CN114540661B - Graphene reinforced copper-molybdenum composite material with three-dimensional network structure and preparation method thereof - Google Patents
Graphene reinforced copper-molybdenum composite material with three-dimensional network structure and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a graphene reinforced copper-molybdenum composite material with a three-dimensional network structure, which comprises three components of Cu, Mo and reduced graphene oxide. The invention also discloses a preparation method of the graphene reinforced copper-molybdenum composite material with the three-dimensional network structure, which comprises the following steps: firstly, carrying out cation modification treatment on Cu powder; secondly, dispersing graphene oxide in an ethanol solution, and then adding copper nitrate to obtain the loaded Cu 2+ GO mixed solution of (1); adding the modified Cu powder into the GO mixed solution, adding Mo powder, and then carrying out in-situ reduction to obtain composite powder; and finally, preparing the graphene reinforced copper-molybdenum composite material by hot-pressing sintering. The method realizes uniform distribution of rGO in the copper-molybdenum composite material, improves the strength and toughness, provides a continuous path for transmission of electrons and phonons by the graphene network, and improves the electric conduction and heat conduction performance of the composite material, thereby obtaining the graphene reinforced copper-molybdenum composite material with excellent comprehensive performance.
Description
Technical Field
The invention belongs to the technical field of copper-based composite material preparation, and particularly relates to a graphene reinforced copper-molybdenum composite material with a three-dimensional network structure and a preparation method of the graphene reinforced copper-molybdenum composite material with the three-dimensional network structure.
Background
The copper-molybdenum composite material is widely applied to the fields of high-voltage switches, microelectronic packaging, instruments and meters and the like due to excellent electric conduction and heat conduction characteristics, high hardness, high elastic modulus, low thermal expansion coefficient and the like. However, copper and molybdenum belong to a binary refractory system, and although the mechanical properties of the copper and molybdenum alloy prepared by the traditional processes such as mechanical alloying, infiltration method, liquid-phase sintering method and injection molding are improved, the electrical and thermal conductivity of the material is usually sacrificed, so that the wider application of the copper and molybdenum alloy is limited. As a two-dimensional material with a honeycomb-shaped lamellar structure, graphene becomes an ideal reinforcement of a metal matrix composite material due to excellent strength, ultrahigh carrier mobility, thermal conductivity and other properties. Therefore, the graphene is introduced into the copper-molybdenum composite material, and the composite material with excellent mechanical property and electric and heat conducting properties is expected to be obtained.
The existing preparation methods of the graphene reinforced copper-based composite material include a ball milling method, a molecular-level blending method, an in-situ growth method, an electrochemical method, a casting method, a rolling method and the like. Although the physical properties and mechanical properties are improved to different degrees by the methods, the problems of self-aggregation caused by strong van der waals force between graphene sheets, poor interface wettability between graphene and metal and the like are not solved effectively, so that the excellent intrinsic properties of graphene cannot be fully exerted. Different from two-dimensional graphene, the three-dimensional reticular graphene is a non-planar three-dimensional fluctuating spatial structure, and the isotropy of the three-dimensional reticular graphene enables the dispersion among the sheets to be more uniform. Meanwhile, the supercontinuum sheet layer can form a network-shaped communicating channel in the metal matrix, so that the supercontinuum sheet layer is tightly combined with metal in a three-dimensional space, the electric conduction and heat conduction performance of the composite material can be obviously improved, and the toughness and toughness of the composite material are improved at the same time. Therefore, the development of the graphene reinforced copper-molybdenum composite material with the three-dimensional network structure and the preparation method have important engineering significance and practical value.
Disclosure of Invention
The invention aims to provide a graphene reinforced copper-molybdenum composite material with a three-dimensional network structure.
