CN114855237B - 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 65
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 title claims abstract description 59
- 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 title claims abstract description 59
- 238000000576 coating method Methods 0.000 title claims abstract description 54
- 239000011248 coating agent Substances 0.000 title claims abstract description 51
- 239000002131 composite material Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000005260 corrosion Methods 0.000 claims abstract description 37
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 36
- 230000007797 corrosion Effects 0.000 claims abstract description 35
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 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
- 239000002245 particle Substances 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000003792 electrolyte Substances 0.000 claims abstract description 26
- 229910000838 Al alloy Inorganic materials 0.000 claims abstract description 23
- 238000003756 stirring Methods 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 16
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 claims abstract description 15
- 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 13
- 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
- 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
- 239000007787 solid Substances 0.000 claims abstract description 7
- 239000003446 ligand Substances 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- 230000005764 inhibitory process Effects 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 12
- 238000004140 cleaning Methods 0.000 claims description 8
- 238000009210 therapy by ultrasound Methods 0.000 claims description 8
- 125000002883 imidazolyl group Chemical group 0.000 claims description 6
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 6
- 239000000839 emulsion Substances 0.000 claims description 5
- 244000137852 Petrea volubilis Species 0.000 claims description 4
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 238000005498 polishing Methods 0.000 claims description 4
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 abstract description 9
- 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
- 230000000694 effects Effects 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 239000000758 substrate Substances 0.000 abstract description 3
- 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
- 230000007547 defect Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 4
- 230000007774 longterm Effects 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- -1 adding ethyltriamine Chemical compound 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 230000008439 repair process Effects 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 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
- 239000011159 matrix material Substances 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
- 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
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- AEOCXXJPGCBFJA-UHFFFAOYSA-N ethionamide Chemical compound CCC1=CC(C(N)=S)=CC=N1 AEOCXXJPGCBFJA-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000007781 pre-processing 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
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—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-resistant micro-arc oxidation composite coating, which comprises the steps of dissolving dimethyl imidazole and zinc nitrate hexahydrate in dimethylformamide, adding ethyltriamine, adjusting pH to be alkaline, carrying out ultrasonic stirring, carrying out centrifugal separation to obtain white solid, and washing and drying to obtain ZIF-8 particles; adding ZIF-8 particles into deionized water, performing ultrasonic dispersion, and then dissolving sodium silicate nonahydrate, potassium hydroxide and sodium hexametaphosphate into the deionized water to prepare an electrolyte; and 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 ligand with corrosion inhibition in ZIF-8 is adsorbed on the metal surface, so that the substrate is protected from corrosion, and the corrosion resistance of the substrate is improved.
Description
Technical Field
The invention relates to preparation of a high corrosion-resistant composite coating, in particular to a preparation method of a ZIF-8 doped high corrosion-resistant 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 marine equipment manufacturing industry, and is light in weight, high in specific strength, easy to process and form, low-temperature resistant and the like, so that the aluminum alloy is increasingly applied in the ship manufacturing industry. However, the aluminum alloy itself has the disadvantages of low hardness, poor wear resistance and poor corrosion resistance in the marine environment, which limits the use of the aluminum alloy in the marine field. The micro-arc oxidation technology is used as a novel surface treatment technology, and the ceramic film layer with better wear resistance, corrosion resistance and electrical insulation performance and high bonding strength with the matrix can be prepared on the surface of the aluminum alloy. However, in the micro-arc oxidation process, the micro-arc oxidation coating is affected by spark discharge, and has more micropores, so that the corrosion resistance is greatly affected, and the application of the micro-arc oxidation coating in a corrosion environment is restricted. Therefore, it is necessary to eliminate the influence of the defects of the coating structure on the performance thereof by adopting the necessary means.
