CN108264041B - Graphene oxide/copper oxide composite powder, preparation method thereof and preparation method of graphene/copper composite material with micro-layered structure - Google Patents
Graphene oxide/copper oxide composite powder, preparation method thereof and preparation method of graphene/copper composite material with micro-layered structure Download PDFInfo
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Abstract
Graphene oxide/copper oxide composite powder, a preparation method thereof and a preparation method of a micro-layered graphene/copper composite material belong to the field of powder metallurgy. The invention aims to solve the technical problems that due to the difficulty in compounding graphene and metal copper, the tensile strength of a composite material is not ideal. According to the method, firstly, graphene oxide and copper salt are fully mixed, copper hydroxide is precipitated on the surfaces of graphene oxide sheets by controlling parameters such as reaction temperature, pH value and the like, and the nanorods can be lodged on the surfaces of the graphene oxide sheets to form good combination and contribute to self-assembly between the sheets, so that the composite powder with the lamellar structure is formed. And then reducing and sintering to obtain the graphene/copper-based composite material with the microscopic laminated structure. The method has the advantages of cheap raw materials, simpler equipment and operation, easy batch production, high strength of the composite material and good electric and thermal conductivity.
Description
Technical Field
The invention belongs to the field of powder metallurgy; in particular to graphene oxide/copper oxide composite powder and a preparation method thereof, and a preparation method of a graphene/copper composite material with a micro-layered structure.
Background
The copper and the copper alloy have good mechanical property and excellent processing property, are easy to cast, plastically process and the like, and more importantly, the copper and the copper alloy have good corrosion resistance, heat conduction and electric conductivity, so the copper and the copper alloy can be widely applied to the industrial fields of electronics, electrical and mechanical manufacture and the like. But the shortages of the room temperature strength, the high temperature performance, the abrasion performance and the like of the copper limit the wider application of the copper. With the rapid development of modern aerospace and electronic technologies, more and higher requirements are put on the use of copper, namely, on the basis of ensuring good physical properties of copper such as electric conduction and heat conduction, the material is required to have higher strength, lower thermal expansion property, good frictional wear property and the like. Copper-based composites are one of the directions in which new high-strength, high-conductivity and high-wear-resistance materials are developed.
Graphene is a novel material consisting of a single layer of carbon atoms. Because of its advantages of ultrahigh mechanical performance, super-strong electric and heat conductivity, and super-large specific surface area, it has been paid extensive attention by researchers. The Young modulus and tensile strength of the single-layer graphene are respectively as high as 1TPa and 130GPa, and the electron mobility is 200,000cm2V-1s-1While the specific surface area is as high as 2600m2g-1And a density of only 2.2g cm3. These characteristics make graphene an excellent choice for copper-based composite material reinforcement.
However, the conventional method faces many problems in the aspects of graphene uniform dispersion and composite material preparation, and it is difficult to prepare a copper-based composite material with excellent performance. Therefore, in recent years, researchers have continuously proposed new methods, and hopefully, the enhancement of the copper-based composite material by the graphene can be realized.
Chu et al (Phys Status solid A,2014,211:184- & ltSUB & gt 190.) successfully prepares the graphene/copper-based composite material by combining a high-energy ball milling method and a hot-pressing sintering method, and the graphene can still be uniformly dispersed in a copper matrix when the volume fraction of the graphene is up to 8%. The tensile yield strength of the material is 321MPa, and the elastic modulus is 105 GPa. However, researches show that the high-energy ball milling method can damage the graphene structure, and the graphene subjected to long-time high-energy ball milling can be converted into amorphous carbon, so that the enhancement effect is influenced. Hwang et al (Advanced Materials,2013,25: 6724-. The tensile test result shows that the elastic modulus and the yield strength of the graphene/copper-based composite material with the volume fraction of 2.5% are respectively 131GPa and 284MPa, which are equivalent to 1.3 times and 1.8 times of pure copper, but the difference with the theoretical value is still large. Inspired by the structure of a pearl layer, Xiong et al (Acs Nano,2015,9:6934-6943) pour a Reduced Graphene Oxide (RGO) solution into a porous copper preform, the RGO is absorbed into pores of the copper preform in the drying and reducing process, and then the copper preform is compacted into a composite material, wherein the graphene/copper-based composite material has a brick mud structure of the pearl layer and has the tensile strength of 233 MPa. The strength of the composite material prepared by the method is improved compared with that of a pure copper material, but is still far lower than expected.
