CN115161647A - Method for improving copper surface oxidation after copper-clad ceramic substrate welding - Google Patents
Method for improving copper surface oxidation after copper-clad ceramic substrate welding Download PDFInfo
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- CN115161647A CN115161647A CN202210819764.8A CN202210819764A CN115161647A CN 115161647 A CN115161647 A CN 115161647A CN 202210819764 A CN202210819764 A CN 202210819764A CN 115161647 A CN115161647 A CN 115161647A
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- 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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/10—Other heavy metals
- C23G1/103—Other heavy metals copper or alloys of copper
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- 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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
- C23G1/20—Other heavy metals
Abstract
The invention discloses a method for improving copper surface oxidation after welding of a copper-clad ceramic substrate. The oxidation-resistant film is removed by using the processes of acid washing, water washing, alkali washing, water washing, drying and the like, so that the effect that the copper-clad ceramic substrate is not oxidized after being welded at a client is achieved. Meanwhile, modified silicon dioxide is added in the pickling process, so that concentrated sulfuric acid is prevented from corroding the copper plate and influencing the use performance. However, the copper-clad ceramic substrate without the anti-oxidation layer can cause the color difference of the copper surface, and the copper-clad ceramic substrate can be oxidized and the like under the long-term transportation and moisture contact 2 The baking process solves the problem, and the copper-clad ceramic substrate without the oxidation resistant layer, which meets the production requirement, is prepared.
Description
Technical Field
The invention relates to the technical field of copper-clad substrates, in particular to a method for improving copper surface oxidation after welding of a copper-clad ceramic substrate.
Background
The AMB refers to a process or a product for sintering a copper sheet and a ceramic chip together by using an active metal brazing material at a high temperature in vacuum, and is widely applied to the fields of electric automobiles, wind power generation, high-speed rails and the like. In order to prevent the products from being oxidized in the laser cutting process, an oxidation resisting method commonly used in the industry is as follows: a layer of nanoscale organic antioxidant film is generated on the surface of a product by using an antioxidant through a horizontal chemical line, the main component of the antioxidant is azole organic matter, lone pair electrons and copper ions of the azole organic matter are combined into a covalent bond to be attached to the surface of the product, and the purpose of isolating air and moisture is achieved. The oxidation-resistant film can also prevent the surface of the product from being slightly oxidized due to long processing time in the laser cutting process.
Although the oxidation-resistant film can effectively reduce the oxidation risk of products in the processes of cutting, packaging, transporting and storing, when a customer performs chip welding, the residual oxidation-resistant layer is easy to adsorb formic acid in the atmosphere, and the formic acid can be slowly decomposed into CO and H in the subsequent placing process 2 O, thereby causing oxidation of the copper surface to different degrees and influencing the use.
In order to remove the oxidation resistant film without influencing the surface state of the product, the invention provides a method for improving the oxidation of the copper surface after the welding of a copper-clad ceramic substrate.
Disclosure of Invention
The invention aims to provide a method for improving copper surface oxidation after welding of a copper-clad ceramic substrate, so as to solve the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme:
a method for improving copper surface oxidation after welding of a copper-clad ceramic substrate comprises the following steps:
the method comprises the following steps: preparing 10-15wt% of micro-etching liquid medicine by using sulfuric acid and hydrogen peroxide, taking the copper-clad ceramic substrate, carrying out acid washing for 50-70s and 50-70s at 25-35 ℃ by using the micro-etching liquid medicine, washing for 50-70s by using concentrated sulfuric acid, removing slight oxidation and oil stain on the surface of the copper-clad ceramic substrate, and washing for 4-5min;
step two: performing alkali washing for 400-600s at 35-45 ℃ and 35-45kHz ultrasonic frequency by using 2-4wt% of surfactant, and performing water washing for 150-210s at 35-45kHz ultrasonic frequency to obtain the copper-clad ceramic substrate without the oxidation resistant layer;
step three: and dehydrating the copper-clad ceramic substrate without the oxidation resistant layer, drying the copper-clad ceramic substrate at 90-110 ℃ for 100-140s by using nitrogen, and removing residual moisture to obtain the processed copper-clad ceramic substrate.
