CN115181873B - Copper-modified graphene oxide-based composite material, and preparation method and application thereof - Google Patents
Copper-modified graphene oxide-based composite material, and preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 19
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- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
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- 230000009467 reduction Effects 0.000 claims description 8
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- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- 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 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/05—Mixtures of metal powder with non-metallic powder
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
- B22F9/22—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds using gaseous reductors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
- B22F2003/1051—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding by electric discharge
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/25—Process efficiency
Abstract
The invention provides a preparation method of a copper-modified graphene oxide-based composite material, which comprises the following steps: a) Mixing copper salt with graphene oxide dispersion liquid, and performing ultrasonic dispersion to obtain a mixed solution; b) Evaporating the mixed solution to dryness to obtain powder; c) Heat-treating the powder at 50-400 ℃ for 5-24 hours to obtain heat-treated powder; d) Reducing the heat-treated powder in a hydrogen-containing atmosphere to obtain reduced powder; e) And (3) in a vacuum environment, performing spark plasma sintering on the reduced powder to obtain the copper modified graphene oxide-based composite material. The invention can prepare the novel light specific gravity graphene-based composite material with high strength, abrasion resistance, low friction coefficient and other excellent performance cooperation. The invention also provides a copper-modified graphene oxide-based composite material and application thereof.
Description
Technical Field
The invention belongs to the technical field of carbon-based composite materials, and particularly relates to a copper-modified graphene oxide-based composite material, a preparation method and application thereof.
Background
With the rapid development of aerospace technology, high-performance composite materials are becoming more and more widely used, wherein carbon-based composite materials (such as carbon fiber composite materials) are becoming important structural components in the form of gradually replacing metals on carrier rockets, space shuttles and satellites. Graphene, which is a member of the carbon material family, is a two-dimensional nanomaterial in a honeycomb structure composed of sp2 hybridized orbitals of carbon atoms, and has low density, high strength (130 GPa), high elastic modulus (1 TPa), excellent heat conduction performance and high electric conduction performance. Therefore, graphene-based composites have great potential in the aerospace field for developing high-performance light-weight composites. However, when preparing the bulk graphene-based composite material, the problems of aggregation, weak interlayer interface bonding, irregular orientation and the like of graphene can cause the performance of the bulk graphene-based composite material to be greatly reduced, which limits the exertion of the excellent performance of the bulk graphene-based composite material and the practical application of the bulk graphene-based composite material.
The mother-of-pearl shell is mainly formed by mutually stacking and arranging 95vol.% of aragonite sheet inorganic layers and 5vol.% of organic layers in a stacking way, thus forming the composite ceramic material with a unique brick-mud layered structure, and the composite ceramic material has higher tensile strength (70-100 MPa) and excellent fracture toughness (4-10 MPa.m) 0.5 ) The main toughening mechanisms are the extraction of the venturi stone chips, the viscoelastic action of the organic matrix, the multiple occurrence of cracks, the deflection of the cracks and the bridging of the cracks. A great deal of research shows that the organic matrix plays a vital role in obtaining high strength and excellent fracture toughness of the mother-of-pearl shells. In recent years, a bionic technology is adopted to prepare the graphene-based composite material, so that the graphene-based composite material is widely focused by students at home and abroad, namely, the graphene with a two-dimensional layered structure is subjected to bionic design by a unique 'brick-mud' layered structure of mother-of-pearl shells, wherein the graphene is used as a 'brick', an organic polymer material is introduced at an interlayer interface of the graphene as 'mud', and the interfacial synergistic effect is utilized, so that the performance of the graphene-based composite material is improved.
It is worth noting that although the performance of the graphene-based composite material can be greatly improved by introducing an organic polymer material between graphene layers, the composite material serving in important high-new technical equipment in China such as aerospace and the like often bears strong friction and wear under extremely severe service conditions such as high/low temperature (wide temperature range), high speed, heavy load, oxidation, corrosion and the like, and the low mechanical property, thermal stability, electric conduction and heat conduction performance of the organic polymer material limit the practical application of the graphene-based composite material prepared by the bionic preparation in the aerospace field.
Disclosure of Invention
The invention aims to provide a copper-modified graphene oxide-based composite material, a preparation method and application thereof.
The invention provides a preparation method of a copper-modified graphene oxide-based composite material, which comprises the following steps:
a) Mixing copper salt with graphene oxide dispersion liquid, and performing ultrasonic dispersion to obtain a mixed liquid;
b) Evaporating the mixed solution to dryness to obtain powder;
c) Heat-treating the powder at 50-400 ℃ for 5-24 hours to obtain heat-treated powder;
d) Reducing the heat-treated powder in a hydrogen-containing atmosphere to obtain reduced powder;
e) And (3) in a vacuum environment, performing spark plasma sintering on the reduced powder to obtain the copper modified graphene oxide-based composite material.
