CN116287850A - Preparation method of graphene modified copper-based composite material - Google Patents
Preparation method of graphene modified copper-based composite material Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 76
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- -1 graphene modified copper Chemical class 0.000 title claims abstract description 9
- 238000000498 ball milling Methods 0.000 claims abstract description 73
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 59
- 239000000843 powder Substances 0.000 claims abstract description 49
- 238000005245 sintering Methods 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 29
- 239000010949 copper Substances 0.000 claims abstract description 28
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052802 copper Inorganic materials 0.000 claims abstract description 27
- 238000007731 hot pressing Methods 0.000 claims abstract description 22
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 16
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 12
- 238000003746 solid phase reaction Methods 0.000 claims abstract description 11
- 238000000151 deposition Methods 0.000 claims abstract description 10
- 230000008021 deposition Effects 0.000 claims abstract description 9
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 7
- 239000000956 alloy Substances 0.000 claims abstract description 7
- 239000002245 particle Substances 0.000 claims abstract description 6
- 229910002530 Cu-Y Inorganic materials 0.000 claims description 23
- 239000002270 dispersing agent Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 11
- 239000012300 argon atmosphere Substances 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 239000000725 suspension Substances 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 8
- 229910002804 graphite Inorganic materials 0.000 claims description 7
- 239000010439 graphite Substances 0.000 claims description 7
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 238000005516 engineering process Methods 0.000 claims description 4
- 238000003825 pressing Methods 0.000 claims description 4
- 238000011946 reduction process Methods 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 150000001879 copper Chemical class 0.000 claims 9
- 239000011159 matrix material Substances 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 6
- 239000013078 crystal Substances 0.000 abstract description 5
- 238000000280 densification Methods 0.000 abstract description 3
- 239000006185 dispersion Substances 0.000 abstract description 3
- 238000005728 strengthening Methods 0.000 abstract description 3
- 239000003945 anionic surfactant Substances 0.000 abstract description 2
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000009792 diffusion process Methods 0.000 abstract description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- 239000004570 mortar (masonry) Substances 0.000 description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 150000001247 metal acetylides Chemical class 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
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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
- B22F1/12—Metallic powder containing non-metallic particles
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- 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
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Abstract
A preparation method of a graphene modified copper-based composite material comprises the following steps: step one, molecular blending deposition; step two, thermal reduction; step three, solid phase reaction ball milling; and step four, vacuum hot-pressing sintering. According to the preparation method, the graphene copper-based composite material with good dispersibility is obtained by a molecular blending deposition method, and sodium dodecyl benzene sulfonate is used as an anionic surfactant, so that the uniform dispersibility of graphene in a copper matrix is remarkably improved, and excellent conductivity is obtained; the oxide particles are added into the copper matrix by using a solid-phase reaction ball milling method, so that the dispersion strengthening effect is achieved, and the mechanical property of the material is obviously improved; the heating and pressurizing functions are beneficial to the contact diffusion of powder particles during the vacuum hot-pressing sintering, the good vacuum degree in the hot-pressing process can reduce the sintering temperature, inhibit the growth of crystals, remove the gas in air holes, improve the densification degree of the material, and obtain the superfine even nano-structured copper-based alloy with more uniform grain structure and higher density.
Description
Technical Field
The invention belongs to the technical field of high-strength and high-conductivity copper-based composite materials, and particularly relates to a preparation method of a graphene modified copper-based composite material.
Background
Copper and copper alloy have the advantages of easy processing, excellent electrical property and thermal property, and the like, and are widely applied to the fields of electronic appliances and aerospace, in particular to the large-scale application of electronic information industries such as resistance welding electrodes, integrated circuit lead frames, electric vacuum devices, high-power microwave tubes, and the like. Nevertheless, the development requirements of the current working conditions have not been met due to the deficiencies of mechanical properties, high temperature properties, etc., and in order to obtain high performance copper alloys, a second phase is introduced into the copper matrix to prepare copper matrix composites, such as carbides (SiC) and oxides (Y 2 O 3 、AI 2 0 3 、HfO 2 Etc.) can significantly improve the mechanical properties of the copper alloy as a reinforcing phase, but also limit the electrical conductivity thereof.
Disclosure of Invention
Aiming at the problems of the background technology, the invention designs a preparation method of a graphene modified copper-based composite material, which aims at: the preparation method of the graphene modified copper-based composite material can not only remarkably improve the mechanical properties of the material, but also has excellent conductivity, and meets the use requirements.
