WO2021208232A1 - Nano silver-copper alloy material and preparation method therefor - Google Patents

Nano silver-copper alloy material and preparation method therefor Download PDF

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Publication number
WO2021208232A1
WO2021208232A1 PCT/CN2020/097269 CN2020097269W WO2021208232A1 WO 2021208232 A1 WO2021208232 A1 WO 2021208232A1 CN 2020097269 W CN2020097269 W CN 2020097269W WO 2021208232 A1 WO2021208232 A1 WO 2021208232A1
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silver
copper
nano
alloy material
metal wire
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PCT/CN2020/097269
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French (fr)
Chinese (zh)
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曹文
吴银隆
陈鑫宏
杨柳
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深圳市捷安纳米复合材料有限公司
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Publication of WO2021208232A1 publication Critical patent/WO2021208232A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/12—Making metallic powder or suspensions thereof using physical processes starting from gaseous material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D39/00—Filtering material for liquid or gaseous fluids
    • B01D39/14—Other self-supporting filtering material ; Other filtering material
    • 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
    • B22F9/14—Making metallic powder or suspensions thereof using physical processes using electric discharge
    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C5/00—Alloys based on noble metals
    • C22C5/06—Alloys based on silver
    • C22C5/08—Alloys based on silver with copper as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
    • D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
    • D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning

Definitions

  • the invention relates to the technical field of new materials, in particular to a nano-silver-copper alloy material and a preparation method thereof.
  • Silver has been recognized as a safe and reliable sterilization material.
  • the bactericidal effect of nano-silver is even more difficult to replace with other inorganic materials.
  • the patent with the application number CN201710834160.X discloses that the present invention provides a method for preparing a silver alloy composite nanomaterial, which includes the following steps: combining silver with at least one of copper, zinc, magnesium, aluminum, and titanium. Obtain the composite metal wire rod; the composite metal wire rod is used as the anode conductor of the DC power supply, and the arc formed with the cathode makes the tip of the anode conductor metal wire rod vaporize and evaporate to produce smoke-like metal atom clusters, silver metal atoms, copper and zinc At least one of the metal atoms of magnesium, aluminum, and titanium is fully mixed to form a gaseous alloy; while the metal is vaporized, the gaseous alloy is rapidly cooled with an air flow of 0.5 to 1.5 times the speed of sound; the cooled powder is collected, The silver alloy composite nano material is obtained; but there are still the following shortcomings: (1) The preparation method of the silver alloy composite nano material uses supersonic cooling air to cool the gas metal, and the obtained composite nano material is silver metal and
  • the purpose of the present invention is to provide a nano-silver-copper alloy material and a preparation method thereof: (1) After cooling the gaseous alloy by a supersonic inert gas flow, the obtained nano-silver metal and nano- When the copper metal alloy material is cooled at room temperature, only the copper metal atoms exposed on the outer surface will be oxidized, while the copper metal atoms inside are not oxidized. The silver metal atoms are not easily oxidized at room temperature. It is easy to oxidize at high temperature, so the silver metal atoms are not oxidized, which solves the problem that the existing silver alloy composite nanomaterials are composited by silver metal and other metal oxides.
  • the alloy particles are carried into the filter layer by inert gas flow for gas-solid separation and collection, and the nano-silver-copper alloy material is obtained.
  • the filter layer is made of ultra-fine fibers. The membrane allows the inert gas flow to carry alloy particles into the filter layer. The inert gas flow passes through the filter holes and passes through the filter layer, while the alloy particles are retained by the filter layer. The separation effect of the nanoparticles is not very good, and the nanoparticles will be discharged with the gas, resulting in waste of resources and high cost.
  • a nano-silver-copper alloy material is composed of the following weight percentage components:
  • the rest is copper
  • the alloy material is composed of a mixture of nano silver-copper alloy particles with a particle size of 15 nm-50 nm, and the copper metal atoms on the outer surface of the alloy material are formed as copper oxide.
  • the particle size of the nano-silver-copper alloy particles is 15nm-30nm.
  • the method for preparing the nano-silver-copper alloy material includes the following steps:
  • Step S1 combining silver and copper to prepare a composite metal wire rod
  • Step S2 the composite metal wire rod is used as the anode conductor of the DC power supply, and the arc formed with the cathode causes the tip of the anode conductor metal wire rod to vaporize and evaporate, producing a smoke-like metal atom group, and the silver metal atom and the copper metal atom are fully mixed, Forming a gaseous alloy; wherein the temperature of the arc formed by the anode conductor and the cathode is above 5000°C;
  • Step S3 while the metal is vaporized, the gaseous alloy is cooled with an inert gas flow of 1 to 1.4 times the speed of sound;
  • Step S4 collecting the powder after cooling at normal temperature to obtain the nano-silver-copper alloy material.
  • the step S3 also includes: mixing the cooled alloy and the inert gas stream with air, enter the powder collection device through a pipe, and perform gas-solid separation.
  • the inert gas flow is a helium flow.
  • a nano-silver-copper alloy material is prepared by the following steps:
  • Step 1 Preparation of metal wire rod: silver metal wire and copper metal wire are braided into a mixed metal wire with a diameter of 6mm-8mm, and then cold-rolled and rolled into a composite metal wire rod with a diameter of 5mm;
  • Step 2 Vaporization: Use the composite metal wire rod as the anode conductor, and form an arc with the cathode under the conditions of a DC voltage of 36 volts and a current of 1050 amperes, so that the tip of the anode conductor's metal rod is vaporized and vaporized to produce a smoke-like metal Atomic group, the silver metal atom and copper atom are fully mixed to form a gaseous alloy;
  • Step 3 Condensation: With the vaporization of the metal, the gaseous alloy is separated from the high-temperature area with an inert gas flow of 1 to 1.4 times the speed of sound, and the gaseous alloy is rapidly cooled, so that when the metal returns from the gaseous state to the solid state, alloy particles of 15nm-50nm are formed;
  • Step 4 Collection: the inert gas flow carries the alloy particles into the filter layer for gas-solid separation and collection to obtain the nano-silver-copper alloy material.
  • the filter material in the filter layer is a copolymer of polytetrafluoroethylene and propylene, or a copolymer of vinyl fluoride and propylene.
  • the gas-solid separation of the alloy particles is achieved by the electrostatic adsorption of the filter layer to form a soft agglomeration effect, and the method for obtaining the electrostatic adsorption capacity of the filter layer is to charge the filter layer with an electrode.
  • the purity of the silver metal wire and the copper metal wire are both 99.9%, and the diameter of the silver metal wire and the copper metal wire are both 0.4 mm to 0.8 mm.
  • the temperature of the arc is above 5000° C., and the length of the arc is 30 mm.
  • a method for preparing a nano-silver-copper alloy material includes the following steps:
  • Step T1 Dissolve the polymer in the mixed solvent to obtain the polymer spinning solution, inject the polymer spinning solution into the outer tube of the coaxial spinneret of the electrostatic spinning equipment, and send the gas into the inner of the coaxial spinneret Tube, perform coaxial electrospinning to obtain superfine fibers;
  • Step T2 Directly deposit the ultrafine fibers on the receiving electrode plate to form an ultrafine fiber filter membrane to obtain the filter layer, wherein the diameter of the ultrafine fibers is 0.1 ⁇ m-9 ⁇ m, and the thickness of the ultrafine fiber membrane is 0.5 mm ⁇ 5mm, the diameter of the filter hole is 0.1 ⁇ m ⁇ 7 ⁇ m.
  • the mixed solvent is chloroform, tetrahydrofuran, N,N-dimethylformamide, N,N-dimethylacetamide, isopropyl Alcohol, formic acid, acetic acid, methanol, ethanol, butanol, carbon disulfide and water, and consists of two kinds of low boiling point solvent and high boiling point solvent, wherein the boiling point of the low boiling point solvent is lower than 60°C, and the high boiling point solvent The boiling point of the boiling point solvent is higher than the low boiling point solvent, and the volume ratio of the low boiling point solvent to the high boiling point solvent is 1-8:1; the polymer is polyglycolic acid, polylactic acid, polycaprolactone, Polyoxymethylene, polystyrene, polymethyl methacrylate, polyethylene oxide, aliphatic polyester copolymer, polyamide, polycarbonate, polyurethane, polyethylene oxide, polyvinyl
  • the method for preparing a nano-silver-copper alloy material of the present invention after cooling the gaseous alloy by a supersonic inert gas flow, obtains an alloy material of nano-silver metal and nano-copper metal.
  • the silver metal atoms When cooled at room temperature, Only the copper metal atoms exposed on the outer surface will be oxidized, while the copper metal atoms inside are not oxidized. Because the silver metal atoms are not easily oxidized at room temperature, they are easily oxidized only at high temperatures. Therefore, the silver metal atoms are not easily oxidized. Oxidation, therefore, the electrical conductivity and sterilization performance of the alloy material is better.
  • Nano alloy particles are only 15nm-50nm in size, and the particle size is very small. The smaller the particle size of the nano alloy particles, the exposed surface The more the number of metal atoms, the stronger the bactericidal and virus-killing ability; secondly, the copper metal atoms on the outer surface of the nano-alloy material are oxides, which can ensure the safety of the alloy material in application, because copper metal powder Unsafe, easy to burn and explode;
  • the combined material composed of metallic silver atoms and metallic copper atoms has better conductivity than the materials composed of metallic silver atoms and metal oxides (belonging to semiconductors). It not only has better sterilization performance, but also expands the use of electronic and Broader application prospects in the field of new energy.
  • the nano-silver-copper alloy material of the present invention is made into a medical sterilization product. After being tested by an authoritative institution, it has reached Antibacterial rate of over 99%;
  • the method for preparing a nano-silver-copper alloy material of the present invention is to carry alloy particles into a filter layer by an inert gas flow for gas-solid separation and collection to obtain the nano-silver-copper alloy material, and the filter layer is made of ultrafine fibers
  • the ultrafine fiber membrane is made so that when the inert gas stream carries alloy particles into the filter layer, the inert gas stream passes through the filter holes and passes through the filter layer, while the alloy particles are intercepted by the filter layer; this preparation method completes the inert gas and nano alloy particles
  • the effective separation effectively reduces the discharge of nano-alloy particles with inert gas, avoids wasting resources, and saves costs.
  • Fig. 1 is an enlarged view of the scanning electron microscope of the nano-silver-copper alloy material of the present invention.
  • this embodiment is a nano-silver-copper alloy material, and the alloy material is composed of the following weight percentage components:
  • the rest is copper
  • the alloy material is composed of a mixture of nano silver-copper alloy particles with a particle size of 15 nm-50 nm, and the copper metal atoms on the outer surface of the alloy material are formed as copper oxide.