The invention also aims to provide a preparation method of the graphene reinforced copper-molybdenum composite material with the three-dimensional network structure, and the method realizes continuous distribution and uniform dispersion of the redox graphene (rGO) in the copper-molybdenum composite material and solves the problems of easy agglomeration and difficult dispersion of graphene sheets by a method combining surface modification, electrostatic self-assembly and in-situ reduction. And then, promoting the rGO to form an isotropic communication passage in the matrix by a hot-pressing sintering technology, so as to obtain the rGO reinforced copper-molybdenum composite material with a three-dimensional network structure. In addition, the molybdenum carbide generated at the interface in the sintering process realizes the metallurgical bonding of the Cu and Mo interface, and is beneficial to further improving the performance of the composite material.
The first technical scheme adopted by the invention is that the graphene reinforced copper-molybdenum composite material with the three-dimensional net structure comprises the following components in percentage by mass: cu 78.5-89.9 wt.%; 10.0-20.0 wt.% Mo; 0.1-1.5 wt.% of redox graphene, wherein the sum of the mass percentages of the components is 100%.
The second technical scheme adopted by the invention is that the preparation method of the graphene reinforced copper-molybdenum composite material with the three-dimensional net structure comprises the following specific steps:
step 1, weighing the following raw materials in percentage by mass: 78.5-89.9 wt.% of Cu powder; 10.0-20.0 wt.% of Mo powder; 0.1-1.5 wt.% of graphene oxide, wherein the sum of the mass percentages of the components is 100%;
step 3, adding graphene oxide into ethanol, performing ultrasonic dispersion for 1-2 hours, and then adding Cu (NO) 3 ) 2 ·3H 2 O is magnetically stirred for 0.5 to 1 hour to obtain the loaded Cu 2+ The graphene oxide mixed solution of (a);
step 4, adding the modified Cu powder obtained in the step 1 into the Cu loaded in the step 3 2+ Magnetically stirring the graphene oxide mixed solution for 0.5-1 h, then adding Mo, and magnetically stirring for 0.5-1 h to obtain a GO/Cu-Mo mixed solution;
step 5, dropwise adding an ascorbic acid solution into the GO/Cu-Mo mixed solution obtained in the step 4, adding NaOH to adjust the pH value to 10-12, then putting the mixture into a water bath kettle at the temperature of 90-100 ℃, magnetically stirring the mixture for 6-8 hours, and completely drying the mixture to obtain in-situ reduced graphene oxide reinforced copper-molybdenum composite powder;
and 6, putting the reduced graphene oxide reinforced copper-molybdenum composite powder obtained in the step 5 into a graphite mold for prepressing, then putting the graphite mold into a vacuum hot-pressing sintering furnace for sintering to 900-950 ℃, preserving heat for 30-45 min, and finally cooling along with the furnace to obtain the graphene reinforced copper-molybdenum composite material with the three-dimensional network structure.
The present invention is also characterized in that,
in the step 2, the concentration of the ethanol solution of Cetyl Trimethyl Ammonium Bromide (CTAB) is 0.3-0.6 mg/ml, and the magnetic stirring speed is 300-400 rpm;
in the step 3, the concentration of the graphene oxide solution is 0.4-7.5 mg/ml, and the graphene oxide and Cu are 2+ The mass ratio of (1: 5) - (10), and the magnetic stirring speed is 300-400 rpm;
in the step 5, the solubility of the ascorbic acid solution is 8.0-30.0 mg/ml, and the mass ratio of the graphene oxide to the ascorbic acid is 1: 0.4-1.6;
in the step 6, the pressing pressure of the graphite mold is 8-10 MPa, the pressure maintaining time is 10-20 s, and the vacuum degree in the vacuum hot-pressing sintering furnace is not lower than 1 multiplied by 10 -3 Pa, and the temperature rise speed is 30-40 ℃/min.
The preparation method has the beneficial effects that the graphene reinforced copper-molybdenum composite material with the three-dimensional network structure, which is obtained by the preparation method, realizes continuous dispersion and uniform distribution of reduced graphene oxide in a metal matrix, and solves the problems of easy agglomeration and difficult dispersion of graphene in a copper-based composite material; the constructed three-dimensional reticular graphene structure forms an isotropic continuous channel in the copper-molybdenum composite material, so that the electric conduction and heat conduction performance of the composite material is improved, the load transfer is facilitated, and the reinforcing and toughening effects are realized. In addition, the molybdenum carbide generated in situ at the interface of the copper and the molybdenum strengthens the combination between the copper and the molybdenum interface, and further improves the performance of the composite material.
