CN103831549A - Method for preparing carbon nano tube reinforced copper-based composite brazing filler metal based on in-situ reaction - Google Patents
Method for preparing carbon nano tube reinforced copper-based composite brazing filler metal based on in-situ reaction Download PDFInfo
- Publication number
- CN103831549A CN103831549A CN201410102456.9A CN201410102456A CN103831549A CN 103831549 A CN103831549 A CN 103831549A CN 201410102456 A CN201410102456 A CN 201410102456A CN 103831549 A CN103831549 A CN 103831549A
- Authority
- CN
- China
- Prior art keywords
- copper
- carbon
- nano tube
- powder
- prepared
- 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.)
- Pending
Links
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
-
- 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
- C23C16/50—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 using electric discharges
- C23C16/513—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 using electric discharges using plasma jets
Abstract
The invention discloses a method for preparing carbon nano tube enhanced copper-based composite brazing filler metal based on an in-situ reaction, relates to a method for preparing the carbon nano tube enhanced copper-based composite brazing filler metal and aims at solving the problem that an existing method for preparing the carbon nano tube enhanced copper-based composite brazing filler metal is poor in carbon nano tube evenness and dispersibility and incomplete in structure. The method includes the steps that a NiNO3/Cu mixture is prepared, the NiNO3/Cu mixture is evenly laid on a silicon wafer and arranged in a plasma enhanced chemical vapor deposition vacuum device, hydrogen is led in, the temperature is raised, the carbon source gas is led in, deposition is performed, after deposition is over, the carbon source gas stops being led in, and finally the temperature is reduced to the room temperature to obtain carbon nano tube/copper composite powder; the metal powder and the carbon nano tube/copper composite powder are evenly mixed, and the carbon nano tube enhanced copper-based composite brazing filler metal is obtained.
Description
Technical field
The present invention relates to prepare the method for carbon nanotube reinforced copper-base composite soldering.
Background technology
Soldering is the one in welding method, its main method is to adopt to make solder than the low-melting metal material of mother metal, by weldment with solder is heated to above solder fusing point and lower than mother metal fusion temperature, utilize liquid solder soak mother metal, fill play movement and and mother metal mutually spread and then realize being connected between material.Soldering can solve the problem being connected between dissimilar metal and between pottery, composite and metal, in the sophisticated industries such as general industry and Aeronautics and Astronautics such as machinery, motor, all has a wide range of applications.Similar with other welding methods, the Main Weak Links of brazing member is at welding point place, and the key parameters such as strength of welded joint size, stress distribution and the scope of application have the performance that depends on greatly solder.In practice, usually improve joint performance by add all kinds of reinforcements in solder, reinforcement can be selected graininess, can be also fibrous, sheet, can be both metallic compound, can be also nano-carbide.
CNT is to be rolled seamless, the hollow cylindrical structure that form by certain spiral angle by Graphene, has high elastic modelling quantity and hot strength, low-density and thermal coefficient of expansion, has again good toughness, heat-resisting quantity and chemical stability simultaneously.Rely on these excellent performances, CNT can be used as wild phase in articulamentum material increases the wetability of solder, simultaneously all right refinement seam organization, alleviates soldered fitting stress, improves joint mechanical performance and high-temperature behavior, has expanded the joint scope of application and reliability.
In the preparation method of general carbon nanotube reinforced copper-base composite soldering, there is even carbon nanotube bad dispersibility and the large class problem of structural intergrity bad two in big city: because conventional method preparation temperature is high, copper powder particles is very easily reunited, the CNT of growing on copper powder can be very inhomogeneous, affected the dispersiveness of CNT in composite soldering; Other preparation method itself again usually can destroying carbon nanometer tube self structure, reduced carbon nano-tube material strengthening the property in composite soldering.Therefore, there is great realistic meaning in the urgent need to finding a kind of new preparation method to solve an above-mentioned difficult problem.
Summary of the invention
There is the problem of even carbon nanotube bad dispersibility and structural intergrity in the preparation method that the present invention will solve existing carbon nanotube reinforced copper-base composite soldering, and provides a kind of reaction in-situ to prepare the method for carbon nanotube reinforced copper-base composite soldering.
