CN111451107A - Preparation method of high-adhesion and high-corrosion-resistance fluorinated graphene coating - Google Patents
Preparation method of high-adhesion and high-corrosion-resistance fluorinated graphene coating Download PDFInfo
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- CN111451107A CN111451107A CN202010270030.XA CN202010270030A CN111451107A CN 111451107 A CN111451107 A CN 111451107A CN 202010270030 A CN202010270030 A CN 202010270030A CN 111451107 A CN111451107 A CN 111451107A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/18—Processes for applying liquids or other fluent materials performed by dipping
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/002—Pretreatement
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
- B05D3/0254—After-treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
Abstract
The invention discloses a preparation method of a high-adhesion and high-corrosion-resistance fluorinated graphene coating, which comprises the following steps of: uniformly mixing a silane coupling agent, alcohol, a corrosion inhibitor, butyl titanate and deionized water to form a mixed solution, then adjusting the pH value of the mixed solution to 3-5, uniformly mixing by adopting ultrasonic oscillation, and hydrolyzing at 25-50 ℃ for 12-72 h to obtain a silane hydrolysis solution; mixing epoxy resin, fluorinated graphene and a diluent, ball-milling and stirring for 0.5-10 h, then adding a curing agent, and uniformly mixing to obtain fluorinated graphene modified epoxy resin; placing the pretreated metal substrate in a silane hydrolysis solution for soaking for 30-120 s, and then drying and curing; and (3) coating fluorinated graphene modified epoxy resin with the thickness of 30-200 mu m on the surface of the metal matrix subjected to silanization treatment, and then drying and curing to obtain the high-adhesion and high-corrosion-resistance fluorinated graphene coating. The fluorinated graphene coating obtained by the method has high corrosion resistance, improves the bonding strength of the coating and a metal matrix, and can protect the metal matrix for a long time.
Description
Technical Field
The invention belongs to the technical field of heavy-duty anticorrosive coatings in marine environments, and particularly relates to a preparation method of a high-adhesion and high-corrosion-resistance fluorinated graphene coating.
Background
Organic coatings have become one of the most important means of corrosion protection in the marine field. The fluorinated graphene is prepared by fluorinating graphene with carbon atom sp2Hybrid conversion to sp3Hybridized and part sp of graphene is reserved2And (5) structure. The fluorinated graphene not only retains the characteristic of a two-dimensional planar structure of graphene, but also has the characteristics of low surface energy, strong hydrophobicity and high stability due to fluorocarbon bonds, so that the fluorinated graphene has the structural and performance characteristics of two materials, namely graphene and teflon. Therefore, compared with graphene, the fluorinated graphene has wider application prospects in the fields of corrosion resistance, wear resistance, super hydrophobicity and oleophobicity and the like. However, the introduction of the fluorinated graphene tends to reduce the surface energy of the organic coating, so that the bonding strength between the coating and the metal substrate is reduced, and the long-term protection of the coating on the metal substrate is seriously affected.
Therefore, how to improve the adhesion of the coating added with the fluorinated graphene, improve the bonding strength between the coating and the metal substrate, and realize the long-term protection of the coating on the metal substrate is a technical problem to be solved by those skilled in the art.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a preparation method of a high-adhesion and high-corrosion-resistance fluorinated graphene coating, and the coating obtained by the method has high corrosion resistance, improves the bonding strength of the coating and a metal matrix, and is beneficial to long-term protection of the coating on the metal matrix.
A preparation method of a high-adhesion and high-corrosion-resistance fluorinated graphene coating comprises the following steps:
(1) preparing a silane hydrolysis solution, namely uniformly mixing a silane coupling agent, alcohol, a corrosion inhibitor, butyl titanate and deionized water to form a mixed solution, wherein the mixed solution contains 100-200 m L/L of the silane coupling agent, 180-300 m L/L of the alcohol, 0.5-2 g/L of the corrosion inhibitor, 0.1-2 g/L of butyl titanate and the balance of deionized water;
(2) preparing fluorinated graphene modified epoxy resin: mixing the components in a mass ratio of 10: 0.1-0.8: 1-10 of epoxy resin, fluorinated graphene and a diluent are mixed, ball-milled and stirred for 0.5-10 hours, and then a curing agent is added and mixed uniformly to obtain fluorinated graphene modified epoxy resin for later use;
(3) silanization treatment: placing the pretreated metal matrix into the silane hydrolysis solution obtained in the step (1) to soak for 30-120 s, and then drying and curing to obtain a silanized metal matrix;
(4) coating: and (4) coating fluorinated graphene modified epoxy resin with the thickness of 30-200 mu m on the surface of the silanized metal matrix obtained in the step (3), and then drying and curing to obtain the high-adhesion and high-corrosion-resistance fluorinated graphene coating on the surface of the metal matrix.