Preferably, the third step: and (3) carrying out slow pulling dehydration treatment on the copper-clad ceramic substrate with the oxidation resisting layer removed at 35-45 ℃ for 15-25s, taking out, placing in an isopropanol solution, carrying out IPA dehydration at 15-22 ℃, drying with nitrogen gas at 90-110 ℃ for 100-140s, and removing residual moisture to obtain the treated copper-clad ceramic substrate.
Preferably, in the first step, the concentrated sulfuric acid contains modified silica.
Preferably, the preparation method of the modified silica comprises the following steps: taking silicon dioxide loaded with a corrosion inhibitor and N, N-dimethylformamide, carrying out ultrasonic dispersion for 50-70min, adding hexadecyl trimethoxy silane and triethylamine under the protection of nitrogen, reacting for 22-26h at 100-110 ℃, filtering, washing and drying to obtain the modified silicon dioxide.
Preferably, the preparation method of the silica loaded with the corrosion inhibitor comprises the following steps: taking deionized water and ethanol, stirring uniformly, adding ammonia water to adjust the pH value to 9.5-10.5, adding fatty alcohol-polyoxyethylene ether and benzotriazole, stirring uniformly, heating to 50-60 ℃, adding n-silicon ethyl acetate, reacting for 16-20h, filtering, washing and drying to obtain the silicon dioxide loaded with the corrosion inhibitor.
Preferably, the pH value of the surfactant is 10-10.5.
Preferably, the preparation method of the surfactant comprises the following steps: adding monoethanolamine into deionized water, stirring uniformly, adding ethylene glycol monobutyl ether, and stirring uniformly to obtain the surfactant.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention provides a method for improving copper surface oxidation after welding a copper-clad ceramic substrate, which uses the processes of acid washing, water washing, alkali washing, water washing, drying and the likeThe oxidation-resistant film is removed, so that the effect that the copper-clad ceramic substrate is not oxidized after being welded at a client is achieved. However, the copper-clad ceramic substrate without the anti-oxidation layer can cause the color difference of the copper surface, and the copper-clad ceramic substrate can be oxidized and the like under the long-term transportation and moisture contact 2 The baking solves the problem, and the copper-clad ceramic substrate without the oxidation resistant layer is prepared.
(2) Preparing the silica carrying the corrosion inhibitor, modifying the silica, and grafting long-chain alkyl on the silica so that the modified silica has lipophilicity. The modified silicon dioxide is added in the pickling process, the pickling time of concentrated sulfuric acid is controlled within 70s, slight oxidation and oil stains on the surface of the copper-clad ceramic substrate are effectively removed, over-corrosion of a copper sheet in the pickling process is prevented, and the copper sheet can be easily removed by a hydrophilic and oleophilic surfactant in the alkali washing process, so that the processability of the copper-clad substrate is improved.
(3) The oxidation resistant film and the modified silicon dioxide layer are complex compounds generated by the reaction of copper ions and azole organic matters, and during alkaline cleaning, an alkaline surfactant is used, and the alkaline surfactant contains water and organic alkali: monoethanolamine and surfactant: ethylene glycol monobutyl ether has the amphiphilic property of hydrophile lipophile, lipophilicity ensures that an organic membrane can be dissolved in the organic membrane after the ethylene glycol monobutyl ether is contacted with the surface of the organic membrane, and the hydrophile ensures that the removed objects can be cleaned in subsequent washing at all levels, thereby finally realizing the removal of an antioxidation layer and a modified silicon dioxide layer.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The method comprises the following steps: preparing 13wt% of microetching liquid medicine by taking sulfuric acid and hydrogen peroxide, taking the copper-clad ceramic substrate, carrying out acid washing for 60s and 60s at 30 ℃ by using the microetching liquid medicine, carrying out acid washing for 60s by using 4wt% of concentrated sulfuric acid, removing slight oxidation and oil stain on the surface of the copper-clad ceramic substrate, and washing for 4.5min.