Reaction in-situ is prepared a method for carbon nanotube reinforced copper-base composite soldering, specifically carries out according to following steps:
One, copper powders and six water nickel nitrate particles are mixed, obtain mixture, then mixture is joined in absolute ethyl alcohol; obtaining mixed solution, mixed solution is stirred, is then at 60 ℃～80 ℃ in temperature; be uniformly mixed solution to absolute ethyl alcohol and all evaporate, obtain NiNO
3/ Cu mixture;
The mass ratio of described copper powders and six water nickel nitrate particles is 1:(0.095～0.105);
Two, NiNO step 1 being prepared
3/ Cu mixture is evenly laid on silicon chip, then surface is covered with to NiNO
3the silicon chip of/Cu mixture is placed in plasma enhanced chemical vapor deposition vacuum plant, being evacuated to pressure is below 5Pa, pass into hydrogen take gas flow as 19sccm～21sccm, regulating vacuum pumping rate is 190Pa～210Pa by pressure control in plasma enhanced chemical vapor deposition vacuum plant, and is in 30min, temperature to be heated up to most 750 ℃～790 ℃ under 190Pa～210Pa and hydrogen atmosphere at pressure;
Three, pass into carbon-source gas, the gas flow that regulates hydrogen is that the gas flow of 10sccm, carbon-source gas is 40sccm,
And to regulate vacuum pumping rate be 500Pa～700Pa 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 170W～180W, pressure is that 500Pa～700Pa and temperature are to deposit under 750 ℃～790 ℃ conditions, sedimentation time is 10min～30min, after deposition finishes, close radio-frequency power supply and heating power supply, stop passing into carbon-source gas, regulating the gas flow of hydrogen is 20sccm, 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 atmosphere, to be 750 ℃～790 ℃ from temperature to be cooled to room temperature at pressure, obtain carbon nano tube/copper composite powder,
Four, the carbon nano tube/copper composite powder of being prepared by metal dust and step 3 is put into ball mill, grinds and is stirred to powder and mix, and obtains carbon nanotube reinforced copper-base composite soldering.
The invention has the beneficial effects as follows: 1, the present invention can be incorporated into CNT as reinforcement in copper base composite soldering, can alleviate the thermal stress of joint, improve mechanical property and the applied at elevated temperature performance of joint.
2, the carbon nanotube reinforced copper-base solder that application invention method utilizes plasma chemical vapor deposition equipment to prepare, CNT in composite soldering good dispersion, do not reunite, structural integrity, can make the further performance of strengthening the property of CNT.
3, the present invention is simple, efficient, and cost is lower, is beneficial to very much suitability for industrialized production.
The present invention prepares the method for carbon nanotube reinforced copper-base composite soldering for a kind of reaction in-situ.
Accompanying drawing explanation
Fig. 1 is the SEM picture of carbon nano tube/copper composite powder in embodiment mono-, multiplication factor 50.0K;
Fig. 2 is the SEM picture of carbon nano tube/copper composite powder in embodiment mono-, multiplication factor 200K;
Fig. 3 is the Raman spectrum picture of carbon nano tube/copper composite powder in embodiment mono-; 1 is D peak; 2 is G 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 reaction in-situ described in present embodiment is prepared the method for carbon nanotube reinforced copper-base composite soldering, specifically carry out according to following steps:
One, copper powders and six water nickel nitrate particles are mixed, obtain mixture, then mixture is joined in absolute ethyl alcohol; obtaining mixed solution, mixed solution is stirred, is then at 60 ℃～80 ℃ in temperature; be uniformly mixed solution to absolute ethyl alcohol and all evaporate, obtain NiNO
3/ Cu mixture;
The mass ratio of described copper powders and six water nickel nitrate particles is 1:(0.095～0.105);
Two, NiNO step 1 being prepared
3/ Cu mixture is evenly laid on silicon chip, then surface is covered with to NiNO
3the silicon chip of/Cu mixture is placed in plasma enhanced chemical vapor deposition vacuum plant, being evacuated to pressure is below 5Pa, pass into hydrogen take gas flow as 19sccm～21sccm, regulating vacuum pumping rate is 190Pa～210Pa by pressure control in plasma enhanced chemical vapor deposition vacuum plant, and is in 30min, temperature to be heated up to most 750 ℃～790 ℃ under 190Pa～210Pa and hydrogen atmosphere at pressure;
Three, pass into carbon-source gas, regulating the gas flow of hydrogen is 10sccm, the gas flow of carbon-source gas is 40sccm, and to regulate vacuum pumping rate be 500Pa～700Pa 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 170W～180W, pressure is that 500Pa～700Pa and temperature are to deposit under 750 ℃～790 ℃ conditions, sedimentation time is 10min～30min, after deposition finishes, close radio-frequency power supply and heating power supply, stop passing into carbon-source gas, regulating the gas flow of hydrogen is 20sccm, 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 atmosphere, to be 750 ℃～790 ℃ from temperature to be cooled to room temperature at pressure, obtain carbon nano tube/copper composite powder,
Four, the carbon nano tube/copper composite powder of being prepared by metal dust and step 3 is put into ball mill, grinds and is stirred to powder and mix, and obtains carbon nanotube reinforced copper-base composite soldering.
