CN112894047A - Method for improving dissimilar metal fusion soldering joint performance through carbon nano tube - Google Patents
Method for improving dissimilar metal fusion soldering joint performance through carbon nano tube Download PDFInfo
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- 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
- B23K31/00—Processes relevant to this subclass, specially adapted for particular articles or purposes, but not covered by only one of the preceding main groups
- B23K31/02—Processes relevant to this subclass, specially adapted for particular articles or purposes, but not covered by only one of the preceding main groups relating to soldering or welding
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- 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
- B23K1/00—Soldering, e.g. brazing, or unsoldering
- B23K1/19—Soldering, e.g. brazing, or unsoldering taking account of the properties of the materials to be soldered
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- 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
- B23K1/00—Soldering, e.g. brazing, or unsoldering
- B23K1/20—Preliminary treatment of work or areas to be soldered, e.g. in respect of a galvanic coating
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- 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
- B23K2103/00—Materials to be soldered, welded or cut
- B23K2103/18—Dissimilar materials
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Abstract
The invention belongs to the field of alloy welding, and particularly discloses a method for improving the performance of a dissimilar metal fusion-brazing joint through a carbon nano tube. The method comprises the following steps: vertically growing carbon nanotubes on the surface of the high-melting-point metal plate, and enabling the axes of the carbon nanotubes to be uniformly distributed along the width of a welding seam; and butting and welding one side of the high-melting-point metal plate, on which the carbon nano tubes are grown, with the low-melting-point metal plate, and modifying the dissimilar metal fusion brazing interface microstructure by using the carbon nano tubes so as to improve the joint performance. According to the invention, the carbon nano tube vertically grows on the surface of the high-melting-point metal plate and is welded with the low-melting-point metal plate, so that a metal fusion brazing cross-section microstructure is modified by the carbon nano tube to form a structure similar to a steel bar-concrete structure, and finally, the purposes of improving an interface structure and improving the joint performance are achieved; and the carbon nano tube is not required to be infiltrated into the welding line by other materials in the processing process, so that the method has the advantages of simple operation and high efficiency.
Description
Technical Field
The invention belongs to the field of alloy welding, and particularly relates to a method for improving the performance of a dissimilar metal fusion-brazing joint through a carbon nano tube.
Background
Dissimilar metal welding such as titanium/aluminum dissimilar metal welding has wide application space in the fields of transportation, aerospace and the like, and is an important means for realizing light weight of equipment. However, because of the extremely low solubility of titanium in aluminum at room temperature, a large amount of brittle intermetallic compounds are formed in conventional fusion braze welds, severely affecting weld quality. In recent years, researchers have proposed a method for brazing dissimilar metals of titanium/aluminum, which uses the difference in melting point between two metals of titanium/aluminum, and which can reduce the formation of intermetallic compounds and the thickness of an intermetallic compound layer to some extent by applying energy to the aluminum side having a low melting point during welding to melt the aluminum side and slightly melt the titanium side, but has not yet effectively solved the problem of poor mechanical properties of joints. Therefore, developing a proper welding process and improving the mechanical property of the titanium/aluminum dissimilar metal welding joint are key problems to be solved urgently.
The structural morphology of the weld seam directly affects the mechanical properties of the welded joint. Researches show that the grains can be refined and the joint performance can be enhanced by adding the reinforcing phase into the welding seam. The materials used as the weld structure reinforcing phase are various, wherein the carbon nano tube has excellent mechanical property and is one of the commonly used weld reinforcing phases. Researchers at home and abroad directly mix the carbon nano tube with metal powder or welding flux, and the mixture is added into a welding line in the welding process to form a reinforcing phase. In addition, part of researchers grow the carbon nano tubes on the foam metal and then add the carbon nano tubes as an intermediate layer into the welding line to serve as a reinforcing phase of the welding line, and the method is successfully applied to welding of titanium and ceramic materials and has a good connecting effect.