Step two: preparation of the surfactant: adding 6L of monoethanolamine into 90L of deionized water, stirring uniformly, adding 150mL of ethylene glycol monobutyl ether, and stirring uniformly to obtain the surfactant.
Step three: and (3) carrying out alkali washing for 500s at 40 ℃ and 40kHz ultrasonic frequency by using a surfactant, and washing for 170s at 40kHz ultrasonic frequency to obtain the copper-clad ceramic substrate with the oxidation-resistant layer removed.
Step four: and (3) carrying out slow pulling dehydration treatment on the copper-clad ceramic substrate with the oxidation resisting layer removed at 40 ℃ for 20s, taking out, placing in an isopropanol solution, carrying out IPA dehydration at 17 ℃, drying with nitrogen gas at 100 ℃ for 120s, and removing residual moisture to obtain the treated copper-clad ceramic substrate.
Example 2
The method comprises the following steps: preparing a 10wt% microetching liquid medicine from sulfuric acid and hydrogen peroxide, taking the copper-clad ceramic substrate, carrying out acid washing for 50s and 50s at 25 ℃ by using the microetching liquid medicine, carrying out acid washing for 50s by using 4wt% concentrated sulfuric acid for 50s, removing slight oxidation and oil stains on the surface of the copper-clad ceramic substrate, and washing for 4min.
Step two: preparation of the surfactant: adding 5L of monoethanolamine into 80L of deionized water, stirring uniformly, adding 100mL of ethylene glycol monobutyl ether, and stirring uniformly to obtain the surfactant.
Step three: and (3) carrying out alkali washing for 400s at 35 ℃ and 35kHz ultrasonic frequency by using a surfactant, and washing for 150s at 35kHz ultrasonic frequency to obtain the copper-clad ceramic substrate with the oxidation-resistant layer removed.
Step four: and (3) carrying out slow pulling dehydration treatment on the copper-clad ceramic substrate with the oxidation resisting layer removed at 35 ℃ for 15s, taking out, placing in an isopropanol solution, carrying out IPA dehydration at 15 ℃, drying for 100s with nitrogen at 90 ℃, and removing residual moisture to obtain the treated copper-clad ceramic substrate.
Example 3
The method comprises the following steps: preparing a microetching liquid medicine with the concentration of 15wt% by using sulfuric acid and hydrogen peroxide, carrying out acid washing on the copper-clad ceramic substrate for 70s at 35 ℃ by using the microetching liquid medicine, washing the copper-clad ceramic substrate for 70s by using water, carrying out acid washing on the copper-clad ceramic substrate for 70s by using concentrated sulfuric acid with the concentration of 4wt%, removing slight oxidation and oil stains on the surface of the copper-clad ceramic substrate, and washing the copper-clad ceramic substrate for 5min by using water.
Step two: preparation of the surfactant: adding 8L of monoethanolamine into 100L of deionized water, stirring uniformly, adding 200mL of ethylene glycol monobutyl ether, and stirring uniformly to obtain the surfactant.
Step three: and (3) washing with an alkali for 600s at the ultrasonic frequency of 45kHz and with a surfactant for 210s at the ultrasonic frequency of 45kHz to obtain the copper-clad ceramic substrate with the antioxidation layer removed.
Step four: and (3) carrying out slow pulling dehydration treatment on the copper-clad ceramic substrate with the oxidation resisting layer removed at 45 ℃ for 25s, taking out, placing in an isopropanol solution, carrying out IPA dehydration at 22 ℃, drying with nitrogen gas at 110 ℃ for 140s, and removing residual moisture to obtain the treated copper-clad ceramic substrate.
Example 4: modified silica was added during the acid washing, and the rest was the same as in example 1.
