CN114632992A - MOFs derivative interface modification layer, preparation method thereof and application thereof in lead-free solder modification - Google Patents
MOFs derivative interface modification layer, preparation method thereof and application thereof in lead-free solder modification Download PDFInfo
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- CN114632992A CN114632992A CN202210091837.6A CN202210091837A CN114632992A CN 114632992 A CN114632992 A CN 114632992A CN 202210091837 A CN202210091837 A CN 202210091837A CN 114632992 A CN114632992 A CN 114632992A
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- 230000004048 modification Effects 0.000 title claims abstract description 33
- 238000012986 modification Methods 0.000 title claims abstract description 33
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 32
- 229910000679 solder Inorganic materials 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 55
- 229910052802 copper Inorganic materials 0.000 claims abstract description 55
- 239000010949 copper Substances 0.000 claims abstract description 55
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 34
- 238000004070 electrodeposition Methods 0.000 claims abstract description 29
- 229910052751 metal Inorganic materials 0.000 claims abstract description 24
- 239000002184 metal Substances 0.000 claims abstract description 24
- 238000003466 welding Methods 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000008367 deionised water Substances 0.000 claims abstract description 15
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 239000013110 organic ligand Substances 0.000 claims abstract description 13
- 150000003839 salts Chemical class 0.000 claims abstract description 13
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 10
- 239000002923 metal particle Substances 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 230000008569 process Effects 0.000 claims abstract description 9
- 230000004913 activation Effects 0.000 claims abstract description 8
- 238000005498 polishing Methods 0.000 claims abstract description 8
- 244000137852 Petrea volubilis Species 0.000 claims abstract description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
- 239000011248 coating agent Substances 0.000 claims description 20
- 238000000576 coating method Methods 0.000 claims description 20
- 239000011259 mixed solution Substances 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 17
- 229910020888 Sn-Cu Inorganic materials 0.000 claims description 10
- 229910019204 Sn—Cu Inorganic materials 0.000 claims description 10
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 8
- 239000012300 argon atmosphere Substances 0.000 claims description 7
- 238000003763 carbonization Methods 0.000 claims description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 6
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 5
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 5
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- 229910020836 Sn-Ag Inorganic materials 0.000 claims description 2
- 229910020994 Sn-Zn Inorganic materials 0.000 claims description 2
- 229910020988 Sn—Ag Inorganic materials 0.000 claims description 2
- 229910009069 Sn—Zn Inorganic materials 0.000 claims description 2
- 239000000758 substrate Substances 0.000 abstract description 12
- 239000002245 particle Substances 0.000 abstract description 7
- 230000004888 barrier function Effects 0.000 abstract description 4
- 239000003575 carbonaceous material Substances 0.000 abstract description 4
- 230000006911 nucleation Effects 0.000 abstract description 4
- 238000010899 nucleation Methods 0.000 abstract description 4
- 229910000765 intermetallic Inorganic materials 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 17
- 238000005219 brazing Methods 0.000 description 16
- 239000000945 filler Substances 0.000 description 11
- 239000010408 film Substances 0.000 description 11
- 238000005476 soldering Methods 0.000 description 11
- 230000004907 flux Effects 0.000 description 10
- 239000013099 nickel-based metal-organic framework Substances 0.000 description 10
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 5
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 description 4
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 description 4
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 description 3
- 229910008433 SnCU Inorganic materials 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 229910007116 SnPb Inorganic materials 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000004100 electronic packaging Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910007637 SnAg Inorganic materials 0.000 description 1
- 229910005728 SnZn Inorganic materials 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 150000002611 lead compounds Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Images
Classifications
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/226—Non-corrosive coatings; Primers applied before welding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/24—Selection of soldering or welding materials proper
- B23K35/26—Selection of soldering or welding materials proper with the principal constituent melting at less than 400 degrees C
- B23K35/262—Sn as the principal constituent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/36—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest
- B23K35/3601—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest with inorganic compounds as principal constituents
- B23K35/3603—Halide salts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/36—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest
- B23K35/365—Selection of non-metallic compositions of coating materials either alone or conjoint with selection of soldering or welding materials
-
- 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
- C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/02—Electrolytic coating other than with metals with organic materials
-
- 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
- B23K2103/08—Non-ferrous metals or alloys
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Engineering & Computer Science (AREA)
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
The invention discloses an MOFs derivative interface modification layer, a preparation method thereof and application in lead-free solder modification, wherein the preparation method comprises the following steps: polishing the copper plate by using sand paper to remove an oxide film, then respectively carrying out ultrasonic activation treatment in hydrochloric acid, deionized water and ethanol, and drying in an oven; adding metal salt and organic ligand serving as metal particle sources into the mixed liquid, and carrying out ultrasonic stirring reaction; and preparing the MOFs surface modification layer by using a cathodic electrodeposition method or a hydrothermal method. According to the invention, a layer of MOFs film is uniformly grown on a substrate by using a cathode electrodeposition method and a hydrothermal reaction method, a porous carbon material is obtained after high-temperature treatment to wrap nano Ni particles, Co particles or Zn particles, the porous carbon material is used as a barrier layer in the welding process to reduce the growth rate of intermetallic compounds, the metal particles provide nucleation sites, the nucleation rate is improved, and the modification effect is fully exerted.
