CN110643999A - Preparation method of self-assembled hole sealing protective film - Google Patents
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- CN110643999A CN110643999A CN201910948706.3A CN201910948706A CN110643999A CN 110643999 A CN110643999 A CN 110643999A CN 201910948706 A CN201910948706 A CN 201910948706A CN 110643999 A CN110643999 A CN 110643999A
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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
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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
- C23C20/00—Chemical coating by decomposition of either solid compounds or suspensions of the coating forming compounds, without leaving reaction products of surface material in the coating
- C23C20/06—Coating with inorganic material, other than metallic material
- C23C20/08—Coating with inorganic material, other than metallic material with compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
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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
- C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
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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
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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
- C25D11/10—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used containing organic acids
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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
- C25D11/18—After-treatment, e.g. pore-sealing
- C25D11/24—Chemical after-treatment
- C25D11/246—Chemical after-treatment for sealing layers
Abstract
The invention relates to a marine anti-corrosion protective film material, in particular to a preparation method of a self-assembled hole sealing protective film for preparing a marine anti-corrosion protective film on a metal surface after anodic oxidation treatment and sol-gel treatment by utilizing a layer-by-layer self-assembly technology (LBL). And depositing the metal surface subjected to anodic oxidation treatment on the metal surface in a sol-gel manner and layer by layer to form the anti-corrosion protective film. The invention has the advantages that the sol-gel hole sealing technology and the layer-by-layer self-assembly technology are perfectly combined, the corrosion inhibition efficiency of the protective film subjected to the layer-by-layer self-assembly technology in a 3.5% NaCl solution is very high, compared with a test piece which is only subjected to anodic oxidation treatment, the surface of the test piece subjected to layer-by-layer self-assembly is smoother, the high resistance is realized, and the potential application prospect in the aspect of marine corrosion protection is huge.
Description
Technical Field
The invention relates to a marine anti-corrosion protective film material, in particular to a preparation method of a self-assembled hole sealing protective film for preparing a marine anti-corrosion protective film on a metal surface after anodic oxidation treatment and sol-gel treatment by utilizing a layer-by-layer self-assembly technology (LBL).
Background
In the marine environment, metal materials are easily corroded and damaged by chloride ions to lose the basic performance, and great harm is caused to economy. The layer-by-layer self-assembly technology (LBL) can control the size, the components and the appearance of a product in the field of functional thin film materials, and the technology is used for metal corrosion prevention, so that a great deal of researchers pay high attention to the technology.
LBL is a technique by which molecular assembly can be achieved at an interface. The first layer-by-layer self-assembly technique in the scientific history was published in 1991 and is a more economical and simple coating to protect metal substrates from attack in corrosive environments, which has attracted much attention in the world. The principle of the LBL technology is that positive electrolyte ions and negative electrolyte ions are alternately adsorbed and deposited layer by layer, and the electrolyte ions are adsorbed and formed into a film layer by layer on a metal matrix through interaction force (electrostatic alternate adsorption, hydrogen bond, covalent bond and charge transfer interaction) between two or more electrolyte ions, so that the metal corrosion resistance is improved. The LBL technology has the advantages of simple preparation method, easy operation, high repeatability, easy control of film thickness and surface appearance, stable performance and capability of generating required multilayer and complex films according to templates. In recent years, the material is widely applied to the fields of physics, chemistry, materials science, nano materials and the like, and is mostly applied to the fields of photoelectric conversion, microelectronics, sensors, thin films and the like at present.
Dingxing pool et al use three precursors to hydrolyze gradually to obtain a composite solution, and prepare a sol-gel coating by a dip coater, which has good corrosion resistance. The coating is prepared on the surface of the titanium alloy by utilizing the sol-gel technology, and has good high-temperature oxidation resistance and shock resistance on a matrix. The Xuanli Jingwai researches on electrolyte self-assembly pervaporation membranes and ion separation membranes in recent years. The Zhaojun adopts a layer-by-layer self-assembly method to alternately deposit and accumulate a mixed solution of Polyethyleneimine (PEI) and polyacrylic acid-graphene oxide (PAA-GO) on the surface of a modified Polyacrylonitrile (PAN) membrane to prepare the monovalent ion selective antifouling composite membrane, and the high-flux and high-selectivity antifouling composite membrane has good application prospects in the aspects of separation and water softening. In order to solve the problem that the sulfonated polyarylethersulfone ketone/phosphotungstic acid (SPPESK/PWA) composite proton exchange membrane prepared by a direct doping method has serious PWA loss, a Sunzuan and the like use Chitosan (CS) and PWA as a poly anion and cation electrolyte pair to carry out electrostatic layer-by-layer self-assembly modification research on the composite membrane, and the method not only improves the proton conductivity of the composite membrane, but also effectively inhibits the PWA loss. In the aspect of layer-by-layer self-assembly models and parameter discussion, Qin-Yuan Juan and the like propose that the layer-by-layer self-assembly of chitosan/sulfonated lignin is an exponential growth process.
So far, there has been no study on the combination of sol-gel technology and layer-by-layer self-assembly technology.
Disclosure of Invention
The invention aims to provide an anti-corrosion protective film prepared on a metal surface by combining an anodic oxidation technology, a sol-gel technology and a layer-by-layer self-assembly technology and a preparation method thereof.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of a self-assembly hole sealing protective film comprises the step of depositing a metal surface subjected to anodic oxidation treatment on the metal surface layer by layer in a sol-gel manner to form an anti-corrosion protective film.
Further, the pretreated substrate is subjected to anodic oxidation on the surface of the substrate to form an anodic oxidation film; then carrying out hole sealing treatment on the mixture by a sol-gel technology; and then LBL self-assembly deposition is carried out on the surface of the matrix, and cleaning is carried out after deposition to obtain a target experimental product.
Further, immersing the substrate with the surface formed with the anodic oxide film in the alumina sol for 1-2min by using an immersion pulling method, then pulling out the liquid level of the alumina sol, coating a layer of sol on the surface of the aluminum alloy, then carrying out heat treatment, completing one-time alumina sol-gel coating, cooling to room temperature, and then repeating the alumina sol-gel coating for 4-8 times, thereby realizing the preparation of the alumina sol film on the metal surface of the substrate.
The preparation of the alumina sol solution comprises the following steps: under the conditions that the temperature is 20-30 ℃ and the humidity is 30-35%, aluminum isopropoxide is taken as a precursor, aluminum isopropoxide is added into n-propanol, the mixture is continuously stirred until the aluminum isopropoxide is completely dissolved, acetylacetone and distilled water with the same mass as the aluminum isopropoxide are respectively added dropwise in the stirring process, finally, 3-5 drops of nitric acid is added as a stabilizer, the mixture is stirred on a magnetic stirrer for 2-3h, and the mixture is aged for 24-48h, so that clear and transparent alumina sol is obtained. Wherein the final concentration of aluminum isopropoxide in the n-propanol is 30-50 mg/ml.
Further, immersing the substrate with the surface formed with the alumina sol film in an aqueous solution containing 2-6mg/L Polyethyleneimine (PEI) for 3-8 minutes, taking out and immersing in distilled water for 1-3 minutes; then immersing in a polyacrylic acid (PAA) aqueous solution with the mole fraction equal to that of polyethyleneimine for 3-8 minutes, taking out and immersing in distilled water for 1-3 minutes to realize one-time circulating self-assembly; and performing self-assembly cycle operation for 10-12 times to deposit and form the anti-corrosion protective film on the metal surface.
The anodic oxidation treatment is to carry out anodic oxidation on the pretreated and cleaned substrate in oxalic acid water solution, wherein the anodic oxidation voltage is controlled to be 50-55V, and the oxidation current density is 1.5-2A/dm2Oxidizing for 60-65min in ice-water bath; then washing with deionized water and drying with cold air to obtain an anodic oxide film; and (5) standby.
Compared with the prior art, the invention has the following beneficial effects:
the invention adopts the combination of the sol-gel technology and the layer-by-layer self-assembly technology to form the anti-corrosion protective film on the surface of the metal test piece, which solves the problems of low corrosion inhibition efficiency, poor electrochemical performance and easy corrosion of the marine anti-corrosion protective film in the previous research; the method specifically comprises the following steps:
1. the perfect combination of the sol-gel technology and the layer-by-layer self-assembly technology improves the compactness of the protective film, and the thickness and the composition are more uniform; furthermore, the surface roughness of the multilayer self-assembled film on the metal surface after LBL deposition is reduced, the anti-contamination performance is better, and the corrosion inhibition efficiency in 3.5% NaCl solution is over 99%.
2. The physical and chemical properties of the film combined by the sol-gel technology and layer-by-layer self-assembly are more excellent; the surface morphology and the roughness of the modified multilayer self-assembled film can be respectively represented by utilizing the excellent corrosion prevention and protection performance of the multilayer self-assembled film on metal materials through a scanning electron microscope SEM and an atomic force microscope AFM. And measuring the electrochemical performance of the self-assembled film by an electrochemical impedance spectroscopy technology, and further analyzing the corrosion resistance and corrosion inhibition efficiency of the self-assembled film.
Drawings
FIG. 1 is SEM images of an aluminum alloy surface according to an embodiment of the present invention, wherein the SEM images include (a) a blank aluminum alloy, (b) an anodic oxide film, (c) a sol-gel film, and (d) an LBL film.
FIG. 2 is an atomic force microscope AFM of a multi-layer self-assembled film according to an embodiment of the present invention (a) a bare aluminum alloy, (b) an anodized film, (c) a sol-gel film, (d) an LBL film; the scanning area is 10X 10 μm2(a)，1×1μm2(b、c、d)。
FIG. 3a1 is an Electrochemical Impedance (EIS) -Nyquist plot of bare aluminum alloy surface and aluminum alloy surface with anodized films according to embodiments of the present invention.
Fig. 3a2 is an Electrochemical Impedance (EIS) -nyquist plot of an aluminum alloy surface sol-gel film and an aluminum alloy surface layer-by-layer self-assembled film according to an embodiment of the present invention.
FIG. 3b is an Electrochemical Impedance (EIS) -Baud plot of various films on the surface of an aluminum alloy according to an embodiment of the present invention.
FIG. 3c is an Electrochemical Impedance (EIS) -Baud plot of various films on the surface of an aluminum alloy according to an embodiment of the present invention.
Fig. 4 is a polarization graph according to an embodiment of the present invention.
Detailed Description
The invention is described in detail below with reference to the figures and examples.
Various performances of the protective film treated by LBL are obviously superior to those of the protective film only using the sol-gel hole sealing technology. The surface morphology and the roughness of the multilayer self-assembled film are respectively characterized by scanning electron microscope SEM, atomic force microscope AFM and X-ray photoelectron spectroscopy XPS technologies. And measuring the electrochemical performance of the self-assembled film by an electrochemical impedance spectroscopy technology, and further analyzing the corrosion resistance and corrosion inhibition efficiency of the self-assembled film. The invention has the advantages that the sol-gel hole sealing technology and the layer-by-layer self-assembly technology are perfectly combined, the corrosion inhibition efficiency of the protective film subjected to the layer-by-layer self-assembly technology in a 3.5% NaCl solution is very high, compared with a test piece which is only subjected to anodic oxidation treatment, the surface of the test piece subjected to layer-by-layer self-assembly is smoother, the high resistance is realized, and the potential application prospect in the aspect of marine corrosion protection is huge.
Example 1
1) Preparing an anodic oxide film on the surface of the aluminum alloy:
the method comprises the steps of polishing a 2A12 aluminum alloy test piece by using sand paper, removing impurities and an oxide film, quickly washing the aluminum alloy test piece by using distilled water until a bright surface appears, then ultrasonically cleaning the aluminum alloy test piece by using acetone, and blow-drying the aluminum alloy test piece to be used as a blank sample for later use. And (3) carrying out oxalic acid anodic oxidation on the blank sample according to the existing mode, then washing with deionized water, and drying with cold air to obtain the aluminum alloy anodic oxide film. The whole anodic oxidation process ensures constant temperature and constant voltage, the temperature is 25-30 ℃, and the voltage is maintained at 50-55V. The electrolyte solution is oxalic acid aqueous solution with the concentration of 30-60g/L prepared by distilled water, the oxalic acid is analytically pure, and after the anodic oxidation process is finished, the anodic oxidation sample is washed and dried by the distilled water and then can be put into a dryer for storage.
2) Preparation of sol-gel film on surface of aluminum alloy
Preparing alumina sol on the anodized aluminum alloy sample treated by the immersion pulling method, hanging the aluminum alloy sample by a thin wire, descending at a uniform rate perpendicular to the sol liquid surface until the aluminum alloy sample completely enters the sol liquid surface, standing in the sol for 1 minute, uniformly pulling out the alumina sol liquid surface at a uniform rate of about 20mm/min to finish the pulling operation, namely coating a layer of sol on the aluminum alloy, and then carrying out heat treatment, wherein the heat treatment test parameters are that the temperature of an oven is set to be 120 ℃, the time is 30 minutes, and the primary alumina sol-gel coating is finished. And repeating the operation after cooling to room temperature for six times. Finally, preparing an alumina sol film on the surface of the aluminum alloy; wherein the sol solution is as follows: under the temperature of 20-30 ℃ and the humidity of 30-35%, adding 2g of aluminum isopropoxide into 50ml of n-propanol by taking the aluminum isopropoxide as a precursor, continuously stirring by using a glass rod until the aluminum isopropoxide is completely dissolved, respectively dropwise adding 2ml of acetylacetone and distilled water in the stirring process, finally adding 3-5 drops of nitric acid as a stabilizer, stirring for 2h on a magnetic stirrer, and aging for 24h to obtain the clear and transparent alumina sol.
3) Preparation of aluminum alloy surface LBL self-assembled film
The aluminum alloy test piece of the prepared alumina sol film is hung by a clean wire and is put into a beaker containing 4mg/L of Polyethyleneimine (PEI) aqueous solution to be soaked for 5 minutes, then is taken out and is put into the beaker with distilled water for 2 minutes, and then is put into the beaker containing 4mg/L of polyacrylic acid (PAA) aqueous solution to be taken out and is put into the beaker with distilled water for 2 minutes after 5 minutes. This is a cycle, labeled (PEI/PAA). Repeating the cycle for ten times for standby, and preparing the polyethyleneimine and polyacrylic acid layer-by-layer self-assembled protective film by the method.
And (3) carrying out performance test on the layer-by-layer self-assembled marine anti-corrosion protective film material prepared by the method:
1) scanning Electron Micrographs (SEM) of the different films:
each sample (each sample was a 2a12 aluminum alloy test piece (blank aluminum alloy), an anodic oxide film (the product obtained in step 1 of example 1), the final product obtained in example (sol-gel film) and a commercially available LBL film) was subjected to a gold-spraying treatment, and surface observation was performed under a scanning electron microscope. (see the figure)
1)
It can be seen from the scanning electron microscope image of the sample in fig. 1 that (a) is a blank aluminum alloy sample with many scratches and (b) is an aluminum alloy sample after anodic oxidation treatment with oxalic acid solution, and it can be seen that the surface film has obvious pores, a small and dense porous structure and uneven and wavy surface. The dissolution of the oxalic acid electrolyte on the oxide film causes uneven surface height of the film; the image (c) is a scanning electron microscope image after sol-gel treatment, and the image (d) is a scanning electron microscope image after LBL, so that the sample surface is covered with more uniform and fine film substances, and a layered structure is not generated. The visual field range has no cracks, fine protrusions and pores, the surface of the film is smoother, uniform and flat, the contact between the film layer and the interface is tight, and the shape is better than that of other three samples.
