CN113020588B - Preparation method of graphene oxide doped tungsten-copper core-shell structure material - Google Patents
Preparation method of graphene oxide doped tungsten-copper core-shell structure material Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 172
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 165
- SBYXRAKIOMOBFF-UHFFFAOYSA-N copper tungsten Chemical group [Cu].[W] SBYXRAKIOMOBFF-UHFFFAOYSA-N 0.000 title claims abstract description 118
- 239000011258 core-shell material Substances 0.000 title claims abstract description 101
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000002245 particle Substances 0.000 claims abstract description 31
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 239000008367 deionised water Substances 0.000 claims abstract description 18
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 18
- 238000005406 washing Methods 0.000 claims abstract description 15
- 238000001291 vacuum drying Methods 0.000 claims abstract description 13
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 12
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 18
- 239000012295 chemical reaction liquid Substances 0.000 claims description 13
- 229910002804 graphite Inorganic materials 0.000 claims description 8
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- 229910052721 tungsten Inorganic materials 0.000 description 25
- 239000010937 tungsten Substances 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 8
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- GQLSFFZMZXULSF-UHFFFAOYSA-N copper;oxotungsten Chemical compound [Cu].[W]=O GQLSFFZMZXULSF-UHFFFAOYSA-N 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
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- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 2
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- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- MEOSMFUUJVIIKB-UHFFFAOYSA-N [W].[C] Chemical compound [W].[C] MEOSMFUUJVIIKB-UHFFFAOYSA-N 0.000 description 1
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- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/17—Metallic particles coated with metal
-
- 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
- B22F3/10—Sintering only
- B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
-
- 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
- B22F3/10—Sintering only
- B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
- B22F2003/1051—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding by electric discharge
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E30/00—Energy generation of nuclear origin
- Y02E30/10—Nuclear fusion reactors
Abstract
The invention discloses a preparation method of a graphene oxide doped tungsten-copper core-shell structure material, which comprises the following steps: 1. preparing tungsten powder and graphene oxide into a tungsten powder dispersion liquid and a graphene oxide dispersion liquid; 2. adding the graphene oxide dispersion liquid into the tungsten powder dispersion liquid; 3. preparing copper acetate, deionized water and ammonia water into an activation solution; 4. dropwise adding the activation solution into the tungsten powder/graphene oxide dispersion liquid; 5. filtering, washing and vacuum drying the reaction solution; 6. and performing discharge plasma sintering on the graphene oxide doped tungsten-copper core-shell structure powder to obtain the graphene oxide doped tungsten-copper core-shell structure material. According to the invention, through in-situ chemical plating, the nano-copper particles are uniformly coated on the surfaces of tungsten powder particles and doped with graphene oxide, and the obtained graphene oxide doped tungsten-copper core-shell structure material is a nanocrystalline composite material and has the advantages of excellent interface wettability, high mechanical property, good heat conductivity and high density.
Description
Technical Field
The invention belongs to the technical field of composite material preparation, and particularly relates to a preparation method of a graphene oxide doped tungsten-copper core-shell structure material.
Background
The tungsten-copper alloy combines the advantages of two components of tungsten and copper, has the characteristics of high temperature resistance, high strength, high density, arc corrosion resistance and the like of tungsten, has the excellent performances of high electric conductivity, heat conductivity, excellent plasticity and the like of copper, and is widely applied to the fields of electric contact materials, electronic packaging materials, armor breaking materials, nuclear fusion materials and the like. With the rapid development of the electronic industry and other high-end technical fields, the application of the tungsten-copper alloy is more extensive, higher requirements on the structure and the performance of the tungsten-copper alloy are also provided, and the tungsten-copper alloy material with excellent interface wettability and high conductivity is required.
The current methods for preparing tungsten-copper alloy mainly comprise a liquid phase sintering method, an infiltration method and a mixed powder direct sintering method. With the development of nanotechnology, the finer the powder, the lower the sintering temperature, and the easier it is to achieve densification. The near-full-density tungsten-copper material can be directly sintered at a lower temperature by adopting superfine or nano tungsten-copper mixed powder. However, the powder sintering method for preparing the tungsten-copper alloy faces two problems: firstly, because of the mutual incompatibility of the two components, the wettability of the tungsten-copper interface is poor, the tungsten-copper interface is difficult to compact in the sintering process, and an ideal microstructure and performance are difficult to obtain; secondly, how to obtain the tungsten-copper mixed powder which is uniformly mixed mainly comprises a ball milling method and a tungsten-copper oxide co-reduction method at present, but the ball milling method can introduce a large amount of impurities, and the preparation process of the co-reduction method is complex.