Preferably, the concentration of the graphene oxide dispersion liquid is 1-10 mg/mL.
Preferably, the copper salt is one or more of copper acetate monohydrate, copper nitrate, copper sulfate and copper chloride;
the mass ratio of graphene oxide in the graphene oxide dispersion liquid to copper in copper salt is 100: (1-100).
Preferably, the temperature evaporated to dryness in step B) is 85-95 ℃.
Preferably, the hydrogen-containing atmosphere is a mixed gas of hydrogen and a protective gas;
the protective gas is one or more of nitrogen, argon and helium; the volume fraction of hydrogen in the hydrogen-containing atmosphere is 20-40%.
Preferably, the temperature of the reduction in the step D) is 100-400 ℃; the time of the reduction in the step D) is 1 to 10 hours.
Preferably, the temperature of the spark plasma sintering is 300-1000 ℃, and the heat preservation time of the spark plasma sintering is 5-30 min;
the heating rate of the spark plasma sintering is 80-150 ℃/min.
Preferably, the pressure of the spark plasma sintering is 20-70 MPa.
The invention provides the copper-modified graphene oxide-based composite material prepared by the preparation method.
The present invention provides the use of a copper-modified graphene oxide-based composite material as described above in the aerospace field.
The invention provides a preparation method of a copper-modified graphene oxide-based composite material, which comprises the following steps: a) Mixing copper salt with graphene oxide dispersion liquid, and performing ultrasonic dispersion to obtain a mixed solution; b) Evaporating the mixed solution to dryness to obtain powder; c) Heat-treating the powder at 50-400 ℃ for 5-24 hours to obtain heat-treated powder; d) Reducing the heat-treated powder in a hydrogen-containing atmosphere to obtain reduced powder; e) And (3) in a vacuum environment, performing spark plasma sintering on the reduced powder to obtain the copper modified graphene oxide-based composite material. According to the invention, an inorganic substance (taking copper ions as an example) is adopted to modify the surface of graphene oxide, a hydrogen reduction method is utilized to obtain copper modified graphene oxide powder, and then the obtained composite powder is utilized to prepare the graphene-based composite material by a spark plasma sintering technology, so that the novel light-weight graphene-based composite material with high strength, abrasion resistance, low friction coefficient and other excellent performance matching is obtained.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only embodiments of the present invention, and that other drawings can be obtained according to the provided drawings without inventive effort for a person skilled in the art.
FIG. 1 is a flow chart of a preparation process of a copper-modified graphene oxide-based composite material;
FIG. 2 is an XRD pattern of sintered products in examples 1 to 4 of the present invention;
FIG. 3 is a graph showing the load-displacement of the sintered product of examples 1 to 4 according to the present invention in a micrometer press-in;
FIG. 4 is a graph showing the variation of friction coefficient with sliding travel of sintered products in examples 1 to 4 of the present invention;
fig. 5 is a graph showing the variation of the press-in depth of the sintered product with the sliding stroke in examples 1 to 4 of the present invention.
Detailed Description
The invention provides a preparation method of a copper-modified graphene oxide-based composite material, which comprises the following steps:
a) Mixing copper salt with graphene oxide dispersion liquid, and performing ultrasonic dispersion to obtain a mixed solution;
b) Evaporating the mixed solution to dryness to obtain powder;
c) Heat-treating the powder at 50-400 ℃ for 5-24 hours to obtain heat-treated powder;
d) Reducing the heat-treated powder in a hydrogen-containing atmosphere to obtain reduced powder;
e) And (3) in a vacuum environment, performing spark plasma sintering on the reduced powder to obtain the copper modified graphene oxide-based composite material.
The preparation process is shown in figure 1, and graphene oxide is added into deionized water for ultrasonic dispersion to obtain graphene oxide dispersion liquid.
In the invention, the surface of the graphene oxide has functional groups, and the source of the graphene oxide is not particularly limited, and the graphene oxide commonly used in the art can be used.
In the present invention, the mass concentration of the graphene oxide dispersion is preferably 1 to 10mg/mL, more preferably 3 to 8mg/mL, such as 1mg/mL,2mg/mL,3mg/mL,4mg/mL,5mg/mL,6mg/mL,7mg/mL,8mg/mL,9mg/mL,10mg/mL, preferably a range having any of the above values as an upper limit or a lower limit.
After the graphene oxide dispersion liquid is obtained, copper salt is added into the graphene oxide dispersion liquid, ultrasonic dispersion is carried out, and a mixed liquid is obtained, wherein copper ions react with graphene oxide functional groups to form functional groups in the process.
In the present invention, the copper salt is preferably a water-soluble copper salt such as one or more of copper acetate monohydrate, copper nitrate, copper sulfate and copper chloride; the mass ratio of graphene oxide to copper in copper salt is preferably 100: (1 to 100), more preferably 100: (10-80), such as 100:1, 100:5,100: 10, 100:15, 100:20, 100:25, 100:30, 100:35, 100:40, 100:45, 100:50, 100:55, 100:60, 100:65, 100:70, 100:75, 100:80, 100:85, 100:90, 100:95, 100:100, preferably a range value having any of the above values as an upper limit or a lower limit.
And then placing the obtained mixed solution on a magnetic stirrer, stirring at a certain temperature until the solution is evaporated to dryness, and obtaining powder. In the present invention, the temperature of the evaporation is preferably 85 to 95 ℃, more preferably 90 ℃.
And carrying out heat treatment on the obtained powder to avoid explosion in the subsequent reduction process, and simultaneously obtaining copper oxide particles attached to the surface of the graphene.
In the present invention, the temperature of the heat treatment is preferably 50 to 400 ℃, more preferably 100 to 350 ℃, such as 50 ℃,100 ℃,150 ℃,200 ℃,250 ℃,300 ℃,350 ℃,400 ℃, preferably a range value in which any of the above values is an upper limit or a lower limit; the time of the heat treatment is preferably 5 to 24 hours, more preferably 10 to 18 hours, and most preferably 12 to 15 hours.
According to the invention, the powder after heat treatment is reduced in a hydrogen-containing atmosphere to obtain reduced powder, and copper oxide is reduced into elemental copper and is adhered to the surface of graphene oxide in the reduction process.
In the present invention, the hydrogen-containing atmosphere is preferably a mixed gas of hydrogen and a protective gas, and the protective gas is preferably one or more of nitrogen, argon and helium; the volume fraction of hydrogen in the hydrogen-containing atmosphere is preferably 20 to 40%, more preferably 25 to 35%, such as 20%,21%,22%,23%,24%,25%,26%,27%,28%,29%,30%,31%,32%,33%,34%,35%,36%,37%,38%,39%,40%, and preferably ranges from any of the above values to the upper or lower limit.
In the present invention, the temperature of the reduction is preferably 100 to 400 ℃, more preferably 150 to 350 ℃, such as 100 ℃,150 ℃,200 ℃,250 ℃,300 ℃,350 ℃,400 ℃, preferably a range value having any of the above values as an upper limit or a lower limit; the time for the reduction is preferably 1 to 10 hours, more preferably 3 to 8 hours, such as 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, and preferably a range having any of the above values as an upper limit or a lower limit.
After the reduced powder is obtained, a layer of graphite paper is paved at the bottom and the side surface of a graphite mold, the reduced powder is placed in the graphite mold, then the graphite mold is placed in a spark plasma sintering system, the reduced powder is compacted, and the plasma sintering system is vacuumized to carry out spark plasma sintering.
In the present invention, the temperature of the spark plasma sintering is preferably 300 to 1000 ℃, more preferably 400 to 800 ℃, such as 300 ℃,400 ℃,500 ℃,600 ℃,700 ℃,800 ℃,900 ℃,1000 ℃, preferably a range value with any of the above values as an upper limit or a lower limit; the holding time of the spark plasma sintering is preferably 5 to 30min, more preferably 10 to 20min, such as 5min,10min,15min,20min,25min,30min, and preferably a range value having any of the above values as an upper limit or a lower limit.
In the present invention, the heating rate of the spark plasma sintering is preferably 80 to 150 ℃ per minute, more preferably 100 to 120 ℃ per minute, such as 80 ℃ per minute, 90 ℃ per minute, 100 ℃ per minute, 110 ℃ per minute, 120 ℃ per minute, 130 ℃ per minute, 140 ℃ per minute, 150 ℃ per minute, and preferably a range value having any of the above values as an upper limit or a lower limit.
In the present invention, the pressure of the spark plasma sintering is preferably 20 to 70MPa, more preferably 30 to 60MPa, such as 20MPa,30MPa,40MPa,50MPa,60MPa,70MPa, and preferably a range having any of the above values as an upper limit or a lower limit.
The invention also provides a copper-modified graphene oxide-based composite material, which is prepared according to the preparation method.
Based on the copper-modified graphene oxide-based composite material prepared by the preparation method, the invention also provides application of the copper-modified graphene oxide-based composite material in the aerospace field.
The invention provides a preparation method of a copper-modified graphene oxide-based composite material, which comprises the following steps: a) Mixing copper salt with graphene oxide dispersion liquid, and performing ultrasonic dispersion to obtain a mixed solution; b) Evaporating the mixed solution to dryness to obtain powder; c) Heat-treating the powder at 50-400 ℃ for 5-24 hours to obtain heat-treated powder; d) Reducing the heat-treated powder in a hydrogen-containing atmosphere to obtain reduced powder; e) And (3) in a vacuum environment, performing spark plasma sintering on the reduced powder to obtain the copper modified graphene oxide-based composite material. According to the invention, an inorganic substance (taking copper ions as an example) is adopted to modify the surface of graphene oxide, a hydrogen reduction method is utilized to obtain copper modified graphene oxide powder, and then the obtained composite powder is utilized to prepare the graphene-based composite material by a spark plasma sintering technology, so that the novel light-weight graphene-based composite material with high strength, abrasion resistance, low friction coefficient and other excellent performance matching is obtained.
In order to further illustrate the present invention, the following examples are provided to describe in detail a copper-modified graphene oxide-based composite material, a preparation method and an application thereof, but they should not be construed as limiting the scope of the present invention.
Example 1
Graphene oxide was heated at 250 ℃ for 12h as a sintered powder. The powder is sintered in a discharge plasma device at a heating rate of 100 ℃/min, a sintering pressure of 50MPa, a sintering temperature of 600 ℃ and a heat preservation time of 10min.
Example 2 of the embodiment
Adding graphene oxide into deionized water, performing ultrasonic dispersion to obtain a graphene oxide dispersion liquid with the concentration of 5mg/mL, and then adding copper acetate monohydrate into the graphene oxide dispersion liquid, performing ultrasonic dispersion for 1h, wherein the mass of copper in the copper acetate monohydrate is calculated according to the molar mass of the copper acetate monohydrate, so that the mass ratio of the graphene oxide to the copper is 100:1. The solution was stirred on a magnetic stirrer at 90 ℃ until the solution evaporated to dryness, the resulting powder was placed in a muffle furnace and heated at 250 ℃ for 12h, the powder was incubated for 4h at 250 ℃ with argon-hydrogen gas (30% hydrogen), and then ground to give GO/1Cu powder as sintered powder. The powder is sintered in a discharge plasma device at a heating rate of 100 ℃/min, a sintering pressure of 50MPa, a sintering temperature of 600 ℃ and a heat preservation time of 10min.
Example 3
Adding graphene oxide into deionized water, performing ultrasonic dispersion to obtain a graphene oxide dispersion liquid with the concentration of 5mg/ml, and then adding copper acetate monohydrate into the graphene oxide dispersion liquid, performing ultrasonic dispersion for 1h, wherein the mass of copper in the copper acetate monohydrate is calculated according to the molar mass of the copper acetate monohydrate, so that the mass ratio of the graphene oxide to the copper is 100:10. The solution was stirred on a magnetic stirrer at 90 ℃ until the solution evaporated to dryness, the resulting powder was placed in a muffle furnace and heated at 250 ℃ for 12h, the powder was incubated for 4h at 250 ℃ with argon-hydrogen gas (30% hydrogen), and then ground to give GO/10Cu powder as sintered powder. The powder is sintered in a discharge plasma device at a heating rate of 100 ℃/min, a sintering pressure of 50MPa, a sintering temperature of 600 ℃ and a heat preservation time of 10min.
Example 4
Adding graphene oxide into deionized water, performing ultrasonic dispersion to obtain a graphene oxide dispersion liquid with the concentration of 5mg/ml, and then adding copper acetate monohydrate into the graphene oxide dispersion liquid, performing ultrasonic dispersion for 1h, wherein the mass of copper in the copper acetate monohydrate is calculated according to the molar mass of the copper acetate monohydrate, so that the mass ratio of the graphene oxide to the copper is 100:100. The solution was stirred on a magnetic stirrer at 90 ℃ until the solution evaporated to dryness, the resulting powder was placed in a muffle furnace and heated at 250 ℃ for 12h, the powder was incubated for 4h at 250 ℃ with argon-hydrogen gas (30% hydrogen), and then ground to give GO/100Cu powder as sintered powder. The powder is sintered in a discharge plasma device at a heating rate of 100 ℃/min, a sintering pressure of 50MPa, a sintering temperature of 600 ℃ and a heat preservation time of 10min.
1) Phase characterization
X-ray diffraction measurements were performed on the products obtained in examples 1 to 4, and as shown in FIG. 2, as clearly shown in FIG. 2, the discharge plasma sintered anode mainly had C-peaks of graphene, cu and Cu 2 O, and with increasing Cu content, cu peak becomes stronger gradually, grapheneThe C peak of (C) becomes weaker gradually, and weak Cu appears 2 The peak of O, indicating that there is also a small amount of Cu 2 O is not fully reduced.
2) Mechanical properties
The load and the indentation depth of the pressure head loading are measured on the surface of the polished sample in real time by adopting instrumented micro indentation (CSM, switzerland), and the hardness and the elastic modulus of the coating are obtained according to the calculation of a load-displacement curve. The test was performed by selecting a diamond spherical indenter with a radius of 20 μm, a maximum load of 100mN, a loading/unloading rate of 200mN/min, and a holding time of 10s.
Fig. 3 and table 1 are instrumented micron indentation load-displacement curves for different sintered samples and their measured mechanical properties. From the results, the mechanical properties were significantly improved with increasing copper content. The hardness of the GO/10Cu sample is improved by 137% compared with that of the GO sample, which shows that the mechanical property of the graphene-based composite material can be obviously improved by adding a small amount of Cu. When the copper content is further improved, the mechanical property of the GO/100Cu sample is not obviously changed, and the copper content is possibly too high, so that copper components in the sintered sample are unevenly distributed, and larger mechanical property difference is generated.
TABLE 1 hardness and elastic modulus of different sintered samples
3) Tribological Properties
The tribological properties of the different sintered samples added were studied using an instrumented micrometer scale (CSM, switzerland) test. A constant load of 100mN was selected for scribing test on the polished sample surface using a diamond spherical indenter with a radius of 20 μm, a scribing rate of 0.5mm/min, and a scribing distance of 0.5mm. In the process of drawing in, the computer records the changes of the load, the lateral force and the pressing depth along with the increase of the drawing-in stroke in real time, and meanwhile, the friction coefficient is obtained according to the ratio of the lateral force to the load.
Fig. 4 to 5 and table 2 show curves and results of the variation of friction coefficient and indentation depth with sliding travel of different sintered samples, it can be seen that the sintered GO samples show the highest friction coefficient and indentation depth, while the friction coefficient of the GO/Cu samples after adding copper particles gradually decreases with increasing copper content, and excellent wear resistance and antifriction performance are shown. The friction coefficients and the pressing depths of the GO/10Cu and the GO/100Cu are close, which indicates that the friction performance of the graphene-based composite material cannot be further improved when the copper content is too high.
TABLE 2 Friction coefficient and indentation depth for different sintered samples
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (8)
1. The preparation method of the copper modified graphene oxide-based composite material comprises the following steps:
a) Mixing copper salt with graphene oxide dispersion liquid, and performing ultrasonic dispersion to obtain a mixed liquid; the concentration of the graphene oxide dispersion liquid is 1-10 mg/mL; the copper salt is one or more of copper acetate monohydrate, copper nitrate, copper sulfate and copper chloride;
the mass ratio of graphene oxide in the graphene oxide dispersion liquid to copper in copper salt is 100: (1-100);
b) Evaporating the mixed solution to dryness to obtain powder;
c) Heat-treating the powder at 50-400 ℃ for 5-24 hours to obtain heat-treated powder;
d) Reducing the heat-treated powder in a hydrogen-containing atmosphere to obtain reduced powder;
e) And (3) in a vacuum environment, performing spark plasma sintering on the reduced powder to obtain the copper modified graphene oxide-based composite material.
2. The process according to claim 1, wherein the evaporation to dryness in step B) is carried out at a temperature of 85 to 95 ℃.
3. The production method according to claim 1, wherein the hydrogen-containing atmosphere is a mixed gas of hydrogen and a protective gas;
the protective gas is one or more of nitrogen, argon and helium; the volume fraction of hydrogen in the hydrogen-containing atmosphere is 20-40%.
4. The method according to claim 1, wherein the temperature of the reduction in step D) is 100 to 400 ℃; the time of the reduction in the step D) is 1 to 10 hours.
5. The preparation method according to claim 1, wherein the temperature of the spark plasma sintering is 300-1000 ℃, and the heat preservation time of the spark plasma sintering is 5-30 min;
the heating rate of the spark plasma sintering is 80-150 ℃/min.
6. The method according to claim 1, wherein the spark plasma sintering pressure is 20 to 70MPa.
7. The copper-modified graphene oxide-based composite material prepared by the preparation method according to any one of claims 1 to 6.
8. Use of the copper-modified graphene oxide-based composite material according to claim 7 in the field of aerospace.
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