WO2023109667A1 - Rare earth modified graphene copper-based composite material, preparation method thereof and application - Google Patents

Rare earth modified graphene copper-based composite material, preparation method thereof and application Download PDF

Info

Publication number
WO2023109667A1
WO2023109667A1 PCT/CN2022/137820 CN2022137820W WO2023109667A1 WO 2023109667 A1 WO2023109667 A1 WO 2023109667A1 CN 2022137820 W CN2022137820 W CN 2022137820W WO 2023109667 A1 WO2023109667 A1 WO 2023109667A1
Authority
WO
WIPO (PCT)
Prior art keywords
copper
graphene
rare earth
composite material
based composite
Prior art date
Application number
PCT/CN2022/137820
Other languages
French (fr)
Chinese (zh)
Inventor
薛冬峰
黄维扬
王鑫
王晓明
Original Assignee
深圳先进技术研究院
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 深圳先进技术研究院 filed Critical 深圳先进技术研究院
Publication of WO2023109667A1 publication Critical patent/WO2023109667A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/05—Mixtures of metal powder with non-metallic powder
    • 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
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/12—Both compacting and sintering
    • B22F3/14—Both compacting and sintering simultaneously
    • 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
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • 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
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60M—POWER SUPPLY LINES, AND DEVICES ALONG RAILS, FOR ELECTRICALLY- PROPELLED VEHICLES
    • B60M1/00—Power supply lines for contact with collector on vehicle
    • B60M1/12—Trolley lines; Accessories therefor
    • B60M1/13—Trolley wires
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/194—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • C22C32/001—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides
    • C22C32/0015—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides with only single oxides as main non-metallic constituents
    • C22C32/0021—Matrix based on noble metals, Cu or alloys thereof
    • 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
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06N—COMPUTING ARRANGEMENTS BASED ON SPECIFIC COMPUTATIONAL MODELS
    • G06N20/00—Machine learning
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
    • H01B1/026—Alloys based on copper
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • 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
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
    • 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
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy

Definitions

  • the invention belongs to the field of materials, in particular to the field of modification of graphene copper-based composite materials, in particular to a rare earth modified graphene copper-based composite material and its preparation method and application.
  • High-strength and high-conductivity copper alloy refers to a class of copper alloy materials that have both high strength and high conductivity, and are widely used in fields such as electric power, electronics, automobiles, home appliances, aerospace, military industry, and nuclear energy.
  • the "Thirteenth Five-Year Plan” pointed out: "In terms of new materials, accelerate the research and development of key strategic materials such as high-strength and high-conductivity copper alloys.”
  • more than 80% of domestic high-end high-strength and high-conductivity copper materials rely on imports, which has become a "stuck neck” problem that restricts the development of corresponding fields in my country.
  • Carbon can form different allotropes due to its valence, including one-dimensional carbon nanotubes, two-dimensional graphene, three-dimensional fullerenes, graphite, carbon fibers, diamonds, etc.
  • These carbon nanomaterials, especially carbon nano Tubes and graphene, due to their excellent intrinsic properties, are expected to be used as reinforcements to achieve ultrahigh conductivity of copper-based composites.
  • rare earth elements are called "industrial monosodium glutamate". Rare earth doping can refine the particle size of copper particles, toughen and strengthen, effectively improve the microstructure and structural defects of copper metal materials, and improve the mechanical strength and resistance of copper-based materials. Corrosive etc.
  • Rare earth modified graphene copper matrix composite material is a composite material that improves its mechanical strength and corrosion resistance without reducing its electrical and thermal conductivity by adding graphene and rare earth elements to copper, which can greatly reduce the contact line and locomotive
  • the loss caused by the sliding contact of the pantograph slide plate to transmit the current can be widely used in the field of high-speed electrified railways, and effectively improve my country's key core technology innovation capabilities.
  • Rare earth resources are important strategic resources in my country, and the high-value utilization of rare earth resources is urgent. With the continuous development of my country's high-tech field, the market capacity and added value of rare earth modified copper-based composite materials will also be further expanded.
  • "Nonferrous Metals Industry Development Plan (2016-2020)” pointed out that high-performance copper-based materials are the key basic materials for the development of high-tech fields in my country. In terms of market, my country's high-end integrated circuits, high-speed rail contact network and various high-performance cutting-edge power transmission copper-based composite materials such as high-conductivity copper alloy strips are heavily dependent on imports.
  • Copper-tin material contact wires and copper-magnesium material contact wires are used on high-speed railways above and above; Germany and Spain use copper-silver material contact wires at speeds of 250-300km/h, and copper-magnesium material contact wires at speeds above 300km/h.
  • the invention provides a rare earth modified graphene copper-based composite material and its preparation method and application.
  • the present invention adopts the intelligent creation technology of rare-earth modified graphene copper-based composite materials by machine learning (analog calculation is based on the model of high-strength and high-conductivity rare-earth modified graphene copper-based composite materials).
  • Copper crystal model and fully consider the influence mechanism of different crystal orientations, different exposed crystal planes and crystal defect density on conductivity, so as to realize the accurate prediction of copper crystal model with ultra-high conductivity.
  • combine DFT calculation with machine learning to study the influence mechanism of the introduction of rare earth elements on the conductivity, strength, hardness, wear resistance and corrosion resistance of copper matrix composites, and establish graphene crystallization in copper nanocrystal materials at different scales.
  • the research on the large-scale application of terminal products of graphene copper-based composite materials can be carried out, which can effectively amplify the copper mirror reaction and establish the macro-preparation process route of graphene copper nanocomposites.
  • the heat exchange between the press die and the extrusion wheel environment, as well as the thermomechanical coupling effect during the molding process can reveal the influence of different molding processes on the performance of end-application products, so as to explore the rules of continuous extrusion molding and realize the optimization of continuous extrusion process parameters. Optimized design.
  • the present invention is based on the following ideas to develop a preparation strategy for rare earth modified graphene copper-based composite materials with high strength and high conductivity: (1) first use machine learning to study the effect of rare earth element introduction on the conductivity, strength, hardness, The impact mechanism of wear resistance and corrosion resistance; (2) Construct a uniform and stable graphene-amine salt-copper ion complex system to effectively solve the problem of poor dispersion of graphene in the copper matrix, and achieve Good interfacial recombination between graphene and copper; (3) preparation of rare earth oxide dispersion-strengthened graphene-copper-based composites with dual nanostructures by mechanical alloying and plasma sintering, establishing and perfecting the plasma sintering mechanism of copper-based materials , performance regulation method and mechanism; (4) further reveal the interfacial recombination mechanism of graphene in the crystallization process of copper crystals, and clarify the wettability mechanism, interfacial bonding law, grain size and distribution of the matrix and reinforcement phase in the
  • a preparation method of rare earth modified graphene copper-based composite material comprising the steps of:
  • the graphene copper-based composite material is ball-milled with the rare earth oxide to obtain a mixed powder, and the obtained mixed powder is subjected to discharge plasma sintering to obtain the rare-earth modified graphene copper-based composite material.
  • the mass ratio of graphite to organic amine is 1:1-1:50;
  • the mass ratio of the first alcohol substance to graphite is 10:1-100:1;
  • the first alcoholic substance and the second alcoholic substance are sec-butanol;
  • the organic amine is selected from one or more of methylamine, ethylenediamine, isopropylamine, isobutylamine, cyclopropylamine, sec-butylamine-tert-butylamine, hexylamine, dodecylamine, hexadecylamine and octadecylamine.
  • the graphite is flake graphite.
  • the concentration of the copper salt in the mixture is 0.5 mol/L-50 mol/L;
  • the percentage of the graphene in the rare earth oxide-modified graphene-copper-based composite material is 0.1wt%-3wt%;
  • the molar ratio of the copper salt to the reducing agent is 1:1-1:10;
  • the copper salt is selected from one or more of copper sulfate, copper nitrate, copper acetate, copper chloride, copper isooctanoate and copper tartrate;
  • the reducing agent is selected from one or more of formaldehyde, acetaldehyde, hydrazine hydrate and sodium borohydride;
  • the second alcohol is sec-butanol.
  • the percentage of the rare earth oxide in the graphene copper matrix composite material modified by the rare earth oxide is 0.1 wt%-0.5wt%;
  • the rare earth oxide is selected from one or more of cerium oxide, lanthanum oxide, rhenium oxide, zirconium oxide and aluminum oxide.
  • step (1) the speed of ball milling in step (1) is 100-800 r/min, ball milling time is 1-36 h;
  • the mass ratio of balls to material is 5:1-20:1.
  • the rotational speed of the centrifugal separation in step (1) is 0-2000 r/min, 2000-6000 r/min, 6000-9000 r/min or >9000 r/min.
  • step (2) the stirring speed in step (2) is 200-800 r/min, and the time is 10-100 min;
  • the temperature of the reduction is 25-80° C., and the time is 10-100 min.
  • step (3) the speed of ball milling in step (3) is 100-800 r/min, ball milling time is 1-36 h;
  • the mass ratio of balls to materials during ball milling in step (3) is 10:1;
  • the pressure environment of the spark plasma sintering is 5-50 MPa, the temperature is 673-1073 K, and the time is 1-10 min;
  • it also includes washing and vacuum drying the mixed powder in step (3).
  • the rare earth modified graphene copper-based composite material prepared by the preparation method described in any one of the above.
  • the contact wire for high-speed rail with a speed of 400 km per hour.
  • the present invention provides a preparation method of rare earth modified graphene copper-based composite material, the specific steps include: separating graphite, organic amines and alcohols in different centrifugal intervals, and dispersing the obtained products in The dispersion liquid is obtained in alcohols, and then copper mirror reaction occurs with copper salt and reduced to prepare graphene copper-based composite materials, mixed with rare earth oxides and ball milled to obtain mixed powder, and finally spark plasma sintering is carried out to obtain rare earth modified graphene copper base composite material.
  • the amount of organic amines modified on the graphene surface can be regulated by changing the amount of organic amines added, and the type of organic amines on the surface of graphene can be regulated by changing the chain length of organic amines.
  • the graphene with specific size and layer number can be obtained by adjusting the interval of centrifugation.
  • the reduction reaction rate can be precisely regulated by changing the amount and type of organic amines on the graphene surface, such as increasing the number of organic amines on the graphene surface or increasing the chain of organic amines can effectively reduce the reduction reaction rate.
  • the plasma sintering mechanism, performance regulation method and mechanism of copper-based materials can be established and improved through the process research of plasma sintering to obtain rare earth modified graphene copper-based composite materials.
  • the present invention proposes to prepare a graphene-copper-based composite material by constructing a uniform and stable graphene-amine salt-copper ion system to solve the problem of poor interfacial bonding between graphene and copper; it proposes to use rare earth oxides to disperse
  • the design and preparation of reinforced copper-based composite materials can greatly improve its mechanical strength without significantly reducing its electrical conductivity. It meets the requirements for high-speed rail contact lines with a speed of 400km per hour.
  • the strength is not less than 800 MPa, the conductivity is not less than 110 IACS%, and the elongation
  • the rate is not less than 3.0%, all of which are superior to similar foreign products, and can occupy a clear advantage in the high-speed railway market.
  • the large-scale and stable preparation technology is a pilot line of copper contact wire for high-speed railways, with an annual production capacity of more than 1,000 tons. economic benefits.
  • Figure 1 is a scheme roadmap for the synthesis of rare earth modified graphene copper matrix composites.
  • step (3) the graphene copper-based composite material powder described in step (2) and 0.1 Wt% lanthanum oxide is mixed, and poured into the ball mill tank according to the ratio of ball:material mass ratio of about 10:1, set the speed at 400 r/min, ball mill 2 h, make it fully mixed evenly, and then wash the mixed product several times to remove excess impurities, and dry it in a vacuum oven at 60°C.
  • the dried composite powder was passed through the MPa and 973 Spark plasma sintering at K5 min, molded into a cake shape of ⁇ 20*10 to prepare rare earth-modified graphene-copper matrix composites.
  • step (2) Fully mix the graphene copper-based composite material powder described in step (2) with 0.5wt% cerium oxide, and pour it into the ball mill tank according to the ratio of ball:material mass ratio of about 10:1, and set the speed at 400 r/min, ball mill 2 h, make it fully mixed evenly, and then wash the mixed product several times to remove excess impurities, and dry it in a vacuum oven at 60°C.
  • the dried composite powder was passed through the MPa and 973 Spark plasma sintering at K5 min, molded into a cake shape of ⁇ 20*10 to prepare rare earth-modified graphene-copper matrix composites.
  • the rare earth modified graphene copper-based composite material obtained in the embodiment is prepared as a contact wire, and its performance is tested according to the corresponding national standards, and its inspection items, methods and performance requirements are shown in Table 1:
  • the contact angle between rare earth oxide and copper substrate is less than 60 degrees
  • the grain size is less than 1 micron
  • the material strength is not less than 800 MPa
  • conductivity not less than 110 IACS% the elongation rate is not less than 3.0%
  • the indicators are better than the level of similar foreign products. Its advantages can occupy a clear advantage in the high-speed railway market and have huge economic benefits.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Theoretical Computer Science (AREA)
  • Software Systems (AREA)
  • Manufacturing & Machinery (AREA)
  • Data Mining & Analysis (AREA)
  • Computer Vision & Pattern Recognition (AREA)
  • Mathematical Physics (AREA)
  • General Engineering & Computer Science (AREA)
  • Medical Informatics (AREA)
  • Evolutionary Computation (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Artificial Intelligence (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Nanotechnology (AREA)
  • Inorganic Chemistry (AREA)
  • Computing Systems (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Manufacture Of Alloys Or Alloy Compounds (AREA)