In present embodiment, CNT has high elastic modelling quantity and hot strength, low-density and thermal coefficient of expansion, has again good toughness, heat-resisting quantity and chemical stability simultaneously.In the time mixing in solder using a little CNT as reinforcement, CNT can play the effect of transmitting stress and load, is conducive to alleviate the thermal stress of joint; The tubular structure of CNT can also play the effect of dispersion-strengtherning and grain refinement, thereby has improved mechanical property and the applied at elevated temperature performance of soldered fitting.
Utilize plasma reinforced chemical vapour deposition method (PECVD) to prepare carbon nanotube reinforced copper-base solder and belong to a kind of in-situ preparation method, on copper matrix, direct growth goes out CNT and can effectively solve scattering problem.In addition, owing to adopting plasma to strengthen, i.e. radio-frequency technique, carbon source can just resolve into active very high carbon-based group at a lower temperature very fast, significantly reduced preparation temperature, copper powder particles is reunited hardly, has further improved dispersion problem.Prepare CNT by PECVD method in addition, in can be effectively general preparation process to the structural damage of CNT own.
The beneficial effect of present embodiment is: 1, present embodiment utilizes plasma reinforced chemical vapour deposition legal system for Graphene/copper powders, Graphene good dispersion, and fault of construction is few; Take action of radio mode, reduced preparation temperature, avoided Graphene that the trend of reuniting occurs simultaneously.
2, prepare Graphene by present embodiment and strengthen Cu-base composites, overall preparation time is short, technique simple, cost is lower, is easy to realize large-scale industrial production.
The specific embodiment two: present embodiment is different from the specific embodiment one: the mass ratio of the copper powders described in step 1 and six water nickel nitrate particles is 1:0.1.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 copper powders purity described in step 1 is 99%～99.99%, particle diameter is 100nm～100 μ m.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: six water nickel nitrate particle purity described in step 1 are 98%～99.99%.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 carbon-source gas described in step 3 is methane.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 metal dust described in step 4 is Sn powder, Ag powder or Mn powder; Metal dust purity described in step 4 is 99%～99.99%, and particle diameter is 100nm～100 μ m.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 reaction in-situ described in the present embodiment is prepared the method for carbon nanotube reinforced copper-base composite soldering, specifically carries out according to following steps:
One, copper powders and six water nickel nitrate particles are mixed, obtain mixture, then mixture is joined in absolute ethyl alcohol; obtaining mixed solution, mixed solution is stirred, is then at 80 ℃ in temperature; be uniformly mixed solution to absolute ethyl alcohol and all evaporate, obtain NiNO
3/ Cu mixture;
The mass ratio of described copper powders and six water nickel nitrate particles is 1:0.1;
Two, NiNO step 1 being prepared
3/ Cu mixture is evenly laid on silicon chip, then surface is covered with to NiNO
3the silicon chip of/Cu mixture is placed in 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 is in 30min, temperature to be heated up to most 790 ℃ under 200Pa and hydrogen atmosphere at pressure;
Three, pass into carbon-source gas, regulating the gas flow of hydrogen is 10sccm, the gas flow of carbon-source gas is 40sccm, and to regulate vacuum pumping rate be 700Pa 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 175W, pressure is that 700Pa and temperature are to deposit under 790 ℃ of conditions, sedimentation time is 15min, after deposition finishes, close radio-frequency power supply and heating power supply, stop passing into carbon-source gas, regulating the gas flow of hydrogen is 20sccm, and to regulate vacuum pumping rate be 150Pa by pressure control in plasma enhanced chemical vapor deposition vacuum plant, be under 150Pa and hydrogen atmosphere, to be 790 ℃ from temperature to be cooled to room temperature at pressure, obtain carbon nano tube/copper composite powder,
Four, the carbon nano tube/copper composite powder of being prepared by metal dust and step 3 is put into ball mill, grinds and is stirred to powder and mix, and obtains carbon nanotube reinforced copper-base composite soldering.