The technical solution of the invention is as follows:
the preparation method of the graphene modified copper-based composite material specifically comprises the following steps:
step one, molecular blending deposition
(1) Dissolving graphene powder in graphene water dispersing agent dissolved with sodium dodecyl benzene sulfonate, and performing ultrasonic dispersion for 45-60min;
(2) Adding a copper nitrate solution into the solution, and continuing ultrasonic dispersion for 2 hours to obtain a suspension;
(3) Drying the suspension obtained in the step (2) to obtain copper-loaded graphene composite powder;
step two, thermal reduction
Placing the copper-loaded graphene composite powder obtained in the first step into a high-temperature tubular furnace, and performing thermal reduction in a hydrogen atmosphere to obtain Cu-Gr composite powder;
step three, solid phase reaction ball milling
Mixing the Cu-Gr composite powder obtained in the second step with Y 2 O 3 Placing the powder in a ball milling tank, completing assembly of the ball milling tank in a vacuum glove box under argon atmosphere, placing the ball milling tank in a planetary ball mill for ball milling after the assembly is completed, wherein the ball milling speed is 300-350r/min, the ball milling time is 10-12 hours, taking out and grinding after the ball milling is completed, and finally obtaining the dispersed Cu-Y 2 O 3 -Gr composite powder;
step four, vacuum hot-pressing sintering
(1) The Cu-Y obtained in the step three is processed 2 O 3 Charging Gr composite powder into assembled graphite mold, and then moldingPlacing the tray into a vacuum hot-pressing sintering furnace, inserting a temperature thermocouple, aligning an infrared thermometer, and starting a vacuumizing procedure;
(2) Setting sintering temperature and pressure process curve, heating to 600deg.C and maintaining for 5min, heating to 900deg.C and maintaining for 5min, cooling to room temperature after maintaining to obtain Cu-Y 2 O 3 -Gr composite.
The graphene powder in the first step has the purity of 99%, the thickness of 3-10nm and the diameter of 7-12 mu m, and is purchased from carbon rare technology (Shenzhen) limited company, wherein the mass fraction of the added graphene powder is less than or equal to 1%.
In the first step, the purity of the sodium dodecyl benzene sulfonate is not lower than 90 percent and the sodium dodecyl benzene sulfonate is purchased from national pharmaceutical group chemical reagent company.
In the first step, the purity of the copper nitrate and the purity of the graphene water dispersing agent are both 100%, the concentration of the copper nitrate solution is 3mol/L, the volume of added graphene water dispersing agent is equal to the added volume of the copper nitrate solution, and the graphene water dispersing agent is purchased from Chengdu Material science and technology Co.
The model of the high-temperature tube furnace for the thermal reduction treatment in the step two is GSL-1200X, the specific thermal reduction process is to raise the temperature to 550-600 ℃ and keep the temperature for 2 hours, then to lower the temperature to 500 ℃ and then to cool the furnace, the heating rate in the thermal reduction process is 10 ℃/min, and the cooling rate is 10 ℃/min.
In the third step, the assembly of the ball milling tank is completed in a vacuum glove box, so that a pure ball milling environment is ensured, the model of the vacuum glove box is ZKX, the planetary ball mill is a QM-QX4 omnibearing planetary ball mill, the ball milling process is carried out under the protection of argon atmosphere, the ball milling tank and the ball milling medium are both made of hard alloy, the ball milling rotating speed is 300-350r/min, the ball milling time is 10-12 hours, and the ball material ratio is 5:1.
y in the third step 2 O 3 The powder had a purity of 99.99% and a particle size of 0.5. Mu.m, and was purchased from Shanghai Yi En chemical technology Co., ltd.
The model of the sintering furnace for vacuum hot-pressing sintering in the step four is FHP-828, the pre-pressing pressure is 10MPa, the sintering temperature is 900 ℃, the sintering time is 5min, the final pressing pressure is 50MPa, and the heat preservation is carried out at 600 ℃ for 5min to remove contained gas.
And in the fourth step, the heating rate of the vacuum hot-pressing sintering is 100 ℃/min, and the cooling rate is 100 ℃/min.
And in the fourth step, the diameter of the graphite mold is 30mm.