2) Atomic Force Microscopy (AFM) of different films:
each sample (each sample was a 2a12 aluminum alloy test piece (blank aluminum alloy), an anodic oxide film (the product obtained in step 1 of example 1), the final product obtained in example (sol-gel film) and a commercially available LBL film) was placed under an atomic force microscope, and surface observation was performed in a tapping mode. (see the figure)
2)
Atomic Force Microscopy (AFM) images of the multi-layer self-assembled film from the stages of FIG. 2, wherein (a) the aluminum alloy substrate, (b) the anodized film, (c) the sol-gel film, (d) the LBL film; the scanning area is 1X 1 μm2. The difference between the wave crest and the wave trough of the surface of the aluminum alloy substrate is as high as 1000nm, which shows that the surface is rough, after the anode, the difference between the wave crest and the wave trough of the surface film is about 360nm, after the sol-gel hole sealing, the difference between the wave crest and the wave trough of the surface film is about 250nm, and after LBL, the difference between the wave crest and the wave trough of the surface film is only about 150nm, which shows that the surface roughness of the aluminum material is lower and lower along with the deposition of. After LBL, the roughness was minimized, indicating a more uniform and smooth surface.
3) Electrochemical impedance testing of different membranes:
each of the samples (each sample was a 2A12 aluminum alloy test piece (blank aluminum alloy), an anodic oxide film (the product obtained in step 1 of example 1), the final product obtained in example (sol-gel film) and a commercially available LBL film) was fixed outside the electrolytic cell, a NaCl solution at a concentration of 3.5% was used as an electrolyte, a saturated calomel electrode was used as a reference electrode, a carbon rod was used as a counter electrode, the test amplitude was 10mV, the test frequency was 10^2-10^5Hz, and an electrochemical impedance test was carried out using a GAMMA electrochemical workstation. (see FIG. 3)
FIG. 3 shows the electrochemical impedance diagram (EIS) of the blank aluminum alloy, anodized film, sol-gel film and LBL film in 3.5 wt.% NaCl solution, and it can be seen that the pure aluminum surface has no corrosion protection performance and the system impedance is only 103Ω·cm2After anodic oxidation, the system impedance is raised to 105Ω·cm2And after sol-gel, the impedance of the system is only improved to 106Ω·cm2After LBL, the system impedance is raised to 108Ω·cm2. It is generally accepted that the system impedance is below 106Ω·cm2It has no protective ability and is higher than 108Ω·cm2The protective film has excellent protective performance, and the protective effect of the LBL film is obvious.
4) Polarization curve testing of different films:
each sample (each sample was a 2a12 aluminum alloy test piece (blank aluminum alloy), an anodic oxide film (product obtained in step 1 of example 1), a final product obtained in example (sol-gel film), and a commercially available LBL film) was fixed outside the electrolytic cell, a NaCl solution with a concentration of 3.5% was used as an electrolyte, a saturated calomel electrode was used as a reference electrode, a carbon rod was used as a counter electrode, and a polarization curve test was performed using a gamy electrochemical workstation. (see FIG. 4)
From the polarization of the self-assembled film in 3.5 wt.% NaCl solution in FIG. 4, it can be seen that the corrosion potential of the LBL film is shifted up, at least 200mV higher than that of other films, and the self-corrosion current density is two orders of magnitude lower than that of other films, which fully indicates that the LBL film has low metal corrosion rate under protection and excellent corrosion resistance.