The preparation method has the advantages of organically combining the advantages of surface modification, electrostatic self-assembly, in-situ reduction and vacuum hot-pressing sintering technologies. Firstly, the cation modified Cu powder and anions carried by the surface of Graphene Oxide (GO) form an electrostatic self-assembly effect in a solution, and graphene oxide with opposite charges is adsorbed on the surface of the modified Cu ions under the action of electrostatic attraction. GO lamella on the surface of Cu particles is coated under the action of green reducing agent ascorbic acidIn-situ reduction to continuously distributed reduced graphene oxide (rGO), and Cu loaded on the surface of GO 2+ And also reduced to nano-copper particles. In the hot-pressing sintering process, the rGO generated in situ on the surface of Cu particles is welded under the combined action of externally applied pressure and a thermal stress effect generated by the difference of thermal expansion coefficients of metal Cu and graphene, so that the rGO reduced in situ on the surface of Cu powder is promoted to form a continuous three-dimensional network structure in a matrix, and a continuous channel is provided for the transmission of electrons, phonons and loads. In addition, the communicated graphene three-dimensional network has stronger restriction effect on the matrix crystal grains in the further sintering process, and the growth of the matrix crystal grains is more effectively hindered. Meanwhile, the rGO on the surface of the Cu and the Mo generate molybdenum carbide in situ at the interface, and the molybdenum carbide is used as a traditional reinforcing phase, so that the copper-based composite material has high hardness and corrosion resistance, and the performance of the copper-based composite material is further optimized.
Drawings
FIG. 1 is a flow chart of a preparation method of a graphene reinforced copper-molybdenum composite material with a three-dimensional network structure according to the invention;
FIG. 2 is a low magnification photograph of the morphology of the graphene reinforced copper molybdenum composite powder with a three-dimensional network structure according to the present invention;
FIG. 3 is a high magnification photograph of the morphology of the graphene reinforced copper-molybdenum composite powder with a three-dimensional network structure according to the present invention;
fig. 4 is a microstructure of a graphene reinforced copper molybdenum bulk composite material having a three-dimensional network structure according to the present invention.
Detailed Description
The graphene reinforced copper-molybdenum composite material with the three-dimensional network structure comprises 78.5-89.9% of Cu, 10.0-20.0% of Mo and 0.1-1.5% of reduced graphene oxide (rGO), and the sum of the mass percentages of the Cu, the Mo and the rGO is 100%.
The preparation method of the graphene reinforced copper-molybdenum composite material with the three-dimensional network structure is shown in figure 1, and comprises the following specific steps:
step 1, firstly, 157-179.8 g of Cu powder is weighed and added into 400-500 ml of 0.3-0.6 mg/ml cetyl trimethyl ammonium bromide ethanol solution, magnetic stirring is carried out at the speed of 300-400 rpm for 0.5-1 h, and cation modified Cu powder is obtained by washing and centrifuging;
step 3, adding the modified Cu powder obtained in the step 1 into the mixed solution obtained in the step 2, performing magnetic stirring for 0.5-1 h, realizing uniform coating and continuous dispersion of graphene oxide on the surface of the modified Cu powder under the action of electrostatic self-assembly, then adding 20-40 g of Mo powder, and performing magnetic stirring for 0.5-1 h to obtain a GO/Cu-Mo mixed solution;
step 4, measuring 40-60 ml of ascorbic acid solution with the concentration of 8-30 mg/ml, dropwise adding the ascorbic acid solution into the mixed solution obtained in the step 3, wherein the mass ratio of Graphene Oxide (GO) to ascorbic acid is 1: 0.4-1.6, adding NaOH to adjust the pH value to 10-12, then putting the mixture into a water bath kettle at the temperature of 90-100 ℃, magnetically stirring the mixture for 6-8 hours, and completely drying the mixture to obtain graphene reinforced copper-molybdenum composite powder synthesized by in-situ reduction;
step 5, putting the composite powder obtained in the step 4 into a graphite die for prepressing, keeping the pressure for 10-20 s at 8-10 MPa, then putting the graphite die into a vacuum hot-pressing sintering furnace, and vacuumizing until the vacuum degree is not lower than 1 multiplied by 10 -3 Pa, heating to 900-950 ℃ at a heating speed of 30-40 ℃/min, sintering, keeping the temperature for 30-45 min, applying axial pressure of 30-45 MPa while sintering, and finally cooling along with a furnace to obtain the graphene reinforced copper-molybdenum composite material (rGO/Cu-Mo) with a three-dimensional network structure.
