CN109694967B - Preparation method of copper/graphene composite material - Google Patents
Preparation method of copper/graphene composite material Download PDFInfo
- Publication number
- CN109694967B CN109694967B CN201910030345.4A CN201910030345A CN109694967B CN 109694967 B CN109694967 B CN 109694967B CN 201910030345 A CN201910030345 A CN 201910030345A CN 109694967 B CN109694967 B CN 109694967B
- Authority
- CN
- China
- Prior art keywords
- copper
- sintering
- sample
- composite material
- graphene composite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
- C22C32/0084—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ carbon or graphite as the main non-metallic constituent
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a preparation method of a copper/graphene composite material, which adopts the following raw materials: graphite: the volume percentage of zirconium is 62-70 percent to 30 percent to 0-8 percent; the preparation method comprises the following steps: (1) and (3) calculating: firstly, designing the specification of a sample, and weighing the sample according to the proportion; (2) weighing: weighing the sample on a balance by using the calculated data; (3) mixing materials: uniformly mixing copper, graphite and zirconium to obtain a mixed material; (4) cold pressing and tabletting: tabletting the mixed material by using a tablet machine and a metal mold to obtain a sample; (5) and (3) measuring the density: comparing with the designed theoretical density to obtain the density; (6) and (3) sintering: and (3) delivering the sample into a sintering furnace for sintering, and after sintering is completed, cooling to obtain the copper/graphene composite material.
Description
Technical Field
The invention relates to the technical field of carbon material science, in particular to a preparation method of a copper/graphene composite material.
Background
Graphene (Graphene) is a new material with a monolayer sheet structure composed of carbon atoms. Graphene has been considered as a hypothetical structure that cannot exist stably alone until 2004, and was successfully obtained by micro-mechanical exfoliation in experiments for the first time by anderley haim and costatin norworth schloff of the university of manchester, uk, and thus the nobel prize in 2010 was obtained.
Graphene is the thinnest (0.335nm) and the hardest nano material in the world at present, is almost completely transparent, has the absorption rate of only 2.3 percent, has the thermal conductivity coefficient as high as 5300W/m.K, is higher than carbon materials such as carbon nanotubes and diamond, has good electronic conductivity, has the electron mobility higher than 15000cm 2/V.s at normal temperature, has the resistivity of only 10-6 omega.cm, and is the material with the smallest resistivity in the world at present. Since 2004, there are many reports about graphene research, and there are more than 400 reports about Science and Nature, and the potential application fields include field effect transistors, flexible transparent electrodes, touch screens, printed electronics, novel composite materials, sensors, catalyst carriers, gene sequencing, energy storage devices, and the like.
The connection between each carbon atom in graphene is very flexible, and when external mechanical force is applied, the surface of each carbon atom is bent and deformed, so that the carbon atoms do not need to be rearranged to adapt to external force, and the structure is kept stable. The research group of the university of columbia, usa, has conducted a lot of tests and found that graphene is the strongest material in the world so far, and it is estimated that if graphene is used to form a film (thickness of about 100 nm) having a thickness corresponding to that of a common plastic food packaging bag, it will withstand the pressure of about two tons of heavy articles without breaking. Meanwhile, graphene is the substance with the highest known strength, is harder than diamond, and has the strength 100 times higher than that of the best steel in the world.
An experimental result of champagne division of university of illinois, usa, shows that the crystal orientation of the graphene edge can have a quite important influence on the electrical performance of the graphene edge. Researchers deposit nano-scale graphene on a clean semiconductor surface and slice the nano-scale graphene, and then probe the electronic structure of the graphene with atomic resolution by using a scanning tunneling microscope. The results show that the jagged edge (zig zagedge) exhibits a strong edge state, while the chair edge (armchairedge) does not appear similar. Graphene sheets with dimensions less than 10nm, with edges predominantly sawtooth-type, exhibit metallic, rather than the previously expected semiconducting properties. The results of this experiment show that in order to use graphene in nanoelectronic devices, engineering control of the edges must be focused to obtain uniform material properties. On a graphene sheet of 5nm size, as long as a small section of the edge is sawtooth-shaped, the material will change from a semiconductor to a conductor.
The advanced materials and nanotechnology system of Beijing university academy of industry, and the Sunwei professor research group of applied physics and technology research center of Beijing university apply spin polarization density functional theory, and research finds that when hydrogen atoms are adsorbed on partial carbon atoms of graphene, pi bonds of the graphene are destroyed, each carbon atom which is not hydrogenated generates an unpaired 2p electron, long-range exchange coupling is formed between the carbon atoms, stable ferromagnetism is formed, and the Curie temperature is about 278-417K. The method is more controllable and operable than the currently known method, can not only keep the integrity of the graphene skeleton structure and the uniform distribution of magnetism, but also avoid the destruction of magnetism caused in the nano-ribbon assembly process.