Description
Technical Field
The invention relates to the technical field of soldering, in particular to an MOFs derivative interface modification layer, a preparation method thereof and application thereof in lead-free solder modification.
Background
In the electronic packaging industry, SnPb solder is widely used due to its excellent properties. However, the toxicity of lead and lead compounds is a concern, and countries and regions such as japan and the european union have issued laws that prohibit the use of lead in electronic packaging. Therefore, a new lead-free solder is required to replace the conventional SnPb solder. The novel lead-free solder obtained by domestic researchers is obtained by modifying the existing lead-free solder (SnAgCu, SnZn, SnCu and SnAg), for example, the performance or the comprehensive performance of a certain aspect is improved by adding metal particles, alloy elements, rare earth elements and the like. However, the addition of these elements does not fundamentally solve the disadvantages of lead-free solders.
In recent years, methods for preparing novel lead-free solders by doping have become a bottleneck, and there are few reports on enhancing the lead-free solders by substrate surface modification. Jeong-Won Yoon et al improve the performance of Sn3.5Ag5Bi solder by chemical nickel plating on a copper substrate, and a nickel coating is used as a diffusion barrier between the solder and the substrate so as to reduce the thickness of an intermetallic compound layer and improve the welding performance of the Sn3.5Ag5Bi solder, but phosphorus is generated in the chemical plating process, and phosphorus and nickel react to form Ni in the aging process3P, reducing joint performance. Yong-Ho Ko et al improve the performance of SnCu lead-free solder by pasting graphene on a copper substrate layer by layerThe graphene is used as a barrier layer, so that mutual diffusion between the brazing filler metal and the substrate is reduced, and the welding performance is improved. At present, a substrate surface modification method with low cost, no harm and simple operation procedure is urgently needed in the market to improve the performance of the lead-free solder.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide an MOFs derivative interface modification layer, a preparation method thereof and application in lead-free solder modification.
In order to realize the purpose, the invention adopts the technical scheme that:
a preparation method of an MOFs derivative interface modification layer comprises the following steps:
step 1, polishing a copper plate by using sand paper to remove an oxide film, then respectively carrying out ultrasonic activation treatment in hydrochloric acid, deionized water and ethanol, and drying in an oven;
step 2, preparing the MOFs surface modification layer by any one of the following methods:
(1) adding metal salt and organic ligand serving as metal particle sources into the mixed liquid, and carrying out ultrasonic stirring reaction; putting the mixed solution obtained by the reaction into an electrolytic cell, performing electrodeposition on the copper plate treated in the step 1 by using a cathode electrodeposition method, and finally drying to obtain a sheet-shaped, layered or granular MOFs coating;
(2) adding metal salt and organic ligand serving as metal particle sources into the mixed liquid, and carrying out ultrasonic stirring reaction; and (2) pouring the mixed solution obtained by the reaction into a hydrothermal reaction kettle, putting the copper plate treated in the step (1) into the reaction kettle by using a hydrothermal method for reaction, and finally drying to obtain the MOFs plating layer with the sheet, layer or particle shape.
In the step 1, the drying temperature is 50-80 ℃ and the time is 6-12 h.
