CN111254476A - Preparation method of pure copper surface corrosion-resistant black micro-arc oxidation film - Google Patents
Preparation method of pure copper surface corrosion-resistant black micro-arc oxidation film Download PDFInfo
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- CN111254476A CN111254476A CN202010122757.3A CN202010122757A CN111254476A CN 111254476 A CN111254476 A CN 111254476A CN 202010122757 A CN202010122757 A CN 202010122757A CN 111254476 A CN111254476 A CN 111254476A
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/34—Anodisation of metals or alloys not provided for in groups C25D11/04 - C25D11/32
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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
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/024—Anodisation under pulsed or modulated current or potential
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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
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/026—Anodisation with spark discharge
Abstract
The invention provides a preparation method of a pure copper surface corrosion-resistant black micro-arc oxidation film, which takes pure copper as a matrix, takes a mixed solution containing aluminate, silicate, hypophosphite, sulfate and tungstate as an electrolyte solution, and adopts a pulse power supply to carry out micro-arc oxidation treatment to generate the corrosion-resistant black micro-arc oxidation film on the pure copper surface.
Description
Technical Field
The invention discloses a material surface treatment technology, relates to a surface ceramic treatment technology of pure copper, and particularly relates to a method for preparing a black corrosion-resistant micro-arc oxidation film on the surface of the pure copper.
Background
Copper has the characteristics of good strength, mechanical processing performance, excellent electric and heat conduction performance and the like. Has been widely used in various fields such as industry, military and civil use for a long time, and is one of essential important metal materials. However, the corrosion resistance of copper is poor, and the loss of all countries in the world caused by copper corrosion accounts for a certain proportion of the income of the nation, GDP. Therefore, it is of great significance to improve the corrosion resistance of copper.
In addition, modern industry has certain requirements on the color of the coating, and black is particularly favored as a popular "wild" color. The production of black coatings has also been an area of endeavor in the coating of metal surfaces.
Micro-arc oxidation is a metal surface strengthening technology developed in recent years, and can prepare a high-hardness wear-resistant and corrosion-resistant coating on the metal surface, so that the performance of a metal matrix is greatly improved. Micro-arc oxidation technology has become a hotspot in the field of material surface research. However, the technology has been directly applied to the surface treatment of the valve metal and the alloy thereof, such as Al, Mg, Ti and the alloy thereof, and the effect of direct application to the surface of ferrous metal and other nonferrous metals such as copper is not good. Breakthrough has been made and more reports have been made on the application of steel materials, while micro-arc oxidation has relatively less reports on copper.
The micro-arc oxidation technology is considered by many scholars as a practical metal surface strengthening and functionalization technology, has been greatly applied to the surfaces of valve metals and alloys thereof such as Al, Mg, Ti and alloys thereof, and is considered to have wider application prospect. The micro-arc oxidation technology is considered to be only suitable for valve metals for a long time, and the reason is that a layer of oxide film can quickly grow on the surface of the metal in the initial stage of an anode electrode of the valve metals such as aluminum magnesium and the like, and a three-phase two-interface system of metal-oxide film-electrolyte is quickly formed. The metal-oxide film layer-electrolyte system has a significant effect of hindering the anode current. These metals allow a larger cathodic current to pass through the electrolysis process, while the anodic current is smaller, i.e. anodic current is difficult to pass through, and these metals show a high impedance under the action of the anode, which drops the voltage drop of the whole system to the metal surface, which is the reason for the higher voltage drop of the anode. When the anode voltage drops to its breakdown voltage, a breakdown discharge is generated, upon which the micro-arc oxidation technique is based. Practice proves that if micro-arc discharge generated by breakdown can be well formed into a film and attached to the surface of base metal, the micro-arc discharge has great strengthening and protecting effects on the metal. Of course, micro-arc oxidation can be used from the viewpoint of functional coating or film, i.e. for preparing and obtaining the functional coating or film, not or only from the viewpoint of strengthening and protecting the base metal, such as photocatalytic and electrocatalytic functional film on the surface of titanium alloy, etc.
Other common metals such as steel, copper, zinc and the like do not belong to valve metals, and the micro-arc oxidation technology can not be directly applied to non-valve metals such as steel, copper, zinc and the like generally for a long time. However, on one hand, the micro-arc oxidation technology has various advantages, and on the other hand, the metal materials such as steel, copper and the like are still the most commonly used metal materials. Scholars at home and abroad try to directly research the micro-arc oxidation of steel and copper.