Kim et al (Nature Communication,2013,4,2114:1-7) adopt a nano-lamination method to prepare a single-layer graphene reinforced copper-based and nickel-based composite material, obtain an abnormally significant reinforcing effect, and the compressive strength of the composite material respectively reaches 1.5 GPa and 4 GPa. The compressive yield strength of the graphene is improved by 10 times, and the great potential of the graphene as a reinforcement for a metal matrix composite is shown. The composite material prepared by the method has extremely high compressive strength, but is difficult to obtain a large composite material block due to the excessively complex process, so that the method is difficult to be applied to large-scale actual production.
Disclosure of Invention
At present, the following methods are used for preparing the graphene copper-based composite material. The ball milling method and the molecular mixing method mainly aim at realizing the uniform dispersion of graphene in a copper matrix, and the composite structure of graphene and copper is not designed, so that the performance of the composite material is generally low. Although the composite material with a layered structure can be obtained by adopting the surface adsorption method, the tensile strength of the composite material is not ideal due to factors such as weak bonding force between graphene and a copper matrix. The composite material prepared by the nano-lamination method is undoubtedly the most excellent in performance, but the material is very thin, and various technologies such as CVD, graphene transfer and physical vapor deposition need to be utilized, so that the process is complicated, the requirement on equipment is high, and the composite material is not suitable for mass production.
Aiming at the problems, the invention provides a method for preparing a graphene/copper composite material with a microscopic layered structure, which has the advantages of cheap raw materials, simpler equipment and operation, easiness in batch production, high strength and good electric and thermal conductivity. According to the method, firstly, graphene oxide and copper salt are fully mixed, copper hydroxide is precipitated on the surfaces of graphene oxide sheets by controlling parameters such as reaction temperature, pH value and the like, and the nanorods can be lodged on the surfaces of the graphene oxide sheets to form good combination and contribute to self-assembly between the sheets, so that the composite powder with the lamellar structure is formed. And then reducing and sintering to obtain the graphene/copper-based composite material with the microscopic laminated structure.
The graphene oxide/copper oxide composite powder is prepared by mixing a copper salt solution and a graphene oxide solution, uniformly stirring, then dropwise adding or adding a sodium hydroxide solution at one time until the pH value is 7-15, washing with water until the pH value is neutral, and drying; the method specifically comprises the following steps: mixing the copper salt solution and the graphene oxide solution, and stirring for 5-120 min; and then dropwise adding or adding a sodium hydroxide solution at 1-45 ℃ in one step until the pH value is 7-15, washing with deionized water until the solution is neutral, and drying to obtain the graphene oxide/copper oxide composite powder.
Further, the copper salt in the copper salt solution is one or more of copper acetate, copper formate, copper sulfate, copper nitrate or copper chloride which are mixed (mixture, and the various copper salts are mixed according to any ratio).
The mass ratio of the graphene oxide to the copper in the copper salt solution is (0.001-10): 100.
The concentration of the graphene oxide solution is 0.5-50 mg/ml.
The concentration of the sodium hydroxide solution is 0.5-25 mol/L.
Dropping sodium hydroxide solution at 10-30 ℃.
The drying temperature is 70-200 ℃.
The composite powder prepared by the method has a microscopic layered structure.