  • the preparation method of the nano-silver-copper alloy material includes the following steps:
  • Step S1 combining silver and copper to prepare a composite metal wire rod
  • Step S2 the composite metal wire rod is used as the anode conductor of the DC power supply, and the arc formed with the cathode causes the tip of the anode conductor metal wire rod to vaporize and evaporate, producing a smoke-like metal atom group, and the silver metal atom and the copper metal atom are fully mixed, Forming a gaseous alloy; wherein the temperature of the arc formed by the anode conductor and the cathode is above 5000°C;
  • Step S3 while the metal is vaporized, the gaseous alloy is cooled with an inert gas flow of 1 to 1.4 times the speed of sound;
  • Step S4 collecting the powder after cooling at normal temperature to obtain the nano-silver-copper alloy material.
  • the step S3 further includes: mixing the cooled alloy and the inert gas stream with air, enter the powder collection device through the pipe, and then perform gas-solid separation, wherein the powder collection device can be the prior art
  • the powder collection device may be the filter layer in the specific embodiment of the present invention, and the filter layer plays a role of gas-solid separation.
  • the flow of inert gas is a flow of helium.
  • the nano-silver-copper alloy material includes the following components by weight: 40 parts of silver metal wire and 60 parts of copper metal wire;
  • the nano-silver-copper alloy material is prepared by the following steps:
  • Step 1 Prepare the silver metal wire and the copper metal wire to obtain a composite metal wire rod
  • Step 2 Use the composite metal wire rod as the anode conductor of the DC power supply, and the arc formed with the cathode will vaporize and evaporate the tip of the metal wire rod of the anode conductor, producing a smoke-like metal atom group, and the silver metal atom and the copper atom are fully mixed. Forming a gaseous alloy;
  • Step 3 At the same time as the metal is vaporized, the gaseous alloy is cooled with an inert gas flow of 1 to 1.4 times the speed of sound;
  • Step 4 The inert gas flow carries the alloy particles into the filter layer for gas-solid separation and collection to obtain the nano-silver-copper alloy material.
  • the purity of the silver metal wire and the copper metal wire are both 99.9%, and the diameter of the silver metal wire and the copper metal wire are both 0.4 mm to 0.8 mm.
  • a preparation method of nano-silver-copper alloy material includes the following steps:
  • Step 1 Preparation of metal wire rod: silver metal wire and copper metal wire are braided into a mixed metal wire with a diameter of 6mm-8mm, and then cold rolled into a composite metal wire rod with a diameter of 5mm;
  • Step 2 Vaporization: Use the composite metal wire rod as the anode conductor, and form an arc with the cathode under the conditions of a DC voltage of 36 volts and a current of 1050 amperes, so that the tip of the anode conductor's metal rod is vaporized and vaporized to produce a smoke-like metal Atomic group, the silver metal atom and copper atom are fully mixed to form a gaseous alloy;
  • Step 3 Condensation: As the metal vaporizes, the gaseous alloy is separated from the high-temperature area with an inert gas flow of 1 to 1.4 times the speed of sound, and then rapidly cooled, so that when the metal returns from the gas state to the solid state, 15-30 nanometer alloy particles are formed ;
  • Step 4 Collection: the inert gas flow carries the alloy particles into the filter layer for gas-solid separation and collection to obtain the nano-silver-copper alloy material.
  • the temperature of the arc is above 5000° C., and the length of the arc is 30 mm.
  • the preparation method of the filter layer includes the following steps:
  • Step T1 Dissolve the polymer in the mixed solvent to obtain the polymer spinning solution, inject the polymer spinning solution into the outer tube of the coaxial spinneret of the electrostatic spinning equipment, and send the gas into the inner of the coaxial spinneret Tube, perform coaxial electrospinning to obtain superfine fibers;
  • Step T2 Directly deposit the ultrafine fibers on the receiving electrode plate to form an ultrafine fiber filter membrane to obtain the filter layer, wherein the diameter of the ultrafine fibers is 0.1 ⁇ m-9 ⁇ m, and the thickness of the ultrafine fiber membrane is 0.5 mm ⁇ 5mm, the diameter of the filter hole is 0.1 ⁇ m ⁇ 7 ⁇ m.
  • the mixed solvent is chloroform, tetrahydrofuran, N,N-dimethylformamide, N,N-dimethylacetamide, isopropanol, formic acid, acetic acid, methanol, ethanol, butanol, carbon disulfide and water.
  • the low-boiling point solvent has a boiling point lower than 60°C
  • the high-boiling point solvent has a higher boiling point than the low-boiling point solvent
  • the low-boiling point solvent is The volume ratio of the high boiling point solvent is 1-8:1;
  • the polymer is polyglycolic acid, polylactic acid, polycaprolactone, polyoxymethylene, polystyrene, polymethyl methacrylate, polyethylene oxide , Aliphatic polyester copolymer, polyamide, polycarbonate, polyurethane, polyethylene oxide, polyvinyl alcohol, cellulose acetate, polyacrylic acid, polyacrylamide, polyvinylpyrrolidone or hydroxypropyl cellulose.
  • the mixed solvent can be N,N-dimethylformamide and formic acid; and the polymer is polymethyl methacrylate.
  • the nano-silver-copper alloy material of Example 1 was made into a medical sterilization product, and tested by an authoritative organization, and tested against Escherichia coli and Staphylococcus aureus, which represent conventional bacteria, and methicillin-resistant Staphylococcus aureus, which represents super bacteria. Both reach an antibacterial rate of 99.15%;
  • this embodiment is a nano-silver-copper alloy material, and the alloy material is composed of the following weight percentage components:
  • the rest is copper
  • the alloy material is composed of a mixture of nano silver-copper alloy particles with a particle size of 15 nm-30 nm, and the copper metal atoms on the outer surface of the alloy material are formed as copper oxide.
  • the preparation method of the nano-silver-copper alloy material includes the following steps:
  • Step S1 combining silver and copper to prepare a composite metal wire rod
  • Step S2 the composite metal wire rod is used as the anode conductor of the DC power supply, and the arc formed with the cathode causes the tip of the anode conductor metal wire rod to vaporize and evaporate, producing a smoke-like metal atom group, and the silver metal atom and the copper metal atom are fully mixed, Forming a gaseous alloy; wherein the temperature of the arc formed by the anode conductor and the cathode is above 5000°C;
  • Step S3 while the metal is vaporized, the gaseous alloy is cooled with an inert gas flow of 1 to 1.4 times the speed of sound;
  • Step S4 collecting the powder after cooling at normal temperature to obtain the nano-silver-copper alloy material.
  • the flow of inert gas is a flow of helium.
  • the nano-silver-copper alloy material includes the following components by weight: 60 parts of silver metal wire and 40 parts of copper metal wire;
  • the nano-silver-copper alloy material is prepared by the following steps:
  • Step 1 Prepare the silver metal wire and the copper metal wire to obtain a composite metal wire rod
  • Step 2 Use the composite metal wire rod as the anode conductor of the DC power supply, and the arc formed with the cathode will vaporize and evaporate the tip of the metal wire rod of the anode conductor, producing a smoke-like metal atom group, and the silver metal atom and the copper atom are fully mixed. Forming a gaseous alloy;
  • Step 3 At the same time as the metal is vaporized, the gaseous alloy is cooled with an inert gas flow of 1 to 1.4 times the speed of sound;
  • Step 4 The inert gas flow carries the alloy particles into the filter layer for gas-solid separation and collection to obtain the nano-silver-copper alloy material.
  • the purity of the silver metal wire and the copper metal wire are both 99.9%, and the diameter of the silver metal wire and the copper metal wire are both 0.4 mm to 0.8 mm.
  • a preparation method of nano-silver-copper alloy material includes the following steps:
  • Step 1 Preparation of metal wire rod: silver metal wire and copper metal wire are braided into a mixed metal wire with a diameter of 6mm-8mm, and then cold rolled into a composite metal wire rod with a diameter of 5mm;
  • Step 2 Vaporization: Use the composite metal wire rod as the anode conductor, and form an arc with the cathode under the conditions of a DC voltage of 36 volts and a current of 1050 amperes, so that the tip of the anode conductor's metal rod is vaporized and vaporized to produce a smoke-like metal Atomic group, the silver metal atom and copper atom are fully mixed to form a gaseous alloy;
  • Step 3 Condensation: With the vaporization of the metal, the gaseous alloy is separated from the high-temperature area with an inert gas flow of 1 to 1.4 times the speed of sound, and rapid cooling is performed to make the metal return to the solid state from the gas state to form alloy particles of 15 nm to 30 nm ;
  • Step 4 Collection: the inert gas flow carries the alloy particles into the filter layer for gas-solid separation and collection to obtain the nano-silver-copper alloy material.
  • the electrostatic adsorption capacity of the filter material of the filter layer allows the silver-copper alloy particles to quickly form a soft agglomeration effect.
  • the size of the soft agglomerate is 50 ⁇ m or more, which can More silver-copper alloy particles are trapped in the soft aggregates, which improves the yield and the overall performance of the material.
  • the filter material can be a copolymer of acid, alkali and high temperature resistant polytetrafluoroethylene and propylene, or Copolymer of vinyl fluoride and propylene.
  • the gas-solid separation of the alloy particles is achieved by the electrostatic adsorption of the filter layer to form a soft agglomeration effect, and the method for obtaining the electrostatic adsorption capacity of the filter layer is to charge the filter layer with an electrode.
  • the temperature of the arc is above 5000° C., and the length of the arc is 30 mm.
  • the preparation method of the filter layer includes the following steps:
  • Step T1 Dissolve the polymer in the mixed solvent to obtain the polymer spinning solution, inject the polymer spinning solution into the outer tube of the coaxial spinneret of the electrostatic spinning equipment, and send the gas into the inner of the coaxial spinneret Tube, perform coaxial electrospinning to obtain superfine fibers;
  • Step T2 Directly deposit the ultrafine fibers on the receiving electrode plate to form an ultrafine fiber filter membrane to obtain the filter layer, wherein the diameter of the ultrafine fibers is 0.1 ⁇ m-9 ⁇ m, and the thickness of the ultrafine fiber membrane is 0.5 mm ⁇ 5mm, the diameter of the filter hole is 0.1 ⁇ m ⁇ 7 ⁇ m.
  • the mixed solvent is tetrahydrofuran and ethanol, and the polymer is polyglycolic acid.
  • the nano-silver-copper alloy material of Example 2 was made into a medical sterilization product, and tested by an authoritative organization to test Escherichia coli and Staphylococcus aureus, which represent conventional bacteria, and methicillin-resistant Staphylococcus aureus, which represents super bacteria. Both reach 99.46% antibacterial rate;
  • this embodiment is a nano-silver-copper alloy material, and the alloy material is composed of the following weight percentage components:
  • the rest is copper
  • the alloy material is composed of a mixture of nano silver-copper alloy particles with a particle size of 15 nm-50 nm, and the copper metal atoms on the outer surface of the alloy material are formed as copper oxide.
  • the preparation method of the nano-silver-copper alloy material includes the following steps:
  • Step S1 combining silver and copper to prepare a composite metal wire rod
  • Step S2 the composite metal wire rod is used as the anode conductor of the DC power supply, and the arc formed with the cathode causes the tip of the anode conductor metal wire rod to vaporize and evaporate, producing a smoke-like metal atom group, and the silver metal atom and the copper metal atom are fully mixed, Forming a gaseous alloy; wherein the temperature of the arc formed by the anode conductor and the cathode is above 5000°C;
  • Step S3 while the metal is vaporized, the gaseous alloy is cooled with an inert gas flow of 1 to 1.4 times the speed of sound;
  • Step S4 collecting the powder after cooling at normal temperature to obtain the nano-silver-copper alloy material.