In the step 2, the metal salt is one or more of nickel chloride, cobalt nitrate or zinc nitrate, and the organic ligand is one or more of 2-methylimidazole and terephthalic acid; the mixed liquid is dimethylformamide, deionized water and ethanol according to the volume ratio of 1: (0.1-1): (0.1-1) the mixed liquid; the molar ratio of the metal salt to the organic ligand is 1: (0.1-1); the ultrasonic stirring reaction is carried out at room temperature for 10-20 min.
In the step 2, the voltage of cathode electrodeposition is-1.0 to-5.0V, and the electrodeposition time is 1 to 30 min.
In the step 2, the hydrothermal temperature is 80-150 ℃ and the hydrothermal time is 6-24 h.
An MOFs derivative interface modification layer prepared by the method.
The application of the MOFs derivative interface modification layer in lead-free solder modification comprises the following steps:
step a, placing an MOFs/copper plate in a tube furnace for carbonization to obtain nano metal particles @ carbon material/copper plate;
and b, putting the nano metal particles @ carbon material/copper plate obtained in the step a on a lead-free solder for welding.
In the step a, the carbonization process comprises the following steps: heating the tube furnace at 1-5 deg.C/min under the protection of argon atmosphere, and maintaining at 400-1000 deg.C for 1-8 h.
In the step b, the lead-free solder is one of Sn-Cu, Sn-Ag and Sn-Zn solder; after welding, the temperature is raised at a rate of 1-10 ℃/s, and is kept at 200 ℃ for 1-5min at 100-.
Has the advantages that: according to the invention, a layer of MOFs film is uniformly grown on a substrate by using a cathode electrodeposition method and a hydrothermal reaction method, a porous carbon material is obtained after high-temperature treatment to wrap nano Ni particles, Co particles or Zn particles, the porous carbon material is used as a barrier layer in the welding process to reduce the growth rate of intermetallic compounds, the metal particles provide nucleation sites, the nucleation rate is improved, and the modification effect is fully exerted.
Drawings
FIG. 1 is a scanning electron micrograph of electrodeposited Ni-MOF;
fig. 2 is a cross-sectional view of SnCu lead-free solder being soldered on a copper plate, wherein (a) the copper plate is unmodified and (b) the copper plate is modified with Ni-MOF.
Detailed Description
The invention discloses a preparation method of an MOFs derivative interface modification layer, which comprises the following steps:
step 1, polishing a copper plate by using sand paper to remove an oxide film, then respectively carrying out ultrasonic activation treatment in hydrochloric acid, deionized water and ethanol, and drying in an oven; wherein the drying temperature is 50-80 ℃ and the drying time is 6-12 h;
step 2, preparing the MOFs surface modification layer by any one of the following methods:
(1) adding metal salt and organic ligand serving as metal particle sources into the mixed liquid, and carrying out ultrasonic stirring reaction; putting the mixed solution obtained by the reaction into an electrolytic cell, performing electrodeposition on the copper plate treated in the step 1 by using a cathode electrodeposition method, and finally drying to obtain a sheet-shaped, layered or granular MOFs coating; wherein the cathode electrodeposition voltage is-1.0 to-5.0V, and the electrodeposition time is 1 to 30 min;
(2) adding metal salt and organic ligand serving as metal particle sources into the mixed liquid, and carrying out ultrasonic stirring reaction; pouring the mixed solution obtained by the reaction into a hydrothermal reaction kettle, putting the copper plate treated in the step 1 into the reaction kettle by using a hydrothermal method for reaction, and finally drying to obtain the sheet, layered or granular MOFs coating; wherein the hydrothermal temperature is 80-150 ℃, and the hydrothermal time is 6-24 h;
wherein, the metal salt is one or more of nickel chloride, cobalt nitrate or zinc nitrate, and the organic ligand is one or more of 2-methylimidazole and terephthalic acid; the mixed liquid is dimethylformamide, deionized water and ethanol according to the volume ratio of 1: (0.1-1): (0.1-1) the mixed liquid; the molar ratio of the metal salt to the organic ligand is 1: (0.1-1); the ultrasonic stirring reaction is carried out at room temperature for 10-20 min.
