AU2021338582A1 - Magnesium alloy ultra-high porosity micro-arc oxidation coating, preparation method and application thereof - Google Patents
Magnesium alloy ultra-high porosity micro-arc oxidation coating, preparation method and application thereof Download PDFInfo
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- 239000011248 coating agent Substances 0.000 title claims abstract description 68
- 238000000576 coating method Methods 0.000 title claims abstract description 68
- 238000007745 plasma electrolytic oxidation reaction Methods 0.000 title claims abstract description 59
- 229910000861 Mg alloy Inorganic materials 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 238000004506 ultrasonic cleaning Methods 0.000 claims abstract description 19
- 238000004070 electrodeposition Methods 0.000 claims abstract description 17
- 230000004888 barrier function Effects 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 16
- 238000005530 etching Methods 0.000 claims description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 12
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 10
- 238000001723 curing Methods 0.000 claims description 8
- 239000010935 stainless steel Substances 0.000 claims description 7
- 229910001220 stainless steel Inorganic materials 0.000 claims description 7
- 238000000861 blow drying Methods 0.000 claims description 6
- 239000011775 sodium fluoride Substances 0.000 claims description 6
- 235000013024 sodium fluoride Nutrition 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 238000006555 catalytic reaction Methods 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 5
- 239000008103 glucose Substances 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 5
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 5
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 5
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 claims description 5
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 4
- PJAIMBYNTXNOCN-UHFFFAOYSA-N 3,6-dibromo-1h-indole Chemical compound BrC1=CC=C2C(Br)=CNC2=C1 PJAIMBYNTXNOCN-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- GXGAKHNRMVGRPK-UHFFFAOYSA-N dimagnesium;dioxido-bis[[oxido(oxo)silyl]oxy]silane Chemical compound [Mg+2].[Mg+2].[O-][Si](=O)O[Si]([O-])([O-])O[Si]([O-])=O GXGAKHNRMVGRPK-UHFFFAOYSA-N 0.000 claims description 4
- 239000000391 magnesium silicate Substances 0.000 claims description 4
- 229940099273 magnesium trisilicate Drugs 0.000 claims description 4
- 229910000386 magnesium trisilicate Inorganic materials 0.000 claims description 4
- 235000019793 magnesium trisilicate Nutrition 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 239000004753 textile Substances 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 abstract description 4
- 239000000956 alloy Substances 0.000 abstract description 4
- 238000004381 surface treatment Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 33
- 239000011148 porous material Substances 0.000 description 10
- 238000012876 topography Methods 0.000 description 9
- 230000007797 corrosion Effects 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 235000011007 phosphoric acid Nutrition 0.000 description 4
- 238000007619 statistical method Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 150000003016 phosphoric acids Chemical class 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000005524 ceramic coating Methods 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000000803 paradoxical effect Effects 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
Classifications
-
- 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
- C25D11/30—Anodisation of magnesium or alloys based thereon
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Abstract
The present invention relates to the field of material surface treatment, and in particular
to a magnesium alloy ultra-high porosity micro-arc oxidation coating, preparation method
and application thereof. After the magnesium alloy is subjected to the pretreatment, the
ultrasonic cleaning, the barrier film preparation, the cathode micro-arc electrodeposition, and
the anode micro-arc oxidation in sequence, an ultra-high porosity micro-arc oxidation coating
with excellent bonding strength and mechanical properties can be prepared on the surface of
the alloy. The micro-arc oxidation coating has a porosity of not less than 50% and a
micropore diameter of 0.5-3 tm. All the steps of the method are performed stepwise with
clear objectives, respective advantages of the cathode micro-arc electrodeposition and the
anode micro-arc oxidation are fully combined, and a high-quality target coating can be
formed with only one power supply unit, thereby providing a new idea for preparing a
magnesium alloy ultra-high porosity micro-arc oxidation coating.
Description
The present invention relates to the field of material surface treatment, and in particular to a magnesium alloy ultra-high porosity micro-arc oxidation coating, preparation method and application thereof.