Graphene oxide has excellent physical, chemical, optical and electrical properties, and due to the coexistence structure of various oxygen-containing functional groups on the basal plane and the edge of the graphene sheet layer skeleton, the conductivity and the band gap of the graphene oxide can be adjusted by regulating the type and the number of the contained oxygen-containing functional groups. Graphene oxide is a novel carbon material with excellent performance, and has a high specific surface area and rich functional groups on the surface. The graphene oxide composite material including a polymer composite material and an inorganic composite material has a wide application field, and thus doping of a metal with graphene oxide becomes another important research point.
Therefore, the preparation of the graphene oxide doped tungsten copper material with excellent wettability of the interface, high conductivity and uniform mixing is a problem to be solved at present.
Disclosure of Invention
The technical problem to be solved by the present invention is to provide a method for preparing a graphene oxide doped tungsten-copper core-shell structure material, aiming at the defects of the prior art. According to the method, the tungsten powder is subjected to in-situ chemical plating by utilizing the higher activity of the tungsten powder, so that nano copper particles are gradually nucleated and grown on the surfaces of the tungsten particles and gradually coated with the tungsten particles, and the graphene oxide is doped in a tungsten-copper core-shell structure, so that the nano copper particles are uniformly coated on the surfaces of the tungsten powder particles and doped with the graphene oxide, the problem that the copper and the graphene oxide are uniformly dispersed in a tungsten matrix is solved, and the obtained graphene oxide doped tungsten-copper core-shell structure material is a nanocrystalline composite material and has the advantages of excellent interface wettability, high mechanical property, good heat conductivity and high density.
In order to solve the technical problems, the technical scheme provided by the invention is as follows: a preparation method of a graphene oxide doped tungsten-copper core-shell structure material is characterized by comprising the following steps:
step one, respectively adding tungsten powder and graphene oxide into deionized water, and then sequentially stirring and ultrasonically treating to respectively obtain a tungsten powder dispersion liquid and a graphene oxide dispersion liquid;
step two, stirring the tungsten powder dispersion liquid obtained in the step one, and then dropwise adding the graphene oxide dispersion liquid obtained in the step one to obtain a tungsten powder/graphene oxide dispersion liquid;
adding copper acetate into deionized water, then adding ammonia water, and performing ultrasonic treatment to obtain an activated solution;
step four, dropwise adding the activating solution obtained in the step three into the tungsten powder/graphene oxide dispersion liquid obtained in the step two under the conditions of water bath and stirring for reaction to obtain a reaction liquid;
step five, sequentially filtering, washing and vacuum-drying the reaction liquid obtained in the step four to obtain graphene oxide doped tungsten-copper core-shell structure powder;
and step six, placing the graphene oxide doped tungsten-copper core-shell structure powder obtained in the step five into a graphite mould, and then performing discharge plasma sintering to obtain the graphene oxide doped tungsten-copper core-shell structure material.
Respectively dispersing tungsten powder and graphene oxide into deionized water, dropwise adding the graphene oxide dispersion liquid into the tungsten powder dispersion liquid, mixing uniformly to obtain tungsten powder/graphene oxide dispersion liquid, adding copper acetate into the deionized water, adding ammonia water to obtain an activated solution, dropwise adding the activated solution into the tungsten powder/graphene oxide dispersion liquid under the conditions of water bath and stirring, mixing uniformly by dropwise adding, complexing with copper ions by using ammonia water as a complexing agent during a reaction process to stabilize the reaction, performing in-situ chemical plating by using the higher activity of the tungsten powder to ensure that nano copper particles gradually grow on the surfaces of the tungsten particles and coat the tungsten particles, doping the graphene oxide into a tungsten-copper core-shell structure, filtering, centrifuging and washing precipitates in the reaction liquid to remove impurity ions on the surfaces of the tungsten particles, performing vacuum drying to obtain tungsten oxide doped-copper core-shell structure powder, and finally placing the powder in a graphite discharge mold to perform discharge and other ions, thereby obtaining the tungsten oxide doped tungsten-copper core-shell structure, and preparing the doped tungsten oxide-copper core shell structure material according to various requirements.