The MOFs derivative interface modification layer can be applied to lead-free solder modification, and comprises the following specific steps:
step a, placing the MOFs/copper plate in a tubular furnace for high-temperature treatment, heating the tubular furnace at 1-5 ℃/min under the protection of argon atmosphere, and preserving the heat at 400-1000 ℃ for 1-8h to obtain nano metal particles @ carbon material/copper plate;
step b, welding treatment
Placing the nano metal particles @ carbon material/copper plate in a brazing furnace, uniformly coating rosin soldering flux on the surface, coating the soldering flux on the surface of the lead-free brazing filler metal, then placing the lead-free brazing filler metal on the nano metal particles @ carbon material/copper plate for welding, wherein the heating rate is 1-10 ℃/s, keeping the temperature at 200 ℃ for 1-5min, then heating to 200 ℃ at 1-10 ℃/s, keeping the temperature at 300 ℃ for 1-10min, and cooling to room temperature by air.
The present invention will be further described with reference to the following examples.
Example 1
(1) Substrate pretreatment
And (3) polishing the copper plate by 1500-mesh sand paper to remove an oxide film, then respectively carrying out ultrasonic activation treatment for 15min in hydrochloric acid with the concentration of 2M, deionized water and ethanol, and carrying out vacuum drying treatment at 60 ℃.
(2) Ni-MOF film preparation
Uniformly mixing 40ml of dimethylformamide, 5ml of deionized water and 5ml of ethanol, and weighing 0.0415gH2Adding the mixed solution into BDC, carrying out ultrasonic treatment for 15min to dissolve the mixed solution, and then adding 0.1188g of NiCl2·6H2Dissolving by ultrasonic for 15min to form a mixed solution; and (3) then, filling the mixed solution into an electrolytic cell, and carrying out electrodeposition on the copper plate in the step (1) by using a cathode electrodeposition method, wherein the electrodeposition voltage is-1.8V, and the electrodeposition time is 4 min. And (3) cleaning the Ni-MOF/copper plate obtained after electrodeposition with ethanol for several times, and drying for 12h in an environment of 60 ℃ to obtain the Ni-MOF coating which is shown in figure 1 and is in a sheet shape.
(3) Preparation of nano Ni particle @ carbon material
And (3) placing the Ni-MOF/copper plate obtained in the step (2) into a tube furnace for high-temperature treatment, heating the tube furnace at 2 ℃/min under the protection of argon atmosphere, and preserving heat at 500 ℃ for 2h to obtain the nano Ni particles @ carbon material/copper plate.
(4) Welding process
The method comprises the steps of placing the nano Ni particles @ carbon material/copper plate in a brazing furnace, uniformly coating rosin soldering flux on the surface of the nano Ni particles @ carbon material/copper plate, coating the soldering flux on the surface of the Sn-Cu brazing filler metal, then placing the Sn-Cu brazing filler metal on the nano Ni particles @ carbon material/copper plate for welding, heating at the rate of 2.5 ℃/s, keeping the temperature at 150 ℃ for 1min, then heating to 250 ℃ at the rate of 1.5 ℃/s, keeping the temperature for 5min, and cooling to room temperature. The intermetallic cross-section after welding is shown in fig. 2.
Example 2
(1) Substrate pretreatment
And (3) polishing the copper plate by 1500-mesh sand paper to remove an oxide film, then respectively carrying out ultrasonic activation treatment for 15min in hydrochloric acid with the concentration of 2M, deionized water and ethanol, and carrying out vacuum drying treatment at 60 ℃.
(2) Ni-MOF film preparation
Uniformly mixing 16ml of dimethylformamide, 1ml of deionized water and 1ml of ethanol, and weighing 0.0623gH2Adding the mixed solution into BDC, carrying out ultrasonic treatment for 15min to dissolve the mixed solution, and then adding 0.0447g of NiCl2·6H2Dissolving by ultrasonic for 15min to form a mixed solution; and pouring the mixed solution into a 50ml hydrothermal reaction kettle, binding the copper plate obtained in the step 1 by using a raw material belt, hanging the copper plate on the inner wall of the reaction kettle, and reacting at the hydrothermal temperature of 140 ℃ for 12 hours. And washing the Ni-MOF/copper plate obtained by hydrothermal for several times by using ethanol, and drying for 12h in an environment of 60 ℃ to obtain the flaky Ni-MOF coating.
