CN115283664A - Cu-Al 2 O 3 Cold spraying composite powder and preparation method and application thereof - Google Patents
Cu-Al 2 O 3 Cold spraying composite powder and preparation method and application thereof Download PDFInfo
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- 238000010288 cold spraying Methods 0.000 title claims abstract description 98
- 239000000843 powder Substances 0.000 title claims abstract description 69
- 239000002131 composite material Substances 0.000 title claims abstract description 64
- 229910017767 Cu—Al Inorganic materials 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 86
- 239000010949 copper Substances 0.000 claims abstract description 53
- 238000000576 coating method Methods 0.000 claims abstract description 48
- 239000011248 coating agent Substances 0.000 claims abstract description 47
- 229910052802 copper Inorganic materials 0.000 claims abstract description 47
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 44
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 32
- 230000008569 process Effects 0.000 claims abstract description 30
- 239000000758 substrate Substances 0.000 claims abstract description 23
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 21
- 239000002245 particle Substances 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims description 13
- 238000000151 deposition Methods 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000012159 carrier gas Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 5
- 239000006228 supernatant Substances 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 125000003158 alcohol group Chemical group 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims 1
- 229910045601 alloy Inorganic materials 0.000 claims 1
- 238000003466 welding Methods 0.000 abstract description 20
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 abstract description 14
- 238000005219 brazing Methods 0.000 abstract description 9
- 238000005476 soldering Methods 0.000 abstract description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 abstract description 4
- 229910000765 intermetallic Inorganic materials 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 239000000945 filler Substances 0.000 abstract description 2
- 229910000679 solder Inorganic materials 0.000 description 13
- 230000008021 deposition Effects 0.000 description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 8
- 238000005507 spraying Methods 0.000 description 7
- 230000006872 improvement Effects 0.000 description 6
- 238000009736 wetting Methods 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 5
- 229910018182 Al—Cu Inorganic materials 0.000 description 4
- 238000009713 electroplating Methods 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000003892 spreading Methods 0.000 description 4
- 230000007480 spreading Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 244000137852 Petrea volubilis Species 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
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- 238000006243 chemical reaction Methods 0.000 description 2
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 2
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- 239000007921 spray Substances 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- 229910017755 Cu-Sn Inorganic materials 0.000 description 1
- 229910017927 Cu—Sn Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
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- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
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- 238000001878 scanning electron micrograph Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/12—Metallic powder containing non-metallic particles
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
- C22C32/001—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides
- C22C32/0015—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides with only single oxides as main non-metallic constituents
- C22C32/0036—Matrix based on Al, Mg, Be or alloys thereof
-
- 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
- C23C24/00—Coating starting from inorganic powder
- C23C24/02—Coating starting from inorganic powder by application of pressure only
- C23C24/04—Impact or kinetic deposition of particles
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
The invention provides Cu-Al 2 O 3 Cold spraying composite powder, preparation method and application thereof, and Cu-Al 2 O 3 The components of the cold spraying composite powder are dendritic copper powder and alpha-Al 2 O 3 The dendritic copper powder and alpha-Al 2 O 3 The particle size of (A) is 25 to 45 μm, and the mass ratio is 1. Cu-Al adopting the technical scheme of the invention 2 O 3 Cold spraying composite powder on the surface of aluminum by low-pressure cold spraying, the obtained coating has high bonding strength with the aluminum substrate and low porosity, and meanwhile, the tin-based brazing filler metal can be wetted and spread on the cold spraying copper layer, and sufficient intermetallic compounds are generated at the interfaceAnd forming interconnection for subsequent soldering. In addition, the cold spraying process does not need to treat the aluminum oxide in the cold spraying layer on the surface of the aluminum, the whole process can be carried out in the air atmosphere, the environment is protected, the energy consumption is low, and a new solution is provided for local welding of the aluminum.
Description
Technical Field
Hair brushBelongs to the technical field of the preparation of a coating capable of brazing, and particularly relates to Cu-Al 2 O 3 Cold spraying composite powder and its preparation process and application.
Background
In modern industrial production, materials with different properties need to be welded into composite parts in order to meet various performance requirements of workpieces, and Al-Cu heterogeneous joints are important. At present, the Al/Cu composite joint has urgent needs in the fields of electronic industry, power transmission and distribution and building, so that the Al/Cu composite joint has very important application value for solving the connection problem of Al-Cu dissimilar materials.
At present, the connection of Al-Cu dissimilar metals is mainly welding, but common fusion welding, friction stir welding, brazing and the like have many problems. Excessive heat input can promote the generation of brittle intermetallic compounds at joints in the welding process, and influence the mechanical property and mechanical property of the joints; the microstructure at the joint is also complicated due to high temperature, and oxidation and the like easily occur in the welding process; the welding process is complex and the requirement on welding conditions is high, so that the workpiece has low processability, and the joint of the workpiece often has large residual stress; meanwhile, the welding is difficult to accurately weld a specific area, the base metal around the joint is influenced by heat to a greater or lesser extent, and unpredictable performance fluctuation is caused to the workpiece.
Electroplating is often used to solve local welding of Al by electroplating a copper layer, a nickel layer, etc. on the Al surface, followed by soldering. However, since Al is very easily oxidized, the electroplating process needs to be strictly controlled, the conditions are harsh, and the electroplating solution is not environment-friendly and is difficult to treat.
Disclosure of Invention
Aiming at the technical problems, the invention discloses Cu-Al 2 O 3 The cold spraying composite powder and the preparation method and application thereof are adopted, and the coating obtained by cold spraying the composite powder on the surface of aluminum can solve the problems of the connection of the aluminum and copper dissimilar metals, and has the advantages of low cost, high reliability and environmental protection.
In contrast, the technical scheme adopted by the invention is as follows:
Cu-Al 2 O 3 The cold spraying composite powder comprises dendritic copper powder and alpha-Al 2 O 3 The dendritic copper powder and alpha-Al 2 O 3 Has a particle diameter of 25 to 45 mu m, the dendritic copper powder and alpha-Al 2 O 3 The mass ratio of (A) to (B) is 1:0.2 to 1.
As a further improvement of the invention, the dendritic copper powder and alpha-Al 2 O 3 The mass ratio of (A) to (B) is 1: 1.
The invention also discloses the Cu-Al 2 O 3 The preparation method of the cold spraying composite powder comprises the following steps:
step S1, the dendritic copper powder and alpha-Al are treated 2 O 3 Carrying out pretreatment;
step S2, mixing the dendritic copper powder and alpha-Al 2 O 3 Adding solvent, mixing, pouring out supernatant, and vacuum drying to obtain Cu-Al powder 2 O 3 And (4) cold spraying the composite powder.
As a further improvement of the present invention, in step S1, the pretreatment includes: using a 250-mesh screen to respectively carry out treatment on the dendritic copper powder and the alpha-Al 2 O 3 Sieving, and soaking the sieved powder in ethanol. The purpose of sieving is in order to remove the granule that the particle diameter is great, prevents to block up the meal outlet in follow-up cold spraying process, increases the continuity of confession powder process.
As a further improvement of the invention, in step S2, the solvent is alcohol, and a planetary stirrer is adopted for mixing for 3-10min. Further, the mixing time was 5min. Mixing the powders in a planetary mixer, pouring out the supernatant, and drying in a vacuum drying oven to obtain Cu-Al with uniform components 2 O 3 And (3) compounding the powder.
By adopting the technical scheme, the alcohol powder mixing is carried out in the planetary stirrer, and the advantages of short time consumption, good powder mixing effect, easy operation and the like are achieved. Specifically, two kinds of powders added in sequence are placed in a container, and absolute ethyl alcohol is added, so that the flow of particles in the powder mixing process is maximally increased while the chemical properties of the powders are not influenced, and the uniformly dispersed composite powder is obtained.
