal powder of a desired size can also be obtained by other means.
  • the composite metal powder precursor is uniformly mixed with a suitable size and amount of carbon material powder or ceramic material powder to achieve the purpose of separating the composite metal powder precursor with the carbon material powder or with the ceramic material powder.
  • the method for preparing a composite metal powder precursor and a carbon material powder or a ceramic powder uniformly mixed powder is as follows: 1) a method of mixing a composite metal powder precursor with a carbon material powder or a ceramic material powder, i) adopting a mechanical method uniformity Mixing; ii) mixing uniformly in a liquid (water, ethanol, etc.); iii) assisting dispersion by a dispersing agent, mixing with a carbon material powder or a ceramic material powder, mixing and drying to obtain a carbon material or a ceramic material.
  • a uniform mixed powder of metal particles 1) mixing the metal oxide or metal salt with the carbon material powder or the ceramic material powder in the above manner, in a reducing atmosphere (such as hydrogen, ammonia, carbon monoxide, a mixed gas thereof, etc.) Annealing to obtain a uniformly mixed powder of the composite metal powder precursor and the carbon material powder or the ceramic material powder.
  • a reducing atmosphere such as hydrogen, ammonia, carbon monoxide, a mixed gas thereof, etc.
  • the uniformly mixed composite metal powder precursor/carbon material or ceramic material mixed powder in a vacuum or atmosphere (including hydrogen, ammonia, nitrogen, argon, and a mixed gas thereof, etc.) at a temperature of at least the composite metal
  • the melting temperature of a metal in the precursor preferably at a temperature higher than 40-100 ° C of the melting point of the metal; holding time: ensuring that one or more metals are completely melted, preferably for a period of 4 min to 10 min.
  • Short-time insulation can reduce the interdiffusion between metal droplets and carbon materials or ceramic materials, and ensure the non-wetting or low wettability of metal droplets at the interface of carbon materials or ceramic materials; cooling method: 1) fast cooling, The composite metal particles are maintained in the shape of a liquid metal sphere, and at the same time, the macrosegregation of the alloy material composition can be overcome and the diffusion of the carbon material or the ceramic material to the metal particles at a high temperature can be reduced. 2) Quick cooling combined with slow cooling, cooling to the melting point and then slowly cooling, can obtain composite micron and nano metal spheres with good crystallinity.
  • the carbon material powder or the ceramic material powder in the heat-treated composite metal powder precursor/carbon material or ceramic material mixed powder is removed to obtain a core-shell structured micro- and nano-composite metal spherical powder.
  • the cleaning method includes: 1) after immersing in a liquid (such as water or an organic solvent), using a core-shell composite metal and a carbon material or a ceramic material having a large difference in density, ultrasonic cleaning, removing carbon material powder or ceramic material Powder, obtaining a core-shell composite metal spherical powder; 2) obtaining a core-shell composite metal spherical powder by centrifugation, filtration or external magnetic field after immersion in a liquid; 3) using a core-shell structure composite metal particle and carbon material or Different from the shape and size of the ceramic material, the two are separated by a suitable sieve.
  • the method for producing a core-shell structured composite metal spherical powder of the present invention is most suitable for a metal spherical powder having a diameter of 50 nm to 1 mm.
  • the diameter is larger than 1 mm, since the spheroidized droplets are melted, the sphericity is deteriorated due to their own gravity, and it is difficult to obtain a composite metal sphere having a high sphericity during the cooling process. Therefore, the composite metal spherical powder The diameter is preferably 1 mm or less.
  • the diameter of the composite metal spherical powder is preferably 50 nm or more.
  • the mixed powder of the mixed copper ferrite powder/graphite powder is placed in an alumina crucible, placed in a heating zone of the annealing furnace, evacuated to 6 ⁇ 10 -3 Pa, and pressurized with 0.01 Mpa of hydrogen and 0.03 Mpa.
  • Argon gas was heated to 800 ° C for reduction, and after 60 minutes of heat retention, an iron/copper uniform composite powder precursor was obtained. Thereafter, the vacuum was evacuated to 5.4 Pa, and argon gas of 0.02 MPa was introduced, and the heating zone of the annealing furnace was heated to 1100 ° C (higher than the melting point of copper). After the heat retention for 10 minutes, the crucible was pulled out of the heating zone to be cooled.
  • Fig. 1 is a scanning electron micrograph of the appearance of the obtained core-shell composite metal sphere.
  • Fig. 2 is a metallographic view of the obtained core-shell composite metal sphere. According to the method for producing a core-shell composite metal spherical powder of the present invention, it was confirmed that a core-shell composite metal microsphere having a copper-coated iron can be obtained.
  • the mixed powder of the above-mentioned mixed iron hydroxide, copper hydroxide and graphite was placed in an alumina crucible and operated in the same manner as in Example 1.
  • the micro-spherical powder scanning electron microscope prepared by the obtained copper-clad iron core-shell structure is shown in FIG. 3, and the cross-sectional metallographic figure is shown in FIG. 4, and it is confirmed that the copper-coated iron core-shell composite metal microspheres can be obtained.