The preparation method of the graphene oxide doped tungsten-copper core-shell structure material is characterized in that the particle size of the tungsten powder in the step one is 20 nm-5 microns. According to the invention, by controlling the granularity of tungsten powder, the grain range of the prepared graphene oxide doped tungsten-copper core-shell structure material reaches the nanometer to micron level, the applicable tungsten powder has a wide granularity range and industrial value, and graphene oxide doped tungsten-copper core-shell structure powder and graphene oxide doped tungsten-copper core-shell structure material with various particle sizes are obtained.
The preparation method of the graphene oxide doped tungsten-copper core-shell structure material is characterized in that in the second step, the mass of graphene oxide in the tungsten powder/graphene oxide dispersion liquid is 0.1-1% of the mass of tungsten powder. According to the invention, the content of graphene oxide in the graphene oxide doped tungsten-copper core-shell structure material is controlled by the proportion of the graphene oxide and the tungsten powder, so that the graphene oxide doped tungsten-copper core-shell structure material has the optimal interface wettability, mechanical property, heat conductivity and density.
The preparation method of the graphene oxide doped tungsten-copper core-shell structure material is characterized in that the temperature of the water bath in the fourth step is 25-80 ℃, and the reaction time is 30 min-12 h. According to the invention, through controlling the temperature of the water bath and the reaction time, the nano copper particles are gradually nucleated and grown on the surfaces of the tungsten particles, the tungsten particles are gradually coated, and the graphene oxide is doped in the tungsten-copper core-shell structure, so that the preparation of the graphene oxide doped tungsten-copper core-shell structure is realized at room temperature, the energy loss is reduced, the reaction condition is reduced, and the reaction is carried out at a higher temperature, so that the method has the advantage of high reaction rate.
The preparation method of the graphene oxide doped tungsten-copper core-shell structure material is characterized in that in the fifth step, the mass fraction of copper in the graphene oxide doped tungsten-copper core-shell structure powder is not more than 50%. According to the invention, the mass fraction of tungsten in the graphene oxide doped tungsten-copper core-shell structure powder is controlled by controlling the mass fraction of copper, so that excellent arc corrosion resistance is ensured when the graphene oxide doped tungsten-copper core-shell structure material is used as an electric contact material.
The preparation method of the graphene oxide doped tungsten-copper core-shell structure material is characterized in that the washing times in the fifth step are not less than 3. According to the invention, the precipitate obtained after the reaction solution is filtered is washed by filtering and centrifuging by using deionized water, so that impurity ions on the surface of the tungsten-copper core-shell structure doped graphene oxide powder are fully removed, the purity of the tungsten-copper core-shell structure doped graphene oxide powder is improved, and the performance of the tungsten-copper core-shell structure doped graphene oxide material is ensured.
The preparation method of the graphene oxide doped tungsten-copper core-shell structure material is characterized in that the discharge plasma sintering conditions in the sixth step are as follows: the temperature is 750-1100 ℃, the pressure is 20-120 MPa, the time is 3-10 min, and the heating rate is 50-200 ℃. According to the invention, through discharge plasma sintering, under the conditions of high temperature and high pressure, the tungsten-copper core-shell structure powder doped with graphene oxide is tightly combined, the tungsten-copper core-shell structure material doped with graphene oxide in various shapes is prepared according to the use requirement, the structural function integration and high densification of the tungsten-copper core-shell structure material doped with graphene oxide are realized, the tungsten and the graphene oxide are partially or completely reacted by controlling the temperature and the sintering time to obtain the nanocrystalline composite material, the wettability of an interface between tungsten and copper is improved, the mechanical property, the heat conduction property and the density are improved, the powder particles in a solid state are reacted in a short time by controlling the pressure to obtain the compact material, the density is improved, the reaction efficiency is improved by controlling the temperature rise rate, the crystal particles are prevented from growing up, and the performance of the tungsten-copper core-shell structure material doped with graphene oxide is further improved.