The method comprises the following steps: preparation of modified silica:
taking 100mL of deionized water and 50mL of ethanol, stirring uniformly, adding ammonia water to adjust the pH value to 10, adding 0.5g of fatty alcohol-polyoxyethylene ether and 0.6g of benzotriazole (purchased from Wuhanfuxin remote science and technology Co., ltd.), stirring uniformly, heating to 55 ℃, adding 6mL of n-silicon ethyl acetate, reacting for 18 hours, filtering, washing and drying to obtain the silicon dioxide loaded with the corrosion inhibitor.
Taking 3g of silica loaded with a corrosion inhibitor, 100mLN and N-dimethylformamide, carrying out ultrasonic dispersion for 60min, adding 4g of hexadecyl trimethoxy silane and 0.5mL of triethylamine under the protection of nitrogen, reacting for 24h at 105 ℃, filtering, washing and drying to obtain the modified silica.
Step two: preparing 13wt% microetching liquid medicine by taking sulfuric acid and hydrogen peroxide, taking a copper-clad ceramic substrate, and carrying out acid washing for 60s and water washing for 60s at 30 ℃ by using the microetching liquid medicine; taking concentrated sulfuric acid with the concentration of 4wt%The concentration of the extract was 120 mg/kg -1 The modified silicon dioxide is prepared into a concentrated sulfuric acid solution with the concentration of 4wt% containing the modified silicon dioxide, the concentrated sulfuric acid solution containing the modified silicon dioxide is used for acid washing for 60s, slight oxidation and oil stain on the surface of the copper-clad ceramic substrate are removed, and the water washing is carried out for 4.5min.
Step three: preparation of the surfactant: adding 6L of monoethanolamine into 90L of deionized water, stirring uniformly, adding 150mL of ethylene glycol monobutyl ether, and stirring uniformly to obtain the surfactant.
Step four: and (3) carrying out alkali washing for 500s at 40 ℃ and 40kHz ultrasonic frequency by using a surfactant, and washing for 170s at 40kHz ultrasonic frequency to obtain the copper-clad ceramic substrate with the oxidation-resistant layer removed.
Step five: and (3) carrying out slow-pull dehydration treatment on the copper-clad ceramic substrate with the oxidation resisting layer removed at 40 ℃ for 20s, taking out, placing in an isopropanol solution, carrying out IPA dehydration at 17 ℃, drying with nitrogen at 100 ℃ for 120s, and removing residual moisture to obtain the treated copper-clad ceramic substrate.
Example 5: the modified silica was added during the acid washing, and the rest was the same as in example 1.
The method comprises the following steps: preparation of modified silica:
taking 100mL of deionized water and 50mL of ethanol, stirring uniformly, adding ammonia water to adjust the pH value to 9.5, adding 0.5g of fatty alcohol-polyoxyethylene ether and 0.6g of benzotriazole (purchased from Wuhanfuxin far-tech Co., ltd.), stirring uniformly, heating to 50 ℃, adding 6mL of ethyl n-silacetate, reacting for 16h, filtering, washing and drying to obtain the silicon dioxide loaded with the corrosion inhibitor.
Taking 3g of silica loaded with a corrosion inhibitor, 100mLN and N-dimethylformamide, carrying out ultrasonic dispersion for 50min, adding 4g of hexadecyl trimethoxy silane and 0.5mL of triethylamine under the protection of nitrogen, reacting for 22h at 100 ℃, filtering, washing and drying to obtain the modified silica.
Step two: preparing 13wt% microetching solution from sulfuric acid and hydrogen peroxide, pickling copper-coated ceramic substrate with the microetching solution at 30 deg.C for 60s, washing with water for 60s, collecting 4wt% concentrated sulfuric acid and 120 mg/kg -1 The modified silicon dioxide is prepared into a concentrated sulfuric acid solution with the concentration of 4wt% containing the modified silicon dioxide, the concentrated sulfuric acid solution containing the modified silicon dioxide is used for pickling for 60s, slight oxidation and oil stain on the surface of the copper-clad ceramic substrate are removed, and the copper-clad ceramic substrate is washed with water for 4.5min.
Step three: preparation of the surfactant: adding 6L of monoethanolamine into 90L of deionized water, stirring uniformly, adding 150mL of ethylene glycol monobutyl ether, and stirring uniformly to obtain the surfactant.
Step four: and (3) carrying out alkali washing for 500s by using an alkali surfactant at 40 ℃ and the ultrasonic frequency of 40kHz, and washing for 170s at the ultrasonic frequency of 40kHz to obtain the copper-clad ceramic substrate with the antioxidation layer removed.
Step five: and (3) carrying out slow pulling dehydration treatment on the copper-clad ceramic substrate with the oxidation resisting layer removed at 40 ℃ for 20s, taking out, placing in an isopropanol solution, carrying out IPA dehydration at 17 ℃, drying with nitrogen gas at 100 ℃ for 120s, and removing residual moisture to obtain the treated copper-clad ceramic substrate.
Example 6: the modified silica was added during the acid washing, and the rest was the same as in example 1.
The method comprises the following steps: preparation of modified silica:
taking 100mL of deionized water and 50mL of ethanol, stirring uniformly, adding ammonia water to adjust the pH value to 10.5, adding 0.5g of fatty alcohol-polyoxyethylene ether and 0.6g of benzotriazole (purchased from Wuhanfuxin remote science and technology Co., ltd.), stirring uniformly, heating to 60 ℃, adding 6mL of n-silicon ethyl acetate, reacting for 20 hours, filtering, washing, and drying to obtain the silicon dioxide loaded with the corrosion inhibitor.
Taking 3g of silica loaded with a corrosion inhibitor, 100mLN and N-dimethylformamide, ultrasonically dispersing for 70min, adding 4g of hexadecyl trimethoxy silane and 0.5mL of triethylamine under the protection of nitrogen, reacting for 26h at 110 ℃, filtering, washing and drying to obtain the modified silica.
Step two: preparing 13wt% microetching solution from sulfuric acid and hydrogen peroxide, pickling copper-coated ceramic substrate with the microetching solution at 30 deg.C for 60s, washing with water for 60s, and collecting 4wt% concentrated sulfuric acid and 120 mg/kg -1 The modified silicon dioxide is prepared into a concentrated sulfuric acid solution with the concentration of 4wt% containing the modified silicon dioxide, the concentrated sulfuric acid solution containing the modified silicon dioxide is used for acid washing for 60s, slight oxidation and oil stain on the surface of the copper-clad ceramic substrate are removed, and the water washing is carried out for 4.5min.
Step three: preparation of the surfactant: adding 6L of monoethanolamine into 90L of deionized water, stirring uniformly, adding 150mL of ethylene glycol monobutyl ether, and stirring uniformly to obtain the surfactant.
Step four: and (3) carrying out alkali washing for 500s at 40 ℃ and 40kHz ultrasonic frequency by using a surfactant, and washing for 170s at 40kHz ultrasonic frequency to obtain the copper-clad ceramic substrate with the oxidation-resistant layer removed.
Step five: and (3) carrying out slow pulling dehydration treatment on the copper-clad ceramic substrate with the oxidation resisting layer removed at 40 ℃ for 20s, taking out, placing in an isopropanol solution, carrying out IPA dehydration at 17 ℃, drying with nitrogen gas at 100 ℃ for 120s, and removing residual moisture to obtain the treated copper-clad ceramic substrate.
Comparative example 1: the procedure was as in example 1 except that the solution was not washed with alkali.
The method comprises the following steps: preparing 13wt% of microetching liquid medicine by taking sulfuric acid and hydrogen peroxide, taking the copper-clad ceramic substrate, carrying out acid washing for 60s and 60s at 30 ℃ by using the microetching liquid medicine, carrying out acid washing for 60s by using 4wt% of concentrated sulfuric acid, removing slight oxidation and oil stain on the surface of the copper-clad ceramic substrate, and washing for 4.5min.
Step two: and (3) carrying out slow-pull dehydration treatment on the copper-clad ceramic substrate at 40 ℃ for 20s, taking out, placing in an isopropanol solution, carrying out IPA dehydration at 17 ℃, drying with nitrogen at 100 ℃ for 120s, and removing residual moisture to obtain the treated copper-clad ceramic substrate.
Comparative example 2: the corrosion inhibitor-loaded silica was not modified, and the procedure was otherwise the same as in example 4.
The method comprises the following steps: preparation of modified silica:
taking 100mL of deionized water and 50mL of ethanol, stirring uniformly, adding ammonia water to adjust the pH value to 10, adding 0.5g of fatty alcohol-polyoxyethylene ether and 0.6g of benzotriazole (purchased from Wuhanfuxin remote science and technology Co., ltd.), stirring uniformly, heating to 55 ℃, adding 6mL of n-silicon ethyl acetate, reacting for 18 hours, filtering, washing and drying to obtain the silicon dioxide loaded with the corrosion inhibitor.
Step two: preparing 13wt% microetching liquid medicine by using sulfuric acid and hydrogen peroxide, and performing acid washing on the copper-clad ceramic substrate for 60s at 30 ℃ and water washing for 60s by using the microetching liquid medicine; taking 4wt% concentrated sulfuric acid, 120mg kg -1 The silicon dioxide loaded with the corrosion inhibitor is prepared into a concentrated sulfuric acid solution with the concentration of 4wt% containing modified silicon dioxide, the concentrated sulfuric acid solution containing the modified silicon dioxide is used for pickling for 60s, slight oxidation and oil stain on the surface of the copper-clad ceramic substrate are removed, and the copper-clad ceramic substrate is washed for 4.5min.
Step three: preparation of the surfactant: adding 6L of monoethanolamine into 90L of deionized water, stirring uniformly, adding 150mL of ethylene glycol monobutyl ether, and stirring uniformly to obtain the surfactant.
Step four: and (3) carrying out alkali washing for 500s at 40 ℃ and 40kHz ultrasonic frequency by using a surfactant, and washing for 170s at 40kHz ultrasonic frequency to obtain the copper-clad ceramic substrate with the antioxidation layer removed.
Step five: and (3) carrying out slow pulling dehydration treatment on the copper-clad ceramic substrate with the oxidation resisting layer removed at 40 ℃ for 20s, taking out, placing in an isopropanol solution, carrying out IPA dehydration at 17 ℃, drying with nitrogen gas at 100 ℃ for 120s, and removing residual moisture to obtain the treated copper-clad ceramic substrate.
Experiment 1
The copper-clad ceramic substrates prepared in examples 1 to 6, comparative example 1 and comparative example 2 were subjected to a performance test. Heating a heating platform of a vacuum eutectic furnace to 160 ℃, keeping the temperature for 10min, directly placing the copper-clad ceramic substrate on the heating platform of the vacuum eutectic furnace, introducing formic acid for 2min, heating the formic acid to 300 ℃ at a flow rate of 4L/min, keeping the temperature for 20min in a high-temperature stage, cooling, taking out, and observing the surface oxidation condition of the copper-clad ceramic substrate.
Reacting for 1h, taking out, and observing the surface oxidation condition of the copper-clad ceramic substrate.
And (4) conclusion: as can be seen from the data in the table, comparative example 1 has no alkali washing step, does not remove the surface antioxidation layer, and the surface of the copper-clad ceramic substrate is oxidized in the subsequent processing, thereby affecting the processing performance. Comparative example 2 the silica film layer loaded with the corrosion inhibitor cannot be completely cleaned in the alkali washing process, and the surface of the copper-coated ceramic substrate is oxidized in the subsequent processing, so that the subsequent processing treatment is influenced.
Experiment 2
Two copper plates with the size of 4cm multiplied by 3cm multiplied by 0.2cm are taken, weighed and subjected to a corrosion resistance test. Soaking the sample 1 in 4wt% sodium chloride solution for 5 days; sample 2 was placed in a 120 mg.kg addition -1 Is immersed in a 3% by weight sodium chloride solution for 5 days, taken out, washed, dried and weighed, the data obtained being as shown in the following table:
| corrosion inhibition efficiency% | |
| Sample No. 1 | 26.2 |
| Sample No. 2 | 91.7 |
And (4) conclusion: as can be seen from the data in the table, the modified silicon dioxide loaded with benzotriazole in sample 2 can play a role in corrosion resistance.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. A method for improving copper surface oxidation after copper-clad ceramic substrate welding is characterized in that: the method comprises the following steps:
the method comprises the following steps: preparing 10-15wt% of micro-etching liquid medicine by using sulfuric acid and hydrogen peroxide, taking the copper-clad ceramic substrate, carrying out acid washing for 50-70s and 50-70s at 25-35 ℃ by using the micro-etching liquid medicine, washing for 50-70s by using concentrated sulfuric acid, removing slight oxidation and oil stain on the surface of the copper-clad ceramic substrate, and washing for 4-5min;
step two: performing alkali washing for 400-600s at 35-45 ℃ and 35-45kHz ultrasonic frequency by using 2-4wt% of surfactant, and performing water washing for 150-210s at 35-45kHz ultrasonic frequency to obtain the copper-clad ceramic substrate without the oxidation resistant layer;
step three: and dehydrating the copper-clad ceramic substrate without the antioxidation layer, drying the copper-clad ceramic substrate at 90-110 ℃ for 100-140s by using nitrogen, and removing residual moisture to obtain the treated copper-clad ceramic substrate.
2. The method for improving the copper surface oxidation of the copper-clad ceramic substrate after welding according to claim 1, wherein the method comprises the following steps: the third step is that: and (3) carrying out slow pulling dehydration treatment on the copper-clad ceramic substrate with the oxidation resisting layer removed at 35-45 ℃ for 15-25s, taking out, placing in an isopropanol solution, carrying out IPA dehydration at 15-22 ℃, drying with nitrogen gas at 90-110 ℃ for 100-140s, and removing residual moisture to obtain the treated copper-clad ceramic substrate.
3. The method for improving copper surface oxidation after welding of the copper-clad ceramic substrate according to claim 1, wherein the method comprises the following steps: in the first step, the concentrated sulfuric acid contains modified silicon dioxide.
4. The method for improving copper surface oxidation after welding of the copper-clad ceramic substrate according to claim 3, wherein the method comprises the following steps: the preparation method of the modified silicon dioxide comprises the following steps: taking silicon dioxide loaded with a corrosion inhibitor and N, N-dimethylformamide, carrying out ultrasonic dispersion for 50-70min, adding hexadecyl trimethoxy silane and triethylamine under the protection of nitrogen, reacting for 22-26h at 100-110 ℃, filtering, washing and drying to obtain the modified silicon dioxide.
5. The method for improving copper surface oxidation after welding of the copper-clad ceramic substrate according to claim 4, wherein the method comprises the following steps: the preparation method of the corrosion inhibitor-loaded silicon dioxide comprises the following steps: taking deionized water and ethanol, stirring uniformly, adding ammonia water to adjust the pH value to 9.5-10.5, adding fatty alcohol-polyoxyethylene ether and benzotriazole, stirring uniformly, heating to 50-60 ℃, adding n-silicon ethyl acetate, reacting for 16-20h, filtering, washing and drying to obtain the silicon dioxide loaded with the corrosion inhibitor.
6. The method for improving the copper surface oxidation of the copper-clad ceramic substrate after welding according to claim 1, wherein the method comprises the following steps: the pH value of the surfactant is 10-10.5.
7. The method for improving copper surface oxidation after welding of the copper-clad ceramic substrate according to claim 1, wherein the method comprises the following steps: the preparation method of the surfactant comprises the following steps: and adding monoethanolamine into deionized water, uniformly stirring, adding ethylene glycol monobutyl ether, and uniformly stirring to obtain the surfactant.
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