The invention also discloses the Cu-Al 2 O 3 Application of cold spraying composite powder, cu-Al 2 O 3 The cold spraying composite powder is used for depositing on the surface of the aluminum substrate to form a cold spraying composite copper layer with high density and strong binding force.
Further, DYME @423 low-pressure cold spraying equipment is adopted for cold spraying, and the carrier gas is low-cost compressed air.
The invention also discloses a Cu-Al which can be brazed 2 O 3 The Cu-Al is sprayed by low-pressure cold spraying 2 O 3 The cold spraying composite powder is deposited on the surface of the aluminum substrate to form a cold spraying composite copper layer with high density and strong binding force.
As a further improvement of the invention, the low-pressure cold spraying is carried out using a DYME @423 low-pressure cold spraying apparatus. In order to improve the quality of the coating, the conventional cold spraying process usually adopts high-pressure cold spraying and assists inert gas as carrier gas to increase the speed of particles, so that the coating with high density and few pores is obtained. The technical scheme simplifies the experimental complexity, and adopts low-pressure cold spraying equipment with the lowest cost and compressed air as carrier gas to carry out the cold spraying process.
Further, before cold spraying, the aluminum substrate is pretreated, and the surface of the aluminum substrate is polished by abrasive paper, so that oil stains on the surface of the aluminum substrate are removed, and the influence of impurities such as the oil stains on the deposition process of the composite powder is prevented; and wiping the surface of the Al plate by using a piece of dust-free cloth stained with absolute ethyl alcohol, and removing SiC particles possibly left after sanding by using abrasive paper.
As a further improvement of the invention, the cold spraying conditions are as follows: the powder discharging speed is 0.5-1.0 g/s, the distance between the Laval nozzle and the substrate is 10-20 mm, the moving speed of the Laval nozzle is 200-300mm/s, the cold spraying temperature is 0-400 ℃, the carrier gas in the cold spraying process is compressed air, and the consumption of the compressed air is 0.3-0.4mm 3 And/min. By adopting the technical scheme, the Cu-Al is added 2 O 3 The cold spraying composite powder is subjected to cold spraying under the parameters to obtainThe cold spraying layer is compact and has no obvious holes, the porosity of the cold spraying copper layer on the surface of the aluminum is lower than 3.2 percent, and the resistivity is
Surface hardness of 77.2
12.3 HV 0.3 After 1500 cold and hot impact cycles, the copper-based composite cold spraying layer still does not fall off (the temperature is between 40 ℃ below zero and 125 ℃ below zero is one cycle, and the heat preservation time is 15min at the highest temperature and the lowest temperature), the whole body shows extremely high reliability because the inner pores of the coating are less, the components are uniform, the crack propagation caused by nonuniform heat conduction does not occur between the coatings, and meanwhile, al 2 O 3 The aluminum alloy is directly contacted with an Al plate in the cold spraying process to form a pinning effect, and the strength and the reliability of the coating are improved.
Compared with the prior art, the invention has the beneficial effects that:
firstly, the Cu-Al adopting the technical scheme of the invention 2 O 3 The cold spraying composite powder is sprayed on the surface of aluminum through low-pressure cold spraying, the obtained coating (composite copper layer) has high bonding strength with an aluminum substrate, the porosity is low, and meanwhile, the tin-based solder can be proved to be wetted and spread on the cold spraying copper layer, namely, the coating has the capability of being wetted with the tin-based solder and can be used for the subsequent soldering process. In addition, the cold spraying process does not need to treat alumina in the coating, a small amount of alumina is directly combined with the Al substrate to form an interlocking structure so as to improve the reliability of the coating, and the rest alumina is uniformly distributed in the copper coating to tamp the coating and improve the density of the coating. The whole process can be carried out in the air atmosphere, and the method is an environment-friendly and low-energy-consumption local coating modification method.
Secondly, the Cu-Al of the technical scheme of the invention 2 O 3 The dendritic copper powder and the alumina powder with lower cost are selected as the composite powder, low-pressure cold spraying equipment with lower cost and compressed air are used as carrier gas in the cold spraying process, the whole experimental flow is simple, complex and high-cost treatment means are not needed, and the finally obtained coating has the quality according to the requirementsThe product can reach industrial level and has the potential of large-scale industrial production.