Compared with the prior art, the invention has the following advantages:
1. according to the method, the tungsten powder is subjected to in-situ chemical plating by utilizing the higher activity of the tungsten powder, so that the nano copper particles are gradually nucleated and grown on the surfaces of the tungsten particles and gradually coated with the tungsten particles, and the graphene oxide is doped in a tungsten-copper core shell structure, so that the nano copper particles are uniformly coated on the surfaces of the tungsten powder particles and doped with the graphene oxide, the problem that the copper and the graphene oxide are uniformly dispersed in a tungsten matrix is solved, the temperature of discharge plasma sintering is remarkably reduced, the density is improved, and the obtained graphene oxide doped tungsten-copper core shell structure material is a nanocrystalline composite material and has the advantages of excellent interface wettability, high mechanical property, good heat conducting property and high density.
2. The invention adopts an in-situ chemical plating method, effectively avoids impurities introduced by a ball milling method, avoids using reducing agents such as hydrazine hydrate and the like, simplifies the integral preparation process and has little pollution to the environment; by controlling the temperature of the water bath and the reaction time, the preparation of the graphene oxide doped tungsten-copper core-shell structure at room temperature is realized, the energy loss is reduced, and the reaction conditions are reduced.
3. According to the invention, graphene oxide is added into the tungsten-copper core-shell structure, tungsten carbon can be generated in situ at a tungsten-copper interface, the interface wettability is obviously improved, the mechanical property, the heat conduction property and the density are improved, compared with other reinforced phases, the graphene oxide per se has better conductivity, and the conductivity of the material is maintained while the mechanical property is improved.
4. The method does not need to use an ammonia evaporation process for evaporating the ammonia water until the pH value of the solution reaches neutral, ensures that the ammonia water is always in the solution, ensures that the reaction process is carried out under the alkaline condition, can effectively accelerate the reaction speed, shortens the preparation time and simplifies the preparation process.
5. According to the invention, the activation solution is dropwise added into the tungsten powder/graphene oxide dispersion liquid, so that the reaction process is better controlled, and the coating uniformity is ensured, thereby ensuring the uniformity of the graphene oxide doped tungsten-copper core-shell structure material.
6. The tungsten powder used in the invention has a large particle size range, can obtain graphene oxide-doped tungsten-copper core-shell structure powder and graphene oxide-doped tungsten-copper core-shell structure materials with various particle sizes, and has industrial value.
The technical solution of the present invention is further described in detail by the accompanying drawings and examples.
Drawings
Fig. 1 is a process flow diagram of the preparation of the graphene oxide doped tungsten-copper core-shell structure material according to the present invention.
Fig. 2 is a low-magnification SEM image of the graphene oxide-doped tungsten-copper core-shell structure powder prepared in example 1 of the present invention.
Fig. 3 is a high-magnification SEM image of the graphene oxide-doped tungsten-copper core-shell structure powder prepared in example 1 of the present invention.
Fig. 4 is an EDS diagram of tungsten in the graphene oxide-doped tungsten-copper core-shell structure powder prepared in example 1 of the present invention.
Fig. 5 is an EDS diagram of copper in the graphene oxide-doped tungsten-copper core-shell structured powder prepared in example 1 of the present invention.
Detailed Description
As shown in fig. 1, the specific process for preparing the graphene oxide doped tungsten-copper core-shell structure material comprises the following steps: respectively adding tungsten powder and graphene oxide into deionized water to respectively obtain tungsten powder dispersion liquid and graphene oxide dispersion liquid, dropwise adding the graphene oxide dispersion liquid into the tungsten powder dispersion liquid to obtain tungsten powder/graphene oxide dispersion liquid, adding copper acetate into the deionized water, then adding ammonia water to obtain an activation solution, dropwise adding the activation solution into the tungsten powder/graphene oxide dispersion liquid to obtain a reaction solution, sequentially filtering, washing and vacuum drying the reaction solution to obtain graphene oxide doped tungsten-copper nuclear shell structure powder, and performing discharge plasma sintering on the graphene oxide doped tungsten-copper nuclear shell structure powder to obtain the graphene oxide doped tungsten-copper nuclear shell structure material.
The present invention is described in detail in examples 1 to 3.
Example 1
The embodiment comprises the following steps:
step one, respectively adding 50g of tungsten powder and 0.2g of graphene oxide into 200mL of deionized water, and then sequentially stirring and ultrasonically treating to obtain a tungsten powder dispersion liquid and a graphene oxide dispersion liquid; the granularity of the tungsten powder is 20 nm-5 mu m;
step two, stirring the tungsten powder dispersion liquid obtained in the step one, and then dropwise adding the graphene oxide dispersion liquid obtained in the step one to obtain tungsten powder/graphene oxide dispersion liquid;
step three, adding 62g of copper acetate into 200mL of deionized water, then adding 100mL of ammonia water, and performing ultrasonic treatment to obtain an activation solution;
step four, dropwise adding the activating solution obtained in the step three into the tungsten powder/graphene oxide dispersion liquid obtained in the step two under the conditions of water bath and stirring for reaction to obtain a reaction liquid; the temperature of the water bath is 45 ℃, and the reaction time is 6 hours;
step five, sequentially filtering, washing and vacuum drying the reaction liquid obtained in the step four to obtain graphene oxide doped tungsten-copper core-shell structure powder; the mass fraction of copper in the graphene oxide doped tungsten-copper core-shell structure powder is 40%; the temperature of the vacuum drying is 80 ℃; the number of washing times is 4;
placing the graphene oxide doped tungsten-copper core-shell structure powder obtained in the fifth step into a graphite mold, and then performing discharge plasma sintering to obtain a graphene oxide doped tungsten-copper core-shell structure material; the discharge plasma sintering conditions are as follows: the temperature is 900 ℃, the pressure is 40MPa, the sintering time is 10min, and the heating rate is 100 ℃/min.
Through detection, the graphene oxide-doped tungsten-copper core-shell structure material prepared in the embodiment has the mass fraction of 0.4% of graphene oxide, the mass fraction of copper is 40% and the balance is tungsten, the tensile strength of the graphene oxide-doped tungsten-copper core-shell structure material is 543.4MPa, the conductivity is 59.7% IACS, the compactness is 91.1% and the Vickers hardness is 234.8HV 0.2 。
Fig. 2 is a low-power SEM image of the graphene oxide-doped tungsten-copper core-shell structure powder prepared in this embodiment, and fig. 3 is a high-power SEM image of the graphene oxide-doped tungsten-copper core-shell structure powder prepared in this embodiment, and as can be seen from fig. 2 and fig. 3, copper particles and graphene oxide are attached to the surface of the graphene oxide-doped tungsten-copper core-shell structure powder, which illustrates that the tungsten powder can be completely coated with the copper particles after in-situ chemical plating, and copper is plated on the surface of the tungsten particles by in-situ chemical plating, and the graphene oxide is doped, so that the dispersibility is good, and no obvious agglomeration phenomenon occurs, thereby laying a good foundation for the next sintering.
Fig. 4 is an EDS diagram of tungsten in the graphene oxide-doped tungsten-copper core-shell structure powder prepared in this example, fig. 5 is an EDS diagram of copper in the graphene oxide-doped tungsten-copper core-shell structure powder prepared in this example, and as can be seen from fig. 4 and 5, tungsten and copper in the graphene oxide-doped tungsten-copper core-shell structure powder are uniformly distributed, which illustrates that the surface of the tungsten powder is coated with copper particles grown in situ.
Comparative example 1
The comparative example comprises the following steps:
adding 50g of tungsten powder into 200mL of deionized water, and then sequentially stirring and ultrasonically treating to obtain a tungsten powder dispersion liquid; the granularity of the tungsten powder is 20 nm-5 mu m;
step two, adding 62g of copper acetate into 200mL of deionized water, then adding 100mL of ammonia water, and performing ultrasonic treatment to obtain an activated solution;
step three, dropwise adding the activated solution obtained in the step two into the tungsten powder dispersion liquid obtained in the step one under the conditions of water bath and stirring for reaction to obtain a reaction liquid; the temperature of the water bath is 45 ℃, and the reaction time is 6 hours;
step five, sequentially filtering, washing and vacuum drying the reaction liquid obtained in the step four to obtain tungsten-copper core-shell structure powder; the mass fraction of copper in the tungsten-copper core-shell structure powder is 40%; the temperature of the vacuum drying is 80 ℃; the number of washing times is 4;
sixthly, placing the tungsten-copper core-shell structure powder obtained in the fifth step into a graphite mould, and then performing discharge plasma sintering to obtain a tungsten-copper core-shell structure material; the discharge plasma sintering conditions are as follows: the temperature is 900 ℃, the pressure is 40MPa, the sintering time is 10min, and the heating rate is 100 ℃/min.
The tungsten-copper core-shell structure material prepared by the comparative example is detected to have the mass fraction of copper of 40 percent and the balance of tungsten, the tensile strength of the tungsten-copper core-shell structure material is 482.7MPa, the electric conductivity is 20.7 percent IACS, the compactness is 86.5 percent, and the Vickers hardness is 227.4HV 0.2 。
Compared with the embodiment 1, the comparison of the comparative example 1 and the embodiment 1 shows that after the graphene oxide is doped in the tungsten-copper core-shell structure material, the tensile strength, the density and the Vickers hardness of the obtained graphene oxide doped tungsten-copper core-shell structure material are all improved, and particularly the conductivity is improved by more than 35%.
Comparative example 2
This comparative example comprises the following steps:
step one, ball milling 50g of tungsten powder, 0.2g of graphene oxide and 62g of copper acetate for 2.5 hours at the rotating speed of 150rpm to obtain tungsten-copper-graphene oxide mixed powder;
placing the tungsten-copper graphene oxide mixed powder obtained in the step one in a graphite mold, and then performing discharge plasma sintering to obtain a tungsten-copper graphene oxide material; the discharge plasma sintering conditions are as follows: the temperature is 900 ℃, the pressure is 40MPa, the sintering time is 10min, and the heating rate is 100 ℃/min.
Through detection, the mass fraction of the graphene oxide in the tungsten-copper graphene oxide material prepared by the comparative example is 0.4%, the mass fraction of copper is 40%, and the balance is tungstenThe copper graphene oxide material had a tensile strength of 376.7MPa, an electrical conductivity of 30.4% IACS, a density of 80.3%, and a Vickers hardness of 201.2HV 0.2 。
Compared with the example 1, the comparison of the comparative example 2 shows that the copper is plated on the surfaces of the tungsten particles by adopting an in-situ chemical plating method, and the graphene oxide is doped, so that the tensile strength, the conductivity, the density and the Vickers hardness of the obtained graphene oxide doped tungsten-copper core-shell structure material are all improved.
Example 2
The embodiment comprises the following steps:
step one, respectively adding 50g of tungsten powder and 0.5g of graphene oxide into 200mL of deionized water, and then sequentially stirring and ultrasonically treating to obtain a tungsten powder dispersion liquid and a graphene oxide dispersion liquid; the granularity of the tungsten powder is 1-5 mu m;
step two, stirring the tungsten powder dispersion liquid obtained in the step one, and then dropwise adding the graphene oxide dispersion liquid obtained in the step one to obtain a tungsten powder/graphene oxide dispersion liquid;
step three, adding 78g of copper acetate into 200mL of deionized water, then adding 100mL of ammonia water, and performing ultrasonic treatment to obtain an activated solution;
step four, dropwise adding the activating solution obtained in the step three into the tungsten powder/graphene oxide dispersion liquid obtained in the step two under the conditions of water bath and stirring for reaction to obtain a reaction liquid; the temperature of the water bath is 80 ℃, and the reaction time is 30min;
step five, sequentially filtering, washing and vacuum drying the reaction liquid obtained in the step four to obtain graphene oxide doped tungsten-copper core-shell structure powder; the mass fraction of copper in the graphene oxide doped tungsten-copper core-shell structure powder is 50%; the temperature of the vacuum drying is 80 ℃; the number of washing times is 5;
placing the graphene oxide doped tungsten-copper core-shell structure powder obtained in the fifth step into a graphite mold, and then performing discharge plasma sintering to obtain a graphene oxide doped tungsten-copper core-shell structure material; the discharge plasma sintering conditions are as follows: the temperature is 1100 ℃, the pressure is 20MPa, the sintering time is 3min, and the heating rate is 200 ℃/min.