The present invention will be described in detail with reference to specific examples.
Example 1
Step 1, firstly weighing 179.8g of Cu powder, adding the Cu powder into 500ml of hexadecyl trimethyl ammonium bromide ethanol solution with the concentration of 0.6mg/ml, magnetically stirring for 1h at the speed of 400rpm, washing and centrifuging to obtain cation modified Cu powder;
step 3, adding the modified Cu powder obtained in the step 1 into the mixed solution obtained in the step 2, performing magnetic stirring for 1h, realizing uniform coating and continuous dispersion of GO on the surface of the modified Cu powder under the action of electrostatic self-assembly, then adding 20g of Mo powder, and performing magnetic stirring for 0.5h to obtain a GO/Cu-Mo mixed solution;
step 4, measuring 40ml of ascorbic acid solution with the concentration of 8.0mg/ml, dropwise adding the ascorbic acid solution into the mixed solution obtained in the step 3, wherein the mass ratio of GO to ascorbic acid is 1:1.6, adding NaOH to adjust the pH value to 10, then placing the mixture into a 90 ℃ water bath kettle, magnetically stirring the mixture for 6 hours, and completely drying the mixture to obtain in-situ reduced graphene reinforced copper-molybdenum composite powder;
step 5, putting the composite powder obtained in the step 4 into a graphite die for prepressing, wherein the pressing pressure is 8MPa, the pressure is maintained for 10s, then putting the graphite die into a vacuum hot-pressing sintering furnace, and vacuumizing until the vacuum degree is not lower than 1 multiplied by 10 -3 Pa, heating to 900 ℃ at a heating rate of 30 ℃/min, preserving heat for 30min, applying axial pressure of 30MPa while sintering, and finally cooling along with the furnace to obtain the graphene-reinforced copper-molybdenum composite material (rGO/Cu-Mo) with a three-dimensional network structure.
In this example, the densification and conductivity of the 0.1 wt.% rGO/Cu-10 wt.% Mo composite material were 97.4% and 83.3% IACS, respectively, with a tensile strength of 288MPa and an elongation of 6.4%.
Example 2
Step 1, firstly weighing 179.4g of Cu powder, adding the Cu powder into 500ml of 0.6mg/ml hexadecyl trimethyl ammonium bromide ethanol solution, magnetically stirring for 1h at the speed of 400rpm, washing and centrifuging to obtain cation modified Cu powder;
step 3, adding the modified Cu powder obtained in the step 1 into the mixed solution obtained in the step 2, performing magnetic stirring for 1h, realizing uniform coating and continuous dispersion of GO on the surface of the modified Cu powder under the action of electrostatic self-assembly, then adding 20g of Mo powder, and performing magnetic stirring for 0.5h to obtain a GO/Cu-Mo mixed solution;
step 4, measuring 40ml of ascorbic acid solution with the concentration of 18.0mg/ml, dropwise adding the ascorbic acid solution into the mixed solution obtained in the step 3, wherein the mass ratio of GO to ascorbic acid is 1:1.2, adding NaOH to adjust the pH value to 10, then placing the mixture into a 90 ℃ water bath kettle, magnetically stirring the mixture for 6 hours, and completely drying the mixture to obtain in-situ reduced graphene reinforced copper-molybdenum composite powder;
step 5, putting the composite powder obtained in the step 4 into a graphite die for prepressing, wherein the pressing pressure is 8MPa, the pressure is maintained for 10s, then putting the graphite die into a vacuum hot-pressing sintering furnace, and vacuumizing until the vacuum degree is not lower than 1 multiplied by 10 -3 Pa, heating to 900 ℃ at a heating rate of 30 ℃/min, preserving heat for 30min, applying axial pressure of 30MPa while sintering, and finally cooling along with the furnace to obtain the graphene-reinforced copper-molybdenum composite material (rGO/Cu-Mo) with a three-dimensional network structure.
