WO2020034929A1 - Procédé de traitement électrochimique anti-oxydation destiné à un matériau cuivreux - Google Patents

Procédé de traitement électrochimique anti-oxydation destiné à un matériau cuivreux Download PDF

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WO2020034929A1
WO2020034929A1 PCT/CN2019/100291 CN2019100291W WO2020034929A1 WO 2020034929 A1 WO2020034929 A1 WO 2020034929A1 CN 2019100291 W CN2019100291 W CN 2019100291W WO 2020034929 A1 WO2020034929 A1 WO 2020034929A1
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formate
electrochemical
copper foil
copper
reconstruction
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PCT/CN2019/100291
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Chinese (zh)
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郑南峰
彭健
吴炳辉
毛和旭
郝树强
符昂
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厦门大学
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    • 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

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  • the invention belongs to the field of material surface treatment, and particularly relates to an oxidation-resistant electrochemical treatment method for a copper material.
  • Copper is one of the oldest base metal materials used by humans. Copper has very good electrical conductivity (second only to silver), thermal conductivity, excellent formability and lower price, and is widely used in the fields of electrical power industry, machinery and vehicle manufacturing industry, chemical industry, construction industry, defense industry, etc. . However, copper materials are easily oxidized in the natural environment, and the surface is easily corroded, thereby degrading their physical and chemical properties, which manifests as a rapid decline in electrical and thermal conductivity, which limits their applications.
  • the main anti-oxidation and anti-corrosion surface treatment methods of copper are:
  • a relatively inert metal such as gold, palladium, silver, or chromium, is plated on the surface of the copper material by chemical plating or vacuum evaporation.
  • organic stabilizers introduce a small amount of organic stabilizers, such as amines, aldehydes, phenols, and carboxylic acids, to reduce the oxide film on the surface of the copper material to metallic copper and inhibit its oxidation.
  • organic stabilizers such as amines, aldehydes, phenols, and carboxylic acids
  • CN105970261A discloses a chrome-free treatment process for preventing oxidation of copper foil. Specifically, the copper foil electroplated from the green foil is subjected to a pickling pretreatment, followed by a roughening process, Curing process, blackening process, galvanizing process, oxidation prevention process, organic film process and drying process. While improving the oxidation resistance of copper foil, the use of chrome metal and other harmful elements to the human body and the environment is avoided. However, zinc sulphate and other environmentally hazardous metals are introduced during the operation, and higher temperatures are required for drying. At the same time, the operation steps are complicated, and a long cycle will inevitably bring a lot of costs.
  • EP0541997A2 discloses a surface treatment method of copper foil for printed circuits.
  • the surface of the copper foil is plated with a passivation film of chromium oxide or zinc oxide, which can resist 270 ° C. high temperature.
  • chromium oxide or zinc oxide which can resist 270 ° C. high temperature.
  • CN106399996A discloses a copper foil anti-oxidation treatment liquid, a preparation method and a device thereof.
  • the copper foil anti-oxidation treatment liquid contains oil hydroxybenzotriazole, 0.05-0.1 g / L, 2-mercaptobenzotriazole 0.02 ⁇ 0.05g / L, silver nitrate 0.1 ⁇ 0.5g / L, sodium molybdate 0.1 ⁇ 0.5g / L, phosphoric acid 0.05 ⁇ 0.1g / L, boric acid 0.5 ⁇ 3g / L, the rest For pure water.
  • the obtained anti-oxidation passivation film is stable under high temperature conditions and does not contain zinc metal, which solves the problems of instability such as reduction in resistance of copper foil.
  • this method improves the oxidation resistance of copper powder, it is necessary to add expensive reagents such as benzotriazole and silver nitrate, which will inevitably bring cost increase.
  • the purpose of the present invention is to overcome the above drawbacks of anti-oxidation treatment of copper materials by using existing methods, and to provide a new anti-oxidation electrochemical treatment method of copper materials.
  • the present invention provides a method for electrochemically treating a copper material against oxidation.
  • the method includes using the copper material as a working electrode, and sequentially performing electrochemical reconstruction and electrochemical deposition in an electrolyte containing a stabilizer.
  • the stabilizer is a compound capable of providing formate, so that formate is adsorbed on the surface of the copper material.
  • the electrochemical treatment usually uses a three-electrode system, wherein the working electrode is a copper material, the reference electrode is preferably a saturated calomel electrode, and the counter electrode is preferably at least one of a platinum electrode, a graphite electrode, and a glassy carbon electrode.
