CN110695373A - Preparation method of graphene-coated rare earth element-loaded copper composite material with double-layer harmonic structure - Google Patents
Preparation method of graphene-coated rare earth element-loaded copper composite material with double-layer harmonic structure Download PDFInfo
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- CN110695373A CN110695373A CN201910971498.9A CN201910971498A CN110695373A CN 110695373 A CN110695373 A CN 110695373A CN 201910971498 A CN201910971498 A CN 201910971498A CN 110695373 A CN110695373 A CN 110695373A
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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
- B22F9/16—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
- B22F9/26—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions using gaseous reductors
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/17—Metallic particles coated with metal
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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
- 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
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- 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
- C01B32/184—Preparation
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- 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
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C9/00—Alloys based on copper
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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
- B22F9/16—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
- B22F2009/245—Reduction reaction in an Ionic Liquid [IL]
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- C—CHEMISTRY; METALLURGY
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- C01B2204/00—Structure or properties of graphene
- C01B2204/04—Specific amount of layers or specific thickness
Abstract
The invention relates to a graphene-coated rare earth element-loaded copper composite material with a double-layer harmonic structure, which is characterized by comprising a rare earth element-loaded small-particle-size copper, wherein the small-particle-size copper is loaded on a large-particle-size copper, and the outside of the graphene-coated rare earth element-loaded copper composite material is coated with a layer of graphene to improve the strength and the elongation of the copper-graphene composite material. Copper powder is used as a parent material of the copper-graphene composite material, the adopted graphene grows in situ on the surface of copper through a carbon source, and rare earth elements are added for modification. The invention also provides a preparation method of the composite material.
Description
Technical Field
The invention relates to a preparation method of a novel double-layer harmonic structure with rare earth elements loaded with small-particle-size copper and small-particle-size copper loaded with large-particle-size copper, and belongs to the technical fields of military industry, aerospace, automobile manufacturing, electronic appliances and the like.
Background
In recent years, researchers have conducted extensive studies to meet the demand for structural materials having excellent mechanical properties, and composite materials are widely used in the fields of aerospace, national defense, transportation and the like due to their excellent overall properties, particularly designability of their structures and properties. The metal-based composite material is a composite material which is artificially combined with one or more metal or nonmetal reinforcing phases by taking metal and alloy thereof as a matrix. Due to higher strength, wear resistance and good electric and thermal conductivity, the material can be suitable for extreme space environments such as vacuum, ionizing radiation and plasma. The copper-based composite material has high Young's modulus, good electric and thermal conductivity and good processability, is more and more widely applied and has great development potential in high-end fields such as integrated circuits, electronic and electric products, aerospace, automobiles and the like, and becomes an important composite material in the 21 st century. With the addition of reinforcing phase fibers, particles, graphene and the like, although the strength of the composite material can be improved, the electrical conductivity and thermal conductivity of the composite material can be reduced, so that a novel structure is designed, and the problem of realizing bidirectional improvement of reinforcement and toughening is a problem which is urgently needed to be solved at present.
Document [1] indicates that by designing a microstructure, forming a "harmonic structure" material can simultaneously increase the strength and ductility of the composite material, thereby improving mechanical properties. Essentially, it is a heterogeneous microstructure consisting of a bimodal particle size distribution in which a tough coarse grain region is surrounded by a continuous three-dimensional network region with a high-strength ultrafine grain structure, forming a coarse and fine grain distribution. Coarse grains can improve toughness, while fine grains can improve strength. Many metals and alloys with this structure have both superior strength and ductility compared to homogeneous materials of the same type. At present, similar structures are not suitable for copper base, and the application of other materials is limited to single-layer harmonic structure.
Whether a double-layer harmonic structure is realized or not, the solution of the problem provides a new technical scheme for the research of the metal matrix composite material.
Reference to the literature
[1]Khalil,Nur Zalikha,et al.Application ofAl-Si semi-solid reactionfor fabricating harmonic structured Al basedalloy.[J]Materials transactions57(9)(2016):1433-1439.