Abstract

A rare earth modified graphene copper-based composite material, a preparation method thereof, and an application. The specific steps of the preparation method comprise: after carrying out ball milling on graphite, an organic amine and an alcohol substance, carrying out separation in different centrifugal intervals; dispersing the obtained product into an alcohol substance to obtain a dispersion liquid, then carrying out a copper mirror reaction with a copper salt, and carrying out a reduction to prepare a graphene copper-based composite material; carrying out mixed ball milling with a rare earth oxide to obtain a mixed powder, and finally carrying out spark plasma sintering, to obtain a rare earth modified graphene copper-based composite material. The graphene copper-based composite material is prepared by constructing a uniform and stable graphene-amine salt-copper ion system, solving the problem of poor interface bonding between graphene and copper; with the design and preparation of a rare earth oxide dispersion strengthened copper-based composite material, the mechanical strength of a copper-based composite material can be greatly improved while the electrical conductivity is not obviously reduced.

Description

一种稀土改性石墨烯铜基复合材料及其制备方法和应用A kind of rare earth modified graphene copper-based composite material and its preparation method and application 技术领域technical field
本发明属于材料领域，具体涉及石墨烯铜基复合材料的改性领域，特别是一种稀土改性石墨烯铜基复合材料及其制备方法和应用。The invention belongs to the field of materials, in particular to the field of modification of graphene copper-based composite materials, in particular to a rare earth modified graphene copper-based composite material and its preparation method and application.
背景技术Background technique
高强高导铜合金是指同时具有高强度和高导电的一类铜合金材料，广泛应用于电力、电子、汽车、家电、航空航天、军工及核能等领域。“十三五”规划中指出：“在新材料方面，加快高强高导铜合金等关键战略材料的研发”。然而国内高端的高强高导铜材80%以上依赖进口，成为制约我国相应领域发展的“卡脖子”问题。因此，研发新型高强高导铜合金契合国家在关键战略材料领域的重大部署，有利于突破国外科技垄断、摆脱进口依赖，提高我国在相关领域的国际竞争力。High-strength and high-conductivity copper alloy refers to a class of copper alloy materials that have both high strength and high conductivity, and are widely used in fields such as electric power, electronics, automobiles, home appliances, aerospace, military industry, and nuclear energy. The "Thirteenth Five-Year Plan" pointed out: "In terms of new materials, accelerate the research and development of key strategic materials such as high-strength and high-conductivity copper alloys." However, more than 80% of domestic high-end high-strength and high-conductivity copper materials rely on imports, which has become a "stuck neck" problem that restricts the development of corresponding fields in my country. Therefore, the development of new high-strength and high-conductivity copper alloys is in line with the country's major deployment in the field of key strategic materials, which is conducive to breaking through foreign technology monopoly, getting rid of import dependence, and improving my country's international competitiveness in related fields.
近年来，随着铁路电气化的高速发展，铁路运输一再提速，对于电气化铁路用接触线性能要求越来越高。尤其是面向新一代时速400km高铁用铜基材料接触线需要在导电率、机械强度、耐磨耗性能、耐腐蚀性等诸多方面进一步改良。因此，发展高强度高导电的铜基复合材料已成为铜基新材料研究的新热点。在铜基复合材料体系中，增强体的选择是影响电导率最重要的因素。碳因其化合价能形成不同的同素异形体，包括一维的碳纳米管，二维的石墨烯，三维的富勒烯、以及石墨、碳纤维、金刚石等，这些碳纳米材料，尤其是碳纳米管和石墨烯，因其优异的本征性能，有望作为增强体实现铜基复合材料超高导电性能。此外，稀土元素被称为““工业味精”，稀土掺杂可细化铜颗粒粒径、增韧增强，有效改善铜金属材料的显微组织和结构缺陷，提高铜基材料的机械强度和抗腐蚀性等。In recent years, with the rapid development of railway electrification, the speed of railway transportation has been increased again and again, and the performance requirements for contact wires for electrified railways are getting higher and higher. Especially for the new generation of 400km/h high-speed rail, copper-based material contact wires need to be further improved in many aspects such as electrical conductivity, mechanical strength, wear resistance, and corrosion resistance. Therefore, the development of high-strength and high-conductivity copper-based composite materials has become a new hot spot in the research of copper-based new materials. In the copper matrix composite system, the choice of reinforcement is the most important factor affecting the electrical conductivity. Carbon can form different allotropes due to its valence, including one-dimensional carbon nanotubes, two-dimensional graphene, three-dimensional fullerenes, graphite, carbon fibers, diamonds, etc. These carbon nanomaterials, especially carbon nano Tubes and graphene, due to their excellent intrinsic properties, are expected to be used as reinforcements to achieve ultrahigh conductivity of copper-based composites. In addition, rare earth elements are called "industrial monosodium glutamate". Rare earth doping can refine the particle size of copper particles, toughen and strengthen, effectively improve the microstructure and structural defects of copper metal materials, and improve the mechanical strength and resistance of copper-based materials. Corrosive etc.
我国作为全球最大的装备制造和消费市场，发展新型高端铜基复合材料技术，有利于攻克制约我国高端铜基材料产业发展的关键技术难题。稀土改性石墨烯铜基复合材料是通过在铜中加入石墨烯和稀土元素来提高其机械强度和抗腐蚀性而又不降低其导电导热性的复合材料，能够极大限度降低接触线与机车受电弓滑板滑动接触传输电流产生的损耗，可广泛用于高速电气化铁路领域，切实提高我国关键核心技术创新能力。As the world's largest equipment manufacturing and consumer market, my country's development of new high-end copper-based composite material technology will help overcome key technical problems that restrict the development of my country's high-end copper-based material industry. Rare earth modified graphene copper matrix composite material is a composite material that improves its mechanical strength and corrosion resistance without reducing its electrical and thermal conductivity by adding graphene and rare earth elements to copper, which can greatly reduce the contact line and locomotive The loss caused by the sliding contact of the pantograph slide plate to transmit the current can be widely used in the field of high-speed electrified railways, and effectively improve my country's key core technology innovation capabilities.
稀土资源是我国的重要战略资源，稀土资源的高值化利用具有紧迫性。随着我国高新科技领域不断发展，稀土改性铜基复合材料的市场容量和附加值也将进一步扩大。《有色金属工业发展规划（2016—2020）》指出高性能铜基材料是我国重点发展高新技术领域的关键基础材料。市场方面，我国高端集成电路、高铁接触网路以及大型发电机所需各种高性能尖端输电铜基复合材料如高导电铜合金带材等严重依赖进口。Rare earth resources are important strategic resources in my country, and the high-value utilization of rare earth resources is urgent. With the continuous development of my country's high-tech field, the market capacity and added value of rare earth modified copper-based composite materials will also be further expanded. "Nonferrous Metals Industry Development Plan (2016-2020)" pointed out that high-performance copper-based materials are the key basic materials for the development of high-tech fields in my country. In terms of market, my country's high-end integrated circuits, high-speed rail contact network and various high-performance cutting-edge power transmission copper-based composite materials such as high-conductivity copper alloy strips are heavily dependent on imports.