  • the electrolyte is a mixed solution of a stabilizer and a polar solvent.
  • the weight ratio of the stabilizer to the polar solvent is from 1:10 to 1: 100, and more preferably from 1:15 to 1:90.
  • the stabilizer can be various existing compounds capable of providing formate, preferably formic acid and / or formate.
  • the specific examples of the formate include, but are not limited to, lithium formate, sodium formate, cesium formate, magnesium formate, aluminum triformate, potassium formate, ammonium formate, calcium formate, zinc formate, iron formate, copper formate, and strontium formate. At least one of barium formate, beryllium formate, nickel formate, cobalt formate, and manganese formate.
  • the mass ratio of the stabilizer to the copper material is preferably 10: 1 to 1: 10000.
  • the type of the polar solvent is not particularly limited in the present invention, and may be water and / or various polar organic solvents, and is preferably selected from water, amide solvents, alcohol solvents, ester solvents, and ethers. At least one of solvents.
  • the specific examples of the amide-based solvent include, but are not limited to, at least one of formamide, dimethylformamide, diethylformamide, dimethylacetamide, diethylacetamide, and dimethylpropionamide.
  • Specific examples of the alcohol-based solvent include, but are not limited to, at least one of a monohydric alcohol, a dihydric alcohol, and a polyhydric alcohol.
  • ester-based solvent examples include, but are not limited to, ethyl acetate, methyl acetate, n-butyl acetate, n-pentyl acetate, ethyl valerate, ethyl propionate, ethyl butyrate, ethyl lactate, At least one of ethyl nonanoate, triethyl phosphate, ethyl hexanoate, ethyl formate, ethyl cyclohexanoate, ethyl heptanoate and ethyl cinnamate.
  • ether-based solvent include, but are not limited to, at least one of methyl ether, diethyl ether, diphenyl ether, ethylene oxide, and tetrahydrofuran.
  • the pH of the electrolyte ranges from 4 to 13, and more preferably from 5 to 11.
  • the method for adjusting the pH of the electrolyte to the above range may generally include adding an acid or an alkali to the electrolyte. The specific operation is well known to those skilled in the art, and details are not described herein.
  • the purpose of the electrochemical reconstruction is to restructure the crystal plane of the copper material, so that it is at least partially converted from the original (111) or (100) crystal plane to the (110) crystal plane, so as to facilitate subsequent electrochemical deposition.
  • the electrochemical reconstruction may use at least one of cyclic voltammetry, square wave voltammetry, and differential pulse voltammetry.
  • the electrochemical window of the electrochemical reconstruction is preferably -5V to 5V, more preferably -2V to 1V, and most preferably -1V to 0.5V; the scanning speed is preferably 10 -1 to 10 3 mV / s, and more preferably It is 1 to 10 2 mV / s, and most preferably 5 to 20 mV / s.
  • the temperature of the electrochemical reconstruction is preferably -70 to 200 ° C, more preferably 10 to 100 ° C, and most preferably room temperature to 60 ° C.
  • the number of scanning cycles is preferably 1 to 1000 cycles, more preferably 1 to 100 cycles, and most preferably 1 to 10 cycles.
  • the purpose of the electrochemical deposition is to make the formate in the electrolyte adhere to the surface of the copper material by electroplating.
  • the electrochemical deposition may use at least one of a constant potential deposition method, a constant current deposition method, and an underpotential deposition method.
  • the potential range of the potentiostatic deposition method is preferably -5V to 5V, more preferably -5V to 0V, and most preferably -2V to 0V
  • the current range of the constant current deposition method is preferably 10 -3 to 10 3 mA / cm 2 , more preferably 10 -2 to 10 2 mA / cm 2 , and most preferably 10 -1 to 10 1 mA / cm 2 .
  • the temperature of the electrochemical deposition is preferably -70 to 200 ° C, more preferably 0 to 200 ° C, and most preferably room temperature to 60 ° C.
  • the time is preferably 0.1 to 1000min, more preferably 1 to 100min, and most preferably It is 5 to 30 minutes.
  • the electrochemical reconstruction and electrochemical deposition may adopt a sealed type or an open type, preferably a sealed type, so as to reduce external interference.
  • the present invention does not specifically limit the type of the copper-containing material, and it can be any existing copper material, including pure copper materials (copper copper, brass), copper alloys, etc., which can be specifically selected from copper foil, At least one of foamed copper, copper powder, copper cable, copper faucet, copper nanowire, and copper wire.
