CN103817466A - Method for efficiently preparing graphene-reinforcing copper-based composite brazing filler metal at low temperature - Google Patents

Abstract

The invention discloses a low-temperature and high-efficiency method for preparing graphene-reinforced copper-based composite solder, and the invention relates to a method for preparing graphene-reinforced copper-based composite solder. The invention aims to solve the problems of poor graphene dispersion, many surface defects, high preparation temperature and low efficiency when the graphene-reinforced copper-based composite solder is prepared by the traditional method. Method: Put the copper powder in the plasma-enhanced chemical vapor deposition vacuum device, pass in hydrogen gas, keep it warm at high temperature, and then pass in argon gas and carbon source gas for deposition. After the deposition is completed, stop the introduction of carbon source gas. Finally, cool down to below room temperature to obtain graphene/copper composite powder, and then mix metal powder or alloy powder with graphene/copper composite powder evenly to obtain graphene-reinforced copper-based composite solder. The invention is used for a low-temperature and high-efficiency method for preparing graphene-reinforced copper-based composite solder.

Description

A low-temperature and high-efficiency method for preparing graphene-reinforced copper-based composite solder

technical field

The invention relates to a method for preparing graphene-reinforced copper-based composite solder.

Background technique

Brazing is one of the three major welding methods (fusion welding, pressure welding, and brazing). It mainly uses metal materials with a lower melting point than the base metal as the solder, and heats the weldment and the solder to a temperature higher than the melting point of the solder. Below the melting temperature of the base metal, the liquid solder is used to wet the base metal, fill the joint gap and diffuse with the base metal to realize the connection of the weldment. It is widely used in many fields such as machinery, electrical machinery, instrumentation, and electronic technology. The strength, hardness, heat resistance, corrosion resistance and other performance indicators of the brazed joint are directly related to the solder. Adding reinforcements such as particles, fibers, and layers to the solder can effectively improve the performance of the brazed joint. With the continuous development of science and technology, nanomaterials (such as nanoparticles, nanowires, nanosheets, etc.) have become a research hotspot in the field of welding as reinforcements to enhance solder.

Graphene is a new material with a single-layer sheet structure composed of carbon atoms. Due to the special structure of graphene, graphene has excellent electrical, thermal and mechanical properties compared with other materials. It shows great application prospects in many aspects such as electronic devices, composite materials and electrochemical energy storage materials. Studies have shown that adding 0.1% of graphene sheets prepared by redox method to Sn-Ag-Cu solder can significantly improve the wettability and mechanical properties of the solder. It can be seen that graphene has broad application prospects in strengthening solder and improving the performance of solder.

At present, the commonly used preparation methods of graphene include mechanical exfoliation method, redox graphite method and chemical vapor deposition method. The graphene prepared by mechanical exfoliation is of high quality, but the process is complex and the yield is low, making it difficult for practical application. Although the redox graphite method has the characteristics of low cost and large output, the process is relatively complicated, the structure of graphene is severely damaged, there are many surface defects, and the electrical and mechanical properties are poor. Graphene prepared by chemical vapor deposition has large size and few defects, but the preparation temperature is high, the time is long, and the efficiency is low, which is difficult for practical application.

Due to the limitations of the preparation process of graphene materials, there are two difficulties in the preparation method of graphene-reinforced composite solder: (1) the dispersion of graphene, it is difficult to achieve the uniformity of graphene in composite solder by traditional mechanical ball milling Dispersion, the uniform dispersion of graphene is often achieved by surface chemical modification methods, and the process is more complicated. (2) The problem of graphene structure defects. According to the actual preparation process requirements and the requirements of the addition amount, the graphene obtained by the redox graphite method is often used. For this reason, there are many graphene structure defects in the composite solder. Due to the fact that the structurally damaged graphene easily reacts with the active elements in the composite solder at higher temperatures, the wide application of graphene materials in composite solder is limited.

Contents of the invention

The present invention solves the problems of poor graphene dispersion, many surface defects, high preparation temperature and low efficiency when preparing graphene-reinforced copper-based composite solder by traditional methods, and provides a low-temperature and high-efficiency preparation of graphene-reinforced copper-based composite solder. method of feeding.

A low-temperature and high-efficiency method for preparing graphene-reinforced copper-based composite solder, specifically carried out according to the following steps:

1. Put the copper powder in the plasma-enhanced chemical vapor deposition vacuum device, evacuate until the pressure is below 5Pa, feed hydrogen gas with a gas flow rate of 18sccm-22sccm, and adjust the vacuuming speed to put the plasma-enhanced chemical vapor deposition in the vacuum device. The pressure is controlled at 190Pa～210Pa, and the temperature is raised to 500℃～700℃ within 40min under the pressure of 190Pa～210Pa and hydrogen atmosphere, and the temperature is kept at 500℃～700℃ for 25min～35min;

2. Introduce argon and carbon source gas, adjust the gas flow of hydrogen to 40 sccm, argon gas to 80 sccm, and carbon source gas to 1 sccm to 8 sccm, and adjust the vacuuming speed to vacuum the plasma-enhanced chemical vapor deposition The pressure in the device is controlled at 800Pa to 1000Pa, and then the deposition is carried out under the conditions of the deposition system RF power frequency of 13.56MHz, RF power of 190W to 210W, pressure of 800Pa to 1000Pa and temperature of 500°C to 700°C, and the deposition time is 10s to 300s, after the deposition is over, turn off the radio frequency power supply and the heating power supply, stop feeding the carbon source gas, continue to feed hydrogen and argon with the gas flow rate of hydrogen at 40 sccm and the gas flow of argon at 80 sccm, and adjust the vacuuming speed to draw the plasma The pressure in the enhanced chemical vapor deposition vacuum device is controlled at 150Pa to 200Pa, and the graphene/copper composite powder is obtained by cooling from a temperature of 500°C to 700°C to room temperature under a pressure of 150Pa to 200Pa and an atmosphere of hydrogen and argon;

3. Put the metal powder or alloy powder and the graphene/copper composite powder prepared in step 2 into a ball mill, grind and stir until the powder is evenly mixed, and then obtain the graphene-reinforced copper-based composite solder.

The beneficial effects of the present invention are: 1. The present invention utilizes plasma-enhanced chemical vapor deposition (PECVD) to decompose the carbon source (CH ₄ ) very quickly into highly active carbon groups through the action of radio frequency. The catalytic reaction can grow graphene on the metal surface in a short time. It can realize the effective growth of graphene on the surface of Cu powder at low temperature.

2. The present invention utilizes plasma to enhance the effect of radio frequency, which not only avoids high-temperature pyrolysis of carbon source gas, but also greatly improves the decomposition efficiency of carbon source gas (CH ₄ ), that is, feeding a small amount of carbon source gas (CH ₄ ) will also A large number of active carbon groups are generated, thereby effectively reducing the preparation temperature and improving the preparation efficiency.

3. The method of the present invention is simple, efficient, low-cost, and convenient for industrial production. The graphene in the prepared graphene-enhanced copper-based composite solder has high quality and uniform dispersion, and can effectively improve the performance of the copper-based composite solder.

The invention is used for a low-temperature and high-efficiency method for preparing graphene-reinforced copper-based composite solder.

Description of drawings

Fig. 1 is the Raman spectrogram of graphene/copper composite powder in embodiment one; 1 is D peak; 2 is G peak; 3 is 2D peak;

Fig. 2 is the optical microscope picture that graphene is transferred to SiO ₂ /Si substrate in embodiment one;

3 is a Raman spectrum of graphene transferred to SiO ₂ /Si substrate in Example 1; 1 is D peak; 2 is G peak; 3 is 2D peak.

Detailed ways

The technical solution of the present invention is not limited to the specific embodiments listed below, but also includes any combination of the specific embodiments.

Specific embodiment one: a kind of low-temperature high-efficiency method for preparing graphene-reinforced copper-based composite solder described in this embodiment is specifically carried out according to the following steps:

1. Put the copper powder in the plasma-enhanced chemical vapor deposition vacuum device, evacuate until the pressure is below 5Pa, feed hydrogen gas with a gas flow rate of 18sccm-22sccm, and adjust the vacuuming speed to put the plasma-enhanced chemical vapor deposition in the vacuum device. The pressure is controlled at 190Pa～210Pa, and the temperature is raised to 500℃～700℃ within 40min under the pressure of 190Pa～210Pa and hydrogen atmosphere, and the temperature is kept at 500℃～700℃ for 25min～35min;

2. Introduce argon and carbon source gas, adjust the gas flow of hydrogen to 40 sccm, argon gas to 80 sccm, and carbon source gas to 1 sccm to 8 sccm, and adjust the vacuuming speed to vacuum the plasma-enhanced chemical vapor deposition The pressure in the device is controlled at 800Pa to 1000Pa, and then the deposition is carried out under the conditions of the deposition system RF power frequency of 13.56MHz, RF power of 190W to 210W, pressure of 800Pa to 1000Pa and temperature of 500°C to 700°C, and the deposition time is 10s to 300s, after the deposition is over, turn off the radio frequency power supply and the heating power supply, stop feeding the carbon source gas, continue to feed hydrogen and argon with the gas flow rate of hydrogen at 40 sccm and the gas flow of argon at 80 sccm, and adjust the vacuuming speed to draw the plasma The pressure in the enhanced chemical vapor deposition vacuum device is controlled at 150Pa to 200Pa, and the graphene/copper composite powder is obtained by cooling from a temperature of 500°C to 700°C to room temperature under a pressure of 150Pa to 200Pa and an atmosphere of hydrogen and argon;

3. Put the metal powder or alloy powder and the graphene/copper composite powder prepared in step 2 into a ball mill, grind and stir until the powder is evenly mixed, and then obtain the graphene-reinforced copper-based composite solder.

The basic principle of low-temperature and high-efficiency preparation of graphene-reinforced copper-based composite solder involved in this embodiment: using plasma-enhanced chemical vapor deposition (PECVD), the carbon source (CH ₄ ) can be decomposed very quickly by radio frequency These carbon groups have very high activity, and graphene can be grown on the metal surface in a short time after the catalytic reaction of the metal catalyst. In addition, due to the effect of radio frequency, it not only avoids high-temperature pyrolysis of carbon source gas, but also greatly improves the decomposition efficiency of carbon source gas (CH ₄ ), that is, a small amount of carbon source gas (CH ₄ ) will also produce a large amount of activated carbon. group, thereby effectively reducing the preparation temperature and improving the preparation efficiency. In the present invention, copper is selected as the substrate. Since the solubility of carbon atoms in copper is relatively low, graphene can be grown in a self-limited manner by carbon atom adsorption. The graphene formed in this manner is not only of high quality, but also has good dispersibility. Applying the graphene-reinforced copper powder prepared by this method to make copper-based composite solder can make the composite solder obtain a series of excellent properties.

The beneficial effects of this embodiment are: 1. This embodiment utilizes plasma-enhanced chemical vapor deposition (PECVD) to decompose carbon source (CH ₄ ) very quickly into highly active carbon groups through radio frequency. The catalytic reaction of the metal catalyst can grow graphene on the metal surface in a short time. It can realize the effective growth of graphene on the surface of Cu powder at low temperature.

2. This embodiment utilizes plasma-enhanced radio frequency to not only avoid high-temperature pyrolysis of carbon source gas, but also greatly improve the decomposition efficiency of carbon source gas (CH ₄ ), that is, introducing a small amount of carbon source gas (CH ₄ ) also A large number of active carbon groups will be produced, thereby effectively reducing the preparation temperature and improving the preparation efficiency.

3. The method of this embodiment is simple, efficient, low-cost, and convenient for industrial production. The graphene in the prepared graphene-reinforced copper-based composite solder has high quality and uniform dispersion, which can effectively improve the performance of the copper-based composite solder.

Embodiment 2: This embodiment differs from Embodiment 1 in that the copper powder described in Step 1 has a purity of 99%-99.99%, and a particle diameter of 100 nm-100 μm. Others are the same as in the first embodiment.

Embodiment 3: This embodiment differs from Embodiment 1 or Embodiment 2 in that the carbon source gas described in step 2 is methane. Others are the same as in the first or second embodiment.

Embodiment 4: This embodiment differs from Embodiment 1 to Embodiment 3 in that: the metal powder described in step 3 has a purity of 99% to 99.99%, and a particle diameter of 100 nm to 100 μm; the alloy powder has a purity of 99%~99.99%, particle diameter is 100nm~100μm. Others are the same as those in Embodiments 1 to 3.

Embodiment 5: This embodiment differs from Embodiment 1 to Embodiment 4 in that the metal powder described in Step 3 is Sn powder, Ag powder, P powder or Mn powder. Others are the same as the specific embodiments 1 to 4.

Embodiment 6: This embodiment differs from Embodiment 1 to Embodiment 5 in that the alloy powder described in step 3 is Sn-Ag powder or Ag-Zn powder. Others are the same as those in Embodiments 1 to 5.

Adopt the following examples to verify the beneficial effects of the present invention:

Embodiment one:

A kind of low-temperature and high-efficiency method for preparing graphene-reinforced copper-based composite solder described in this embodiment is specifically carried out according to the following steps:

1. Put the copper powder in the plasma-enhanced chemical vapor deposition vacuum device, evacuate until the pressure is below 5Pa, feed hydrogen gas with a gas flow rate of 20 sccm, adjust the vacuuming speed to control the pressure in the plasma-enhanced chemical vapor deposition vacuum device 200Pa, and the temperature is raised to 600°C within 40min under the pressure of 200Pa and hydrogen atmosphere, and the temperature is kept at 600°C for 30min;

2. Introduce argon and CH ₄ , adjust the flow rate of hydrogen gas to 40 sccm, the flow rate of argon gas to 80 sccm and the gas flow rate of CH ₄ to 2 sccm, and adjust the vacuum speed to control the pressure in the plasma-enhanced chemical vapor deposition vacuum device to 1000Pa , and then deposited under the conditions of RF power frequency of 13.56MHz, RF power of 200W, pressure of 1000Pa and temperature of 600°C, the deposition time was 60s. After the deposition, the RF power and heating power were turned off, and the carbon Source gas, continue to pass into argon and hydrogen with the hydrogen gas flow rate of 40 sccm and the argon gas flow rate of 80 sccm, and adjust the vacuum speed to control the pressure in the plasma-enhanced chemical vapor deposition vacuum device to 200Pa, when the pressure is 200Pa and hydrogen and cooling from a temperature of 600°C to room temperature under an argon atmosphere to obtain a graphene/copper composite powder;

3. Put the metal Sn powder and the graphene/copper composite powder prepared in step 2 into a ball mill, grind and stir for 45 minutes until the powders are evenly mixed, and then the graphene-reinforced copper-based composite solder is obtained.

The copper powder described in step 1 has a purity of 99.9% to 99.95%, and a particle diameter of 300 mesh.

The metal Sn powder described in step three has a purity of 99.95% and a particle diameter of 300 mesh.

The Raman spectrogram of the graphene/copper composite powder prepared in embodiment one is as shown in Figure 1, and 1 is D peak; 2 is G peak; 3 is 2D peak; Good material quality;

The optical microscope observation of graphene can only _transfer graphene to SiO ₂ /Si substrate. The optical microscope image of graphene transferred to SiO ₂ /Si substrate is as described in 2. As shown in Figure 3, 1 is the D peak; 2 is the G peak; 3 is the 2D peak; it can be seen that there is no obvious quality defect after the transfer, the size is uniform, and there is no before the transfer. Convenient transfer is also one of the advantages of the PECVD method .

The graphene in the prepared graphene-reinforced copper-based composite solder has high quality and uniform dispersion, which can effectively improve the performance of the copper-based composite solder.

Embodiment two:

A kind of low-temperature and high-efficiency method for preparing graphene-reinforced copper-based composite solder described in this embodiment is specifically carried out according to the following steps:

1. Put the copper powder in the plasma-enhanced chemical vapor deposition vacuum device, evacuate until the pressure is below 5Pa, feed hydrogen gas with a gas flow rate of 20 sccm, adjust the vacuuming speed to control the pressure in the plasma-enhanced chemical vapor deposition vacuum device 200Pa, and the temperature is raised to 500°C within 40min under the pressure of 200Pa and hydrogen atmosphere, and the temperature is kept at 500°C for 30min;

2. Introduce argon and CH ₄ , adjust the flow rate of hydrogen gas to 40 sccm, the flow rate of argon gas to 80 sccm and the gas flow rate of CH ₄ to 2 sccm, and adjust the vacuum speed to control the pressure in the plasma-enhanced chemical vapor deposition vacuum device to 1000Pa , and then deposited under the conditions of RF power frequency of 13.56MHz, RF power of 200W, pressure of 1000Pa, and temperature of 500°C. The deposition time was 90s. After the deposition, the RF power and heating power were turned off, and the introduction of carbon Source gas, continue to pass into argon and hydrogen with the hydrogen gas flow rate of 40 sccm and the argon gas flow rate of 80 sccm, and adjust the vacuum speed to control the pressure in the plasma-enhanced chemical vapor deposition vacuum device to 200Pa, when the pressure is 200Pa and hydrogen and cooling from a temperature of 500°C to room temperature under an argon atmosphere to obtain a graphene/copper composite powder;

3. Put the metal Sn powder and the graphene/copper composite powder prepared in step 2 into a ball mill, grind and stir for 45 minutes until the powders are evenly mixed, and then the graphene-reinforced copper-based composite solder is obtained.

The copper powder described in step 1 has a purity of 99.9% to 99.95%, and a particle diameter of 300 mesh.

The metal Sn powder described in step three has a purity of 99.95% and a particle diameter of 300 mesh.

The graphene in the graphene/copper composite powder prepared in this embodiment is uniform in size, has few defects, and most of the graphene is 1-3 layers.

The graphene in the prepared graphene-reinforced copper-based composite solder has high quality and uniform dispersion, which can effectively improve the performance of the copper-based composite solder.

Embodiment three:

A kind of low-temperature and high-efficiency method for preparing graphene-reinforced copper-based composite solder described in this embodiment is specifically carried out according to the following steps:

1. Put the copper powder in the plasma-enhanced chemical vapor deposition vacuum device, evacuate until the pressure is below 5Pa, feed hydrogen gas with a gas flow rate of 20 sccm, adjust the vacuuming speed to control the pressure in the plasma-enhanced chemical vapor deposition vacuum device 200Pa, and the temperature is raised to 600°C within 40min under the pressure of 200Pa and hydrogen atmosphere, and the temperature is kept at 600°C for 30min;

2. Introduce argon and CH ₄ , adjust the flow rate of hydrogen gas to 40 sccm, the flow rate of argon gas to 80 sccm and the gas flow rate of CH ₄ to 8 sccm, and adjust the vacuuming speed to control the pressure in the plasma-enhanced chemical vapor deposition vacuum device to 1000Pa , and then deposited under the conditions of RF power frequency of 13.56MHz, RF power of 200W, pressure of 1000Pa and temperature of 600°C, the deposition time was 10s. After the deposition, the RF power and heating power were turned off, and the carbon Source gas, continue to pass into argon and hydrogen with the hydrogen gas flow rate of 40 sccm and the argon gas flow rate of 80 sccm, and adjust the vacuum speed to control the pressure in the plasma-enhanced chemical vapor deposition vacuum device to 200Pa, when the pressure is 200Pa and hydrogen and cooling from a temperature of 600°C to room temperature under an argon atmosphere to obtain a graphene/copper composite powder;

3. Put the metal Sn powder and the graphene/copper composite powder prepared in step 2 into a ball mill, grind and stir for 45 minutes until the powders are evenly mixed, and then the graphene-reinforced copper-based composite solder is obtained.

The copper powder described in step 1 has a purity of 99.9% to 99.95%, and a particle diameter of 300 mesh.

The metal Sn powder described in step three has a purity of 99.95% and a particle diameter of 300 mesh.

The graphene in the graphene/copper composite powder prepared in this embodiment is uniform in size, has few defects, and most of the graphene is 1-3 layers.

The graphene in the prepared graphene-reinforced copper-based composite solder has high quality and uniform dispersion, which can effectively improve the performance of the copper-based composite solder.

Embodiment four:

A kind of low-temperature and high-efficiency method for preparing graphene-reinforced copper-based composite solder described in this embodiment is specifically carried out according to the following steps:

1. Put the copper powder in the plasma-enhanced chemical vapor deposition vacuum device, evacuate until the pressure is below 5Pa, feed hydrogen gas with a gas flow rate of 20 sccm, adjust the vacuuming speed to control the pressure in the plasma-enhanced chemical vapor deposition vacuum device 200Pa, and the temperature is raised to 600°C within 40min under the pressure of 200Pa and hydrogen atmosphere, and the temperature is kept at 600°C for 30min;

2. Introduce argon and CH ₄ , adjust the flow rate of hydrogen gas to 40 sccm, the flow rate of argon gas to 80 sccm and the gas flow rate of CH ₄ to 8 sccm, and adjust the vacuuming speed to control the pressure in the plasma-enhanced chemical vapor deposition vacuum device to 1000Pa , and then deposited under the condition of RF power frequency of 13.56MHz, RF power of 200W, pressure of 1000Pa and temperature of 600°C, the deposition time was 30s. After the deposition, the RF power and heating power were turned off, and the carbon Source gas, continue to pass into argon and hydrogen with the hydrogen gas flow rate of 40 sccm and the argon gas flow rate of 80 sccm, and adjust the vacuum speed to control the pressure in the plasma-enhanced chemical vapor deposition vacuum device to 200Pa, when the pressure is 200Pa and hydrogen and cooling from a temperature of 600°C to room temperature under an argon atmosphere to obtain a graphene/copper composite powder;

3. Put the metal Ag powder and the graphene/copper composite powder prepared in step 2 into a ball mill, grind and stir for 45 minutes until the powders are evenly mixed, and then the graphene-reinforced copper-based composite solder is obtained.

The copper powder described in step 1 has a purity of 99.9% to 99.95%, and a particle diameter of 300 mesh.

The metal Ag powder described in step 3 has a purity of 99.95% and a particle diameter of 300 mesh.

The graphene in the graphene/copper composite powder prepared in this example is uniform in size, has few defects, and most of the graphene has 3-5 layers.

The graphene in the prepared graphene-reinforced copper-based composite solder has high quality and uniform dispersion, which can effectively improve the performance of the copper-based composite solder.

Embodiment five:

A kind of low-temperature and high-efficiency method for preparing graphene-reinforced copper-based composite solder described in this embodiment is specifically carried out according to the following steps:

1. Put the copper powder in the plasma-enhanced chemical vapor deposition vacuum device, evacuate until the pressure is below 5Pa, feed hydrogen gas with a gas flow rate of 20 sccm, adjust the vacuuming speed to control the pressure in the plasma-enhanced chemical vapor deposition vacuum device 200Pa, and the temperature is raised to 700°C within 40min under the pressure of 200Pa and hydrogen atmosphere, and the temperature is kept at 700°C for 30min;

2. Introduce argon and CH ₄ , adjust the flow rate of hydrogen gas to 40 sccm, the flow rate of argon gas to 80 sccm and the gas flow rate of CH ₄ to 8 sccm, and adjust the vacuuming speed to control the pressure in the plasma-enhanced chemical vapor deposition vacuum device to 1000Pa , and then deposited under the conditions of RF power frequency of 13.56MHz, RF power of 200W, pressure of 1000Pa and temperature of 700°C. The deposition time was 30s. After the deposition, the RF power and heating power were turned off, and the carbon Source gas, continue to pass into argon and hydrogen with the hydrogen gas flow rate of 40 sccm and the argon gas flow rate of 80 sccm, and adjust the vacuum speed to control the pressure in the plasma-enhanced chemical vapor deposition vacuum device to 200Pa, when the pressure is 200Pa and hydrogen and cooling from a temperature of 700°C to room temperature under an argon atmosphere to obtain a graphene/copper composite powder;

3. Put the metal Ag powder and the graphene/copper composite powder prepared in step 2 into a ball mill, grind and stir for 45 minutes until the powders are evenly mixed, and then the graphene-reinforced copper-based composite solder is obtained.

The copper powder described in step 1 has a purity of 99.9% to 99.95%, and a particle diameter of 300 mesh.

The metal Ag powder described in step 3 has a purity of 99.95% and a particle diameter of 300 mesh.

The graphene in the graphene/copper composite powder prepared in this embodiment is uniform in size, has few defects, and most of the graphene has more than 3 layers.

The graphene in the prepared graphene-reinforced copper-based composite solder has high quality and uniform dispersion, which can effectively improve the performance of the copper-based composite solder.

Claims (6)

1. efficient cryogenic is prepared Graphene and strengthens a method for copper base composite soldering, it is characterized in that a kind of efficient cryogenic prepares the method that Graphene strengthens copper base composite soldering and carry out according to following steps:

One, copper powder is placed in to plasma enhanced chemical vapor deposition vacuum plant, being evacuated to pressure is below 5Pa, pass into hydrogen take gas flow as 18sccm～22sccm, regulating vacuum pumping rate is 190Pa～210Pa by pressure control in plasma enhanced chemical vapor deposition vacuum plant, and be in 40min, temperature to be heated up to most 500 ℃～700 ℃ under 190Pa～210Pa and hydrogen atmosphere at pressure, and be to be incubated 25min～35min at 500 ℃～700 ℃ in temperature;

Two, pass into argon gas and carbon-source gas, regulating the gas flow of hydrogen is 40sccm, argon gas flow is 80sccm, the gas flow of carbon-source gas is 1sccm～8sccm, and to regulate vacuum pumping rate be 800Pa～1000Pa by pressure control in plasma enhanced chemical vapor deposition vacuum plant, then be 13.56MHz in depositing system radio-frequency power supply frequency, radio-frequency power is 190W～210W, pressure is that 800Pa～1000Pa and temperature are to deposit under 500 ℃～700 ℃ conditions, sedimentation time is 10s～300s, after deposition finishes, close radio-frequency power supply and heating power supply, stop passing into carbon-source gas, continue take the gas flow of hydrogen as 40sccm, argon gas flow is that 80sccm passes into hydrogen and argon gas, and to regulate vacuum pumping rate be 150Pa～200Pa by pressure control in plasma enhanced chemical vapor deposition vacuum plant, be under 150Pa～200Pa and hydrogen and argon gas atmosphere, to be 500 ℃～700 ℃ from temperature to be cooled to room temperature at pressure, obtain Graphene/copper composite powder,

Three, Graphene/copper composite powder of being prepared by metal dust or alloy powder and step 2 is put into ball mill, grinds and is stirred to powder and mix, and obtains Graphene and strengthens copper base composite soldering.

2. a kind of efficient cryogenic according to claim 1 is prepared the method for Graphene enhancing copper base composite soldering, it is characterized in that the copper powder purity described in step 1 is 99%～99.99%, and particle diameter is 100nm～100 μ m.

3. a kind of efficient cryogenic according to claim 1 is prepared the method for Graphene enhancing copper base composite soldering, it is characterized in that the carbon-source gas described in step 2 is methane.

4. a kind of efficient cryogenic according to claim 1 is prepared the method for Graphene enhancing copper base composite soldering, it is characterized in that the metal dust purity described in step 3 is 99%～99.99%, and particle diameter is 100nm～100 μ m; Described alloy powder purity is 99%～99.99%, and particle diameter is 100nm～100 μ m.

5. a kind of efficient cryogenic according to claim 1 is prepared the method for Graphene enhancing copper base composite soldering, it is characterized in that the metal dust described in step 3 is Sn powder, Ag powder, P powder or Mn powder.

6. a kind of efficient cryogenic according to claim 1 is prepared the method for Graphene enhancing copper base composite soldering, it is characterized in that the alloy powder described in step 3 is Sn-Ag powder or Ag-Zn powder.

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