In this example, the densification and electrical conductivity of the 0.3 wt.% rGO/Cu-10 wt.% Mo composite material were 98.0% and 84.5% IACS, respectively, with a tensile strength of 302MPa and an elongation of 7.7%.
Example 3
Step 1, firstly weighing 179.0g of Cu powder, adding the Cu powder into 500ml of 0.6mg/ml hexadecyl trimethyl ammonium bromide ethanol solution, magnetically stirring for 1h at the speed of 400rpm, washing and centrifuging to obtain cation modified Cu powder;
step 3, adding the modified Cu powder obtained in the step 1 into the mixed solution obtained in the step 2, performing magnetic stirring for 1h, realizing uniform coating and continuous dispersion of GO on the surface of the modified Cu powder under the action of electrostatic self-assembly, then adding 20g of Mo powder, and performing magnetic stirring for 0.5h to obtain a GO/Cu-Mo mixed solution;
step 4, measuring 40ml of ascorbic acid solution with the concentration of 25mg/ml, dropwise adding the ascorbic acid solution into the mixed solution obtained in the step 3, wherein the mass ratio of GO to ascorbic acid is 1:1, adding NaOH to adjust the pH value to 10, then placing the mixture into a 90 ℃ water bath kettle, magnetically stirring the mixture for 6 hours, and completely drying the mixture to obtain in-situ reduced graphene reinforced copper-molybdenum composite powder;
step 5, putting the composite powder obtained in the step 4 into a graphite die for prepressing, wherein the pressing pressure is 8MPa, the pressure is maintained for 10s, then putting the graphite die into a vacuum hot-pressing sintering furnace, and vacuumizing until the vacuum degree is not lower than 1 multiplied by 10 -3 Pa, heating to 900 ℃ at a heating rate of 30 ℃/min, preserving heat for 30min, applying axial pressure of 30MPa while sintering, and finally cooling along with the furnace to obtain the graphene-reinforced copper-molybdenum composite material (rGO/Cu-Mo) with a three-dimensional network structure.
In this example, the densification and conductivity of the 0.5 wt.% rGO/Cu-10 wt.% Mo composite material were 98.3% and 86.7% IACS, respectively, with a tensile strength of 316MPa and an elongation of 9.3%.
Example 4
Step 1, weighing 178g of Cu powder, adding into 500ml of 0.6mg/ml hexadecyl trimethyl ammonium bromide ethanol solution, magnetically stirring for 1h at the speed of 400rpm, washing and centrifuging to obtain cation modified Cu powder;
step 3, adding the modified Cu powder obtained in the step 1 into the mixed solution obtained in the step 2, performing magnetic stirring for 1h, realizing uniform coating and continuous dispersion of GO on the surface of the modified Cu powder under the action of electrostatic self-assembly, then adding 20g of Mo powder, and performing magnetic stirring for 0.5h to obtain a GO/Cu-Mo mixed solution;
step 4, measuring 40ml of ascorbic acid solution with the concentration of 30.0mg/ml, dropwise adding the ascorbic acid solution into the mixed solution obtained in the step 3, wherein the mass ratio of GO to ascorbic acid is 1:0.6, adding NaOH to adjust the pH value to 10, then placing the mixture into a 90 ℃ water bath kettle, magnetically stirring the mixture for 6 hours, and completely drying the mixture to obtain in-situ reduced graphene reinforced copper-molybdenum composite powder;
step 5, putting the composite powder obtained in the step 4 into a graphite die for prepressing, wherein the pressing pressure is 8MPa, the pressure is maintained for 10s, then putting the graphite die into a vacuum hot-pressing sintering furnace, and vacuumizing until the vacuum degree is not lower than 1 multiplied by 10 -3 Pa, heating to 900 ℃ at a heating rate of 30 ℃/min, preserving heat for 30min, applying axial pressure of 30MPa while sintering, and finally cooling along with the furnace to obtain the graphene-reinforced copper-molybdenum composite material (rGO/Cu-Mo) with a three-dimensional network structure.
In this example, the densification and electrical conductivity of the 1.0 wt.% rGO/Cu-10 wt.% Mo composite was 98.5% and 88.9% IACS, the tensile strength was 330MPa, and the elongation was 10.2%.
Example 5
Step 1, firstly, weighing 177g of Cu powder, adding the Cu powder into 500ml of 0.6mg/ml hexadecyl trimethyl ammonium bromide ethanol solution, magnetically stirring for 1h at the speed of 400rpm, washing and centrifuging to obtain cation modified Cu powder;
step 3, adding the modified Cu powder obtained in the step 1 into the mixed solution obtained in the step 2, performing magnetic stirring for 1h, realizing uniform coating and continuous dispersion of GO on the surface of the modified Cu powder under the action of electrostatic self-assembly, then adding 20g of Mo powder, and performing magnetic stirring for 0.5h to obtain a GO/Cu-Mo mixed solution;
step 4, measuring 40ml of ascorbic acid solution with the concentration of 30.0mg/ml, dropwise adding the ascorbic acid solution into the mixed solution obtained in the step 3, wherein the mass ratio of GO to ascorbic acid is 1:0.4, adding NaOH to adjust the pH value to 10, then placing the mixture into a 90 ℃ water bath kettle, magnetically stirring the mixture for 6 hours, and completely drying the mixture to obtain in-situ reduced graphene reinforced copper-molybdenum composite powder;
step 5, putting the composite powder obtained in the step 4 into a graphite die for prepressing, wherein the pressing pressure is 8MPa, the pressure is maintained for 10s, then putting the graphite die into a vacuum hot-pressing sintering furnace, and vacuumizing until the vacuum degree is not lower than 1 multiplied by 10 -3 Pa, heating to 900 ℃ at a heating rate of 30 ℃/min, preserving heat for 30min, applying axial pressure of 30MPa while sintering, and finally cooling along with the furnace to obtain the graphene-reinforced copper-molybdenum composite material (rGO/Cu-Mo) with a three-dimensional network structure.
In this example, the density and electrical conductivity of the 1.5wt.% rGO/Cu-10 wt.% Mo composite material were 97.5% and 86.0% IACS, respectively, the tensile strength was 308MPa, and the elongation was 8.9%.
Example 6
Step 1, firstly, 157g of Cu powder is weighed and added into 400ml of 0.4mg/ml hexadecyl trimethyl ammonium bromide ethanol solution, magnetic stirring is carried out for 0.5h at the speed of 300rpm, and cation modified Cu powder is obtained by washing and centrifuging;
step 3, adding the modified Cu powder obtained in the step 1 into the mixed solution obtained in the step 2, performing magnetic stirring for 1h, realizing uniform coating and continuous dispersion of GO on the surface of the modified Cu powder under the action of electrostatic self-assembly, then adding 40g of Mo powder, and performing magnetic stirring for 0.5h to obtain a GO/Cu-Mo mixed solution;
step 4, measuring 60ml of ascorbic acid solution with the concentration of 30.0mg/ml, dropwise adding the ascorbic acid solution into the mixed solution obtained in the step 3, wherein the mass ratio of GO to ascorbic acid is 1:0.6, adding NaOH to adjust the pH value to 12, then placing the mixture into a 100 ℃ water bath kettle, magnetically stirring the mixture for 8 hours, and completely drying the mixture to obtain in-situ reduced graphene reinforced copper-molybdenum composite powder;
step 5, putting the composite powder obtained in the step 4 into a graphite die for prepressing, wherein the pressing pressure is 10MPa, the pressure is maintained for 20s, then putting the graphite die into a vacuum hot-pressing sintering furnace, and vacuumizing until the vacuum degree is not lower than 1 multiplied by 10 -3 Pa, heating to 950 ℃ at a heating rate of 40 ℃/min, preserving heat for 45min, applying axial pressure of 45MPa while sintering, and finally cooling along with the furnace to obtain the graphene-reinforced copper-molybdenum composite material (rGO/Cu-Mo) with a three-dimensional network structure.
In this example, the density and conductivity of the 1.5wt.% rGO/Cu-20 wt.% Mo composite material were 97.4% and 84.2% IACS, respectively, the tensile strength was 320MPa, and the elongation was 7.0%.
The combination of the embodiment shows that the density and the conductivity of the Cu-Mo composite material without the added rGO prepared under the same process conditions are 93.5 percent and 78.8 percent IACS respectively, the tensile strength is 236MPa, and the elongation is 6.1 percent. The conductivity, tensile strength and elongation of the three-dimensional network configuration rGO reinforced Cu-Mo composite material were 88.9% IACS, 363MPa and 13.2% respectively at an rGO content of 1 wt.%. Compared with Cu-Mo, the conductivity, the tensile strength and the elongation are respectively improved by 12.8 percent, 39.8 percent and 67.2 percent. Fig. 2 is a graph of the morphology of 1.0 wt.% rGO enhanced Cu-Mo composite powder, and it can be seen that rGO lamellae having a thin corrugated shape are uniformly coated on the surface of Cu particles and are continuously distributed in the Cu surface, which illustrates that the problem of agglomeration among the rGO lamellae due to van der waals forces is effectively solved. As can be seen from the high-power photograph in fig. 3, a large number of uniformly distributed nano-copper particles are loaded on the surface of rGO, which is beneficial to improving the sintering compactness between rGO and a copper matrix, thereby promoting the interface bonding of the composite material. Fig. 4 is a microstructure photograph of the surface of 1.0 wt.% rGO reinforced Cu-Mo bulk composite after corrosion, which shows that rGO is distributed in a continuous path in a copper matrix, and illustrates that in a vacuum hot-pressing sintering process, applied external pressure and a large thermal stress effect is generated by a difference in thermal expansion coefficient between metal Cu and graphene, so that rGO lamellae reduced in situ on the surface of Cu powder are welded and the bonding with a matrix interface is promoted. The above examples show that the formation of the graphene network can simultaneously realize the improvement of the strength and toughness of the copper-molybdenum-based composite material. In addition, the graphene network provides a continuous path for the transmission of electrons and phonons, and the electric conduction and heat conduction performance of the copper-based composite material is improved.
Claims (6)
1. The graphene reinforced copper-molybdenum composite material with the three-dimensional network structure is characterized by comprising the following components in percentage by mass: cu 78.5-89.9 wt.%; 10.0-20.0 wt.% Mo; 0.1-1.5 wt.% of reduced graphene oxide, wherein the sum of the mass percentages of the components is 100%;
the specific preparation method of the graphene reinforced copper-molybdenum composite material comprises the following steps:
step 1, weighing the following raw materials in percentage by mass: 78.5-89.9 wt.% of Cu powder; 10.0-20.0 wt.% of Mo powder; 0.1-1.5 wt.% of graphene oxide, wherein the sum of the mass percentages of the components is 100%;
step 2, adding the Cu powder weighed in the step 1 into an ethanol solution of cetyl trimethyl ammonium bromide, magnetically stirring for 0.5-1 h, and then washing and centrifuging to obtain modified Cu powder;
step 3, adding graphene oxide into ethanol, performing ultrasonic dispersion for 1-2 hours, and then adding Cu (NO) 3 ) 2 ·3H 2 O is magnetically stirred for 0.5 to 1 hour to obtain the loaded Cu 2+ The graphene mixed solution of (a);
step 4, adding the modified Cu powder obtained in the step 2 into the Cu loaded in the step 3 2+ Magnetically stirring the graphene mixed solution for 0.5-1 h, then adding Mo, and further magnetically stirring for 0.5-1 h to obtain a GO/Cu-Mo mixed solution;
step 5, dropwise adding an ascorbic acid solution into the GO/Cu-Mo mixed solution obtained in the step 4, adding NaOH to adjust the pH value to 10-12, then putting the mixture into a water bath kettle at the temperature of 90-100 ℃, magnetically stirring the mixture for 6-8 hours, and completely drying the mixture to obtain in-situ reduced graphene reinforced copper-molybdenum composite powder;
and 6, putting the graphene reinforced copper-molybdenum composite powder obtained in the step 5 into a graphite mold for prepressing, then putting the graphite mold into a vacuum hot-pressing sintering furnace for sintering to 900-950 ℃, preserving heat for 30-45 min, and finally cooling along with the furnace to obtain the graphene reinforced copper-molybdenum composite material with the three-dimensional network structure.