(3) Preparation of nano Ni particle @ carbon material
And (3) placing the Ni-MOF/copper plate obtained in the step (2) into a tube furnace for high-temperature treatment, heating the tube furnace at 2 ℃/min under the protection of argon atmosphere, and preserving heat at 500 ℃ for 2h to obtain the nano Ni particles @ carbon material/copper plate.
(4) Welding process
Putting the nano Ni particles @ carbon material/copper plate in a brazing furnace, uniformly coating rosin soldering flux on the surface, coating the soldering flux on the surface of the Sn-Cu brazing filler metal, then putting the Sn-Cu brazing filler metal on the nano Ni particles @ carbon material/copper plate for welding, keeping the temperature at 150 ℃ for 1min at the heating rate of 2.5 ℃/s, then keeping the temperature at 250 ℃ for 5min at the heating rate of 1.5 ℃/s, and cooling the temperature to room temperature by air.
Example 3
(1) Substrate pretreatment
And (3) polishing the copper plate by 1500-mesh sand paper to remove an oxide film, then respectively carrying out ultrasonic activation treatment for 15min in hydrochloric acid with the concentration of 2M, deionized water and ethanol, and carrying out vacuum drying treatment at 60 ℃.
(2) ZIF-67 film preparation
Uniformly mixing 40ml of dimethylformamide, 5ml of deionized water and 5ml of ethanol, weighing 0.0205g of di-methylimidazole, adding the mixture into the mixed solution, performing ultrasonic treatment for 15min to dissolve the di-methylimidazole, and adding 0.1455g of Co (NO)3)2·6H2Dissolving by ultrasonic for 15min to form a mixed solution; and (3) then, filling the mixed solution into an electrolytic cell, and carrying out electrodeposition on the copper plate in the step (1) by using a cathode electrodeposition method, wherein the electrodeposition voltage is-1.8V, and the electrodeposition time is 4 min. And (3) washing the ZIF-67/copper plate obtained after electrodeposition with ethanol for several times, and drying at 70 ℃ for 12h to obtain a granular ZIF-67 coating.
(3) Preparation of nano Co particle @ carbon material
And (3) putting the ZIF-67/copper plate obtained in the step (2) into a tube furnace for carbonization, heating the tube furnace at 2 ℃/min under the protection of argon atmosphere, and keeping the temperature at 650 ℃ for 2h to obtain the nano Co particles @ carbon material/copper plate.
(4) Welding process
Placing the nano Co particles @ carbon material/copper plate in a brazing furnace, uniformly coating rosin soldering flux on the surface, coating the soldering flux on the surface of the Sn-Cu brazing filler metal, then placing the Sn-Cu brazing filler metal on the nano Co particles @ carbon material/copper plate for welding, wherein the heating rate is 2.5 ℃/s, keeping the temperature at 150 ℃ for 1min, then heating to 250 ℃ at 1.5 ℃/s, keeping the temperature for 5min, and cooling to room temperature by air.
Example 4
(1) Substrate pretreatment
And (3) polishing the copper plate by 1500-mesh abrasive paper to remove an oxide film, then respectively performing ultrasonic activation treatment in hydrochloric acid with the concentration of 2M, deionized water and ethanol for 15min, and performing vacuum drying treatment at 60 ℃.
(2) ZIF-8 film preparation
Uniformly mixing 40ml of dimethylformamide, 5ml of deionized water and 5ml of ethanol, weighing 0.0205g of di-methylimidazole, adding into the mixed solution, dissolving by ultrasonic treatment for 15min, and adding 0.1487gZn (NO)3)2·6H2Dissolving by ultrasonic for 15min to form a mixed solution; subsequently, the mixed solution was charged into an electrolytic cell, and the copper plate in step (1) was electrodeposited by using a cathodeCarrying out electrodeposition with the electrodeposition voltage of-1.8V and the electrodeposition time of 4 min. And (3) washing the ZIF-8/copper plate obtained after electrodeposition with ethanol for several times, and drying at 70 ℃ for 12h to obtain a granular ZIF-8 coating.