  • the present invention adopts an electrochemical method to allow formate to be plated on the surface of a copper material, and to achieve the adsorption of formate through the synergistic effect of electrochemical reconstruction and electrochemical deposition, thereby enhancing the oxidation resistance of the copper material.
  • the electrochemically treated copper material of the present invention has stronger oxidation resistance (including high temperature oxidation resistance), salt and alkali corrosion resistance and higher electrical conductivity than before treatment, and can be used for electric wires, printed circuit boards, and motors. , Transformers, sanitary and other fields.
  • the invention has simple operation, mild conditions, and low cost, and can achieve effective oxidation and corrosion treatment of various copper materials at normal temperature.
  • the copper material processed by the method provided by the present invention has good oxidation resistance, avoids the use of potentially toxic metals such as lead, chromium, cadmium or cyanide, and complies with the relevant provisions of the Environmental Protection Law of the People's Republic of China.
  • FIG. 1 is an SEM image of the unmodified copper foil in Example 1 placed in a 0.1M NaOH solution at room temperature for 10 hours, indicating that the unmodified copper foil is easily oxidized and corroded, and the surface becomes rough.
  • FIG. 2 is an SEM image of the formate-modified copper foil in Example 1 placed at room temperature in a 0.1M NaOH solution for 10 hours at room temperature, which shows that the surface of the copper foil after the formate modification is still smooth and flat, and the oxidation resistance is significantly enhanced.
  • FIG. 3 is an optical photograph of the unmodified plated copper in Example 7 which is left at room temperature for 24 h in a 3 wt% NaCl solution, which illustrates that the unmodified plated copper is easily oxidized and corroded, and the surface is dull.
  • FIG. 4 is an optical photo of the formate-modified copper plated in Example 7 placed at room temperature for 10 hours in a 3% by weight NaCl solution, illustrating that the surface of the copper foil after the formate modification is still smooth, uniform in color, and the oxidation resistance is significantly enhanced.
  • FIG. 5 is an x-ray diffraction spectrum of the copper before and after electrochemical reconstruction of the coated copper in Example 8.
  • the peak of the (110) crystal plane of the copper after the electrochemical reconstruction is significantly enhanced, indicating that formate has induced copper surface occurrence. Refactored.
  • Figure 1 is an SEM image of unmodified copper foil placed in a 0.1M NaOH solution at room temperature for 10 hours, indicating that the unmodified copper foil is easily oxidized and corroded, so that the surface becomes rough;
  • Figure 2 is formate modified copper foil at 0.1
  • the SEM image of M in NaOH solution at room temperature for 10 hours shows that the surface of the copper foil is smooth and flat, and the oxidation resistance is significantly enhanced after formate modification.
  • Cyclic voltammetry (scanning speed: 50mV / s, scanning range: -1.5 ⁇ 0.5V) was used to scan the surface of copper foil twice at 45 ° C.
  • the surface of the copper foil was electrochemically reconstructed.
  • the copper foil before and after the electrochemical reconstruction was subjected to an x-ray diffraction test.
  • the results showed that the (110) crystal plane of the copper foil after the electrochemical reconstruction had obvious x-ray diffraction peaks.
  • the enhancement indicates that formate induces remodeling of the copper surface.
  • the cyclic voltammetry technology (scanning speed: 50mV / s, scanning range: -1.5 to 0.5V) was used to scan the copper foil surface twice at 30 ° C to perform electrochemical reconstruction of the copper foil surface and the electrochemical weight was changed.
  • X-ray diffraction tests were performed on the copper foil before and after the formation, and the results showed that the x-ray diffraction peak of the (110) crystal plane of the copper foil after electrochemical reconstruction was significantly enhanced, indicating that formate induced copper surface reconstruction.
  • the current step technology was used for electrochemical deposition at a constant potential of -0.65V for 8 minutes, washed with ethanol, and blown with nitrogen to obtain an anti-oxidation copper foil.
  • the copper foil before and after the treatment was 0.1M.
  • the SEM test was performed after leaving the solution in NaOH solution at room temperature for 10 hours. The results showed that the copper foil modified with formate had a smoother and smoother surface, and its oxidation resistance was improved.