广东在铜基板材、管材和线材方面已形成初步技术成果和产业化，但是在高端铜基材料研发积累和产业化方面明显不足。国内在铜基材料组分设计与加工制造方面存在卡脖子问题。另外，稀土是我国的战略资源，将高端铜基材料开发与稀土资源优势相结合开发铜基稀土复合材料，既可以促进铜行业结构调整和转型升级，助推铜产业的高端化发展；又可以拉动稀土精深加工发展，尤其是高丰度稀土的综合利用，从而形成铜基新材料产业链与稀土产业链相互融合、良性互动的格局。因此，研究和开发高强度高导电铜基复合材料符合国家当前优先发展高技术产业化政策，具有重大战略意义和价值。Guangdong has formed preliminary technical achievements and industrialization in copper-based materials, pipes and wires, but it is obviously insufficient in research and development accumulation and industrialization of high-end copper-based materials. Domestically, there are neck problems in the design and processing of copper-based material components. In addition, rare earths are my country's strategic resources. Combining the development of high-end copper-based materials with the advantages of rare earth resources to develop copper-based rare earth composite materials can not only promote the structural adjustment, transformation and upgrading of the copper industry, but also promote the high-end development of the copper industry; Stimulate the development of rare earth intensive processing, especially the comprehensive utilization of high-abundance rare earths, thus forming a pattern of mutual integration and positive interaction between the copper-based new material industry chain and the rare earth industry chain. Therefore, the research and development of high-strength and high-conductivity copper-based composite materials is in line with the current national policy of giving priority to the development of high-tech industrialization, and has great strategic significance and value.
纯铜的导电性能很好，但机械强度较低。长期以来，在铜接触线方面，一直存在高强度和高导电率之间的矛盾。人们在解决高强度和高导电率这对矛盾时，大都是在尽可能少的降低铜导线导电率的前提下，采用固溶强化、变形强化或沉淀强化来提高铜材强度。例如，高速轨道用接触导线一般添加一些高熔点、高硬度、低固溶度的金属，借助合金质点的纤维状排列来提高铜线材的强度和耐磨性。目前，世界各国高速电气化铁路均采用铜合金材料接触线。日本最初在时速210km的新干线上采用纯铜材料，由于耐磨性能差，运行两年左右就要换线，经过研究试验决定采用耐磨性能较好的铜锡材料接触线；法国在时速350km及以上的高速铁路上采用铜锡材料接触线和铜镁材料接触线；德国、西班牙在时速250-300km采用铜银材料接触线，在时速300km以上采用铜镁材料接触线。Pure copper conducts electricity very well, but has low mechanical strength. There has long been a tension between high strength and high conductivity when it comes to copper contact wires. When people solve the contradiction between high strength and high conductivity, most of them use solid solution strengthening, deformation strengthening or precipitation strengthening to improve the strength of copper on the premise of reducing the conductivity of copper wire as little as possible. For example, contact wires for high-speed rails generally add some metals with high melting point, high hardness, and low solid solubility, and use the fibrous arrangement of alloy particles to improve the strength and wear resistance of copper wires. At present, high-speed electrified railways all over the world use copper alloy contact wires. Japan initially used pure copper material on the Shinkansen with a speed of 210km/h. Due to poor wear resistance, the line needs to be replaced after two years of operation. After research and testing, it was decided to use copper-tin material contact wire with better wear resistance; France has a speed of 350km/h. Copper-tin material contact wires and copper-magnesium material contact wires are used on high-speed railways above and above; Germany and Spain use copper-silver material contact wires at speeds of 250-300km/h, and copper-magnesium material contact wires at speeds above 300km/h.
虽然我国在高速列车建设方面起步较晚，电力机车接触线制造技术相对落后，但是随着近些年我国高速电气化铁路建设迅猛发展，在高性能铜基接触线方面的研究取得可喜的成绩。自2003年起，我国自主创新的“上引连续挤压冷加工成型技术”应用于铜银合金材料接触线生产，已在电气化铁路中推广15000km以上，可适用于时速250-300km的高速电气化铁路；随后，进一步发展了铜镁合金接触线，其机械强度更高，并且仍保有较高的导电率，可适用于时速350km的高速电气化铁路。上述产品性能大大高于现行的铁道行业标准TB/T2809-2005《电气化铁道用铜及铜合金接触线》，优于国外同类产品水平，为我国高速电气化铁路发展提供了更好地条件。近年来，随着铁路电气化的高速发展，铁路运输一再提速，对于电气化铁路用接触线性能要求越来越高。尤其是面向新一代400km高铁用铜基材料接触线需要在导电率、机械强度、耐磨耗性能、耐腐蚀性等诸多方面进一步改良。因此，发展新型高端铜基复合材料技术逐渐成为铜基新材料研究的新热点。Although my country started late in the construction of high-speed trains and the manufacturing technology of contact wires for electric locomotives is relatively backward, with the rapid development of high-speed electrified railway construction in my country in recent years, gratifying achievements have been made in the research of high-performance copper-based contact wires. Since 2003, my country's self-innovated "upward continuous extrusion cold forming technology" has been applied to the production of contact wires made of copper-silver alloy materials, and has been promoted in electrified railways for more than 15,000km, and can be applied to high-speed electrified railways with a speed of 250-300km per hour; Subsequently, the copper-magnesium alloy contact wire was further developed, which has higher mechanical strength and still maintains high electrical conductivity, which can be applied to high-speed electrified railways with a speed of 350km per hour. The performance of the above products is much higher than the current railway industry standard TB/T2809-2005 "Copper and Copper Alloy Contact Wires for Electrified Railways", superior to similar foreign products, and provides better conditions for the development of my country's high-speed electrified railways. In recent years, with the rapid development of railway electrification, the speed of railway transportation has been increased again and again, and the performance requirements for contact wires for electrified railways are getting higher and higher. Especially for the new generation of 400km high-speed rail, copper-based material contact wires need to be further improved in many aspects such as electrical conductivity, mechanical strength, wear resistance, and corrosion resistance. Therefore, the development of new high-end copper-based composite material technology has gradually become a new hotspot in the research of new copper-based materials.
技术问题technical problem
为了发展新型高端铜基复合材料，尤其是发展高强高导的稀土改性石墨烯铜基复合材料，需要关注如何构建均匀稳定的“石墨烯-胺盐-铜离子”络合物体系，获得良好界面结合的石墨烯铜基复合材料，进而弥补因稀土氧化物掺杂导致导电性下降，以及如何实现稀土氧化物弥散强化石墨烯铜基材料界面复合方式，以获得具有高强高导稀土改性石墨烯铜基复合材料等问题。为了解决现有技术的不足，本发明提供了一种稀土改性石墨烯铜基复合材料及其制备方法和应用。In order to develop new high-end copper-based composite materials, especially the development of high-strength and high-conductivity rare-earth modified graphene copper-based composite materials, it is necessary to pay attention to how to construct a uniform and stable "graphene-amine salt-copper ion" complex system to obtain good results. Graphene-copper-based composite materials bonded at the interface, and then make up for the decrease in conductivity caused by rare earth oxide doping, and how to realize the interfacial compounding method of rare-earth oxide dispersion-strengthened graphene-copper-based materials to obtain rare-earth modified graphite with high strength and high conductivity Alkene copper-based composite materials and other issues. In order to solve the deficiencies of the prior art, the invention provides a rare earth modified graphene copper-based composite material and its preparation method and application.
技术解决方案technical solution