(3) Preparation of nano Zn particle @ carbon material
And (3) putting the ZIF-8/copper plate obtained in the step (2) into a tube furnace for carbonization, heating the tube furnace at 2 ℃/min under the protection of argon atmosphere, and keeping the temperature at 600 ℃ for 2h to obtain the nano Zn particle @ carbon material/copper plate.
(4) Welding process
Putting the nano Zn particles @ carbon material/copper plate in a brazing furnace, uniformly coating rosin soldering flux on the surface, coating the soldering flux on the surface of the Sn-Cu brazing filler metal, then putting the Sn-Cu brazing filler metal on the nano Zn particles @ carbon material/copper plate for welding, keeping the temperature at 150 ℃ for 1min at the heating rate of 2.5 ℃/s, then keeping the temperature at 250 ℃ for 5min at the heating rate of 1.5 ℃/s, and cooling the temperature to room temperature by air.
The above description is only of the preferred embodiments of the present invention, and it should be noted that: it will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the principles of the invention and these are intended to be within the scope of the invention.
Claims (10)
1. A preparation method of an MOFs derivative interface modification layer is characterized by comprising the following steps: the method comprises the following steps:
step 1, polishing a copper plate by using sand paper to remove an oxide film, then respectively carrying out ultrasonic activation treatment in hydrochloric acid, deionized water and ethanol, and drying in an oven;
step 2, preparing the MOFs surface modification layer by any one of the following methods:
(1) adding metal salt and organic ligand serving as metal particle sources into the mixed liquid, and carrying out ultrasonic stirring reaction; putting the mixed solution obtained by the reaction into an electrolytic cell, performing electrodeposition on the copper plate treated in the step (1) by using a cathode electrodeposition method, and finally drying to obtain a sheet-shaped, layered or granular MOFs coating;
(2) adding metal salt and organic ligand serving as metal particle sources into the mixed liquid, and carrying out ultrasonic stirring reaction; and (3) pouring the mixed solution obtained by the reaction into a hydrothermal reaction kettle, putting the copper plate treated in the step (1) into the reaction kettle by using a hydrothermal method for reaction, and finally drying to obtain the sheet, layered or granular MOFs coating.
2. The method of preparing a MOFs derivative interface modification layer according to claim 1, wherein: in the step 1, the drying temperature is 50-80 ℃ and the time is 6-12 h.
3. The method for preparing an interface modification layer of MOFs derivatives according to claim 1, wherein: in the step 2, the metal salt is one or more of nickel chloride, cobalt nitrate or zinc nitrate, and the organic ligand is one or more of 2-methylimidazole and terephthalic acid; the mixed liquid is dimethylformamide, deionized water and ethanol according to the volume ratio of 1: (0.1-1): (0.1-1) the mixed liquid; the molar ratio of the metal salt to the organic ligand is 1: (0.1-1); the ultrasonic stirring reaction is carried out at room temperature for 10-20 min.
4. The method for preparing an interface modification layer of MOFs derivatives according to claim 1, wherein: in the step 2, the voltage of cathode electrodeposition is-1.0 to-5.0V, and the electrodeposition time is 1 to 30 min.
5. The method of preparing a MOFs derivative interface modification layer according to claim 1, wherein: in the step 2, the hydrothermal temperature is 80-150 ℃ and the hydrothermal time is 6-24 h.
6. An interface modification layer of MOFs derivatives prepared by the method of claim 1.
7. Use of the MOFs derivative interface modification layer according to claim 6 for lead-free solder modification.
8. Use according to claim 7, characterized in that: the method comprises the following steps:
step a, placing an MOFs/copper plate in a tube furnace for carbonization to obtain nano metal particles @ carbon materials/copper plates;
and b, putting the nano metal particles @ carbon material/copper plate obtained in the step a on a lead-free solder for welding.
9. Use according to claim 8, characterized in that: in the step a, the carbonization process comprises the following steps: heating the tubular furnace at 1-5 ℃/min under the protection of argon atmosphere, and keeping the temperature at 400-1000 ℃ for 1-8 h.
10. Use according to claim 8, characterized in that: in the step b, the lead-free solder is one of Sn-Cu, Sn-Ag and Sn-Zn solder; after welding, the temperature is raised at a rate of 1-10 ℃/s, and is kept at 200 ℃ for 1-5min at 100-.
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