Further, the silane coupling agent is one or two of tetramethoxysilane, tetraethoxysilane, gamma-epoxypropyl trimethoxy silane, gamma-aminopropyl trimethoxy silane, gamma-mercaptopropyl trimethoxy silane and bis-1, 2 (triethoxysilyl) ethane.
Further, the corrosion inhibitor is one or more of cerous nitrate, lanthanum chloride, 8-hydroxyquinoline, sodium dodecyl sulfate, benzotriazole and urotropine.
Further, in the step (1), phytic acid is adopted to adjust the pH value.
Further, in the step (2), the fluorination degree of the fluorinated graphene is 10-65%, the size is 0.5-5 μm, and the thickness is 2-10 nm.
Further, the diluent is a mixture of xylene and n-butanol, and the mass ratio of the xylene to the n-butanol is 2: 1.
Further, the curing agent is a polyamide curing agent.
Further, in the step (3), the metal matrix is subjected to silanization treatment after being pretreated by grinding, polishing, alkali washing, water washing and the like.
Further, in the step (3), the drying and curing temperature is 30-120 ℃, and the curing time is 60-300 min.
Further, in the step (4), the drying and curing temperature is 25-120 ℃, and the curing time is 12-72 hours.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the method, the metal matrix is silanized, then the surface of the silanized metal matrix is coated with the coating, and the silane film formed through silanization serves as a bridge between the metal matrix and the coating, so that the problem of the bonding force between the fluorinated graphene coating and the metal matrix is solved.
2. The silane hydrolysis solution contains the corrosion inhibitor, and the addition of the corrosion inhibitor is beneficial to the hydrolysis of the silane coupling agent, inhibits the adsorption among silicon hydroxyl groups, deepens the hydrolysis degree of the silane coupling agent and improves the content of the silicon hydroxyl groups in the solution. The increase of the content of the silicon hydroxyl is beneficial to improving the reaction degree of the surface of the metal matrix and the silane film and enhancing the bonding strength of the silane film and the metal matrix, and also increases the chelating amount of unreacted silicon hydroxyl in the silane film and epoxy groups in the epoxy resin, enhances the bonding strength of the coating and the silane film and further enhances the bonding strength of the coating and the metal matrix; meanwhile, the corrosion inhibitor has a good corrosion inhibition effect on the metal matrix.
In addition, the added butyl titanate can form particles which are included among silane molecules, centers are established among the silane molecules, and the arrangement of the silane molecules is improved, so that the density of a silane film is improved, the path of corrosive ions reaching a metal matrix is prolonged, and the corrosion resistance of the metal matrix is improved.
Therefore, the bonding strength of the silane film, the metal matrix and the fluorinated graphene modified epoxy resin can be further improved through the synergistic effect of the corrosion inhibitor and the butyl titanate, and the long-term corrosion resistance of the coating can be further improved.
Drawings
Figure 1-macroscopic picture of the drawing experiment of the fluorinated graphene coating of example 1 and comparative example 1.
Figure 2-low frequency impedance modulus curves for the fluorinated graphene coatings of example 1 and comparative example 1.