Copper powder purity described in step 1 is 99.9%～99.95%, and particle diameter is 300 orders.
Six water nickel nitrate particle purity described in step 1 are 98%.
Carbon-source gas described in step 3 is methane.
Metal dust described in step 4 is Sn powder; Metal Sn powder purity described in step 4 is 99.95%, and particle diameter is 300 orders.
In embodiment mono-the SEM picture of carbon nano tube/copper composite powder as shown in Figure 1, multiplication factor 50.0K, even carbon nanotube is dispersed in copper powder particles as seen from the figure.
In embodiment mono-the SEM picture of carbon nano tube/copper composite powder as shown in Figure 2, multiplication factor 200K, as seen from the figure, the length of carbon nanotube of growing in copper powder particles can reach 2～4um, caliber is between 10～15nm.
In embodiment mono-, as shown in Figure 3,1 is D peak to the Raman spectrum picture of carbon nano tube/copper composite powder; 2 is G peak, and as seen from the figure, CNT degree of graphitization is fine, and purity is very high.The CNT Cu-Sn solder that CNT/Cu composite powder is prepared thus can significantly improve soldered fitting performance.
Embodiment bis-:
A kind of reaction in-situ described in the present embodiment is prepared the method for carbon nanotube reinforced copper-base composite soldering, specifically carries out according to following steps:
One, copper powders and six water nickel nitrate particles are mixed, obtain mixture, then mixture is joined in absolute ethyl alcohol; obtaining mixed solution, mixed solution is stirred, is then at 80 ℃ in temperature; be uniformly mixed solution to absolute ethyl alcohol and all evaporate, obtain NiNO
3/ Cu mixture;
The mass ratio of described copper powders and six water nickel nitrate particles is 1:0.1;
Two, NiNO step 1 being prepared
3/ Cu mixture is evenly laid on silicon chip, then surface is covered with to NiNO
3the silicon chip of/Cu mixture is placed in 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 is in 30min, temperature to be heated up to most 750 ℃ under 200Pa and hydrogen atmosphere at pressure;
Three, pass into carbon-source gas, regulating the gas flow of hydrogen is 10sccm, the gas flow of carbon-source gas is 40sccm, and to regulate vacuum pumping rate be 700Pa 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 175W, pressure is that 700Pa and temperature are to deposit under 750 ℃ of conditions, sedimentation time is 15min, after deposition finishes, close radio-frequency power supply and heating power supply, stop passing into carbon-source gas, regulating the gas flow of hydrogen is 20sccm, and to regulate vacuum pumping rate be 150Pa by pressure control in plasma enhanced chemical vapor deposition vacuum plant, be under 150Pa and hydrogen atmosphere, to be 790 ℃ from temperature to be cooled to room temperature at pressure, obtain carbon nano tube/copper composite powder,
Four, the carbon nano tube/copper composite powder of being prepared by metal dust and step 3 is put into ball mill, grinds and is stirred to powder and mix, and obtains carbon nanotube reinforced copper-base composite soldering.
Copper powder purity described in step 1 is 99.9%～99.95%, and particle diameter is 300 orders.
Six water nickel nitrate particle purity described in step 1 are 98%.
Carbon-source gas described in step 3 is methane.
Metal dust described in step 4 is Sn powder; Metal Sn powder purity described in step 4 is 99.95%, and particle diameter is 300 orders.
In CNT/Cu composite powder that this example obtains, even carbon nanotube is dispersed in copper powder particles, and the length of carbon nanotube of growing in copper powder particles can reach 1～3um, and caliber is between 10～15nm, CNT degree of graphitization is better, and purity is higher.The CNT Cu-Sn solder that CNT/Cu composite powder is prepared thus can significantly improve soldered fitting performance.
Embodiment tri-:
A kind of reaction in-situ described in the present embodiment is prepared the method for carbon nanotube reinforced copper-base composite soldering, specifically carries out according to following steps:
One, copper powders and six water nickel nitrate particles are mixed, obtain mixture, then mixture is joined in absolute ethyl alcohol; obtaining mixed solution, mixed solution is stirred, is then at 80 ℃ in temperature; be uniformly mixed solution to absolute ethyl alcohol and all evaporate, obtain NiNO
3/ Cu mixture;
The mass ratio of described copper powders and six water nickel nitrate particles is 1:0.1;
Two, NiNO step 1 being prepared
3/ Cu mixture is evenly laid on silicon chip, then surface is covered with to NiNO
3the silicon chip of/Cu mixture is placed in 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 is in 30min, temperature to be heated up to most 750 ℃ under 200Pa and hydrogen atmosphere at pressure;
Three, pass into carbon-source gas, regulating the gas flow of hydrogen is 10sccm, the gas flow of carbon-source gas is 40sccm, and to regulate vacuum pumping rate be 500Pa 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 175W, pressure is that 500Pa and temperature are to deposit under 750 ℃ of conditions, sedimentation time is 15min, after deposition finishes, close radio-frequency power supply and heating power supply, stop passing into carbon-source gas, regulating the gas flow of hydrogen is 20sccm, and to regulate vacuum pumping rate be 150Pa by pressure control in plasma enhanced chemical vapor deposition vacuum plant, be under 150Pa and hydrogen atmosphere, to be 790 ℃ from temperature to be cooled to room temperature at pressure, obtain carbon nano tube/copper composite powder,
Four, the carbon nano tube/copper composite powder of being prepared by metal dust and step 3 is put into ball mill, grinds and is stirred to powder and mix, and obtains carbon nanotube reinforced copper-base composite soldering.
Copper powder purity described in step 1 is 99.9%～99.95%, and particle diameter is 300 orders.
Six water nickel nitrate particle purity described in step 1 are 98%.
Carbon-source gas described in step 3 is methane.
Metal dust described in step 4 is Sn powder; Metal Sn powder purity described in step 4 is 99.95%, and particle diameter is 300 orders.
In CNT/Cu composite powder that this example obtains, even carbon nanotube is dispersed in copper powder particles, and the length of carbon nanotube of growing in copper powder particles can reach 1～3um, and caliber is between 7～12nm, and CNT degree of graphitization is good, purity is high.Can significantly improve soldered fitting performance through the CNT Cu-Sn solder that CNT/Cu composite powder is prepared thus.
Claims (6)
1. reaction in-situ is prepared a method for carbon nanotube reinforced copper-base composite soldering, it is characterized in that a kind of reaction in-situ prepares the method for carbon nanotube reinforced copper-base composite soldering and carry out according to following steps:
One, copper powders and six water nickel nitrate particles are mixed, obtain mixture, then mixture is joined in absolute ethyl alcohol; obtaining mixed solution, mixed solution is stirred, is then at 60 ℃～80 ℃ in temperature; be uniformly mixed solution to absolute ethyl alcohol and all evaporate, obtain NiNO
3/ Cu mixture;
The mass ratio of described copper powders and six water nickel nitrate particles is 1:(0.095～0.105);
Two, NiNO step 1 being prepared
3/ Cu mixture is evenly laid on silicon chip, then surface is covered with to NiNO
3the silicon chip of/Cu mixture is placed in plasma enhanced chemical vapor deposition vacuum plant, being evacuated to pressure is below 5Pa, pass into hydrogen take gas flow as 19sccm～21sccm, regulating vacuum pumping rate is 190Pa～210Pa by pressure control in plasma enhanced chemical vapor deposition vacuum plant, and is in 30min, temperature to be heated up to most 750 ℃～790 ℃ under 190Pa～210Pa and hydrogen atmosphere at pressure;
Three, pass into carbon-source gas, regulating the gas flow of hydrogen is 10sccm, the gas flow of carbon-source gas is 40sccm, and to regulate vacuum pumping rate be 500Pa～700Pa 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 170W～180W, pressure is that 500Pa～700Pa and temperature are to deposit under 750 ℃～790 ℃ conditions, sedimentation time is 10min～30min, after deposition finishes, close radio-frequency power supply and heating power supply, stop passing into carbon-source gas, regulating the gas flow of hydrogen is 20sccm, 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 atmosphere, to be 750 ℃～790 ℃ from temperature to be cooled to room temperature at pressure, obtain carbon nano tube/copper composite powder,
Four, the carbon nano tube/copper composite powder of being prepared by metal dust and step 3 is put into ball mill, grinds and is stirred to powder and mix, and obtains carbon nanotube reinforced copper-base composite soldering.
2. a kind of reaction in-situ according to claim 1 is prepared the method for carbon nanotube reinforced copper-base composite soldering, it is characterized in that the mass ratio of the copper powders described in step 1 and six water nickel nitrate particles is 1:0.1.
3. a kind of reaction in-situ according to claim 1 is prepared the method for carbon nanotube reinforced copper-base composite soldering, it is characterized in that the copper powders purity described in step 1 is 99%～99.99%, and particle diameter is 100nm～100 μ m.
4. a kind of reaction in-situ according to claim 1 is prepared the method for carbon nanotube reinforced copper-base composite soldering, it is characterized in that six water nickel nitrate particle purity described in step 1 are 98%～99.99%.
5. a kind of reaction in-situ according to claim 1 is prepared the method for carbon nanotube reinforced copper-base composite soldering, it is characterized in that the carbon-source gas described in step 3 is methane.
6. a kind of reaction in-situ according to claim 1 is prepared the method for carbon nanotube reinforced copper-base composite soldering, it is characterized in that the metal dust described in step 4 is Sn powder, Ag powder or Mn powder; Metal dust purity described in step 4 is 99%～99.99%, and particle diameter is 100nm～100 μ m.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410102456.9A CN103831549A (en) | 2014-03-19 | 2014-03-19 | Method for preparing carbon nano tube reinforced copper-based composite brazing filler metal based on in-situ reaction |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410102456.9A CN103831549A (en) | 2014-03-19 | 2014-03-19 | Method for preparing carbon nano tube reinforced copper-based composite brazing filler metal based on in-situ reaction |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103831549A true CN103831549A (en) | 2014-06-04 |
Family
ID=50795616
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410102456.9A Pending CN103831549A (en) | 2014-03-19 | 2014-03-19 | Method for preparing carbon nano tube reinforced copper-based composite brazing filler metal based on in-situ reaction |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103831549A (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105397344A (en) * | 2015-12-23 | 2016-03-16 | 哈尔滨工业大学 | Preparation method of in-situ growth graphene/carbon nano tube reinforced Ti-based brazing filler metal |
| CN105478944A (en) * | 2015-12-28 | 2016-04-13 | 哈尔滨工业大学 | Method for brazing hard alloy and steel with assistance of carbon nano tube |
| CN105779962A (en) * | 2016-03-18 | 2016-07-20 | 上海理工大学 | Preparation method for copper-carbon nano tube (CNT) composite powder |
| CN108611511A (en) * | 2018-05-08 | 2018-10-02 | 上海理工大学 | A kind of three-dimensional intercommunication CNTs/Cu composite material and preparation methods |
| CN108611510A (en) * | 2018-05-08 | 2018-10-02 | 上海理工大学 | A kind of CNTs/Cu composite material and preparation methods |
| CN108611520A (en) * | 2018-05-08 | 2018-10-02 | 上海理工大学 | A kind of copper-based in-situ composite material and preparation method thereof |
| CN108927609A (en) * | 2018-08-13 | 2018-12-04 | 深圳市亿铖达工业有限公司 | A kind of preparation method of compound lead-free tin cream |
| CN109550941A (en) * | 2018-11-15 | 2019-04-02 | 中国科学院过程工程研究所 | A kind of carbon nanotube cladding titanium spherical shape composite granule and preparation method thereof |
| CN112974795A (en) * | 2021-02-05 | 2021-06-18 | 中国人民解放军陆军装甲兵学院 | Composite powder for additive manufacturing and remanufacturing and preparation method thereof, and metal-based composite forming layer and preparation method thereof |
| CN114589432A (en) * | 2022-03-08 | 2022-06-07 | 湘潭大学 | Copper-plated carbon nanotube reinforced Ag-Cu-Ti composite solder and preparation method thereof |
| CN114850732A (en) * | 2022-06-21 | 2022-08-05 | 齐齐哈尔大学 | Preparation method of graphene-reinforced tin-based composite solder |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004011178A1 (en) * | 2002-07-26 | 2004-02-05 | The Government Of The United States Of America, As Represented By The Secretary Of The Navy | Synthesis of metal nanoparticle compositions from metallic and ethynyl compounds |
| CN1730688A (en) * | 2005-08-29 | 2006-02-08 | 天津大学 | Vapour deposition in situ reaction method for preparing carbon nanotube reinforced aluminium matrix composite material |
| CN1888103A (en) * | 2006-07-17 | 2007-01-03 | 天津大学 | Vapor depositing in-situ reaction process for preparing carbon nanotube reinforced copper-base composite material |
| CN102320591A (en) * | 2011-06-22 | 2012-01-18 | 天津大学 | Method for directly growing mesh carbon nanotubes on copper substrate |
| 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 |
-
2014
- 2014-03-19 CN CN201410102456.9A patent/CN103831549A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004011178A1 (en) * | 2002-07-26 | 2004-02-05 | The Government Of The United States Of America, As Represented By The Secretary Of The Navy | Synthesis of metal nanoparticle compositions from metallic and ethynyl compounds |
| CN1730688A (en) * | 2005-08-29 | 2006-02-08 | 天津大学 | Vapour deposition in situ reaction method for preparing carbon nanotube reinforced aluminium matrix composite material |
| CN1888103A (en) * | 2006-07-17 | 2007-01-03 | 天津大学 | Vapor depositing in-situ reaction process for preparing carbon nanotube reinforced copper-base composite material |
| CN102320591A (en) * | 2011-06-22 | 2012-01-18 | 天津大学 | Method for directly growing mesh carbon nanotubes on copper substrate |
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| QI JUNLEI .ETC: "In-situ synthesis of CNTS reinforced Ti based brazing powder by PECVD", 《CHINA WELDING》 * |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105397344A (en) * | 2015-12-23 | 2016-03-16 | 哈尔滨工业大学 | Preparation method of in-situ growth graphene/carbon nano tube reinforced Ti-based brazing filler metal |
| CN105478944A (en) * | 2015-12-28 | 2016-04-13 | 哈尔滨工业大学 | Method for brazing hard alloy and steel with assistance of carbon nano tube |
| CN105779962A (en) * | 2016-03-18 | 2016-07-20 | 上海理工大学 | Preparation method for copper-carbon nano tube (CNT) composite powder |
| CN105779962B (en) * | 2016-03-18 | 2018-07-31 | 上海理工大学 | A kind of preparation method at copper-carbon nano-tube composite powder end |
| CN108611520B (en) * | 2018-05-08 | 2019-05-31 | 上海理工大学 | A kind of copper-based in-situ composite material and preparation method thereof |
| CN108611511A (en) * | 2018-05-08 | 2018-10-02 | 上海理工大学 | A kind of three-dimensional intercommunication CNTs/Cu composite material and preparation methods |
| CN108611510A (en) * | 2018-05-08 | 2018-10-02 | 上海理工大学 | A kind of CNTs/Cu composite material and preparation methods |
| CN108611520A (en) * | 2018-05-08 | 2018-10-02 | 上海理工大学 | A kind of copper-based in-situ composite material and preparation method thereof |
| CN108611511B (en) * | 2018-05-08 | 2019-08-09 | 上海理工大学 | A kind of three-dimensional intercommunication CNTs/Cu composite material and preparation method |
| CN108927609B (en) * | 2018-08-13 | 2020-08-07 | 深圳市亿铖达工业有限公司 | Preparation method of composite lead-free solder paste |
| CN108927609A (en) * | 2018-08-13 | 2018-12-04 | 深圳市亿铖达工业有限公司 | A kind of preparation method of compound lead-free tin cream |
| CN109550941A (en) * | 2018-11-15 | 2019-04-02 | 中国科学院过程工程研究所 | A kind of carbon nanotube cladding titanium spherical shape composite granule and preparation method thereof |
| CN109550941B (en) * | 2018-11-15 | 2020-05-26 | 中国科学院过程工程研究所 | Carbon nano tube coated titanium spherical composite powder and preparation method thereof |
| CN112974795A (en) * | 2021-02-05 | 2021-06-18 | 中国人民解放军陆军装甲兵学院 | Composite powder for additive manufacturing and remanufacturing and preparation method thereof, and metal-based composite forming layer and preparation method thereof |
| CN114589432A (en) * | 2022-03-08 | 2022-06-07 | 湘潭大学 | Copper-plated carbon nanotube reinforced Ag-Cu-Ti composite solder and preparation method thereof |
| 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 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103831549A (en) | Method for preparing carbon nano tube reinforced copper-based composite brazing filler metal based on in-situ reaction | |
| CN103817466B (en) | A kind of efficient cryogenic prepares the method that Graphene strengthens copper base composite soldering | |
| CN103789744B (en) | A kind of in-situ growing carbon nano tube strengthens the preparation method of silver-based electric contact material | |
| CN103773985B (en) | A kind of efficient original position prepares the method that Graphene strengthens Cu-base composites | |
| CN104625283B (en) | The method of three dimensional structure Graphene composite interlayer assistant brazing | |
| CN105397344B (en) | Growth in situ graphene and CNT strengthen the method for Ti base solders | |
| Ozden et al. | Density variant carbon nanotube interconnected solids | |
| CN102383071B (en) | Method for preparing carbon nano tube enhanced titanium-base compound material by in-suit reaction | |
| CN106346100B (en) | A kind of method of carbon nanotube enhancing three-dimensional structure middle layer assistant brazing | |
| CN103276322A (en) | In-situ grown carbon-nanotube-reinforced aluminum-base solder and preparation method thereof | |
| CN108296586A (en) | A kind of SiO2The method for welding of-BN composite ceramics and Invar alloys | |
| CN103061112A (en) | Composite material of silicon carbide and carbon nanotube and preparation method thereof | |
| CN108620767B (en) | Preparation method of composite solder for brazing quartz short fiber reinforced silicon dioxide composite material and Invar alloy | |
| CN105478944A (en) | Method for brazing hard alloy and steel with assistance of carbon nano tube | |
| CN102534300B (en) | Method for preparing in-situ growing carbon nano tube reinforcing TiNi high-temperature solders | |
| CN107758633A (en) | A kind of preparation method for growing straight boron nitride nanometer line | |
| CN104711457A (en) | High temperature solder and application thereof | |
| CN105836727A (en) | Method for low-cost preparation of multi-walled carbon nanotubes | |
| CN103252506A (en) | Preparation method of nanometer molybdenum powder containing homodisperse carbon nano tubes | |
| CN112756608A (en) | Preparation method for in-situ generation of liquid absorbent core material of copper-clad iron heat pipe | |
| CN105295098B (en) | A kind of graphene oxide, CNT multi-arm determine the preparation method of configuration heat filling | |
| CN102925728B (en) | Preparation method of binderless nanometer tungsten carbide cemented carbide | |
| CN107936472B (en) | Preparation method of high-thermal-conductivity epoxy composite material | |
| CN102950292B (en) | Production method of submicron-order copper-manganesenickle alloy powder | |
| CN107163912A (en) | A kind of MWCNTSWave absorbing agent, its preparation method and absorbing material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20140604 |