本发明采用机器学习稀土改性石墨烯铜基复合材料智能创制技术（模拟计算获得基于高强高导稀土改性石墨烯铜基复合材料模型），首先，通过DFT理论计算，构建基于高导电性的铜晶体模型，并充分考虑其不同晶体取向、不同暴露晶面以及晶体缺陷密度等对导电性的影响机制，实现对超高导电性能的铜晶体模型的精准预测。其次，将DFT计算与机器学习相结合，研究稀土元素引入对铜基复合材料导电性、强度、硬度、耐磨性及耐蚀性的影响机制，建立不同尺度下石墨烯在铜纳米晶体材料结晶过程中的界面跨尺度复合机制，进而揭示稀土氧化物和石墨烯引入对铜基复合材料导电性、强度、硬度及耐磨性等影响机理。最后，基于Sabatier原理，利用高通量DFT计算对所设计的模型进行高通量筛选，获得基于高强高导稀土改性石墨烯铜基复合材料模型，为实验室制备高强度高导电的石墨烯铜基复合材料提供理论指导。同时开展石墨烯铜基复合材料的终端产品规模化应用研究，可以将铜镜反应进行有效放大进而建立石墨烯铜纳米复合材料的宏量制备工艺路线，通过充分考虑挤压成型过程中材料与挤压模具、挤压轮环境之间的热交换，以及成型过程中的热力耦合效应，可以揭示不同成型工艺对终端应用产品性能的影响，以探索连续挤压成型规律，实现连续挤压工艺参数的优化设计。The present invention adopts the intelligent creation technology of rare-earth modified graphene copper-based composite materials by machine learning (analog calculation is based on the model of high-strength and high-conductivity rare-earth modified graphene copper-based composite materials). Copper crystal model, and fully consider the influence mechanism of different crystal orientations, different exposed crystal planes and crystal defect density on conductivity, so as to realize the accurate prediction of copper crystal model with ultra-high conductivity. Secondly, combine DFT calculation with machine learning to study the influence mechanism of the introduction of rare earth elements on the conductivity, strength, hardness, wear resistance and corrosion resistance of copper matrix composites, and establish graphene crystallization in copper nanocrystal materials at different scales. The cross-scale recombination mechanism of the interface in the process, and then reveal the influence mechanism of the introduction of rare earth oxides and graphene on the conductivity, strength, hardness and wear resistance of copper-based composites. Finally, based on the Sabatier principle, high-throughput screening of the designed model was carried out using high-throughput DFT calculations, and a high-strength and high-conductivity rare earth modified graphene copper-based composite material model was obtained to prepare high-strength and high-conductivity graphene for the laboratory Copper matrix composites provide theoretical guidance. At the same time, the research on the large-scale application of terminal products of graphene copper-based composite materials can be carried out, which can effectively amplify the copper mirror reaction and establish the macro-preparation process route of graphene copper nanocomposites. The heat exchange between the press die and the extrusion wheel environment, as well as the thermomechanical coupling effect during the molding process, can reveal the influence of different molding processes on the performance of end-application products, so as to explore the rules of continuous extrusion molding and realize the optimization of continuous extrusion process parameters. Optimized design.
本发明的是基于以下思路发展一种具有高强高导稀土改性石墨烯铜基复合材料的制备策略：（1）先利用机器学习研究稀土元素引入对铜基复合材料导电性、强度、硬度、耐磨性及耐蚀性的影响机制；（2）构建均匀稳定石墨烯-胺盐-铜离子络合物体系，有效解决石墨烯在铜基体中分散性较差的问题，在原子水平上实现石墨烯与铜之间良好的界面复合；（3）通过机械合金化和等离子烧结法制备具有双纳米结构的稀土氧化物弥散强化石墨烯铜基复合材料，建立并完善铜基材料的等离子烧结机理、性能调控方法及机理；（4）进一步揭示石墨烯在铜晶体结晶过程中界面跨尺度复合机制，阐明基体和增强相在烧结过程中润湿性机理、界面结合规律、晶粒尺寸及分布的演化规律；（5）最后建立双纳米结构铜基复合材料的烧结工艺，突破稀土改性石墨烯铜基复合材料均匀植入工业化制备技术难题，满足时速400km高铁用铜基材料接触线应用指标，助推铜基材料产业的高端化发展。The present invention is based on the following ideas to develop a preparation strategy for rare earth modified graphene copper-based composite materials with high strength and high conductivity: (1) first use machine learning to study the effect of rare earth element introduction on the conductivity, strength, hardness, The impact mechanism of wear resistance and corrosion resistance; (2) Construct a uniform and stable graphene-amine salt-copper ion complex system to effectively solve the problem of poor dispersion of graphene in the copper matrix, and achieve Good interfacial recombination between graphene and copper; (3) preparation of rare earth oxide dispersion-strengthened graphene-copper-based composites with dual nanostructures by mechanical alloying and plasma sintering, establishing and perfecting the plasma sintering mechanism of copper-based materials , performance regulation method and mechanism; (4) further reveal the interfacial recombination mechanism of graphene in the crystallization process of copper crystals, and clarify the wettability mechanism, interfacial bonding law, grain size and distribution of the matrix and reinforcement phase in the sintering process Evolution law; (5) Finally, the sintering process of dual nanostructured copper-based composite materials is established, which breaks through the technical problems of uniform implantation of rare-earth modified graphene copper-based composite materials in industrialized preparation, and meets the application indicators of copper-based material contact lines for 400km/h high-speed rail. Boost the high-end development of the copper-based material industry.
一种稀土改性石墨烯铜基复合材料的制备方法，包括如下步骤：A preparation method of rare earth modified graphene copper-based composite material, comprising the steps of:
（1）将石墨、有机胺和第一醇类物质一起球磨，球磨产物进行离心分离，所得离心产物分散于第二醇类物质中，得到表面修饰有机胺的石墨烯分散液；(1) ball milling graphite, organic amine and the first alcohol substance together, centrifuging the ball milled product, dispersing the obtained centrifuged product in the second alcohol substance, and obtaining a graphene dispersion liquid of the surface-modified organic amine;
（2）将铜盐溶解于第三醇类物质中，得到混合物，加入表面修饰有机胺的石墨烯分散液，搅拌处理，获得石墨烯—有机胺—铜络合物分散液，随后在还原剂作用下还原，形成石墨烯铜基复合材料；(2) Dissolve the copper salt in the third alcohol to obtain a mixture, add the graphene dispersion of surface-modified organic amine, and stir to obtain the graphene-organic amine-copper complex dispersion, and then add the graphene-organic amine-copper complex dispersion to the reducing agent Reduction under action to form a graphene copper-based composite material;
（3）将石墨烯铜基复合材料与稀土氧化物进行球磨，得到混合粉末，将所得混合粉末进行放电等离子烧结，即得稀土改性石墨烯铜基复合材料。(3) The graphene copper-based composite material is ball-milled with the rare earth oxide to obtain a mixed powder, and the obtained mixed powder is subjected to discharge plasma sintering to obtain the rare-earth modified graphene copper-based composite material.
进一步地，所述石墨与有机胺的质量比为1：1-1：50；Further, the mass ratio of graphite to organic amine is 1:1-1:50;
进一步地，所述第一醇类物质与石墨质量比为10：1-100：1；Further, the mass ratio of the first alcohol substance to graphite is 10:1-100:1;
优选地，所述第一醇类物质和第二醇类物质为仲丁醇；Preferably, the first alcoholic substance and the second alcoholic substance are sec-butanol;
优选地，所述有机胺选自甲胺、乙二胺、异丙胺、异丁胺、环丙胺、仲丁胺叔丁胺、己胺、十二胺、十六胺和十八胺中的一种或几种；Preferably, the organic amine is selected from one or more of methylamine, ethylenediamine, isopropylamine, isobutylamine, cyclopropylamine, sec-butylamine-tert-butylamine, hexylamine, dodecylamine, hexadecylamine and octadecylamine. Several;
优选地，所述石墨为鳞片石墨。Preferably, the graphite is flake graphite.
进一步地，所述铜盐在混合物中的浓度为0.5 mol/L-50 mol/L；Further, the concentration of the copper salt in the mixture is 0.5 mol/L-50 mol/L;
进一步地，所述石墨烯在稀土氧化物改性的石墨烯铜基复合材料的百分比为0.1wt%-3wt%；Further, the percentage of the graphene in the rare earth oxide-modified graphene-copper-based composite material is 0.1wt%-3wt%;
进一步地，所述铜盐与还原剂的摩尔比为1：1-1：10；Further, the molar ratio of the copper salt to the reducing agent is 1:1-1:10;
优选地，所述铜盐选自硫酸铜、硝酸铜、醋酸铜，氯化铜、异辛酸铜和酒石酸铜中的一种或几种；Preferably, the copper salt is selected from one or more of copper sulfate, copper nitrate, copper acetate, copper chloride, copper isooctanoate and copper tartrate;
优选地，所述还原剂选自甲醛、乙醛、水合肼和硼氢化钠中的一种或几种；Preferably, the reducing agent is selected from one or more of formaldehyde, acetaldehyde, hydrazine hydrate and sodium borohydride;
优选地，所述第二醇类物质为仲丁醇。Preferably, the second alcohol is sec-butanol.
进一步地，所述稀土氧化物在稀土氧化物改性的石墨烯铜基复合材料的百分比为0.1 wt%-0.5wt%；Further, the percentage of the rare earth oxide in the graphene copper matrix composite material modified by the rare earth oxide is 0.1 wt%-0.5wt%;
优选地，所述稀土氧化物选自氧化铈、氧化镧、氧化铼、氧化锆和氧化铝中的一种或几种。Preferably, the rare earth oxide is selected from one or more of cerium oxide, lanthanum oxide, rhenium oxide, zirconium oxide and aluminum oxide.
进一步地，步骤（1）中所述球磨的速度为100-800 r/min，球磨时间为1-36 h；Further, the speed of ball milling in step (1) is 100-800 r/min, ball milling time is 1-36 h;
优选地，步骤（1）中球磨时，球与料的质量比为5：1-20：1。Preferably, during ball milling in step (1), the mass ratio of balls to material is 5:1-20:1.
进一步地，步骤（1）中所述离心分离的转速为0-2000 r/min，2000-6000 r/min，6000-9000 r/min或＞9000 r/min。Further, the rotational speed of the centrifugal separation in step (1) is 0-2000 r/min, 2000-6000 r/min, 6000-9000 r/min or >9000 r/min.
进一步地，步骤（2）中搅拌处理的速度为200-800 r/min，时间为10-100 min；Further, the stirring speed in step (2) is 200-800 r/min, and the time is 10-100 min;
优选地，所述还原的温度为25-80℃，时间为10-100 min。Preferably, the temperature of the reduction is 25-80° C., and the time is 10-100 min.
进一步地，步骤（3）中所述球磨的速度为100-800 r/min，球磨时间为1-36 h；Further, the speed of ball milling in step (3) is 100-800 r/min, ball milling time is 1-36 h;
优选地，步骤（3）中球磨时球与料的质量比为10：1；Preferably, the mass ratio of balls to materials during ball milling in step (3) is 10:1;
优选地，所述放电等离子烧结的压力环境为5-50 MPa，温度为673-1073 K，时间为1-10 min；Preferably, the pressure environment of the spark plasma sintering is 5-50 MPa, the temperature is 673-1073 K, and the time is 1-10 min;
优选地，还包括对步骤（3）中所述混合粉末进行洗涤和真空干燥处理。Preferably, it also includes washing and vacuum drying the mixed powder in step (3).
以上任一项所述制备方法制备的稀土改性石墨烯铜基复合材料。The rare earth modified graphene copper-based composite material prepared by the preparation method described in any one of the above.
一种稀土改性石墨烯铜基复合材料在高铁用接触线中的应用；Application of a rare earth modified graphene copper-based composite material in contact wires for high-speed rail;
优选地，在时速400 km高铁用接触线中的应用。Preferably, it is applied in the contact wire for high-speed rail with a speed of 400 km per hour.
有益效果Beneficial effect
本发明的有益效果为：The beneficial effects of the present invention are:
（1）本发明提供了一种稀土改性石墨烯铜基复合材料的制备方法，具体步骤包括：将石墨、有机胺和醇类物质球后在不同的离心区间进行分离，将所得产物分散到醇类物质中得到分散液，然后与铜盐发生铜镜反应并还原制备石墨烯铜基复合材料，与稀土氧化物混合球磨得到混合粉末，最后进行放电等离子烧结，即得稀土改性石墨烯铜基复合材料。(1) The present invention provides a preparation method of rare earth modified graphene copper-based composite material, the specific steps include: separating graphite, organic amines and alcohols in different centrifugal intervals, and dispersing the obtained products in The dispersion liquid is obtained in alcohols, and then copper mirror reaction occurs with copper salt and reduced to prepare graphene copper-based composite materials, mixed with rare earth oxides and ball milled to obtain mixed powder, and finally spark plasma sintering is carried out to obtain rare earth modified graphene copper base composite material.
在用有机胺修饰石墨烯时，可以通过改变有机胺的添加量来调控石墨烯表面修饰有机胺的量，可以通过改变有机胺的链长来调控石墨烯表面有机胺的种类，可以通过球磨时间来获得改变石墨烯产量，可以通过离心分离区间调整来获得特定尺寸和层数的石墨烯。When modifying graphene with organic amines, the amount of organic amines modified on the graphene surface can be regulated by changing the amount of organic amines added, and the type of organic amines on the surface of graphene can be regulated by changing the chain length of organic amines. To change the output of graphene, the graphene with specific size and layer number can be obtained by adjusting the interval of centrifugation.
在利用铜镜反应并还原制备石墨烯铜基复合材料时，可以通过改变石墨烯表面有机胺的数量和种类来精准调控还原反应速率，例如增加石墨烯表面有机胺的数量或增加有机胺的链长均可以有效降低还原反应速率。When using copper mirror reaction and reduction to prepare graphene copper-based composites, the reduction reaction rate can be precisely regulated by changing the amount and type of organic amines on the graphene surface, such as increasing the number of organic amines on the graphene surface or increasing the chain of organic amines can effectively reduce the reduction reaction rate.
通过对等离子烧结获得稀土改性石墨烯铜基复合材料的工艺研究，可以建立并完善铜基材料的等离子烧结机理、性能调控方法及机理。The plasma sintering mechanism, performance regulation method and mechanism of copper-based materials can be established and improved through the process research of plasma sintering to obtain rare earth modified graphene copper-based composite materials.
（2）本发明提出通过构建均匀稳定的石墨烯-胺盐-铜离子体系来制备石墨烯铜基复合材料，解决石墨烯与铜之间界面结合性较差的问题；提出利用稀土氧化物弥散强化铜基复合材料的设计与制备，在不明显降低导电性的同时可以大大提高其机械强度，满足时速400km高铁接触线用强度不低于800 MPa，导电性不低于110 IACS%，伸长率不低于3.0%的指标，均优于国外同类产品水平，可以在高速铁路市场占据明显优势，在大规模稳定制备技术为高铁用铜接触线中试线，年产能大于1000吨，具有巨大的经济效益。(2) The present invention proposes to prepare a graphene-copper-based composite material by constructing a uniform and stable graphene-amine salt-copper ion system to solve the problem of poor interfacial bonding between graphene and copper; it proposes to use rare earth oxides to disperse The design and preparation of reinforced copper-based composite materials can greatly improve its mechanical strength without significantly reducing its electrical conductivity. It meets the requirements for high-speed rail contact lines with a speed of 400km per hour. The strength is not less than 800 MPa, the conductivity is not less than 110 IACS%, and the elongation The rate is not less than 3.0%, all of which are superior to similar foreign products, and can occupy a clear advantage in the high-speed railway market. The large-scale and stable preparation technology is a pilot line of copper contact wire for high-speed railways, with an annual production capacity of more than 1,000 tons. economic benefits.
附图说明Description of drawings
图1为稀土改性石墨烯铜基复合材料合成的方案路线图。Figure 1 is a scheme roadmap for the synthesis of rare earth modified graphene copper matrix composites.
本发明的实施方式Embodiments of the present invention
为了更清楚地理解本发明，现参照下列实施例及附图进一步描述本发明。实施例仅用于解释而不以任何方式限制本发明。实施例中，各原始试剂材料均可商购获得，未注明具体条件的实验方法为所属领域熟知的常规方法和常规条件，或按照仪器制造商所建议的条件。In order to understand the present invention more clearly, the present invention will now be further described with reference to the following examples and accompanying drawings. The examples are for illustration only and do not limit the invention in any way. In the examples, each original reagent material can be obtained commercially, and the experimental methods without specific conditions are conventional methods and conventional conditions well known in the art, or according to the conditions suggested by the instrument manufacturer.