The preparation method of the microscopic laminated structure graphene/copper composite material is completed by the following steps:
firstly, carrying out reduction treatment on the graphene oxide/copper oxide composite powder prepared by the method for 0.5-10 hours at the temperature of 200-400 ℃ under the condition of a reducing atmosphere, wherein the reducing atmosphere is hydrogen or a mixed gas of hydrogen and an inert gas;
secondly, treating by using a plasma electric spark sintering method, a vacuum hot-pressing sintering method or a sheath hot-rolling method to obtain the graphene/copper composite material with the microscopic laminated structure;
wherein, the volume content of hydrogen in the mixed gas is not less than 7 percent, and the inert gas is one or the mixture of a plurality of argon, nitrogen, argon and nitrogen (the mixture, various inert gases are mixed according to any ratio).
The reaction parameters of the electric spark sintering method are as follows: the sintering temperature is 500-900 ℃, the sintering pressure is 5-60 MPa, and the sintering time is 3-60 min.
The reaction parameters of the vacuum hot-pressing sintering are as follows: the sintering temperature is 700-950 ℃, the sintering pressure is 20-100 MPa, and the sintering time is 3-240 min.
The sheath hot rolling reaction parameters are as follows: the rolling temperature is 500-800 ℃, and the rolling amount is 1-70%.
The graphene oxide and the copper salt are used as raw materials, so that the graphene oxide is low in price, simple in equipment and operation and easy to produce in batches;
compared with the traditional preparation methods such as a molecular level mixing method, a ball milling method and the like, the invention can obtain the composite material with a microscopic layered structure and can realize the design of the material structure.
The composite material prepared by the invention has the advantages of high strength, good electric conductivity and thermal conductivity and the like.
Drawings
FIG. 1 shows a composite powder that has been freeze-dried according to a first embodiment;
FIG. 2 is a metallographic photograph showing a micro-layered structure after etching of the surface of the composite material according to the first embodiment;
FIG. 3 is a tensile curve of one embodiment of a composite;
FIG. 4 is an XRD spectrum of composite powder prepared at different temperatures;
FIG. 5 is an SEM photograph of a composite powder prepared at 20 ℃;
FIG. 6 is an SEM photograph of a composite powder prepared at 40 ℃;
FIG. 7 is an SEM photograph of a composite powder prepared at 50 ℃;
FIG. 8 is a tensile curve of composites prepared at different temperatures;
FIG. 9 is an XRD spectrum of composite powders prepared at different pH values;
FIG. 10 is a tensile curve of composites prepared at different pH values.
Detailed Description
The first embodiment is as follows: the graphene oxide/copper oxide composite powder according to the present embodiment is prepared by the following steps: dissolving copper acetate in deionized water to obtain a copper salt solution with the concentration of 0.29mol/L, mixing the copper salt solution and a graphene oxide solution with the concentration of 1mg/ml according to the mass ratio of the graphene oxide to the copper in the copper salt of 0.0066:100, and stirring for 30 min; then dropwise adding a sodium hydroxide solution with the concentration of 4mol/L at the temperature of 20 ℃ till the pH value is 13.6, washing the solution to be neutral by using deionized water, and drying the solution at the temperature of 110 ℃ to obtain the graphene oxide/copper oxide composite powder (a microscopic layered structure).
The method for preparing the graphene/copper composite material with the micro-layered structure by using the graphene oxide/copper oxide composite powder obtained by the embodiment comprises the following steps:
firstly, carrying out reduction treatment on graphene oxide/copper oxide composite powder for 5 hours at the temperature of 400 ℃ under the reducing atmosphere condition, wherein the reducing atmosphere is a mixed gas of hydrogen and argon with the hydrogen content of 17% (volume);
and step two, treating by using a plasma spark sintering method, wherein the sintering temperature is 600 ℃, the sintering pressure is 40MPa, and the sintering time is 5min, so that the graphene/copper composite material with the microscopic laminated structure and the graphene volume fraction of 2.5% is obtained. The electrical conductivity of the composite was 65.67% IACS.
The composite powder and the composite material prepared in the present embodiment were tested, and the results are shown in fig. 1 to 3.
As is clear from fig. 1, the copper compound in the composite powder prepared in the present embodiment completely covers the graphene oxide sheets in the form of nano sheets.
As can be seen from fig. 2, the sintered composite material exhibits a micro-layered structure.