  • the flow of inert gas is a flow of helium.
  • the nano-silver-copper alloy material includes the following components by weight: 80 parts of silver metal wire and 20 parts of copper metal wire;
  • the nano-silver-copper alloy material is prepared by the following steps:
  • Step 1 Prepare the silver metal wire and the copper metal wire to obtain a composite metal wire rod
  • Step 2 Use the composite metal wire rod as the anode conductor of the DC power supply, and the arc formed with the cathode will vaporize and evaporate the tip of the metal wire rod of the anode conductor, producing a smoke-like metal atom group, and the silver metal atom and the copper atom are fully mixed. Forming a gaseous alloy;
  • Step 3 At the same time as the metal is vaporized, the gaseous alloy is cooled with an inert gas flow of 1 to 1.4 times the speed of sound;
  • Step 4 The inert gas flow carries the alloy particles into the filter layer for gas-solid separation and collection to obtain the nano-silver-copper alloy material.
  • the purity of the silver metal wire and the copper metal wire are both 99.9%, and the diameter of the silver metal wire and the copper metal wire are both 0.4 mm to 0.8 mm.
  • a preparation method of nano-silver-copper alloy material includes the following steps:
  • Step 1 Preparation of metal wire rod: silver metal wire and copper metal wire are braided into a mixed metal wire with a diameter of 6mm-8mm, and then cold-rolled and rolled into a composite metal wire rod with a diameter of 5mm;
  • Step 2 Vaporization: Use the composite metal wire rod as the anode conductor, and form an arc with the cathode under the conditions of a DC voltage of 36 volts and a current of 1050 amperes, so that the tip of the anode conductor's metal rod is vaporized and vaporized to produce a smoke-like metal Atomic group, the silver metal atom and copper atom are fully mixed to form a gaseous alloy;
  • Step 3 Condensation: With the vaporization of the metal, the gaseous alloy is separated from the high-temperature area with an inert gas flow of 1 to 1.4 times the speed of sound, and the gaseous alloy is rapidly cooled, so that when the metal returns from the gaseous state to the solid state, alloy particles of 15nm-50nm are formed;
  • Step 4 Collection: the inert gas flow carries the alloy particles into the filter layer for gas-solid separation and collection to obtain the nano-silver-copper alloy material.
  • the temperature of the arc is above 5000° C., and the length of the arc is 30 mm.
  • the preparation method of the filter layer includes the following steps:
  • Step T1 Dissolve the polymer in the mixed solvent to obtain the polymer spinning solution, inject the polymer spinning solution into the outer tube of the coaxial spinneret of the electrostatic spinning equipment, and send the gas into the inner of the coaxial spinneret Tube, perform coaxial electrospinning to obtain superfine fibers;
  • Step T2 Directly deposit the ultrafine fibers on the receiving electrode plate to form an ultrafine fiber filter membrane to obtain the filter layer, wherein the diameter of the ultrafine fibers is 0.1 ⁇ m-9 ⁇ m, and the thickness of the ultrafine fiber membrane is 0.5 mm ⁇ 5mm, the diameter of the filter hole is 0.1 ⁇ m ⁇ 7 ⁇ m.
  • the mixed solvent is chloroform and acetic acid, and the polymer is hydroxypropyl cellulose.
  • the nano-silver-copper alloy material of Example 3 was made into a medical sterilization product, and tested by an authoritative organization to test E. coli and Staphylococcus aureus, which represent conventional bacteria, and methicillin-resistant Staphylococcus aureus, which represents super bacteria. Both reached an antibacterial rate of 99.87%.
  • the description with reference to the terms “one embodiment”, “example”, “specific example”, etc. means that the specific feature, structure, material or characteristic described in combination with the embodiment or example is included in at least the present invention. In one embodiment or example. In this specification, the schematic representations of the above-mentioned terms do not necessarily refer to the same embodiment or example. Moreover, the described specific features, structures, materials or characteristics can be combined in any one or more embodiments or examples in a suitable manner.

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Abstract

Disclosed are a nano silver-copper alloy material and a preparation method therefor. The nano silver-copper alloy material is composed of a mixture of nano silver-copper alloy particles with a particle size of 15-50 nm, and the copper metal atoms at the outer surface of the alloy material are formed into a copper oxide. In the preparation method, when a gaseous alloy is cooled at room temperature after being cooled by a supersonic inert gas flow, only the copper metal atoms exposed on the outer surface will be oxidized, and the silver metal atom will not be oxidized, and therefore, the alloy material has a better conductive performance, and furthermore, the particle size of the nano-alloy particles is small, the number of metal atoms exposed on the surface is great, and the bactericidal ability and the virucidal ability thereof are strong; and in the preparation method, by entering the inert gas flow carrying the alloy particles into a filter layer for gas-solid separation and collection, the inert gas flow passes through the filter layer via a filter hole, and the alloy particles are trapped by the filter layer, such that the discharge of the nano-alloy particles with the inert gas is effectively reduced, the waste of resources is avoided, and costs are saved on.

Description

一种纳米银铜合金材料及其制备方法Nano silver-copper alloy material and preparation method thereof 技术领域Technical field
本发明涉及新材料技术领域，具体涉及一种纳米银铜合金材料及其制备方法。The invention relates to the technical field of new materials, in particular to a nano-silver-copper alloy material and a preparation method thereof.
背景技术Background technique
银作为一种安全可靠的杀菌材料，已得到公认。纳米银的杀菌效果，更是其它无机材料难以替代。但是，在纳米银的生产方法上，以及各个行业的推广应用上，存在着不同程度的技术障碍。Silver has been recognized as a safe and reliable sterilization material. The bactericidal effect of nano-silver is even more difficult to replace with other inorganic materials. However, there are varying degrees of technical obstacles in the production methods of nano-silver and the promotion and application of various industries.
申请号为CN201710834160.X的专利公开了本发明提供了一种银合金复合纳米材料的制备方法，其包括以下步骤：将银与铜、锌、镁、铝、钛金属中的至少一种组合制备得到复合金属线棒；将复合金属线棒作为直流电源的阳极导体，与阴极形成的电弧，使阳极导体的金属线棒尖端气化蒸发，产生烟雾状的金属原子团，银金属原子与铜、锌、镁、铝、钛金属原子中的至少一种充分混合，形成气态合金；伴随金属气化的同时，用0.5～1.5倍音速的空气气流将气态合金进行快速冷却；收集冷却后的粉体，得到银合金复合纳米材料；但仍然存在以下不足之处：（1）该银合金复合纳米材料的制备方法使用超音速的冷却空气进行冷却气体金属，得到的复合纳米材料，是银金属和其它金属氧化物（本质上属于半导体）复合而成，其它金属均属于完全的氧化状态，导电性能还不够优异，杀菌性能还有待提升；（2）该银合金复合纳米材料的制备方法中的气体和纳米颗粒的分离效果还需进一步优化，因为纳米颗粒会随着气体排出，造成了资源浪费，成本大。The patent with the application number CN201710834160.X discloses that the present invention provides a method for preparing a silver alloy composite nanomaterial, which includes the following steps: combining silver with at least one of copper, zinc, magnesium, aluminum, and titanium. Obtain the composite metal wire rod; the composite metal wire rod is used as the anode conductor of the DC power supply, and the arc formed with the cathode makes the tip of the anode conductor metal wire rod vaporize and evaporate to produce smoke-like metal atom clusters, silver metal atoms, copper and zinc At least one of the metal atoms of magnesium, aluminum, and titanium is fully mixed to form a gaseous alloy; while the metal is vaporized, the gaseous alloy is rapidly cooled with an air flow of 0.5 to 1.5 times the speed of sound; the cooled powder is collected, The silver alloy composite nano material is obtained; but there are still the following shortcomings: (1) The preparation method of the silver alloy composite nano material uses supersonic cooling air to cool the gas metal, and the obtained composite nano material is silver metal and other metals Oxide (essentially a semiconductor) is compounded, other metals are in a completely oxidized state, the conductivity is not excellent enough, and the sterilization performance needs to be improved; (2) The gas and nanometer in the preparation method of the silver alloy composite nanomaterial The separation effect of the particles needs to be further optimized, because the nanoparticles will be discharged with the gas, resulting in a waste of resources and a high cost.
技术问题technical problem
为了克服上述的技术问题，本发明的目的在于提供了一种纳米银铜合金材料及其制备方法：（1）通过超音速的惰性气体气流来冷却气态合金后，获得的是纳米银金属和纳米铜金属的合金材料，在常温下冷却时，只有裸露在外表面的铜金属原子会被氧化，而内部的铜金属原子没有被氧化，银金属原子由于在常温下是不容易被氧化的，只有在高温下才容易氧化，因此银金属原子未被氧化，解决了现有的银合金复合纳米材料是银金属和其它金属氧化物复合而成，其它金属均属于完全的氧化状态，导电性能不够好，杀菌性能还有待提升的问题；（2）通过惰性气体气流携带合金颗粒进入过滤层进行气固分离并且收集，得到该纳米银铜合金材料，该过滤层为由超细纤维制成的超细纤维膜，使得惰性气体气流携带合金颗粒进入过滤层时，惰性气体气流经过过滤孔穿过过滤层，而合金颗粒被过滤层截留，解决了现有的银合金复合纳米材料的制备方法中的气体和纳米颗粒的分离效果不太好，纳米颗粒会随着气体排出，造成了资源浪费，成本大的问题。In order to overcome the above technical problems, the purpose of the present invention is to provide a nano-silver-copper alloy material and a preparation method thereof: (1) After cooling the gaseous alloy by a supersonic inert gas flow, the obtained nano-silver metal and nano- When the copper metal alloy material is cooled at room temperature, only the copper metal atoms exposed on the outer surface will be oxidized, while the copper metal atoms inside are not oxidized. The silver metal atoms are not easily oxidized at room temperature. It is easy to oxidize at high temperature, so the silver metal atoms are not oxidized, which solves the problem that the existing silver alloy composite nanomaterials are composited by silver metal and other metal oxides. Other metals are in a completely oxidized state, and the conductivity is not good enough. The sterilization performance still needs to be improved; (2) The alloy particles are carried into the filter layer by inert gas flow for gas-solid separation and collection, and the nano-silver-copper alloy material is obtained. The filter layer is made of ultra-fine fibers. The membrane allows the inert gas flow to carry alloy particles into the filter layer. The inert gas flow passes through the filter holes and passes through the filter layer, while the alloy particles are retained by the filter layer. The separation effect of the nanoparticles is not very good, and the nanoparticles will be discharged with the gas, resulting in waste of resources and high cost.