Through detection, in the graphene oxide-doped tungsten-copper core-shell structure material prepared in the embodiment, the mass fraction of graphene oxide is 1%, the mass fraction of copper is 50%, and the balance is tungsten, the tensile strength of the graphene oxide-doped tungsten-copper core-shell structure material is 503.4MPa, the conductivity of the graphene oxide-doped tungsten-copper core-shell structure material is 70.7% iacs, the density of the graphene oxide-doped tungsten-copper core-shell structure material is 93.1%, and the vickers hardness of the graphene oxide-doped tungsten-copper core-shell structure material is 204.8HV 0.2 。
Example 3
The embodiment comprises the following steps:
step one, respectively adding 50g of tungsten powder and 0.05g of graphene oxide into 200mL of deionized water, and then sequentially stirring and ultrasonically treating to obtain a tungsten powder dispersion liquid and a graphene oxide dispersion liquid; the granularity of the tungsten powder is 20 nm-1 mu m;
step two, stirring the tungsten powder dispersion liquid obtained in the step one, and then dropwise adding the graphene oxide dispersion liquid obtained in the step one to obtain tungsten powder/graphene oxide dispersion liquid;
step three, adding 47g of copper acetate into 200mL of deionized water, then adding 100mL of ammonia water, and performing ultrasonic treatment to obtain an activated solution;
step four, dropwise adding the activating solution obtained in the step three into the tungsten powder/graphene oxide dispersion liquid obtained in the step two under the conditions of water bath and stirring for reaction to obtain a reaction liquid; the temperature of the water bath is 25 ℃, and the reaction time is 12 hours;
step five, sequentially filtering, washing and vacuum drying the reaction liquid obtained in the step four to obtain graphene oxide doped tungsten-copper core-shell structure powder; the mass fraction of copper in the graphene oxide doped tungsten-copper core-shell structure powder is 40%; the temperature of the vacuum drying is 80 ℃; the number of washing times is 3;
placing the graphene oxide doped tungsten-copper core-shell structure powder obtained in the fifth step into a graphite mold, and then performing discharge plasma sintering to obtain a graphene oxide doped tungsten-copper core-shell structure material; the discharge plasma sintering conditions are as follows: the temperature is 750 ℃, the pressure is 120MPa, the sintering time is 3min, and the heating rate is 50 ℃/min.
Through detection, in the graphene oxide-doped tungsten-copper core-shell structure material prepared in the embodiment, the mass fraction of graphene oxide is 0.1%, the mass fraction of copper is 30%, and the balance is tungsten, the tensile strength of the graphene oxide-doped tungsten-copper core-shell structure material is 583.4MPa, the conductivity is 52.7% iacs, the density is 85.1%, and the vickers hardness is 294.8HV 0.2 。
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the present invention in any way. Any simple modification, change and equivalent changes of the above embodiments according to the technical essence of the invention are still within the protection scope of the technical solution of the invention.
Claims (7)
1. A preparation method of a graphene oxide doped tungsten-copper core-shell structure material is characterized by comprising the following steps:
step one, respectively adding tungsten powder and graphene oxide into deionized water, and then sequentially stirring and ultrasonically treating to respectively obtain a tungsten powder dispersion liquid and a graphene oxide dispersion liquid;
step two, stirring the tungsten powder dispersion liquid obtained in the step one, and then dropwise adding the graphene oxide dispersion liquid obtained in the step one to obtain tungsten powder/graphene oxide dispersion liquid;
adding copper acetate into deionized water, then adding ammonia water, and performing ultrasonic treatment to obtain an activated solution;
step four, dropwise adding the activating solution obtained in the step three into the tungsten powder/graphene oxide dispersion liquid obtained in the step two under the conditions of water bath and stirring for reaction to obtain a reaction liquid;
step five, sequentially filtering, washing and vacuum-drying the reaction liquid obtained in the step four to obtain graphene oxide doped tungsten-copper core-shell structure powder;
and sixthly, placing the graphene oxide doped tungsten-copper core-shell structure powder obtained in the fifth step into a graphite mold, and then performing discharge plasma sintering to obtain the graphene oxide doped tungsten-copper core-shell structure material.
2. The preparation method of the graphene oxide doped tungsten-copper core-shell structure material according to claim 1, wherein the particle size of the tungsten powder in the first step is 20nm to 5 μm.
3. The method for preparing a graphene oxide doped tungsten-copper core-shell structure material according to claim 1, wherein the mass of graphene oxide in the tungsten powder/graphene oxide dispersion liquid in the second step is 0.1-1% of the mass of tungsten powder.
4. The preparation method of the graphene oxide doped tungsten-copper core-shell structure material according to claim 1, wherein the temperature of the water bath in the fourth step is 25-80 ℃, and the reaction time is 30 min-12 h.