As can be seen from fig. 3, the tensile strength of the composite material prepared by the method of the present embodiment reached 748MPa, which is about 5 times that of pure copper.
The second embodiment is as follows: the graphene oxide/copper oxide composite powder according to the present embodiment is prepared by the following steps: dissolving copper acetate in deionized water to obtain a copper salt solution with the concentration of 0.28mol/L, mixing the copper salt solution and a graphene oxide solution with the concentration of 1mg/ml according to the mass ratio of graphene oxide to copper in the copper salt of 0.0136:100, and stirring for 30 min; then dropwise adding a sodium hydroxide solution with the concentration of 4mol/L at the temperature of 20 ℃ till the pH value is 13.6, washing the solution to be neutral by using deionized water, and drying the solution at the temperature of 110 ℃ to obtain the graphene oxide/copper oxide composite powder (a microscopic layered structure).
The method for preparing the graphene/copper composite material with the micro-layered structure by using the graphene oxide/copper oxide composite powder obtained by the embodiment comprises the following steps:
firstly, carrying out reduction treatment on graphene oxide/copper oxide composite powder for 5 hours at the temperature of 400 ℃ under the reducing atmosphere condition, wherein the reducing atmosphere is a mixed gas of hydrogen and argon with the hydrogen content of 17% (volume);
and step two, treating by using a plasma spark sintering method, wherein the sintering temperature is 600 ℃, the sintering pressure is 40MPa, and the sintering time is 5min, so that the graphene/copper composite material with the microscopic laminated structure and the graphene volume fraction of 5% is obtained. The electrical conductivity of the composite was 69.12% IACS.
The third concrete implementation mode: the graphene oxide/copper oxide composite powder according to the present embodiment is prepared by the following steps: dissolving copper acetate in deionized water to obtain a copper salt solution with the concentration of 0.29mol/L, mixing the copper salt solution and a graphene oxide solution with the concentration of 1mg/ml according to the mass ratio of the graphene oxide to the copper in the copper salt of 0.0066:100, and stirring for 30 min; then dropwise adding a sodium hydroxide solution with the concentration of 4mol/L at the temperature of 40 ℃ till the pH value is 13.6, washing the solution to be neutral by using deionized water, and drying the solution at the temperature of 110 ℃ to obtain the graphene oxide/copper oxide composite powder (a microscopic layered structure).
The method for preparing the graphene/copper composite material with the micro-layered structure by using the graphene oxide/copper oxide composite powder obtained by the embodiment comprises the following steps:
firstly, carrying out reduction treatment on graphene oxide/copper oxide composite powder for 5 hours at the temperature of 400 ℃ under the reducing atmosphere condition, wherein the reducing atmosphere is a mixed gas of hydrogen and argon with the hydrogen content of 17% (volume);
and step two, treating by using a plasma spark sintering method, wherein the sintering temperature is 600 ℃, the sintering pressure is 40MPa, and the sintering time is 5min, so that the graphene/copper composite material with the microscopic laminated structure and the graphene volume fraction of 2.5% is obtained. The electrical conductivity of the composite was 69.04% IACS.
The fourth concrete implementation mode: the graphene oxide/copper oxide composite powder according to the present embodiment is prepared by the following steps: dissolving copper acetate in deionized water to obtain a copper salt solution with the concentration of 0.29mol/L, mixing the copper salt solution and a graphene oxide solution with the concentration of 1mg/ml according to the mass ratio of the graphene oxide to the copper in the copper salt of 0.0066:100, and stirring for 30 min; and dropwise adding a sodium hydroxide solution with the concentration of 4mol/L to the pH value of 8 at the temperature of 20 ℃, washing the solution to be neutral by using deionized water, and drying the solution at the temperature of 110 ℃ to obtain the graphene oxide/copper oxide composite powder (a microscopic layered structure).