  • the copper foil before and after the treatment was placed in a 0.1M NaOH solution at room temperature for 10 hours and then subjected to SEM tests. The results showed that the formate-modified copper foil had a smoother and smoother surface, and its oxidation resistance was improved.
  • the x-ray diffraction test of the copper foil showed that the x-ray diffraction peak of the (110) crystal plane of the copper foil was significantly enhanced after electrochemical reconstruction, indicating that formate induced the reconstruction of the copper surface.
  • a current step technology was used for electrochemical deposition at a constant potential of -0.68V for 15 minutes, and the mixture was washed with a mixed solvent of ethanol / H 2 O and dried with nitrogen to obtain an anti-oxidation copper foil.
  • the copper foil before and after the treatment was placed in a 0.1M NaOH solution at room temperature for 10 hours and then subjected to SEM tests. The results showed that the formate-modified copper foil had a smoother and smoother surface, and its oxidation resistance was improved.
  • Figure 3 is an optical photo of unmodified copper plated at room temperature in a 0.1M NaCl solution for 24 hours, illustrating that the unmodified copper plated is susceptible to oxidative corrosion and thus surface oxidation;
  • Figure 4 is a formate modified copper plated at 0.1M NaCl solution at room temperature The optical photo that was left for 10 hours showed that the surface of the copper foil was smooth and flat, and the oxidation resistance was significantly enhanced after formate modification.
  • the x-ray diffraction spectra before and after the electrochemical reconstruction of the coated copper are shown in FIG. 5. It can be seen from the results in FIG. 5 that the x-ray diffraction peak of the (110) crystal plane of the plated copper after electrochemical reconstruction is significantly enhanced, indicating that formate-induced copper surface reconstruction has occurred. Subsequent electrochemical deposition at 40 ° C with a constant potential of -0.6V for 10 min can obtain anti-oxidation coated copper. The copper before and after the treatment was placed in a 0.1M NaOH solution at room temperature for 10 hours and then subjected to SEM tests. Results It shows that the formate-modified copper has a smoother and smoother surface, and it can be seen that its oxidation resistance is improved.
  • Step 1 Surface cleaning. A copper foil with a length of 3 cm, a width of 1 cm, and a thickness of 25 m was placed in an ethanol solution of 1 wt% formic acid, washed with ultrasound for 5 minutes to remove surface organics and oxides, and dried by nitrogen purging.
  • Step two electrochemical reconstruction and electrochemical deposition.
  • Electrolyte solution prepare a 1 wt% sodium formate aqueous solution, and adjust the pH of the solution to 9;
  • Step 3 Wash with ethanol and dry.
  • the SEM test was performed after the copper foil before and after treatment in a 0.1M NaOH solution at room temperature for 10 hours. The results showed that the copper foil modified with formate had a smoother and smoother surface, and its oxidation resistance was improved.
  • Step 1 Surface cleaning. A copper foil with a length of 4 cm, a width of 2 cm, and a thickness of 30 ⁇ m was placed in an ethanol solution of 1.5% formic acid, and the surface organic matter and oxides were removed by ultrasonic washing for 3 min, and then dried by nitrogen purging.
  • Step two electrochemical reconstruction and electrochemical deposition.
  • Electrolyte solution prepare a 2 wt% sodium formate aqueous solution and adjust the pH of the solution to 10;
  • Step 3 Wash with ethanol and dry.
  • the SEM test was performed after the copper foil before and after treatment in a 0.1M NaOH solution at room temperature for 10 hours. The results showed that the copper foil modified with formate had a smoother and smoother surface, and its oxidation resistance was improved.
  • Step 1 Surface cleaning. A copper foil with a length of 3 cm, a width of 0.5 cm, and a thickness of 20 ⁇ m was placed in a 0.5 wt% formic acid in ethanol solution, ultrasonically washed for 8 minutes to remove surface organics and oxides, and dried by nitrogen purging.
  • Step two electrochemical reconstruction and electrochemical deposition.
  • Electrolyte solution prepare a 5 wt% sodium formate aqueous solution and adjust the pH of the solution to 8;
  • Step 3 Wash with ethanol and dry.
  • the SEM test was performed after the copper foil before and after treatment in a 0.1M NaOH solution at room temperature for 10 hours. The results showed that the copper foil modified with formate had a smoother and smoother surface, and its oxidation resistance was improved.
  • Step 1 Surface cleaning. A 5 cm long, 3 cm wide and 40 ⁇ m thick copper foil was taken and placed in a 2 wt% formic acid in ethanol solution, and the surface organic matter and oxides were removed by ultrasonic cleaning for 1 min, and then dried by nitrogen purging.
