CN112522703A - Fluorine-free super-hydrophobic Zn-MOF composite coating on surface of magnesium alloy and preparation method thereof - Google Patents
Fluorine-free super-hydrophobic Zn-MOF composite coating on surface of magnesium alloy and preparation method thereof Download PDFInfo
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- 229910000861 Mg alloy Inorganic materials 0.000 title claims abstract description 76
- 238000000576 coating method Methods 0.000 title claims abstract description 38
- 229910007566 Zn-MOF Inorganic materials 0.000 title claims abstract description 36
- 239000011248 coating agent Substances 0.000 title claims abstract description 36
- 239000013094 zinc-based metal-organic framework Substances 0.000 title claims abstract description 36
- 239000002131 composite material Substances 0.000 title claims abstract description 25
- 230000003075 superhydrophobic effect Effects 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000007745 plasma electrolytic oxidation reaction Methods 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 238000001035 drying Methods 0.000 claims abstract description 14
- 238000011282 treatment Methods 0.000 claims abstract description 13
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 11
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 11
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 11
- 235000021355 Stearic acid Nutrition 0.000 claims abstract description 7
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 7
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000008117 stearic acid Substances 0.000 claims abstract description 7
- 238000005238 degreasing Methods 0.000 claims abstract description 6
- 238000004140 cleaning Methods 0.000 claims abstract description 4
- 239000011159 matrix material Substances 0.000 claims abstract description 4
- 238000005498 polishing Methods 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000011734 sodium Substances 0.000 claims description 10
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 239000012530 fluid Substances 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims description 3
- 235000019254 sodium formate Nutrition 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 3
- 229910000406 trisodium phosphate Inorganic materials 0.000 claims description 3
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 3
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 2
- 239000004280 Sodium formate Substances 0.000 claims description 2
- KYIDJMYDIPHNJS-UHFFFAOYSA-N ethanol;octadecanoic acid Chemical compound CCO.CCCCCCCCCCCCCCCCCC(O)=O KYIDJMYDIPHNJS-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 238000012986 modification Methods 0.000 claims 1
- 230000004048 modification Effects 0.000 claims 1
- 238000005260 corrosion Methods 0.000 abstract description 19
- 230000007797 corrosion Effects 0.000 abstract description 19
- 239000000758 substrate Substances 0.000 abstract description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052731 fluorine Inorganic materials 0.000 abstract description 2
- 239000011737 fluorine Substances 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 10
- 230000010287 polarization Effects 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 4
- 239000011701 zinc Substances 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012621 metal-organic framework Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229940075397 calomel Drugs 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- 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
- C23C28/04—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 only coatings of inorganic non-metallic material
-
- C—CHEMISTRY; METALLURGY
- 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
- C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
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- C—CHEMISTRY; METALLURGY
- 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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
- C23G1/22—Light metals
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Metallurgy (AREA)
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- Mechanical Engineering (AREA)
- Electrochemistry (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
The invention discloses a fluorine-free super-hydrophobic Zn-MOF composite coating on the surface of magnesium alloy and a preparation method thereof. The fluorine-free super-hydrophobic Zn-MOF composite coating on the surface of the magnesium alloy specifically comprises a micro-arc oxidation layer, a Zn-MOF layer and a stearic acid layer which are sequentially attached to the surface of the magnesium alloy. Sequentially polishing, degreasing and ultrasonically cleaning a magnesium alloy matrix, and then performing micro-arc oxidation treatment to form a micro-arc oxidation film on the surface; and (3) placing the magnesium alloy into a polytetrafluoroethylene reaction kettle for high-temperature high-pressure reaction to form a Zn-MOF coating, finally treating the Zn-MOF coating by using a low-surface-energy substance stearic acid, and drying to obtain the fluorine-free super-hydrophobic Zn-MOF composite coating on the surface of the magnesium alloy. The preparation method is simple in preparation process and free of fluorine, the composite coating has good binding force with the magnesium alloy substrate, can be uniformly distributed on the surface of the magnesium alloy, has low corrosion current density, achieves the super-hydrophobic effect, and shows good corrosion resistance.
Description
Technical Field
The invention belongs to a metal material corrosion-resistant super-hydrophobic composite coating, and particularly relates to a fluorine-free super-hydrophobic Zn-MOF composite coating on the surface of a magnesium alloy and a preparation method thereof.
Background
Magnesium and its alloys are ideal green engineering materials with many excellent properties, such as low density, excellent biocompatibility and degradability, high strength ratio, etc. Has wide application prospect in the fields of automobiles, aerospace industry, electronic products and the like. However, magnesium alloys are relatively reactive and have a very negative potential, which makes them susceptible to corrosion in humid air, and this drawback severely limits their large-scale use. To address this problem, researchers have introduced a number of treatments. Micro-arc oxidation (MAO) is more commonly used in a number of coating preparation methods. This is due to its satisfactory coating properties, including high adhesion to the substrate, high microhardness, and high corrosion resistance. However, since the micro-arc discharge causes the formation of volcano-like micro-pores on the surface, a path for a corrosive medium to contact with the magnesium alloy is provided, resulting in a decrease in the corrosion resistance of the film. Metal organic framework Materials (MOFs) are novel nanomaterials that have been vigorously developed over time due to their wide variety, adjustable morphology, high stability, and high specific surface area. The application aims to construct a Zn-MOF coating on the surface of a micro-arc oxidation layer, so that active and passive protection capabilities are provided for a magnesium alloy substrate, and the occurrence of a corrosion process is inhibited.
Disclosure of Invention
The invention aims to provide a fluorine-free super-hydrophobic Zn-MOF composite coating on the surface of a magnesium alloy and a preparation method thereof.
The fluorine-free super-hydrophobic Zn-MOF composite coating on the surface of the magnesium alloy comprises a micro-arc oxidation layer, a Zn-MOF layer and a stearic acid layer which are sequentially attached to the surface of the magnesium alloy.
The specific steps for preparing the fluorine-free super-hydrophobic Zn-MOF composite coating on the surface of the magnesium alloy are as follows:
(1) magnesium alloy pretreatment
Sequentially grinding and polishing the magnesium alloy matrix by using 180#, 600#, 1000# and 1500# metallographic abrasive paper, cleaning and drying; then placing the magnesium alloy into alkaline degreasing liquid for 1-5 min at the temperature of 60-80 ℃, then respectively carrying out ultrasonic cleaning for 10-15 min by using ethanol solution and deionized water, and drying to obtain the treated magnesium alloy; the alkaline degreasing fluid comprises the following components: 15-20 g/L NaOH, 30-40 g/L Na2CO3And 15-20 g/L of Na3PO4。
(2) Micro arc oxidation treatment
At room temperature, placing the treated magnesium alloy obtained in the step (1) as an anode and a stainless steel sheet as a cathode in a micro-arc oxidation solution for micro-arc oxidation treatment by using pulse voltage to obtain a micro-arc oxidation treated magnesium alloy carrier; the electrical parameters were set as: the frequency is 50-200 Hz, the duty ratio is 30-50%, the termination voltage is 180-220V, and the micro-arc oxidation time is 30-40 min; the micro-arc oxidation solution comprises the following components: 10-15 g/L NaOH, 5-10 g/L Na2SiO3、5~10 g/L NaF、4~6 g/L Na2B4O7、1~5 g/L Na2WO4、3~5 mL/L C3H8O3And 3-5 mL/L C6H15NO3。
(3) Zn-MOF coating preparation
Preparing a mixed solution according to the molar ratio of zinc nitrate hexahydrate, sodium formate, 2-methylimidazole and methanol being 1:1:1.5:374, ultrasonically dispersing the mixed solution at room temperature for 10-20 min, transferring the mixed solution into a polytetrafluoroethylene lining reaction kettle, vertically hanging the micro-arc oxidation treatment magnesium alloy carrier obtained in the step (2) in the polytetrafluoroethylene lining reaction kettle, carrying out constant-temperature synthesis reaction at 80-120 ℃ for 2-6 h, naturally cooling the reaction product in the air to room temperature after the reaction is finished, taking out the magnesium alloy carrier, washing the magnesium alloy carrier with deionized water for 5-10 times, and drying the magnesium alloy carrier at 50 ℃ for later use.
Weighing 0.49-0.89 g of 2-methylimidazole, mixing the 2-methylimidazole in 30 mL of methanol, carrying out ultrasonic treatment at room temperature for 10-20 min until the mixture is dissolved, transferring the obtained solution to a polytetrafluoroethylene lining reaction kettle, simultaneously vertically hanging the magnesium alloy carrier obtained in the step one in the polytetrafluoroethylene lining reaction kettle, carrying out constant-temperature reaction at 80-120 ℃ for 12-20 h, cooling the magnesium alloy carrier in the air to room temperature after the reaction is finished, taking out the magnesium alloy carrier, washing the magnesium alloy carrier with a micro-arc oxidation layer and a Zn-MOF layer for 5-10 times by using deionized water, and drying the magnesium alloy carrier at 50 ℃ to obtain the magnesium alloy carrier with the micro-arc oxidation.
(4) Preparation of composite coatings
Placing the magnesium alloy carrier attached with the micro-arc oxidation layer and the Zn-MOF layer obtained in the step (3) in 0.1 mol/L C18H36O2Modifying in (stearic acid) ethanol solution for 90-120 min, then washing with deionized water for 5-10 times, and drying at 50 ℃ for 2-4 h to obtain the fluorine-free super-hydrophobic Zn-MOF composite coating on the surface of the magnesium alloy.
The preparation method is simple in preparation process and free of fluorine, and the Zn-MOF composite coating has good binding force with the magnesium alloy substrate and can be uniformly distributed on the surface of the magnesium alloy. The water contact angle test shows that the composite coating achieves the super-hydrophobic effect, and the polarization curve test shows that the composite coating also has good corrosion resistance.
Drawings
Fig. 1 is a water contact angle diagram (a), an SEM image (b), and an EDS elemental distribution diagram (c) of the composite coating layer obtained in example 1.
Fig. 2 is a water contact angle diagram (a), an SEM image (b), and an EDS elemental distribution diagram (c) of the composite coating layer obtained in example 4.
Figure 3 is a phase characterization XRD pattern of example 1.
Fig. 4 is a potentiodynamic polarization curve for example 1 and example 4.
FIG. 5 is a graph comparing the corrosion potential and corrosion current density for examples 1 and 4.
Detailed Description
The invention is explained below with reference to the embodiments by means of the figures.
Example 1:
(1) magnesium alloy pretreatment
The magnesium alloy matrix adopts 180#, 600#, 1000#, and 15 # in sequenceAnd (5) grinding and polishing the No. 00 metallographic abrasive paper, cleaning and drying. Then placing the mixture in alkaline degreasing fluid (20 g/L NaOH and 30 g/L Na) at 60 DEG C2CO3、20 g/L Na3PO4) Performing ultrasonic cleaning for 1 min with ethanol solution and deionized water for 10 min, and drying.
(2) Micro arc oxidation treatment
The micro-arc oxidation is carried out in a silicate system by adopting pulse voltage, at room temperature, the magnesium alloy treated in the step (1) is used as an anode, a stainless steel sheet is used as a cathode, the magnesium alloy is placed in a micro-arc oxidation solution to be subjected to micro-arc oxidation treatment by adopting the pulse voltage, and the set electrical parameters are as follows: the frequency is 50 Hz, the duty ratio is 30 percent, the termination voltage is 220V, and the micro-arc oxidation time is 30 min; the micro-arc oxidation solution used in the process comprises the following components: 11 g/L NaOH, 5 g/L Na2SiO3，8 g/L NaF，4 g/L Na2B4O7，1 g/L Na2WO4，5 mL/L C3H8O3，4 mL/L C6H15NO3。
(3) Zn-MOF coating preparation
1.0 Zn (NO)3)2•6H2O：1.0 HCOONa：1.5 C4H6N2：374 CH3And (3) preparing a Zn-MOF synthetic solution according to the molar ratio of OH, ultrasonically dissolving for 10 min at room temperature, transferring into a polytetrafluoroethylene lining reaction kettle, and simultaneously putting the magnesium alloy carriers treated in the step (2) into the kettle together, wherein the magnesium alloy carriers are vertically hung in the kettle, and the synthesis condition is 100 ℃ and the constant temperature is kept for 4 hours. And after the reaction is finished, naturally cooling the magnesium alloy sheet to room temperature in the air, taking out the magnesium alloy sheet, slowly washing the magnesium alloy sheet for 8 times by using deionized water, and drying the magnesium alloy sheet at 50 ℃ for later use.
② 0.49 g of 2-methylimidazole is weighed and mixed in 30 mL of methanol, and ultrasonic treatment is carried out for 10 min at room temperature until dissolution. And then transferring the mixed solution into a reaction kettle with a polytetrafluoroethylene lining, and simultaneously vertically hanging the magnesium alloy sheet of the first step into the reaction kettle, and keeping the temperature at 100 ℃ for 12 hours. After the reaction is finished, the reaction product is cooled to room temperature in the air, taken out and washed by deionized water for 8 times, and dried at 50 ℃.
The sample was then tested for its water contact angle using a water drop static contact angle tester (see fig. 1 a), which has a water contact angle of 128.90 °. The surface morphology and element distribution were observed by scanning electron microscopy (sem) and its accompanying Energy Dispersive Spectroscopy (EDS) (see fig. 1b and 1 c). The coating prepared by the embodiment has a flat and uniform surface distributed on the surface of the magnesium alloy, and can completely cover micropores of a micro-arc oxidation film of a bottom layer, and the coating contains C, N, O, Zn elements. The surface of the sample was scanned by X-ray to obtain XRD pattern (see FIG. 3), and two phases of ZnO and Zn-MOF mainly existed. The corrosion resistance of the fluorine-free super-hydrophobic Zn-MOF composite coating of this example was characterized, and a test was performed using a CHI760 electrochemical workstation in a three-electrode system (a calomel electrode as a reference electrode, a platinum electrode as an auxiliary electrode, and a magnesium alloy surface coating as a working electrode), and 3.5wt.% of sodium chloride solution was used as an electrolyte. And (3) selecting a potentiodynamic polarization curve to research the corrosion resistance of the magnesium alloy surface coating, and after the open-circuit potential is stable, adopting a scanning rate of 5 mV/s and a voltage window of +/-100 mV of the open-circuit potential. The polarization curve of the sample is shown in fig. 4, and the corrosion potential and corrosion current density of the sample are shown in fig. 5. It can be seen that the MAO/Zn-MOF coating has a more positive potential.
Example 2: the concentration of 2-methylimidazole in step (3) of example 1 was set to 0.69 g, and the other treatment was conducted in accordance with example 1, and the water contact angle was 129.16 °.
Example 3: the concentration of 2-methylimidazole in step (3) of example 1 was set to 0.89 g, and the other treatment was conducted in accordance with example 1, and the water contact angle was 128.13 °.
Example 4: the Zn-MOF coating sample of example 1 was dipped in 0.1 mol/L ethanol solution of stearic acid at room temperature for 120 min, then taken out and washed with deionized water for 7 times, dried at 50 ℃ for 4 h, and otherwise treated in the same manner as in example 1. Its water contact angle was 150.01 ° (see fig. 2 a), surface topography and element distribution (see fig. 2b and 2 c). The coating prepared by the embodiment has a flat and uniform surface, is evenly distributed on the surface of the magnesium alloy, can completely cover micropores of a micro-arc oxidation film of a bottom layer, and contains C, N, O, Zn elements. The corrosion resistance of the samples was tested by potentiodynamic polarization curves (see fig. 4), the corrosion potential of the samples and the corrosion current density (see fig. 5). It can be seen that the MAO/Zn-MOF/SA composite coating has the smallest corrosion current density and better corrosion resistance.
Example 5: the Zn-MOF coated sample of example 2 was dipped in 0.1 mol/L ethanol solution of stearic acid at room temperature for 120 min, then taken out and washed with deionized water for 7 times, dried at 50 ℃ for 4 h, otherwise treated in the same manner as in example 2, and had a water contact angle of 151.43 deg..
Example 6: the Zn-MOF coated sample of example 3 was dipped in 0.1 mol/L ethanol solution of stearic acid at room temperature for 120 min, then taken out and washed with deionized water for 7 times, dried at 50 ℃ for 4 h, otherwise treated in the same manner as in example 3 with a water contact angle of 148.95 deg..
Claims (2)
1. A fluorine-free super-hydrophobic Zn-MOF composite coating on the surface of magnesium alloy is characterized in that: the fluorine-free super-hydrophobic Zn-MOF composite coating on the surface of the magnesium alloy comprises a micro-arc oxidation layer, a Zn-MOF layer and a stearic acid layer which are sequentially attached to the surface of the magnesium alloy.
2. The preparation method of the fluorine-free super-hydrophobic Zn-MOF composite coating on the surface of the magnesium alloy according to claim 1, which is characterized by comprising the following specific steps:
(1) magnesium alloy pretreatment
Sequentially grinding and polishing the magnesium alloy matrix by using 180#, 600#, 1000# and 1500# metallographic abrasive paper, cleaning and drying; then placing the magnesium alloy into alkaline degreasing liquid for 1-5 min at the temperature of 60-80 ℃, then respectively carrying out ultrasonic cleaning for 10-15 min by using ethanol solution and deionized water, and drying to obtain the treated magnesium alloy; the alkaline degreasing fluid comprises the following components: 15-20 g/L NaOH, 30-40 g/L Na2CO3And 15-20 g/L of Na3PO4；
(2) Micro arc oxidation treatment
At room temperature, the processed magnesium alloy obtained in the step (1) is used as an anode, a stainless steel sheet is used as a cathode, and the magnesium alloy is placed in a micro-arc oxidation solutionPerforming micro-arc oxidation treatment in the liquid by adopting pulse voltage to obtain a magnesium alloy carrier subjected to micro-arc oxidation treatment; the electrical parameters were set as: the frequency is 50-200 Hz, the duty ratio is 30-50%, the termination voltage is 180-220V, and the micro-arc oxidation time is 30-40 min; the micro-arc oxidation solution comprises the following components: 10-15 g/L NaOH, 5-10 g/L Na2SiO3、5~10 g/L NaF、4~6 g/L Na2B4O7、1~5 g/L Na2WO4、3~5 mL/L C3H8O3And 3-5 mL/L C6H15NO3；
(3) Zn-MOF coating preparation
Preparing a mixed solution according to the molar ratio of zinc nitrate hexahydrate to sodium formate to 2-methylimidazole to methanol of 1:1:1.5:374, ultrasonically dispersing the mixed solution at room temperature for 10-20 min, transferring the mixed solution into a polytetrafluoroethylene lining reaction kettle, vertically hanging the micro-arc oxidation treatment magnesium alloy carrier obtained in the step (2) in the polytetrafluoroethylene lining reaction kettle, carrying out constant-temperature synthesis reaction at 80-120 ℃ for 2-6 h, naturally cooling the reaction product in the air to room temperature after the reaction is finished, taking out the magnesium alloy carrier, washing the magnesium alloy carrier with deionized water for 5-10 times, and drying the magnesium alloy carrier at 50 ℃ for later use;
weighing 0.49-0.89 g of 2-methylimidazole, mixing the 2-methylimidazole in 30 mL of methanol, performing ultrasonic treatment at room temperature for 10-20 min until the mixture is dissolved, transferring the obtained solution to a polytetrafluoroethylene lining reaction kettle, simultaneously vertically hanging the magnesium alloy carrier obtained in the step one in the polytetrafluoroethylene lining reaction kettle, performing constant-temperature reaction at 80-120 ℃ for 12-20 h, cooling the magnesium alloy carrier in air to room temperature after the reaction is finished, taking out the magnesium alloy carrier, washing the magnesium alloy carrier with a micro-arc oxidation layer and a Zn-MOF layer for 5-10 times by using deionized water, and drying the magnesium alloy carrier at 50 ℃ to obtain the magnesium alloy carrier with the micro-arc oxidation layer and the;
(4) preparation of composite coatings
And (3) placing the magnesium alloy carrier attached with the micro-arc oxidation layer and the Zn-MOF layer obtained in the step (3) in 0.1 mol/L stearic acid ethanol solution for modification for 90-120 min, then washing with deionized water for 5-10 times, and drying at 50 ℃ for 2-4 h to obtain the fluorine-free super-hydrophobic Zn-MOF composite coating on the surface of the magnesium alloy.
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