5. The method for preparing a graphene oxide doped tungsten-copper core-shell structure material according to claim 1, wherein the mass fraction of copper in the graphene oxide doped tungsten-copper core-shell structure powder in the fifth step is not more than 50%.
6. The method for preparing the graphene oxide doped tungsten-copper core-shell structure material according to claim 1, wherein the number of washing in the fifth step is not less than 3.
7. The method for preparing the graphene oxide doped tungsten-copper core-shell structure material according to claim 1, wherein the discharge plasma sintering conditions in the sixth step are as follows: the temperature is 750-1100 ℃, the pressure is 20-120 MPa, the time is 3-10 min, and the heating rate is 50 ℃/min-200 ℃ min.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000035616A1 (en) * | 1998-12-16 | 2000-06-22 | Celsia S.P.A. | Process for the production of tungsten-copper composite sinterable powders |
| JP2005194566A (en) * | 2004-01-06 | 2005-07-21 | Yamaha Corp | Tungsten-copper composite powder, its production method, and method of producing sintered alloy using the same |
| CN101288905A (en) * | 2008-06-03 | 2008-10-22 | 西安理工大学 | Preparation method of copper cladding tungsten composite powder |
| CN101429597A (en) * | 2007-11-09 | 2009-05-13 | 北京有色金属研究总院 | Ultrafine molybdenum powder or ultrafine tungsten powder with surface clad copper |
| CN101537491A (en) * | 2009-04-30 | 2009-09-23 | 北京科技大学 | Preparation method of copper-coated tungsten composite powder |
| CN106238727A (en) * | 2016-08-23 | 2016-12-21 | 合肥工业大学 | A kind of preparation method of Cu bag W composite granule |
| CN106498209A (en) * | 2016-10-28 | 2017-03-15 | 西安理工大学 | A kind of preparation method of doped graphene tungsten-copper alloy |
| CN108893637A (en) * | 2018-07-02 | 2018-11-27 | 西安交通大学 | A kind of preparation method of copper-tungsten doped graphene |
| CN110172632A (en) * | 2019-03-20 | 2019-08-27 | 河南科技大学 | A kind of graphene oxide enhancing dispersion copper tungsten chromium electrical contact material and preparation method thereof |
| CN112126838A (en) * | 2020-09-30 | 2020-12-25 | 全球能源互联网研究院有限公司 | Copper-tungsten alloy material and preparation method and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020130658A1 (en) * | 2018-12-19 | 2020-06-25 | 서울대학교산학협력단 | Tungsten-doped graphene oxide film, method for manufacturing same, and electron emitter including same |
-
2021
- 2021-02-26 CN CN202110220075.0A patent/CN113020588B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000035616A1 (en) * | 1998-12-16 | 2000-06-22 | Celsia S.P.A. | Process for the production of tungsten-copper composite sinterable powders |
| JP2005194566A (en) * | 2004-01-06 | 2005-07-21 | Yamaha Corp | Tungsten-copper composite powder, its production method, and method of producing sintered alloy using the same |
| CN101429597A (en) * | 2007-11-09 | 2009-05-13 | 北京有色金属研究总院 | Ultrafine molybdenum powder or ultrafine tungsten powder with surface clad copper |
| CN101288905A (en) * | 2008-06-03 | 2008-10-22 | 西安理工大学 | Preparation method of copper cladding tungsten composite powder |
| CN101537491A (en) * | 2009-04-30 | 2009-09-23 | 北京科技大学 | Preparation method of copper-coated tungsten composite powder |
| CN106238727A (en) * | 2016-08-23 | 2016-12-21 | 合肥工业大学 | A kind of preparation method of Cu bag W composite granule |
| CN106498209A (en) * | 2016-10-28 | 2017-03-15 | 西安理工大学 | A kind of preparation method of doped graphene tungsten-copper alloy |
| CN108893637A (en) * | 2018-07-02 | 2018-11-27 | 西安交通大学 | A kind of preparation method of copper-tungsten doped graphene |
| CN110172632A (en) * | 2019-03-20 | 2019-08-27 | 河南科技大学 | A kind of graphene oxide enhancing dispersion copper tungsten chromium electrical contact material and preparation method thereof |
| CN112126838A (en) * | 2020-09-30 | 2020-12-25 | 全球能源互联网研究院有限公司 | Copper-tungsten alloy material and preparation method and application thereof |
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