Example 2
The difference from example 1 is that the substrate is replaced by a titanium alloy:
1) preparation of titanium alloy surface anodic oxide film
And (3) polishing the titanium alloy test piece by using sand paper, removing impurities and an oxide film until a bright surface appears, quickly washing the titanium alloy test piece by using distilled water, then ultrasonically cleaning the titanium alloy test piece by using acetone, and blow-drying the titanium alloy test piece to be used as a blank sample for later use. And (3) carrying out oxalic acid anodic oxidation on the blank sample according to the existing mode, then washing with deionized water and drying with cold air to obtain the titanium alloy anodic oxide film. The whole anodic oxidation process ensures constant temperature and constant voltage, the temperature is 25-30 ℃, and the voltage is maintained at 50-55V. The electrolyte solution is an oxalic acid aqueous solution with the concentration of 30-60g/L prepared from distilled water, the oxalic acid is analytically pure, and after the anodic oxidation process is completed, the anodic oxidation sample is washed and dried by the distilled water and then can be stored in a dryer.
2) Preparation of titanium alloy surface sol-gel film
Preparing alumina sol on the titanium alloy test piece of the anodized film by using an immersion pulling method, hanging the titanium alloy test piece by using a thin wire, descending at a uniform rate perpendicular to the sol liquid surface until the titanium alloy test piece completely enters the sol liquid surface, standing in the sol for 1 minute, pulling out the alumina sol liquid surface at a uniform rate of about 20mm/min to ensure the uniformity of the prepared sol gel film, coating a layer of sol on the aluminum alloy after the pulling operation is finished, and then carrying out heat treatment. The heat treatment test parameters are that the temperature of the oven is set to be 120 ℃, the time is 30 minutes, and the alumina sol-gel coating is completed once. And repeating the operation after cooling to room temperature for six times. Finally, preparing an alumina sol film on the surface of the titanium alloy; wherein the sol solution is as follows: under the conditions that the temperature is 20-30 ℃ and the humidity is 30-35%, aluminum isopropoxide is taken as a precursor, 2g of aluminum isopropoxide is added into 50ml of n-propanol, a glass rod is used for continuously stirring until the aluminum isopropoxide is completely dissolved, 2ml of acetylacetone and distilled water are respectively added dropwise in the stirring process, finally, 3-5 drops of nitric acid are added to be taken as a stabilizer, stirring is carried out on a magnetic stirrer for 2 hours, and aging is carried out for 24 hours, so that the clear and transparent alumina sol is obtained.
3) Preparation of titanium alloy surface LBL self-assembled film
The titanium alloy test piece of the prepared alumina sol film is hung by a clean wire and is put into a beaker containing 3mg/L Polyethyleneimine (PEI) solution to be soaked for 6 minutes, then the titanium alloy test piece is taken out and is put into the beaker with distilled water to be soaked for 3 minutes, and then the titanium alloy test piece is put into the beaker with 3mg/L polyacrylic acid (PAA) solution to be soaked for 6 minutes, then the titanium alloy test piece is taken out and is put into the beaker with distilled water to be soaked for 3 minutes. This is a cycle, labeled (PEI/PAA). Repeating the cycle for ten times for standby, and preparing the polyethyleneimine and polyacrylic acid layer-by-layer self-assembled protective film by the method.
The obtained protective film is obtained by combining the sol-gel technology and the layer-by-layer self-assembly technology, the compactness is improved, and the thickness and the composition are more uniform; furthermore, the surface roughness of the multilayer self-assembled film on the metal surface after LBL deposition is reduced.
It should be understood that various changes, substitutions, combinations and alterations can be made by those skilled in the art without departing from the scope of the invention as defined by the appended claims.
Claims (6)
1. A preparation method of a self-assembled hole sealing protective film is characterized by comprising the following steps: and depositing the metal surface subjected to anodic oxidation treatment on the metal surface in a sol-gel manner and layer by layer to form the anti-corrosion protective film.
2. The method for preparing the self-assembled hole sealing protective film according to claim 1, wherein: anodizing the pretreated substrate on the surface of the substrate to form an anodic oxide film; then carrying out hole sealing treatment on the mixture by a sol-gel technology; and then LBL self-assembly deposition is carried out on the surface of the matrix, and cleaning is carried out after deposition to obtain a target experimental product.