  • the mixed powder of the above-mentioned mixed iron hydroxide and silver oxide powder/graphite powder was placed in an alumina crucible. Put the crucible into the heating zone of the annealing furnace, evacuate to 6 ⁇ 10 -3 Pa, pass 0.01Mpa of hydrogen and 0.03Mpa of argon, heat to 800 °C for reduction, and keep warm for 60 minutes to obtain iron/silver uniform. Composite powder precursor. Thereafter, the vacuum was evacuated to 5.4 Pa, and argon gas of 0.02 MPa was introduced, and the heating zone of the annealing furnace was heated to 1050 ° C (higher than the melting point of silver). After the heat preservation for 10 minutes, the crucible was pulled out of the heating zone to be cooled.
  • Fig. 5 and Fig. 6 are scanning electron micrographs and backscattered electron images of the obtained composite metal powder, and it can be seen from the backscattered electron image that the metallic silver is coated on the surface of the metallic iron. Its section metallographic diagram is similar to Figure 2. According to the method for producing a core-shell composite metal spherical powder of the present invention, it was confirmed that a silver-coated iron core-shell composite metal microsphere can be obtained.
  • nano silver powder and micron copper powder as raw materials, silver powder of about 100 nanometers and electrolytic copper powder of about 5 micrometers were weighed at a weight ratio of 1:4. After ultrasonic dispersion in a small amount of anhydrous alcohol for 30 minutes, the alcohol was evaporated to dryness with stirring to obtain a copper/silver composite powder precursor.
  • the copper/silver composite powder precursor and the graphite powder having a size of about 400 nm were mechanically stirred and uniformly mixed again at a mass ratio of 1:1.
  • the mixed powder of the above-mentioned mixed silver-copper powder/graphite powder was placed in an alumina crucible and placed in a non-heating zone of the annealing furnace. After evacuating to 6 ⁇ 10 -3 Pa, argon gas of 0.02 MPa is introduced, the heating zone of the annealing furnace is heated to 1050 ° C, and the crucible containing the silver-copper mixed powder/graphite mixed powder is pushed to 1050 ° C (higher than silver). The melting point of the heating zone, after 10 minutes of incubation, the crucible is pulled out of the heating zone to cool.
  • FIG. 7 is a scanning electron micrograph of the obtained core-shell composite metal sphere, and the copper and silver elements of the cross section were obtained. As shown in Fig. 8 and Fig. 9, it was confirmed that a core-shell composite metal microsphere in which a silver-rich alloy was coated with a copper-rich alloy was obtained.
  • Silver acetate and copper acetate were dissolved in hot water and stirring was continued.
  • An excessive amount of potassium hydroxide solution was gradually added dropwise during the stirring to form a copper and silver precipitated powder.
  • the precipitate was filtered and washed with a large amount of deionized water to remove other ions and impurities and dried.
  • the dried copper hydroxide and silver oxide were precipitated and ground to form a fine powder, and uniformly mixed with 400 nm of graphite powder.
  • the mixed powder of the above mixed copper hydroxide and silver oxide powder/graphite powder is placed in an alumina crucible, placed in a heating zone of the annealing furnace, evacuated to 6 ⁇ 10 -3 Pa, and 0.01 Mpa of hydrogen and 0.03 Mpa are introduced.
  • the argon gas was heated to 600 ° C for reduction, and after 60 minutes of heat retention, a copper/silver uniform composite powder precursor was obtained. Thereafter, the vacuum was evacuated to 5.4 Pa, and argon gas of 0.02 MPa was introduced, and the heating zone of the annealing furnace was heated to 1030 ° C (higher than the melting point of silver). After the heat retention for 10 minutes, the crucible was pulled out of the heating zone to be cooled.
  • the mixed powder was soaked with alcohol and washed by ultrasonication to obtain a micro-spherical powder of a silver-coated copper core-shell structure.
  • the color is silvery white
  • Fig. 10 is a scanning electron micrograph of the appearance of the obtained composite metal sphere.
  • the copper and silver elements of the cross section are similar to those of Figs. 8 and 9. According to the method for producing a core-shell composite metal spherical powder of the present invention, it was confirmed that a silver-rich copper-rich core-shell composite microsphere can be obtained.
  • the mixed powder of the above mixed silver oxide, copper hydroxide, nickel hydroxide and graphite powder is placed in an alumina crucible, placed in a heating zone of the annealing furnace, evacuated to 6 ⁇ 10 -3 Pa, and passed through 0.01 Mpa. Hydrogen and 0.03 MPa of argon were heated to 600 ° C for reduction, and after 60 minutes of incubation, a copper/nickel/silver uniform composite powder precursor was obtained. Thereafter, the vacuum was evacuated to 5.4 Pa, and argon gas of 0.02 MPa was introduced, and the heating zone of the annealing furnace was heated to 1050 ° C (higher than the melting point of silver). After the heat preservation for 10 minutes, the crucible was pulled out of the heating zone to be cooled.
  • the mixed powder is soaked with alcohol and washed by ultrasonication to obtain a micro-spherical powder of a silver-rich alloy-coated copper-nickel alloy core-shell structure.
  • the color is silvery white
  • FIG. 11 is a scanning electron micrograph of the appearance of the obtained composite metal ball, and the cross-sectional structure is similar to FIG. 2 and FIG.
  • According to the method for producing a core-shell composite metal spherical powder of the present invention it was confirmed that a core-shell composite metal microsphere having a silver-rich alloy-enriched copper-nickel alloy can be obtained.