The method for directly adding the carbon nano tube and the metal powder or the welding flux into the welding seam in a mixed mode is simple and convenient to operate and high in efficiency. However, since the carbon nanotubes are easily agglomerated at the nanoscale, it is difficult to uniformly mix the carbon nanotubes by the method, and thus the effect of the carbon nanotubes in reinforcing the weld is reduced. Secondly, the welding temperature is difficult to control in the actual welding process, and if the temperature is too high, the carbon nano tube can be damaged, so that the enhancement effect can be reduced; if the temperature is too low, the metal may not melt sufficiently to form a molten pool. The method of growing carbon nanotubes on a metal foam and then adding the carbon nanotubes as an intermediate layer to a weld can make the carbon nanotubes uniformly distributed, but this method is relatively easy to implement under experimental conditions and is not easy to operate in industrial production. The two methods have great difficulty in regulating and controlling the spatial distribution state of the carbon nano tube in the welding seam; meanwhile, the carbon nano tube only plays a role in improving the central structure of the welding seam and enhancing the strength of the welding seam, and the microstructure at the interface is not modified in a targeted manner, so that the problem of joint performance deterioration caused by interface embrittlement cannot be solved obviously.
Disclosure of Invention
In view of the above-mentioned disadvantages and/or needs for improvement of the prior art, the present invention provides a method for improving the performance of a dissimilar metal fusion-brazed joint through carbon nanotubes, wherein carbon nanotubes are vertically grown on the surface of a high-melting-point metal plate, and then are welded to a low-melting-point metal plate, so that a metal fusion-brazed cross-sectional microstructure is modified by the carbon nanotubes to form a structure similar to a "steel bar-concrete" structure, and finally, the purpose of improving the interface structure and the joint performance is achieved.
In order to achieve the purpose, the invention provides a method for improving the performance of a dissimilar metal fusion-brazing joint through a carbon nano tube, which comprises the following steps:
s1 vertically growing carbon nanotubes on the surface of the high-melting-point metal plate, and enabling the axes of the carbon nanotubes to be uniformly distributed along the width of the welding seam;
s2, butting and welding the side of the high-melting-point metal plate where the carbon nanotubes grow with the low-melting-point metal plate, and modifying the dissimilar metal fusion brazing interface microstructure by using the carbon nanotubes so as to improve the joint performance.
More preferably, the dissimilar metal is a titanium/aluminum dissimilar metal, a copper/magnesium dissimilar metal, a copper/aluminum dissimilar metal, a steel/aluminum dissimilar metal, or a titanium/magnesium dissimilar metal.
As a further preferable mode, in step S1, carbon nanotubes are grown on the surface of the refractory metal plate by a chemical vapor deposition method.
As a further preferred method for growing carbon nanotubes by chemical vapor deposition, the method comprises: heating a high-melting-point metal plate in a mixed atmosphere of rare gas and hydrogen, then dropwise adding a carbon-philic catalyst solution on the surface of the high-melting-point metal plate to grow carbon nanotubes on the surface of the high-melting-point metal plate, and finally introducing air to remove amorphous carbon on the surface of the carbon nanotubes.
More preferably, the heating temperature is 600 ℃ to 850 ℃.
Further preferably, the concentration of the hydrophilic catalyst solution is 3 wt% to 9 wt%, and the growth density of the carbon nanotubes is controlled by controlling the concentration of the hydrophilic catalyst solution.
Further preferably, the solute of the hydrophilic catalyst solution is ferrocene, iron powder, cobalt powder, nickel nitrate hexahydrate or iron nitrate nonahydrate, and the solvent of the hydrophilic catalyst solution is water, ethanol, ammonia water or xylene.
More preferably, the dropping rate of the hydrophilic catalyst solution is 0.07mL/min to 0.1 mL/min.
Further preferably, the pretreatment of the refractory metal plate before the growth of the carbon nanotubes specifically comprises the following steps:
(a) polishing the high-melting-point metal plate, removing impurities on the surface of the high-melting-point metal plate, and putting the high-melting-point metal plate into an acetone solution for cleaning;
(b) etching the surface of the cleaned high-melting-point metal plate, and then cleaning and drying the surface;
(c) and respectively connecting the etched high-melting-point metal plate and the etched platinum sheet with the positive electrode and the negative electrode of a direct-current power supply, and applying 10-30V of anode bias voltage to perform surface oxidation treatment, thereby finally finishing the pretreatment work of the high-melting-point metal plate.
Generally, compared with the prior art, the above technical solution conceived by the present invention mainly has the following technical advantages:
1. according to the invention, the carbon nano tube vertically grows on the surface of the high-melting-point metal plate and is welded with the low-melting-point metal plate, so that a metal fusion brazing cross-section microstructure is modified by the carbon nano tube to form a structure similar to a steel bar-concrete structure, and finally, the purposes of improving an interface structure and improving the joint performance are achieved; in addition, the carbon nanotubes do not need to be infiltrated into the welding seam by other materials in the processing process, so that the method has the advantages of simple operation and high efficiency, and meanwhile, the axis of the carbon nanotubes is uniformly distributed along the width direction of the welding seam, so that the section structure of the welding seam can be effectively enhanced, and the connection between the welding seam and the base metal is enhanced;
2. particularly, the invention adopts the chemical vapor deposition method to grow the carbon nano tube, and the concentration of the carbon nano tube is adjusted by controlling the concentration of the carbon-philic catalyst solution, so that the concentration of the generated carbon nano tube can be effectively controlled, and the carbon nano tube can be ensured not to have agglomeration phenomenon;
3. in addition, the invention can effectively control the growth speed and quality of the carbon nano tube by optimizing the heating temperature and the dropping speed of the carbon-philic catalyst.
Drawings
FIG. 1 is a flow chart of the present invention for improving the performance of a dissimilar metal fusion-brazed joint through carbon nanotubes;
FIG. 2 is a block diagram of single-walled carbon nanotubes and multi-walled carbon nanotubes, wherein (a) is single-walled carbon nanotubes and (b) is multi-walled carbon nanotubes;
fig. 3 is a schematic diagram of the distribution of carbon nanotubes in a weld.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
As shown in fig. 1, an embodiment of the present invention provides a method for improving properties of a dissimilar metal fusion-brazed joint through a carbon nanotube, the method including the following steps:
s1 the dissimilar metal is titanium/aluminum dissimilar metal, copper/magnesium dissimilar metal, steel/aluminum dissimilar metal or titanium/magnesium dissimilar metal, the carbon nanotube vertically grows on the surface of the metal plate with higher melting point in the dissimilar metal, so that the axis of the carbon nanotube is uniformly distributed along the width of the welding seam, wherein the carbon nanotube grows on the surface of the metal plate with high melting point by preferably adopting a chemical vapor deposition method, and the specific flow is as follows:
heating a high-melting-point metal plate to 600-850 ℃ in a mixed atmosphere of rare gas and hydrogen, then dropwise adding a carbon-philic catalyst solution on the surface of the high-melting-point metal plate to grow carbon nanotubes on the surface of the high-melting-point metal plate, and finally introducing air to remove amorphous carbon on the surface of the carbon nanotubes;
s2, butting and welding the side of the high-melting-point metal plate where the carbon nanotubes grow with the low-melting-point metal plate, and modifying the dissimilar metal fusion brazing interface microstructure by using the carbon nanotubes, so as to improve the joint performance.
FIGS. 2 (a) and (b) show the spatial structures of single-walled carbon nanotubes and multi-walled carbon nanotubes, respectively, since each carbon atom undergoes SP during the formation of the carbon nanotubes2The carbon nano tube is hybridized and is connected with other three carbon atoms through covalent bonds, a single electron on a P orbit which does not participate in hybridization forms a delocalized pi bond with single electrons of other carbon atoms, and the chemical bonds are the strongest chemical bonds in nature, so that the carbon nano tube has very excellent mechanical properties and is a good weld joint structure reinforcing material.
Further, the solute of the hydrophilic catalyst solution is ferrocene, iron powder, cobalt powder, nickel nitrate hexahydrate or iron nitrate nonahydrate, the solvent of the hydrophilic catalyst solution is water, ethanol, ammonia water or xylene, the concentration of the hydrophilic catalyst solution is 3-6 wt%, and the growth density of the carbon nano tube is controlled by controlling the concentration of the hydrophilic catalyst solution. Too high concentration of the carbon-philic catalyst solution can lead to too dense grown carbon nanotubes and prevent molten pool metal from fully wetting high-melting-point parent metal; otherwise, the carbon nanotubes are too sparse, and the reinforcing effect is not obvious. The dropping speed of the solution of the hydrophilic catalyst is 0.07ml/min to 0.1ml/min, so that the phenomenon that the hydrophilic catalyst is not easy to be separated out from the solution quickly due to the overhigh dropping speed of the solution is avoided, and meanwhile, the insufficient supply of the catalyst is avoided.
Further, the method for pretreating the high-melting-point metal plate before growing the carbon nano tube specifically comprises the following steps:
(a) polishing the high-melting-point metal plate, removing impurities on the surface of the high-melting-point metal plate, and putting the high-melting-point metal plate into an acetone solution for cleaning;
(b) etching the surface of the cleaned high-melting-point metal plate, and then cleaning and drying the surface;
(c) and respectively connecting the etched high-melting-point metal plate and the etched platinum sheet with the positive electrode and the negative electrode of a direct-current power supply, and applying 10-30V of anode bias voltage to perform surface oxidation treatment, thereby finally finishing the pretreatment work of the high-melting-point metal plate.
The welding of titanium/aluminum dissimilar materials is a technical difficulty in the welding field, and the fusion brazing is an important method for realizing the connection of titanium/aluminum dissimilar metals. However, since titanium has a very low solubility in aluminum at room temperature, a large amount of brittle intermetallic compounds are generated at the joint interface, and a thick brittle layer is formed, which seriously affects the welding quality. The prior art method mainly improves the structure performance of the center of the welding seam, and rarely relates to the strengthening of the interface structure of the joint. In a preferred embodiment of the invention, a vertical array of carbon nanotubes is generated on the surface of a titanium alloy, and then butt-jointed with the aluminum alloy to carry out aluminum/titanium dissimilar metal fusion brazing, so that the carbon nanotubes modify a titanium/aluminum dissimilar metal fusion fiber interface microstructure to form a structure similar to a reinforcing steel bar-concrete structure, and finally the purposes of improving the interface structure and improving the joint performance are achieved through experiments. Selecting a TC4 titanium alloy plate with the thickness of 100mm multiplied by 50mm multiplied by 2mm and a 6061 aluminum plate with the thickness of 100mm multiplied by 50mm multiplied by 2mm, wherein the content of key elements of the TC4 titanium alloy is that Fe is less than or equal to 0.3 wt%, C is less than or equal to 0.1 wt%, N is less than or equal to 0.05 wt%, H is less than or equal to 0.015 wt%, O is less than or equal to 0.2 wt%, Al is more than or equal to 5.5 wt% and less than or equal to 6.8 wt%, V is more than or equal to 3.5 wt% and less than or equal to 4; the 6061 aluminum alloy comprises key elements of more than or equal to 0.15 wt% and less than or equal to 0.4 wt% of Cu, less than or equal to 0.15 wt% of Mn, more than or equal to 0.8 wt% and less than or equal to 1.2 wt% of Mg, less than or equal to 0.25 wt% of Zn, more than or equal to 0.04 wt% and less than or equal to 0.35 wt% of Cr, less than or equal to 0.15 wt% of Ti, more than or equal to 0.4 wt% and less than or equal to 0.8 wt% of Si, less than or equal. The melting point of pure titanium is about 1668 ℃, the melting point of pure aluminum is about 660 ℃, and the difference between the melting points of the pure titanium and the pure aluminum is large, so that the pure titanium and the pure aluminum are suitable for being connected by brazing. The laser was chosen as the heat source for the fusion brazing in this example because the energy of the laser is concentrated and the location of the heat input is easily controlled.
The method is to directly utilize a chemical vapor deposition method to realize the vertical array of the carbon nanotubes on the TC4 titanium alloy, and in order to enable the carbon nanotubes to be used as a weld interface structure reinforcing phase and simultaneously strengthen the connection between a weld and a base material, the distribution of the carbon nanotubes in the weld is required to be as shown in figure 3. To achieve this effect, the experiment was carried out as follows:
(1) the TC4 titanium alloy was ground. Respectively using 180 parts of surfaces to be welded of TC4 titanium alloy plates#，360#，800#，1200#The carborundum abrasive paper is used for grinding for 2-4 min until no obvious scratch is formed on the surface of the TC4 titanium alloy. The TC4 titanium alloy is polished to remove most of the oxide layer on the surface of the alloy, reduce the roughness of the surface, create a good growth plane for the growth of the carbon nanotubes and prevent the appearance of the microscopic surface of the material from influencing the growth of the carbon nanotubes.
(2) And removing impurities and oil stains on the surface of the TC4 titanium alloy plate. Placing TC4 titanium alloy plate into acetone (C)3H6O) solution, and then ultrasonic cleaning is carried out for 3-8 min. The surface of the TC4 titanium alloy plate may have a lot of oil stains attached thereon, the existence of the oil stains can prevent the catalyst from being well embedded into the surface of the TC4 titanium alloy, and meanwhile, the carbon-philic catalyst cannot be fully captured in the growth process of the carbon nano tubeTrapping carbon atoms.
(3) And etching the surface of the TC4 titanium alloy plate. Putting the cleaned TC4 titanium alloy plate into a reactor with the volume ratio of HF: HNO3：H2O is 1: 4: and 5, etching for 15-40 s in the mixed solution. The TC4 titanium alloy plate is etched to remove oxide particles attached to the surface, but the etching time is not long enough, otherwise, the surface of the material is over-corroded.
(4) And cleaning the residual etching liquid on the surface of the TC4 titanium alloy plate. The etched TC4 titanium alloy sheet was rinsed with ionized water and the surface was blow-dried with nitrogen to prevent re-oxidation of the surface.
(5) And (3) carrying out microscopic electrochemical corrosion treatment on the surface of the TC4 titanium alloy plate. Immersing a TC4 titanium alloy plate and a platinum sheet into 0.1-0.5 wt% hydrofluoric acid (HF) electrolyte solution, respectively connecting with a positive electrode and a negative electrode of a direct current power supply, and applying an anode bias voltage of 10-30V for maintaining for 3-5 min. The surface of the TC4 board forms a nanometer pit under the action of electrochemical corrosion, which is beneficial to the reliable connection of the carbon nanotube and the substrate. Meanwhile, researches show that the anode corrosion surface within 3min is flat, and unevenness can be caused after more than 5 min.
(6) Placing the treated TC4 titanium alloy plate into a quartz tube reactor, and introducing argon (Ar) and hydrogen (H) into the reaction vessel at the speed of 800-1200 ml/min and 80-120 ml/min respectively2) The air in the reactor is vented to prevent surface oxidation. And heating by using a tubular resistance furnace with a program temperature controller until the temperature of the TC4 board is 800-840 ℃, and keeping the temperature.
(7) Adding 0.3-0.7 g of ferrocene Fe (C)5H5)2Dissolving in 20-30 ml of dimethylbenzene C8H10And injecting the mixture into a quartz tube reactor through a capillary tube by using a peristaltic pump at the speed of 0.06-0.12 ml/min, wherein the temperature of the opening of the capillary tube is about 200 ℃. The process lasts for 25-35 min, and the specific time is controlled according to the length of the required carbon nano tube.
(8) And after the reaction is finished, closing the peristaltic pump, closing the hydrogen for 8-12 min, stopping heating, and naturally cooling the TC4 titanium alloy plate under the protection of argon to prevent oxidation. When the furnace temperature is reduced to about 450 ℃, argon is closed, a seal is opened, and air is introduced to carry out air oxidation on the generated carbon nano tube to remove the amorphous carbon on the surface.
(9) The side of TC4 plate on which carbon nanotubes are grown is butted with a 6061 aluminum alloy plate which is treated by removing an oxidation film. And adjusting the laser power to 3600-3800W, 0 defocusing amount, 0.2-0.8 mm offset (deviated to the aluminum alloy side) and a welding speed of 60-80 mm/min for welding.
According to the method, the carbon nanotubes grow in a vertical array on the TC4 titanium alloy by directly utilizing a chemical vapor deposition method, and in order to ensure that the carbon nanotubes are used as a weld interface structure reinforcing phase and simultaneously can strengthen the connection between a weld and a base material, the distribution of the carbon nanotubes in the weld is shown in figure 3.
The improved technical solution of the present invention is further described below with reference to specific examples.
Example 1
S1, heating a titanium alloy plate to 820 ℃ in a mixed atmosphere of rare gas and hydrogen, dissolving ferrocene in xylene to obtain a carbon-philic catalyst solution with the mass fraction of 6%, dropwise adding the carbon-philic catalyst solution onto the surface of the titanium alloy plate at the speed of 0.08ml/min to grow carbon nanotubes on the surface of the titanium alloy plate, and finally introducing air to remove amorphous carbon on the surface of the carbon nanotubes so that the axes of the carbon nanotubes are uniformly distributed along the width of a welding seam;
s2, butting and welding the side of the titanium alloy plate where the carbon nano tubes grow with the aluminum alloy plate, and modifying the titanium/aluminum dissimilar metal fusion brazing interface microstructure by using the carbon nano tubes so as to improve the joint performance.
Example 2
S1, heating a copper alloy plate to 600 ℃ in a mixed atmosphere of rare gas and hydrogen, dissolving ferric nitrate nonahydrate in water to obtain a carbon-philic catalyst solution with the mass fraction of 4.5%, dropwise adding the carbon-philic catalyst solution on the surface of the copper alloy plate at the speed of 0.06ml/min to grow carbon nanotubes on the surface of the copper alloy plate, and finally introducing air to remove amorphous carbon on the surface of the carbon nanotubes so that the axes of the carbon nanotubes are uniformly distributed along the width of a welding seam;
s2, butting and welding the side of the copper alloy plate where the carbon nano tubes grow with the magnesium alloy plate, and modifying the dissimilar metal fusion brazing interface microstructure by using the carbon nano tubes so as to improve the joint performance.
Example 3
S1, heating a copper alloy plate to 650 ℃ in a mixed atmosphere of rare gas and hydrogen, dissolving nickel nitrate hexahydrate in ammonia water to obtain a carbon-philic catalyst solution with the mass fraction of 3%, dropwise adding the carbon-philic catalyst solution on the surface of the copper alloy plate at the speed of 0.07ml/min to grow carbon nanotubes on the surface of the copper alloy plate, and finally introducing air to remove amorphous carbon on the surface of the carbon nanotubes so that the axes of the carbon nanotubes are uniformly distributed along the width of a welding seam;
s2, butting and welding the side of the copper alloy plate where the carbon nano tubes grow with the aluminum alloy plate, and modifying the dissimilar metal fusion brazing interface microstructure by using the carbon nano tubes so as to improve the joint performance.
Example 4
S1, heating a steel plate to 700 ℃ in a mixed atmosphere of rare gas and hydrogen, dissolving iron powder in ethanol to obtain a carbon-philic catalyst solution with the mass fraction of 5%, dropwise adding the carbon-philic catalyst solution on the surface of the steel plate at the speed of 0.1ml/min to grow carbon nanotubes on the surface of the steel plate, and finally introducing air to remove amorphous carbon on the surface of the carbon nanotubes so that the axes of the carbon nanotubes are uniformly distributed along the width of a welding seam;
s2, butting and welding one side of the steel plate with the carbon nano tubes with an aluminum alloy plate, and modifying the dissimilar metal fusion brazing interface microstructure by using the carbon nano tubes so as to improve the joint performance.
Example 5
S1, heating a titanium alloy plate to 850 ℃ in a mixed atmosphere of rare gas and hydrogen, dissolving ferrocene in xylene to obtain a carbon-philic catalyst solution with the mass fraction of 4%, dropwise adding the carbon-philic catalyst solution onto the surface of the titanium alloy plate at the speed of 0.09ml/min to grow carbon nanotubes on the surface of the titanium alloy plate, and finally introducing air to remove amorphous carbon on the surface of the carbon nanotubes so that the axes of the carbon nanotubes are uniformly distributed along the width of a welding seam;
s2, butting and welding the side of the titanium alloy plate where the carbon nano tubes grow with the magnesium alloy plate, and modifying the dissimilar metal fusion brazing interface microstructure by using the carbon nano tubes so as to improve the joint performance.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (9)
1. A method for improving the performance of dissimilar metal fusion-brazed joints by using carbon nanotubes is characterized by comprising the following steps:
s1 vertically growing carbon nanotubes on the surface of the high-melting-point metal plate, and enabling the axes of the carbon nanotubes to be uniformly distributed along the width of the welding seam;
s2, butting and welding the side of the high-melting-point metal plate where the carbon nanotubes grow with the low-melting-point metal plate, and modifying the dissimilar metal fusion brazing interface microstructure by using the carbon nanotubes so as to improve the joint performance.
2. The method of improving properties of a dissimilar metal fusion brazed joint via carbon nanotubes of claim 1, wherein the dissimilar metal is a titanium/aluminum dissimilar metal, a copper/magnesium dissimilar metal, a copper/aluminum dissimilar metal, a steel/aluminum dissimilar metal, or a titanium/magnesium dissimilar metal.
3. The method for improving properties of a dissimilar metal fusion soldered joint by carbon nanotubes as claimed in claim 1, wherein in step S1, carbon nanotubes are grown on the surface of the refractory metal plate by chemical vapor deposition.
4. The method for improving the performance of the dissimilar metal fusion-soldered joint by the carbon nanotube according to claim 3, wherein the method for growing the carbon nanotube by the chemical vapor deposition method comprises the following steps: heating a high-melting-point metal plate in a mixed atmosphere of rare gas and hydrogen, then dropwise adding a carbon-philic catalyst solution on the surface of the high-melting-point metal plate to grow carbon nanotubes on the surface of the high-melting-point metal plate, and finally introducing air to remove amorphous carbon on the surface of the carbon nanotubes.
5. The method for improving the performance of a dissimilar metal fusion soldered joint by carbon nanotubes as claimed in claim 4, wherein the heating temperature is 600 ℃ to 850 ℃.
6. The method for improving the performance of the dissimilar metal fusion soldered joint through the carbon nanotube according to claim 4, wherein the concentration of the hydrophilic catalyst solution is 3 wt% to 9 wt%, and the growth density of the carbon nanotube is controlled by controlling the concentration of the hydrophilic catalyst solution.
7. The method for improving the performance of the dissimilar metal fusion-brazed joint through the carbon nanotube according to claim 4, wherein the solute of the hydrophilic catalyst solution is ferrocene, iron powder, cobalt powder, nickel nitrate hexahydrate or iron nitrate nonahydrate, and the solvent of the hydrophilic catalyst solution is water, ethanol, ammonia water or xylene.
8. The method for improving properties of a dissimilar metal fusion soldered joint using carbon nanotubes as claimed in claim 4, wherein the dropping speed of said solution of the hydrophilic catalyst is 0.07 to 0.1 mL/min.
9. The method for improving the performance of the dissimilar metal fusion-brazing joint through the carbon nanotube according to any one of claims 1 to 8, wherein the pretreatment is performed on the high-melting-point metal plate before the carbon nanotube is grown, and the method specifically comprises the following steps:
(a) polishing the high-melting-point metal plate, removing impurities on the surface of the high-melting-point metal plate, and putting the high-melting-point metal plate into an acetone solution for cleaning;
(b) etching the surface of the cleaned high-melting-point metal plate, and then cleaning and drying the surface;
(c) and respectively connecting the etched high-melting-point metal plate and the etched platinum sheet with the positive electrode and the negative electrode of a direct-current power supply, and applying 10-30V of anode bias voltage to perform surface oxidation treatment, thereby finally finishing the pretreatment work of the high-melting-point metal plate.
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