技术解决方案Technical solutions
本发明的目的可以通过以下技术方案实现：The purpose of the present invention can be achieved through the following technical solutions:
一种纳米银铜合金材料，所述合金材料由以下重量百分比组分组成：A nano-silver-copper alloy material, the alloy material is composed of the following weight percentage components:
银                           40～80%；silver 40～80%;
其余为铜；The rest is copper;
所述的合金材料由粒径为15nm～50nm的纳米银铜合金颗粒混合构成，所述合金材料的外表面的铜金属原子形成为氧化铜。The alloy material is composed of a mixture of nano silver-copper alloy particles with a particle size of 15 nm-50 nm, and the copper metal atoms on the outer surface of the alloy material are formed as copper oxide.
作为本发明进一步的方案：所述的纳米银铜合金颗粒的粒径为15nm～30nm 。As a further solution of the present invention: the particle size of the nano-silver-copper alloy particles is 15nm-30nm.
作为本发明进一步的方案：所述的纳米银铜合金材料的制备方法，包括以下步骤：As a further solution of the present invention: the method for preparing the nano-silver-copper alloy material includes the following steps:
步骤S1，将银与铜组合制备得到复合金属线棒；Step S1, combining silver and copper to prepare a composite metal wire rod;
步骤S2，将复合金属线棒作为直流电源的阳极导体，与阴极形成的电弧，使阳极导体的金属线棒尖端气化蒸发，产生烟雾状的金属原子团，银金属原子与铜金属原子充分混合，形成气态合金；其中，所述阳极导体与阴极形成的电弧的温度为5000℃以上；Step S2, the composite metal wire rod is used as the anode conductor of the DC power supply, and the arc formed with the cathode causes the tip of the anode conductor metal wire rod to vaporize and evaporate, producing a smoke-like metal atom group, and the silver metal atom and the copper metal atom are fully mixed, Forming a gaseous alloy; wherein the temperature of the arc formed by the anode conductor and the cathode is above 5000°C;
步骤S3，伴随金属气化的同时，用1～1 .4倍音速的惰性气体气流将气态合金进行冷却；Step S3, while the metal is vaporized, the gaseous alloy is cooled with an inert gas flow of 1 to 1.4 times the speed of sound;
步骤S4，收集在常温下冷却后的粉体，得到纳米银铜合金材料。Step S4, collecting the powder after cooling at normal temperature to obtain the nano-silver-copper alloy material.
作为本发明进一步的方案：所述步骤S3还包括：将冷却后的合金以及惰性气体气流与空气混合，通过管道进入粉体收集装置后进行气固分离。As a further solution of the present invention, the step S3 also includes: mixing the cooled alloy and the inert gas stream with air, enter the powder collection device through a pipe, and perform gas-solid separation.
作为本发明进一步的方案：所述惰性气体气流为氦气气流。As a further solution of the present invention: the inert gas flow is a helium flow.
一种纳米银铜合金材料由以下步骤制备得到：A nano-silver-copper alloy material is prepared by the following steps:
步骤一：制备金属线棒：将银金属丝与铜金属丝编织成直径为6mm～8mm的混合金属线，经过冷轧压延成直径为5mm的复合金属线棒；Step 1: Preparation of metal wire rod: silver metal wire and copper metal wire are braided into a mixed metal wire with a diameter of 6mm-8mm, and then cold-rolled and rolled into a composite metal wire rod with a diameter of 5mm;
步骤二：气化：将复合金属线棒作为阳极导体，在直流电压36伏，电流1050安的条件下，与阴极形成电弧，使阳极导体的金属线棒尖端气化蒸发，产生烟雾状的金属原子团，银金属原子与铜原子中充分混合，形成气态合金；Step 2: Vaporization: Use the composite metal wire rod as the anode conductor, and form an arc with the cathode under the conditions of a DC voltage of 36 volts and a current of 1050 amperes, so that the tip of the anode conductor's metal rod is vaporized and vaporized to produce a smoke-like metal Atomic group, the silver metal atom and copper atom are fully mixed to form a gaseous alloy;
步骤三：冷凝：伴随金属气化的同时，用1～1.4倍音速的惰性气体气流将气态合金脱离高温区域，进行快速冷却，使金属从气态回到固态时，形成15nm～50nm的合金颗粒；Step 3: Condensation: With the vaporization of the metal, the gaseous alloy is separated from the high-temperature area with an inert gas flow of 1 to 1.4 times the speed of sound, and the gaseous alloy is rapidly cooled, so that when the metal returns from the gaseous state to the solid state, alloy particles of 15nm-50nm are formed;
步骤四：收集：惰性气体气流携带合金颗粒进入过滤层进行气固分离并且收集，得到该纳米银铜合金材料。Step 4: Collection: the inert gas flow carries the alloy particles into the filter layer for gas-solid separation and collection to obtain the nano-silver-copper alloy material.
作为本发明进一步的方案：所述过滤层中的过滤材料为聚四氟乙烯与丙烯的共聚物，或者为氟乙烯与丙烯的共聚物。As a further solution of the present invention: the filter material in the filter layer is a copolymer of polytetrafluoroethylene and propylene, or a copolymer of vinyl fluoride and propylene.
作为本发明进一步的方案：所述合金颗粒的气固分离是通过过滤层的静电吸附形成软团聚效应实现的，所述过滤层获得静电吸附能力的方法为用电极对所述过滤层进行充电获得。As a further solution of the present invention: the gas-solid separation of the alloy particles is achieved by the electrostatic adsorption of the filter layer to form a soft agglomeration effect, and the method for obtaining the electrostatic adsorption capacity of the filter layer is to charge the filter layer with an electrode. .
作为本发明进一步的方案：所述银金属丝、铜金属丝的纯度均为99.9%，所述银金属丝、铜金属丝的的直径均为0.4mm～0.8mm。As a further solution of the present invention: the purity of the silver metal wire and the copper metal wire are both 99.9%, and the diameter of the silver metal wire and the copper metal wire are both 0.4 mm to 0.8 mm.
作为本发明进一步的方案：所述电弧的温度为5000℃以上，电弧的长度为30mm。As a further solution of the present invention: the temperature of the arc is above 5000° C., and the length of the arc is 30 mm.
作为本发明进一步的方案：一种纳米银铜合金材料的制备方法，所述过滤层的制备方法包括以下步骤：As a further solution of the present invention: a method for preparing a nano-silver-copper alloy material, the method for preparing the filter layer includes the following steps:
步骤T1、将聚合物溶解于混合溶剂中得到聚合物纺丝液，将聚合物纺丝液注入静电纺丝设备的同轴喷丝头的外管，将气体送入同轴喷丝头的内管，进行同轴静电纺丝，得到超细纤维；Step T1: Dissolve the polymer in the mixed solvent to obtain the polymer spinning solution, inject the polymer spinning solution into the outer tube of the coaxial spinneret of the electrostatic spinning equipment, and send the gas into the inner of the coaxial spinneret Tube, perform coaxial electrospinning to obtain superfine fibers;
步骤T2、将超细纤维直接沉积在接收电极板上，形成超细纤维过滤膜，得到该过滤层，其中，超细纤维的直径为0.1μm～9μm，所述超细纤维膜的厚度为0.5 mm～5mm，过滤孔的直径为0.1μm～7μm。Step T2: Directly deposit the ultrafine fibers on the receiving electrode plate to form an ultrafine fiber filter membrane to obtain the filter layer, wherein the diameter of the ultrafine fibers is 0.1 μm-9 μm, and the thickness of the ultrafine fiber membrane is 0.5 mm～5mm, the diameter of the filter hole is 0.1μm～7μm.
作为本发明进一步的方案：一种纳米银铜合金材料的制备方法，包所述混合溶剂为氯仿、四氢呋喃、N，N-二甲基甲酰胺、N，N-二甲基乙酰胺、异丙醇、甲酸、乙酸、甲醇、乙醇、丁醇、二硫化碳和水中的两种，且由低沸点溶剂和高沸点溶剂两种组成，其中，所述低沸点溶剂的沸点低于60℃，所述高沸点溶剂的沸点高于所述低沸点溶剂，所述低沸点溶剂与所述高沸点溶剂的体积比为1～8:1；所述聚合物为聚羟基乙酸、聚乳酸、聚己内酯、聚甲醛、聚苯乙烯、聚甲基丙烯酸甲酯、聚环氧乙烷、脂肪族聚酯共聚物、聚酰胺、聚碳酸酯、聚氨酯、聚氧化乙烯、聚乙烯醇、醋酸纤维素、聚丙烯酸、聚丙烯酰胺、聚乙烯基吡咯烷酮或羟丙基纤维素。As a further solution of the present invention: a method for preparing nano-silver-copper alloy material, the mixed solvent is chloroform, tetrahydrofuran, N,N-dimethylformamide, N,N-dimethylacetamide, isopropyl Alcohol, formic acid, acetic acid, methanol, ethanol, butanol, carbon disulfide and water, and consists of two kinds of low boiling point solvent and high boiling point solvent, wherein the boiling point of the low boiling point solvent is lower than 60°C, and the high boiling point solvent The boiling point of the boiling point solvent is higher than the low boiling point solvent, and the volume ratio of the low boiling point solvent to the high boiling point solvent is 1-8:1; the polymer is polyglycolic acid, polylactic acid, polycaprolactone, Polyoxymethylene, polystyrene, polymethyl methacrylate, polyethylene oxide, aliphatic polyester copolymer, polyamide, polycarbonate, polyurethane, polyethylene oxide, polyvinyl alcohol, cellulose acetate, polyacrylic acid , Polyacrylamide, polyvinylpyrrolidone or hydroxypropyl cellulose.
有益效果Beneficial effect
本发明的有益效果：The beneficial effects of the present invention:
（1）本发明的一种纳米银铜合金材料的制备方法，通过超音速的惰性气体气流来冷却气态合金后，获得的是纳米银金属和纳米铜金属的合金材料，在常温下冷却时，只有裸露在外表面的铜金属原子会被氧化，而内部的铜金属原子没有被氧化，银金属原子由于在常温下是不容易被氧化的，只有在高温下才容易氧化，因此银金属原子未被氧化，因此，该合金材料的导电性能、杀菌性能更好，该材料的导电性能越优良，就会对微生物的生物电场干扰能力越强，从而杀死微生物的能力越强，从而能够杀死超级细菌和病毒，并且，在自然常温下氧化，有效地阻止了银金属的原子团聚，纳米合金颗粒只有15nm～50nm大小，粒径非常小，而该纳米合金颗粒的粒径越小，那么表面裸露的金属原子数量越多，杀菌能力、杀病毒能力也就越强；其次，该纳米合金材料的外表面铜金属原子为氧化物，可以保证该合金材料在应用时的安全性，因为铜金属粉末不安全，容易燃烧和爆炸；(1) The method for preparing a nano-silver-copper alloy material of the present invention, after cooling the gaseous alloy by a supersonic inert gas flow, obtains an alloy material of nano-silver metal and nano-copper metal. When cooled at room temperature, Only the copper metal atoms exposed on the outer surface will be oxidized, while the copper metal atoms inside are not oxidized. Because the silver metal atoms are not easily oxidized at room temperature, they are easily oxidized only at high temperatures. Therefore, the silver metal atoms are not easily oxidized. Oxidation, therefore, the electrical conductivity and sterilization performance of the alloy material is better. The better the electrical conductivity of the material, the stronger the bioelectric field interference ability of microorganisms, and the stronger the ability to kill microorganisms, which can kill super Bacteria and viruses, and oxidized at normal temperature, effectively prevent the agglomeration of silver metal atoms. Nano alloy particles are only 15nm-50nm in size, and the particle size is very small. The smaller the particle size of the nano alloy particles, the exposed surface The more the number of metal atoms, the stronger the bactericidal and virus-killing ability; secondly, the copper metal atoms on the outer surface of the nano-alloy material are oxides, which can ensure the safety of the alloy material in application, because copper metal powder Unsafe, easy to burn and explode;
另外，金属银原子与金属铜原子的结合构成材料，比金属银原子与金属氧化物（属于半导体）构成材料，具有更好的导电性能，不仅具有更优异的杀菌性能，同时拓展了在电子及新能源领域的更广泛的应用前景。In addition, the combined material composed of metallic silver atoms and metallic copper atoms has better conductivity than the materials composed of metallic silver atoms and metal oxides (belonging to semiconductors). It not only has better sterilization performance, but also expands the use of electronic and Broader application prospects in the field of new energy.
对得到的银铜合金复合纳米材料进行扫描电镜和透射电镜检测，可见得到的颗粒比较均匀；Scanning electron microscopy and transmission electron microscopy were performed on the obtained silver-copper alloy composite nanomaterials, and it can be seen that the obtained particles were relatively uniform;
本发明的纳米银铜合金材料做成医用杀菌产品，经权威机构进行测试，对代表常规菌种的大肠杆菌和金黄色葡萄球菌，以及代表超级细菌的耐甲氧西林金黄色葡萄球菌，均达到99%以上的抗菌率；The nano-silver-copper alloy material of the present invention is made into a medical sterilization product. After being tested by an authoritative institution, it has reached Antibacterial rate of over 99%;
（2）本发明的一种纳米银铜合金材料的制备方法，通过惰性气体气流携带合金颗粒进入过滤层进行气固分离并且收集，得到该纳米银铜合金材料，该过滤层为由超细纤维制成的超细纤维膜，使得惰性气体气流携带合金颗粒进入过滤层时，惰性气体气流经过过滤孔穿过过滤层，而合金颗粒被过滤层截留；该制备方法完成了惰性气体和纳米合金颗粒的有效分离，有效地减少了纳米合金颗粒随着惰性气体排出，避免浪费了资源，节约了成本。(2) The method for preparing a nano-silver-copper alloy material of the present invention is to carry alloy particles into a filter layer by an inert gas flow for gas-solid separation and collection to obtain the nano-silver-copper alloy material, and the filter layer is made of ultrafine fibers The ultrafine fiber membrane is made so that when the inert gas stream carries alloy particles into the filter layer, the inert gas stream passes through the filter holes and passes through the filter layer, while the alloy particles are intercepted by the filter layer; this preparation method completes the inert gas and nano alloy particles The effective separation effectively reduces the discharge of nano-alloy particles with inert gas, avoids wasting resources, and saves costs.
附图说明Description of the drawings
下面结合附图对本发明作进一步的说明。The present invention will be further described below in conjunction with the accompanying drawings.
    图1是本发明中纳米银铜合金材料的电子显微镜扫描放大图。... Fig. 1 is an enlarged view of the scanning electron microscope of the nano-silver-copper alloy material of the present invention.
本发明的最佳实施方式The best mode of the present invention
在此处键入本发明的最佳实施方式描述段落。Type here a paragraph describing the best mode of the present invention.
本发明的实施方式Embodiments of the present invention
下面将结合本发明实施例，对本发明实施例中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一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其它实施例，都属于本发明保护的范围。The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative work shall fall within the protection scope of the present invention.
实施例1：Example 1:
请参阅图1～7所示，本实施例为一种纳米银铜合金材料，所述合金材料由以下重量百分比组分组成：Please refer to Figures 1-7, this embodiment is a nano-silver-copper alloy material, and the alloy material is composed of the following weight percentage components:
银                           40%；silver 40%;
其余为铜；The rest is copper;
所述的合金材料由粒径为15nm-50nm的纳米银铜合金颗粒混合构成，所述合金材料的外表面的铜金属原子形成为氧化铜。The alloy material is composed of a mixture of nano silver-copper alloy particles with a particle size of 15 nm-50 nm, and the copper metal atoms on the outer surface of the alloy material are formed as copper oxide.
所述的纳米银铜合金材料的制备方法，包括以下步骤：The preparation method of the nano-silver-copper alloy material includes the following steps:
步骤S1，将银与铜组合制备得到复合金属线棒；Step S1, combining silver and copper to prepare a composite metal wire rod;
步骤S2，将复合金属线棒作为直流电源的阳极导体，与阴极形成的电弧，使阳极导体的金属线棒尖端气化蒸发，产生烟雾状的金属原子团，银金属原子与铜金属原子充分混合，形成气态合金；其中，所述阳极导体与阴极形成的电弧的温度为5000℃以上；Step S2, the composite metal wire rod is used as the anode conductor of the DC power supply, and the arc formed with the cathode causes the tip of the anode conductor metal wire rod to vaporize and evaporate, producing a smoke-like metal atom group, and the silver metal atom and the copper metal atom are fully mixed, Forming a gaseous alloy; wherein the temperature of the arc formed by the anode conductor and the cathode is above 5000°C;
步骤S3，伴随金属气化的同时，用1～1 .4倍音速的惰性气体气流将气态合金进行冷却；Step S3, while the metal is vaporized, the gaseous alloy is cooled with an inert gas flow of 1 to 1.4 times the speed of sound;
步骤S4，收集在常温下冷却后的粉体，得到纳米银铜合金材料。Step S4, collecting the powder after cooling at normal temperature to obtain the nano-silver-copper alloy material.
在本发明中，述步骤S3还包括：将冷却后的合金以及惰性气体气流与空气混合，通过管道进入粉体收集装置后进行气固分离，其中，粉体收集装置可以是采用现有技术中的粉体收集装置或者为本发明具体实施方式中的过滤层，通过过滤层起到气固分离作用。In the present invention, the step S3 further includes: mixing the cooled alloy and the inert gas stream with air, enter the powder collection device through the pipe, and then perform gas-solid separation, wherein the powder collection device can be the prior art The powder collection device may be the filter layer in the specific embodiment of the present invention, and the filter layer plays a role of gas-solid separation.
所述惰性气体气流为氦气气流。The flow of inert gas is a flow of helium.
该纳米银铜合金材料包括以下重量份组分：40份银金属丝、60份铜金属丝；The nano-silver-copper alloy material includes the following components by weight: 40 parts of silver metal wire and 60 parts of copper metal wire;
该纳米银铜合金材料由以下步骤制备得到：The nano-silver-copper alloy material is prepared by the following steps:
步骤一：将银金属丝与铜金属丝制备得到复合金属线棒；Step 1: Prepare the silver metal wire and the copper metal wire to obtain a composite metal wire rod;
步骤二：将复合金属线棒作为直流电源的阳极导体，与阴极形成的电弧，使阳极导体的金属线棒尖端气化蒸发，产生烟雾状的金属原子团，银金属原子与铜原子中充分混合，形成气态合金；Step 2: Use the composite metal wire rod as the anode conductor of the DC power supply, and the arc formed with the cathode will vaporize and evaporate the tip of the metal wire rod of the anode conductor, producing a smoke-like metal atom group, and the silver metal atom and the copper atom are fully mixed. Forming a gaseous alloy;
步骤三：伴随金属气化的同时，用1～1.4倍音速的惰性气体气流将气态合金进行冷却；Step 3: At the same time as the metal is vaporized, the gaseous alloy is cooled with an inert gas flow of 1 to 1.4 times the speed of sound;
步骤四：惰性气体气流携带合金颗粒进入过滤层进行气固分离并且收集，得到该纳米银铜合金材料。Step 4: The inert gas flow carries the alloy particles into the filter layer for gas-solid separation and collection to obtain the nano-silver-copper alloy material.
所述银金属丝、铜金属丝的纯度均为99.9%，所述银金属丝、铜金属丝的的直径均为0.4mm～0.8mm。The purity of the silver metal wire and the copper metal wire are both 99.9%, and the diameter of the silver metal wire and the copper metal wire are both 0.4 mm to 0.8 mm.
一种纳米银铜合金材料的制备方法，包括以下步骤：A preparation method of nano-silver-copper alloy material includes the following steps:
步骤一：制备金属线棒：将银金属丝与铜金属丝编织成直径为6mm～8mm的混合金属线，经过冷轧压延成直径为5mm的复合金属线棒；Step 1: Preparation of metal wire rod: silver metal wire and copper metal wire are braided into a mixed metal wire with a diameter of 6mm-8mm, and then cold rolled into a composite metal wire rod with a diameter of 5mm;
步骤二：气化：将复合金属线棒作为阳极导体，在直流电压36伏，电流1050安的条件下，与阴极形成电弧，使阳极导体的金属线棒尖端气化蒸发，产生烟雾状的金属原子团，银金属原子与铜原子中充分混合，形成气态合金；Step 2: Vaporization: Use the composite metal wire rod as the anode conductor, and form an arc with the cathode under the conditions of a DC voltage of 36 volts and a current of 1050 amperes, so that the tip of the anode conductor's metal rod is vaporized and vaporized to produce a smoke-like metal Atomic group, the silver metal atom and copper atom are fully mixed to form a gaseous alloy;
步骤三：冷凝：伴随金属气化的同时，用1～1.4倍音速的惰性气体气流将气态合金脱离高温区域，进行快速冷却，使金属从气态回到固态时，形成15～30纳米的合金颗粒；Step 3: Condensation: As the metal vaporizes, the gaseous alloy is separated from the high-temperature area with an inert gas flow of 1 to 1.4 times the speed of sound, and then rapidly cooled, so that when the metal returns from the gas state to the solid state, 15-30 nanometer alloy particles are formed ；
步骤四：收集：惰性气体气流携带合金颗粒进入过滤层进行气固分离并且收集，得到该纳米银铜合金材料。Step 4: Collection: the inert gas flow carries the alloy particles into the filter layer for gas-solid separation and collection to obtain the nano-silver-copper alloy material.
所述电弧的温度为5000℃以上，电弧的长度为30mm。The temperature of the arc is above 5000° C., and the length of the arc is 30 mm.
所述过滤层的制备方法包括以下步骤：The preparation method of the filter layer includes the following steps:
步骤T1、将聚合物溶解于混合溶剂中得到聚合物纺丝液，将聚合物纺丝液注入静电纺丝设备的同轴喷丝头的外管，将气体送入同轴喷丝头的内管，进行同轴静电纺丝，得到超细纤维；Step T1: Dissolve the polymer in the mixed solvent to obtain the polymer spinning solution, inject the polymer spinning solution into the outer tube of the coaxial spinneret of the electrostatic spinning equipment, and send the gas into the inner of the coaxial spinneret Tube, perform coaxial electrospinning to obtain superfine fibers;
步骤T2、将超细纤维直接沉积在接收电极板上，形成超细纤维过滤膜，得到该过滤层，其中，超细纤维的直径为0.1μm～9μm，所述超细纤维膜的厚度为0.5 mm～5mm，过滤孔的直径为0.1μm～7μm。Step T2: Directly deposit the ultrafine fibers on the receiving electrode plate to form an ultrafine fiber filter membrane to obtain the filter layer, wherein the diameter of the ultrafine fibers is 0.1 μm-9 μm, and the thickness of the ultrafine fiber membrane is 0.5 mm～5mm, the diameter of the filter hole is 0.1μm～7μm.
所述混合溶剂为氯仿、四氢呋喃、N，N-二甲基甲酰胺、N，N-二甲基乙酰胺、异丙醇、甲酸、乙酸、甲醇、乙醇、丁醇、二硫化碳和水中的两种，且由低沸点溶剂和高沸点溶剂两种组成，其中，所述低沸点溶剂的沸点低于60℃，所述高沸点溶剂的沸点高于所述低沸点溶剂，所述低沸点溶剂与所述高沸点溶剂的体积比为1～8:1；所述聚合物为聚羟基乙酸、聚乳酸、聚己内酯、聚甲醛、聚苯乙烯、聚甲基丙烯酸甲酯、聚环氧乙烷、脂肪族聚酯共聚物、聚酰胺、聚碳酸酯、聚氨酯、聚氧化乙烯、聚乙烯醇、醋酸纤维素、聚丙烯酸、聚丙烯酰胺、聚乙烯基吡咯烷酮或羟丙基纤维素。The mixed solvent is chloroform, tetrahydrofuran, N,N-dimethylformamide, N,N-dimethylacetamide, isopropanol, formic acid, acetic acid, methanol, ethanol, butanol, carbon disulfide and water. , And consists of a low-boiling point solvent and a high-boiling point solvent, wherein the low-boiling point solvent has a boiling point lower than 60°C, the high-boiling point solvent has a higher boiling point than the low-boiling point solvent, and the low-boiling point solvent is The volume ratio of the high boiling point solvent is 1-8:1; the polymer is polyglycolic acid, polylactic acid, polycaprolactone, polyoxymethylene, polystyrene, polymethyl methacrylate, polyethylene oxide , Aliphatic polyester copolymer, polyamide, polycarbonate, polyurethane, polyethylene oxide, polyvinyl alcohol, cellulose acetate, polyacrylic acid, polyacrylamide, polyvinylpyrrolidone or hydroxypropyl cellulose.
所述混合溶剂在本具体实施方式中可以为N，N-二甲基甲酰胺、甲酸两种；所述聚合物为聚甲基丙烯酸甲酯。In this embodiment, the mixed solvent can be N,N-dimethylformamide and formic acid; and the polymer is polymethyl methacrylate.
将实施例1的纳米银铜合金材料做成医用杀菌产品，经权威机构进行测试，对代表常规菌种的大肠杆菌和金黄色葡萄球菌，以及代表超级细菌的耐甲氧西林金黄色葡萄球菌，均达到99.15%的抗菌率；The nano-silver-copper alloy material of Example 1 was made into a medical sterilization product, and tested by an authoritative organization, and tested against Escherichia coli and Staphylococcus aureus, which represent conventional bacteria, and methicillin-resistant Staphylococcus aureus, which represents super bacteria. Both reach an antibacterial rate of 99.15%;
实施例2：Example 2:
请参阅图1～7所示，本实施例为一种纳米银铜合金材料，所述合金材料由以下重量百分比组分组成：Please refer to Figures 1-7, this embodiment is a nano-silver-copper alloy material, and the alloy material is composed of the following weight percentage components:
银                           60%；silver 60%;
其余为铜；The rest is copper;
所述的合金材料由粒径为15nm-30nm的纳米银铜合金颗粒混合构成，所述合金材料的外表面的铜金属原子形成为氧化铜。The alloy material is composed of a mixture of nano silver-copper alloy particles with a particle size of 15 nm-30 nm, and the copper metal atoms on the outer surface of the alloy material are formed as copper oxide.
所述的纳米银铜合金材料的制备方法，包括以下步骤：The preparation method of the nano-silver-copper alloy material includes the following steps:
步骤S1，将银与铜组合制备得到复合金属线棒；Step S1, combining silver and copper to prepare a composite metal wire rod;
步骤S2，将复合金属线棒作为直流电源的阳极导体，与阴极形成的电弧，使阳极导体的金属线棒尖端气化蒸发，产生烟雾状的金属原子团，银金属原子与铜金属原子充分混合，形成气态合金；其中，所述阳极导体与阴极形成的电弧的温度为5000℃以上；Step S2, the composite metal wire rod is used as the anode conductor of the DC power supply, and the arc formed with the cathode causes the tip of the anode conductor metal wire rod to vaporize and evaporate, producing a smoke-like metal atom group, and the silver metal atom and the copper metal atom are fully mixed, Forming a gaseous alloy; wherein the temperature of the arc formed by the anode conductor and the cathode is above 5000°C;
步骤S3，伴随金属气化的同时，用1～1 .4倍音速的惰性气体气流将气态合金进行冷却；Step S3, while the metal is vaporized, the gaseous alloy is cooled with an inert gas flow of 1 to 1.4 times the speed of sound;
步骤S4，收集在常温下冷却后的粉体，得到纳米银铜合金材料。Step S4, collecting the powder after cooling at normal temperature to obtain the nano-silver-copper alloy material.
所述惰性气体气流为氦气气流。The flow of inert gas is a flow of helium.
该纳米银铜合金材料包括以下重量份组分：60份银金属丝、40份铜金属丝；The nano-silver-copper alloy material includes the following components by weight: 60 parts of silver metal wire and 40 parts of copper metal wire;
该纳米银铜合金材料由以下步骤制备得到：The nano-silver-copper alloy material is prepared by the following steps:
步骤一：将银金属丝与铜金属丝制备得到复合金属线棒；Step 1: Prepare the silver metal wire and the copper metal wire to obtain a composite metal wire rod;
步骤二：将复合金属线棒作为直流电源的阳极导体，与阴极形成的电弧，使阳极导体的金属线棒尖端气化蒸发，产生烟雾状的金属原子团，银金属原子与铜原子中充分混合，形成气态合金；Step 2: Use the composite metal wire rod as the anode conductor of the DC power supply, and the arc formed with the cathode will vaporize and evaporate the tip of the metal wire rod of the anode conductor, producing a smoke-like metal atom group, and the silver metal atom and the copper atom are fully mixed. Forming a gaseous alloy;
步骤三：伴随金属气化的同时，用1～1.4倍音速的惰性气体气流将气态合金进行冷却；Step 3: At the same time as the metal is vaporized, the gaseous alloy is cooled with an inert gas flow of 1 to 1.4 times the speed of sound;
步骤四：惰性气体气流携带合金颗粒进入过滤层进行气固分离并且收集，得到该纳米银铜合金材料。Step 4: The inert gas flow carries the alloy particles into the filter layer for gas-solid separation and collection to obtain the nano-silver-copper alloy material.
所述银金属丝、铜金属丝的纯度均为99.9%，所述银金属丝、铜金属丝的的直径均为0.4mm～0.8mm。The purity of the silver metal wire and the copper metal wire are both 99.9%, and the diameter of the silver metal wire and the copper metal wire are both 0.4 mm to 0.8 mm.
一种纳米银铜合金材料的制备方法，包括以下步骤：A preparation method of nano-silver-copper alloy material includes the following steps:
步骤一：制备金属线棒：将银金属丝与铜金属丝编织成直径为6mm～8mm的混合金属线，经过冷轧压延成直径为5mm的复合金属线棒；Step 1: Preparation of metal wire rod: silver metal wire and copper metal wire are braided into a mixed metal wire with a diameter of 6mm-8mm, and then cold rolled into a composite metal wire rod with a diameter of 5mm;
步骤二：气化：将复合金属线棒作为阳极导体，在直流电压36伏，电流1050安的条件下，与阴极形成电弧，使阳极导体的金属线棒尖端气化蒸发，产生烟雾状的金属原子团，银金属原子与铜原子中充分混合，形成气态合金；Step 2: Vaporization: Use the composite metal wire rod as the anode conductor, and form an arc with the cathode under the conditions of a DC voltage of 36 volts and a current of 1050 amperes, so that the tip of the anode conductor's metal rod is vaporized and vaporized to produce a smoke-like metal Atomic group, the silver metal atom and copper atom are fully mixed to form a gaseous alloy;
步骤三：冷凝：伴随金属气化的同时，用1～1.4倍音速的惰性气体气流将气态合金脱离高温区域，进行快速冷却，使金属从气态回到固态时，形成15nm～30 nm的合金颗粒；Step 3: Condensation: With the vaporization of the metal, the gaseous alloy is separated from the high-temperature area with an inert gas flow of 1 to 1.4 times the speed of sound, and rapid cooling is performed to make the metal return to the solid state from the gas state to form alloy particles of 15 nm to 30 nm ；
步骤四：收集：惰性气体气流携带合金颗粒进入过滤层进行气固分离并且收集，得到该纳米银铜合金材料。Step 4: Collection: the inert gas flow carries the alloy particles into the filter layer for gas-solid separation and collection to obtain the nano-silver-copper alloy material.
在本发明中，通过利用了纳米银铜合金优良的导电性能，过滤层的过滤材料具有的静电吸附能力让银铜合金颗粒迅速形成软团聚效应，软团聚体的尺寸为50μm以上，从而能够把更多的银铜合金颗粒截留在软团聚体中，提升了成品率，也提高了材料的综合性能，其中过滤材料可以是耐酸碱耐高温的聚四氟乙烯与丙烯的共聚物，或者为氟乙烯与丙烯的共聚物。In the present invention, through the use of the excellent electrical conductivity of the nano silver-copper alloy, the electrostatic adsorption capacity of the filter material of the filter layer allows the silver-copper alloy particles to quickly form a soft agglomeration effect. The size of the soft agglomerate is 50μm or more, which can More silver-copper alloy particles are trapped in the soft aggregates, which improves the yield and the overall performance of the material. The filter material can be a copolymer of acid, alkali and high temperature resistant polytetrafluoroethylene and propylene, or Copolymer of vinyl fluoride and propylene.
在本发明中，所述合金颗粒的气固分离是通过过滤层的静电吸附形成软团聚效应实现的，所述过滤层获得静电吸附能力的方法为用电极对所述过滤层进行充电获得。In the present invention, the gas-solid separation of the alloy particles is achieved by the electrostatic adsorption of the filter layer to form a soft agglomeration effect, and the method for obtaining the electrostatic adsorption capacity of the filter layer is to charge the filter layer with an electrode.