Disclosure of Invention
The invention aims to provide a novel double-layer harmonic structure which is formed by loading small-particle-size copper on a rare earth element coated by graphene, reloading the small-particle-size copper on large-particle-size copper, uniformly mixing the rare earth element, copper powder, copper acetate, cane sugar and the like by heating in water bath, preparing a double-layer harmonic structure which is formed by loading the rare earth element on the small-particle-size copper, reloading the small-particle-size copper on the large-particle-size copper and wrapping a layer of graphene on the periphery of the double-layer harmonic structure. The structure can effectively overcome the defect of inverted relation between strength and elongation in the traditional powder metallurgy method. The method not only can improve the wettability of the copper-graphene interface and enable the copper-graphene interface to have high bonding strength, but also can not reduce the elongation of the copper-graphene interface while enabling the copper-graphene interface to have high strength due to the double-layer harmonic structure, and has good industrial application prospect. The purpose of the invention is realized by the following technical scheme:
the graphene-coated rare earth element-loaded copper composite material with the double-layer harmonic structure is characterized by comprising rare earth element-loaded small-particle-size copper, the small-particle-size copper is loaded on large-particle-size copper again, the double-layer harmonic structure with the strength and the elongation of the copper-graphene composite material improved by coating a layer of graphene outside is adopted, copper powder is used as a base material of the copper-graphene composite material, the adopted graphene grows in situ on the surface of the copper through a carbon source, and the rare earth element is added for modification.
Furthermore, the diameter of the copper powder particles is 1-600 μm. And adding a carbon source of cane sugar into the copper surface, and uniformly loading the copper surface through a water bath heating process. One or two of copper acetate and copper nitrate are reduced by dipping to form small-particle-size copper powder loaded on a large-particle-size copper base material, and rare earth elements are loaded on small-particle-size copper obtained by dipping and reducing one or two of copper acetate and copper nitrate, so that the rare earth elements are loaded on the small-particle-size copper, and the small-particle-size copper is loaded on a double-layer harmonic structure of the large-particle-size copper. Graphene obtained by in-situ growth is adopted, and the number of graphene layers is controlled to be 1-20. The graphene grown in situ plays a role in limiting the growth of internal particles and limiting the range.
The invention also provides a preparation method of the copper-graphene double-layer harmonic structure composite material, which comprises the following steps: the method comprises the following steps:
1) according to the mass ratio (0.6-3): 12:(0.5-4): (0.13-0.19) weighing rare earth element Y (NO)3)2·6H2Adding one or two of O, copper powder, copper acetate and copper nitrate and sucrose into anhydrous ethanol and water, and uniformly dispersing at 60-90 deg.C in water bath;
2) dipping and reducing the uniformly dispersed mixture obtained in the step 1) for 0.5-4h in the atmosphere of reducing gas at the temperature of 450-950 ℃;
3) putting the obtained powder into a hot-pressing grinding tool for high-temperature sintering to prepare the rare earth element reinforced copper-based composite material, wherein the hot-pressing temperature is as follows: 700 ℃ and 1000 ℃.
Drawings
FIG. 1 shows the morphology of original 400 mesh copper powder
FIG. 2 original 1 μm copper powder morphology
FIG. 3 is the XRD spectrum of example 1 after immersion
FIG. 4 shows the morphology of the powder after immersion reduction in example 1
FIG. 5 shows the powder form after immersion reduction in example 2
FIG. 6 shows the powder form after immersion reduction in example 3
FIG. 7 is the energy spectrum of the powder after immersion reduction in example 1
Detailed Description
The present invention is further illustrated by the following examples, which are intended to be illustrative only and not limiting.
Example 1
1) According to the mass ratio of 3: 12:1.5: 0.16 weighing rare earth element Y (NO)3)2·6H2O, copper powder with the particle size of 400 meshes, copper acetate and sucrose, adding absolute ethyl alcohol and water, and uniformly dispersing the mixture in a water bath kettle at the temperature of 70 ℃;
2) dipping and reducing the uniformly dispersed mixture obtained in the step 1) in a reducing gas atmosphere at 600 ℃;
3) putting the obtained powder into a hot-pressing grinding tool for high-temperature sintering to prepare the rare earth element reinforced copper-based composite material, wherein the hot-pressing temperature is as follows: 800 ℃.