In cooperation with the Advanced Photon Source (APS) in the alcong national laboratory of the U.S. department of energy and the fradrick-sertz materials research laboratory at the ebits university, champagne, researchers performed scattering experiments using inelastic X-rays found that graphene very effectively shielded the coulomb force interaction, allowing the electrons to behave like a simple independent electron in a semimetal. Their research revealed several issues, including why individual graphene cannot become insulators as predicted. Experiments also demonstrate a new approach to ultrafast kinetic studies, opening up a new window for understanding the most fundamental properties of materials.
The electric contact material is widely applied to a switching device in the current transmission and conversion process, and plays a role in connecting and disconnecting a circuit and the like. At present, silver and its alloy are mainly used at home and abroad as base materials, and the electric conductivity and the thermal conductivity of copper are most similar to those of silver, so that the copper is rich in resources and low in cost, and is the first choice of silver-free electric contact materials.
However, copper is easily oxidized by arc ablation, and the oxidation product has high resistance, which causes problems of heat generation, failure and the like, and the conventional copper-based electric contact material cannot fundamentally solve the problems. In addition, the copper-based composite material is widely applied to the fields of automobiles, aviation, microelectronics and the like, and the introduction of traditional reinforcing phases such as oxide and carbide nano particles improves the mechanical property of the copper-based composite material, but the reduction of the electrical conductivity and the thermal conductivity brought by the traditional reinforcing phases makes the copper-based composite material difficult to be applied in some fields.
Graphene is a material having a special planar honeycomb two-dimensional structure, and has attracted much attention since 2004 due to its excellent mechanical properties, electrical conductivity, and thermal conductivity (single-layer graphene has a thermal conductivity superior to carbon materials such as carbon nanotubes).
In addition, Graphene Nano Sheets (GNSs) stacked by single-layer graphene also have excellent performance, are considered as an ideal reinforcement of a metal composite material, and are expected to bring improvement on comprehensive performance of a copper-based composite material.
However, the preparation of graphene/copper composites faces many difficulties due to the dispersion problem of graphene and poor bonding force caused by weak van der waals force action with the metal substrate.
Disclosure of Invention
The invention discloses a preparation method of a copper/graphene composite material.
The invention is realized by the following technical scheme:
a preparation method of a copper/graphene composite material adopts raw materials comprising copper, graphite and zirconium, wherein the raw materials comprise: graphite: the volume percentage of zirconium is 62-70 percent to 30 percent to 0-8 percent;
the method for preparing the copper/graphene composite material by adopting the raw materials comprises the following steps:
(1) and (3) calculating: firstly, designing the specification of a sample, multiplying the total volume by the volume percentage content of copper, graphite and zirconium respectively to obtain the volume occupied by the three elements, then multiplying the obtained volume by the corresponding element density to obtain the mass of the corresponding three elements, and finally weighing the sample in proportion;
(2) weighing: weighing the sample on a balance by using the calculated data;
(3) mixing materials: uniformly mixing copper, graphite and zirconium to obtain a mixed material;
(4) cold pressing and tabletting: tabletting the mixed material by using a tablet machine and a metal mold to obtain a sample;
(5) and (3) measuring the density: treating the surface layer of the sample by using a wax layer, testing the actual density of the sample by using a drainage method, and comparing the actual density with the designed theoretical density to obtain the density;
(6) and (3) sintering: and (3) delivering the sample into a sintering furnace for sintering, and after sintering is completed, cooling to obtain the copper/graphene composite material.
The mixing mode adopts a ball milling tank or a mortar for mixing.
The pressure in the ball milling tank is 0-1 Pa.
According to the mixing mode, polymethyl methacrylate is used as a solid carbon source, copper, graphite and zirconium are uniformly mixed through a ball mill, the temperature is increased to 1200 ℃ at the speed of 50 ℃/min, hydrogen and argon are introduced at the temperature of 1200 ℃, the temperature is kept for 25-30min under the atmosphere of the hydrogen and the argon, and then the mixture is obtained through furnace cooling under the atmosphere of the hydrogen and the argon.
The ball milling time of the ball mill is 6-8h, and the rotating speed of the ball mill is 300-500 r/min.
The pressure of the tablet press is set at 600MPa, and the pressure is maintained for 20 min.
The sintering furnace adopts a vacuum molybdenum wire sintering furnace to carry out non-pressurized sintering.
And the sintering furnace adopts a vacuum hot-pressing sintering furnace for pressure sintering.
