CN114525566B - Surface micro-arc oxidation-high-temperature oxidation method for copper and copper alloy - Google Patents
Surface micro-arc oxidation-high-temperature oxidation method for copper and copper alloy Download PDFInfo
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- CN114525566B CN114525566B CN202111605990.8A CN202111605990A CN114525566B CN 114525566 B CN114525566 B CN 114525566B CN 202111605990 A CN202111605990 A CN 202111605990A CN 114525566 B CN114525566 B CN 114525566B
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- 239000010949 copper Substances 0.000 title claims abstract description 65
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 63
- 230000003647 oxidation Effects 0.000 title claims abstract description 33
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 31
- 229910000881 Cu alloy Inorganic materials 0.000 title abstract description 18
- 238000007745 plasma electrolytic oxidation reaction Methods 0.000 claims abstract description 34
- 239000003792 electrolyte Substances 0.000 claims abstract description 15
- 238000001816 cooling Methods 0.000 claims abstract description 13
- 238000005498 polishing Methods 0.000 claims abstract description 12
- 238000004140 cleaning Methods 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 9
- 239000001301 oxygen Substances 0.000 claims abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000005520 cutting process Methods 0.000 claims abstract description 8
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 8
- 239000010439 graphite Substances 0.000 claims abstract description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000000956 alloy Substances 0.000 claims description 13
- 229910045601 alloy Inorganic materials 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 230000007797 corrosion Effects 0.000 abstract description 11
- 238000005260 corrosion Methods 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 6
- 238000004381 surface treatment Methods 0.000 abstract description 4
- 239000000853 adhesive Substances 0.000 abstract description 3
- 230000001070 adhesive effect Effects 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 16
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 238000000137 annealing Methods 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000010791 quenching Methods 0.000 description 4
- 230000000171 quenching effect Effects 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000005275 alloying Methods 0.000 description 3
- 238000005253 cladding Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000004372 laser cladding Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000007750 plasma spraying Methods 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000002310 reflectometry Methods 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 244000137852 Petrea volubilis Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229940116318 copper carbonate Drugs 0.000 description 1
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000007712 rapid solidification Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
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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
- C25D11/34—Anodisation of metals or alloys not provided for in groups C25D11/04 - C25D11/32
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
The invention belongs to the technical field of material surface treatment, and in particular relates to a surface micro-arc oxidation-high-temperature oxidation method of copper and copper alloy, which comprises the following steps: s1, polishing a sample step by step after cutting, cleaning and drying; s2, taking the sample obtained in the step S1 as an anode, taking a graphite plate as a cathode, and placing the sample in electrolyte for micro-arc oxidation treatment; s3, carrying out high-temperature treatment at 150-600 ℃ on the sample obtained in the S2 in an oxygen atmosphere, and then cooling to room temperature. The invention firstly obtains the film with good corrosion resistance by micro-arc oxidation treatment, then adopts a high-temperature oxidation means to finally lead the surface to generate the wear-resistant and corrosion-resistant film, thereby retaining the good corrosion resistance of the surface film after copper and copper alloy are subjected to the micro-arc oxidation treatment, and simultaneously solving the problem of poor adhesive force of the film formed after the micro-arc oxidation treatment by using the high-temperature oxidation treatment method, and greatly prolonging the service life.
Description
Technical Field
The invention belongs to the technical field of material surface treatment, and particularly relates to a surface micro-arc oxidation-high-temperature oxidation method of copper and copper alloy.
Background
Pure copper has good electrical conductivity, thermal conductivity, ductility and corrosion resistance. Pure copper is low in price and wide in use, and is mainly applied to electrical equipment such as generators, buses, cables, switching devices, transformers and the like and heat exchanger materials. Pure copper is often contacted with carbon dioxide and water vapor in the air in the application scenes, but the pure copper is easy to react with water and carbon dioxide to generate basic copper carbonate, so that the service life of copper devices is prolonged, accidents are reduced, and the corrosion resistance and the wear resistance of copper are extremely important. Among the numerous treatment modes, the surface treatment has the advantages of wide application range, large span, low price and the like, and the surface treatment methods applied to copper and copper alloys mainly comprise plasma spraying, laser cladding, laser alloying, laser surface quenching and remelting.
Plasma spraying is a material surface strengthening and surface modifying technology, and has the advantages of simple operation, low equipment maintenance cost, good regulation performance and the like, but the high heat conduction characteristic of copper and copper alloy materials amplifies the defect of poor binding force between a substrate and a coating, so that the wear resistance of the obtained coating is greatly reduced. The laser cladding utilizes high-power laser beams to rapidly melt the metal matrix and cladding powder, and is metallurgically combined with the matrix after rapid solidification. The method is suitable for the surface strengthening of key copper parts applied under extreme conditions, but the problems of difficult formation of a molten pool, poor combination of a cladding layer and a copper matrix, stress cracking of the cladding layer and the like are easy to occur in surface laser cladding due to the characteristics of high heat conductivity, high infrared reflectivity and high thermal expansion rate of copper and copper alloy. The laser surface alloying is to melt the powder of alloy element, ceramic, etc. on the surface of the base material by using high energy laser beam to form an alloy layer on the surface of the base body. The laser alloying technology overcomes the limitation of high laser reflectivity of copper and copper alloy matrixes by means of preset powder and the like, and realizes metallurgical bonding of the surfaces of the matrixes and alloy raw material powder, but the limitation of long technological process and high technical complexity of preparing the preset layer is not widely applied. Laser surface quenching and remelting are achieved by virtue of the rapid fusing effect brought about by the high energy density of the laser. The laser quenching and remelting technology on the surface of the copper alloy can lead the surface size to be almost unchanged, the depth to be controllable and the processing flow to be short, but can lead the internal stress of the surface layer of the material to be improved and the tissue to have periodical changes perpendicular to the scanning direction while being fused rapidly, thereby causing the cracking of the laser quenching and remelting area. Therefore, the conventional process cannot give consideration to the corrosion resistance and adhesion of the film formed on the surface of copper and its alloys.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a surface micro-arc oxidation-high temperature oxidation method for copper and copper alloy, wherein a micro-arc oxidation treatment mode is used to obtain a film layer with good corrosion resistance on the surface of copper and copper alloy, then high temperature oxidation treatment is carried out to enable gas to enter into a hole between a substrate and the film layer through the hole of the film layer to form a transition layer, and the mode keeps the corrosion resistance of metal after the micro-arc oxidation treatment, and meanwhile, the adhesive force of the film layer is greatly improved.
The invention aims to provide a surface micro-arc oxidation-high temperature oxidation method of copper and copper alloy, which comprises the following steps:
s1, cutting a sample, polishing step by step, cleaning and drying;
s2, taking the sample obtained in the step S1 as an anode, taking a graphite plate as a cathode, placing the sample in electrolyte for micro-arc oxidation treatment, and then washing and drying;
and S3, performing high-temperature treatment on the sample obtained in the step S2 in an oxygen atmosphere, and then cooling to room temperature.
Preferably, in S1, the polishing mode is that SiC sand paper of 240#, 400#, 600#, 1000# and 2000# is sequentially used for polishing.
Preferably, in S1, the solvent for cleaning is ethanol or acetone.
Preferably, in S2, the electrolyte is Na 2 SiO 3 ·9H 2 Mixed solution of O and NaOH.
Preferably, na 2 SiO 3 ·9H 2 The concentration of the O solution is 15-35g/L, and the concentration of the NaOH solution is 2-6g/L.
Preferably, in S2, the technological parameters of the micro-arc oxidation are as follows: the voltage is 650-750V, the current density is 2-6A/cm 2 The pulse frequency is 100-500Hz, and the duty ratio is 20-60%.
Preferably, in S2, the time of the micro-arc oxidation treatment is 10-50min.
Preferably, in S2, the washing is performed with deionized water and then dried.
Preferably, in S3, the gas flow rate of the oxygen is 0-600mL/min.
Preferably, in S3, the process parameters of the high temperature treatment are: heating for 5-10min, maintaining the temperature for 30-60min after heating to the target temperature, and cooling at a speed of 5-10 ℃/min.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, the film layer with good corrosion resistance is obtained on the surface of copper and the alloy thereof in a micro-arc oxidation treatment mode, and then high-temperature oxidation treatment is carried out, so that gas enters into the pores between the substrate and the film layer through the pores of the film layer to form an oxide film, the pores are filled, the corrosion resistance of the film layer after the micro-arc oxidation treatment of metal is reserved, and meanwhile, the adhesive force of the film layer is greatly improved.
Drawings
FIG. 1 is a macroscopic appearance of the copper surface film prepared in example 1;
FIG. 2 is a scanning electron microscope image of the copper surface films prepared in example 1 and comparative example 1; wherein, (a) is comparative example 1 and (b) is example 1;
FIG. 3 is a cross-sectional electron microscope scan of copper surface films prepared in example 1 and comparative example 1; wherein, (a) is comparative example 1 and (b) is example 1;
FIG. 4 is an X-ray diffraction pattern of the copper surface film prepared in example 1;
FIG. 5 is a potentiodynamic polarization plot of the copper surface film prepared in example 1;
FIG. 6 is a graph showing friction coefficients of the copper surface film prepared in example 1 and the copper surface film prepared in comparative example 1;
FIG. 7 is a graph showing adhesion test of the copper surface film prepared in example 1 and the copper surface film prepared in comparative example 1; wherein, (a) is comparative example 1 and (b) is example 1.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the data in the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
It should be noted that the technical terms used in the present invention are only for describing specific embodiments, and are not intended to limit the scope of the present invention, and various raw materials, reagents, instruments and equipment used in the following embodiments of the present invention may be purchased commercially or prepared by existing methods unless otherwise specifically described.
Example 1
A surface micro-arc oxidation-high temperature oxidation method for copper and copper alloy comprises the following steps:
s1, cutting pure copper into 15 x 5mm, sequentially polishing with 240# SiC abrasive paper, 400# SiC abrasive paper, 600# SiC abrasive paper, 1000# SiC abrasive paper and 2000# SiC abrasive paper, cleaning with ethanol, and drying;
s2, firstly, configuring 28.42g/L Na 2 SiO 3 ·9H 2 Electrolyte of O and 4g/L NaOH, the volume is 5L, then the sample obtained in the step S1 is used as an anode, a graphite plate is used as a cathode, the sample is placed in the electrolyte for micro-arc oxidation treatment, and a constant current mode is adopted for treatment, wherein the voltage of a pulse power supply is 500V, and the current density is 4.44A/cm 2 The pulse frequency is 200Hz, the duty ratio is plus 50 percent and minus 30 percent, the micro-arc oxidation is carried out for 25 minutes, and after the micro-arc oxidation is carried out, the sample is taken out, washed by deionized water and dried;
s3, placing the sample obtained in the S2 into a tubular annealing furnace, introducing oxygen, regulating the gas flow to 300mL/min for high-temperature oxidation treatment, setting the heating time to 10min, heating at 150 ℃, then keeping the temperature for 30min, cooling at room temperature, wherein the cooling rate is 5 ℃/min, and taking out the sample after the sample is cooled at room temperature.
Example 2
A surface micro-arc oxidation-high temperature oxidation method for copper and copper alloy comprises the following steps:
s1, cutting pure copper into 15 x 5mm, sequentially polishing with 240# SiC abrasive paper, 400# SiC abrasive paper, 600# SiC abrasive paper, 1000# SiC abrasive paper and 2000# SiC abrasive paper, cleaning with ethanol, and drying;
s2, firstly, 35g/L Na is configured 2 SiO 3 ·9H 2 Electrolyte of O and 6g/L NaOH, the volume is 5L, then the sample obtained in the step S1 is taken as an anode, a graphite plate is taken as a cathode, the sample is placed in the electrolyte for micro-arc oxidation treatment, and a constant current mode is adopted for treatment, wherein the voltage of a pulse power supply is 550V, and the current density is 4.44A/cm 2 The pulse frequency is 200Hz, the duty ratio is plus 60 percent and minus 40 percent, the micro-arc oxidation is carried out for 30 minutes, and after the micro-arc oxidation is carried out, the sample is taken out, washed by deionized water and dried;
s3, placing the sample obtained in the S2 into a tubular annealing furnace, introducing oxygen, regulating the gas flow to 400mL/min for high-temperature oxidation treatment, setting the heating time to 8min, heating at 200 ℃, then keeping the temperature for 30min, cooling at room temperature, wherein the cooling rate is 5 ℃/min, and taking out the sample after the sample is cooled at room temperature.
Example 3
A surface micro-arc oxidation-high temperature oxidation method for copper and copper alloy comprises the following steps:
s1, cutting pure copper into 15 x 5mm, sequentially polishing with 240# SiC abrasive paper, 400# SiC abrasive paper, 600# SiC abrasive paper, 1000# SiC abrasive paper and 2000# SiC abrasive paper, cleaning with ethanol, and drying;
s2, firstly, 40g/L Na is configured 2 SiO 3 ·9H 2 Electrolyte of O and 8g/L NaOH, the volume is 5L, then the sample obtained in the step S1 is used as an anode, a graphite plate is used as a cathode, the sample is placed in the electrolyte for micro-arc oxidation treatment, and a constant current mode is adopted for treatment, wherein the voltage of a pulse power supply is 600V, and the current density is 4.44A/cm 2 The pulse frequency is 200Hz, the duty ratio is plus 70 percent and minus 30 percent, the micro-arc oxidation is carried out for 40 minutes, and after the micro-arc oxidation is carried out, the sample is taken out, washed by deionized water and dried;
s3, placing the sample obtained in the S2 into a tubular annealing furnace, introducing oxygen, regulating the gas flow to 300mL/min for high-temperature oxidation treatment, setting the heating time to 10min, heating at 600 ℃, then keeping the temperature for 40min, cooling at room temperature, wherein the cooling rate is 10 ℃/min, and taking out the sample after the sample is cooled at room temperature.
Example 4
A surface micro-arc oxidation-high temperature oxidation method for copper and copper alloy comprises the following steps:
s1, cutting pure copper into 15 x 5mm, sequentially polishing with 240# SiC abrasive paper, 400# SiC abrasive paper, 600# SiC abrasive paper, 1000# SiC abrasive paper and 2000# SiC abrasive paper, cleaning with ethanol, and drying;
s2, firstly, configuring 45g/L Na 2 SiO 3 ·9H 2 Electrolyte of O and 10g/L NaOH, the volume is 5L, then the sample obtained in the step S1 is taken as an anode, a graphite plate is taken as a cathode, the sample is placed in the electrolyte for micro-arc oxidation treatment, and a constant current mode is adopted for treatment, wherein the voltage of a pulse power supply is 750V, and the current density is 4.44A/cm 2 The pulse frequency is 200Hz, the duty ratio is plus 50 percent and minus 50 percent, the micro-arc oxidation is carried out for 40 minutes, and after the micro-arc oxidation is carried out, the sample is taken out, washed by deionized water and dried;
s3, placing the sample obtained in the S2 into a tubular annealing furnace, introducing oxygen, regulating the gas flow to be 600mL/min for high-temperature oxidation treatment, setting the heating time to be 5min, heating at 250 ℃, then keeping the temperature for 60min, cooling at room temperature, wherein the cooling rate is 8 ℃/min, and taking out the sample after the sample is cooled at room temperature.
Comparative example 1
A surface micro-arc oxidation-high temperature oxidation method for copper and copper alloy comprises the following steps:
s1, cutting pure copper into 15 x 5mm, sequentially polishing with 240# SiC abrasive paper, 400# SiC abrasive paper, 600# SiC abrasive paper, 1000# SiC abrasive paper and 2000# SiC abrasive paper, cleaning with ethanol, and drying;
s2, firstly, configuring 28.42g/L Na 2 SiO 3 ·9H 2 Electrolyte of O and 4g/L NaOH, the volume is 5L, then the sample obtained in the step S1 is used as an anode, a graphite plate is used as a cathode, the sample is placed in the electrolyte for micro-arc oxidation treatment, and a constant current mode is adopted for treatment, wherein the voltage of a pulse power supply is 500V, and the current density is 4.44A/cm 2 The pulse frequency is 200Hz, the duty ratio is plus 50 percent and minus 30 percent, the micro-arc oxidation is carried out for 25 minutes, and the sample is taken out after the beam is formed, washed by deionized water and dried.
Fig. 1 is a macroscopic view of the copper surface film prepared in example 1, and the film layer of the copper surface film is black in color as shown in fig. 1.
FIG. 2 is a scanning electron microscope image of the copper surface films prepared in example 1 and comparative example 1; wherein, (a) is comparative example 1 and (b) is example 1. As shown in fig. 2 (b), compared with comparative example 1 of fig. 2 (a) after only micro-arc oxidation, the pore size and density of the surface film of the pure copper sample treated by the micro-arc oxidation-high temperature oxidation method on the copper surface of example 1 are obviously reduced.
FIG. 3 is a cross-sectional electron microscope scan of copper surface films prepared in example 1 and comparative example 1; wherein, (a) is comparative example 1 and (b) is example 1. As shown in FIG. 3 (b), the film layer prepared in example 1 was very tightly bonded to the interface of the substrate, and the film layer on the surface of the pure copper sample was treated by a micro-arc oxidation-high temperature oxidation method to about 20. Mu.m.
Fig. 4 is an X-ray diffraction diagram of the copper surface film prepared in example 1, and as shown in fig. 4, the film layer of the copper surface film is mainly CuO after the micro-arc oxidation treatment and then the high-temperature oxidation treatment in example 1.
FIG. 5 is a graph showing the polarization of the potentiodynamic film of the copper surface film prepared in example 1. As shown in FIG. 5, in example 1, the corrosion current density is significantly reduced from that of Cu by 5.6X10 after the micro-arc oxidation treatment and then the high-temperature oxidation treatment - 6 A/cm 2 (Cu) was reduced to 1.6X10 -6 A/cm 2 。
Fig. 6 is a graph showing friction coefficients of the copper surface film prepared in example 1 and the copper surface film prepared in comparative example 1, the friction coefficient of the copper surface film subjected to the micro-arc oxidation and the high temperature oxidation is reduced to a certain extent compared with that of the copper surface film subjected to the micro-arc oxidation only, and when the adhesion is tested by a drawing method, as shown in fig. 7, the adhesion of the copper surface film prepared in example 1 and the copper surface film prepared in comparative example 1 is tested, about half of the surface film obtained in example 1 by the micro-arc oxidation-high temperature oxidation method is not drawn as shown in fig. 7 (b), while the surface film obtained in comparative example 1 is completely drawn by the micro-arc oxidation only as shown in fig. 7 (a), which shows that the adhesion of the film layer obtained by the micro-arc oxidation-high temperature oxidation method is significantly improved, and the surface wear resistance is improved.
It should be noted that, when numerical ranges are referred to in the present invention, it should be understood that two endpoints of each numerical range and any numerical value between the two endpoints are optional, and because the adopted step method is the same as the embodiment, in order to prevent redundancy, the present invention describes a preferred embodiment. While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. It is therefore intended that the following claims be interpreted as including the preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.
Claims (7)
1. The surface micro-arc oxidation-high temperature oxidation method of copper and the alloy thereof is characterized by comprising the following steps:
s1, cutting a sample, polishing step by step, cleaning and drying;
s2, taking the sample obtained in the step S1 as an anode, taking a graphite plate as a cathode, placing the sample in electrolyte for micro-arc oxidation treatment, and then washing and drying;
the technological parameters of the micro-arc oxidation are as follows: the voltage is 650-750V, the current density is 2-6A/cm 2 Pulse frequency is 100-500Hz, duty ratio is 20-60%;
s3, carrying out high-temperature treatment on the sample obtained in the S2 in an oxygen atmosphere at 150-600 ℃, and then cooling to room temperature;
the gas flow rate of the oxygen is 600-800mL/min;
the technological parameters of the high-temperature treatment are as follows: heating for 5-10min, maintaining the temperature for 30-60min after heating to the target temperature, and cooling at a speed of 5-10 ℃/min.
2. The method for micro-arc oxidation-high temperature oxidation of copper and its alloys according to claim 1, wherein in S1, the polishing is performed by sequentially polishing with 240#, 400#, 600#, 1000# and 2000# SiC sandpaper.
3. The method of micro-arc oxidation-high temperature oxidation of copper and its alloys according to claim 1, wherein in S1, the cleaning solvent is ethanol or acetone.
4. The copper according to claim 1The surface micro-arc oxidation-high temperature oxidation method of the alloy is characterized in that in S2, the electrolyte is Na 2 SiO 3 ·9H 2 Mixed solution of O and NaOH.
5. The method for surface micro-arc oxidation-high temperature oxidation of copper and its alloys according to claim 4, wherein Na 2 SiO 3 ·9H 2 The concentration of the O solution is 15-35g/L, and the concentration of the NaOH solution is 2-6g/L.
6. The method of surface micro-arc oxidation-high temperature oxidation of copper and its alloys according to claim 1, wherein in S2, the time of the micro-arc oxidation treatment is 10-50min.
7. The method for micro-arc oxidation-high temperature oxidation of copper and its alloys according to claim 1, wherein in S2, said rinsing is performed with deionized water and then dried.
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| CN111254476A (en) * | 2020-02-27 | 2020-06-09 | 江苏大学 | Preparation method of pure copper surface corrosion-resistant black micro-arc oxidation film |
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