实施例1Example 1
（1）称取1 g的鳞片石墨材料和200 mg十二胺，量取10 ml的仲丁醇，将鳞片石墨、十二胺以及仲丁醇放入100 ml的球磨罐中，以400 r/min的转速球磨24 h，将球磨产物分别在不同的离心区间（0—2000 r/min,2000—6000 r/min,6000—9000 r/min，＞9000 r/min）进行分离，得到不同离心区间的石墨烯产物，随后将9500 r/min的离心产物进行离心和洗涤，循环3次，将最后的十二胺修饰的石墨烯产物重新分散到仲丁醇中备用，即得到表面修饰十二胺的石墨烯分散液。(1) Weigh 1 g of flake graphite material and 200 mg dodecylamine, measure 10 ml of sec-butanol, put flake graphite, dodecylamine and sec-butanol in 100 ml of ball mill jar, ball milled at 400 r/min for 24 h, the ball milled products were in different centrifugal intervals (0-2000 r/min, 2000—6000 r/min, 6000—9000 r/min, >9000 r/min) for separation to obtain graphene products in different centrifugation intervals, and then 9500 The centrifuged product of r/min was centrifuged and washed, and circulated 3 times, and the last dodecylamine-modified graphene product was redispersed in sec-butanol for subsequent use, to obtain a surface-modified graphene dispersion of dodecylamine.
（2）利用在石墨烯分散的有机体系中的铜镜反应制备石墨烯铜基复合材料，首先将31.4162 g Cu(CH 3COO) 2•H 2O溶解到50 mL仲丁醇中，形成Cu(CH 3COO) 2•H 2O的有机溶液。随后，加入步骤（1）所述表面修饰十二胺的石墨烯分散液，充分搅拌使石墨烯表面修饰的十二胺与铜离子络合形成高度均匀稳定的石墨烯—有机胺—铜络合物分散液，随后在25 ml乙醛作用下还原，形成石墨烯铜基复合材料。 (2) Graphene-copper matrix composites were prepared by copper mirror reaction in graphene-dispersed organic systems. First, 31.4162 g Cu(CH 3 COO) 2 •H 2 O was dissolved in 50 mL sec-butanol to form Cu (CH 3 COO) 2 •H 2 O in organic solution. Subsequently, add the graphene dispersion of surface-modified dodecylamine described in step (1), and fully stir to complex the dodecylamine surface-modified on the graphene with copper ions to form a highly uniform and stable graphene-organic amine-copper complex The material dispersion was then reduced under the action of 25 ml acetaldehyde to form a graphene-copper matrix composite.
（3）将步骤（2）所述石墨烯铜基复合材料粉末与0.1 wt%氧化镧分混合，并按照球：料质量比约为10：1的比例倒入球磨罐中，设置转速为400 r/min，球磨2 h，使其充分混合均匀，然后将混合产物进行多次洗涤，去掉多余的杂质，并于60℃真空干燥箱中干燥。将干燥后的复合材料粉末通过在30 MPa和973 K下放电等离子烧结5 min，模制成Φ20*10的饼状，制备稀土改性石墨烯铜基复合材料。(3) the graphene copper-based composite material powder described in step (2) and 0.1 Wt% lanthanum oxide is mixed, and poured into the ball mill tank according to the ratio of ball:material mass ratio of about 10:1, set the speed at 400 r/min, ball mill 2 h, make it fully mixed evenly, and then wash the mixed product several times to remove excess impurities, and dry it in a vacuum oven at 60°C. The dried composite powder was passed through the MPa and 973 Spark plasma sintering at K5 min, molded into a cake shape of Φ20*10 to prepare rare earth-modified graphene-copper matrix composites.
实施例2Example 2
（1）称取1g的鳞片石墨材料和200 mg十二胺，量取10 ml的仲丁醇，将鳞片石墨、十二胺以及仲丁醇放入100 ml的球磨罐中，以400 r/min的转速球磨24 h，将球磨产物分别在不同的离心区间（0—2000 r/min,2000—6000 r/min,6000—9000 r/min，＞9000 r/min）进行分离，得到不同离心区间的石墨烯产物，随后将8000 r/min不同区间的离心产物进行离心和洗涤，循环3次，将最后的十二胺修饰的石墨烯产物重新分散到仲丁醇中备用，即得到表面修饰十二胺的石墨烯分散液。(1) Weigh 1g of flake graphite material and 200 mg dodecylamine, measure 10 ml of sec-butanol, put flake graphite, dodecylamine and sec-butanol in 100 ml of ball mill jar to 400 r/min speed ball mill 24 h, the ball milled products were in different centrifugal intervals (0-2000 r/min, 2000—6000 r/min, 6000—9000 r/min, >9000 r/min) for separation to obtain graphene products in different centrifugation intervals, and then 8000 The centrifuged products in different intervals of r/min were centrifuged and washed, and the cycle was repeated 3 times, and the final dodecylamine-modified graphene product was redispersed in sec-butanol for later use, and the surface-modified graphene dispersion of dodecylamine was obtained.
（2）利用在石墨烯分散的有机体系中的铜镜反应制备石墨烯铜基复合材料，首先将15.7081 g Cu(CH 3COO) 2•H 2O溶解到10 mL仲丁醇中，形成Cu(CH 3COO) 2•H 2O的有机溶液。随后，加入步骤（1）所述表面修饰十二胺的石墨烯分散液，充分搅拌使石墨烯表面修饰的十二胺与铜离子络合形成高度均匀稳定的石墨烯—有机胺—铜络合物分散液，随后在10 ml甲醛作用下还原，形成石墨烯铜基复合材料。 (2) Graphene-copper matrix composites were prepared by copper mirror reaction in graphene-dispersed organic systems. First, 15.7081 g Cu(CH 3 COO) 2 •H 2 O was dissolved in 10 mL sec-butanol to form Cu (CH 3 COO) 2 •H 2 O in organic solution. Subsequently, add the graphene dispersion of surface-modified dodecylamine described in step (1), and fully stir to complex the dodecylamine surface-modified on the graphene with copper ions to form a highly uniform and stable graphene-organic amine-copper complex The material dispersion was then reduced under the action of 10 ml formaldehyde to form a graphene-copper matrix composite.
（2）将步骤（2）所述石墨烯铜基复合材料粉末与0.5wt%的氧化铈充分混合，并按照球：料质量比约为10：1的比例倒入球磨罐中，设置转速为400 r/min，球磨2 h，使其充分混合均匀，然后将混合产物进行多次洗涤，去掉多余的杂质，并于60℃真空干燥箱中干燥。将干燥后的复合材料粉末通过在30 MPa和973 K下放电等离子烧结5 min，模制成Φ20*10的饼状，制备稀土改性石墨烯铜基复合材料。(2) Fully mix the graphene copper-based composite material powder described in step (2) with 0.5wt% cerium oxide, and pour it into the ball mill tank according to the ratio of ball:material mass ratio of about 10:1, and set the speed at 400 r/min, ball mill 2 h, make it fully mixed evenly, and then wash the mixed product several times to remove excess impurities, and dry it in a vacuum oven at 60°C. The dried composite powder was passed through the MPa and 973 Spark plasma sintering at K5 min, molded into a cake shape of Φ20*10 to prepare rare earth-modified graphene-copper matrix composites.
实验例Experimental example
将实施例得到的稀土改性石墨烯铜基复合材料制备为接触线，并按照相应的国家标准测试其性能，其检验项目及方法和性能要求如表1所示：The rare earth modified graphene copper-based composite material obtained in the embodiment is prepared as a contact wire, and its performance is tested according to the corresponding national standards, and its inspection items, methods and performance requirements are shown in Table 1:
表1 石墨烯铜基材料可靠性指标及应用环境指标Table 1 Reliability indicators and application environment indicators of graphene copper-based materials
Figure dest_path_image001
Figure dest_path_image001
检测结果表明：稀土氧化物与铜基体接触角小于60度、晶粒尺寸小于1微米，材料强度不低于800 MPa，导电性不低于110 IACS%，伸长率不低于3.0%，各项指标优于国外同类产品水平，其优势可以在高速铁路市场占据明显优势，具有巨大的经济效益。The test results show that: the contact angle between rare earth oxide and copper substrate is less than 60 degrees, the grain size is less than 1 micron, and the material strength is not less than 800 MPa, conductivity not less than 110 IACS%, the elongation rate is not less than 3.0%, and the indicators are better than the level of similar foreign products. Its advantages can occupy a clear advantage in the high-speed railway market and have huge economic benefits.
显然，上述实施例仅仅是为清楚地说明所作的举例，而并非对实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。而由此所引伸出的显而易见的变化或变动仍处于本发明创造的保护范围之中。Apparently, the above-mentioned embodiments are only examples for clear description, rather than limiting the implementation. For those of ordinary skill in the art, other changes or changes in different forms can be made on the basis of the above description. It is not necessary and impossible to exhaustively list all the implementation manners here. And the obvious changes or changes derived therefrom are still within the scope of protection of the present invention.