所述电弧的温度为5000℃以上，电弧的长度为30mm。The temperature of the arc is above 5000° C., and the length of the arc is 30 mm.
所述过滤层的制备方法包括以下步骤：The preparation method of the filter layer includes the following steps:
步骤T1、将聚合物溶解于混合溶剂中得到聚合物纺丝液，将聚合物纺丝液注入静电纺丝设备的同轴喷丝头的外管，将气体送入同轴喷丝头的内管，进行同轴静电纺丝，得到超细纤维；Step T1: Dissolve the polymer in the mixed solvent to obtain the polymer spinning solution, inject the polymer spinning solution into the outer tube of the coaxial spinneret of the electrostatic spinning equipment, and send the gas into the inner of the coaxial spinneret Tube, perform coaxial electrospinning to obtain superfine fibers;
步骤T2、将超细纤维直接沉积在接收电极板上，形成超细纤维过滤膜，得到该过滤层，其中，超细纤维的直径为0.1μm～9μm，所述超细纤维膜的厚度为0.5 mm～5mm，过滤孔的直径为0.1μm～7μm。Step T2: Directly deposit the ultrafine fibers on the receiving electrode plate to form an ultrafine fiber filter membrane to obtain the filter layer, wherein the diameter of the ultrafine fibers is 0.1 μm-9 μm, and the thickness of the ultrafine fiber membrane is 0.5 mm～5mm, the diameter of the filter hole is 0.1μm～7μm.
所述混合溶剂为四氢呋喃、乙醇两种，所述聚合物为聚羟基乙酸。The mixed solvent is tetrahydrofuran and ethanol, and the polymer is polyglycolic acid.
将实施例2的纳米银铜合金材料做成医用杀菌产品，经权威机构进行测试，对代表常规菌种的大肠杆菌和金黄色葡萄球菌，以及代表超级细菌的耐甲氧西林金黄色葡萄球菌，均达到99.46%的抗菌率；The nano-silver-copper alloy material of Example 2 was made into a medical sterilization product, and tested by an authoritative organization to test Escherichia coli and Staphylococcus aureus, which represent conventional bacteria, and methicillin-resistant Staphylococcus aureus, which represents super bacteria. Both reach 99.46% antibacterial rate;
实施例3：Example 3:
请参阅图1～7所示，本实施例为一种纳米银铜合金材料，所述合金材料由以下重量百分比组分组成：Please refer to Figures 1-7, this embodiment is a nano-silver-copper alloy material, and the alloy material is composed of the following weight percentage components:
银                           80%；silver 80%;
其余为铜；The rest is copper;
所述的合金材料由粒径为15nm-50nm的纳米银铜合金颗粒混合构成，所述合金材料的外表面的铜金属原子形成为氧化铜。The alloy material is composed of a mixture of nano silver-copper alloy particles with a particle size of 15 nm-50 nm, and the copper metal atoms on the outer surface of the alloy material are formed as copper oxide.
所述的纳米银铜合金材料的制备方法，包括以下步骤：The preparation method of the nano-silver-copper alloy material includes the following steps:
步骤S1，将银与铜组合制备得到复合金属线棒；Step S1, combining silver and copper to prepare a composite metal wire rod;
步骤S2，将复合金属线棒作为直流电源的阳极导体，与阴极形成的电弧，使阳极导体的金属线棒尖端气化蒸发，产生烟雾状的金属原子团，银金属原子与铜金属原子充分混合，形成气态合金；其中，所述阳极导体与阴极形成的电弧的温度为5000℃以上；Step S2, the composite metal wire rod is used as the anode conductor of the DC power supply, and the arc formed with the cathode causes the tip of the anode conductor metal wire rod to vaporize and evaporate, producing a smoke-like metal atom group, and the silver metal atom and the copper metal atom are fully mixed, Forming a gaseous alloy; wherein the temperature of the arc formed by the anode conductor and the cathode is above 5000°C;
步骤S3，伴随金属气化的同时，用1～1 .4倍音速的惰性气体气流将气态合金进行冷却；Step S3, while the metal is vaporized, the gaseous alloy is cooled with an inert gas flow of 1 to 1.4 times the speed of sound;
步骤S4，收集在常温下冷却后的粉体，得到纳米银铜合金材料。Step S4, collecting the powder after cooling at normal temperature to obtain the nano-silver-copper alloy material.
所述惰性气体气流为氦气气流。The flow of inert gas is a flow of helium.
该纳米银铜合金材料包括以下重量份组分：80份银金属丝、20份铜金属丝；The nano-silver-copper alloy material includes the following components by weight: 80 parts of silver metal wire and 20 parts of copper metal wire;
该纳米银铜合金材料由以下步骤制备得到：The nano-silver-copper alloy material is prepared by the following steps:
步骤一：将银金属丝与铜金属丝制备得到复合金属线棒；Step 1: Prepare the silver metal wire and the copper metal wire to obtain a composite metal wire rod;
步骤二：将复合金属线棒作为直流电源的阳极导体，与阴极形成的电弧，使阳极导体的金属线棒尖端气化蒸发，产生烟雾状的金属原子团，银金属原子与铜原子中充分混合，形成气态合金；Step 2: Use the composite metal wire rod as the anode conductor of the DC power supply, and the arc formed with the cathode will vaporize and evaporate the tip of the metal wire rod of the anode conductor, producing a smoke-like metal atom group, and the silver metal atom and the copper atom are fully mixed. Forming a gaseous alloy;
步骤三：伴随金属气化的同时，用1～1.4倍音速的惰性气体气流将气态合金进行冷却；Step 3: At the same time as the metal is vaporized, the gaseous alloy is cooled with an inert gas flow of 1 to 1.4 times the speed of sound;
步骤四：惰性气体气流携带合金颗粒进入过滤层进行气固分离并且收集，得到该纳米银铜合金材料。Step 4: The inert gas flow carries the alloy particles into the filter layer for gas-solid separation and collection to obtain the nano-silver-copper alloy material.
所述银金属丝、铜金属丝的纯度均为99.9%，所述银金属丝、铜金属丝的的直径均为0.4mm～0.8mm。The purity of the silver metal wire and the copper metal wire are both 99.9%, and the diameter of the silver metal wire and the copper metal wire are both 0.4 mm to 0.8 mm.
一种纳米银铜合金材料的制备方法，包括以下步骤：A preparation method of nano-silver-copper alloy material includes the following steps:
步骤一：制备金属线棒：将银金属丝与铜金属丝编织成直径为6mm～8mm的混合金属线，经过冷轧压延成直径为5mm的复合金属线棒；Step 1: Preparation of metal wire rod: silver metal wire and copper metal wire are braided into a mixed metal wire with a diameter of 6mm-8mm, and then cold-rolled and rolled into a composite metal wire rod with a diameter of 5mm;
步骤二：气化：将复合金属线棒作为阳极导体，在直流电压36伏，电流1050安的条件下，与阴极形成电弧，使阳极导体的金属线棒尖端气化蒸发，产生烟雾状的金属原子团，银金属原子与铜原子中充分混合，形成气态合金；Step 2: Vaporization: Use the composite metal wire rod as the anode conductor, and form an arc with the cathode under the conditions of a DC voltage of 36 volts and a current of 1050 amperes, so that the tip of the anode conductor's metal rod is vaporized and vaporized to produce a smoke-like metal Atomic group, the silver metal atom and copper atom are fully mixed to form a gaseous alloy;
步骤三：冷凝：伴随金属气化的同时，用1～1.4倍音速的惰性气体气流将气态合金脱离高温区域，进行快速冷却，使金属从气态回到固态时，形成15nm～50nm的合金颗粒；Step 3: Condensation: With the vaporization of the metal, the gaseous alloy is separated from the high-temperature area with an inert gas flow of 1 to 1.4 times the speed of sound, and the gaseous alloy is rapidly cooled, so that when the metal returns from the gaseous state to the solid state, alloy particles of 15nm-50nm are formed;
步骤四：收集：惰性气体气流携带合金颗粒进入过滤层进行气固分离并且收集，得到该纳米银铜合金材料。Step 4: Collection: the inert gas flow carries the alloy particles into the filter layer for gas-solid separation and collection to obtain the nano-silver-copper alloy material.
所述电弧的温度为5000℃以上，电弧的长度为30mm。The temperature of the arc is above 5000° C., and the length of the arc is 30 mm.
所述过滤层的制备方法包括以下步骤：The preparation method of the filter layer includes the following steps:
步骤T1、将聚合物溶解于混合溶剂中得到聚合物纺丝液，将聚合物纺丝液注入静电纺丝设备的同轴喷丝头的外管，将气体送入同轴喷丝头的内管，进行同轴静电纺丝，得到超细纤维；Step T1: Dissolve the polymer in the mixed solvent to obtain the polymer spinning solution, inject the polymer spinning solution into the outer tube of the coaxial spinneret of the electrostatic spinning equipment, and send the gas into the inner of the coaxial spinneret Tube, perform coaxial electrospinning to obtain superfine fibers;
步骤T2、将超细纤维直接沉积在接收电极板上，形成超细纤维过滤膜，得到该过滤层，其中，超细纤维的直径为0.1μm～9μm，所述超细纤维膜的厚度为0.5 mm～5mm，过滤孔的直径为0.1μm～7μm。Step T2: Directly deposit the ultrafine fibers on the receiving electrode plate to form an ultrafine fiber filter membrane to obtain the filter layer, wherein the diameter of the ultrafine fibers is 0.1 μm-9 μm, and the thickness of the ultrafine fiber membrane is 0.5 mm～5mm, the diameter of the filter hole is 0.1μm～7μm.
所述混合溶剂为氯仿、乙酸两种，所述聚合物为羟丙基纤维素。The mixed solvent is chloroform and acetic acid, and the polymer is hydroxypropyl cellulose.
将实施例3的纳米银铜合金材料做成医用杀菌产品，经权威机构进行测试，对代表常规菌种的大肠杆菌和金黄色葡萄球菌，以及代表超级细菌的耐甲氧西林金黄色葡萄球菌，均达到99.87%的抗菌率。The nano-silver-copper alloy material of Example 3 was made into a medical sterilization product, and tested by an authoritative organization to test E. coli and Staphylococcus aureus, which represent conventional bacteria, and methicillin-resistant Staphylococcus aureus, which represents super bacteria. Both reached an antibacterial rate of 99.87%.
工业实用性Industrial applicability
在本说明书的描述中，参考术语“一个实施例”、“示例”、“具体示例”等的描述意指结合该实施例或示例描述的具体特征、结构、材料或者特点包含于本发明的至少一个实施例或示例中。在本说明书中，对上述术语的示意性表述不一定指的是相同的实施例或示例。而且，描述的具体特征、结构、材料或者特点可以在任何的一个或多个实施例或示例中以合适的方式结合。In the description of this specification, the description with reference to the terms "one embodiment", "example", "specific example", etc. means that the specific feature, structure, material or characteristic described in combination with the embodiment or example is included in at least the present invention. In one embodiment or example. In this specification, the schematic representations of the above-mentioned terms do not necessarily refer to the same embodiment or example. Moreover, the described specific features, structures, materials or characteristics can be combined in any one or more embodiments or examples in a suitable manner.
序列表自由内容Sequence Listing Free Content
以上内容仅仅是对本发明所作的举例和说明，所属本技术领域的技术人员对所描述的具体实施例做各种各样的修改或补充或采用类似的方式替代，只要不偏离发明或者超越本权利要求书所定义的范围，均应属于本发明的保护范围。The above content is merely an example and description of the present invention. Those skilled in the art make various modifications or additions to the specific embodiments described or use similar methods to replace them, as long as they do not deviate from the invention or exceed the rights. The scope defined by the requirements shall all belong to the protection scope of the present invention.

Claims (12)

  1. 一种纳米银铜合金材料，其特征在于，所述合金材料由以下重量百分比组分组成：A nano-silver-copper alloy material, characterized in that the alloy material is composed of the following weight percentage components:
    银                           40～80%；silver 40～80%;
    其余为铜；The rest is copper;
    所述的合金材料由粒径为15nm～50nm的纳米银铜合金颗粒混合构成，所述合金材料的外表面的铜金属原子形成为氧化铜。The alloy material is composed of a mixture of nano silver-copper alloy particles with a particle size of 15 nm-50 nm, and the copper metal atoms on the outer surface of the alloy material are formed as copper oxide.
  2. 根据权利要求1所述的纳米银铜合金材料，其特征在于，所述的纳米银铜合金颗粒的粒径为15nm～30nm。The nano-silver-copper alloy material of claim 1, wherein the particle size of the nano-silver-copper alloy particles is 15nm-30nm.
  3. 一种如权利要求1或2所述的纳米银铜合金材料的制备方法，其特征在于，包括以下步骤：A method for preparing nano-silver-copper alloy material according to claim 1 or 2, characterized in that it comprises the following steps:
    步骤S1，将银与铜组合制备得到复合金属线棒；Step S1, combining silver and copper to prepare a composite metal wire rod;
    步骤S2，将复合金属线棒作为直流电源的阳极导体，与阴极形成的电弧，使阳极导体的金属线棒尖端气化蒸发，产生烟雾状的金属原子团，银金属原子与铜金属原子充分混合，形成气态合金；其中，所述阳极导体与阴极形成的电弧的温度为5000℃以上；Step S2, the composite metal wire rod is used as the anode conductor of the DC power supply, and the arc formed with the cathode causes the tip of the anode conductor metal wire rod to vaporize and evaporate, producing a smoke-like metal atom group, and the silver metal atom and the copper metal atom are fully mixed, Forming a gaseous alloy; wherein the temperature of the arc formed by the anode conductor and the cathode is above 5000°C;
    步骤S3，伴随金属气化的同时，用1～1 .4倍音速的惰性气体气流将气态合金进行冷却；Step S3, while the metal is vaporized, the gaseous alloy is cooled with an inert gas flow of 1 to 1.4 times the speed of sound;
    步骤S4，收集在常温下冷却后的粉体，得到纳米银铜合金材料。Step S4, collecting the powder after cooling at normal temperature to obtain the nano-silver-copper alloy material.
  4. 根据权利要求3所述的纳米银铜合金材料的制备方法，其特征在于，所述步骤S3还包括：将冷却后的合金以及惰性气体气流与空气混合，通过管道进入粉体收集装置后进行气固分离。The method for preparing nano-silver-copper alloy materials according to claim 3, wherein the step S3 further comprises: mixing the cooled alloy and the inert gas flow with air, and then enter the powder collection device through the pipe to perform the gas Solid separation.
  5. 根据权利要求3所述的纳米银铜合金材料的制备方法，其特征在于，所述惰性气体气流为氦气气流。The method for preparing nano-silver-copper alloy material according to claim 3, wherein the inert gas flow is a helium flow.
  6. 一种纳米银铜合金材料的制备方法，其特征在于，包括以下步骤：A preparation method of nano-silver-copper alloy material is characterized in that it comprises the following steps:
    步骤一：制备金属线棒：将银金属丝与铜金属丝编织成直径为6mm～8mm的混合金属线，经过冷轧压延成直径为5mm的复合金属线棒；Step 1: Preparation of metal wire rod: silver metal wire and copper metal wire are braided into a mixed metal wire with a diameter of 6mm-8mm, and then cold-rolled and rolled into a composite metal wire rod with a diameter of 5mm;
    步骤二：气化：将复合金属线棒作为阳极导体，在直流电压36伏，电流1050安的条件下，与阴极形成电弧，使阳极导体的金属线棒尖端气化蒸发，产生烟雾状的金属原子团，银金属原子与铜原子中充分混合，形成气态合金；Step 2: Vaporization: Use the composite metal wire rod as the anode conductor, and form an arc with the cathode under the conditions of a DC voltage of 36 volts and a current of 1050 amperes, so that the tip of the anode conductor's metal rod is vaporized and vaporized to produce a smoke-like metal Atomic group, the silver metal atom and copper atom are fully mixed to form a gaseous alloy;
    步骤三：冷凝：伴随金属气化的同时，用1～1.4倍音速的惰性气体气流将气态合金脱离高温区域，进行快速冷却，使金属从气态回到固态时，形成15nm～50nm的合金颗粒；Step 3: Condensation: With the vaporization of the metal, the gaseous alloy is separated from the high-temperature area with an inert gas flow of 1 to 1.4 times the speed of sound, and the gaseous alloy is rapidly cooled, so that when the metal returns from the gaseous state to the solid state, alloy particles of 15nm-50nm are formed;
    步骤四：收集：惰性气体气流携带合金颗粒进入过滤层进行气固分离并且收集，得到该纳米银铜合金材料。Step 4: Collection: the inert gas flow carries the alloy particles into the filter layer for gas-solid separation and collection to obtain the nano-silver-copper alloy material.
  7. 根据权利要求6所述的纳米银铜合金材料的制备方法，其特征在于，所述过滤层中的过滤材料为聚四氟乙烯与丙烯的共聚物，或者为氟乙烯与丙烯的共聚物。The method for preparing a nano-silver-copper alloy material according to claim 6, wherein the filter material in the filter layer is a copolymer of polytetrafluoroethylene and propylene, or a copolymer of vinyl fluoride and propylene.
  8. 根据权利要求6所述的纳米银铜合金材料的制备方法，其特征在于，所述合金颗粒的气固分离是通过过滤层的静电吸附形成软团聚效应实现的，所述过滤层获得静电吸附能力的方法为用电极对所述过滤层进行充电获得。The method for preparing nano-silver-copper alloy material according to claim 6, wherein the gas-solid separation of the alloy particles is achieved by the electrostatic adsorption of the filter layer to form a soft agglomeration effect, and the filter layer obtains the electrostatic adsorption capacity The method is obtained by charging the filter layer with an electrode.
  9. 根据权利要求6所述的纳米银铜合金材料的制备方法，其特征在于，所述银金属丝、铜金属丝的纯度均为99.9%，所述银金属丝、铜金属丝的的直径均为0.4mm～0.8mm。The method for preparing a nano-silver-copper alloy material according to claim 6, wherein the purity of the silver metal wire and the copper metal wire are both 99.9%, and the diameters of the silver metal wire and the copper metal wire are both 0.4mm～0.8mm.
  10. 根据权利要求6所述的一种纳米银铜合金材料的制备方法，其特征在于，所述电弧的温度为5000℃以上，电弧的长度为30mm。The method for preparing a nano-silver-copper alloy material according to claim 6, wherein the temperature of the arc is above 5000°C, and the length of the arc is 30 mm.
  11. 根据权利要求6所述的纳米银铜合金材料的制备方法，其特征在于，所述过滤层的制备方法包括以下步骤：The preparation method of nano-silver-copper alloy material according to claim 6, wherein the preparation method of the filter layer comprises the following steps:
    步骤T1、将聚合物溶解于混合溶剂中得到聚合物纺丝液，将聚合物纺丝液注入静电纺丝设备的同轴喷丝头的外管，将气体送入同轴喷丝头的内管，进行同轴静电纺丝，得到超细纤维；Step T1: Dissolve the polymer in the mixed solvent to obtain the polymer spinning solution, inject the polymer spinning solution into the outer tube of the coaxial spinneret of the electrostatic spinning equipment, and send the gas into the inner of the coaxial spinneret Tube, perform coaxial electrospinning to obtain superfine fibers;
    步骤T2、将超细纤维直接沉积在接收电极板上，形成超细纤维过滤膜，得到该过滤层，其中，超细纤维的直径为0.1μm～9μm，所述超细纤维膜的厚度为0.5 mm～5mm，过滤孔的直径为0.1μm～7μm。Step T2: Depositing the ultrafine fibers directly on the receiving electrode plate to form an ultrafine fiber filter membrane to obtain the filter layer, wherein the diameter of the ultrafine fibers is 0.1 μm-9 μm, and the thickness of the ultrafine fiber membrane is 0.5 mm～5mm, the diameter of the filter hole is 0.1μm～7μm.
  12. 根据权利要求11所述的纳米银铜合金材料的制备方法，其特征在于，所述混合溶剂为氯仿、四氢呋喃、N，N-二甲基甲酰胺、N，N-二甲基乙酰胺、异丙醇、甲酸、乙酸、甲醇、乙醇、丁醇、二硫化碳和水中的两种，且由低沸点溶剂和高沸点溶剂两种组成，其中，所述低沸点溶剂的沸点低于60℃，所述高沸点溶剂的沸点高于所述低沸点溶剂，所述低沸点溶剂与所述高沸点溶剂的体积比为1～8:1；所述聚合物为聚羟基乙酸、聚乳酸、聚己内酯、聚甲醛、聚苯乙烯、聚甲基丙烯酸甲酯、聚环氧乙烷、脂肪族聚酯共聚物、聚酰胺、聚碳酸酯、聚氨酯、聚氧化乙烯、聚乙烯醇、醋酸纤维素、聚丙烯酸、聚丙烯酰胺、聚乙烯基吡咯烷酮或羟丙基纤维素。The method for preparing nano-silver-copper alloy materials according to claim 11, wherein the mixed solvent is chloroform, tetrahydrofuran, N,N-dimethylformamide, N,N-dimethylacetamide, iso Two kinds of propanol, formic acid, acetic acid, methanol, ethanol, butanol, carbon disulfide and water, and are composed of a low boiling point solvent and a high boiling point solvent, wherein the boiling point of the low boiling point solvent is lower than 60°C, the The boiling point of the high boiling point solvent is higher than the low boiling point solvent, and the volume ratio of the low boiling point solvent to the high boiling point solvent is 1-8:1; the polymer is polyglycolic acid, polylactic acid, polycaprolactone , Polyoxymethylene, polystyrene, polymethyl methacrylate, polyethylene oxide, aliphatic polyester copolymer, polyamide, polycarbonate, polyurethane, polyethylene oxide, polyvinyl alcohol, cellulose acetate, poly Acrylic acid, polyacrylamide, polyvinylpyrrolidone or hydroxypropyl cellulose.
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