The invention has the beneficial effects that: unlike traditional copper-base composite material with mechanical performance raised and electric and heat conducting performance sacrificed, the present invention obtains graphene-copper-base composite material with excellent dispersivity via molecular blending deposition process. The ideal two-dimensional planar structure and the excellent specific surface area of the graphene enable the graphene to have very high adsorption capacity, meanwhile, sodium dodecyl benzene sulfonate is used as an anionic surfactant, and has a conductive effect, so that the graphene and copper ions have an ion pi effect, a large amount of copper ions are adsorbed by the graphene to form a loaded copper graphene compound, the uniform dispersibility of the graphene in a copper matrix is remarkably improved, and excellent conductive performance is obtained; the solid-phase reaction ball milling method is used for adding oxide particles into a copper matrix to achieve the dispersion strengthening effect, and in the process, the matrix alloying improves the interface combination of graphene and copper, and the mechanical property of the material is obviously improved; the vacuum hot-pressing sintering technology has the advantages of high sintering speed, high processing efficiency, high sample densification degree and the like, and the contact diffusion of powder particles is facilitated by the simultaneous actions of heating and pressurizing, the good vacuum degree in the hot-pressing process can reduce the sintering temperature, inhibit the growth of crystals, remove gas in air holes and improve the densification degree of materials, so that the copper-based alloy with the ultra-fine or even nano-structure, which has more uniform grain structure and higher density, is obtained. In general, the composition design and the preparation process of the invention realize the excellent comprehensive properties of high strength and high conductivity of the copper-based material.
Drawings
FIG. 1 is a 2000 times Cu-1wt.% Y 2 O 3 -SEM topography of 0.3wt.% Gr composite block.
FIG. 2 is a Cu-1wt.% Y at 3000 times 2 O 3 -tensile fracture morphology of 0.3wt.% Gr composite.
FIG. 3 is a 1000 times Cu-1wt.% Y 2 O 3 -0.3wt.% Gr composite metallographic structure map.
Detailed Description
The invention is further described below with reference to the drawings and specific examples.
Example 1
Cu-Y in the present embodiment 2 O 3 Gr composite material is prepared by molecular blending deposition, thermal reduction, solid phase reaction ball milling and vacuum hot-pressing sintering, wherein Y 2 O 3 Is 1% by mass and Gr is 0.1% by mass.
Cu-Y in the present embodiment 2 O 3 The preparation method of the Gr composite material is as follows:
step one, molecular blending deposition: firstly, 0.02g of graphene powder with the purity of 99% is dissolved in graphene water dispersing agent dissolved with sodium dodecyl benzene sulfonate, the volume of the graphene water dispersing agent is 103ml, the adding amount of the sodium dodecyl benzene sulfonate is 0.5g, and the graphene water dispersing agent is subjected to ultrasonic dispersion for 45min; adding 103ml of copper nitrate solution with the concentration of 3mol/L into the solution, continuing to ultrasonically disperse for 2 hours to obtain a suspension, drying the obtained suspension to obtain a precursor, and fully grinding the obtained precursor in a mortar to obtain the copper-loaded graphene composite powder;
step two, thermal reduction: placing the obtained copper-loaded graphene composite powder into a high-temperature tubular furnace, and performing thermal reduction in a hydrogen atmosphere to obtain Cu-Gr composite powder; the thermal reduction temperature is increased to 600 ℃ for 2 hours, then the temperature is reduced to 500 ℃ and then the furnace is cooled, wherein the temperature rising rate is 10 ℃/min, and the temperature reducing rate is 10 ℃/min;
step three, solid phase reaction ball milling, namely mixing the Cu-Gr composite powder prepared in the step two with Y 2 O 3 Placing the powder in a ball milling tank, Y 2 O 3 The mass fraction of the ball milling tank is 1%, the ball milling tank is assembled in the argon atmosphere of a vacuum glove box, the ball milling process is guaranteed to be carried out under the protection of the argon atmosphere, the ball milling tank and the ball milling medium are made of hard alloy, after the assembly is completed, the ball milling tank is placed in a planetary ball mill for ball milling, the ball milling rotating speed is 300r/min, the ball milling time is 10 hours, and after the ball milling is completed, the ball milling tank is taken out for grinding, and finally the dispersed ball mill is obtainedCu-Y 2 O 3 20g of Gr composite powder;
step four, vacuum hot-pressing sintering: the Cu-Y obtained in the step three is processed 2 O 3 Putting Gr composite powder into an assembled graphite mould, putting the mould on a tray, putting the mould into a vacuum hot-pressing sintering furnace, inserting a temperature thermocouple, aligning an infrared thermometer, and starting a vacuumizing procedure; setting sintering temperature and pressure process curve, heating to 600deg.C and maintaining for 5min, heating to 900deg.C and maintaining for 5min, cooling to room temperature after maintaining to obtain Cu-Y 2 O 3 -Gr composite.