  • Step two electrochemical reconstruction and electrochemical deposition.
  • Electrolyte solution prepare a 10 wt% sodium formate aqueous solution, and adjust the pH of the solution to 10;
  • Step 3 Wash with ethanol and dry.
  • the SEM test was performed after the copper foil before and after treatment in a 0.1M NaOH solution at room temperature for 10 hours. The results showed that the copper foil modified with formate had a smoother and smoother surface, and its oxidation resistance was improved.
  • Step 1 Surface cleaning: take 25 ⁇ m thick copper foil, cut into 1cm ⁇ 3cm rectangular size, soak it in ethanol solution containing 1wt% formic acid, and sonicate for 5min, wash away the remaining organics and oxides on the surface, and then sonicate with ethanol Rinse 3 times and dry with a nitrogen purge.
  • Step 2 electrolyte preparation: the dried copper foil is used as the working electrode, the saturated calomel electrode is used as the reference electrode, and the platinum sheet electrode is used as the counter electrode.
  • Step 3 Electrochemical reconstruction and electrochemical deposition: At room temperature, using cyclic voltammetry (scanning speed: 10mV / s, scanning range: -1 to 0.5V), perform a scanning cycle at 45 ° C. Reconstruction.
  • the copper foil before and after electrochemical reconstruction was subjected to x-ray diffraction test. The results showed that the x-ray diffraction peak of the (110) crystal plane of the copper foil after electrochemical reconstruction was significantly enhanced, indicating that the formate induced
  • the copper surface was reconstituted; afterwards, it was deposited at a constant potential of -0.4V for 30 min to obtain an anti-oxidation copper foil.
  • Step 4 Wash with ethanol and dry.
  • the SEM test was performed after the copper foil before and after treatment in a 0.1M NaOH solution at room temperature for 10 hours. The results showed that the copper foil modified with formate had a smoother and smoother surface, and its oxidation resistance was improved.
  • Step 1 Surface cleaning: take 25 ⁇ m thick copper foil, cut into 1cm ⁇ 3cm rectangular size, soak it in ethanol solution containing 1wt% formic acid, and sonicate for 5min, wash away the remaining organics and oxides on the surface, and then sonicate with ethanol Rinse 3 times and dry with a nitrogen purge.
  • Step 2 electrolyte preparation: the dried copper foil is used as the working electrode, the saturated calomel electrode is used as the reference electrode, and the platinum sheet electrode is used as the counter electrode.
  • Step 3 Electrochemical reconstruction and electrochemical deposition: At room temperature, using cyclic voltammetry (scanning speed: 10mV / s, scanning range: -1 to 0.5V), perform a scanning cycle at 55 ° C. Reconstruction.
  • the copper foil before and after electrochemical reconstruction was subjected to x-ray diffraction test. The results showed that the x-ray diffraction peak of the (110) crystal plane of the copper foil after electrochemical reconstruction was significantly enhanced, indicating that the formate induced
  • the copper surface was restructured; afterwards, it was deposited at a constant potential of -1.0V for 30 minutes to obtain an anti-oxidation copper foil.
  • Step 4 Wash with ethanol and dry.
  • the SEM test was performed after the copper foil before and after treatment in a 0.1M NaOH solution at room temperature for 10 hours. The results showed that the copper foil modified with formate had a smoother and smoother surface, and its oxidation resistance was improved.
  • Step 1 Surface cleaning: take 25 ⁇ m thick copper foil, cut into 1 ⁇ 3cm 2 rectangles, soak it in an ethanol solution containing 1wt% formic acid, and sonicate for 5min, wash away the remaining organic matter and oxides on the surface, and then use ethanol Sonicate 3 times and dry with a nitrogen purge.
  • Step 2 electrolyte preparation: the dried copper foil is used as the working electrode, the saturated calomel electrode is used as the reference electrode, and the platinum sheet electrode is used as the counter electrode.
  • Step 3 Electrochemical reconstruction and electrochemical deposition: At room temperature, using cyclic voltammetry (scanning speed: 10mV / s, scanning range: -1 to 0.5V), scan for 3 cycles at 25 ° C. Reconstruction.
  • the copper foil before and after electrochemical reconstruction was subjected to x-ray diffraction test. The results showed that the x-ray diffraction peak of the (110) crystal plane of the copper foil after electrochemical reconstruction was significantly enhanced, indicating that the formate induced
  • the copper surface was reconstituted; afterwards, it was deposited at a constant potential of -0.7V for 30 min to obtain an oxidation-resistant copper foil.
  • Step 4 Wash with ethanol and dry.
  • the SEM test was performed after the copper foil before and after treatment in a 0.1M NaOH solution at room temperature for 10 hours. The results showed that the copper foil modified with formate had a smoother and smoother surface, and its oxidation resistance was improved.
  • Embodiment 16 is a diagrammatic representation of Embodiment 16:
  • Step 1 Surface cleaning: take 25 ⁇ m thick copper foil, cut into 1 ⁇ 3cm 2 rectangles, soak it in an ethanol solution containing 1wt% formic acid, and sonicate for 5min, wash away the remaining organic matter and oxides on the surface, and then use ethanol Sonicate 3 times and dry with a nitrogen purge.
  • Step 2 electrolyte preparation: the dried copper foil is used as the working electrode, the saturated calomel electrode is used as the reference electrode, and the platinum sheet electrode is used as the counter electrode.
  • Step 3 Electrochemical reconstruction and electrochemical deposition: at room temperature, using square wave voltammetry (scanning speed: 10mV / s, scanning range: -1 ⁇ 0.5V), scanning at 35 ° C for 5 cycles
  • the copper foil before and after electrochemical reconstruction was subjected to x-ray diffraction test.
  • the results showed that the x-ray diffraction peak of the (110) crystal plane of the copper foil after electrochemical reconstruction was significantly enhanced, indicating that formate Reconstruction of the copper surface was induced; then, a copper foil with anti-oxidation treatment was obtained by electrochemical deposition at a constant potential of -0.6V for 30 min.
  • Step 4 Wash with ethanol and dry.
  • the SEM test was performed after the copper foil before and after treatment in a 0.1M NaOH solution at room temperature for 10 hours. The results showed that the copper foil modified with formate had a smoother and smoother surface, and its oxidation resistance was improved.
  • Example 2 Surface treatment was performed on the copper foil according to the method of Example 1. The difference was that the step of electrochemical reconstruction using cyclic voltammetry was not included. Instead, the cleaned copper foil was subjected to potentiostatic electrochemistry in an electrolyte solution. After deposition, an anti-oxidation-treated copper foil was obtained, and the SEM test was performed. The results showed that the copper foil was left in a 0.1M NaOH solution at room temperature for 10 hours, and the entire surface was smooth and flat, but local oxidation corrosion appeared. Its oxidation resistance has been mentioned to a certain extent, but it still needs to be improved.

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Abstract

L'invention concerne le domaine du traitement superficiel de matériau, et concerne précisément un procédé de traitement électrochimique anti-oxydation destiné à un matériau cuivreux. Le procédé comprend l'utilisation d'un matériau cuivreux en tant qu'électrode de travail, et la mise en œuvre séquentielle d'une reconstruction électrochimique et d'un dépôt électrochimique dans un électrolyte contenant un stabilisant. Le stabilisant est un composé apte à fournir du formiate, de sorte que du formiate soit adsorbé sur une surface du matériau cuivreux. Le procédé électrochimique est destiné à permettre le placage de formiate sur la surface du matériau cuivreux, ce qui permet de renforcer la propriété anti-oxydation du matériau cuivreux. Le procédé est simple à mettre en œuvre ; et présente de bons atouts, de faibles coûts et de grandes perspectives d'applications industrielles.
PCT/CN2019/100291 2018-08-17 2019-08-13 Procédé de traitement électrochimique anti-oxydation destiné à un matériau cuivreux WO2020034929A1 (fr)

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CN101613868A (zh) * 2009-04-30 2009-12-30 上海电力学院 一种在铜电极表面形成自组装缓蚀膜的方法
CN106669432A (zh) * 2016-12-20 2017-05-17 华南理工大学 一种利用电沉积方法修饰不锈钢网制备金属有机骨架膜的方法
CN107460464A (zh) * 2017-08-28 2017-12-12 厦门大学 一种含铜材料的表面处理方法
CN107470609A (zh) * 2017-08-28 2017-12-15 厦门大学 一种抗氧化的铜纳米线的制备方法
CN109161946A (zh) * 2018-08-17 2019-01-08 厦门大学 一种铜材料抗氧化的电化学处理方法

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