For steel, a valve metal layer, generally an aluminum layer, is prepared on the surface of a steel material, and then micro-arc oxidation treatment is performed. For example, a series of methods such as thermal spraying/micro-arc oxidation, plasma spraying/micro-arc oxidation, hot dipping aluminum/micro-arc oxidation and the like mainly differ from the method of plating an aluminum layer by adopting different methods, recently, the micro-arc oxidation is directly treated on the surface of steel, and some breakthrough progresses are obtained, so that the application of the micro-arc oxidation is widened from the technical aspect, and the micro-arc oxidation theory is enriched from the principle. For metallic copper and its alloy, there is no published report on direct micro-arc oxidation treatment. The present invention has been made in view of the above circumstances.
The invention utilizes the characteristics of the micro-arc oxidation technology to expand the matrix metal to pure copper, realizes the preparation of the high-hardness black micro-arc oxidation film on the surface of the pure copper in a proper electrolyte system, and achieves the aim of further improving the performance of the pure copper.
Disclosure of Invention
In order to overcome the defect that the micro-arc oxidation technology is directly applied to the surface treatment of the traditional non-valve metal pure copper, the invention provides a method for preparing a protective coating on the surface of the pure copper by utilizing the micro-arc oxidation technology, which is a new technology for preparing an oxide ceramic film on the surface of the pure copper. The surface of the pure copper is ceramized by a micro-arc oxidation method, the corrosion resistance of the copper is improved, and the black color which is widely used is obtained.
The present invention achieves the above-described object by the following technical means.
The preparation method of the pure copper surface corrosion-resistant black micro-arc oxidation film is characterized by comprising the following steps of:
(1) firstly, simple oil removal, decontamination and cleaning are carried out;
(2) placing a pure copper matrix in an electrolyte solution to be used as an anode, and performing micro-arc oxidation treatment by adopting a pulse power supply; the electrolyte solution contains the following components in proper concentration: aluminates, silicates, hypophosphites, sulfates, tungstates;
(3) and cleaning and drying the metal sample with the micro-arc oxidation film on the surface.
Further, the micro-arc oxidation treatment process comprises the following steps: the applied voltage is 0-680v, the frequency is 60-3000Hz, and the peak current density is 6-12A/cm2The treatment time is 10-60 min.
Further, the electrolyte comprises the following concentrations of substances: 20-60g/l of sodium silicate, 2-10g/l of sodium aluminate, 0.8-1.6g/l of sodium hypophosphite, 0.5-2g/l of sodium sulfate and 0.5-2g/l of sodium tungstate.
Further, the measured electrochemical corrosion current density of the prepared oxide film was 1.32 x 10-7A/cm2The corrosion potential is-172 mv.
Further, the electrolyte comprises the following concentrations of substances: 0.5-2g/l of sodium silicate, 8-10g/l of sodium aluminate, 0.8-1.6g/l of sodium hypophosphite, 0.2-2g/l of sodium sulfate and 0.5-2g/l of sodium tungstate.
Further, the electrochemical corrosion current of the prepared oxide filmDensity 8.76 x 10-6A/cm2The corrosion potential was-152 mv.
Furthermore, the thickness of the micro-arc oxidation film generated on the surface of the pure copper is more than 30 um.
According to the method, pure copper is used as a matrix, the components of the electrolyte are changed, the oxide ceramic membrane is directly prepared from the pure copper, the prepared ceramic membrane is black, the black color is a color with strong affinity, and the coordination and matching performance is very good.
The invention has the advantages that: (1) different energy supply modes and proper electrolyte systems provided by different power supply modes are utilized to activate and enhance the chemical process of copper on the anode to generate plasma reaction, so that the plasma liquid-phase electrolytic deposition ceramic membrane of copper is realized, and the application range of the plasma liquid-phase electrolytic deposition technology is expanded. (2) The main phase of the film layer can be adjusted, for example, aluminum oxide is used as the main phase, and the thickness can be adjusted, and is generally more than 30 um. (3) Besides the common film layer, the preparation of the black color film layer with unique affinity can be realized while the ceramic film layer is prepared, the coordination and matching performance is very good, and conditions are created for further development and decoration performance on the basis of keeping the good performance of the film layer.