Claims (10)

  1. 一种稀土改性石墨烯铜基复合材料的制备方法，其特征在于，包括如下步骤：A kind of preparation method of rare earth modified graphene copper-based composite material, is characterized in that, comprises the steps:
    （1）将石墨、有机胺和第一醇类物质一起球磨，球磨产物进行离心分离，所得离心产物分散于第二醇类物质中，得到表面修饰有机胺的石墨烯分散液；(1) ball milling graphite, organic amine and the first alcohol substance together, centrifuging the ball milled product, dispersing the obtained centrifuged product in the second alcohol substance, and obtaining a graphene dispersion liquid of the surface-modified organic amine;
    （2）将铜盐溶解于第三醇类物质中，得到混合物，加入表面修饰有机胺的石墨烯分散液，搅拌处理，获得石墨烯—有机胺—铜络合物分散液，随后在还原剂作用下还原，形成石墨烯铜基复合材料；(2) Dissolve the copper salt in the third alcohol to obtain a mixture, add the graphene dispersion of surface-modified organic amine, and stir to obtain the graphene-organic amine-copper complex dispersion, and then add the graphene-organic amine-copper complex dispersion to the reducing agent Reduction under action to form a graphene copper-based composite material;
    （3）将石墨烯铜基复合材料与稀土氧化物进行球磨，得到混合粉末，将所得混合粉末进行放电等离子烧结，即得稀土改性石墨烯铜基复合材料。(3) The graphene copper-based composite material is ball-milled with the rare earth oxide to obtain a mixed powder, and the obtained mixed powder is subjected to discharge plasma sintering to obtain the rare-earth modified graphene copper-based composite material.
  2. 如权利要求1所述的制备方法，其特征在于，所述石墨与有机胺的质量比为1：1-1：50；The preparation method according to claim 1, wherein the mass ratio of the graphite to the organic amine is 1:1-1:50;
    所述第一醇类物质与石墨质量比为10：1-100：1；The mass ratio of the first alcohol substance to graphite is 10:1-100:1;
    优选地，所述第一醇类物质和第二醇类物质为仲丁醇；Preferably, the first alcoholic substance and the second alcoholic substance are sec-butanol;
    优选地，所述有机胺选自甲胺、乙二胺、异丙胺、异丁胺、环丙胺、仲丁胺叔丁胺、己胺、十二胺、十六胺和十八胺中的一种或几种；Preferably, the organic amine is selected from one or more of methylamine, ethylenediamine, isopropylamine, isobutylamine, cyclopropylamine, sec-butylamine-tert-butylamine, hexylamine, dodecylamine, hexadecylamine and octadecylamine. Several;
    优选地，所述石墨为鳞片石墨。Preferably, the graphite is flake graphite.
  3. 如权利要求1所述的制备方法，其特征在于，所述铜盐在混合物中的浓度为0.5 mol/L-50 mol/L；preparation method as claimed in claim 1, is characterized in that, the concentration of described copper salt in mixture is 0.5 mol/L-50 mol/L;
    所述石墨烯在稀土氧化物改性的石墨烯铜基复合材料的百分比为0.1wt%-3wt%；The percentage of the graphene in the graphene-copper-based composite material modified by rare earth oxide is 0.1wt%-3wt%;
    所述铜盐与还原剂的摩尔比为1：1-1：10；The molar ratio of the copper salt to the reducing agent is 1:1-1:10;
    优选地，所述铜盐选自硫酸铜、硝酸铜、醋酸铜，氯化铜、异辛酸铜和酒石酸铜中的一种或几种；Preferably, the copper salt is selected from one or more of copper sulfate, copper nitrate, copper acetate, copper chloride, copper isooctanoate and copper tartrate;
    优选地，所述还原剂选自甲醛、乙醛、水合肼和硼氢化钠中的一种或几种；Preferably, the reducing agent is selected from one or more of formaldehyde, acetaldehyde, hydrazine hydrate and sodium borohydride;
    优选地，所述第二醇类物质为仲丁醇。Preferably, the second alcohol is sec-butanol.
  4. 如权利要求1所述的制备方法，其特征在于，所述稀土氧化物在稀土氧化物改性的石墨烯铜基复合材料的百分比为0.1 wt%-0.5wt%；The preparation method according to claim 1, wherein the percentage of the rare earth oxide in the graphene copper-based composite material modified by the rare earth oxide is 0.1 wt%-0.5wt%;
    优选地，所述稀土氧化物选自氧化铈、氧化镧、氧化铼、氧化锆和氧化铝中的一种或几种。Preferably, the rare earth oxide is selected from one or more of cerium oxide, lanthanum oxide, rhenium oxide, zirconium oxide and aluminum oxide.
  5. 如权利要求1所述的制备方法，其特征在于，步骤（1）中所述球磨的速度为100-800 r/min，球磨时间为1-36 h；The preparation method according to claim 1, characterized in that the ball milling speed in step (1) is 100-800 r/min, ball milling time is 1-36 h;
    优选地，步骤（1）中球磨时，球与料的质量比为5：1-20：1。Preferably, during ball milling in step (1), the mass ratio of balls to material is 5:1-20:1.
  6. 如权利要求1所述的制备方法，其特征在于，步骤（1）中所述离心分离的转速为0-2000 r/min，2000-6000 r/min，6000-9000 r/min或＞9000 r/min。The preparation method according to claim 1, characterized in that the rotational speed of the centrifugal separation in step (1) is 0-2000 r/min, 2000-6000 r/min, 6000-9000 r/min or >9000 r /min.
  7. 如权利要求1所述的制备方法，其特征在于，步骤（2）中搅拌处理的速度为200-800 r/min，时间为10-100 min；The preparation method according to claim 1, characterized in that, the speed of the stirring treatment in step (2) is 200-800 r/min, and the time is 10-100 min;
    优选地，所述还原的温度为25-80℃，时间为10-100 min。Preferably, the temperature of the reduction is 25-80° C., and the time is 10-100 min.
  8. 如权利要求1所述的制备方法，其特征在于，步骤（3）中所述球磨的速度为100-800 r/min，球磨时间为1-36 h；The preparation method according to claim 1, characterized in that the ball milling speed in step (3) is 100-800 r/min, ball milling time is 1-36 h;
    优选地，步骤（3）中球磨时球与料的质量比为10：1；Preferably, the mass ratio of balls to materials during ball milling in step (3) is 10:1;
    优选地，所述放电等离子烧结的压力环境为5-50 MPa，温度为673-1073 K，时间为1-10 min；Preferably, the pressure environment of the spark plasma sintering is 5-50 MPa, the temperature is 673-1073 K, and the time is 1-10 min;
    优选地，还包括对步骤（3）中所述混合粉末进行洗涤和真空干燥处理。Preferably, it also includes washing and vacuum drying the mixed powder in step (3).
  9. 权利要求1-8任一项所述制备方法制备的稀土改性石墨烯铜基复合材料。The rare earth modified graphene copper matrix composite material prepared by the preparation method described in any one of claims 1-8.
  10. 一种稀土改性石墨烯铜基复合材料在高铁用接触线中的应用；Application of a rare earth modified graphene copper-based composite material in contact wires for high-speed rail;
    优选地，在时速400 km高铁用接触线中的应用。Preferably, at a speed of 400 Application of contact wire for km high-speed rail.
PCT/CN2022/137820 2021-12-15 2022-12-09 Rare earth modified graphene copper-based composite material, preparation method thereof and application WO2023109667A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202111538654.6A CN114480899B (en) 2021-12-15 2021-12-15 Rare earth modified graphene copper-based composite material and preparation method and application thereof
CN202111538654.6 2021-12-15