The sintering temperature of the vacuum hot-pressing sintering furnace is 900 ℃, the pressure is 30Mpa, and the pressure maintaining time is 3 h.
The operation method of the vacuum hot-pressing sintering furnace comprises the following steps:
a. lofting: checking whether the circuit and the water path are normal, opening a hearth of the sintering furnace for loading samples, and closing the hearth;
b. vacuumizing: opening the high vacuum valve, and gradually reaching high vacuum degree;
c. heating: heating to 200 deg.C at a speed of 4 deg.C/min, heating to 900 deg.C under 30MPa for 3 hr, and heating to 200 deg.C or above;
d. sampling: and (3) after the heat preservation time is up, closing the heating switch, reducing the pressure when the temperature is reduced to 300-400 ℃, turning off the high vacuum valve when the temperature is reduced to 200 ℃, turning off the power supply when the temperature is reduced to 100 ℃, turning off the water, naturally cooling, then discharging gas, and opening the furnace for sampling.
The invention has the advantages that:
1. the copper/graphene composite material prepared by the method provided by the invention has the advantages of good corrosion resistance of a finished product, no toxicity, environmental protection and long service life;
2. according to the preparation method, the graphene not only forms a heat channel, but also changes the metallographic structure of copper, and the heat conductivity value of the composite material at room temperature is improved by 25% compared with that of pure copper, and is up to about 386W/(m.K);
3. the material prepared by the process is simple, is beneficial to mass production, adopts a material with wide market as a raw material, and meets the requirements of downstream industries;
4. the copper/graphene composite material prepared by the invention has sp of graphene2The structure can form a protective layer to prevent active reactants from contacting with the copper substrate, thereby improving the oxidation resistance;
5. according to the copper/graphene composite material prepared by the invention, graphene is uniformly dispersed in a copper matrix, dislocation movement is effectively blocked, and the yield strength and the tensile strength of the copper/graphene composite material are respectively increased by 233.3% and 35.7% compared with those of pure copper
6. Copper is easily oxidized into verdigris (basic copper carbonate) at normal temperature, and can be oxidized into copper oxide or cuprous oxide by heating. Graphene has a monoatomic layer thickness, low density, excellent chemical and thermodynamic stability, has an impermeable effect on gas molecules, and has strong oxidation resistance, and in addition, graphene can stably exist at a high temperature of 1500 ℃ under vacuum, so that graphene becomes an ideal protective layer due to the characteristics of graphene.
Drawings
Fig. 1 is a flow chart of a method for preparing a copper/graphene composite material according to the present invention.
Detailed Description
In order to make the technical solutions and advantages of the present invention clearer, the following description clearly and completely describes the technical solutions of the present invention in conjunction with the implementation examples of the present invention.
Referring to the first figure:
a preparation method of a copper/graphene composite material adopts raw materials comprising copper, graphite and zirconium, wherein the raw materials comprise: graphite: the volume percentage of zirconium is 62-70 percent to 30 percent to 0-8 percent;
the method for preparing the copper/graphene composite material by adopting the raw materials comprises the following steps:
(1) and (3) calculating: firstly, designing the specification of a sample, multiplying the total volume by the volume percentage content of copper, graphite and zirconium respectively to obtain the volume occupied by the three elements, then multiplying the obtained volume by the corresponding element density to obtain the mass of the corresponding three elements, and finally weighing the sample in proportion;
(2) weighing: weighing the sample on a balance by using the calculated data;
(3) mixing materials: uniformly mixing copper, graphite and zirconium to obtain a mixed material;
(4) cold pressing and tabletting: tabletting the mixed material by using a tablet machine and a metal mold to obtain a sample;
(5) and (3) measuring the density: treating the surface layer of the sample by using a wax layer, testing the actual density of the sample by using a drainage method, and comparing the actual density with the designed theoretical density to obtain the density;
(6) and (3) sintering: and (3) delivering the sample into a sintering furnace for sintering, and after sintering is completed, cooling to obtain the copper/graphene composite material.
The mixing mode adopts a ball milling tank or a mortar for mixing.
The pressure in the ball milling tank is 0-1 Pa.
According to the mixing mode, polymethyl methacrylate is used as a solid carbon source, copper, graphite and zirconium are uniformly mixed through a ball mill, the temperature is increased to 1200 ℃ at the speed of 50 ℃/min, hydrogen and argon are introduced at the temperature of 1200 ℃, the temperature is kept for 25-30min under the atmosphere of the hydrogen and the argon, and then the mixture is obtained through furnace cooling under the atmosphere of the hydrogen and the argon.
The ball milling time of the ball mill is 6-8h, and the rotating speed of the ball mill is 300-500 r/min.
The pressure of the tablet press is set at 600MPa, and the pressure is maintained for 20 min.
The sintering furnace adopts a vacuum molybdenum wire sintering furnace to carry out non-pressurized sintering.
And the sintering furnace adopts a vacuum hot-pressing sintering furnace for pressure sintering.
The sintering temperature of the vacuum hot-pressing sintering furnace is 900 ℃, the pressure is 30Mpa, and the pressure maintaining time is 3 h.
The operation method of the vacuum hot-pressing sintering furnace comprises the following steps:
a. lofting: checking whether the circuit and the water path are normal, opening a hearth of the sintering furnace for loading samples, and closing the hearth;
b. vacuumizing: opening the high vacuum valve, and gradually reaching high vacuum degree;
c. heating: heating to 200 deg.C at a speed of 4 deg.C/min, heating to 900 deg.C under 30MPa for 3 hr, and heating to 200 deg.C or above;
d. sampling: and (3) after the heat preservation time is up, closing the heating switch, reducing the pressure when the temperature is reduced to 300-400 ℃, turning off the high vacuum valve when the temperature is reduced to 200 ℃, turning off the power supply when the temperature is reduced to 100 ℃, turning off the water, naturally cooling, then discharging gas, and opening the furnace for sampling.
Example 1
A preparation method of a copper/graphene composite material adopts raw materials comprising copper, graphite and zirconium, wherein the raw materials comprise: graphite: the volume percentage of the zirconium is 62 percent to 30 percent to 8 percent;
the method for preparing the copper/graphene composite material by adopting the raw materials comprises the following steps:
(1) and (3) calculating: firstly, designing the specification of a sample, multiplying the total volume by the volume percentage content of copper, graphite and zirconium respectively to obtain the volume occupied by the three elements, then multiplying the obtained volume by the corresponding element density to obtain the mass of the corresponding three elements, and finally weighing the sample in proportion;
(2) weighing: weighing the sample on a balance by using the calculated data;
(3) mixing materials: uniformly mixing copper, graphite and zirconium to obtain a mixed material;
(4) cold pressing and tabletting: tabletting the mixed material by using a tablet machine and a metal mold to obtain a sample;
(5) and (3) measuring the density: treating the surface layer of the sample by using a wax layer, testing the actual density of the sample by using a drainage method, and comparing the actual density with the designed theoretical density to obtain the density;
(6) and (3) sintering: and (3) delivering the sample into a sintering furnace for sintering, and after sintering is completed, cooling to obtain the copper/graphene composite material.
The mixing mode adopts a ball milling tank or a mortar for mixing.
The pressure in the ball milling tank is 0-1 Pa.
According to the mixing mode, polymethyl methacrylate is used as a solid carbon source, copper, graphite and zirconium are uniformly mixed through a ball mill, the temperature is increased to 1200 ℃ at the speed of 50 ℃/min, hydrogen and argon are introduced at the temperature of 1200 ℃, the temperature is kept for 25-30min under the atmosphere of the hydrogen and the argon, and then the mixture is obtained through furnace cooling under the atmosphere of the hydrogen and the argon.
The ball milling time of the ball mill is 6-8h, and the rotating speed of the ball mill is 300-500 r/min.
The pressure of the tablet press is set at 600MPa, and the pressure is maintained for 20 min.
The sintering furnace adopts a vacuum molybdenum wire sintering furnace to carry out non-pressurized sintering.
And the sintering furnace adopts a vacuum hot-pressing sintering furnace for pressure sintering.
The sintering temperature of the vacuum hot-pressing sintering furnace is 900 ℃, the pressure is 30Mpa, and the pressure maintaining time is 3 h.
The operation method of the vacuum hot-pressing sintering furnace comprises the following steps:
a. lofting: checking whether the circuit and the water path are normal, opening a hearth of the sintering furnace for loading samples, and closing the hearth;
b. vacuumizing: opening the high vacuum valve, and gradually reaching high vacuum degree;
c. heating: heating to 200 deg.C at a speed of 4 deg.C/min, heating to 900 deg.C under 30MPa for 3 hr, and heating to 200 deg.C or above;
d. sampling: and (3) after the heat preservation time is up, closing the heating switch, reducing the pressure when the temperature is reduced to 300-400 ℃, turning off the high vacuum valve when the temperature is reduced to 200 ℃, turning off the power supply when the temperature is reduced to 100 ℃, turning off the water, naturally cooling, then discharging gas, and opening the furnace for sampling.
Example 2
A preparation method of a copper/graphene composite material adopts raw materials comprising copper, graphite and zirconium, wherein the raw materials comprise: graphite: the volume percentage of zirconium is 65 percent to 30 percent to 5 percent;
the method for preparing the copper/graphene composite material by adopting the raw materials comprises the following steps:
(1) and (3) calculating: firstly, designing the specification of a sample, multiplying the total volume by the volume percentage content of copper, graphite and zirconium respectively to obtain the volume occupied by the three elements, then multiplying the obtained volume by the corresponding element density to obtain the mass of the corresponding three elements, and finally weighing the sample in proportion;
(2) weighing: weighing the sample on a balance by using the calculated data;
(3) mixing materials: uniformly mixing copper, graphite and zirconium to obtain a mixed material;
(4) cold pressing and tabletting: tabletting the mixed material by using a tablet machine and a metal mold to obtain a sample;
(5) and (3) measuring the density: treating the surface layer of the sample by using a wax layer, testing the actual density of the sample by using a drainage method, and comparing the actual density with the designed theoretical density to obtain the density;
(6) and (3) sintering: and (3) delivering the sample into a sintering furnace for sintering, and after sintering is completed, cooling to obtain the copper/graphene composite material.
The mixing mode adopts a ball milling tank or a mortar for mixing.
The pressure in the ball milling tank is 0-1 Pa.
According to the mixing mode, polymethyl methacrylate is used as a solid carbon source, copper, graphite and zirconium are uniformly mixed through a ball mill, the temperature is increased to 1200 ℃ at the speed of 50 ℃/min, hydrogen and argon are introduced at the temperature of 1200 ℃, the temperature is kept for 25-30min under the atmosphere of the hydrogen and the argon, and then the mixture is obtained through furnace cooling under the atmosphere of the hydrogen and the argon.
The ball milling time of the ball mill is 6-8h, and the rotating speed of the ball mill is 300-500 r/min.
The pressure of the tablet press is set at 600MPa, and the pressure is maintained for 20 min.
The sintering furnace adopts a vacuum molybdenum wire sintering furnace to carry out non-pressurized sintering.
And the sintering furnace adopts a vacuum hot-pressing sintering furnace for pressure sintering.
The sintering temperature of the vacuum hot-pressing sintering furnace is 900 ℃, the pressure is 30Mpa, and the pressure maintaining time is 3 h.
The operation method of the vacuum hot-pressing sintering furnace comprises the following steps:
a. lofting: checking whether the circuit and the water path are normal, opening a hearth of the sintering furnace for loading samples, and closing the hearth;
b. vacuumizing: opening the high vacuum valve, and gradually reaching high vacuum degree;
c. heating: heating to 200 deg.C at a speed of 4 deg.C/min, heating to 900 deg.C under 30MPa for 3 hr, and heating to 200 deg.C or above;
d. sampling: and (3) after the heat preservation time is up, closing the heating switch, reducing the pressure when the temperature is reduced to 300-400 ℃, turning off the high vacuum valve when the temperature is reduced to 200 ℃, turning off the power supply when the temperature is reduced to 100 ℃, turning off the water, naturally cooling, then discharging gas, and opening the furnace for sampling.
Example 3
A preparation method of a copper/graphene composite material adopts raw materials comprising copper and graphite, wherein the raw materials comprise: the volume percentage of the graphite is 70 percent to 30 percent;
the method for preparing the copper/graphene composite material by adopting the raw materials comprises the following steps:
(1) and (3) calculating: firstly, designing the specification of a sample, multiplying the total volume by the volume percentage of copper and graphite respectively to obtain the volume occupied by the two elements, then multiplying the obtained volume by the corresponding element density to obtain the mass of the corresponding two elements, and finally weighing the sample in proportion;
(2) weighing: weighing the sample on a balance by using the calculated data;
(3) mixing materials: uniformly mixing copper and graphite to obtain a mixed material;
(4) cold pressing and tabletting: tabletting the mixed material by using a tablet machine and a metal mold to obtain a sample;
(5) and (3) measuring the density: treating the surface layer of the sample by using a wax layer, testing the actual density of the sample by using a drainage method, and comparing the actual density with the designed theoretical density to obtain the density;
(6) and (3) sintering: and (3) delivering the sample into a sintering furnace for sintering, and after sintering is completed, cooling to obtain the copper/graphene composite material.
The mixing mode adopts a ball milling tank or a mortar for mixing.
The pressure in the ball milling tank is 0-1 Pa.
According to the mixing mode, polymethyl methacrylate is used as a solid carbon source, copper and graphite are uniformly mixed through a ball mill, the temperature is increased to 1200 ℃ at the speed of 50 ℃/min, hydrogen and argon are introduced at the temperature of 1200 ℃, the temperature is kept for 25-30min under the atmosphere of the hydrogen and the argon, and then the mixture is obtained through furnace cooling under the atmosphere of the hydrogen and the argon.
The ball milling time of the ball mill is 6-8h, and the rotating speed of the ball mill is 300-500 r/min.
The pressure of the tablet press is set at 600MPa, and the pressure is maintained for 20 min.
The sintering furnace adopts a vacuum molybdenum wire sintering furnace to carry out non-pressurized sintering.
And the sintering furnace adopts a vacuum hot-pressing sintering furnace for pressure sintering.
The sintering temperature of the vacuum hot-pressing sintering furnace is 900 ℃, the pressure is 30Mpa, and the pressure maintaining time is 3 h.
The operation method of the vacuum hot-pressing sintering furnace comprises the following steps:
a. lofting: checking whether the circuit and the water path are normal, opening a hearth of the sintering furnace for loading samples, and closing the hearth;
b. vacuumizing: opening the high vacuum valve, and gradually reaching high vacuum degree;
c. heating: heating to 200 deg.C at a speed of 4 deg.C/min, heating to 900 deg.C under 30MPa for 3 hr, and heating to 200 deg.C or above;
d. sampling: and (3) after the heat preservation time is up, closing the heating switch, reducing the pressure when the temperature is reduced to 300-400 ℃, turning off the high vacuum valve when the temperature is reduced to 200 ℃, turning off the power supply when the temperature is reduced to 100 ℃, turning off the water, naturally cooling, then discharging gas, and opening the furnace for sampling.
The performance test results of the copper/graphene composite material prepared in the examples are shown in the following table:
description of the drawings:
1) measuring and calculating the density by adopting a drainage method in the volume density measurement, wherein the experimental condition is room temperature;
2) a universal testing machine is used for testing the tensile strength, the size of a sample is 6mm multiplied by 9.5mm, and the experimental condition is room temperature;
3) flexural strength test was measured using an Instron3369 materials mechanics tester, U.S. with sample dimensions of 38mm x 6mm x 3mm and a loading rate of 1.00000 mm/min. The experimental conditions were room temperature;
4) the resistivity test was conducted using a double arm bridge, and the test dimensions were 55mm × 5mm × 5 mm. The experimental conditions were room temperature;
5) the abrasion resistance test adopts an M-2000 type ring block tester, and the sample size is 18mm multiplied by 12 mm. The experimental conditions were room temperature;
6) the Vickers hardness measurement adopts a Vickers hardness meter, the pressure is 1Kg, the pressure maintaining time is 10s, and the experimental conditions are room temperature.
Therefore, after copper, zirconium and graphite are mechanically mixed, the copper, zirconium and graphite are effectively combined with a copper matrix through methods such as sintering, hot pressing and the like, the characteristics of high conductivity and excellent mechanical property of graphene can be organically combined with the characteristics of conductivity, heat conductivity, corrosion resistance and easiness in forming of copper, and the high-performance copper/graphene composite material is prepared.
The above description is not intended to limit the present invention, and the present invention is not limited to the above examples, and those skilled in the art should understand that they can make various changes, modifications, additions and substitutions within the spirit and scope of the present invention.
Claims (6)
1. The preparation method of the copper/graphene composite material is characterized in that the adopted raw materials comprise copper, graphite and zirconium, wherein the weight ratio of copper: graphite: the volume percentage of zirconium is 62-70 percent to 30 percent to 0-8 percent;
the method for preparing the copper/graphene composite material by adopting the raw materials comprises the following steps:
(1) and (3) calculating: firstly, designing the specification of a sample, multiplying the total volume by the volume percentage content of copper, graphite and zirconium respectively to obtain the volume occupied by the three elements, then multiplying the obtained volume by the corresponding element density to obtain the mass of the corresponding three elements, and finally weighing the sample in proportion;
(2) weighing: weighing the sample on a balance by using the calculated data;
(3) mixing materials: uniformly mixing copper, graphite and zirconium to obtain a mixed material; the mixing mode adopts a ball milling tank or a mortar for mixing; the pressure in the ball milling tank is 0-1 Pa; according to the mixing mode, polymethyl methacrylate is used as a solid carbon source, copper, graphite and zirconium are uniformly mixed by a ball mill, the temperature is increased to 1200 ℃ at the speed of 50 ℃/min, hydrogen and argon are introduced at the temperature of 1200 ℃, the temperature is kept for 25-30min under the atmosphere of the hydrogen and the argon, and then the mixture is obtained by furnace cooling under the atmosphere of the hydrogen and the argon; the ball milling time of the ball mill is 6-8h, and the rotating speed of the ball mill is 300-500 r/min;
(4) cold pressing and tabletting: tabletting the mixed material by using a tablet machine and a metal mold to obtain a sample;
(5) and (3) measuring the density: treating the surface layer of the sample by using a wax layer, testing the actual density of the sample by using a drainage method, and comparing the actual density with the designed theoretical density to obtain the density;
(6) and (3) sintering: and (3) delivering the sample into a sintering furnace for sintering, and after sintering is completed, cooling to obtain the copper/graphene composite material.
2. The method for preparing the copper/graphene composite material according to claim 1, wherein: the pressure of the tablet press is set at 600MPa, and the pressure is maintained for 20 min.
3. The method for preparing the copper/graphene composite material according to claim 1, wherein: the sintering furnace adopts a vacuum molybdenum wire sintering furnace to carry out non-pressurized sintering.
4. The method for preparing the copper/graphene composite material according to claim 1, wherein: and the sintering furnace adopts a vacuum hot-pressing sintering furnace for pressure sintering.
5. The method for preparing the copper/graphene composite material according to claim 4, wherein: the sintering temperature of the vacuum hot-pressing sintering furnace is 900 ℃, the pressure is 30Mpa, and the pressure maintaining time is 3 h.
6. The method for preparing the copper/graphene composite material according to claim 4, wherein: the operation method of the vacuum hot-pressing sintering furnace comprises the following steps:
a. lofting: checking whether the circuit and the water path are normal, opening a hearth of the sintering furnace for loading samples, and closing the hearth;
b. vacuumizing: opening the high vacuum valve, and gradually reaching high vacuum degree;
c. heating: heating to 200 deg.C at a speed of 4 deg.C/min, heating to 900 deg.C under 30MPa for 3 hr, and heating to 200 deg.C or above;
d. sampling: and (3) after the heat preservation time is up, closing the heating switch, reducing the pressure when the temperature is reduced to 300-400 ℃, turning off the high vacuum valve when the temperature is reduced to 200 ℃, turning off the power supply when the temperature is reduced to 100 ℃, turning off the water, naturally cooling, then discharging gas, and opening the furnace for sampling.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910030345.4A CN109694967B (en) | 2019-01-14 | 2019-01-14 | Preparation method of copper/graphene composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910030345.4A CN109694967B (en) | 2019-01-14 | 2019-01-14 | Preparation method of copper/graphene composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109694967A CN109694967A (en) | 2019-04-30 |
| CN109694967B true CN109694967B (en) | 2020-12-25 |
Family
ID=66233221
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910030345.4A Active CN109694967B (en) | 2019-01-14 | 2019-01-14 | Preparation method of copper/graphene composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109694967B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110227825B (en) * | 2019-05-16 | 2022-07-26 | 湖南华瑞康源科技有限公司 | Method for preparing graphene/copper/cuprous oxide composite powder by low-energy ball milling |
| CN113977133A (en) * | 2021-10-27 | 2022-01-28 | 国网河南省电力公司电力科学研究院 | Corrosion-resistant composite brazing filler metal for copper-aluminum transition wire clamp and preparation method thereof |
| CN114029494B (en) * | 2021-11-11 | 2022-08-02 | 西北有色金属研究院 | Preparation method of spiral graphene film/copper laminated composite material |
| CN114425622A (en) * | 2022-01-28 | 2022-05-03 | 荣成市宏程新材料有限公司 | Powder metallurgy composite material and preparation method thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104874803A (en) * | 2015-05-06 | 2015-09-02 | 天津大学 | Method for preparing graphene/copper composite material by in-situ catalysis of solid carbon source on surfaces of copper powders |
| JP2016000843A (en) * | 2014-06-11 | 2016-01-07 | 片野染革株式会社 | Spherical composite metal fine particle and manufacturing method therefor |
| CN105364068A (en) * | 2015-10-19 | 2016-03-02 | 天津大学 | Manufacturing method for three-dimensional graphene in-situ clad-copper composite material |
| WO2016200913A1 (en) * | 2015-06-08 | 2016-12-15 | Bourque Industries, Inc. | Method of making a high efficiency electrical wire |
| CN108359825A (en) * | 2018-02-11 | 2018-08-03 | 太原理工大学 | A kind of preparation method of ceramics-graphene enhancing Cu-base composites |
| CN108515189A (en) * | 2018-04-02 | 2018-09-11 | 大同新成新材料股份有限公司 | A kind of preparation method of graphene carbon/carbon-copper composite material |
| CN108517435A (en) * | 2018-05-21 | 2018-09-11 | 西南交通大学 | A kind of magnetic-levitation train nano-sized carbon enhancing Cu-base composites and preparation method thereof |
| CN108911694A (en) * | 2018-07-19 | 2018-11-30 | 大同新成新材料股份有限公司 | A kind of preparation method of graphene plating copper powder pantograph carbon slide composite material |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005038912A1 (en) * | 2002-10-11 | 2005-04-28 | Chien-Min Sung | Carbonaceous heat spreader and associated methods |
-
2019
- 2019-01-14 CN CN201910030345.4A patent/CN109694967B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016000843A (en) * | 2014-06-11 | 2016-01-07 | 片野染革株式会社 | Spherical composite metal fine particle and manufacturing method therefor |
| CN104874803A (en) * | 2015-05-06 | 2015-09-02 | 天津大学 | Method for preparing graphene/copper composite material by in-situ catalysis of solid carbon source on surfaces of copper powders |
| WO2016200913A1 (en) * | 2015-06-08 | 2016-12-15 | Bourque Industries, Inc. | Method of making a high efficiency electrical wire |
| CN105364068A (en) * | 2015-10-19 | 2016-03-02 | 天津大学 | Manufacturing method for three-dimensional graphene in-situ clad-copper composite material |
| CN108359825A (en) * | 2018-02-11 | 2018-08-03 | 太原理工大学 | A kind of preparation method of ceramics-graphene enhancing Cu-base composites |
| CN108515189A (en) * | 2018-04-02 | 2018-09-11 | 大同新成新材料股份有限公司 | A kind of preparation method of graphene carbon/carbon-copper composite material |
| CN108517435A (en) * | 2018-05-21 | 2018-09-11 | 西南交通大学 | A kind of magnetic-levitation train nano-sized carbon enhancing Cu-base composites and preparation method thereof |
| CN108911694A (en) * | 2018-07-19 | 2018-11-30 | 大同新成新材料股份有限公司 | A kind of preparation method of graphene plating copper powder pantograph carbon slide composite material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109694967A (en) | 2019-04-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109694967B (en) | Preparation method of copper/graphene composite material | |
| Zhang et al. | Review of nano-phase effects in high strength and conductivity copper alloys | |
| Cheng et al. | Copper nanowire based transparent conductive films with high stability and superior stretchability | |
| Huang et al. | MoS 2 quantum dot-decorated MXene nanosheets as efficient hydrogen evolution electrocatalysts | |
| Sun et al. | Formation of silicon carbide nanotubes and nanowires via reaction of silicon (from disproportionation of silicon monoxide) with carbon nanotubes | |
| Kim et al. | Hardness and wear resistance of carbon nanotube reinforced Cu matrix nanocomposites | |
| Wei et al. | Enhancement of mechanical properties and conductivity in carbon nanotubes (CNTs)/Cu matrix composite by surface and intratube decoration of CNTs | |
| Yu et al. | Silver nanoparticle-based thermal interface materials with ultra-low thermal resistance for power electronics applications | |
| JP5707628B2 (en) | Graphene roll-to-roll transfer method, graphene roll-to-roll transfer apparatus, graphene roll manufacturing method, and element manufacturing method | |
| Raghubanshi et al. | The properties and applications of helical carbon fibers and related materials: a review | |
| US20110315934A1 (en) | Method for fabrication of functionalized graphene reinforced composite conducting plate | |
| CN106584976A (en) | High-conductivity graphene/copper-based layered composite material and preparation method thereof | |
| Li et al. | Preparation of 2D MoSe2/PEDOT: PSS composite and its thermoelectric properties | |
| Lin et al. | Excellent anti-arc erosion performance and corresponding mechanisms of a nickel-belt-reinforced silver-based electrical contact material | |
| Chang et al. | Low-temperature solution-processable Ni (OH) 2 ultrathin nanosheet/N-graphene nanohybrids for high-performance supercapacitor electrodes | |
| Bae et al. | Transport phenomena in an anisotropically aligned single-wall carbon nanotube film | |
| Zhou et al. | Significant strengthening effect in few-layered MXene-reinforced Al matrix composites | |
| Yang et al. | In-situ generated graphene from wheat flour for enhancing mechanical and electrical properties of copper matrix composites | |
| Zhong et al. | Dispersing and coating of transition metals Co, Fe and Ni on carbon materials | |
| Zuo et al. | Enhanced electrical conductivity and hardness of Copper/Carbon Nanotubes composite by tuning the interface structure | |
| Tong et al. | Enhancing mechanical properties of copper matrix composite by adding SiO2 quantum dots reinforcement | |
| Lu et al. | Epoxy resin/graphite electrically conductive nanosheet nanocomposite | |
| Duy et al. | Growth of carbon nanotubes on stainless steel substrates by DC-PECVD | |
| Ji et al. | Field emission performance of bulk graphene | |
| Wang et al. | Interface structure and properties of CNTs/Cu composites fabricated by electroless deposition and spark plasma sintering |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |