CN114855237A - Preparation method of ZIF-8-doped high-corrosion-resistance micro-arc oxidation composite coating - Google Patents
Preparation method of ZIF-8-doped high-corrosion-resistance micro-arc oxidation composite coating Download PDFInfo
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- 238000007745 plasma electrolytic oxidation reaction Methods 0.000 title claims abstract description 70
- 238000000576 coating method Methods 0.000 title claims abstract description 62
- 239000011248 coating agent Substances 0.000 title claims abstract description 58
- 239000002131 composite material Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims abstract description 45
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 claims abstract description 45
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000005260 corrosion Methods 0.000 claims abstract description 31
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 30
- 230000007797 corrosion Effects 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000008367 deionised water Substances 0.000 claims abstract description 27
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 27
- 239000003792 electrolyte Substances 0.000 claims abstract description 27
- 229910000838 Al alloy Inorganic materials 0.000 claims abstract description 23
- 239000002245 particle Substances 0.000 claims abstract description 22
- 238000003756 stirring Methods 0.000 claims abstract description 15
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 claims abstract description 14
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 12
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000005977 Ethylene Substances 0.000 claims abstract description 11
- 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 abstract description 10
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims abstract description 10
- PHIQPXBZDGYJOG-UHFFFAOYSA-N sodium silicate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-][Si]([O-])=O PHIQPXBZDGYJOG-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims abstract description 10
- 239000007787 solid Substances 0.000 claims abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 7
- 239000010439 graphite Substances 0.000 claims abstract description 7
- 239000003446 ligand Substances 0.000 claims abstract description 6
- 238000000926 separation method Methods 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 11
- 238000009210 therapy by ultrasound Methods 0.000 claims description 11
- 238000004140 cleaning Methods 0.000 claims description 8
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 7
- 125000002883 imidazolyl group Chemical group 0.000 claims description 6
- 239000000839 emulsion Substances 0.000 claims description 5
- 239000008187 granular material Substances 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 4
- 230000002401 inhibitory effect Effects 0.000 claims description 3
- 244000137852 Petrea volubilis Species 0.000 claims description 2
- 238000005498 polishing Methods 0.000 claims description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 7
- 239000013535 sea water Substances 0.000 abstract description 7
- 150000002500 ions Chemical class 0.000 abstract description 5
- 230000004888 barrier function Effects 0.000 abstract description 4
- 239000011159 matrix material Substances 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 230000005764 inhibitory process Effects 0.000 abstract description 2
- 238000001132 ultrasonic dispersion Methods 0.000 abstract 1
- 229910001094 6061 aluminium alloy Inorganic materials 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000919 ceramic Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- 230000007547 defect Effects 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 230000007774 longterm Effects 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 238000011049 filling Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000005595 deprotonation Effects 0.000 description 2
- 238000010537 deprotonation reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000007847 structural defect Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- 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
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/16—Pretreatment, e.g. desmutting
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
Abstract
The invention discloses a preparation method of a ZIF-8-doped high-corrosion-resistance micro-arc oxidation composite coating, which comprises the steps of dissolving dimethyl imidazole and zinc nitrate hexahydrate in dimethyl formamide, adding ethylene triamine, adjusting the pH value to be alkaline, carrying out ultrasonic stirring, carrying out centrifugal separation to obtain a white solid, washing and drying to obtain ZIF-8 particles; adding ZIF-8 particles into deionized water, performing ultrasonic dispersion, and dissolving sodium silicate nonahydrate, potassium hydroxide and sodium hexametaphosphate in the deionized water to prepare electrolyte; and (3) placing the aluminum alloy workpiece serving as an anode into the prepared electrolyte, taking graphite as a cathode, and performing micro-arc oxidation treatment on the aluminum alloy workpiece by adopting a pulse direct-current power supply in a constant-current mode. The composite coating has excellent barrier effect and can prevent corrosive ions in seawater from entering the coating. Meanwhile, the imidazole-based ligand with corrosion inhibition in the ZIF-8 is adsorbed on the surface of metal, so that the matrix is protected from corrosion, and the corrosion resistance of the matrix is improved.
Description
Technical Field
The invention relates to preparation of a high-corrosion-resistance composite coating, in particular to a preparation method of a ZIF-8-doped high-corrosion-resistance micro-arc oxidation composite coating, and belongs to the technical field of anti-corrosion materials in marine environments.
Background
6061 aluminum alloy is used as a common material in the manufacturing industry of marine equipment, and is easy to machine and form and has high specific strength and low temperature resistance and the like, so that the aluminum alloy is increasingly applied to the manufacturing industry of ships and warships. However, the low hardness, poor wear resistance and poor corrosion resistance in the marine environment of the aluminum alloy itself limit the use of the aluminum alloy in the marine field. The micro-arc oxidation technology is a novel surface treatment technology, and can prepare a ceramic film layer with good wear resistance, corrosion resistance and electrical insulation performance and high bonding strength with a matrix on the surface of the aluminum alloy. However, in the micro-arc oxidation process, the micro-arc oxidation coating is affected by spark discharge, more micropores are generally formed in the micro-arc oxidation coating, and the corrosion resistance is greatly affected, so that the application of the micro-arc oxidation coating in a corrosion environment is limited. Therefore, the necessary means for eliminating the influence of the structural defects of the coating on the performance of the coating are needed.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a preparation method of a ZIF-8-doped high-corrosion-resistance micro-arc oxidation composite coating, which can effectively repair the problems of micro-hole and micro-crack structure defects of the micro-arc oxidation coating and improve the corrosion resistance of the micro-arc oxidation coating.
The technical scheme of the invention is realized as follows:
a preparation method of a ZIF-8-doped high-corrosion-resistance micro-arc oxidation composite coating comprises the step of placing an aluminum alloy workpiece in electrolyte for micro-arc oxidation treatment, wherein the electrolyte contains ZIF-8 particles.
Further, the ZIF-8 particles carry corrosion inhibiting imidazole groups.
The preparation method comprises the following specific steps:
(1) preparation of ZIF-8 granules: sequentially dissolving dimethylimidazole and zinc nitrate hexahydrate in dimethylformamide, adding ethylene triamine, adjusting the pH value to 9-12 by using a sodium hydroxide solution, simultaneously carrying out ultrasonic stirring for 1h for 2-3 h to obtain a white emulsion, carrying out centrifugal separation to obtain a white solid, alternately washing the white solid by using methanol and deionized water for 3-5 times, and then carrying out vacuum drying at 40-60 ℃ to obtain white powdery ZIF-8 micron particles; according to the invention, zinc nitrate hexahydrate and dimethylimidazole respectively provide metal ions and imidazolyl ligands for ZIF-8 as main reactants, dimethylformamide is used as a solvent, and ethylene triamine is used as a crystallization accelerator to mainly accelerate deprotonation of dimethylimidazole and promote crystal nucleation of ZIF-8; the size of the obtained ZIF-8 particles is about 300 nanometers, pores are lower than the diameter of chloride ions in seawater to be 6.64A, the particles have a good barrier effect on the chloride ions, a labyrinth effect is played in the micro-arc oxidation coating, further diffusion of corrosive ions can be hindered, in addition, under the long-term seawater soaking, the ZIF-8 release imidazole ligands are adsorbed on the surface of the coating, an anode type corrosion inhibitor effect is played, and the long-term corrosion resistance of the micro-arc oxidation coating is improved.
(2) Pretreatment of a workpiece: polishing an aluminum alloy workpiece by using water abrasive paper to ensure that the surface of the aluminum alloy workpiece is smooth;
(3) preparing electrolyte: adding ZIF-8 micron particles prepared in the step (1) into deionized water, performing ultrasonic treatment to fully disperse the ZIF-8 micron particles, and sequentially dissolving sodium silicate nonahydrate, potassium hydroxide and sodium hexametaphosphate in the deionized water after the ultrasonic treatment to prepare electrolyte for later use;
(4) preparing a composite coating: placing the aluminum alloy workpiece after pretreatment as an anode into a prepared electrolyte, and taking graphite as a cathode, wherein the distance between the cathode and the anode is 10 cm; and (3) carrying out micro-arc oxidation treatment on the aluminum alloy workpiece by adopting a pulse direct-current power supply in a constant-current mode, and after the treatment is finished, cleaning the prepared micro-arc oxidation composite coating by using deionized water and drying the cleaned micro-arc oxidation composite coating.
In the step (1), the molar ratio of zinc ions in zinc nitrate hexahydrate to imidazole groups in a dimethyl imidazole ligand is 1: 1-5, and the molar ratio of zinc ions to dimethylformamide and ethylene triamine is 1:8.36: 0.044;
specifically, the electrolyte prepared by the method comprises the following components in concentration: 1-3 g/L ZIF-8 micron particles, 5-8 g/L sodium silicate nonahydrate, 1-4 g/L potassium hydroxide and 1-4 g/L sodium hexametaphosphate. Sodium silicate nonahydrate is used as a main electrolyte component, potassium hydroxide and sodium hexametaphosphate are used as additives, the pH value of the electrolyte is adjusted, the conductivity of the solution is improved, the micro-arc oxidation coating is promoted to grow on the surface of the aluminum alloy rapidly, ZIF-8 stably exists in the electrolyte, negative Zeta potential is presented in the solution, and the ZIF-8 migrates to the anode of the aluminum alloy under the power-on condition to promote the micro-arc oxidation coating to form a film.
The parameters of the pulse micro-arc oxidation equipment in the micro-arc oxidation process are as follows: the current density is 5.18 to 6.64A/dm 2 The frequency is 800-1500 Hz, the duty ratio is 17-35%, and the micro-arc oxidation time is 10 min.
And (4) in the micro-arc oxidation treatment process of the step (4), continuously stirring the electrolyte by using a magnetic stirrer at the stirring speed of 500 rpm.
Preferably, the pretreatment of the workpiece in the step (2) is to polish the surface of the aluminum alloy workpiece by using water-milled sand paper with the mesh numbers of 180#, 1200#, and 2000# in sequence until the surface of the material is flat, has no obvious scratch or no obvious pit; and then immersing the polished aluminum alloy workpiece into normal-temperature deionized water for ultrasonic cleaning for 1min, cleaning for 3-5 times, and drying by cold air.
Preferably, in the step (1), the concentration of the sodium hydroxide solution is 10mol/L, the sodium hydroxide solution is adjusted to be alkaline, and the pH is 9.2, so that the deprotonation process of the dimethyl imidazole can be accelerated, and the ZIF-8 nucleation can be promoted.
Preferably, in step (3), the ultrasonic power is 25W.
Compared with the prior art, the invention has the following beneficial effects:
1. the material ZIF-8 (with the pore diameter as low as 3A) with the anticorrosion potential in the coating has an excellent barrier effect on chloride ions (with the radius of 6.64A) in seawater, and can prevent corrosive ions in seawater from entering the coating. Meanwhile, the imidazole-based ligand with corrosion inhibition in the ZIF-8 is adsorbed on the metal surface, so that the substrate is protected from corrosion, the corrosion resistance of the substrate is improved, and the ZIF-8 is suitable for surface treatment of aluminum alloy in a marine corrosion-prone environment.
2. The operation process and the electrolyte system related by the invention have simple components, and the cost is effectively reduced.
3. The process of the invention has no pollution to the environment.
Drawings
Figure 1-scanning and energy spectra of the coatings of example 1 and comparative example 1.
FIG. 2-Low frequency impedance modulus plot for the coatings of example 1 and comparative example 1.
Detailed Description
The present invention will be described in detail with reference to the accompanying drawings and specific embodiments in order to explain technical contents, objects, and effects of the invention in detail.
Example 1
(1) Preparation of ZIF-8 granules: sequentially dissolving dimethylimidazole and zinc nitrate hexahydrate in dimethylformamide, adding ethylene triamine, wherein the molar ratio of the dimethylimidazole to the zinc nitrate hexahydrate to the dimethylformamide to the ethylene triamine is 1:1:8.36:0.044, adjusting the pH value of the solution to 9.2 by using a sodium hydroxide solution with the concentration of 10mol/L, simultaneously carrying out ultrasonic stirring for 1h and 3 h to obtain a white emulsion, wherein the stirring speed is 300 rpm, carrying out centrifugal separation to obtain a white solid, alternately washing for 4 times by using methanol and deionized water, and then carrying out vacuum drying at 40 ℃ to obtain a white powdery ZIF-8 micron-grade material.
(2) Workpiece treatment: the micro-arc oxidation anode material is 6061 aluminum alloy, and is processed into a rectangular sample with the diameter of 35mm multiplied by 30mm multiplied by 5mm, and a hole is drilled right above the top end of the sample, and the diameter of the hole is 3 mm. Sequentially grinding the front and the side of a sample by using 180#, 1200# and 2000# water abrasive paper until the surface of the material is flat, and no obvious scratch or pit exists; and (3) immersing the polished 6061 aluminum alloy workpiece into normal-temperature deionized water for ultrasonic cleaning for 1min, cleaning for 3-5 times, and drying by cold air.
(3) Electrolyte preparation: and (2) filling 1.5L of deionized water into a 2L container, adding 3 g/L of ZIF-8 particles prepared in the step (1), adding 6 g/L of sodium silicate nonahydrate, 2 g/L of potassium hydroxide and 1 g/L of sodium hexametaphosphate after ultrasonic treatment for 1h (ultrasonic power is 25W), adding the next component after the former component is fully dissolved, and simultaneously putting the container into an ultrasonic cleaning machine while stirring under ultrasonic treatment to promote the dissolution of the components. Finally deionized water was added to 2L.
(4) Sample preparation: the pretreated 6061 aluminum alloy workpiece is used as an anode and placed into a prepared electrolyte, graphite is used as a cathode, a pulse direct current power supply is adopted to carry out micro-arc oxidation treatment on the 6061 aluminum alloy workpiece in a constant current mode, and the micro-arc oxidation parameter is that the current density is 6A/dm 2 Frequency is 1000 Hz, duty ratio is 20 percent, and micro-arc oxidation time is 10 min. In the micro-arc oxidation treatment process, a magnetic stirrer is adopted to continuously stir the electrolyte, and the stirring speed is 500 rpm. The test adopts double cathodes which are respectively arranged at two sides of a workpiece, and the distance between the cathode and the anode is 10 cm; and cleaning the prepared micro-arc oxidation composite coating with deionized water, drying with hot air, and placing into a sample bag for drying and storage.
The thickness of the micro-arc oxidation composite ceramic membrane obtained in the embodiment is 6 +/-0.8 μm.
Comparative example 1
The 6061 aluminum alloy workpiece was polished and cleaned according to the method of step (2) in example 1, and dried for use. 6 g/L of sodium silicate nonahydrate, 2 g/L of potassium hydroxide and 1 g/L of sodium hexametaphosphate are sequentially dissolved in 1.5L of deionized water, and simultaneously, in the preparation process, a beaker needs to be placed into an ultrasonic cleaning machine to be stirred while ultrasonic treatment is carried out, so that the dissolution of components is promoted. Finally deionized water was added to 2L. And then, taking a 6061 aluminum alloy workpiece as an anode, taking a graphite electrode as a cathode, and setting the distance between the anode and the cathode to be 10 cm. Adopts a single-stage pulse power supply and has a current density of 6A/dm 2 The frequency is 1000 Hz, the duty ratio is 20 percent, and the micro-arc oxidation time is 10 minArc oxidation coating.
The thickness of the micro-arc oxidation composite ceramic membrane obtained in the embodiment is 5 +/-0.4 mu m.
The micro-morphology of the surface of the micro-arc oxidation coatings prepared in the example 1 and the comparative example 1 is shown in fig. 1, the surface pores of the micro-arc oxidation coating obtained in the comparative example 1 are obvious, and the surface of the micro-arc oxidation composite coating obtained in the example 1 is attached with a large amount of ZIF-8 particles, so that the disc-shaped molten pool is relatively reduced. From the results of the energy spectrum, the atomic ratio of the key Zn element of the coating ZIF-8 in comparative example 1 was 0%, and the atomic ratio of the Zn element of the composite coating in example 1 was 2.16%.
The coatings obtained in example 1 and comparative example 1 were subjected to electrochemical impedance spectroscopy in 3.5 wt% NaCl solution, and the low-frequency impedance modulus curve of the coating after 360h testing is shown in FIG. 2, and the long-term low-frequency impedance modulus of example 1 is always maintained at 10 7 ~10 8 Ω•cm 2 While the long-term low-frequency impedance modulus of comparative example 1 was always maintained at 10 4 ~10 5 Ω•cm 2 Compared with the common micro-arc oxidation coating, the corrosion resistance of the ZIF-8-doped micro-arc oxidation composite coating is improved by 2 orders of magnitude, which shows that the ZIF-8-repaired micro-arc oxidation coating has good corrosion resistance.
Example 2
(1) Preparation of ZIF-8 granules: sequentially dissolving dimethylimidazole and zinc nitrate hexahydrate in dimethylformamide, adding ethylene triamine, wherein the molar ratio of the dimethylimidazole to the zinc nitrate hexahydrate to the dimethylformamide to the ethylene triamine is 3:1:8.36:0.044, adjusting the pH value to 9.2 by using a sodium hydroxide solution with the concentration of 10mol/L, simultaneously carrying out ultrasonic stirring for 1h to obtain a white emulsion, carrying out centrifugal separation to obtain a white solid, alternately washing for 4 times by using methanol and deionized water, and then carrying out vacuum drying at 50 ℃ to obtain a white powdery ZIF-8 micron-grade material.
(2) Workpiece treatment: the process described in example 1 is referred to.
(3) Electrolyte preparation: and (2) filling 1.5L of deionized water into a 2L container, adding 2 g/L of ZIF-8 particles prepared in the step (1), adding 8 g/L of sodium silicate nonahydrate, 1 g/L of potassium hydroxide and 3 g/L of sodium hexametaphosphate after performing ultrasonic treatment in 25W ultrasonic equipment for 1 hour, fully dissolving the former component, then adding the next component, and simultaneously putting the container into an ultrasonic cleaning machine while performing ultrasonic treatment and stirring to promote the dissolution of the components in the preparation process. Finally deionized water was added to 2L.
(4) Sample preparation: the pretreated 6061 aluminum alloy workpiece is used as an anode and placed into a prepared electrolyte, graphite is used as a cathode, a pulse direct current power supply is adopted to carry out micro-arc oxidation treatment on the 6061 aluminum alloy workpiece in a constant current mode, and the current density is 6.64A/dm 2 Frequency 800 Hz, duty ratio 17 percent and micro-arc oxidation time 10 min. The test adopts double cathodes which are respectively arranged at two sides of a workpiece, and the distance between the cathode and the anode is 10 cm; and cleaning the prepared micro-arc oxidation composite coating with deionized water, drying with hot air, and placing into a sample bag for drying and storage.
The thickness of the micro-arc oxidation composite ceramic membrane is 5.8 +/-0.6 mu m, a large number of ZIF-8 particles are attached to the surface, a plurality of ceramic balls are arranged on the surface, and the atomic ratio of Zn element is 2.29%; the low-frequency impedance modulus value in the short-term impedance test is maintained at 10 7 ~10 8 Ω•cm 2 . The result shows that the ZIF-8 can effectively repair the defects of the micro-arc oxidation coating and ensure that the coating has good corrosion resistance.
Example 3
(1) Preparation of ZIF-8 granules: sequentially dissolving dimethylimidazole and zinc nitrate hexahydrate in dimethylformamide, adding ethylene triamine, wherein the molar ratio of the dimethylimidazole to the zinc nitrate hexahydrate to the dimethylformamide to the ethylene triamine is 5:1:8.36:0.044, adjusting the pH value of a 10mol/L sodium hydroxide solution to 9.2, simultaneously carrying out ultrasonic stirring for 1h to obtain a white emulsion, carrying out centrifugal separation to obtain a white solid, alternately washing for 4 times by using methanol and deionized water, and then carrying out vacuum drying at 60 ℃ to obtain a white powdery ZIF-8 micron-grade material.
(2) Workpiece treatment: the process described in example 1 is referred to.
(3) Electrolyte preparation: and (2) filling 1.5L of deionized water into a 2L container, adding the ZIF-8 particles prepared in the step (1) according to the amount of 1 g/L, carrying out ultrasonic treatment in 25W ultrasonic equipment for 1h, adding 5 g/L of sodium silicate nonahydrate, 4 g/L of potassium hydroxide and 4 g/L of sodium hexametaphosphate, fully dissolving the former component, then adding the next component, and simultaneously putting the container into an ultrasonic cleaning machine while carrying out ultrasonic treatment and stirring to promote the dissolution of the components in the preparation process. Finally deionized water was added to 2L.
(4) Sample preparation: the pretreated 6061 aluminum alloy workpiece is used as an anode and placed into a prepared electrolyte, graphite is used as a cathode, a pulse direct current power supply is adopted to carry out micro-arc oxidation treatment on the 6061 aluminum alloy workpiece in a constant current mode, and the current density is 5.18A/dm 2 The frequency is 1500 Hz, the duty ratio is 35 percent, and the micro-arc oxidation time is 10 min. The test adopts double cathodes which are respectively arranged at two sides of a workpiece, and the distance between the cathode and the anode is 10 cm; and cleaning the prepared micro-arc oxidation composite coating with deionized water, drying with hot air, and placing into a sample bag for drying and storage.
The thickness of the micro-arc oxidation composite ceramic membrane is 5.4 +/-0.3 mu m, a large number of ZIF-8 particles are attached to the surface, a plurality of ceramic balls are arranged on the surface, and the atomic ratio of Zn element is 0.89%; the low-frequency impedance modulus value in the short-term impedance test is maintained at 10 7 ~10 8 Ω•cm 2 . The result shows that the ZIF-8 can effectively repair the defects of the micro-arc oxidation coating and ensure that the coating has good corrosion resistance.
According to the invention, the micro-pore microcrack defect of the micro-arc oxidation coating is repaired by the ZIF-8 material, and the ZIF-8 has an excellent barrier effect on chloride ions in seawater and can prevent corrosive ions in seawater from entering the coating; the adsorption of the ZIF-8 material to corrosive ions and the self-carried corrosion-inhibiting imidazole group effectively prevent corrosive media from entering the coating through pores to corrode a metal matrix, and the corrosion resistance of the micro-arc oxidation coating is improved.
Finally, it should be noted that the above-mentioned examples of the present invention are only examples for illustrating the present invention, and are not intended to limit the embodiments of the present invention. Variations and modifications in other variations will occur to those skilled in the art upon reading the foregoing description. Not all embodiments are exhaustive. All obvious changes and modifications of the present invention are within the scope of the present invention.
Claims (10)
1. A preparation method of a ZIF-8-doped high-corrosion-resistance micro-arc oxidation composite coating is characterized in that an aluminum alloy workpiece is placed in an electrolyte for micro-arc oxidation treatment, wherein the electrolyte contains ZIF-8 particles.
2. The method for preparing the ZIF-8-doped highly corrosion-resistant micro-arc oxidation composite coating according to claim 1, wherein the ZIF-8 particles carry corrosion-inhibiting imidazole groups.
3. The preparation method of the ZIF-8-doped highly corrosion-resistant micro-arc oxidation composite coating according to claim 1, which is characterized by comprising the following steps:
(1) preparation of ZIF-8 granules: sequentially dissolving dimethylimidazole and zinc nitrate hexahydrate in dimethylformamide, adding ethylene triamine, adjusting the pH value to 9-12 by using a sodium hydroxide solution, simultaneously carrying out ultrasonic stirring for 1h for 2-3 h to obtain a white emulsion, carrying out centrifugal separation to obtain a white solid, alternately washing the white solid by using methanol and deionized water for 3-5 times, and then carrying out vacuum drying at 40-60 ℃ to obtain white powdery ZIF-8 micron particles;
(2) pretreatment of a workpiece: polishing an aluminum alloy workpiece by using water abrasive paper to ensure that the surface of the aluminum alloy workpiece is smooth;
(3) preparing electrolyte: adding ZIF-8 micron particles prepared in the step (1) into deionized water, performing ultrasonic treatment to fully disperse the ZIF-8 micron particles, and sequentially dissolving sodium silicate nonahydrate, potassium hydroxide and sodium hexametaphosphate in the deionized water after the ultrasonic treatment to prepare electrolyte for later use;
(4) preparing a composite coating: placing the aluminum alloy workpiece after pretreatment as an anode into a prepared electrolyte, taking graphite as a cathode, and setting the distance between the cathode and the anode to be 10 cm; and (3) carrying out micro-arc oxidation treatment on the aluminum alloy workpiece in a constant current mode by adopting a pulse direct current power supply, and after the treatment is finished, cleaning and drying the prepared micro-arc oxidation composite coating by using deionized water.
4. The preparation method of the ZIF-8-doped highly corrosion-resistant micro-arc oxidation composite coating according to claim 3, wherein in the step (1), the molar ratio of zinc ions in zinc nitrate hexahydrate to imidazole groups in a dimethylimidazole ligand is 1: 1-5, and the molar ratio of zinc ions to dimethylformamide and ethylenetriamine is 1:8.36: 0.044.
5. The preparation method of the ZIF-8-doped highly corrosion-resistant micro-arc oxidation composite coating according to claim 3, wherein the prepared electrolyte comprises the following components in concentration: 1-3 g/L ZIF-8 micron particles, 5-8 g/L sodium silicate nonahydrate, 1-4 g/L potassium hydroxide and 1-4 g/L sodium hexametaphosphate.
6. The preparation method of the ZIF-8-doped highly corrosion-resistant micro-arc oxidation composite coating according to claim 3, wherein parameters of pulse micro-arc oxidation equipment in the micro-arc oxidation process are as follows: the current density is 5.18 to 6.64A/dm 2 The frequency is 800-1500 Hz, the duty ratio is 17-35%, and the micro-arc oxidation time is 10 min.
7. The preparation method of the ZIF-8-doped highly corrosion-resistant micro-arc oxidation composite coating according to claim 3, wherein in the micro-arc oxidation treatment in the step (4), the electrolyte is continuously stirred by a magnetic stirrer at a stirring speed of 500 rpm.
8. The preparation method of the ZIF-8-doped high corrosion resistance micro-arc oxidation composite coating according to claim 3, wherein the workpiece pretreatment in the step (2) is to polish the surface of the aluminum alloy workpiece by using water-milled sand paper with the mesh numbers of 180#, 1200#, and 2000#, until the surface of the material is flat, no obvious scratch or no obvious pit is formed; and then immersing the polished aluminum alloy workpiece into normal-temperature deionized water for ultrasonic cleaning for 1min, cleaning for 3-5 times, and drying by cold air.
9. The preparation method of the ZIF-8-doped highly corrosion-resistant micro-arc oxidation composite coating according to claim 2, wherein in the step (1), the concentration of the sodium hydroxide solution is 10mol/L, and the pH is adjusted to be alkaline and 9.2.
10. The preparation method of the ZIF-8-doped highly corrosion-resistant micro-arc oxidation composite coating according to claim 2, wherein in the step (3), the ultrasonic power is 25W.
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