Thirdly, experiments prove that the tin-based solder can be in a state higher than the melting point and can be brazed with Cu-Al in the technical scheme of the invention 2 O 3 The cold spraying composite coating is wetted and spread, and sufficient intermetallic compounds are generated at the interface, so that the cold spraying composite coating is interconnected with the copper substrate, and the cold spraying coating on the aluminum surface has the brazing capacity; meanwhile, a sandwich (Cu-SAC 305-cold spraying copper layer/Al) welding spot is prepared, the actual welding process is simulated, the average shear strength of the welding spot is 34.9MPa, the fracture position is positioned in the cold spraying copper layer instead of the interface of the coating and the substrate, the high reliability of the cold spraying copper layer and the feasibility of brazing are indirectly reflected, and a new solution is provided for the local welding of Al-Cu.
Drawings
FIG. 1 shows Cu-Al of example 1 of the present invention 2 O 3 And (3) a topography of the copper-based composite powder.
Fig. 2 is an SEM cross-sectional view of the cold sprayed copper layer on the aluminum surface in example 2 of the present invention, in which 0201 is an aluminum substrate, 0202 is copper in the copper-based composite powder, and 0203 is alumina in the copper-based composite powder.
FIG. 3 is a TEM cross-sectional view of a cold-sprayed copper layer on an aluminum surface and the results of surface scanning and local line scanning of Cu and Al in example 2 of the present invention, wherein (a) is a TEM cross-sectional view of a cold-sprayed copper layer on an aluminum surface, (b) is a surface scanning view of Cu and Al, and (c) is the results of local line scanning.
FIG. 4 is a graphical representation of the morphology of a powder cold spray coating of different composition of comparative example 1 of the present invention; wherein, (a) is the morphology and surface microstructure of the coating formed by the spherical copper powder on the surface of the aluminum substrate after the cold spraying process, and (b) is the spherical copper powder: the mass ratio of the dendritic copper powder is 1:1, forming the appearance and the cross-sectional view of a coating on the surface of the aluminum substrate after the cold spraying process.
FIG. 5 is a graph showing the wetting and spreading of Sn balls on a cold sprayed copper layer in example 3 of the present invention.
FIG. 6 is a cross-sectional view showing the wet spreading of SAC305 solder paste on a cold sprayed copper layer according to example 3 of the present invention.
Fig. 7 is a schematic diagram of Cu-Cu solder joints in example 3 of the present invention, wherein 1 is a 5 × 1cm Cu bump, 2 is SAC305 solder paste, 3 is a cold-sprayed Cu layer, and 4 is an aluminum substrate.
FIG. 8 is a diagram showing the actual effect of forming a solder joint by soldering in example 3 of the present invention.
Detailed Description
Preferred embodiments of the present invention are described in further detail below.
Cu-Al 2 O 3 The cold spraying composite powder comprises dendritic copper powder and alpha-Al 2 O 3 The dendritic copper powder and alpha-Al 2 O 3 Has a particle diameter of 25 to 45 mu m, the dendritic copper powder and alpha-Al 2 O 3 The mass ratio of (A) to (B) is 1:0.2 to 1. The preparation method comprises the following steps:
step S1, the dendritic copper powder and alpha-Al are treated 2 O 3 Carrying out pretreatment;
step S2, mixing the dendritic copper powder and alpha-Al 2 O 3 Adding solvent, mixing, pouring out supernatant, and vacuum drying to obtain Cu-Al powder 2 O 3 And (4) cold spraying the composite powder.
The Cu-Al obtained above 2 O 3 The cold spraying composite powder is subjected to low-pressure cold spraying on the surface of aluminum to form the Cu-Al capable of brazing 2 O 3 The cold spray composite coating.
The following description will be given with reference to specific examples.
Example 1
Cu-Al 2 O 3 The preparation of the composite powder comprises the following steps:
firstly, selecting dendritic copper powder with the particle size range of 25-45 mu m and polyhedral alpha-Al 2 O 3 ；
Secondly, weighing copper powder and aluminum oxide with different mass ratios, and respectively placing the copper powder and the aluminum oxide into each specific container filled with alcohol; wherein, the different mass ratios are respectively as follows: 1:0, 1:0.2, 1: 0.4, 1: 0.6, 1: 0.8, 1: 1.
Thirdly, sealing the container in a planetary stirrer and rotating for 5min;
fourthly, taking out the container, pouring out the supernatant, and drying the composite powder in vacuum to obtain the Cu-XAl containing the reinforcing phases with different contents 2 O 3 Composite powder (X =0, 20%,40%,60%,80%,100%; where X is the mass ratio of alumina to copper powder).
The composite powder with different mass ratios is adopted to carry out cold spraying on the surface of aluminum to obtain a coating, and detection of the coating shows that the density of the coating is improved along with the increase of the content of aluminum oxide, the porosity is reduced from 8.32% to 3.2%, the strength of the coating is increased from 23.2MPa to 34.9MPa, and the fracture position is transferred to the interior of the coating from the interface of the coating and the substrate. Therefore, with the increase of the content of the aluminum oxide, the direct combination probability of the aluminum oxide and the aluminum substrate is increased, an interlocking structure is formed, and the combination strength is favorably improved.
For containing different contents of Al 2 O 3 When the cold spraying temperature is 400 ℃, the deposition efficiency is increased from 1.6% to 16.7% and then is reduced to 4.2% along with the increase of the content of the aluminum oxide, because the content of the aluminum oxide plays a positive role in the deposition of the cold spraying particles in a certain range, but the content of the aluminum oxide is too high, the collision among the aluminum oxide particles becomes a main combination mode in the cold spraying process, and the aluminum oxide cannot generate plastic deformation to form combination, so the deposition efficiency is reduced, but the reduction of the deposition efficiency does not influence the improvement of the combination strength. The cold spraying temperature is obviously improved on the deposition efficiency, and the deposition efficiency of the same particles at the cold spraying temperature of 400 ℃ is obviously higher than that at the temperature of 200 ℃, because the higher the temperature is, the larger the molecular kinetic energy is, the larger the kinetic energy transferred to the particles is, and the deposition efficiency of the particles is improved.
By contrast, the mass ratio of copper to alumina was 1: the composite powder of 1 can prepare a coating with higher density and more uniformity, otherwise, the thickness of the coating along the center of the nozzle is obviously higher than that of the coating at the deviation position in other proportions.
The mass ratio of copper to aluminum oxide is 1:1 Cu-Al obtained 2 O 3 The morphology of the composite powder is shown in FIG. 1, canThe mixture is dispersed uniformly, and the local aggregation phenomenon which is not beneficial to deposition does not occur. In the composite powder, the dendritic copper powder has larger contact area, so that mechanical combination is favorably formed in the coating, and the wetting and spreading of the brazing filler metal are favorably realized on the surface of the coating; the aluminum oxide is used as a reinforcing phase, the copper powder has larger kinetic energy in the cold spraying process, and the prismatic structure is favorable for mechanical bonding among particles, thereby playing a key role in improving the density of the coating.
Example 2
The mass ratio of copper to aluminum oxide is 1: 1. the obtained Cu-Al 2 O 3 The composite powder of (2) is subjected to Cu-Al treatment on the surface of aluminum 2 O 3 And (4) preparing a cold spraying coating.
Step one, pretreatment of an aluminum plate: selecting 5 x 3 x 1cm industrial aluminum plates, and polishing the surfaces of the aluminum plates by using abrasive paper to remove surface oil stains so as to prevent the surface oil stains from having negative influence on the deposition of the copper-based composite powder; and then soaking the polished aluminum plate in alcohol and wiping the surface of the aluminum plate by using a dust-free cloth to remove SiC particle residues of the sand paper. And finally, placing the treated aluminum plate on a clamp.
And step two, setting parameters of low-pressure cold spraying equipment: the powder discharging speed is 0.5-1.0 g/s, the distance between the Laval nozzle and the substrate is 10-20 mm, the moving speed of the Laval nozzle is 200-300mm/s, the cold spraying temperature is 0-400 ℃, the carrier gas in the cold spraying process is compressed air, and the consumption of the compressed air is 0.3-0.4mm 3 Min; the moving position of the Laval nozzle in the cold spraying process is controlled by adjusting the X-Y axis, so that a rectangular area of Cu-Al with the thickness of 50-200 mu m is formed on the surface of the Al plate 2 O 3 And (4) composite coating.
Wherein the interface between the coating and the substrate is shown in FIG. 2, SEM images show that Cu-Al is macroscopically observed 2 O 3 The composite powder and the aluminum substrate form compact combination after the cold spraying process, no large pores are formed in the coating, the thickness is uniform, and Al is contained in the coating 2 O 3 Distributed inside the copper and no aggregation occurs, indicating that the alumina plays a positive role in the deposition of the copper powder during the cold spraying process.
The interface is observed more carefully by using a transmission electron microscope, as shown in fig. 3, the Cu-Al interface is subjected to surface scanning and local linear scanning, copper atoms are diffused into aluminum under high-speed impact, and an atomic diffusion layer of about 100 nm is formed, which indicates that copper and aluminum are metallurgically bonded in the cold spraying process, and this is the root cause of strong bonding force of the coating.
Comparative example 1
And (3) preparing copper-based composite powder cold spraying layers with different components.
In this comparative example, the selected cold spray coating was made from pure spherical copper powder and dendritic copper: spherical copper powder =1:1 (mass ratio), and in the experimental process, the morphology of the copper powder in the composite copper-based powder has great influence on the finally generated cold spray coating. When spherical powder is selected, the appearance and surface of the cold spray coating are shown in fig. 4 (a), so that the spherical powder is strongly plastically deformed, the particles are tightly stacked, but the cold spray coating is still thin after the cold spray time is increased, which is caused by too much kinetic energy consumed among spherical copper powder in the collision process. In order to reduce the energy consumed by the collision among particles, dendritic copper powder is doped in the spherical copper powder for increasing the contact area, and the ratio of the dendritic copper powder: spherical copper powder =1: the appearance and the cross section of the cold spray coating formed by the composite powder of 1 are shown in fig. 4 (b), spherical and dendritic powder with severe plastic deformation can be seen in the coating, the thickness is obviously increased, but a large number of pores exist in the coating, and the reliability of the coating is still lower.
Example 3
And (3) welding application of a copper-based cold spray coating on the surface of aluminum.
The purpose of preparing the cold sprayed layer on the surface of the aluminum is to achieve local aluminum bronze welding, and therefore the copper-based cold sprayed layer needs to have brazing capability. The solder balls with the diameter of 400 mu m are melted on the cold spraying copper layer in a laser welding mode, the formed salient points are shown in figure 5, the two bumps are compared with the copper pad, the solder balls melted by the laser have similar wetting behavior, and the feasibility of the cold spraying copper layer on the surface of the Al for industrial production is verified.
Adding SAC305 solder paste dropwise on the copper-based composite coating on the aluminum surface, and adding at 250 DEG CThe solder paste was observed wetting on the cold sprayed copper layer hot for 30 s. The formed bump has the appearance and the cross section as shown in FIG. 6, in the wetting process, the wetting spreading area of the SAC305 is gradually increased, and the finally generated bump is glossy; the cross sections of the convex points and the cold spraying copper layers are also analyzed, and an intermetallic compound Cu is generated at the interface 6 Sn 5 The Cu-Sn diffusion between the cold spraying copper layer and the soldering paste in the heating process is explained to form the metallurgical bonding, and the copper layer formed by the cold spraying method on the surface of the aluminum has the brazing capability.
In the presence of Cu-Al 2 O 3 The surface of the cold sprayed layer prepared from the composite powder was printed with a 50 μm layer of SAC305 solder paste through a steel mesh, and 5 × 5 mm copper blocks sanded with sand paper were placed on the layer of solder paste to form the sandwich structure shown in fig. 8. Experiments prove that the welding spot is placed on a heating table at 250 ℃ and reacts for 90s to form a reliable welding spot, no pressure is applied in the reaction process, and the appearance of the welding spot after reaction is shown in figure 8.
The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and it is not intended that the invention be limited to these specific details. For those skilled in the art to which the invention pertains, numerous simple deductions or substitutions may be made without departing from the spirit of the invention, which shall be deemed to belong to the scope of the invention.
Claims (8)
1. Cu-Al 2 O 3 The cold spraying composite powder is characterized in that: the components of the alloy are dendritic copper powder and alpha-Al 2 O 3 The dendritic copper powder and alpha-Al 2 O 3 Has a particle diameter of 25 to 45 mu m, the dendritic copper powder and alpha-Al 2 O 3 The mass ratio of (A) to (B) is 1:0.2 to 1.
2. The Cu-Al of claim 1 2 O 3 The cold spraying composite powder is characterized in that: the dendritic copper powder and alpha-Al 2 O 3 The mass ratio of (A) to (B) is 1: 1.
3. Cu-Al according to claim 1 or 2 2 O 3 The preparation method of the cold spraying composite powder is characterized by comprising the following steps:
step S1, the dendritic copper powder and alpha-Al are treated 2 O 3 Carrying out pretreatment;
step S2, mixing the dendritic copper powder and alpha-Al 2 O 3 Adding solvent, mixing, pouring out supernatant, and vacuum drying to obtain Cu-Al powder 2 O 3 And (5) cold spraying the composite powder.
4. The Cu-Al of claim 3 2 O 3 The preparation method of the cold spraying composite powder is characterized by comprising the following steps:
in step S1, the pretreatment includes: using a 250-mesh screen to respectively carry out treatment on the dendritic copper powder and the alpha-Al 2 O 3 Sieving, and soaking the sieved powder in ethanol.
5. The Cu-Al of claim 4 2 O 3 The preparation method of the cold spraying composite powder is characterized by comprising the following steps: in the step S2, the solvent is alcohol, and a planetary stirrer is adopted for mixing for 3-10min.
6. Cu-Al according to claim 1 or 2 2 O 3 The application of the cold spraying composite powder is characterized in that: the Cu-Al 2 O 3 The cold spraying composite powder is used for depositing on the surface of the aluminum substrate to form a cold spraying composite copper layer with high density and strong binding force.
7. Braze-able Cu-Al 2 O 3 The preparation method of the cold spraying composite coating is characterized by comprising the following steps: cu-Al according to claim 1 or 2 by means of low-pressure cold spraying 2 O 3 The cold spraying composite powder is deposited on the surface of the aluminum substrate to form a cold spraying composite copper layer with high density and strong binding force.
8. According to claim 7The above-mentioned braze-able Cu-Al 2 O 3 The preparation method of the cold spraying composite coating is characterized by comprising the following steps: carrying out cold spraying by using DYME @423 low-pressure cold spraying equipment under the following cold spraying conditions: the powder discharging speed is 0.5-1.0 g/s, the distance between the Laval nozzle and the substrate is 10-20 mm, the moving speed of the Laval nozzle is 200-300mm/s, the cold spraying temperature is 0-400 ℃, the carrier gas in the cold spraying process is compressed air, and the consumption of the compressed air is 0.3-0.4mm 3 /min。
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116038178A (en) * | 2023-02-27 | 2023-05-02 | 中国机械总院集团宁波智能机床研究院有限公司 | Brazing filler metal for superhard cutter and preparation method and application thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1876365A (en) * | 2006-07-05 | 2006-12-13 | 西安理工大学 | Cu-Al2O3 gradient composite material coating and its preparation method |
| CN101643899A (en) * | 2009-09-05 | 2010-02-10 | 中国船舶重工集团公司第七二五研究所 | Preparation method of different-metal material welding middle layer |
| CN106048667A (en) * | 2016-07-19 | 2016-10-26 | 哈尔滨工业大学深圳研究生院 | Connecting method based on electroplating and applied to same metal or dissimilar metal |
| JP2018188689A (en) * | 2017-04-28 | 2018-11-29 | 株式会社神戸製鋼所 | Composite particle, material for cold spraying, covering material, and method of manufacturing the same |
| CN109773364A (en) * | 2017-11-10 | 2019-05-21 | 河南智联寰宇知识产权运营有限公司 | Aluminium base brazing material and preparation method thereof |
| CN112501537A (en) * | 2020-11-11 | 2021-03-16 | 中国电子科技集团公司第三十八研究所 | Aluminum alloy surface low-temperature brazing modified coating and preparation method thereof |
| CN112548414A (en) * | 2020-12-07 | 2021-03-26 | 东莞仁海科技股份有限公司 | Environment-friendly copper-aluminum welding process |
| CN112981387A (en) * | 2021-02-08 | 2021-06-18 | 浙江工业大学 | Method for preparing aluminum oxide reinforced copper-based wear-resistant heat-conducting and electric-conducting coating through laser-assisted low-pressure cold spraying |
-
2022
- 2022-07-13 CN CN202210820331.4A patent/CN115283664A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1876365A (en) * | 2006-07-05 | 2006-12-13 | 西安理工大学 | Cu-Al2O3 gradient composite material coating and its preparation method |
| CN101643899A (en) * | 2009-09-05 | 2010-02-10 | 中国船舶重工集团公司第七二五研究所 | Preparation method of different-metal material welding middle layer |
| CN106048667A (en) * | 2016-07-19 | 2016-10-26 | 哈尔滨工业大学深圳研究生院 | Connecting method based on electroplating and applied to same metal or dissimilar metal |
| JP2018188689A (en) * | 2017-04-28 | 2018-11-29 | 株式会社神戸製鋼所 | Composite particle, material for cold spraying, covering material, and method of manufacturing the same |
| CN109773364A (en) * | 2017-11-10 | 2019-05-21 | 河南智联寰宇知识产权运营有限公司 | Aluminium base brazing material and preparation method thereof |
| CN112501537A (en) * | 2020-11-11 | 2021-03-16 | 中国电子科技集团公司第三十八研究所 | Aluminum alloy surface low-temperature brazing modified coating and preparation method thereof |
| CN112548414A (en) * | 2020-12-07 | 2021-03-26 | 东莞仁海科技股份有限公司 | Environment-friendly copper-aluminum welding process |
| CN112981387A (en) * | 2021-02-08 | 2021-06-18 | 浙江工业大学 | Method for preparing aluminum oxide reinforced copper-based wear-resistant heat-conducting and electric-conducting coating through laser-assisted low-pressure cold spraying |
Non-Patent Citations (4)
| Title |
|---|
| HELI KOIVULUOTO AND PETRI VUORISTO: "Effect of Powder Type and Composition on Structure and Mechanical Properties of Cu+Al2O3 Coatings Prepared by using Low-Pressure Cold Spray Process", vol. 19, no. 5, pages 1081 - 1092 * |
| SHINJI FUKUMOTO ET.AL: "Characteristics and Microstructural Development of Cold-Sprayed Copper Coating on Aluminum", vol. 60, no. 4, pages 602 - 610 * |
| TOMASZ WOJDAT ET.AL: "Soldering aluminium to copper with the use of interlayers deposited by cold spraying", vol. 16, no. 2016, pages 835 - 844 * |
| 郭海珠等: "《等离子表面冶金纳米涂层材料与性能研究》", 华南理工大学出版社, pages: 128 - 15 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116038178A (en) * | 2023-02-27 | 2023-05-02 | 中国机械总院集团宁波智能机床研究院有限公司 | Brazing filler metal for superhard cutter and preparation method and application thereof |
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