The information disclosed in this Background section is only intended to enhance the understanding to the general background of the present invention and should not necessarily be taken as an acknowledgement or any form of implication that this information forms the prior art already known to a person of ordinary skill in the art. In recent years, micro-arc oxidation technology has been more widely applied in the field of magnesium alloy surface treatment. A ceramic coating with magnesium oxide as the main phase can be prepared and formed on the surface of a magnesium alloy by the micro-arc oxidation technology. The ceramic coating is not only firmly bonded to the substrate, but also has the characteristics of high hardness and good insulation. Therefore, the wear resistance and corrosion resistance of the magnesium alloy substrate can be greatly enhanced. In terms of the microstructural morphology of the surface of the coating, the most significant characteristic of the micro-arc oxidation coating is that it is not a completely closed coating, but has some micropores distributed in the outermost layer. These pores are traces caused by the breakdown of high voltage discharge during the micro-arc oxidation process, and are unavoidable in the micro-arc oxidation technology. Previously, in order to make the magnesium alloy have higher corrosion resistance and mechanical properties, a lot of researches have been conducted focusing on how to reduce or even completely remove the pore structure in the coating after the micro-arc oxidation. In recent years, increasing the specific surface area of the magnesium alloy has become more and more important for realizing and expressing the functions of the magnesium alloy as the magnesium alloy has been extensively applied in various special functional fields. Some researchers are keenly aware that the micropore structure in the micro-arc oxidation coating on the surface of the magnesium alloy is a beneficial structure in the fields of catalysis, energy, environment, etc. Therefore, in some cases, how to make the micropore structure in the micro-arc oxidation coating more developed and increase the porosity of the coating has become the subject of research. Previously, the most commonly used technical approach to reduce the pore structure in the micro-arc oxidation coating is to control the micro-arc discharge breakdown effect by adjusting various electrical parameters in the micro-arc oxidation process, thereby optimizing the growth of pores. However, the inventors have found that when it is expected to obtain a developed pore structure in the micro-arc oxidation coating, the micro-arc oxidation using the above reverse adjustment of process parameters often leads to looseness in structure, decrease in bonding strength, and significant reduction in mechanical properties of the micro-arc oxidation coating. Therefore, it is of great significance to develop an ultra-high porosity micro-arc oxidation coating with excellent bonding strength and mechanical properties.
In order to solve the defects in the prior art, the present invention provides a magnesium alloy ultra-high porosity micro-arc oxidation coating, preparation method and application thereof. The method fully combines respective advantages of cathode micro-arc electrodeposition and anode micro-arc oxidation, a high-quality target coating can be prepared and formed with only one power supply unit, and an ultra-high porosity micro-arc oxidation coating with excellent bonding strength and mechanical properties is obtained, thereby providing a new idea for preparing the magnesium alloy ultra-high porosity micro-arc oxidation coating. In order to achieve the above technical purposes, a first aspect of the present invention provides a method for preparing a magnesium alloy ultra-high porosity micro-arc oxidation coating, comprising: (1) pretreating a cleaned magnesium alloy sample by placing the sample into an etching solution; (2) ultrasonically cleaning the pretreated magnesium alloy sample by placing the sample into an ultrasonic cleaning solution, then taking out the sample and blow-drying the sample for later use; (3) ultrasonically soaking the ultrasonically cleaned sample by placing the sample into a barrier film preparation solution, then taking out the sample, drying and curing the sample by placing the sample into an oven, and after ending the drying and curing, cooling the sample for later use by taking out the sample; (4) performing cathode micro-arc electrodeposition by placing the sample obtained in step (3) into a catholyte and using the sample as a cathode and a graphite sheet as an anode; (5) performing anode micro-arc oxidation by placing the sample subjected to the cathode micro-arc electrodeposition into an anolyte and using the sample as an anode and stainless steel as a cathode; and (6) rinsing the sample with water and ethanol in sequence, and blow-drying the sample. A second aspect of the present invention provides an ultra-high porosity micro-arc oxidation coating obtained by the above preparation method, where the micro-arc oxidation coating has a porosity of not less than 50% and a micropore diameter of 0.5-3 pm. A third aspect of the present invention provides application of the above magnesium alloy ultra-high porosity micro-arc oxidation coating in the fields of environment, catalysis, energy, military industry, aerospace, automobiles, textile or machinery. One or more specific embodiments of the present invention have at least the following beneficial effects: (1) After the magnesium alloy is subjected to the pretreatment, the ultrasonic cleaning, the barrier film preparation, the cathode micro-arc electrodeposition, and the anode micro-arc oxidation in sequence, an ultra-high porosity micro-arc oxidation coating with excellent bonding strength and mechanical properties can be prepared on the surface of the alloy. The micro-arc oxidation coating has a porosity of not less than 50% and a micropore diameter of 0.5-3 tm. (2) According to the method for preparing a magnesium alloy ultra-high porosity micro-arc oxidation coating of the present invention, all the steps are performed stepwise with clear objectives, respective advantages of the cathode micro-arc electrodeposition and the anode micro-arc oxidation are fully combined, and a high-quality target coating can be formed with only one power supply unit. (3) The present invention provides a new idea for preparing a magnesium alloy ultra-high porosity micro-arc oxidation coating, and also has certain value for promoting the application of a magnesium alloy with a high specific surface area in the fields of catalysis, energy, environment, etc.
The accompanying drawings constituting a part of the present invention are used for providing a further understanding of the present invention. The schematic embodiments and description of the present invention are intended to explain the present invention, and do not constitute improper restriction to the invention. FIG. 1 is a microscopic surface topography of a coating prepared in embodiment 1 of the present invention. FIG. 2 is a surface topography of the coating prepared in embodiment 1 of the present invention after a cross-cut test for adhesion of the coating is performed. FIG. 3 is a microscopic surface topography of a coating prepared in embodiment 2 of the present invention. FIG. 4 is a microscopic surface topography of a coating prepared in comparative example 1. FIG. 5 is a microscopic surface topography of a coating prepared in comparative example 2.
It should be noted that, the following detailed descriptions are all exemplary, and are intended to provide further descriptions of the present invention. Unless otherwise specified, all technical and scientific terms used herein have the same meanings as those usually understood by a person of ordinary skill in the art to which the present invention belongs. It should be noted that the terms used herein are merely used for describing specific implementations, and are not intended to limit exemplary implementations of the present invention. As used herein, the singular form is also intended to include the plural form unless the context clearly dictates otherwise. In addition, it should further be understood that, terms "comprise" and/or "include" used in this specification indicate that there are features, steps, operations, devices, components, and/or combinations thereof. As introduced in the BACKGROUND, in view of the problems of looseness in structure, decrease in bonding strength, and significant reduction in mechanical properties of the micro-arc oxidation coating caused by the reverse adjustment of process parameters of the micro-arc oxidation to obtain the developed pore structure, the present invention provides a method for preparing a magnesium alloy ultra-high porosity micro-arc oxidation coating, comprising:
(1) pretreating a cleaned magnesium alloy sample by placing the sample into an etching solution; (2) ultrasonically cleaning the pretreated magnesium alloy sample by placing the sample into an ultrasonic cleaning solution, then taking out the sample and blow-drying the sample for later use; (3) ultrasonically soaking the ultrasonically cleaned sample by placing the sample into a barrier film preparation solution, then taking out the sample, drying and curing the sample by placing the sample into an oven, and after ending the drying and curing, cooling the sample for later use by taking out the sample; (4) performing cathode micro-arc electrodeposition by placing the sample obtained in step (3) into a catholyte and using the sample as a cathode and a graphite sheet as an anode; (5) performing anode micro-arc oxidation by placing the sample subjected to the cathode micro-arc electrodeposition into an anolyte and using the sample as an anode and stainless steel as a cathode; and (6) rinsing the sample with water and ethanol in sequence, and blow-drying the sample. The aim of the pretreatment is to form dense point corrosion pits on the magnesium alloy substrate, such that the subsequent coating grows on the rough substrate, which facilitates the porosity improvement of the coating. The aim of ultrasonic cleaning is to remove loose corrosion products generated by the pretreatment reaction on one hand, and to neutralize an acid solution remaining in the pretreatment in an alkaline solution environment without causing new corrosion on the other hand. The aim of the barrier film preparation is to cure an insulating coating on the surface of the alloy substrate, so as to facilitate arcing discharge in the cathode micro-arc electrodeposition process. The aim of the cathode micro-arc electrodeposition is to use active ingredients in the catholyte to grow the film, and to prevent direct anode micro-arc oxidation from causing preferential melting to edges of the point corrosion pits prepared in the pretreatment process, thereby weakening the role of the pretreatment on one hand, and to prevent the direct anode micro-arc oxidation from easily generating paradoxical discharge locally at a microscopic tip of the surface of the alloy, resulting in looseness in structure of the coating and reduction in mechanical properties on the other hand. The aim of the anode micro-arc oxidation is to finally prepare an ultra-high porosity micro-arc oxidation coating with excellent bonding strength and mechanical properties by the coordination of various electrical parameters and components of the electrolyte solution. In one or more embodiments of the present invention, where, in step (1), operating conditions of the pretreatment are as follows: the etching solution has a temperature of -30°C, a pretreatment time is 15-50s, and the etching solution is composed of 5-15 vol% phosphoric acid, 0.5-3 g/L sodium fluoride, and the balance of water. In one or more embodiments of the present invention, where, in step (2), operating conditions of the ultrasonic cleaning are as follows: the ultrasonic cleaning solution has a temperature of 10-35°C, a cleaning time is 1-5 min, and the ultrasonic cleaning solution is composed of 3-8 g/L sodium hydroxide, 0.5-3 g/L ammonium citrate, and the balance of water. No ultrasonic frequency is defined, and common ultrasonic cleaning equipment (30-100 KHz) is available. In one or more embodiments of the present invention, in step (3), operating conditions for preparation of a barrier film are a soaking time of 30-60s, a drying temperature of -150°C, and a drying time of 15-30 min, and the barrier film preparation solution is composed of 5-10 g/L magnesium trisilicate, 5-20 mL/L ethylene glycol, and the balance of ethanol. In one or more embodiments of the present invention, in step (4), operating conditions of the cathode micro-arc electrodeposition are a voltage of 100-250 V, a duty cycle of 10-30%, a frequency of 80-150 Hz, and a time of 2-4 min. In one or more embodiments of the present invention, the catholyte is composed of -100 g/L aluminum nitrate, and the balance of ethanol. In one or more embodiments of the present invention, in step (5), operating conditions of the anode micro-arc oxidation are a voltage of 300-450 V, a duty cycle of 5-30%, a frequency of 500-1,000 Hz, and a time of 3-10 min. In one or more embodiments of the present invention, the anolyte is composed of 2-10 g/L sodium hexametaphosphate, 5-15 g/L potassium fluoride dehydrate, 0.2-3 g/L silver nitrate, 0.2-3 g/L glucose, and the balance of water, and before the anolyte is in use, ammonia water needs to be slowly and dropwise added until the solution changes from clear to turbid and clear again. A second aspect of the present invention provides an ultra-high porosity micro-arc oxidation coating obtained by the above preparation method, where the micro-arc oxidation coating has a porosity of not less than 50% and a micropore diameter of 0.5-3 Im. A third aspect of the present invention provides application of the above magnesium alloy ultra-high porosity micro-arc oxidation coating in the fields of environment, catalysis, energy, military industry, aerospace, automobiles, textile or machinery. The technical scheme of the present invention will be further described in detail below in conjunction with specific embodiments and comparative examples, in order that those skilled in the art can understand the technical scheme of the present invention more clearly. Embodiment 1 A magnesium alloy is treated according to the following steps: (1) A cleaned magnesium alloy sample was pretreated by placing the sample into an etching solution composed of: 10 vol% phosphoric acids, 1.5 g/L sodium fluoride, and the balance of water. The etching solution had a temperature of 20°C. The sample was soaked for s. (2) The sample was ultrasonically cleaned by taking the sample out of the etching solution, rinsing the sample with water, and placing the sample into an ultrasonic cleaning solution composed of: 5 g/L sodium hydroxide, 1.5 g/L ammonium citrate, and the balance of water. The ultrasonic cleaning solution had a temperature of 25°C. The sample was cleaned for 3 min. Then the sample was taken out and blow-dried for later use. (3) The sample obtained after the treatment in step (2) was ultrasonically soaked by placing the sample into a barrier film preparation solution composed of: 8 g/L magnesium trisilicate, 15 mL/L ethylene glycol, and the balance of ethanol. The sample was soaked for s. Then sample was dried and cured by taking out the sample and placing the sample into an oven. The drying temperature was 100°C. The drying time was 20 min. After ending the drying and curing, the sample was cooled for later use by taking out the sample. (4) Cathode micro-arc electrodeposition was performed by placing the sample obtained after the treatment in step (3) into a catholyte composed of: 80 g/L aluminum nitrate and the balance of ethanol and using the sample to be treated as a cathode and a graphite sheet as an anode. A voltage of 150 V was applied. The duty cycle was 15%. The frequency was 100 Hz. The time was 3 min. (5) Anode micro-arc oxidation was performed by placing the sample obtained after the treatment in step (4) into an anolyte composed of: 5 g/L sodium hexametaphosphate, 10 g /L potassium fluoride dihydrate, 1 g/L silver nitrate, 1 g/L glucose, and the balance of water, finally, slowly and dropwise adding ammonia water to make the solution change from clear to turbid and clear again, and using the sample to be treated as an anode and stainless steel as a cathode. A voltage of 380 V was applied. The duty cycle was 8%. The frequency was 800 Hz. The time was 6 min.
(6) The sample was rinsed with water and ethanol in sequence, and the sample was blow-dried. The prepared sample was observed with a scanning electron microscope. A microscopic surface topography of the sample is shown in FIG. 1. It can be observed that the surface of the coating has a well-developed pore structure. After statistical analysis, the coating has a porosity of greater than 55% and a micropore diameter of 1.2 pm. A cross-cut test for adhesion of the coating was performed according to the GB/T 9286-1998 standard. After the test, the surface morphology of the sample is shown in FIG. 2. The result shows that the adhesion of the coating is rated as level 1. The microhardness of the coating is 813 HV measured with a digital microhardness tester. Embodiment 2 A magnesium alloy is treated according to the following steps: (1) A cleaned magnesium alloy sample was pretreated by placing the sample into an etching solution composed of: 15 vol% phosphoric acids, 3 g/L sodium fluoride, and the balance of water. The etching solution had a temperature of 20°C. The sample was soaked for s. (2) The sample was ultrasonically cleaned by taking the sample out of the etching solution, rinsing the sample with water, and placing the sample into an ultrasonic cleaning solution composed of: 5 g/L sodium hydroxide, 1.5 g/L ammonium citrate, and the balance of water. The ultrasonic cleaning solution had a temperature of 25°C. The sample was cleaned for 5 min. Then the sample was taken out and blow-dried for later use. (3) The sample obtained after the treatment in step (2) was ultrasonically soaked by placing the sample into a barrier film preparation solution composed of: 8 g/L magnesium trisilicate, 15 mL/L ethylene glycol, and the balance of ethanol. The sample was soaked for s. Then sample was dried and cured by taking out the sample and placing the sample into an oven. The drying temperature was 100°C. The drying time was 20 min. After ending the drying and curing, the sample was cooled for later use by taking out the sample. (4) Cathode micro-arc electrodeposition was performed by placing the sample obtained after the treatment in step (3) into a catholyte composed of: 100 g/L aluminum nitrate and the balance of ethanol and using the sample to be treated as a cathode and a graphite sheet as an anode. A voltage of 200 V was applied. The duty cycle was 20%. The frequency was 100 Hz. The time was 3 min. (5) Anode micro-arc oxidation was performed by placing the sample obtained after the treatment in step (4) into an anolyte composed of: 5 g/L sodium hexametaphosphate, 10 g /L potassium fluoride dihydrate, 2 g/L silver nitrate, 2 g/L glucose, and the balance of water, finally, slowly and dropwise adding ammonia water to make the solution change from clear to turbid and clear again, and using the sample to be treated as an anode and stainless steel as a cathode. A voltage of 400 V was applied. The duty cycle was 15%. The frequency was 600 Hz. The time was 10 min. (6) The sample was rinsed with water and ethanol in sequence, and the sample was blow-dried. The prepared sample was observed with a scanning electron microscope. A microscopic surface topography of the sample is shown in FIG. 3. It can be observed that the surface of the coating has a well-developed pore structure. After statistical analysis, the coating has a porosity of greater than 60% and a micropore diameter of 1.4 Im. The result of a test for adhesion of the coating shows that the adhesion of the coating is rated as level 1. The microhardness of the coating is 861 HV measured with a digital microhardness tester. Comparative example 1 A magnesium alloy is treated according to the following steps: (1) A cleaned magnesium alloy sample was pretreated by placing the sample into an etching solution composed of: 10 vol% phosphoric acids, 1.5 g/L sodium fluoride, and the balance of water. The etching solution had a temperature of 20°C. The sample was soaked for s. (2) The sample was ultrasonically cleaned by taking the sample out of the etching solution, rinsing the sample with water, and placing the sample into an ultrasonic cleaning solution composed of: 5 g/L sodium hydroxide, 1.5 g/L ammonium citrate, and the balance of water. The ultrasonic cleaning solution had a temperature of 25°C. The sample was cleaned for 3 min. Then the sample was taken out and blow-dried for later use. (3) Anode micro-arc oxidation was performed by placing the sample obtained after the treatment in step (2) into an anolyte composed of: 5 g/L sodium hexametaphosphate, 10 g /L potassium fluoride dihydrate, 1 g/L silver nitrate, 1 g/L glucose, and the balance of water, finally, slowly and dropwise adding ammonia water to make the solution change from clear to turbid and clear again, and using the sample to be treated as an anode and stainless steel as a cathode. A voltage of 380 V was applied. The duty cycle was 8%. The frequency was 800 Hz. The time was 6 min. (4) The sample was rinsed with water and ethanol in sequence, and the sample was blow-dried. The prepared sample was observed with a scanning electron microscope. A microscopic surface topography of the sample is shown in FIG. 4. It can be observed that the pore structure on the surface of the coating is less developed than that in embodiment 1. After statistical analysis, the coating has a porosity of less than 40%. In addition, a loose structure is clearly visible on the coating, and the loose structure has an area of up to 50%. The result of a test for adhesion of the coating shows that the adhesion of the coating is rated as level 2, and the hardness is only 214 HV. Comparative example 2 A magnesium alloy is treated according to the following steps: (1) Anode micro-arc oxidation was performed by placing a cleaned magnesium alloy sample into an electrolyte solution composed of: 10 g/L sodium silicate, 5 g/L sodium fluoride, 8 g/L sodium hydroxide, and the balance of water, and using the sample to be treated as an anode and stainless steel as a cathode. A voltage of 380 V was applied. The duty ratio was 8%. The frequency was 800 Hz. The time was 10 min. (2) The sample was rinsed with water and ethanol in sequence, and the sample was blow-dried. The prepared sample was observed with a scanning electron microscope. A microscopic surface topography of the sample is shown in FIG. 5. It can be observed that the surface of the coating has a very less developed pore structure than that in embodiment 1. After statistical analysis, the coating has a porosity of less than 10% and a micropore diameter of up to 5 im which is obviously larger than that in embodiment 1. The above descriptions are merely preferred embodiments of the present invention and are not intended to limit the present invention. A person skilled in the art may make various alterations and variations to the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should fall within the protection scope of the present invention.
Claims (10)
1. A method for preparing a magnesium alloy ultra-high porosity micro-arc oxidation coating, specifically comprising: (1) pretreating a cleaned magnesium alloy sample by placing the sample into an etching solution; (2) ultrasonically cleaning the pretreated magnesium alloy sample by placing the sample into an ultrasonic cleaning solution, then taking out the sample and blow-drying the sample for later use; (3) ultrasonically soaking the ultrasonically cleaned sample by placing the sample into a barrier film preparation solution, then taking out the sample, drying and curing the sample by placing the sample into an oven, and after ending the drying and curing, cooling the sample for later use by taking out the sample; (4) performing cathode micro-arc electrodeposition by placing the sample obtained in step (3) into a catholyte and using the sample as a cathode and a graphite sheet as an anode; (5) performing anode micro-arc oxidation by placing the sample subjected to the cathode micro-arc electrodeposition into an anolyte and using the sample as an anode and stainless steel as a cathode; and (6) rinsing the sample with water and ethanol in sequence, and blow-drying the sample.
2. The preparation method according to claim 1, wherein, in step (1), operating conditions of the pretreatment are as follows: the etching solution has a temperature of -30°C, a treatment time is 15-50s, and the etching solution is composed of 5-15 vol% phosphoric acid, 0.5-3 g/L sodium fluoride, and the balance of water.
3. The preparation method according to claim 1, wherein, in step (2), operating conditions of the ultrasonic cleaning are as follows: the ultrasonic cleaning solution has a temperature of 10-35°C, a cleaning time is 1-5 min, and the ultrasonic cleaning solution is composed of 3-8 g/L sodium hydroxide, 0.5-3 g/L ammonium citrate, and the balance of water.
4. The preparation method according to claim 1, wherein, in step (3), operating conditions for barrier film preparation are a soaking time of 30-60s, a drying temperature of -150°C, and a drying time of 15-30 min, and the barrier film preparation solution is composed of 5-10 g/L magnesium trisilicate, 5-20 mL/L ethylene glycol, and the balance of ethanol.
5. The preparation method according to claim 1, wherein, in step (4), operating conditions of the cathode micro-arc electrodeposition are a voltage of 100-250 V, a duty cycle of 10-30%, a frequency of 80-150 Hz, and a time of 2-4 min.
6. The preparation method according to claim 1, wherein, in step (4), the catholyte is composed of 50-100 g/L aluminum nitrate, and the balance of ethanol.
7. The preparation method according to claim 1, wherein, in step (5), operating conditions of the anode micro-arc oxidation are a voltage of 300-450 V, a duty cycle of -30%, a frequency of 500-1,000 Hz, and a time of 3-10 min.
8. The preparation method according to claim 1, wherein, in step (5), the anolyte is composed of 2-10 g/L sodium hexametaphosphate, 5-15 g/L potassium fluoride dihydrate, 0.2-3 g/L silver nitrate, 0.2-3 g/L glucose, and the balance of water, and before the anolyte is in use, ammonia water needs to be slowly and dropwise added until the solution changes from clear to turbid and clear again.
9. The magnesium alloy ultra-high porosity micro-arc oxidation coating obtained by the preparation method according to any one of claims 1 to 8, having a porosity of not less than % and a micropore diameter of 0.5-3 im.
10. Application of the magnesium alloy ultra-high porosity micro-arc oxidation coating according to claim 9 in the fields of environment, catalysis, energy, military industry, aerospace, automobiles, textile or machinery.
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| PCT/CN2021/084381 WO2022165961A1 (en) | 2021-02-02 | 2021-03-31 | Magnesium alloy ultrahigh-porosity micro-arc oxidation coating, preparation method therefor and use thereof |
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| CN114563322B (en) * | 2022-01-28 | 2023-12-19 | 武汉理工大学 | Characterization and regulation method for aluminum alloy surface corrosion microstructure in aluminum alloy/polymer laminated material |
| CN115142107B (en) * | 2022-06-10 | 2024-05-31 | 中国科学院金属研究所 | Preparation method of environment-friendly conductive protective film on magnesium alloy surface |
| CN115418697A (en) * | 2022-09-23 | 2022-12-02 | 西北有色金属研究院 | Environment-friendly electrolyte for preparing corrosion-resistant coating with high compact structure on surface of magnesium alloy and application of environment-friendly electrolyte |
| CN118007216B (en) * | 2024-04-08 | 2024-07-23 | 上海航天精密机械研究所 | Micro-arc oxidation corrosion-resistant coating for rare earth magnesium alloy and preparation method thereof |
| CN118292075A (en) * | 2024-05-31 | 2024-07-05 | 太原理工大学 | Preparation method of micro-arc oxidation conductive coating on magnesium alloy surface |
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| CN102677127B (en) * | 2012-06-11 | 2014-08-06 | 西北有色金属研究院 | Magnesium alloy microarc oxidation-electrophoresis composite coating and preparation method thereof |
| CN103046100B (en) * | 2013-01-29 | 2015-05-20 | 哈尔滨工业大学 | Method for preparing twin-stage pore micro-arc oxidation ceramic coating through three steps |
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