Disclosure of Invention
Aiming at the defects existing 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 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-resistant 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 particles: sequentially dissolving dimethyl imidazole and zinc nitrate hexahydrate in dimethylformamide, adding ethyltriamine, adjusting the pH to 9-12 by using a sodium hydroxide solution, simultaneously stirring for 2-3 hours by using ultrasonic 1h to obtain a white emulsion, centrifuging at a stirring speed of 300 rpm to obtain a white solid, alternately washing for 3-5 times by using methanol and deionized water, and then drying in vacuum at a temperature of 40-60 ℃ to obtain white powdery ZIF-8 micron particles; according to the invention, zinc nitrate hexahydrate and dimethyl imidazole respectively provide metal ions and imidazolyl ligands for ZIF-8, and the zinc nitrate hexahydrate and the dimethyl imidazole serve as main reactants, while dimethylformamide serves as a solvent, and the ethimide serves as a crystallization promoter to mainly accelerate deprotonation of the dimethyl imidazole and promote crystal nucleation of ZIF-8; the size of the obtained ZIF-8 particles is about 300 nanometers, the pores are lower than the diameter of chloridion in seawater by 6.64A, the ZIF-8 particles have good barrier effect on chloridion, and play a role in preventing corrosion ions from further diffusing in the micro-arc oxidation coating, in addition, the ZIF-8 release imidazole ligands and adsorb on the surface of the coating under the long-term soaking of seawater, so that the anode type corrosion inhibitor plays a role, and the long-term corrosion resistance of the micro-arc oxidation coating is improved.
(2) Pretreatment of a workpiece: polishing the aluminum alloy workpiece by using water-grinding sand paper to make the surface of the aluminum alloy workpiece smooth;
(3) Preparing an electrolyte: firstly 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 then sequentially dissolving sodium silicate nonahydrate, potassium hydroxide and sodium hexametaphosphate into deionized water after ultrasonic treatment to prepare an electrolyte for later use;
(4) Preparation of the composite coating: placing the pretreated aluminum alloy workpiece serving as an anode into a prepared electrolyte, and taking graphite as a cathode, wherein the interval between the cathode and the anode is 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 cleaning and drying the prepared micro-arc oxidation composite coating by deionized water after the treatment is finished.
In the step (1), the molar ratio of zinc ions in zinc nitrate hexahydrate to imidazolyl in the dimethyl imidazole ligand is 1:1-5, and the molar ratio of zinc ions to dimethylformamide to ethyltriamine is 1:8.36:0.044;
specifically, the concentration of each component in the electrolyte prepared by the invention is as follows: 1-3 g/L of ZIF-8 micron particles, 5-8 g/L of sodium silicate nonahydrate, 1-4 g/L of potassium hydroxide and 1-4 g/L of sodium hexametaphosphate. Sodium silicate nonahydrate is used as a main electrolyte component, potassium hydroxide and sodium hexametaphosphate are used as additives, the pH of the electrolyte is regulated, the conductivity of the solution is improved, the surface of an aluminum alloy is promoted to rapidly grow a micro-arc oxidation coating, ZIF-8 stably exists under the electrolyte, negative Zeta potential is presented in the solution, and under the condition of electrifying, ZIF-8 migrates towards the anode direction of the aluminum alloy, and participation in the micro-arc oxidation coating forming process is promoted.
The parameters of the pulse micro-arc oxidation equipment in the micro-arc oxidation process are as follows: the current density is 5.18-6.64A/dm 2 The frequency is 800-1500 Hz, the duty ratio is 17-35%, and the micro-arc oxidation time is 10 min.
In the micro-arc oxidation treatment process of the step (4), the electrolyte is continuously stirred by a magnetic stirrer, and the stirring speed is 500 rpm.
Preferably, the step (2) of preprocessing the workpiece is to sequentially adopt the water-grinding sand paper with the mesh number of 180#, 1200#, 2000# to grind the surface of the aluminum alloy workpiece until the surface of the material is flat, no obvious scratches and no obvious pits are generated; and 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, and the pH is adjusted to be alkaline and 9.2, so that the deprotonation process of the dimethylimidazole can be accelerated, and the ZIF-8 nucleation is 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 anti-corrosion potential in the coating has an excellent barrier effect on chloride ions (with the radius of 6.64A) in the seawater, and prevents corrosion ions in the seawater from entering the inside of the coating. Meanwhile, the imidazole ligand with corrosion inhibition in ZIF-8 is adsorbed on the metal surface, so that the substrate is protected from corrosion, the corrosion resistance is improved, and the method is suitable for the surface treatment of aluminum alloy in the marine corrosion-prone environment.
2. The operation process and the electrolytic liquid system related by the invention have simple components, and effectively reduce the cost.
3. The technological process of the present invention has no environmental pollution.
Drawings
FIG. 1-scanning and energy spectra of the coatings of example 1 and comparative example 1.
FIG. 2-Low frequency impedance mode graphs for coatings of example 1 and comparative example 1.
Detailed Description
The present invention will be described in further detail with reference to the drawings and the detailed description.
Example 1
(1) Preparation of ZIF-8 particles: sequentially dissolving dimethyl imidazole and zinc nitrate hexahydrate in dimethylformamide, adding ethyltriamine, dimethyl imidazole, zinc nitrate hexahydrate, dimethylformamide and ethyltriamine in a molar ratio of 1:1:8.36:0.044, regulating the pH value of the solution to 9.2 by using a 10mol/L sodium hydroxide solution, simultaneously stirring for 3 hours by ultrasound for h to obtain a white emulsion, obtaining a white solid by centrifugal separation at a stirring speed of 300 rpm, alternately washing for 4 times by using methanol and deionized water, and then drying in vacuum at 40 ℃ to obtain the white powdery ZIF-8 micrometer-sized material.
(2) And (3) workpiece treatment: the micro-arc oxidation anode material is made of 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, wherein the diameter of the hole is 3mm. Sequentially polishing the front and the side surfaces of the sample by using No. 180, no. 1200 and No. 2000 water-grinding sand paper until the surface of the material is flat, no obvious scratches and no obvious pits exist; 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: filling deionized water of 1.5L into a container of 2L, adding ZIF-8 particles prepared in the step (1) according to the amount of 3 g/L, adding sodium silicate nonahydrate of 6 g/L, potassium hydroxide of 2 g/L and sodium hexametaphosphate of 1 g/L after ultrasonic treatment of 1h (ultrasonic power of 25W), adding the next component after the former component is fully dissolved, and simultaneously placing the container into an ultrasonic cleaning machine while stirring in the configuration process to promote the dissolution of the components. Finally deionized water was added to 2L.
(4) Sample preparation: placing the 6061 aluminum alloy workpiece subjected to pretreatment into a prepared electrolyte as an anode, taking graphite as a cathode, and adopting a pulse direct-current power supply to perform micro-arc oxidation treatment on the 6061 aluminum alloy workpiece in a constant-current mode, wherein the micro-arc oxidation parameter is that the current density is 6A/dm 2 The frequency is 1000 Hz, the duty ratio is 20%, and the 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 interval between the cathodes and the anodes 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 preserving.
The thickness of the micro-arc oxidation composite ceramic film obtained in this example was 6.+ -. 0.8. Mu.m.
Comparative example 1
The 6061 aluminum alloy workpiece was polished and cleaned as in step (2) of example 1, and dried for use. Sodium silicate nonahydrate 6 g/L, potassium hydroxide 2 g/L and sodium hexametaphosphate 1 g/L are sequentially dissolved in deionized water of 1.5L, and meanwhile, in the configuration process, the beaker is placed into an ultrasonic cleaner while being stirred, so that component dissolution is promoted. Finally deionized water was added to 2L. And then the 6061 aluminum alloy workpiece is taken as an anode, the graphite electrode is taken as a cathode, and the interval between the anode and the cathode is 10 cm. Adopts a single-stage pulse power supply with the current density of 6A/dm 2 Frequency of 1000 Hz, duty cycle of 20%, micro-arc oxidation timeThe micro-arc oxidation coating is prepared under the condition of 10 min.
The thickness of the micro-arc oxidation composite ceramic film obtained in this example was 5.+ -. 0.4. Mu.m.
The micro-arc oxidation coating surface micro-morphology prepared in the example 1 and the comparative example 1 is shown in fig. 1, the micro-arc oxidation coating surface obtained in the comparative example 1 has obvious pores, and the micro-arc oxidation composite coating surface obtained in the example 1 is provided with a large amount of ZIF-8 particles, and the disc-shaped molten pool is relatively reduced. From the energy spectrum results, the atomic ratio of the key Zn element of the coating ZIF-8 in the comparative example 1 is 0%, and the atomic ratio of the Zn element of the composite coating in the example 1 is 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 after 360 hours of testing, the low frequency impedance modulus curve is as shown in FIG. 2, and the long-term low frequency impedance modulus of example 1 was always maintained at 10 7 ~10 8 Ω•cm 2 While the long-term low-frequency impedance mode of comparative example 1 was maintained at 10 at all times 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 particles: sequentially dissolving dimethyl imidazole and zinc nitrate hexahydrate in dimethylformamide, adding ethyltriamine, dimethyl imidazole, zinc nitrate hexahydrate, dimethylformamide and ethyltriamine in a molar ratio of 3:1:8.36:0.044, regulating the pH to 9.2 by using a 10mol/L sodium hydroxide solution, simultaneously stirring for 3 hours by ultrasonic treatment for h to obtain a white emulsion, centrifuging to obtain a white solid, alternately washing for 4 times by using methanol and deionized water, and then drying in vacuum at 50 ℃ to obtain the white powdery ZIF-8 micron-sized material.
(2) And (3) workpiece treatment: the method described with reference to example 1.
(3) Electrolyte preparation: filling deionized water of 1.5L into a container of 2L, adding ZIF-8 particles prepared in the step (1) according to the amount of 2 g/L, adding sodium silicate nonahydrate of 8 g/L, potassium hydroxide of 1 g/L and sodium hexametaphosphate of 3 g/L after ultrasonic treatment of 1h in an ultrasonic device with the power of 25W, adding the next component after the former component is fully dissolved, and simultaneously, putting the container into an ultrasonic cleaning machine while stirring in the configuration process to promote the dissolution of the components. Finally deionized water was added to 2L.
(4) Sample preparation: placing the 6061 aluminum alloy workpiece subjected to pretreatment into a prepared electrolyte as an anode, taking graphite as a cathode, and performing micro-arc oxidation treatment on the 6061 aluminum alloy workpiece in a constant current mode by adopting a pulse direct current power supply, wherein the current density is 6.64A/dm 2 Frequency 800 Hz, duty cycle 17%, micro-arc oxidation time 10 min. The test adopts double cathodes which are respectively arranged at two sides of a workpiece, and the interval between the cathodes and the anodes 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 preserving.
The thickness of the micro-arc oxidation composite ceramic film is 5.8+/-0.6 mu m, a large number of ZIF-8 particles are attached to the surface, more ceramic pellets are arranged on the surface, and the atomic ratio of Zn elements 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 ZIF-8 effectively repairs the defects of the micro-arc oxidation coating, so that the coating has good corrosion resistance.
Example 3
(1) Preparation of ZIF-8 particles: sequentially dissolving dimethyl imidazole and zinc nitrate hexahydrate in dimethylformamide, adding ethyltriamine, dimethyl imidazole, zinc nitrate hexahydrate, dimethylformamide and ethyltriamine in a molar ratio of 5:1:8.36:0.044, regulating the pH value of a 10mol/L sodium hydroxide solution to 9.2, simultaneously stirring the solution with ultrasonic 1h for 3 h to obtain a white emulsion, performing centrifugal separation to obtain a white solid, alternately washing the white solid with methanol and deionized water for 4 times, and then performing vacuum drying at 60 ℃ to obtain the white powdery ZIF-8 micron-sized material.
(2) And (3) workpiece treatment: the method described with reference to example 1.
(3) Electrolyte preparation: filling deionized water of 1.5L into a container of 2L, adding ZIF-8 particles prepared in the step (1) according to the amount of 1 g/L, adding sodium silicate nonahydrate of 5 g/L, potassium hydroxide of 4 g/L and sodium hexametaphosphate of 4 g/L after ultrasonic treatment of 1h in an ultrasonic device with the power of 25W, adding the next component after the former component is fully dissolved, and simultaneously, putting the container into an ultrasonic cleaning machine while stirring in the configuration process to promote the dissolution of the components. Finally deionized water was added to 2L.
(4) Sample preparation: placing the 6061 aluminum alloy workpiece subjected to pretreatment into a prepared electrolyte as an anode, taking graphite as a cathode, and performing micro-arc oxidation treatment on the 6061 aluminum alloy workpiece in a constant current mode by adopting a pulse direct current power supply, wherein the current density is 5.18A/dm 2 Frequency 1500 Hz, duty cycle 35%, micro-arc oxidation time 10 min. The test adopts double cathodes which are respectively arranged at two sides of a workpiece, and the interval between the cathodes and the anodes 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 preserving.
The thickness of the micro-arc oxidation composite ceramic film is 5.4+/-0.3 mu m, a large number of ZIF-8 particles are attached to the surface, more ceramic balls are arranged on the surface, and the atomic ratio of Zn elements 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 ZIF-8 effectively repairs the defects of the micro-arc oxidation coating, so that the coating has good corrosion resistance.
According to the invention, the ZIF-8 material is used for repairing the micro-crack defect of the micro-arc oxidation coating, and the ZIF-8 material has an excellent barrier effect on chloride ions in seawater and prevents corrosive ions in the seawater from entering the coating; the ZIF-8 material is utilized to absorb corrosion ions and carry corrosion inhibition imidazole groups, so that corrosion medium is effectively prevented 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 illustrative of the present invention and are not limiting of the embodiments of the present invention. Other variations and modifications of the present invention will be apparent to those of ordinary skill in the art in light of the foregoing description. Not all embodiments are exhaustive. Obvious changes and modifications which are extended by the technical proposal of the invention are still within the protection scope of the invention.
Claims (6)
1. A preparation method of a ZIF-8 doped high corrosion-resistant micro-arc oxidation composite coating is characterized in that an aluminum alloy workpiece is placed in electrolyte for micro-arc oxidation treatment, wherein the electrolyte contains ZIF-8 particles; the ZIF-8 particles carry corrosion inhibition imidazole groups;
the method comprises the following specific steps:
(1) Preparation of ZIF-8 particles: sequentially dissolving dimethyl imidazole and zinc nitrate hexahydrate in dimethylformamide, adding ethyltriamine, adjusting the pH to 9-12 by using a sodium hydroxide solution, simultaneously stirring for 2-3 hours by using ultrasonic 1h to obtain a white emulsion, centrifuging at a stirring speed of 300 rpm to obtain a white solid, alternately washing for 3-5 times by using methanol and deionized water, and then drying in vacuum at a temperature of 40-60 ℃ to obtain white powdery ZIF-8 micron particles;
(2) Pretreatment of a workpiece: polishing the aluminum alloy workpiece by using water-grinding sand paper to make the surface of the aluminum alloy workpiece smooth;
(3) Preparing an electrolyte: firstly 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 then sequentially dissolving sodium silicate nonahydrate, potassium hydroxide and sodium hexametaphosphate into deionized water after ultrasonic treatment to prepare an electrolyte for later use; the prepared electrolyte has the following components in concentration: 1-3 g/L of ZIF-8 micron particles, 5-8 g/L of sodium silicate nonahydrate, 1-4 g/L of potassium hydroxide and 1-4 g/L of sodium hexametaphosphate;
(4) Preparation of the composite coating: placing the pretreated aluminum alloy workpiece serving as an anode into a prepared electrolyte, and taking graphite as a cathode, wherein the interval between the cathode and the anode is 10 cm; performing micro-arc oxidation treatment on the aluminum alloy workpiece in a constant current mode by adopting a pulse direct current power supply, and cleaning and drying the prepared micro-arc oxidation composite coating by deionized water after the treatment is finished;
in the step (1), the molar ratio of zinc ions in zinc nitrate hexahydrate to imidazolyl in the dimethyl imidazole ligand is 1:1-5, and the molar ratio of zinc ions to dimethylformamide and ethirimide is 1:8.36:0.044.
2. The method for preparing the ZIF-8 doped high corrosion resistant micro-arc oxidation composite coating according to claim 1, wherein parameters of pulse micro-arc oxidation equipment in the micro-arc oxidation process are as follows: the current density is 5.18-6.64A/dm 2 The frequency is 800-1500 Hz, the duty ratio is 17-35%, and the micro-arc oxidation time is 10 min.
3. The method for preparing the ZIF-8 doped high corrosion resistant micro-arc oxidation composite coating according to claim 1, wherein in the micro-arc oxidation treatment process of the step (4), a magnetic stirrer is adopted to continuously stir the electrolyte, and the stirring speed is 500 rpm.
4. The preparation method of the ZIF-8 doped high corrosion-resistant micro-arc oxidation composite coating is characterized in that the pretreatment of the workpiece in the step (2) is to sequentially polish the surface of an aluminum alloy workpiece by using abrasive paper with the mesh number of 180#, 1200#, 2000#, and the polishing is carried out until the surface of the material is flat, no obvious scratch exists and no obvious pit exists; and 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.
5. The method for preparing a ZIF-8 doped high corrosion resistant micro-arc oxidation composite coating according to claim 1, wherein in the step (1), the concentration of sodium hydroxide solution is 10mol/L, and the pH is adjusted to be 9.2.
6. The method for preparing the ZIF-8 doped high corrosion resistant micro-arc oxidation composite coating according to claim 1, wherein in the step (3), the ultrasonic power is 25W.
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