Figure 3-neutral salt spray experimental pictures of fluorinated graphene coatings of example 1 and comparative example 1.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
(1) Preparing a silane hydrolysis solution, namely uniformly mixing a silane coupling agent, alcohol, a corrosion inhibitor, butyl titanate and deionized water to form a mixed solution, wherein the mixed solution contains 100-200 m L/L of the silane coupling agent, 180-300 m L/L of the alcohol, 0.5-2 g/L of the corrosion inhibitor, 0.1-2 g/L of butyl titanate and the balance of deionized water;
the alcohol is methanol and/or ethanol, and is determined according to the selected silane coupling agent, and the silane coupling agent containing methoxyl is selected from methanol; selecting an ethoxy-containing silane coupling agent and ethanol; selecting two silane coupling agents containing methoxy and ethoxy, determining the ratio of methanol to ethanol according to the ratio of the two silane coupling agents, and when the volume ratio of the two silane coupling agents containing methoxy and ethoxy is 1:1, the volume ratio of methanol to ethanol is also 1: 1; when the volume ratio of the methoxy silane coupling agent to the ethoxy silane coupling agent is 2:1, the volume ratio of the methanol to the ethanol is also 2:1, and the like, so as to ensure that the silane coupling agent is fully dissolved.
(2) Preparing fluorinated graphene modified epoxy resin: mixing the components in a mass ratio of 10: 0.1-0.8: 1-10 of epoxy resin, fluorinated graphene and a diluent are mixed, ball-milled and stirred for 0.5-10 hours, and then a curing agent is added and mixed uniformly to obtain fluorinated graphene modified epoxy resin for later use;
(3) silanization treatment: placing the pretreated metal matrix into the silane hydrolysis solution obtained in the step (1) to soak for 30-120 s, and then drying and curing to obtain a silanized metal matrix;
(4) coating: and (4) coating fluorinated graphene modified epoxy resin with the thickness of 30-200 mu m on the surface of the silanized metal matrix obtained in the step (3), and then drying and curing to obtain the high-adhesion and high-corrosion-resistance fluorinated graphene coating on the surface of the metal matrix.
Thus, the silane hydrolysis solution contains the corrosion inhibitor, and the addition of the corrosion inhibitor is beneficial to the hydrolysis of the silane coupling agent, inhibits the adsorption among silicon hydroxyl groups, deepens the hydrolysis degree of the silane coupling agent and improves the content of the silicon hydroxyl groups in the solution; the increase of the content of the silicon hydroxyl is beneficial to improving the reaction degree of the surface of the metal matrix and the silane film and enhancing the bonding strength of the silane film and the metal matrix, the silane film prepared on the surface of the metal matrix contains unpolymerized silicon hydroxyl, and the silicon hydroxyl on the surface of the silane film and the epoxy group are subjected to ring-opening reaction to generate
The epoxy resin coating is connected with the surface of the silane film in a chemical bonding mode, so that the bonding strength between the silane film and the coating is improved, and the bonding strength between the coating and the metal matrix is further enhanced.
In addition, the added butyl titanate can form particles which are included among silane molecules, centers are established among the silane molecules, and the arrangement of the silane molecules is improved, so that the density of a silane film is improved, the path of corrosive ions reaching a metal matrix is prolonged, and the corrosion resistance of the metal matrix is improved.
Therefore, the bonding strength of the silane film, the metal matrix and the fluorinated graphene modified epoxy resin can be further improved through the synergistic effect of the corrosion inhibitor and the butyl titanate, and the long-term corrosion resistance of the coating can be further improved.
In specific implementation, the silane coupling agent is one or two of tetramethoxysilane, tetraethoxysilane, gamma-epoxypropyl trimethoxy silane, gamma-aminopropyl trimethoxy silane, gamma-mercaptopropyl trimethoxy silane and bis-1, 2 (triethoxysilyl) ethane.
In specific implementation, the corrosion inhibitor is one or more of cerium nitrate, lanthanum chloride, 8-hydroxyquinoline, sodium dodecyl sulfate, benzotriazole and urotropin.
In the specific implementation, in the step (1), phytic acid is adopted to adjust the pH value.
The phytic acid is organic acid, not only can adjust the pH of the mixed solution to be acidic to promote the hydrolysis of the silane coupling agent, but also has a corrosion inhibition effect on the metal matrix.
In the step (2), the degree of fluorination of the fluorinated graphene is 10-65%, the size is 0.5-5 μm, and the thickness is 2-10 nm.
The fluorination degree of the fluorinated graphene is 10-65%, so that the obtained coating is ensured to have strong hydrophobicity and high stability. The thickness of the fluorinated graphene is limited to 2-10 nm so as to ensure the characteristics of the fluorinated graphene lamellar structure, so that the lamellar structure forms a labyrinth effect in the service process of the coating, and the diffusion path of a corrosion medium in the coating is increased. Meanwhile, the size of the fluorinated graphene is 0.5-5 μm, the size is too small, the advantages of the lamellar structure of the fluorinated graphene are difficult to highlight, and the arrangement form of the fluorinated graphene in the coating is influenced by the too large size, so that the corrosion resistance of the coating is influenced finally.
In specific implementation, the diluent is a mixture of xylene and n-butanol, and the mass ratio of the xylene to the n-butanol is 2: 1.
In a specific implementation, the curing agent is a polyamide curing agent.
The polyamide curing agent used here is a polyamide 650 curing agent, a polyamide 651 curing agent, or the like, and the amount of the curing agent = (relative molecular mass of the curing agent/number of active hydrogen atoms in an amine molecule) is the epoxy value of × epoxy resin, for example, 100g of epoxy resin.
In the step (3), the metal matrix is subjected to silanization treatment after pretreatment such as grinding, polishing, alkali washing, water washing and the like.
Here, the metal substrate is mainly an aluminum alloy, a magnesium alloy, a titanium alloy, and steel.
In the specific implementation, in the step (3), the drying and curing temperature is 30-120 ℃, and the curing time is 60-300 min.
In the specific implementation, in the step (4), the drying and curing temperature is 25-120 ℃, and the curing time is 12-72 hours.
Example 1
(1) Preparing a silane hydrolysis solution, namely firstly adding 140m L deionized water into a beaker, then adding 40m L methanol, uniformly stirring the mixture on a magnetic stirrer, then adding 20m L gamma-epoxy propyl trimethoxy silane, 0.2g cerium nitrate and 0.2g butyl titanate, uniformly stirring the mixture, then dropwise adding phytic acid to adjust the pH value of the solution to 3.5, fully and uniformly mixing the solution by ultrasonic oscillation for 5min, then placing the mixture in a constant-temperature water bath kettle at 35 ℃, and hydrolyzing the mixture for 48h to obtain the silane hydrolysis solution;
(2) preparing fluorinated graphene modified epoxy resin: epoxy resin, fluorinated graphene and diluent according to a weight ratio of 10: 0.3: 8, wherein the diluent is dimethylbenzene and n-butanol, and the mass ratio of the diluent to the diluent is 2:1, in a mass ratio of 1. Ball-milling and stirring for 0.5h, adding 80g of polyamide 650 curing agent per 100g of epoxy resin E-44, stirring for 10min, and vacuumizing to obtain fluorinated graphene modified epoxy resin;
(3) silanization treatment: placing the aluminum alloy subjected to polishing, alkali washing and water washing in the silane hydrolysis solution obtained in the step (1), soaking for 5min, and then placing in a drying oven at 60 ℃ for curing for 30min to obtain a silanized aluminum alloy;
(4) coating: and (3) coating the surface of the aluminum alloy subjected to silanization treatment in the step (3) with fluorinated graphene modified epoxy resin, controlling the thickness of the coating to be 70 +/-10 microns, and curing at 25-30 ℃ for 72 hours to obtain the fluorinated graphene coating.
Comparative example 1
Preparing the fluorinated graphene modified epoxy resin according to the step (2) of the embodiment 1, coating the fluorinated graphene modified epoxy resin on the surface of the aluminum alloy which is polished, washed with alkali and washed with water, controlling the thickness of the coating to be 70 +/-10 mu m, and curing for 72h at 25-30 ℃ to obtain the fluorinated graphene coating.
1. Drawing test of adhesion
After the fluorinated graphene coatings of examples 1 and 2 were cured, an adhesive was applied to the surface of the coating and the surface of the aluminum alloy cone, the cone was adhered to the surface of the coating, and cured at room temperature for 24 hours. After the adhesive is completely cured, a drawing tester is used for testing, and the obtained adhesion force drawing experiment result is shown in figure 1, the experiment result of comparative example 1 is shown in figure (a) of figure 1, and the adhesion force of the fluorinated graphene coating is 0.85 MPa; the experimental result of example 1 is shown in fig. 1 (b), and the adhesion of the fluorinated graphene coating is 10.12 MPa; therefore, the bonding strength of the fluorinated graphene modified coating and the matrix is remarkably improved through silanization treatment, and the adhesive force is improved from 0.85MPa to 10.12 MPa.
2. Electrochemical impedance spectroscopy experiment
Electrochemical impedance spectrum tests are carried out on the fluorinated graphene coatings obtained in example 1 and comparative example 1 in a 3.5wt% NaCl solution, and after 3000 hours of tests, low-frequency impedance modulus curves are shown in FIG. 2, and the long-term low-frequency impedance modulus of example 1 and comparative example 1 is always maintained at 1010~1011Ω·cm2The result shows that the fluorinated graphene coating has good corrosion resistance.
3. Neutral salt spray test
The aluminum alloys with the fluorinated graphene modified coatings on the surfaces of the aluminum alloys of example 1 and comparative example 1 were placed in a neutral salt spray test box, and tested by using 5% sodium chloride, wherein the test temperature was 35 ℃, and the aluminum alloys were taken out at intervals and photographed. The results of the neutral salt spray test are shown in fig. 3, the salt spray resistance of example 1 (fig. 3, panel (b)) reaches more than 1900h, and the salt spray resistance of comparative example 1 (fig. 3, panel (a)) is less than 360h, which shows that the silanization treatment not only improves the bonding strength between the coating and the aluminum alloy, but also significantly improves the long-term salt spray resistance of the coating, and can better meet the application requirements of marine environment.
Example 2
(1) Preparing a silane prehydrolysis solution, namely firstly adding 120m L deionized water into a beaker, then adding 50m L methanol, uniformly stirring the mixture on a magnetic stirrer, then adding 10ml of gamma-epoxypropyl trimethoxy silane, 20ml of gamma-aminopropyl trimethoxy silane, 0.4g of benzotriazole and 0.1g of butyl titanate, uniformly stirring the mixture, then dropwise adding phytic acid to adjust the pH value of the solution to 4, fully and uniformly mixing the mixture by ultrasonic oscillation for 5min, then placing the mixture in a 35 ℃ constant-temperature water bath kettle, and hydrolyzing the mixture for 20h to obtain a silane hydrolysis solution;
(2) preparing fluorinated graphene modified epoxy resin: epoxy resin, fluorinated graphene and diluent according to a weight ratio of 10: 0.8: 10, wherein the diluent is dimethylbenzene and n-butanol, and the mass ratio of the diluent to the diluent is 2:1, in a mass ratio of 1. Ball-milling and stirring for 0.5h, adding 40g of polyamide 651 curing agent per 100g of epoxy resin E-44, stirring for 10min, and vacuumizing to obtain fluorinated graphene modified epoxy resin;
(3) silanization treatment: placing the carbon steel subjected to polishing, alkali washing and water washing in the silane hydrolysis solution obtained in the step (1), soaking for 1min, and then placing in a 60 ℃ drying oven for curing for 30min to obtain silanized carbon steel;
(4) coating: and (3) coating the surface of the silanized carbon steel obtained in the step (3) with fluorinated graphene modified epoxy resin, controlling the thickness of the coating to be 70 +/-10 microns, and curing at 25-30 ℃ for 72 hours to obtain the fluorinated graphene coating.
The bonding strength of the fluorinated graphene coating and the carbon steel is 11.23 Mpa; the salt spray resistance of the paint can reach more than 2000 h. The results show that the proper silanization treatment not only improves the bonding strength of the coating and the carbon steel, but also obviously improves the long-term salt mist resistance of the coating, and can better meet the application requirements of marine environment.