3. The method for preparing a self-assembled hole sealing protective film according to claim 1 or 2, characterized in that: immersing the substrate with the surface formed with the anodic oxide film in the alumina sol for 1-2min by using an immersion pulling method, then pulling out the liquid level of the alumina sol, coating a layer of sol on the surface of the aluminum alloy, then carrying out heat treatment, completing one-time alumina sol-gel coating, cooling to room temperature, and repeating the alumina sol-gel coating for 4-8 times, thereby realizing the preparation of the alumina sol film on the metal surface of the substrate.
4. The method for preparing a self-assembled hole sealing protective film according to claim 3, wherein: the preparation of the alumina sol solution comprises the following steps: under the conditions that the temperature is 20-30 ℃ and the humidity is 30-35%, aluminum isopropoxide is taken as a precursor, aluminum isopropoxide is added into n-propanol, the mixture is continuously stirred until the aluminum isopropoxide is completely dissolved, acetylacetone and distilled water with the same mass as the aluminum isopropoxide are respectively added dropwise in the stirring process, finally, 3-5 drops of nitric acid is added as a stabilizer, the mixture is stirred on a magnetic stirrer for 2-3h, and the mixture is aged for 24-48h, so that clear and transparent alumina sol is obtained.
5. The method for preparing a self-assembled hole sealing protective film according to claim 1 or 2, characterized in that: immersing the substrate with the surface formed with the alumina sol film in an aqueous solution containing 2-6mg/L Polyethyleneimine (PEI) for 3-8 minutes, taking out and immersing in distilled water for 1-3 minutes; then immersing in a polyacrylic acid (PAA) aqueous solution with the mole fraction equal to that of polyethyleneimine for 3-8 minutes, taking out and immersing in distilled water for 1-3 minutes to realize one-time circulating self-assembly; and performing self-assembly cycle operation for 10-12 times to deposit and form the anti-corrosion protective film on the metal surface.
6. The method for preparing a self-assembled hole sealing protective film according to claim 1 or 2, characterized in that: the anodic oxidation treatment is to carry out anodic oxidation on the pretreated and cleaned substrate in oxalic acid water solution, wherein the anodic oxidation voltage is controlled to be 50-55V, and the oxidation current density is 1.5-2A/dm2Oxidizing for 60-65min in ice-water bath; then washing with deionized water and drying with cold air to obtain an anodic oxide film; and (5) standby.
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| CN201910948706.3A Pending CN110643999A (en) | 2019-09-03 | 2019-10-08 | Preparation method of self-assembled hole sealing protective film |
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Cited By (2)
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| CN111842070A (en) * | 2020-07-01 | 2020-10-30 | 安徽新大陆特种涂料有限责任公司 | Construction method of self-assembled environment-friendly long-acting easy-to-clean anticorrosive coating |
| CN113279035A (en) * | 2021-05-15 | 2021-08-20 | 江门市优博科技有限公司 | Novel sealing agent for aluminum and aluminum alloy anodic oxide film and preparation method thereof |
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| CN108441923A (en) * | 2018-03-23 | 2018-08-24 | 长沙小新新能源科技有限公司 | A kind of hole-sealing technology of magnesium alloy |
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| CN111842070A (en) * | 2020-07-01 | 2020-10-30 | 安徽新大陆特种涂料有限责任公司 | Construction method of self-assembled environment-friendly long-acting easy-to-clean anticorrosive coating |
| CN111842070B (en) * | 2020-07-01 | 2022-10-11 | 安徽新大陆特种涂料有限责任公司 | Construction method of self-assembled environment-friendly long-acting easy-to-clean anticorrosive coating |
| CN113279035A (en) * | 2021-05-15 | 2021-08-20 | 江门市优博科技有限公司 | Novel sealing agent for aluminum and aluminum alloy anodic oxide film and preparation method thereof |
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