Drawings
FIG. 1 is a pictorial view of a sample prepared in example two.
FIG. 2 is an SEM image of a sample prepared in example two.
Detailed Description
The invention will be further described with reference to the following figures and specific examples, but the scope of the invention is not limited thereto.
The first embodiment is as follows:
(1) pure copper is used as a base material, and the base material is washed by clean water and distilled water after being polished by 600#, 1000# and 2000# SiC sand paper and then dried. The dimension of the exposed reaction area of the sample wrapped with polytetrafluoroethylene is 20 mm, 20 mm and 0.2 mm;
(2) preparing the following electrolyte with mass concentration: 20-60g/l of sodium silicate, 2-10g/l of sodium aluminate, 0.8-1.6g/l of sodium hypophosphite, 0.5-2g/l of sodium sulfate and 0.5-2g/l of sodium tungstate;
(3) pure copper is taken as an anode, a pulse power supply is switched on, and the peak current density of the anode is set to be 12A/cm2Anode voltage 0-600V, cathode current density 12A/cm2Frequency 3000Hz, micro-arc oxidation for 30 minutes.
(4) And after the reaction is finished, taking out the sample with the ceramic film layer, washing the sample with the deionized water, and naturally drying the sample.
Generating a film layer with the thickness of about 50 mu m on the surface of a pure copper sample; the ceramic film is dark black in color. The electrochemical polarization curve test is carried out in 3.5% sodium chloride solution by adopting a three-electrode system, a sample with a coating is used as a working electrode, a platinum sheet is used as a counter electrode, a saturated calomel electrode SCE is used as a reference electrode, and the measured electrochemical corrosion current density is 1.32 x 10-7A/cm2The corrosion potential is-172 mv. 4.53 x 10 of blank pure copper sample without coating-6A/cm2-268 mv. Compared with a blank pure copper sample, the corrosion potential of the sample with the micro-arc oxidation coating is improved by nearly 100mv, the corrosion current is reduced by 1 order of magnitude, and the corrosion resistance of the matrix copper is improved.
Example two:
(1) pure copper is used as a base material, and the base material is washed by clean water and distilled water after being polished by 600#, 1000# and 2000# SiC sand paper and then dried. The dimension of the exposed reaction area of the sample wrapped with polytetrafluoroethylene is 20 mm, 20 mm and 0.2 mm;
(2) preparing the following electrolyte with mass concentration: 8-10g/l of sodium aluminate, 0.8-1.6g/l of sodium hypophosphite, 0.2-2g/l of sodium sulfate, 0.5-2g/l of sodium silicate and 0.5-2g/l of sodium tungstate;
(3) pure copper is taken as an anode, a pulse power supply is switched on, and the peak current density of the anode is set to be 6A/cm2Anode voltage 0-550V and cathode current density 6A/cm2Frequency 1000Hz, micro arc oxidation for 50 minutes.
(4) And after the reaction is finished, taking out the sample with the ceramic film layer, washing the sample with the deionized water, and naturally drying the sample.
A film layer with the thickness of about 40 mu m is generated on the surface of the sample; the ceramic film is dark black in color, as shown in FIG. 1The figure 2 shows the appearance of the enclosure. Using the same test method as in example 1, the electrochemical corrosion current density of the coated sample was measured to be 8.76 x 10-6A/cm2The corrosion potential was-152 mv. Compared with a blank pure copper sample, the corrosion potential of the sample with the micro-arc oxidation coating is improved by over 100mv, the corrosion current is reduced by 2 orders of magnitude, and the corrosion resistance of the matrix copper is greatly improved.
The present invention is not limited to the above-described embodiments, and any obvious improvements, substitutions or modifications can be made by those skilled in the art without departing from the spirit of the present invention.
Claims (7)
1. The preparation method of the pure copper surface corrosion-resistant black micro-arc oxidation film is characterized by comprising the following steps of:
(1) firstly, simple oil removal, decontamination and cleaning are carried out;
(2) placing a pure copper matrix in an electrolyte solution to be used as an anode, and performing micro-arc oxidation treatment by adopting a pulse power supply; the electrolyte solution contains the following components in proper concentration: aluminates, silicates, hypophosphites, sulfates, tungstates;
(3) and cleaning and drying the metal sample with the micro-arc oxidation film on the surface.