Example 3
(1) Preparing a silane prehydrolysis solution, namely firstly adding 100m L deionized water into a beaker, then adding 30m L methanol and 30m L ethanol, uniformly stirring the mixture on a magnetic stirrer, then adding 20ml of gamma-epoxypropyl trimethoxy silane, 20ml of bis-1, 2 (triethoxysilyl) ethane, 0.2g of sodium dodecyl sulfate and 0.1g of butyl titanate, uniformly stirring the mixture, then dropwise adding phytic acid to adjust the pH value of the solution to 4.5, fully and uniformly mixing the solution by ultrasonic oscillation for 5min, then placing the solution in a 35 ℃ constant-temperature water bath kettle, and hydrolyzing the solution for 12h to obtain a silane hydrolysis solution;
(2) preparing fluorinated graphene modified epoxy resin: epoxy resin, fluorinated graphene and diluent according to a weight ratio of 10: 0.1: 5, wherein the diluent is dimethylbenzene and n-butanol, and the mass ratio of the diluent to the diluent is 2:1, in a mass ratio of 1. Ball-milling and stirring for 0.5h, adding 46.4g of polyamide 651 curing agent per 100g of epoxy resin E-51, stirring for 10min, and vacuumizing to obtain fluorinated graphene modified epoxy resin;
(3) silanization treatment: placing the titanium alloy subjected to polishing, alkali washing and water washing in the silane hydrolysis solution obtained in the step (1), soaking for 1min, and then placing in a 60 ℃ drying oven for curing for 30min to obtain a titanium alloy subjected to silanization treatment;
(4) coating: and (3) coating the fluorinated graphene modified epoxy resin on the surface of the titanium alloy subjected to silanization treatment in the step (3), controlling the thickness of the coating to be 70 +/-10 microns, and curing for 72 hours at 25-30 ℃ to obtain the fluorinated graphene coating.
The bonding strength of the fluorinated graphene coating and the titanium alloy is 10.5 Mpa; the salt spray resistance of the paint can reach more than 2500 h. The results show that the proper silanization treatment not only improves the bonding strength of the coating and the titanium alloy, but also obviously improves the long-term salt spray resistance of the coating, and can better meet the application requirements of marine environment.
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 high-adhesion and high-corrosion-resistance fluorinated graphene coating is characterized by comprising the following steps:
(1) preparing a silane hydrolysis solution, namely uniformly mixing a silane coupling agent, alcohol, a corrosion inhibitor, butyl titanate and deionized water to form a mixed solution, wherein the mixed solution contains 100-200 m L/L of the silane coupling agent, 180-300 m L/L of the alcohol, 0.5-2 g/L of the corrosion inhibitor, 0.1-2 g/L of butyl titanate and the balance of deionized water;
(2) preparing fluorinated graphene modified epoxy resin: mixing the components in a mass ratio of 10: 0.1-0.8: 1-10 of epoxy resin, fluorinated graphene and a diluent are mixed, ball-milled and stirred for 0.5-10 hours, and then a curing agent is added and mixed uniformly to obtain fluorinated graphene modified epoxy resin for later use;
(3) silanization treatment: placing the pretreated metal matrix into the silane hydrolysis solution obtained in the step (1) to soak for 30-120 s, and then drying and curing to obtain a silanized metal matrix;
(4) coating: and (4) coating fluorinated graphene modified epoxy resin with the thickness of 30-200 mu m on the surface of the silanized metal matrix obtained in the step (3), and then drying and curing to obtain the high-adhesion and high-corrosion-resistance fluorinated graphene coating on the surface of the metal matrix.
2. The method for preparing a high-adhesion high-corrosion-resistance fluorinated graphene coating according to claim 1, wherein the silane coupling agent is one or two of tetramethoxysilane, tetraethoxysilane, gamma-epoxypropyltrimethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-mercaptopropyltrimethoxysilane and bis-1, 2 (triethoxysilyl) ethane.
3. The method for preparing the high-adhesion high-corrosion-resistance fluorinated graphene coating according to claim 1, wherein the corrosion inhibitor is one or more of cerium nitrate, lanthanum chloride, 8-hydroxyquinoline, sodium dodecyl sulfate, benzotriazole and urotropin.
4. The method for preparing the high-adhesion and high-corrosion-resistance fluorinated graphene coating according to claim 1, wherein in the step (1), phytic acid is used for adjusting the pH value.
5. The method for preparing a high-adhesion and high-corrosion-resistance fluorinated graphene coating according to claim 1, wherein in the step (2), the degree of fluorination of the fluorinated graphene is 10-65%, the fluorinated graphene has a size of 0.5-5 μm and a thickness of 2-10 nm.
6. The method for preparing the high-adhesion high-corrosion-resistance fluorinated graphene coating according to claim 1, wherein the diluent is a mixture of xylene and n-butanol, and the mass ratio of the xylene to the n-butanol is 2: 1.
7. The method for preparing a high-adhesion and high-corrosion-resistance fluorinated graphene coating according to claim 1, wherein the curing agent is a polyamide curing agent.
8. The method for preparing the fluorinated graphene coating with high adhesion and high corrosion resistance according to claim 1, wherein in the step (3), the metal substrate is subjected to silanization after being pretreated by grinding, polishing, alkali washing, water washing and the like.
9. The method for preparing a high-adhesion and high-corrosion-resistance fluorinated graphene coating according to claim 1, wherein in the step (3), the drying and curing temperature is 30-120 ℃, and the curing time is 60-300 min.
10. The preparation method of the high-adhesion and high-corrosion-resistance fluorinated graphene coating according to claim 1, wherein in the step (4), the drying and curing temperature is 25-120 ℃, and the curing time is 12-72 hours.
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| CN112442187A (en) * | 2020-11-26 | 2021-03-05 | 山东重山光电材料股份有限公司 | FG @ MOF composite material, coating containing composite material, and preparation method and application of composite material |
| CN112828291A (en) * | 2020-12-31 | 2021-05-25 | 宁波通导电子有限公司 | Manufacturing method of high-temperature operation robot |
| CN114773885A (en) * | 2022-03-29 | 2022-07-22 | 武汉苏泊尔炊具有限公司 | Modified sealing agent, anti-corrosion coating and method for preparing anti-corrosion coating |
| CN114855237A (en) * | 2022-06-07 | 2022-08-05 | 四川轻化工大学 | Preparation method of ZIF-8-doped high-corrosion-resistance micro-arc oxidation composite coating |
| CN115232532A (en) * | 2022-08-10 | 2022-10-25 | 四川轻化工大学 | Preparation method of fluorinated graphene modified epoxy resin coating |
| CN115558422A (en) * | 2022-09-30 | 2023-01-03 | 四川轻化工大学 | Hole sealing solution of self-repairing high-corrosion-resistance hole sealing material and preparation method and application thereof |
| CN116554761A (en) * | 2023-06-20 | 2023-08-08 | 湖北卓熙氟化股份有限公司 | Wear-resistant durable super-hydrophobic coating for windscreen wiper and preparation method thereof |
| CN117089279A (en) * | 2023-10-19 | 2023-11-21 | 广州中海涂装科技有限公司 | Hou Naiyong-resistant silicon-fluorine-acrylic polyurethane finish paint and preparation method thereof |
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| CN114773885A (en) * | 2022-03-29 | 2022-07-22 | 武汉苏泊尔炊具有限公司 | Modified sealing agent, anti-corrosion coating and method for preparing anti-corrosion coating |
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| CN115232532A (en) * | 2022-08-10 | 2022-10-25 | 四川轻化工大学 | Preparation method of fluorinated graphene modified epoxy resin coating |
| CN115558422A (en) * | 2022-09-30 | 2023-01-03 | 四川轻化工大学 | Hole sealing solution of self-repairing high-corrosion-resistance hole sealing material and preparation method and application thereof |
| CN116554761A (en) * | 2023-06-20 | 2023-08-08 | 湖北卓熙氟化股份有限公司 | Wear-resistant durable super-hydrophobic coating for windscreen wiper and preparation method thereof |
| CN116554761B (en) * | 2023-06-20 | 2024-04-19 | 湖北卓熙氟化股份有限公司 | Wear-resistant durable super-hydrophobic coating for windscreen wiper and preparation method thereof |
| CN117089279A (en) * | 2023-10-19 | 2023-11-21 | 广州中海涂装科技有限公司 | Hou Naiyong-resistant silicon-fluorine-acrylic polyurethane finish paint and preparation method thereof |
| CN117089279B (en) * | 2023-10-19 | 2023-12-19 | 广州中海涂装科技有限公司 | Hou Naiyong-resistant silicon-fluorine-acrylic polyurethane finish paint and preparation method thereof |
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