Example 2
1) According to the mass ratio of 3: 12:1.5: 0.16 weighing rare earth element Y (NO)3)2·6H2Adding anhydrous ethanol and water into O, 1-micron copper powder, copper acetate and sucrose, and uniformly dispersing in a 70 ℃ water bath kettle;
2) dipping and reducing the uniformly dispersed mixture obtained in the step 1) in a reducing gas atmosphere at 600 ℃;
3) putting the obtained powder into a hot-pressing grinding tool for high-temperature sintering to prepare the rare earth element reinforced copper-based composite material, wherein the hot-pressing temperature is as follows: 800 ℃.
Example 3
1) According to the mass ratio of 12:1.5: 0.16 weighing copper powder with the particle size of 400 meshes, copper acetate and sucrose, adding absolute ethyl alcohol and water, and uniformly dispersing in a 70 ℃ water bath kettle;
2) dipping and reducing the uniformly dispersed mixture obtained in the step 1) in a reducing gas atmosphere at 600 ℃;
3) putting the obtained powder into a hot-pressing grinding tool for high-temperature sintering to prepare the rare earth element reinforced copper-based composite material, wherein the hot-pressing temperature is as follows: 800 ℃.
Claims (7)
1. The graphene-coated rare earth element-loaded copper composite material with the double-layer harmonic structure is characterized by having the double-layer harmonic structure, wherein the rare earth element-loaded copper with small particle size is loaded on the copper with large particle size, and the copper with small particle size is loaded on the copper with large particle size again, and the graphene-coated rare earth element-loaded copper composite material is coated with one layer of graphene to improve the strength and the elongation of the copper-graphene composite material. Copper powder is used as a parent material of the copper-graphene composite material, the adopted graphene grows in situ on the surface of copper through a carbon source, and rare earth elements are added for modification.
2. The composite material of claim 1, further characterized by: the diameter of the copper powder particles is 1-600 mu m.
3. The composite material of claim 1, further characterized by: and adding a carbon source of cane sugar into the copper surface, and uniformly loading the copper surface through a water bath heating process.
4. The composite material of claim 1, further characterized by: one or two of copper acetate and copper nitrate are reduced by dipping to form small-particle-size copper powder loaded on a large-particle-size copper base material, and rare earth elements are loaded on small-particle-size copper obtained by dipping and reducing one or two of copper acetate and copper nitrate, so that the rare earth elements are loaded on the small-particle-size copper, and the small-particle-size copper is loaded on a double-layer harmonic structure of the large-particle-size copper.
5. The copper-graphene double-layer harmonic structured composite material according to claim 1, further characterized by: graphene obtained by in-situ growth is adopted, and the number of graphene layers is controlled to be 1-20.
6. The copper-graphene double-layer harmonic structured composite material according to claim 1, further characterized by: the graphene grown in situ plays a role in limiting the growth of internal particles and limiting the range.
7. A method of preparing the graphene-coated rare earth element-loaded copper composite material of claim 1, comprising the steps of:
1) according to the mass ratio (0.6-3): 12:(0.5-4): (0.13-0.19) weighing rare earth element Y (NO)3)2·6H2Adding one or two of O, copper powder, copper acetate and copper nitrate and sucrose into anhydrous ethanol and water, and uniformly dispersing under the condition of water bath heating;
2) dipping and reducing the uniformly dispersed mixture obtained in the step 1) for 0.5-4h in the atmosphere of reducing gas at the temperature of 450-950 ℃;
3) putting the obtained powder into a hot-pressing grinding tool for high-temperature sintering to prepare the rare earth element reinforced copper-based composite material, wherein the hot-pressing temperature is as follows: 700 ℃ and 1000 ℃.
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