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Abstract

L'invention concerne un procédé pour la préparation de poudre métallique composite sphérique micrométrique et nanométrique ayant une structure cœur-écorce, ledit procédé comprenant les étapes suivantes : (1) la préparation d'un précurseur de poudre métallique composite; (2) la préparation de la poudre uniformément mélangée avec le précurseur de poudre métallique composite et de la poudre de matière carbonée ou de la poudre de matériau céramique; (3) la fusion de l'un des métaux dans le précurseur métallique composite par l'intermédiaire d'un traitement thermique à haute température et la formation d'une bille métallique composite ayant la structure cœur-écorce après solidification; (4) l'élimination de la poudre de matière carbonée ou de la poudre de matériau céramique pour obtenir la poudre métallique composite sphérique micrométrique et nanométrique ayant la structure cœur-écorce.
PCT/CN2016/071175 2015-02-06 2016-01-18 Procédé pour la préparation de poudre métallique composite sphérique micrométrique et nanométrique ayant une structure cœur-écorce WO2016124073A1 (fr)

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CN201510064436.1A CN104625046B (zh) 2015-02-06 2015-02-06 核壳结构微米和纳米复合金属球形粉末的制造方法
CN201510064436.1 2015-02-06

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Cited By (2)

* Cited by examiner, † Cited by third party
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CN113509939A (zh) * 2021-07-05 2021-10-19 华中科技大学 一种氧化铈包裹微米铜粉及其制备方法和应用
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