Publications (1)

Publication Number Publication Date
WO2023109667A1 true WO2023109667A1 (en) 2023-06-22

Family

ID=81494147

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2022/137820 WO2023109667A1 (en) 2021-12-15 2022-12-09 Rare earth modified graphene copper-based composite material, preparation method thereof and application

Country Status (2)

Country Link
CN (1) CN114480899B (en)
WO (1) WO2023109667A1 (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114480899B (en) * 2021-12-15 2022-12-06 深圳先进技术研究院 Rare earth modified graphene copper-based composite material and preparation method and application thereof
CN116079014B (en) * 2023-02-13 2023-07-04 常州罗尼斯特种导体有限责任公司 High-strength high-conductivity silver-copper alloy wire and preparation method thereof
CN116043054B (en) * 2023-03-22 2023-06-16 厦门凯纳石墨烯技术股份有限公司 Modified graphene composite metal material and preparation method thereof

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102436862A (en) * 2011-09-08 2012-05-02 西北师范大学 Graphene/nanometer copper electric conducting composite material and preparation thereof
CN103952588A (en) * 2014-05-08 2014-07-30 江西理工大学 High-strength and high-conductivity graphene copper-based composite material and preparation method thereof
KR20150134445A (en) * 2014-05-21 2015-12-02 인하대학교 산학협력단 Method for reforming of graphene and method for manufacturing nanocomposite materials using the same
EA201501058A1 (en) * 2015-09-25 2017-03-31 Научно-Исследовательское Учреждение "Институт Ядерных Проблем" Белорусского Государственного Университета (Нии Яп Бгу) METHOD FOR OBTAINING COMPOSITION NANOPARTICLES GRAPHEN / COPPER
CN107164020A (en) * 2017-04-06 2017-09-15 江苏大学 A kind of graphene poly-dopamine copper nano composite material and preparation method thereof
CN110695372A (en) * 2019-10-10 2020-01-17 天津大学 Preparation method for improving copper-graphene interface by using rare earth elements
CN114480899A (en) * 2021-12-15 2022-05-13 深圳先进技术研究院 Rare earth modified graphene copper-based composite material and preparation method and application thereof

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
HUP0001984A3 (en) * 2000-05-23 2002-05-28 Kourganov Konstantin Copper-base contact material, contact stud and method for producing contact stud
CN104862512B (en) * 2015-04-21 2018-03-06 中国科学院宁波材料技术与工程研究所 Improve graphene and the method for Copper substrate adhesion in copper-base graphite alkene composite
CN107723500B (en) * 2017-09-29 2019-02-12 江西理工大学 A kind of graphene-aluminum oxide mixing enhancement copper-base composite material and preparation method thereof
CN109881038B (en) * 2019-03-08 2021-01-01 深圳先进技术研究院 Heat-conducting electromagnetic shielding composite material and preparation method thereof
CN113061768B (en) * 2021-03-22 2023-08-25 中南大学 Preparation method of dispersion strengthening copper-based composite material

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102436862A (en) * 2011-09-08 2012-05-02 西北师范大学 Graphene/nanometer copper electric conducting composite material and preparation thereof
CN103952588A (en) * 2014-05-08 2014-07-30 江西理工大学 High-strength and high-conductivity graphene copper-based composite material and preparation method thereof
KR20150134445A (en) * 2014-05-21 2015-12-02 인하대학교 산학협력단 Method for reforming of graphene and method for manufacturing nanocomposite materials using the same
EA201501058A1 (en) * 2015-09-25 2017-03-31 Научно-Исследовательское Учреждение "Институт Ядерных Проблем" Белорусского Государственного Университета (Нии Яп Бгу) METHOD FOR OBTAINING COMPOSITION NANOPARTICLES GRAPHEN / COPPER
CN107164020A (en) * 2017-04-06 2017-09-15 江苏大学 A kind of graphene poly-dopamine copper nano composite material and preparation method thereof
CN110695372A (en) * 2019-10-10 2020-01-17 天津大学 Preparation method for improving copper-graphene interface by using rare earth elements
CN114480899A (en) * 2021-12-15 2022-05-13 深圳先进技术研究院 Rare earth modified graphene copper-based composite material and preparation method and application thereof

Also Published As

Publication number Publication date
CN114480899A (en) 2022-05-13
CN114480899B (en) 2022-12-06

Similar Documents

Publication Publication Date Title
WO2023109667A1 (en) Rare earth modified graphene copper-based composite material, preparation method thereof and application
CN107723500B (en) A kind of graphene-aluminum oxide mixing enhancement copper-base composite material and preparation method thereof
Luo et al. Mechanical enhancement of copper matrix composites with homogeneously dispersed graphene modified by silver nanoparticles
WO2022041255A1 (en) Method for preparing nano-phase reinforced nickel-based high-temperature alloy using micron ceramic particles
CN105081310A (en) Method for preparing grapheme reinforced aluminum matrix composite material
CN110331325B (en) Nano-alumina reinforced copper-based composite material and preparation method thereof
CN111455208B (en) Nano modified aluminum alloy material, preparation method thereof and energy-saving and environment-friendly electric power fitting manufactured by nano modified aluminum alloy material
CN1686650A (en) Precipitation reduction method of preparing nano-cobalt powder
CN114293051B (en) Preparation method of high-temperature softening resistant high-strength high-conductivity copper-based composite material formed part
CN103276323A (en) Preparation method of high-strength and corrosion-resistant composite heat exchanger tube
CN113215432B (en) Nano silicon carbide particle reinforced copper-based spherical metal powder suitable for 3D printing and preparation method thereof
WO2023040087A1 (en) Graphene-copper matrix composite material, and preparation method therefor and use thereof
CN105936987B (en) A kind of preparation method of aluminium nitride carbon nanotube particulate enhancing aluminum-based alloy material
CN106319570B (en) The carbon-based protectant preparation method of aluminium anode surface oxidation-resistant
Guan et al. Core-shell structure and 3D CNTs networks promote Si@ Cu nanoparticle anodes with enhanced reversible capacity and cyclic performance for Li-ion batteries
Zhang et al. Researches for higher electrical conductivity copper‐based materials
CN112410597B (en) Preparation method of nano WC dispersion strengthened copper
CN111979450B (en) Preparation method of three-dimensional structure nano carbon material reinforced nickel-based composite material
CN102504909A (en) Graphite material for graphite lubricant
CN112080711A (en) Aluminum-based composite material forging and preparation method thereof
CN111471943A (en) High-electric-conductivity and heat-conduction aluminum-based composite material and preparation method thereof
CN112139512B (en) Preparation method of copper-based composite material precursor powder
CN105568189B (en) Method for preparing nanophase containing aluminum-magnesium-silicon alloy wire
CN113088745B (en) Preparation method of zirconium oxide coated carbon nanotube reinforced aluminum matrix composite
CN113388750A (en) Metal glass particle reinforced nanocrystalline copper alloy composite material and preparation method thereof

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22906415

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE