CN103817466A - Method for efficiently preparing graphene-reinforcing copper-based composite brazing filler metal at low temperature - Google Patents
Method for efficiently preparing graphene-reinforcing copper-based composite brazing filler metal at low temperature Download PDFInfo
- Publication number
- CN103817466A CN103817466A CN201410066482.0A CN201410066482A CN103817466A CN 103817466 A CN103817466 A CN 103817466A CN 201410066482 A CN201410066482 A CN 201410066482A CN 103817466 A CN103817466 A CN 103817466A
- Authority
- CN
- China
- Prior art keywords
- graphene
- powder
- copper
- temperature
- hydrogen
- 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.)
- Granted
Links
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 239000002131 composite material Substances 0.000 title claims abstract description 80
- 239000010949 copper Substances 0.000 title claims abstract description 78
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 76
- 238000000034 method Methods 0.000 title claims abstract description 46
- 239000002184 metal Substances 0.000 title claims abstract description 26
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 26
- 238000005219 brazing Methods 0.000 title abstract 6
- 239000000945 filler Substances 0.000 title abstract 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 116
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 101
- 239000007789 gas Substances 0.000 claims abstract description 89
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 82
- 239000000843 powder Substances 0.000 claims abstract description 65
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 49
- 229910052786 argon Inorganic materials 0.000 claims abstract description 41
- 239000001257 hydrogen Substances 0.000 claims abstract description 39
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 39
- 238000000151 deposition Methods 0.000 claims abstract description 18
- 230000008021 deposition Effects 0.000 claims abstract description 10
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 8
- 239000000956 alloy Substances 0.000 claims abstract description 8
- 238000005476 soldering Methods 0.000 claims description 51
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 claims description 32
- 238000005086 pumping Methods 0.000 claims description 24
- 230000002708 enhancing effect Effects 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 17
- 230000001105 regulatory effect Effects 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 238000004062 sedimentation Methods 0.000 claims description 8
- 239000000428 dust Substances 0.000 claims description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 229910020836 Sn-Ag Inorganic materials 0.000 claims description 2
- 229910020988 Sn—Ag Inorganic materials 0.000 claims description 2
- BSWGGJHLVUUXTL-UHFFFAOYSA-N silver zinc Chemical compound [Zn].[Ag] BSWGGJHLVUUXTL-UHFFFAOYSA-N 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 14
- 229910052799 carbon Inorganic materials 0.000 abstract description 12
- 230000007547 defect Effects 0.000 abstract description 9
- 238000005229 chemical vapour deposition Methods 0.000 abstract description 6
- 238000001816 cooling Methods 0.000 abstract 1
- 241000196324 Embryophyta Species 0.000 description 28
- 229910000679 solder Inorganic materials 0.000 description 11
- 239000000463 material Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000001069 Raman spectroscopy Methods 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000003466 welding Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 239000003863 metallic catalyst Substances 0.000 description 3
- 238000000197 pyrolysis Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 241000931526 Acer campestre Species 0.000 description 1
- 229910017944 Ag—Cu Inorganic materials 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
- B23K35/0222—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in soldering, brazing
- B23K35/0244—Powders, particles or spheres; Preforms made therefrom
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/24—Selection of soldering or welding materials proper
- B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
- B23K35/302—Cu as the principal constituent
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/26—Deposition of carbon only
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/4417—Methods specially adapted for coating powder
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to a method for preparing graphene-reinforcing copper-based composite brazing filler metal, in particular to a method for efficiently preparing the graphene-reinforcing copper-based composite brazing filler metal at a low temperature. The method aims to solve the problems that during preparation of the graphene-reinforcing copper-based composite brazing filler metal through a traditional method, the dispersibility of graphene is poor, the number of surface defects is large, the preparation temperature is high, and efficiency is low. The method comprises the steps that firstly, copper powder is placed in a plasma-reinforcing chemical vapor deposition vacuum device, hydrogen is fed into the vacuum device, and the temperature is maintained at a high temperature; secondly, argon and carbon source gas are fed into the vacuum device for deposition, and after deposition is over, feeding of the carbon source gas is stopped; finally, cooling is conducted until the temperature reaches the room temperature, so that grapheme/copper composite powder is obtained, next, metal powder or alloy power is evenly mixed with the grapheme/copper composite powder, and then the graphene-reinforcing copper-based composite brazing filler metal is obtained. The method is used for efficiently preparing the graphene-reinforcing copper-based composite brazing filler metal at a low temperature.
Description
Technical field
The present invention relates to prepare the method for Graphene enhancing copper base composite soldering.
Background technology
Soldering is the one of three large welding methods (melting welding, pressure welding, soldering), mainly to adopt to make solder than the low-melting metal material of mother metal, weldment and solder are heated to above to solder fusing point, lower than mother metal fusion temperature, utilize liquid solder to soak mother metal, fill play movement and realize with the counterdiffusion of mother metal phase the method that is connected weldment.In all extensive application of numerous areas such as machinery, motor, instrument, electronic technology.The performance indications such as the intensity of soldered fitting, hardness, heat resistance, corrosion resistance all have direct relation with solder, add the reinforcements such as particle, fiber, synusia and can effectively improve soldered fitting performance in solder.Along with scientific and technical development, nano material (as nano particle, nano wire, nanometer sheet etc.) strengthens solder as reinforcement and has become the study hotspot of welding field.
Graphene is a kind of new material of the individual layer laminated structure being made up of carbon atom.Due to the particularity of graphene-structured, compared with other materials, Graphene has outstanding electric property, thermal property and mechanical performance.Show huge application prospect in all many-sides such as electronic device, composite and electrochemical energy storage materials.There are some researches prove, in Sn-Ag-Cu solder, add graphene film prepared by 0.1% oxide-reduction method can significantly improve wettability and the mechanical property of solder.As can be seen here, Graphene has broad application prospects at aspects such as strengthening solder, raising solder performances.
At present, the preparation method that Graphene is conventional has three kinds of methods such as mechanical stripping method, redox graphite method, chemical vapour deposition technique.The Graphene quality that mechanical stripping method is prepared is high, but complex process, and productive rate is low, is difficult to practical application.Although redox graphite method has the features such as cost is low, output is large, technique is more complicated, and graphene-structured is destroyed seriously, blemish is extremely many, the poor-performings such as electricity and mechanics.Graphene size prepared by chemical vapour deposition technique is large, defect is few, but preparation temperature is higher and the time is long, efficiency is low, is difficult to practical application.
Due to preparation technology's restriction of grapheme material, cause Graphene to strengthen in the preparation method of composite soldering, there are two difficult points: (1) Graphene dispersion problem, tradition mechanical ball tribulation is to realize dispersed in composite soldering of Graphene, often realize the dispersed of Graphene by chemical modification method, technique is more complicated.(2) graphene-structured defect problem, requires and addition demand according to actual preparation technology, the Graphene that often adopts redox graphite method to obtain, and in composite soldering, graphene-structured defect is more for this reason.Due under higher temperature, the Graphene of structural failure very easily with composite soldering in active element react to each other, limited the extensive use of grapheme material in composite soldering.
Summary of the invention
The present invention will solve conventional method and prepare that the Graphene bad dispersibility, the blemish that when Graphene strengthens copper base composite soldering, exist are many, preparation temperature is high and inefficient problem, and provides a kind of efficient cryogenic to prepare the method for Graphene enhancing copper base composite soldering.
Efficient cryogenic is prepared a method for Graphene enhancing copper base composite soldering, specifically carries 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.
The invention has the beneficial effects as follows: 1, the present invention utilizes plasma reinforced chemical vapour deposition method (PECVD), can be by carbon source (CH by action of radio
4) resolve into very fast and there is mutually highly active carbon-based group, just can the short time through the catalytic reaction of metallic catalyst grow Graphene in metal surface.Can realize low temperature and effectively go out Graphene in the superficial growth of Cu powder.
2, the present invention utilizes plasma to strengthen action of radio, has not only avoided high temperature pyrolysis carbon-source gas, and has increased substantially carbon-source gas (CH
4) decomposition efficiency, pass into a small amount of carbon-source gas (CH
4) also can produce a large amount of activated carbon groups, thus effectively reduce preparation temperature, improved preparation efficiency.
3, method of the present invention is simple, and efficient, low cost, is convenient to suitability for industrialized production, and the quality that the Graphene of preparing strengthens Graphene in copper base composite soldering is high and dispersed, can effectively improve the performance of copper base composite soldering.
The present invention prepares the method for Graphene enhancing copper base composite soldering for a kind of efficient cryogenic.
Accompanying drawing explanation
Fig. 1 is the Raman spectrogram of Graphene/copper composite powder in embodiment mono-; 1 is D peak; 2 is G peak; 3 is 2D peak;
Fig. 2 is that in embodiment mono-, Graphene is transferred to SiO
2the light microscope figure of/Si substrate;
Fig. 3 is that in embodiment mono-, Graphene is transferred to SiO
2the Raman spectrogram of/Si substrate; 1 is D peak; 2 is G peak; 3 is 2D peak.
The specific embodiment
Technical solution of the present invention is not limited to the following cited specific embodiment, also comprises any combination between each specific embodiment.
The specific embodiment one: a kind of efficient cryogenic described in present embodiment is prepared the method for Graphene enhancing copper base composite soldering, specifically carries 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.
Involved efficient cryogenic in present embodiment is prepared the basic principle of Graphene enhancing copper base composite soldering: utilize plasma reinforced chemical vapour deposition method (PECVD), and can be by carbon source (CH by action of radio
4) resolve into very fast carbon-based group, these carbon-based groups have very high activity, just can the short time through the catalytic reaction of metallic catalyst grow Graphene in metal surface.Due to action of radio, not only avoid high temperature pyrolysis carbon-source gas in addition, and increased substantially carbon-source gas (CH
4) decomposition efficiency, pass into a small amount of carbon-source gas (CH
4) also can produce a large amount of activated carbon groups, thus effectively reduce preparation temperature, improved preparation efficiency.The selected copper of the present invention is as matrix, and because the solubility of carbon atom in copper is relatively low, therefore can adsorb the mode growing graphene from restriction by carbon atom, not only quality is high for the Graphene that this kind of mode forms, and good dispersion.The Graphene that should prepare in this way strengthens copper powders and makes copper base composite soldering, can make composite soldering obtain a series of outstanding character.
The beneficial effect of present embodiment is: 1, present embodiment is utilized plasma reinforced chemical vapour deposition method (PECVD), can be by carbon source (CH by action of radio
4) resolve into very fast and there is mutually highly active carbon-based group, just can the short time through the catalytic reaction of metallic catalyst grow Graphene in metal surface.Can realize low temperature and effectively go out Graphene in the superficial growth of Cu powder.
2, present embodiment utilizes plasma to strengthen action of radio, has not only avoided high temperature pyrolysis carbon-source gas, and has increased substantially carbon-source gas (CH
4) decomposition efficiency, pass into a small amount of carbon-source gas (CH
4) also can produce a large amount of activated carbon groups, thus effectively reduce preparation temperature, improved preparation efficiency.
3, the method for present embodiment is simple, and efficient, low cost, is convenient to suitability for industrialized production, and the quality that the Graphene of preparing strengthens Graphene in copper base composite soldering is high and dispersed, can effectively improve the performance of copper base composite soldering.
The specific embodiment two: present embodiment is different from the specific embodiment one: the copper powder purity described in step 1 is 99%～99.99%, particle diameter is 100nm～100 μ m.Other is identical with the specific embodiment one.
The specific embodiment three: present embodiment is different from one of specific embodiment one or two: the carbon-source gas described in step 2 is methane.Other is identical with the specific embodiment one or two.
The specific embodiment four: present embodiment is different from one of specific embodiment one to three: the metal dust purity described in step 3 is 99%～99.99%, particle diameter is 100nm～100 μ m; Described alloy powder purity is 99%～99.99%, and particle diameter is 100nm～100 μ m.Other is identical with the specific embodiment one to three.
The specific embodiment five: present embodiment is different from one of specific embodiment one to four: the metal dust described in step 3 is Sn powder, Ag powder, P powder or Mn powder.Other is identical with the specific embodiment one to four.
The specific embodiment six: present embodiment is different from one of specific embodiment one to five: the alloy powder described in step 3 is Sn-Ag powder or Ag-Zn powder.Other is identical with the specific embodiment one to five.
Adopt following examples to verify beneficial effect of the present invention:
Embodiment mono-:
A kind of efficient cryogenic described in the present embodiment is prepared the method for Graphene enhancing copper base composite soldering, specifically carries 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 20sccm, regulating vacuum pumping rate is 200Pa by pressure control in plasma enhanced chemical vapor deposition vacuum plant, and be in 40min, temperature to be heated up to most 600 ℃ under 200Pa and hydrogen atmosphere at pressure, and be to be incubated 30min at 600 ℃ in temperature;
Two, pass into argon gas and CH
4, regulating hydrogen gas flow is that 40sccm, argon gas flow are 80sccm and CH
4gas flow is 2sccm, and to regulate vacuum pumping rate be 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 200W, pressure is that 1000Pa and temperature are to deposit under 600 ℃ of conditions, sedimentation time is 60s, after deposition finishes, close radio-frequency power supply and heating power supply, stop passing into carbon-source gas, continue take hydrogen gas flow as 40sccm and argon gas flow passes into argon gas and hydrogen as 80sccm, and to regulate vacuum pumping rate be 200Pa by pressure control in plasma enhanced chemical vapor deposition vacuum plant, be under 200Pa and hydrogen and argon gas atmosphere, to be 600 ℃ 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 Sn powder and step 2 is put into ball mill, grinds and stirs 45min and mix to powder, obtains Graphene and strengthens copper base composite soldering.
Copper powder purity described in step 1 is 99.9%～99.95%, and particle diameter is 300 orders.
Metal Sn powder purity described in step 3 is 99.95%, and particle diameter is 300 orders.
As shown in Figure 1,1 is D peak to the Raman spectrogram of Graphene/copper composite powder of preparing in embodiment mono-; 2 is G peak; 3 is 2D peak; Optical maser wavelength is 488nm; The quality of materials that explanation obtains is as seen from the figure good;
Light microscope observation for Graphene can only be transferred to SiO by Graphene
2on/Si matrix, Graphene is transferred to SiO
2the light microscope figure of/Si substrate is as described in 2, and Graphene is transferred to SiO
2as described in Figure 3,1 is D peak to the Raman spectrogram of/Si substrate; 2 is G peak; 3 is 2D peak; After known transfer, there is no obvious mass defect, size homogeneous, does not have before shifting yet, and convenient transfer is also one of advantage of PECVD method.
The quality that the Graphene of preparing strengthens Graphene in copper base composite soldering is high and dispersed, can effectively improve the performance of copper base composite soldering.
Embodiment bis-:
A kind of efficient cryogenic described in the present embodiment is prepared the method for Graphene enhancing copper base composite soldering, specifically carries 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 20sccm, regulating vacuum pumping rate is 200Pa by pressure control in plasma enhanced chemical vapor deposition vacuum plant, and be in 40min, temperature to be heated up to most 500 ℃ under 200Pa and hydrogen atmosphere at pressure, and be to be incubated 30min at 500 ℃ in temperature;
Two, pass into argon gas and CH
4, regulating hydrogen gas flow is that 40sccm, argon gas flow are 80sccm and CH
4gas flow is 2sccm, and to regulate vacuum pumping rate be 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 200W, pressure is that 1000Pa and temperature are to deposit under 500 ℃ of conditions, sedimentation time is 90s, after deposition finishes, close radio-frequency power supply and heating power supply, stop passing into carbon-source gas, continue take hydrogen gas flow as 40sccm and argon gas flow passes into argon gas and hydrogen as 80sccm, and to regulate vacuum pumping rate be 200Pa by pressure control in plasma enhanced chemical vapor deposition vacuum plant, be under 200Pa and hydrogen and argon gas atmosphere, to be 500 ℃ 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 Sn powder and step 2 is put into ball mill, grinds and stirs 45min and mix to powder, obtains Graphene and strengthens copper base composite soldering.
Copper powder purity described in step 1 is 99.9%～99.95%, and particle diameter is 300 orders.
Metal Sn powder purity described in step 3 is 99.95%, and particle diameter is 300 orders.
Graphene size homogeneous in Graphene/copper composite powder that the present embodiment is prepared, defect is little, and Graphene major part is 1-3 layer.
The quality that the Graphene of preparing strengthens Graphene in copper base composite soldering is high and dispersed, can effectively improve the performance of copper base composite soldering.
Embodiment tri-:
A kind of efficient cryogenic described in the present embodiment is prepared the method for Graphene enhancing copper base composite soldering, specifically carries 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 20sccm, regulating vacuum pumping rate is 200Pa by pressure control in plasma enhanced chemical vapor deposition vacuum plant, and be in 40min, temperature to be heated up to most 600 ℃ under 200Pa and hydrogen atmosphere at pressure, and be to be incubated 30min at 600 ℃ in temperature;
Two, pass into argon gas and CH
4, regulating hydrogen gas flow is that 40sccm, argon gas flow are 80sccm and CH
4gas flow is 8sccm, and to regulate vacuum pumping rate be 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 200W, pressure is that 1000Pa and temperature are to deposit under 600 ℃ of conditions, sedimentation time is 10s, after deposition finishes, close radio-frequency power supply and heating power supply, stop passing into carbon-source gas, continue take hydrogen gas flow as 40sccm and argon gas flow passes into argon gas and hydrogen as 80sccm, and to regulate vacuum pumping rate be 200Pa by pressure control in plasma enhanced chemical vapor deposition vacuum plant, be under 200Pa and hydrogen and argon gas atmosphere, to be 600 ℃ 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 Sn powder and step 2 is put into ball mill, grinds and stirs 45min and mix to powder, obtains Graphene and strengthens copper base composite soldering.
Copper powder purity described in step 1 is 99.9%～99.95%, and particle diameter is 300 orders.
Metal Sn powder purity described in step 3 is 99.95%, and particle diameter is 300 orders.
Graphene size homogeneous in Graphene/copper composite powder that the present embodiment is prepared, defect is little, and Graphene major part is 1-3 layer.
The quality that the Graphene of preparing strengthens Graphene in copper base composite soldering is high and dispersed, can effectively improve the performance of copper base composite soldering.
Embodiment tetra-:
A kind of efficient cryogenic described in the present embodiment is prepared the method for Graphene enhancing copper base composite soldering, specifically carries 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 20sccm, regulating vacuum pumping rate is 200Pa by pressure control in plasma enhanced chemical vapor deposition vacuum plant, and be in 40min, temperature to be heated up to most 600 ℃ under 200Pa and hydrogen atmosphere at pressure, and be to be incubated 30min at 600 ℃ in temperature;
Two, pass into argon gas and CH
4, regulating hydrogen gas flow is that 40sccm, argon gas flow are 80sccm and CH
4gas flow is 8sccm, and to regulate vacuum pumping rate be 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 200W, pressure is that 1000Pa and temperature are to deposit under 600 ℃ of conditions, sedimentation time is 30s, after deposition finishes, close radio-frequency power supply and heating power supply, stop passing into carbon-source gas, continue take hydrogen gas flow as 40sccm and argon gas flow passes into argon gas and hydrogen as 80sccm, and to regulate vacuum pumping rate be 200Pa by pressure control in plasma enhanced chemical vapor deposition vacuum plant, be under 200Pa and hydrogen and argon gas atmosphere, to be 600 ℃ 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 A g powder and step 2 is put into ball mill, grinds and stirs 45min and mix to powder, obtains Graphene and strengthens copper base composite soldering.
Copper powder purity described in step 1 is 99.9%～99.95%, and particle diameter is 300 orders.
Metal A g powder purity described in step 3 is 99.95%, and particle diameter is 300 orders.
Graphene size homogeneous in Graphene/copper composite powder of preparing in the present embodiment, defect is less, and Graphene major part is 3-5 layer.
The quality that the Graphene of preparing strengthens Graphene in copper base composite soldering is high and dispersed, can effectively improve the performance of copper base composite soldering.
Embodiment five:
A kind of efficient cryogenic described in the present embodiment is prepared the method for Graphene enhancing copper base composite soldering, specifically carries 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 20sccm, regulating vacuum pumping rate is 200Pa by pressure control in plasma enhanced chemical vapor deposition vacuum plant, and be in 40min, temperature to be heated up to most 700 ℃ under 200Pa and hydrogen atmosphere at pressure, and be to be incubated 30min at 700 ℃ in temperature;
Two, pass into argon gas and CH
4, regulating hydrogen gas flow is that 40sccm, argon gas flow are 80sccm and CH
4gas flow is 8sccm, and to regulate vacuum pumping rate be 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 200W, pressure is that 1000Pa and temperature are to deposit under 700 ℃ of conditions, sedimentation time is 30s, after deposition finishes, close radio-frequency power supply and heating power supply, stop passing into carbon-source gas, continue take hydrogen gas flow as 40sccm and argon gas flow passes into argon gas and hydrogen as 80sccm, and to regulate vacuum pumping rate be 200Pa by pressure control in plasma enhanced chemical vapor deposition vacuum plant, be under 200Pa and hydrogen and argon gas atmosphere, to be 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 A g powder and step 2 is put into ball mill, grinds and stirs 45min and mix to powder, obtains Graphene and strengthens copper base composite soldering.
Copper powder purity described in step 1 is 99.9%～99.95%, and particle diameter is 300 orders.
Metal A g powder purity described in step 3 is 99.95%, and particle diameter is 300 orders.
Graphene size homogeneous in Graphene/copper composite powder that the present embodiment is prepared, defect is few, and Graphene major part is more than 3 layers.
The quality that the Graphene of preparing strengthens Graphene in copper base composite soldering is high and dispersed, can effectively improve the performance of copper base composite soldering.
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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410066482.0A CN103817466B (en) | 2014-02-26 | 2014-02-26 | A kind of efficient cryogenic prepares the method that Graphene strengthens copper base composite soldering |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410066482.0A CN103817466B (en) | 2014-02-26 | 2014-02-26 | A kind of efficient cryogenic prepares the method that Graphene strengthens copper base composite soldering |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103817466A true CN103817466A (en) | 2014-05-28 |
| CN103817466B CN103817466B (en) | 2015-09-09 |
Family
ID=50752906
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410066482.0A Expired - Fee Related CN103817466B (en) | 2014-02-26 | 2014-02-26 | A kind of efficient cryogenic prepares the method that Graphene strengthens copper base composite soldering |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103817466B (en) |
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104400247A (en) * | 2014-09-29 | 2015-03-11 | 哈尔滨工业大学 | Preparation method of high-thermal conductivity graphene-Sn-Ag composite brazing filler metal |
| CN104625283A (en) * | 2014-12-26 | 2015-05-20 | 哈尔滨工业大学 | Auxiliary brazing method for grapheme composite middle layer of three-dimensional structure |
| CN104842089A (en) * | 2015-06-02 | 2015-08-19 | 哈尔滨工业大学 | Composite high-strength lead-free brazing filler metal for electronic packaging and preparation method thereof |
| CN105382440A (en) * | 2015-12-23 | 2016-03-09 | 哈尔滨工业大学 | Graphene-enhanced Al-based composite solder auxiliary soldering method |
| CN105772980A (en) * | 2016-05-19 | 2016-07-20 | 厦门圣之岛金属科技有限公司 | Graphene-tin-based lead-free solder and preparation method thereof |
| CN106001979A (en) * | 2016-05-19 | 2016-10-12 | 厦门圣之岛金属科技有限公司 | Grapheme, zinc oxide crystal whisker and tin base composite material and preparation method thereof |
| CN106365154A (en) * | 2016-08-31 | 2017-02-01 | 孙旭阳 | Preparation method of graphene grown by adopting non-high temperature liquid phase method |
| CN107201485A (en) * | 2017-05-18 | 2017-09-26 | 成都新柯力化工科技有限公司 | It is a kind of to be used to strengthen the graphene masterbatch and preparation method and application method of copper-based material |
| CN108069416A (en) * | 2016-11-14 | 2018-05-25 | 北京大学 | Ultra-clean graphene and preparation method thereof |
| CN108296586A (en) * | 2018-04-25 | 2018-07-20 | 哈尔滨工业大学 | A kind of SiO2The method for welding of-BN composite ceramics and Invar alloys |
| CN108620767A (en) * | 2018-05-08 | 2018-10-09 | 哈尔滨工业大学 | A kind of composite soldering and preparation method thereof for being brazed quartzy short fiber reinforced silicon dioxide composite material and Invar alloys |
| CN108660398A (en) * | 2018-05-24 | 2018-10-16 | 兰州交通大学 | A kind of preparation method of graphene-silicon carbide fibre reinforced metal composite material |
| CN110880547A (en) * | 2018-09-05 | 2020-03-13 | 中科院微电子研究所昆山分所 | Thermoelectric composite material and preparation method thereof |
| CN111112881A (en) * | 2020-01-03 | 2020-05-08 | 苏州优诺电子材料科技有限公司 | Graphene modified low-temperature solder and preparation method thereof |
| CN112427759A (en) * | 2020-10-27 | 2021-03-02 | 哈尔滨工业大学 | ZrC-SiC ceramic and TC4 titanium alloy brazing method |
| CN113430414A (en) * | 2021-06-25 | 2021-09-24 | 哈尔滨工业大学 | Method for improving high-temperature oxidation resistance of AgCu alloy by using three-dimensional network reinforcing phase |
| CN114850732A (en) * | 2022-06-21 | 2022-08-05 | 齐齐哈尔大学 | Preparation method of graphene-reinforced tin-based composite solder |
| CN115846934A (en) * | 2022-12-12 | 2023-03-28 | 广东华智芯电子科技有限公司 | Composite solder and preparation method and packaging method thereof |
| CN116021011A (en) * | 2023-01-09 | 2023-04-28 | 哈尔滨工业大学 | Preparation method of graphene-coated copper powder particle reinforced cold spray copper-based composite coating |
| CN116810210A (en) * | 2023-05-26 | 2023-09-29 | 齐齐哈尔大学 | Composite brazing filler metal and preparation method and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102329976A (en) * | 2011-09-06 | 2012-01-25 | 上海交通大学 | Preparation method of graphene reinforced metal-matrix composite |
| CN102385938A (en) * | 2011-11-10 | 2012-03-21 | 电子科技大学 | Metal matrix graphene composite electrical contact material and preparation method thereof |
| CN102383071A (en) * | 2011-11-09 | 2012-03-21 | 哈尔滨工业大学 | Method for preparing carbon nano tube enhanced titanium-base compound material by in-suit reaction |
| CN102628115A (en) * | 2012-04-01 | 2012-08-08 | 昆明理工大学 | Preparation method of carbon nano tube enhanced copper-based composite material |
| CN102925741A (en) * | 2012-11-08 | 2013-02-13 | 镇江中孚复合材料有限公司 | Copper base solid self-lubricating composite material and method for preparing the same |
| CN103183344A (en) * | 2013-04-24 | 2013-07-03 | 哈尔滨工业大学 | Method for low-temperature and efficient preparation of large-size graphene |
| US20130316167A1 (en) * | 2012-05-25 | 2013-11-28 | Empire Technology Developement LLC | Copper substrate for deposition of graphene |
-
2014
- 2014-02-26 CN CN201410066482.0A patent/CN103817466B/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102329976A (en) * | 2011-09-06 | 2012-01-25 | 上海交通大学 | Preparation method of graphene reinforced metal-matrix composite |
| CN102383071A (en) * | 2011-11-09 | 2012-03-21 | 哈尔滨工业大学 | Method for preparing carbon nano tube enhanced titanium-base compound material by in-suit reaction |
| CN102385938A (en) * | 2011-11-10 | 2012-03-21 | 电子科技大学 | Metal matrix graphene composite electrical contact material and preparation method thereof |
| CN102628115A (en) * | 2012-04-01 | 2012-08-08 | 昆明理工大学 | Preparation method of carbon nano tube enhanced copper-based composite material |
| US20130316167A1 (en) * | 2012-05-25 | 2013-11-28 | Empire Technology Developement LLC | Copper substrate for deposition of graphene |
| CN102925741A (en) * | 2012-11-08 | 2013-02-13 | 镇江中孚复合材料有限公司 | Copper base solid self-lubricating composite material and method for preparing the same |
| CN103183344A (en) * | 2013-04-24 | 2013-07-03 | 哈尔滨工业大学 | Method for low-temperature and efficient preparation of large-size graphene |
Non-Patent Citations (1)
| Title |
|---|
| KIM Y,ETAL: "Strenghtening effect if single-atomic-layer graphene in metal-graphene nanolayered composites", 《NATURE COMMUNICATIONS》 * |
Cited By (31)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104400247A (en) * | 2014-09-29 | 2015-03-11 | 哈尔滨工业大学 | Preparation method of high-thermal conductivity graphene-Sn-Ag composite brazing filler metal |
| CN104625283A (en) * | 2014-12-26 | 2015-05-20 | 哈尔滨工业大学 | Auxiliary brazing method for grapheme composite middle layer of three-dimensional structure |
| CN104842089A (en) * | 2015-06-02 | 2015-08-19 | 哈尔滨工业大学 | Composite high-strength lead-free brazing filler metal for electronic packaging and preparation method thereof |
| CN105382440A (en) * | 2015-12-23 | 2016-03-09 | 哈尔滨工业大学 | Graphene-enhanced Al-based composite solder auxiliary soldering method |
| CN105772980A (en) * | 2016-05-19 | 2016-07-20 | 厦门圣之岛金属科技有限公司 | Graphene-tin-based lead-free solder and preparation method thereof |
| CN106001979A (en) * | 2016-05-19 | 2016-10-12 | 厦门圣之岛金属科技有限公司 | Grapheme, zinc oxide crystal whisker and tin base composite material and preparation method thereof |
| CN106001979B (en) * | 2016-05-19 | 2018-01-30 | 厦门圣之岛金属科技有限公司 | A kind of graphene ZnOw Tin Composite Material and preparation method thereof |
| CN106365154A (en) * | 2016-08-31 | 2017-02-01 | 孙旭阳 | Preparation method of graphene grown by adopting non-high temperature liquid phase method |
| CN108069416B (en) * | 2016-11-14 | 2020-01-07 | 北京大学 | Ultra-clean graphene and preparation method thereof |
| CN108069416A (en) * | 2016-11-14 | 2018-05-25 | 北京大学 | Ultra-clean graphene and preparation method thereof |
| CN107201485A (en) * | 2017-05-18 | 2017-09-26 | 成都新柯力化工科技有限公司 | It is a kind of to be used to strengthen the graphene masterbatch and preparation method and application method of copper-based material |
| CN107201485B (en) * | 2017-05-18 | 2018-08-24 | 成都新柯力化工科技有限公司 | A kind of graphene masterbatch and preparation method and application method for enhancing copper-based material |
| CN108296586A (en) * | 2018-04-25 | 2018-07-20 | 哈尔滨工业大学 | A kind of SiO2The method for welding of-BN composite ceramics and Invar alloys |
| CN108620767A (en) * | 2018-05-08 | 2018-10-09 | 哈尔滨工业大学 | A kind of composite soldering and preparation method thereof for being brazed quartzy short fiber reinforced silicon dioxide composite material and Invar alloys |
| CN108620767B (en) * | 2018-05-08 | 2020-05-12 | 哈尔滨工业大学 | Preparation method of composite solder for brazing quartz short fiber reinforced silicon dioxide composite material and Invar alloy |
| CN108660398A (en) * | 2018-05-24 | 2018-10-16 | 兰州交通大学 | A kind of preparation method of graphene-silicon carbide fibre reinforced metal composite material |
| CN110880547A (en) * | 2018-09-05 | 2020-03-13 | 中科院微电子研究所昆山分所 | Thermoelectric composite material and preparation method thereof |
| CN110880547B (en) * | 2018-09-05 | 2023-09-12 | 昆山微电子技术研究院 | Thermoelectric composite material and preparation method thereof |
| CN111112881A (en) * | 2020-01-03 | 2020-05-08 | 苏州优诺电子材料科技有限公司 | Graphene modified low-temperature solder and preparation method thereof |
| CN111112881B (en) * | 2020-01-03 | 2021-06-04 | 苏州优诺电子材料科技有限公司 | Graphene modified low-temperature solder and preparation method thereof |
| CN112427759B (en) * | 2020-10-27 | 2022-08-26 | 哈尔滨工业大学 | ZrC-SiC ceramic and TC4 titanium alloy brazing method |
| CN112427759A (en) * | 2020-10-27 | 2021-03-02 | 哈尔滨工业大学 | ZrC-SiC ceramic and TC4 titanium alloy brazing method |
| CN113430414B (en) * | 2021-06-25 | 2022-03-01 | 哈尔滨工业大学 | Method for improving high-temperature oxidation resistance of AgCu alloy by using three-dimensional network reinforcing phase |
| CN113430414A (en) * | 2021-06-25 | 2021-09-24 | 哈尔滨工业大学 | Method for improving high-temperature oxidation resistance of AgCu alloy by using three-dimensional network reinforcing phase |
| CN114850732A (en) * | 2022-06-21 | 2022-08-05 | 齐齐哈尔大学 | Preparation method of graphene-reinforced tin-based composite solder |
| CN114850732B (en) * | 2022-06-21 | 2024-01-23 | 齐齐哈尔大学 | Preparation method of graphene reinforced tin-based composite solder |
| CN115846934A (en) * | 2022-12-12 | 2023-03-28 | 广东华智芯电子科技有限公司 | Composite solder and preparation method and packaging method thereof |
| CN116021011A (en) * | 2023-01-09 | 2023-04-28 | 哈尔滨工业大学 | Preparation method of graphene-coated copper powder particle reinforced cold spray copper-based composite coating |
| CN116021011B (en) * | 2023-01-09 | 2023-08-29 | 哈尔滨工业大学 | Preparation method of graphene-coated copper powder particle reinforced cold spray copper-based composite coating |
| CN116810210A (en) * | 2023-05-26 | 2023-09-29 | 齐齐哈尔大学 | Composite brazing filler metal and preparation method and application thereof |
| CN116810210B (en) * | 2023-05-26 | 2024-04-09 | 齐齐哈尔大学 | Method for preparing composite solder |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103817466B (en) | 2015-09-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103817466B (en) | A kind of efficient cryogenic prepares the method that Graphene strengthens copper base composite soldering | |
| CN103773985B (en) | A kind of efficient original position prepares the method that Graphene strengthens Cu-base composites | |
| CN102176338B (en) | Graphene/copper nanowire composite electric-conducting material and preparation method thereof | |
| CN102383071B (en) | Method for preparing carbon nano tube enhanced titanium-base compound material by in-suit reaction | |
| CN105441711B (en) | A kind of preparation method of three-dimensional structure CNTs Reinforced Cu-Base Composites | |
| CN102786756A (en) | Three-dimensional continuous graphene network composite material and its preparation method | |
| CN103183344B (en) | A kind of efficient cryogenic prepares the method for big size graphene | |
| CN103789744B (en) | A kind of in-situ growing carbon nano tube strengthens the preparation method of silver-based electric contact material | |
| Sun et al. | Enhancement of Interfacial Charge Transportation Through Construction of 2D–2D p–n Heterojunctions in Hierarchical 3D CNFs/MoS2/ZnIn2S4 Composites to Enable High‐Efficiency Photocatalytic Hydrogen Evolution | |
| CN105397344B (en) | Growth in situ graphene and CNT strengthen the method for Ti base solders | |
| CN104192826B (en) | A kind of method that improves nano-carbon material electric conductivity | |
| CN106346100B (en) | A kind of method of carbon nanotube enhancing three-dimensional structure middle layer assistant brazing | |
| CN102586869A (en) | Three-dimensional grapheme tube and preparation method thereof | |
| CN108380227B (en) | Hydrogen evolution electrocatalytic material and preparation method thereof | |
| CN110666158A (en) | Method for coating nano copper with graphene | |
| CN105386003A (en) | Preparation method for three-dimensional structure graphene reinforced copper matrix composite material | |
| CN103276322A (en) | In-situ grown carbon-nanotube-reinforced aluminum-base solder and preparation method thereof | |
| CN102658153B (en) | Preparation method of copper substrate surface growth fullerene doped porous carbon nanofibers | |
| CN104386676A (en) | Preparation method of graphene | |
| CN102367570A (en) | Method for preparing diamond-graphene composite film | |
| CN101985352B (en) | Method for preparing multi-walled carbon nanotubes from phthalocyanine iron polymer by high temperature solid-phase cracking | |
| CN108597894A (en) | A kind of preparation method of boron doping porous carbon materials | |
| CN102534300B (en) | Method for preparing in-situ growing carbon nano tube reinforcing TiNi high-temperature solders | |
| CN105478944A (en) | Method for brazing hard alloy and steel with assistance of carbon nano tube | |
| CN109264705A (en) | A kind of preparation method and three-dimensional grapheme-copper composite cable of three-dimensional grapheme film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150909 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |