CN113088966B - Magnesium alloy composite coating and preparation method thereof - Google Patents
Magnesium alloy composite coating and preparation method thereof Download PDFInfo
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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
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- C25D11/026—Anodisation with spark discharge
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
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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
- C25D11/30—Anodisation of magnesium or alloys based thereon
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Abstract
The invention relates to a magnesium alloy composite coating, which is characterized by comprising the following components sequentially connected from inside to outside: the micro-arc oxidation layer is 10-50 mu m in thickness and is formed by micro-arc oxidation treatment of magnesium alloy under electrolyte; the thickness of the epoxy resin transition layer is more than 0 and less than or equal to 50 mu m, and the epoxy resin transition layer is formed by coating epoxy resin on the outer surface of the micro-arc oxidation layer; and the thickness of the polyurea layer is 1-3mm, and the polyurea layer is formed by coating the polyurea on the outer surface of the epoxy resin transition layer. The application also discloses a preparation method of the magnesium alloy composite coating. Compared with the prior art, the magnesium alloy composite coating can improve corrosion resistance and reduce the risk of coating falling off.
Description
Technical Field
The invention belongs to the technical field of metal surface treatment, and particularly relates to a magnesium alloy composite coating and a preparation method thereof.
Background
The magnesium alloy has the advantages of light weight, high specific strength, good shock resistance and the like, and has good application prospect in the field of equipment manufacturing. However, since the electrode potential of magnesium is low, this characteristic causes magnesium and its alloys to be easily corroded, thus greatly limiting the application of magnesium and its alloys.
In order to overcome the defects, the invention patent No. ZL201610313339.6 (patent publication No. CN 105887084B) discloses a preparation method of a magnesium alloy composite coating with a self-repairing function, which comprises the following steps: polishing the surface of the magnesium alloy, degreasing; micro-arc oxidizing electrolyte, controlling current or voltage method, regulating pulse power supply frequency and duty ratio, and micro-arc oxidizingThe interval is 15-60 min; cleaning and drying magnesium alloy after micro-arc oxidation, and placing the magnesium alloy under the pressure of 7-8 multiplied by 10 -3 In a vacuum coating chamber with Pa and 100-200 ℃, regulating argon pressure to 2-3 Pa, pulse bias duty ratio to 20-30%, bias voltage to 800-1000V, and discharging and cleaning for 2-5 min; adopting pure aluminum or pure titanium target material, and ending the argon ion bombardment until the pressure is 3-5 multiplied by 10 -1 Pa, the bias duty ratio is 40-50%, and the bias voltage is 500-1000V; the arc current is 60-120A, and the coating time is 10-60 min.
In another embodiment, the method disclosed in the invention patent application CN201910372634.2 (application publication CN110016707 a) for magnesium alloy micro-arc oxidation and preparation method of micro-arc oxidation iron-containing electrolyte, the magnesium alloy micro-arc oxidation comprises three steps of pretreatment, micro-arc oxidation and post-treatment, and the micro-arc oxidation iron-containing electrolyte comprises the following components: 10-60g/L of phosphate, 1-6g/L of strong alkali, 2-10g/L of complexing agent and 5-20g/L of electrolyte containing iron, wherein the complexing agent is potassium gluconate, triethanolamine or sorbitol, the electrolyte containing iron is potassium iron oxalate, ferric citrate or ferrous sulfate, and the electrolyte has good stability, and the solution still keeps stable and does not generate precipitate under alkaline environment.
The magnesium alloy surface treated by micro-arc oxidation can generate a layer of coating which has corrosion resistance, thereby protecting the magnesium alloy and preventing the magnesium alloy from corrosion.
Disclosure of Invention
The first technical problem to be solved by the invention is to provide a magnesium alloy composite coating capable of improving corrosion resistance aiming at the current state of the art.
The second technical problem to be solved by the invention is to provide a magnesium alloy composite coating capable of reducing the risk of coating falling.
The third technical problem to be solved by the invention is to provide a preparation method of the magnesium alloy composite coating.
The technical scheme adopted by the invention for solving the first technical problem and the second technical problem is as follows: the magnesium alloy composite coating is characterized by comprising the following components sequentially connected from inside to outside:
the micro-arc oxidation layer is 10-50 mu m in thickness and is formed by micro-arc oxidation treatment of magnesium alloy under electrolyte;
the thickness of the epoxy resin transition layer is more than 0 and less than or equal to 50 mu m, and the epoxy resin transition layer is formed by coating epoxy resin on the outer surface of the micro-arc oxidation layer;
and the thickness of the polyurea layer is 1-3mm, and the polyurea layer is formed by coating the polyurea on the outer surface of the epoxy resin transition layer.
Further, the functional layer or the decorative layer is arranged on the outer surface of the polyurea layer, and the thickness of the functional layer or the decorative layer is more than 0 and less than or equal to 200 mu m.
Preferably, the functional layer is a coating with marine antifouling or stealth functions, and the decorative layer is a coating with camouflage patterns. The coating with marine antifouling function can be coated by the existing marine antifouling paint, the main function of the marine antifouling paint is to prevent marine organism from fouling by gradually exuding the antifouling agent in a paint film, and the commercial antifouling paint at present is mainly divided into two types, namely, the antifouling paint containing insecticide, such as hydration type self-polishing antifouling paint, hydrolysis type self-polishing antifouling paint (such as copper acrylate copolymer self-polishing antifouling paint, zinc acrylate copolymer self-polishing antifouling paint and silanized acrylic acid copolymer self-polishing antifouling paint), and mixed self-polishing antifouling paint; and secondly, an anti-fouling paint without insecticide, such as an organosilicon low-surface energy anti-fouling paint. Coatings with stealth function such as existing optical (near infrared containing) stealth coatings, laser stealth coatings, radar stealth coatings, infrared stealth coatings, and the like.
Preferably, the epoxy resin is bisphenol A type epoxy resin with the product mark of E-51. The bisphenol A epoxy resin with the product mark of E-51 is solvent-free epoxy resin, and the solvent-free epoxy resin can release small bubbles upwards in the curing process, and the bubbles can not pass through the surface of the composite coating with the multilayer structure after being dried, and various performance defects such as paint film cracking or matrix falling and the like can be generated by accumulated bubbles. The bisphenol A type epoxy resin with the product mark of E-51 can overcome the defects.
Preferably, the polyurea is a two-component polyurea comprising a polyaspartate resin and an aliphatic polyisocyanate, the polyaspartate resin and the aliphatic polyisocyanate being produced by Zhuhai Boseki chemical Co., ltd. And having a mass ratio of 1:1.
The technical scheme adopted by the invention for solving the third technical problem is as follows: the preparation method of the magnesium alloy composite coating is characterized by comprising the following steps:
1. pre-treating, polishing the surface of the magnesium alloy, then adopting ultrasonic cleaning for 10-40 min, taking out and immersing in chromic acid solution for 5-60 s, wherein the ultrasonic power is 50W, the ultrasonic frequency is 80KHz, and the proportion of the chromic acid solution is as follows: the chromic acid solution contains 200-300 g CrO per liter 3 50-100 g of HF with the mass concentration of 40 percent is taken out from chromic acid solution, firstly washed for 5-10 min by deionized water, then put into NaOH solution with the mass concentration of 5-20g/L for washing for 10-40 s, taken out, washed by deionized water and dried;
2. preparing a micro-arc oxidation layer, immersing the pretreated magnesium alloy into electrolyte, performing micro-arc oxidation treatment by using a double-pulse power supply to obtain a sample with the micro-arc oxidation layer, and then cleaning and drying the sample; the positive voltage of the double-pulse power supply in a constant voltage mode is 250-550V, the negative voltage is 50-250V, the positive and negative pulse ratio is 1:1, the frequency is 300-1000 Hz, the duty ratio of the positive and negative pulses is 5-45%, the micro-arc oxidation time is 10-40 min, and the temperature of electrolyte is 5-30 ℃; the electrolyte comprises the following components:
the film forming agent component adopts one or two of silicate 5-25 g/L and phosphate 10-35 g/L;
complexing agent, which adopts one or two of sodium citrate 5-25 g/L, EDTA-disodium 5-15 g/L;
an arc inhibitor adopts one or two of triethanolamine 5-15 ml/L and glycerol 5-15 ml/L;
other electrolytes are nano Al with the particle size less than or equal to 30nm and KF of 5-30 g/L 2 O 3 0.5～3g/L；
The pH regulator is one or two of 0.5-5 g/L of sodium hydroxide and 0.5-5 g/L of potassium hydroxide;
the balance being water;
the pH value of the electrolyte is 8-12; in the micro-arc oxidation treatment, magnesium alloy is used as an anode, the anode of a double-pulse power supply is connected, stainless steel is used as a cathode, the cathode of the double-pulse power supply is connected, and then the anode and the cathode are put into an electrolytic tank containing electrolyte together for micro-arc oxidation treatment;
3. preparing an epoxy resin transition layer, and coating epoxy resin on the outer surface of the micro-arc oxidation layer within 6 hours after the micro-arc oxidation treatment is completed;
4. and preparing a polyurea layer, and coating polyurea on the outer surface of the epoxy resin transition layer within 6 hours after the preparation of the epoxy resin transition layer to obtain the magnesium alloy composite coating.
Preferably, in the first step, 1000-mesh sand paper is used for polishing the surface of the magnesium alloy.
Preferably, the third and fourth steps are performed by spraying, brushing or dipping.
Preferably, the sample obtained after the micro-arc oxidation treatment in the second step is rinsed for 10-30 min by deionized water, and is put into a drying box with the temperature of 100-120 ℃ for drying for 10-20 min, and then is taken out, placed and cooled to the temperature of below 30 ℃.
Compared with the prior art, the invention has the advantages that: the micro-arc oxidation layer, the epoxy resin transition layer and the polyurea layer with certain thickness are sequentially arranged on the outer surface of the magnesium alloy, so that the corrosion resistance, the water resistance, the scratch resistance and the collision resistance of the magnesium alloy can be effectively improved, and the magnesium alloy can work in a severe atmosphere environment and under water for a long time. And in this application, the micro-arc oxidation layer is the dense outer porous structure of inlayer, pore radius is less, is about 1 micron, and the viscosity of polyurea is big, if the direct coating of polyurea is at the surface on micro-arc oxidation layer, in the hole on micro-arc oxidation layer can not permeate well into to the polyurea, leads to the cohesion of polyurea and micro-arc oxidation layer relatively poor, and this application is through setting up the epoxy transition layer between micro-arc oxidation layer and polyurea layer, all has good cohesion between epoxy transition layer and micro-arc oxidation layer, the polyurea layer, and then improves the adhesive force of whole coating, reduces the risk that the coating drops because of receiving scraping, striking.
Drawings
FIG. 1 is a schematic structural diagram of a magnesium alloy composite coating according to an embodiment of the present invention;
fig. 2 is a schematic structural diagram of a magnesium alloy composite coating according to a second embodiment of the present invention.
Detailed Description
The invention is described in further detail below with reference to the embodiments of the drawings.
Embodiment one:
as shown in FIG. 1, a magnesium alloy composite coating and a preparation method thereof according to a preferred embodiment of the invention are provided, wherein the magnesium alloy composite coating comprises a micro-arc oxidation layer, an epoxy resin transition layer and a polyurea layer which are sequentially connected from inside to outside. Wherein the thickness of the micro-arc oxidation layer is 10 mu m, and the micro-arc oxidation layer is formed by micro-arc oxidation treatment of magnesium alloy under electrolyte. The thickness of the epoxy resin transition layer is 20 mu m, and the epoxy resin transition layer is formed by coating epoxy resin on the outer surface of the micro-arc oxidation layer. The thickness of the polyurea layer was 1mm, which was formed by coating the polyurea on the outer surface of the above-mentioned epoxy resin transition layer.
The epoxy resin in this example is bisphenol A type epoxy resin with the product brand of E-51. The polyurea is a bi-component polyurea and comprises polyaspartate resin and aliphatic polyisocyanate which are manufactured by Zhuhai flying chemical industry Co Ltd and have the model number of F-524, wherein the mass ratio of the polyaspartate resin to the aliphatic polyisocyanate is 1:1.
The preparation method of the magnesium alloy composite coating of the embodiment comprises the following steps:
1. pre-treating, namely polishing the surface of the magnesium alloy by using 1000-mesh sand paper, then cleaning for 10min by adopting ultrasonic waves, taking out, immersing in chromic acid solution for 5s, wherein the ultrasonic power is 50W, the ultrasonic frequency is 80KHz, and the proportion of the chromic acid solution is as follows: 200g of CrO per liter of chromic acid solution 3 And 50g of HF with 40% mass concentration, washing with deionized water for 5min, washing with 5g/L NaOH solution for 10s, and taking outCleaning with deionized water, and drying;
2. preparing a micro-arc oxidation layer, immersing the pretreated magnesium alloy into electrolyte, and performing micro-arc oxidation treatment by using a double-pulse power supply to obtain a sample with the micro-arc oxidation layer; the positive voltage of the double-pulse power supply in a constant voltage mode is 250V, the negative voltage is 50V, the positive and negative pulse ratio is 1:1, the frequency is 300Hz, the duty ratio of the positive and negative pulses is 5%, the micro-arc oxidation time is 10min, and the temperature of electrolyte is 5 ℃; the electrolyte comprises the following components:
the film forming agent adopts silicate 25g/L; the complexing agent adopts 5g/L, EDTA-disodium 5g/L sodium citrate; the arc inhibitor adopts triethanolamine 5ml/L and glycerol 5ml/L; the other electrolyte is KF 5g/L nano Al with the grain diameter less than or equal to 30nm 2 O 3 0.5g/L; the pH regulator is sodium hydroxide 0.5g/L and potassium hydroxide 0.5g/L; the balance of deionized water; in the micro-arc oxidation treatment, magnesium alloy is used as an anode, the anode of a double-pulse power supply is connected, stainless steel is used as a cathode, the cathode of the double-pulse power supply is connected, and then the anode and the cathode are put into an electrolytic tank containing electrolyte together for micro-arc oxidation treatment; and (3) washing with deionized water for 10min after the micro-arc oxidation is completed, putting into a drying box at 100 ℃ for drying for 10min, taking out, placing and cooling to below 30 ℃.
3. Preparing an epoxy resin transition layer, and coating epoxy resin on the outer surface of the micro-arc oxidation layer in a spraying, brushing or dip-coating mode within 6 hours after the micro-arc oxidation treatment is finished; the surface of the micro-arc oxidation layer is dried and the inside is not dried within 6 hours after the micro-arc oxidation treatment is finished;
4. preparing a polyurea layer, and coating polyurea on the outer surface of the epoxy resin transition layer within 6 hours after the preparation of the epoxy resin transition layer to obtain the magnesium alloy composite coating; and the surface of the epoxy resin transition layer is dried and the inside of the epoxy resin transition layer is not dried within 6 hours after the preparation of the epoxy resin transition layer is finished.
The adhesive force of the magnesium alloy composite coating prepared by the embodiment is 7 megapascals, the salt fog resistance is 2000h, and the seawater soaking resistance is more than 1 year.
Embodiment two:
as shown in fig. 2, a magnesium alloy composite coating and a preparation method thereof according to a second preferred embodiment of the present invention are the same as those of the first preferred embodiment, except that the magnesium alloy composite coating further includes a functional layer disposed on an outer surface of the polyurea layer, and the functional layer is a coating having an ocean antifouling function or a stealth function, and the thickness of the functional layer is 100 μm.
The preparation method of the magnesium alloy composite coating of the embodiment is basically the same as that of the first embodiment, and the difference is that the embodiment further comprises: step five, preparing a functional layer, namely coating functional paint on the outer surface of the polyurea layer within 6 hours after the preparation of the polyurea layer, and obtaining the functional layer; within 6 hours after the preparation of the polyurea layer, the surface of the polyurea layer was dried and the inside was not dried.
The adhesive force of the magnesium alloy composite coating prepared by the embodiment is 7 megapascals, the salt fog resistance is 2000h, and the seawater soaking resistance is more than 1 year.
The thickness of the micro-arc oxide layer prepared in this example was 30 μm, and the preparation method was as follows:
1. pre-treating, polishing the surface of the magnesium alloy, then adopting ultrasonic cleaning for 20min, taking out, immersing in chromic acid solution for 20s, wherein the ultrasonic power is 50W, the ultrasonic frequency is 80KHz, and the proportion of the chromic acid solution is as follows: each liter of chromic acid solution contained 250g of CrO 3 And 70g of HF with the mass concentration of 40 percent, taking out from the chromic acid solution, adopting deionized water to wash for 7min, putting into 10g/L NaOH solution to wash for 20s, taking out, cleaning with the deionized water, and drying;
2. preparing a micro-arc oxidation layer, immersing the pretreated magnesium alloy into electrolyte, and performing micro-arc oxidation treatment by using a double-pulse power supply to obtain a sample with the micro-arc oxidation layer; the positive voltage of the double-pulse power supply in a constant voltage mode is 400V, the negative voltage is 100V, the positive and negative pulse ratio is 1:1, the frequency is 800Hz, the duty ratio of the positive and negative pulses is 15%, the micro-arc oxidation time is 25min, and the temperature of electrolyte is 15 ℃; the electrolyte comprises the following components:
the film forming agent adopts the components of35g/L silicate; the complexing agent adopts 25g/L sodium citrate; the arc inhibitor adopts triethanolamine 15ml/L; the other electrolyte is KF 15g/L and nano Al with the particle size less than or equal to 30nm 2 O 3 1.5g/L; the pH regulator is 5g/L of sodium hydroxide; the balance of deionized water; in the micro-arc oxidation treatment, magnesium alloy is used as an anode, the anode of a double-pulse power supply is connected, stainless steel is used as a cathode, the cathode of the double-pulse power supply is connected, and then the anode and the cathode are put into an electrolytic tank containing electrolyte together for micro-arc oxidation treatment; and (3) washing with deionized water for 20min after the micro-arc oxidation is completed, putting into a drying box at 100 ℃ for drying for 15min, taking out, placing and cooling to below 30 ℃.
Embodiment III:
the magnesium alloy composite coating and the preparation method thereof in the embodiment are basically the same as those in the second embodiment, except that the thickness of the micro-arc oxidation layer in the embodiment is 50 μm, the thickness of the epoxy resin transition layer is 30 μm, and the thickness of the polyurea layer is 3mm. The magnesium alloy composite coating of the embodiment also comprises a decorative layer which replaces the functional layer, wherein the decorative layer is a coating with camouflage patterns, and the thickness of the decorative layer is 200 mu m.
The preparation method of the micro-arc oxidation layer in the embodiment is as follows:
firstly, preprocessing, polishing the surface of the magnesium alloy, then adopting ultrasonic cleaning for 40min, taking out, immersing in chromic acid solution for 60s, wherein the ultrasonic power is 50W, the ultrasonic frequency is 80KHz, and the proportion of the chromic acid solution is as follows: each liter of chromic acid solution contained 300g of CrO 3 100g of HF with the mass concentration of 40 percent is taken out from chromic acid solution, then is washed for 10 minutes by deionized water, is put into 20g/L NaOH solution for washing for 40 seconds, is taken out, is washed clean by deionized water and is dried;
preparing a micro-arc oxidation layer, namely immersing the pretreated magnesium alloy into electrolyte, and performing micro-arc oxidation treatment by using a double-pulse power supply to obtain a sample with the micro-arc oxidation layer; the positive voltage of the double-pulse power supply in a constant voltage mode is 550V, the negative voltage is 250V, the positive and negative pulse ratio is 1:1, the frequency is 1000Hz, the duty ratio of the positive and negative pulses is 45%, the micro-arc oxidation time is 40min, and the temperature of electrolyte is 30 ℃; the electrolyte comprises the following components:
the film forming agent adopts silicate 5g/L and phosphate 10g/L; EDTA-disodium 15g/L is adopted as complexing agent; the arc inhibitor adopts glycerin 15ml/L; the other electrolyte is KF 30g/L and nano Al with the particle size less than or equal to 30nm 2 O 3 3g/L; the pH regulator is potassium hydroxide 5g/L; the balance of deionized water; in the micro-arc oxidation treatment, magnesium alloy is used as an anode, the anode of a double-pulse power supply is connected, stainless steel is used as a cathode, the cathode of the double-pulse power supply is connected, and then the anode and the cathode are put into an electrolytic tank containing electrolyte together for micro-arc oxidation treatment; and (3) washing with deionized water for 30min after the micro-arc oxidation is completed, putting into a drying box at 120 ℃ for drying for 20min, taking out, placing and cooling to below 30 ℃.
The adhesive force of the magnesium alloy composite coating prepared by the embodiment is 7 megapascals, the salt fog resistance is 2000h, and the seawater soaking resistance is more than 1 year.
Embodiment four:
the magnesium alloy composite coating and the preparation method thereof in this embodiment are basically the same as those in the first embodiment, except that the thickness of the epoxy resin transition layer in this embodiment is 50 μm and the thickness of the polyurea layer is 2mm.
The adhesive force of the magnesium alloy composite coating prepared by the embodiment is 7 megapascals, the salt fog resistance is 2000h, and the seawater soaking resistance is more than 1 year.
Claims (6)
1. The magnesium alloy composite coating is characterized by comprising the following components sequentially connected from inside to outside:
the micro-arc oxidation layer is 10-50 mu m in thickness and is formed by micro-arc oxidation treatment of magnesium alloy under electrolyte;
the thickness of the epoxy resin transition layer is more than 0 and less than or equal to 50 mu m, and the epoxy resin transition layer is formed by coating epoxy resin on the outer surface of the micro-arc oxidation layer;
the thickness of the polyurea layer is 1-3mm, and the polyurea layer is formed by coating the polyurea on the outer surface of the epoxy resin transition layer;
the epoxy resin is bisphenol A type epoxy resin with the product mark of E-51;
the polyurea is a bi-component polyurea, and comprises polyaspartic acid ester resin with the model number of F-524 and aliphatic polyisocyanate which are produced by Zhuhai flying chemical industry Co., ltd, wherein the mass ratio of the polyaspartic acid ester resin to the aliphatic polyisocyanate is 1:1;
the preparation method of the magnesium alloy composite coating comprises the following steps:
firstly, preprocessing, polishing the surface of the magnesium alloy, then adopting ultrasonic cleaning for 10-40 min, taking out, immersing in chromic acid solution for 5-60 s, wherein the ultrasonic power is 50W, the ultrasonic frequency is 80KHz, and the proportion of the chromic acid solution is as follows: the chromic acid solution contains 200-300 g CrO per liter 3 50-100 g of HF with the mass concentration of 40 percent is taken out from chromic acid solution, firstly washed for 5-10 min by deionized water, then put into NaOH solution with the mass concentration of 5-20g/L for washing for 10-40 s, taken out, washed by deionized water and dried;
preparing a micro-arc oxidation layer, immersing the pretreated magnesium alloy into electrolyte, performing micro-arc oxidation treatment by using a double-pulse power supply to obtain a sample with the micro-arc oxidation layer, and then cleaning and drying the sample; the positive voltage of the double-pulse power supply in a constant voltage mode is 250-550V, the negative voltage is 50-250V, the positive and negative pulse ratio is 1:1, the frequency is 300-1000 Hz, the duty ratio of the positive and negative pulses is 5-45%, the micro-arc oxidation time is 10-40 min, and the temperature of electrolyte is 5-30 ℃; the electrolyte comprises the following components:
the film forming agent component adopts one or two of silicate 5-25 g/L and phosphate 10-35 g/L;
complexing agent, which adopts one or two of sodium citrate 5-25 g/L, EDTA-disodium 5-15 g/L;
an arc inhibitor adopts one or two of triethanolamine 5-15 ml/L and glycerol 5-15 ml/L;
other electrolytes are nano Al with the particle size less than or equal to 30nm and KF of 5-30 g/L 2 O 3 0.5～3g/L；
The pH regulator is one or two of 0.5-5 g/L of sodium hydroxide and 0.5-5 g/L of potassium hydroxide;
the balance being water;
step three, preparing an epoxy resin transition layer, and coating epoxy resin on the outer surface of the micro-arc oxidation layer within 6 hours after the micro-arc oxidation treatment is completed;
and fourthly, preparing a polyurea layer, and coating polyurea on the outer surface of the epoxy resin transition layer within 6 hours after the preparation of the epoxy resin transition layer to obtain the magnesium alloy composite coating.
2. The magnesium alloy composite coating according to claim 1, wherein: the functional layer or the decorative layer is arranged on the outer surface of the polyurea layer, and the thickness of the functional layer or the decorative layer is more than 0 and less than or equal to 200 mu m.
3. The magnesium alloy composite coating according to claim 2, wherein: the functional layer is a coating with marine antifouling function or stealth function, and the decorative layer is a coating with camouflage patterns.
4. The magnesium alloy composite coating according to claim 1, wherein: and in the first step, the surface of the magnesium alloy is polished by 1000-mesh sand paper.
5. The magnesium alloy composite coating according to claim 1, wherein: and in the third step and the fourth step, the coating is carried out in a spray coating, brush coating or dip coating mode.
6. The magnesium alloy composite coating according to claim 1, wherein: and (3) washing the sample obtained after the micro-arc oxidation treatment in the step two with deionized water for 10-30 min, putting the sample into a 100-120 ℃ drying box for drying for 10-20 min, taking out, placing and cooling to below 30 ℃.
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| CN102080248A (en) * | 2011-01-31 | 2011-06-01 | 浙江工业大学 | Preparation method of magnesium alloy micro-arc oxidation film |
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| CN105220198B (en) * | 2015-10-22 | 2017-12-19 | 桂林电子科技大学 | A kind of acid-alkali-corrosive-resisting light metal material elastomer and its manufacturing process |
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| CN108950649A (en) * | 2018-07-02 | 2018-12-07 | 山东科技大学 | A kind of preparation method of magnesium/magnesium alloy surface by micro-arc oxidation water-bath sealing of hole composite coating |
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