2. The method for preparing the black micro-arc oxidation film with the corrosion resistance on the pure copper surface according to claim 1, wherein the micro-arc oxidation treatment process comprises the following steps: the applied voltage is 0-680v, the frequency is 60-3000Hz, and the peak current density is 6-12A/cm2The treatment time is 10-60 min.
3. The method for preparing the black micro-arc oxidation film with the corrosion resistance on the pure copper surface according to claim 1, wherein the electrolyte comprises the following substances in concentration: 20-60g/l of sodium silicate, 2-10g/l of sodium aluminate, 0.8-1.6g/l of sodium hypophosphite, 0.5-2g/l of sodium sulfate and 0.5-2g/l of sodium tungstate.
4. The method for preparing black micro-arc oxide film with pure copper surface corrosion resistance according to claim 3, wherein the measured electrochemical corrosion current density of the prepared oxide film is 1.32 x 10-7A/cm2The corrosion potential is-172 mv.
5. The method for preparing the black micro-arc oxidation film with the corrosion resistance on the pure copper surface according to claim 1, wherein the electrolyte comprises the following substances in concentration: 0.5-2g/l of sodium silicate, 8-10g/l of sodium aluminate, 0.8-1.6g/l of sodium hypophosphite, 0.2-2g/l of sodium sulfate and 0.5-2g/l of sodium tungstate.
6. The method for preparing black micro-arc oxide film with pure copper surface corrosion resistance according to claim 5, wherein the electrochemical corrosion current density of the prepared oxide film is 8.76 x 10-6A/cm2The corrosion potential was-152 mv.
7. The method for preparing the black micro-arc oxide film with the corrosion resistance on the pure copper surface according to claim 1, wherein the thickness of the micro-arc oxide film generated on the pure copper surface is more than 30 um.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114525566A (en) * | 2021-12-25 | 2022-05-24 | 东北大学 | Surface micro-arc oxidation-high temperature oxidation method for copper and copper alloy |
| CN115838956A (en) * | 2022-12-06 | 2023-03-24 | 西北有色金属研究院 | Method for preparing black high-emission composite ceramic coating on surface of magnesium alloy |
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| CN102021632A (en) * | 2010-12-15 | 2011-04-20 | 中国铝业股份有限公司 | Method for preparing protective film on copper alloy surface |
| CN102041538A (en) * | 2009-10-22 | 2011-05-04 | 上海航天精密机械研究所 | Method for preparing aluminum-copper alloy microarc oxidation film |
| CN104831332A (en) * | 2015-04-17 | 2015-08-12 | 江苏大学 | Method for directly generating black corrosion-resistant micro-arc oxidation film layer on steel surface |
| CN110016708A (en) * | 2019-04-16 | 2019-07-16 | 湖南大学 | Suitable for copper and its micro-arc oxidization surface processing method and product of alloy |
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Patent Citations (5)
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| CN101260555A (en) * | 2008-04-18 | 2008-09-10 | 哈尔滨工业大学 | Plasma liquid phase electrolysis method for ceramic film deposited on surface of copper and alloy thereof |
| CN102041538A (en) * | 2009-10-22 | 2011-05-04 | 上海航天精密机械研究所 | Method for preparing aluminum-copper alloy microarc oxidation film |
| CN102021632A (en) * | 2010-12-15 | 2011-04-20 | 中国铝业股份有限公司 | Method for preparing protective film on copper alloy surface |
| CN104831332A (en) * | 2015-04-17 | 2015-08-12 | 江苏大学 | Method for directly generating black corrosion-resistant micro-arc oxidation film layer on steel surface |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114525566A (en) * | 2021-12-25 | 2022-05-24 | 东北大学 | Surface micro-arc oxidation-high temperature oxidation method for copper and copper alloy |
| CN114525566B (en) * | 2021-12-25 | 2023-08-11 | 东北大学 | Surface micro-arc oxidation-high-temperature oxidation method for copper and copper alloy |
| CN115838956A (en) * | 2022-12-06 | 2023-03-24 | 西北有色金属研究院 | Method for preparing black high-emission composite ceramic coating on surface of magnesium alloy |
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