Example 2
Cu-Y in the present embodiment 2 O 3 Gr composite material is prepared by molecular blending deposition, thermal reduction, solid phase reaction ball milling and vacuum hot-pressing sintering, wherein Y 2 O 3 Is 1% by mass and Gr is 0.3% by mass.
Cu-Y in the present embodiment 2 O 3 The preparation method of the Gr composite material is as follows:
step one, molecular blending deposition: firstly, 0.06g of graphene powder with the purity of 99% is dissolved in graphene water dispersing agent dissolved with sodium dodecyl benzene sulfonate, the volume of the graphene water dispersing agent is 102.8ml, the adding amount of the sodium dodecyl benzene sulfonate is 0.5g, and the graphene water dispersing agent is subjected to ultrasonic dispersion for 55min; adding 102.8ml of copper nitrate solution with the concentration of 3mol/L into the solution, continuing to ultrasonically disperse for 2 hours to obtain a suspension, drying the obtained suspension to obtain a precursor, and fully grinding the obtained precursor in a mortar to obtain the copper-loaded graphene composite powder;
step two, thermal reduction: placing the obtained copper-loaded graphene composite powder into a high-temperature tube furnace, and performing thermal reduction under a hydrogen atmosphere to obtain Cu-Gr composite powder, wherein the thermal reduction temperature is increased to 600 ℃, the temperature is kept for 2 hours, and then the copper-loaded graphene composite powder is cooled along with the furnace after being reduced to 500 ℃, wherein the heating rate is 10 ℃/min, and the cooling rate is 10 ℃/min;
step three, solid phase reaction ball milling, namely mixing the Cu-Gr composite powder prepared in the step two with Y 2 O 3 Placing the powder in a ball milling tank, Y 2 O 3 Mass fraction of (2)The number is 1%, the ball milling tank is assembled in the argon atmosphere of a vacuum glove box, the ball milling process is guaranteed to be carried out under the protection of the argon atmosphere, the ball milling tank and the ball milling medium are made of hard alloy, after the assembly is completed, the ball milling tank is placed in a planetary ball mill for ball milling, the ball milling rotating speed is 325r/min, the ball milling time is 11 hours, and after the ball milling is completed, the ball milling tank is taken out for grinding, and finally dispersed Cu-Y is obtained 2 O 3 20g of Gr composite powder;
step four, vacuum hot-pressing sintering: the Cu-Y obtained in the step three is processed 2 O 3 Putting Gr composite powder into an assembled graphite mould, putting the mould on a tray, putting the mould into a vacuum hot-pressing sintering furnace, inserting a temperature thermocouple, aligning an infrared thermometer, and starting a vacuumizing procedure; setting sintering temperature and pressure process curve, heating to 600deg.C and maintaining for 5min, heating to 900deg.C and maintaining for 5min, cooling to room temperature after maintaining to obtain Cu-Y 2 O 3 -Gr composite.
Example 3
Cu-Y in the present embodiment 2 O 3 Gr composite material is prepared by molecular blending deposition, thermal reduction, solid phase reaction ball milling and vacuum hot-pressing sintering, wherein Y 2 O 3 Is 1% by mass and Gr is 0.5% by mass.
Cu-Y in the present embodiment 2 O 3 The preparation method of the Gr composite material is as follows:
step one, molecular blending deposition: firstly, 0.1g of graphene powder with the purity of 99% is dissolved in graphene water dispersing agent dissolved with sodium dodecyl benzene sulfonate, the volume of the graphene water dispersing agent is 102.6ml, the adding amount of the sodium dodecyl benzene sulfonate is 0.5g, and the graphene water dispersing agent is subjected to ultrasonic dispersion for 60min; adding 102.6ml of copper nitrate solution with the concentration of 3mol/L into the solution, continuing to ultrasonically disperse for 2 hours to obtain a suspension, drying the obtained suspension to obtain a precursor, and fully grinding the obtained precursor in a mortar to obtain the copper-loaded graphene composite powder;
step two, thermal reduction: placing the obtained copper-loaded graphene composite powder into a high-temperature tubular furnace, and performing thermal reduction in a hydrogen atmosphere to obtain Cu-Gr composite powder; the thermal reduction temperature is increased to 600 ℃ for 2 hours, then the temperature is reduced to 500 ℃ and then the furnace is cooled, wherein the temperature rising rate is 10 ℃/min, and the temperature reducing rate is 10 ℃/min;
step three, solid phase reaction ball milling, namely mixing the Cu-Gr composite powder prepared in the step two with Y 2 O 3 Placing the powder in a ball milling tank, Y 2 O 3 The ball milling tank is assembled in the argon atmosphere of a vacuum glove box, the ball milling process is guaranteed to be carried out under the protection of the argon atmosphere, the ball milling tank and the ball milling medium are made of hard alloy, after the assembly is completed, the ball milling tank is placed in a planetary ball mill for ball milling, the ball milling rotating speed is 350r/min, the ball milling time is 12 hours, and after the ball milling is completed, the ball milling tank is taken out for grinding, and finally dispersed Cu-Y is obtained 2 O 3 20g of Gr composite powder;
step four, vacuum hot-pressing sintering: the Cu-Y obtained in the step three is processed 2 O 3 Putting Gr composite powder into an assembled graphite mould, putting the mould on a tray, putting the mould into a vacuum hot-pressing sintering furnace, inserting a temperature thermocouple, aligning an infrared thermometer, and starting a vacuumizing procedure; setting sintering temperature and pressure process curve, heating to 600deg.C and maintaining for 5min, heating to 900deg.C and maintaining for 5min, cooling to room temperature after maintaining to obtain Cu-Y 2 O 3 -Gr composite.
For Cu-Y prepared in examples 1 to 3 2 O 3 The Gr composite was subjected to performance tests, the test results being shown in table 1:
TABLE 1 Cu-Y in examples 1-3 2 O 3 Results of the Gr composite conductivity and Vickers hardness Performance test
| Material | Conductivity (% IACS) | Hardness of(HV 0.1 ) |
| Cu-1wt.％Y 2 O 3 | 85.6％ | 125.6 |
| Cu-1wt.％Y 2 O 3 -0.1wt.％Gr | 92.5％ | 117.3 |
| Cu-1wt.％Y 2 O 3 -0.3wt.％Gr | 95.6％ | 120.8 |
| Cu-1wt.％Y 2 O 3 -0.5wt.％Gr | 91.8％ | 105.2 |
As can be seen in FIG. 1, cu-1wt.% Y 2 O 3 -0.3wt.% of graphene in the Gr composite is predominantly distributed at copper matrix grain boundaries.
As can be seen in FIG. 2, cu-1wt.% Y 2 O 3 The ductile fracture of the Gr composite material is generated by 0.3wt.% under the stretching, the addition of Gr promotes the space of heterogeneous nucleation, and the stress generated by dislocation accumulation is reduced due to the grain refinement effect of the graphene, so that a ductile pit or a tearing edge is generated, the fracture surface is mainly in the ductile pit shape, and flaky graphene in the ductile pit can be observed.
As can be seen in FIG. 3, cu-1wt.% Y 2 O 3 0.3wt.% of graphene in the Gr composite material is uniformly dispersed and distributed on the crystal boundary of the copper matrix, the graphene has pinning effect on dislocation and crystal boundary movement, the crystal grains are obviously refined, the components are more uniform, and the copper alloy composite material is effectively improvedThe microstructure of the material improves the mechanical properties of the copper alloy composite material.
As can be seen from Table 1, compared with the conventional preparation of copper-based composite material by dispersion strengthening of oxides, gr-modified Cu-Y 2 O 3 Realizes excellent comprehensive performance of high strength and high conductivity, cu-Y 2 O 3 The Gr composite material has a conductivity of up to 95.6% and a Vickers hardness of up to 120.8HV 0.1 。
Claims (10)
1. A preparation method of a graphene modified copper-based composite material is characterized by comprising the following steps: the method specifically comprises the following steps:
step one, molecular blending deposition
(1) Dissolving graphene powder in graphene water dispersing agent dissolved with sodium dodecyl benzene sulfonate, and performing ultrasonic dispersion for 45-60min;
(2) Adding a copper nitrate solution into the solution, and continuing ultrasonic dispersion for 2 hours to obtain a suspension;
(3) Drying the suspension obtained in the step (2) to obtain copper-loaded graphene composite powder;
step two, thermal reduction
Placing the copper-loaded graphene composite powder obtained in the first step into a high-temperature tubular furnace, and performing thermal reduction in a hydrogen atmosphere to obtain Cu-Gr composite powder;
step three, solid phase reaction ball milling
Mixing the Cu-Gr composite powder obtained in the second step with Y 2 O 3 Placing the powder in a ball milling tank, completing assembly of the ball milling tank in a vacuum glove box under argon atmosphere, placing the ball milling tank in a planetary ball mill for ball milling after the assembly is completed, wherein the ball milling speed is 300-350r/min, the ball milling time is 10-12 hours, taking out and grinding after the ball milling is completed, and finally obtaining the dispersed Cu-Y 2 O 3 -Gr composite powder;
step four, vacuum hot-pressing sintering
(1) The Cu-Y obtained in the step three is processed 2 O 3 Putting Gr composite powder into assembled graphite mould, placing the mould on tray, placing into vacuum hot-pressing sintering furnace, inserting temperature thermocouple, aligning with infrared temperature measurementThe instrument starts a vacuumizing program;
(2) Setting sintering temperature and pressure process curve, heating to 600deg.C and maintaining for 5min, heating to 900deg.C and maintaining for 5min, cooling to room temperature after maintaining to obtain Cu-Y 2 O 3 -Gr composite.
2. The method for preparing the graphene-modified copper-based composite material according to claim 1, which is characterized by comprising the following steps: the graphene powder in the first step has the purity of 99%, the thickness of 3-10nm and the diameter of 7-12 mu m, and is purchased from carbon rare technology (Shenzhen) limited company, wherein the mass fraction of the added graphene powder is less than or equal to 1%.
3. The method for preparing the graphene-modified copper-based composite material according to claim 1, which is characterized by comprising the following steps: in the first step, the purity of the sodium dodecyl benzene sulfonate is not lower than 90 percent and the sodium dodecyl benzene sulfonate is purchased from national pharmaceutical group chemical reagent company.
4. The method for preparing the graphene-modified copper-based composite material according to claim 1, which is characterized by comprising the following steps: in the first step, the purity of the copper nitrate and the purity of the graphene water dispersing agent are both 100%, the concentration of the copper nitrate solution is 3mol/L, the volume of added graphene water dispersing agent is equal to the added volume of the copper nitrate solution, and the graphene water dispersing agent is purchased from Chengdu Material science and technology Co.
5. The method for preparing the graphene-modified copper-based composite material according to claim 1, which is characterized by comprising the following steps: the model of the high-temperature tube furnace for the thermal reduction treatment in the step two is GSL-1200X, the specific thermal reduction process is to raise the temperature to 550-600 ℃ and keep the temperature for 2 hours, then to lower the temperature to 500 ℃ and then to cool the furnace, the heating rate in the thermal reduction process is 10 ℃/min, and the cooling rate is 10 ℃/min.
6. The method for preparing the graphene-modified copper-based composite material according to claim 1, which is characterized by comprising the following steps: in the third step, the assembly of the ball milling tank is completed in a vacuum glove box, so that a pure ball milling environment is ensured, the model of the vacuum glove box is ZKX, the planetary ball mill is a QM-QX4 omnibearing planetary ball mill, the ball milling process is carried out under the protection of argon atmosphere, the ball milling tank and the ball milling medium are both made of hard alloy, the ball milling rotating speed is 300-350r/min, the ball milling time is 10-12 hours, and the ball material ratio is 5:1.
7. the method for preparing the graphene-modified copper-based composite material according to claim 1, which is characterized by comprising the following steps: y in the third step 2 O 3 The powder had a purity of 99.99% and a particle size of 0.5. Mu.m, and was purchased from Shanghai Yi En chemical technology Co., ltd.
8. The method for preparing the graphene-modified copper-based composite material according to claim 1, which is characterized by comprising the following steps: the model of the sintering furnace for vacuum hot-pressing sintering in the step four is FHP-828, the pre-pressing pressure is 10MPa, the sintering temperature is 900 ℃, the sintering time is 5min, the final pressing pressure is 50MPa, and the heat preservation is carried out at 600 ℃ for 5min to remove contained gas.
9. The method for preparing the graphene-modified copper-based composite material according to claim 1, which is characterized by comprising the following steps: and in the fourth step, the heating rate of the vacuum hot-pressing sintering is 100 ℃/min, and the cooling rate is 100 ℃/min.
10. The method for preparing the graphene-modified copper-based composite material according to claim 1, which is characterized by comprising the following steps: and in the fourth step, the diameter of the graphite mold is 30mm.
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