The method for preparing the graphene/copper composite material with the micro-layered structure by using the graphene oxide/copper oxide composite powder obtained by the embodiment comprises the following steps:
firstly, carrying out reduction treatment on graphene oxide/copper oxide composite powder for 5 hours at the temperature of 400 ℃ under the reducing atmosphere condition, wherein the reducing atmosphere is a mixed gas of hydrogen and argon with the hydrogen content of 17% (volume);
and step two, treating by using a plasma spark sintering method, wherein the sintering temperature is 600 ℃, the sintering pressure is 40MPa, and the sintering time is 5min, so that the graphene/copper composite material with the microscopic laminated structure and the graphene volume fraction of 2.5% is obtained. The electrical conductivity of the composite was 64.09% IACS.
The fifth concrete implementation mode: the fourth difference between the present embodiment and the fourth embodiment is that vacuum hot-pressing sintering is adopted to replace the plasma spark sintering method in the second step, the sintering temperature is 800 ℃, the sintering pressure is 50MPa, and the sintering time is 10 min. The other steps and parameters are the same as in embodiment four.
The sixth specific implementation mode: the fourth difference between the present embodiment and the fourth embodiment is that the plasma spark sintering method in the second step is replaced by sheath hot rolling, the rolling temperature is 600 ℃, and the rolling amount is 40%. The other steps and parameters are the same as in embodiment four.
The following tests are adopted to verify the effect of the invention:
first, graphene oxide/copper oxide composite powder is prepared at different temperatures.
The graphene oxide/copper oxide composite powder is prepared by the following steps: dissolving copper acetate in deionized water to obtain a copper salt solution with the concentration of 0.29mol/L, mixing the copper salt solution and a graphene oxide solution with the concentration of 1mg/ml according to the mass ratio of the graphene oxide to the copper in the copper salt of 0.0066:100, and stirring for 30 min; then dropwise adding a sodium hydroxide solution with the concentration of 4mol/L at the temperature of 20 ℃, 40 ℃ or 50 ℃ until the pH value is 13.6, washing with deionized water to be neutral, and drying at the temperature of 110 ℃ to obtain the graphene oxide/copper oxide composite powder.
The XRD spectrogram of the graphene oxide/copper oxide composite powder prepared at different temperatures is shown in fig. 4, and it can be seen from fig. 4 that when the reaction temperature is 20 ℃ and 40 ℃, diffraction peaks in the XRD spectrogram of the composite powder correspond to crystal faces of copper hydroxide and copper oxide, respectively; when the reaction temperature reaches 50 ℃, the characteristic peak of copper hydroxide in the XRD spectrogram disappears, and only the characteristic peak of copper oxide appears. This indicates that the higher reaction temperature (below 50 ℃) completely converts the copper hydroxide in the composite powder to copper oxide.
SEM photographs of the composite powder prepared at different temperatures are shown in fig. 5 to 7. When the reaction temperature is 20 ℃, the copper oxide and the copper hydroxide in the composite powder mainly exist in a nano-sheet form, and the size is about 500 nm. When the reaction temperature is increased to 40 ℃, the size of the nano sheet is reduced to 200-300 nm. When the reaction temperature reaches 50 ℃, the nano-sheets in the composite powder are converted into nano-rod structures.
Composite materials prepared at different temperaturesThe tensile stress strain curve (see method of embodiment one) is shown in fig. 8. The maximum tensile strengths of the composites prepared at room temperature, 40 ℃ and 50 ℃ were 748MPa, 625MPa and 288MPa, respectively. It can be seen that the tensile strength of the composite material gradually decreases with increasing reaction temperature, and that there is no significant yield plateau in the stress-strain curve when the reaction temperature reaches 50 ℃, i.e. the fracture changes from ductile to brittle. This is mainly because, at a relatively low reaction temperature, NaOH is added dropwise to the copper salt solution to form Cu (OH)2，Cu(OH)2The positive charges and the negative charges of GO generate strong interaction, so that the surface of GO lamella adsorbs Cu (OH)2Therefore, overlapping among the sheets is avoided, and graphene can be uniformly dispersed in the copper matrix after reduction and sintering treatment, so that the reinforcing effect is achieved; when the reaction temperature is higher (higher than 50 ℃), more CuO is generated in the reaction system (as shown in figure 9), the CuO is accelerated in thermal motion in the solution along with the rise of the temperature, the particles are easy to combine and grow, the binding force between the CuO and GO is weak, the GO cannot be effectively coated, the graphene is also easy to agglomerate, and finally the tensile strength of the composite material is reduced.
The XRD patterns of the composite powders prepared under different pH values are shown in figure 9. When the pH value is 5.9 and 6.6, diffraction peaks in a spectrogram mainly come from basic copper acetate; with the increase of the pH value, the diffraction peak of the basic copper acetate gradually disappears, and the characteristic peaks of the copper hydroxide and the copper oxide appear. This indicates that the pH value greatly affects the phase composition of the composite powder.
The tensile stress strain curves of the composites prepared at different pH values (see method of embodiment one) are shown in fig. 10. The maximum tensile strengths of the composites prepared at pH 5.9, 6.6 and 13.6 were 514MPa, 459MPa and 748 MPa. It can be seen that the composite material prepared under the condition that the pH is acidic is low in strength. This is because basic copper acetate, although in the form of flaky crystals, is disadvantageous in that it generates a large amount of water and carbon dioxide during pyrolysis, and thus generates a large amount of void defects, thereby improving the strength of the composite material.
Claims (7)
1. The graphene oxide/copper oxide composite powder is characterized in that the composite powder is prepared by uniformly mixing a copper salt solution and a graphene oxide solution, then dropwise adding a sodium hydroxide solution at the temperature of 1 ~ 45 ℃ until the pH value is 8 ~ 13.6.6, washing with water until the pH value is neutral, and drying, wherein the mass ratio of the graphene oxide to copper in the copper salt solution is (0.0066 ~ 0.0136):100, and the copper salt solution is a copper acetate solution.
2. The method for preparing graphene oxide/copper oxide composite powder according to claim 1, wherein the method comprises the following steps:
mixing the copper salt solution and the graphene oxide solution, stirring for 5-120min, then dropwise adding a sodium hydroxide solution at the temperature of 1 ~ 45 ℃ until the pH value is 8 ~ 13.6.6, washing with deionized water until the solution is neutral, and drying to obtain the graphene oxide/copper oxide composite powder.
3. The method according to claim 2, wherein the graphene oxide solution has a concentration of 0.5 ~ 50 mg/ml.
4. The method according to claim 2, wherein the concentration of the sodium hydroxide solution is 0.5 ~ 25 mol/L.
5. The method according to claim 2, wherein the drying temperature is 70 ~ 200 ℃.
6. The preparation method of the micro-laminated structure graphene/copper composite material is characterized by comprising the following steps of:
firstly, carrying out reduction treatment on the graphene oxide/copper oxide composite powder of claim 1 or the graphene oxide/copper oxide composite powder prepared by the method of any one of claims 2 ~ 5 for 0.5 ~ 10h at the temperature of 200 ~ 400 ℃ under the reducing atmosphere condition, wherein the reducing atmosphere is hydrogen or mixed gas of hydrogen and inert gas;
secondly, treating by using a plasma electric spark sintering method, a vacuum hot-pressing sintering method or a sheath hot-rolling method to obtain the graphene/copper composite material with the microscopic laminated structure;
wherein, the volume content of hydrogen in the mixed gas is not less than 3 percent, and the inert gas is argon.
7. The preparation method of the micro-laminated graphene/copper composite material according to claim 6, wherein the reaction parameters of the electric spark sintering method are that the sintering temperature is 500 ~ 900 ℃, the sintering pressure is 5 ~ 80MPa, and the sintering time is 3 ~ 60min, the reaction parameters of the vacuum hot-pressing sintering method are that the sintering temperature is 700 ~ 950 ℃, the sintering pressure is 20 ~ 100MPa, and the sintering time is 3 ~ 240min, and the reaction parameters of the sheathing hot rolling method are that the rolling temperature is 500 ~ 800 ℃, and the rolling amount is 1% ~ 70%.
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