2. The preparation method of the graphene reinforced copper-molybdenum composite material with the three-dimensional network structure according to claim 1, specifically comprising the following steps:
step 1, weighing the following raw materials in percentage by mass: 78.5-89.9 wt.% of Cu powder; 10.0-20.0 wt.% of Mo powder; 0.1-1.5 wt.% of graphene oxide, wherein the sum of the mass percentages of the components is 100%;
step 2, adding the Cu powder weighed in the step 1 into an ethanol solution of cetyl trimethyl ammonium bromide, magnetically stirring for 0.5-1 h, and then washing and centrifuging to obtain modified Cu powder;
step 3, adding graphene oxide into ethanol, performing ultrasonic dispersion for 1-2 hours, and then adding Cu (NO) 3 ) 2 ·3H 2 O is magnetically stirred for 0.5 to 1 hour to obtain the loaded Cu 2+ The graphene mixed solution of (a);
step 4, adding the modified Cu powder obtained in the step 2 into the Cu loaded in the step 3 2+ Magnetically stirring the graphene mixed solution for 0.5-1 h, then adding Mo, and further magnetically stirring for 0.5-1 h to obtain a GO/Cu-Mo mixed solution;
step 5, dropwise adding an ascorbic acid solution into the GO/Cu-Mo mixed solution obtained in the step 4, adding NaOH to adjust the pH value to 10-12, then putting the mixture into a water bath kettle at the temperature of 90-100 ℃, magnetically stirring the mixture for 6-8 hours, and completely drying the mixture to obtain in-situ reduced graphene reinforced copper-molybdenum composite powder;
and 6, putting the graphene reinforced copper-molybdenum composite powder obtained in the step 5 into a graphite mold for prepressing, then putting the graphite mold into a vacuum hot-pressing sintering furnace for sintering to 900-950 ℃, preserving heat for 30-45 min, and finally cooling along with the furnace to obtain the graphene reinforced copper-molybdenum composite material with the three-dimensional network structure.
3. The preparation method of the graphene reinforced copper-molybdenum composite material with the three-dimensional network structure as claimed in claim 2, wherein the concentration of the cetyl trimethyl ammonium bromide solution in the step 2 is 0.3-0.6 mg/ml, and the magnetic stirring speed is 300-400 rpm.
4. The device of claim 2 having a three-dimensional mesh shapeThe preparation method of the graphene reinforced copper-molybdenum composite material with the structure is characterized in that in the step 3, the concentration of the graphene mixed solution is 0.4-7.5 mg/ml, and the graphene and Cu are mixed 2+ The mass ratio of (A) to (B) is 1: 5-10, and the magnetic stirring speed is 300-400 rpm.
5. The preparation method of the graphene-reinforced copper-molybdenum composite material with the three-dimensional network structure according to claim 2, wherein the solubility of the ascorbic acid solution in the step 5 is 8.0-30.0 mg/ml, and the mass ratio of the graphene to the ascorbic acid is 1: 0.4-1.6.
6. The preparation method of the graphene reinforced copper-molybdenum composite material with the three-dimensional network structure according to claim 2, wherein in the step 6, the pressing pressure of the graphite mold is 8-10 MPa, the pressure holding time is 10-20 s, and the vacuum degree in the vacuum hot-pressing sintering furnace is not less than 1 x 10 -3 Pa, axial pressure applied during sintering is 30-45 MPa, and the temperature rise speed is 30-40 ℃/min.
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