WO2021243771A1

WO2021243771A1 - Anti-corrosion system, preparation method therefor, and anti-corrosion coating

Info

Publication number: WO2021243771A1
Application number: PCT/CN2020/098227
Authority: WO
Inventors: 王彬; 黄俊贤
Original assignee: 深圳先进技术研究院
Priority date: 2020-06-03
Filing date: 2020-06-24
Publication date: 2021-12-09
Also published as: CN111675943A

Abstract

Disclosed are an anti-corrosion system, a preparation method therefor, and an anti-corrosion coating, the anti-corrosion system comprising a first functional layer wrapping a protected matrix, wherein the first functional layer contains a fluorine-containing piezoelectric material, and the first functional layer may generate dynamic response current under a stress condition so as to prevent corrosive ions from being transmitted to the protected matrix. The transmission process of corrosive ions in the anti-corrosion system may be actively regulated and controlled by the anti-corrosion system provided by the present invention, and the permeation effect of the corrosive ions in the anti-corrosion system is markedly relieved. Further provided by the present invention is the preparation method for the anti-corrosion system and an application of the anti-corrosion system in a corrosive environment. Meanwhile, also provided by the present invention is the anti-corrosion coating. After the coating is dried to form a coating layer, dynamic response current may be generated under the stress condition so as to prevent corrosive ions from being transmitted to the protected matrix, and the permeation effect of the corrosive ions in the coating layer is markedly relieved.

Description

Anti-corrosion system, preparation method thereof, and anti-corrosion paint

Technical field

The invention relates to the technical field of anti-corrosion materials, in particular to an anti-corrosion system, a preparation method thereof, and an anti-corrosion paint.

Background technique

Metal engineering equipment such as ships and oil production platforms that have been used in the marine environment for a long time will face severe corrosion problems. This is because there are a lot of corrosive substances in the marine environment. Metal corrosion is a worldwide problem. According to relevant survey reports, the world’s annual average direct and indirect losses caused by corrosion can reach billions of dollars, accounting for 3.4% of the global GDP, and ocean corrosion losses account for about the total. One-third of the loss. In recent years, my country’s annual losses due to ocean corrosion have even exceeded the total losses of natural disasters that year. Therefore, the corrosion protection of metals has become an important issue that needs to be solved urgently, especially the research and development of related technologies for marine corrosion protection.

In the engineering field of corrosion protection, commonly used anti-corrosion technologies include: electrochemical cathodic protection, electrochemical anodic protection, corrosion inhibitor protection, development of new corrosion-resistant alloy materials, metal surface protection layers, etc.

(1) The electrochemical cathodic protection method also includes the sacrificial anode cathodic protection method and the forced current cathodic protection method. The basic principle is to make the protected metal reach the protective potential through cathodic polarization, so that the rate of the electrochemical corrosion process is reduced or completely stopped. . This method tends to make the potential of the metal to be protected too negative, resulting in waste of energy and increasing costs. In addition, due to the hydrogen precipitation on the surface, it may cause the danger of hydrogen embrittlement and overprotection.

(2) The electrochemical anode protection method refers to a protection method in which metal is passivated in the corrosive medium under the action of an external anode current, thereby significantly reducing the corrosion rate. This method is usually used in the corrosion protection of strong oxidizing media such as sulfuric acid and organic sulfonic acid. For systems that cannot be passivated or ^{media containing Cl-} ions, anode protection cannot be used, and the scope of application is limited.

(3) The corrosion inhibitor protection method introduces special chemical substances to reduce the corrosion rate of metals. The composition, mechanism and application of corrosion inhibitors are very extensive. It should be noted that many corrosion inhibitors with better performance have been shown to have non-negligible pollution effects on the environment and toxic effects on organisms. For example, the used corrosion inhibitors such as chromium have obvious effects, but they are often toxic to the ecological environment. Some have been banned by developed countries. The choice between slow-release performance and environmental load has become a major issue restricting the practical application of corrosion inhibitors.

(4) The key to the development of new corrosion-resistant alloy materials is to grasp the corrosion resistance mechanism of the material, the corrosion resistance of each element, and the composition and process improvement of alloy materials. However, the laws of metal corrosion are particularly complex. The laws of corrosion are different under different external environments such as different temperatures, humidity, and different corrosive medium concentrations. Therefore, to make breakthroughs in the development of new alloys, it still requires a lot of manpower and Time for basic exploration and research.

(5) The metal surface protective layer includes a metal protective layer and a non-metal coating. Its fundamental purpose is to introduce a physical barrier between the surface of the metal substrate and the corrosive medium to prevent or delay corrosive ions from reaching the coating through diffusion or penetration. Layer-metal interface, causing metal corrosion. Among them, the metal protective layer is generally one or more inert metals are plated on the surface of the protected metal through electroplating, hot-dip plating, infiltration plating, electroless plating, etc., to form a dense metal protective layer; rather than the metal protective layer range It is more extensive, including organic coatings, inorganic coatings and composite coatings. Among them, organic anti-corrosion coatings are widely used because of their simple operation, economical and practical, and excellent anti-corrosion performance.

The above-mentioned existing anti-corrosion technologies have their own advantages and disadvantages. Among them, the existing anti-corrosion coating technology can only function as a physical barrier and can only passively block corrosive substances. However, only relying on its own barrier to serve in the complex seawater environment cannot form a long-term effective barrier to various corrosive substances.

Summary of the invention

In order to solve the problem that the existing anti-corrosion coating can only passively block corrosive substances, the present invention provides a new type of anti-corrosion system with the function of actively regulating the transmission of corrosive ions, and further provides the anti-corrosion system The preparation method.

In order to achieve the above-mentioned object of the invention, the present invention provides an anti-corrosion system, comprising a first functional layer coated on a protected substrate, the first functional layer contains a fluorine-containing piezoelectric material, and the first functional layer Under a force condition, a dynamic response current can be generated to hinder the transmission of corrosive ions to the protected substrate.

Further, the material used to form the first functional layer includes a fluorine-containing piezoelectric material, a nucleating agent, and a solvent.

Preferably, the mass ratio of the fluorine-containing piezoelectric material to the nucleating agent is 10:1 to 200:1.

Preferably, the fluorine-containing piezoelectric material is a fluorine-containing piezoelectric resin.

Preferably, the fluorine-containing piezoelectric resin is selected from polyvinylidene fluoride, vinylidene fluoride-trifluoroethylene copolymer, vinylidene fluoride-chlorotrifluoroethylene copolymer, vinylidene fluoride-hexafluoropropylene copolymer and At least one of vinylidene fluoride-trifluoroethylene-chlorofluoroethylene terpolymer; the nucleating agent is selected from carbon nanotubes, graphene oxide, silica nanoparticles, barium titanate nanoparticles, calcium carbonate At least one of nanoparticles and mica nanoparticles.

Further, the anti-corrosion system further includes at least one second functional layer formed on the first functional layer, and the second functional layer is an anti-corrosion coating.

Preferably, the material used to form the second functional layer includes epoxy resin, auxiliary agent and curing agent.

Preferably, the auxiliary agent is a defoamer and/or a leveling agent.

Preferably, the ratio of the thickness of the first functional layer to the second functional layer is 1:1 to 1:5.

The present invention also provides a method for preparing the above-mentioned anti-corrosion system, including:

Preparing the material used to form the first functional layer according to a selected ratio to form a first precursor solution;

The first precursor solution is coated on the protected substrate, and the first functional layer is formed after drying to obtain an anti-corrosion system including the first functional layer.

Preferably, the preparation method further includes: preparing the material for forming the second functional layer according to a selected ratio to form a second precursor solution;

The second precursor solution is coated on the first functional layer, and after curing, the second functional layer is formed on the first functional layer to obtain the first functional layer and the first functional layer. Anti-corrosion system for the second functional layer.

Based on the above-mentioned anti-corrosion system, the present invention further provides an application of the anti-corrosion system, which is applied to protect metal substrates from corrosion in a corrosive environment.

Further, the corrosive environment is any one of an acidic corrosive environment, an alkaline corrosive environment, a salty corrosive environment, and an aqueous corrosive environment.

Further, in a marine environment, the pressure effect includes the pressure effect caused by the waves hitting the anti-corrosion system, and the pressure effect caused by the tidal effect on the anti-corrosion system.

The present invention also provides an anti-corrosion coating, which contains a fluorine-containing piezoelectric material, a nucleating agent and a solvent.

Further, in the anti-corrosion coating, the mass ratio of the fluorine-containing piezoelectric material to the nucleating agent is 10:1 to 200:1.

Further, the fluorine-containing piezoelectric material is a fluorine-containing piezoelectric resin.

Further, the fluorine-containing piezoelectric resin is selected from polyvinylidene fluoride, vinylidene fluoride-trifluoroethylene copolymer, vinylidene fluoride-chlorotrifluoroethylene copolymer, vinylidene fluoride-hexafluoropropylene copolymer and At least one of vinylidene fluoride-trifluoroethylene-chlorofluoroethylene terpolymer.

Further, the nucleating agent is selected from at least one of carbon nanotubes, graphene oxide, silica nanoparticles, barium titanate nanoparticles, calcium carbonate nanoparticles, and mica nanoparticles.

Further, the solvent is selected from dichloromethane, chloroform, n-hexane, butyrolactone, diethyl ether, ethyl acetate, tetrahydrofuran, dimethyl sulfoxide, N,N-dimethylformamide, N,N -At least one of dimethylacetamide, 1,3-dioxolane, toluene and xylene.

Compared with the prior art, the present invention has the following beneficial effects:

The anti-corrosion system provided by the present invention creatively proposes using piezoelectric fluorine-containing piezoelectric materials as the first functional layer to be applied to the anti-corrosion system. When the first functional layer is subjected to pressure, it can generate a dynamic response current and then Disrupt the transmission process of corrosive ions in the anti-corrosion system, and significantly slow down the penetration of corrosive ions in the anti-corrosion system. Therefore, the anti-corrosion system provided by the present invention can achieve the effect of actively regulating the transmission process of corrosive ions inside the anti-corrosion system.

The preparation method of the anti-corrosion system provided by the present invention has a simple preparation process and low cost. The prepared anti-corrosion system can control the transmission process of corrosive ions in the anti-corrosion system and significantly slow down the penetration of corrosive ions. Therefore, the anti-corrosion system prepared by the above preparation method can achieve the effect of actively controlling the transmission process of corrosive ions inside the coating system.

Description of the drawings

The characteristics and advantages of the embodiments of the present invention will become clearer through the following description in conjunction with the accompanying drawings. In the accompanying drawings:

Figure 1 is a 15-day potentiodynamic polarization curve spectra of four anti-corrosion systems in Example 1, Example 2, Comparative Example 1, and Comparative Example 2;

Figures 2-1 to 2-4 are respectively the Nyquist spectra of the 15-day simulation test of 4 anti-corrosion systems in Example 1, Example 2, Comparative Example 1, and Comparative Example 2;

Figures 3-1 to 3-4 are the electrochemical impedance spectra of the 15-day simulation test of four anti-corrosion systems in Example 1, Example 2, Comparative Example 1, and Comparative Example 2, respectively.

detailed description

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. However, the present invention can be implemented in many different forms, and the present invention should not be construed as being limited to the specific embodiments set forth herein. On the contrary, these embodiments are provided to explain the principle of the present invention and its practical application, so that other skilled in the art can understand various embodiments of the present invention and various modifications suitable for specific anticipated applications.

Based on the problem that the anti-corrosion coating in the prior art can only passively block corrosive substances, the inventor of the present invention provides a new type of anti-corrosion system with the function of actively regulating the transmission of corrosive ions, and further provides The preparation method of the anti-corrosion system.

1. The embodiment of the present invention provides an anti-corrosion system, comprising a first functional layer coated on a protected substrate, the first functional layer contains a fluorine-containing piezoelectric material, and the first functional layer is protected by Under the condition of force, a dynamic response current can be generated to hinder the transmission of corrosive ions to the protected substrate.

In some preferred embodiments, the mass ratio of the fluorine-containing piezoelectric material to the nucleating agent is 10:1 to 200:1.

The fluorine-containing piezoelectric material may be a fluorine-containing piezoelectric material, or a mixture of a fluorine-containing material and a piezoelectric material.

Among them, the fluorine-containing piezoelectric material can be a fluorine-containing piezoelectric resin material, such as: polyvinylidene fluoride, vinylidene fluoride-trifluoroethylene copolymer, vinylidene fluoride-chlorotrifluoroethylene copolymer, and vinylidene fluoride-trifluoroethylene copolymer. At least one of a vinyl fluoride-hexafluoropropylene copolymer and a vinylidene fluoride-trifluoroethylene-chlorofluoroethylene terpolymer.

The nucleating agent may be selected from at least one of carbon nanotubes, graphene oxide, silica nanoparticles, barium titanate nanoparticles, calcium carbonate nanoparticles, and mica nanoparticles.

The solvent is used to dissolve other materials forming the first functional layer, and is generally dried and removed during the preparation process. Solvents include, but are not limited to, dichloromethane, chloroform, n-hexane, butyrolactone, diethyl ether, ethyl acetate, tetrahydrofuran, dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethyl One or more of methyl acetamide, 1,3-dioxolane, toluene and xylene.

In some preferred embodiments, the first functional layer is a fluorine-containing piezoelectric resin coating. Fluorine-containing piezoelectric resin coatings include, but are not limited to, polyvinylidene fluoride coatings, vinylidene fluoride-trifluoroethylene copolymer coatings, vinylidene fluoride-chlorotrifluoroethylene copolymer coatings, vinylidene fluoride- Hexafluoropropylene copolymer coating and vinylidene fluoride-trifluoroethylene-chlorofluoroethylene terpolymer coating.

In some preferred embodiments, at least one second functional layer with anti-corrosion function is also provided on the first functional layer. The function of the second functional layer is to better block corrosive substances and avoid direct exposure of the first functional layer to the corrosive environment, thereby prolonging the service life of the first functional layer. There are many kinds of coating materials with anti-corrosion function, which is inconvenient List them here.

In some preferred embodiments, the material used to form the second functional layer includes epoxy resin, auxiliary agent and curing agent.

In some preferred embodiments, the material used to form the second functional layer further contains a defoaming agent and/or a leveling agent.

In some preferred embodiments, in order to further protect the first functional layer, the ratio of the thickness of the first functional layer to the second functional layer is set to 1:1 to 1:5.

In the anti-corrosion system provided by the embodiment of the present invention, a fluorine-containing piezoelectric material with anti-corrosion and piezoelectricity is used as the first functional layer in the anti-corrosion system. When the first functional layer is subjected to pressure, it can produce a dynamic response The current disturbs the transmission process of corrosive ions in the anti-corrosion system, and significantly slows down the penetration of corrosive ions in the anti-corrosion system. Therefore, the anti-corrosion system provided by the present invention can actively control the transmission process of corrosive ions inside the coating system.

A more specific anti-corrosion mechanism lies in the fact that there is a hydrogen bond between the fluorine atoms in the fluorine-containing piezoelectric material and the hydroxyl groups (FeOOH) present on the metal surface. The fluorine atoms are arranged tightly and orderly on the metal matrix-anticorrosion system interface through hydrogen bonding, and the fluorine atoms themselves are negatively charged and can repel anions, making the corrosive ions in seawater (mainly active anions, such as Cl) ^- ) It is not easy to reach the metal substrate-anti-corrosion system interface; with the response current generated by the fluorine-containing piezoelectric material, it can disrupt the transmission process of corrosive ions to achieve the purpose of preventing corrosive ions.

In the anti-corrosion system provided by other embodiments of the present invention, a piezoelectric material with anti-corrosion and piezoelectricity is used as the first functional layer in the anti-corrosion system, and the anti-corrosion piezoelectric coating is further added The second functional layer with anti-corrosion function. The second functional layer can help to better block corrosive substances, avoid direct exposure of the first functional layer to the corrosive environment, and thereby extend the service life of the first functional layer.

2. The embodiments of the present invention also provide the application of the above-mentioned anti-corrosion system: when the application environment of the anti-corrosion system is in the marine field, the protected substrate is a metal substrate, usually metal engineering equipment such as ships and oil production platforms. The area covered by the first functional layer is generally an area that may be contacted by corrosive substances in the application environment. The first functional layer can cover these areas fully or selectively. The specific coverage area needs to be based on actual needs and Selection is required, so it is inconvenient to limit this in the present invention.

The pressure effect in the marine environment includes, but is not limited to, the pressure effect caused by the waves hitting the anti-corrosion system, and the pressure effect caused by the tidal effect on the anti-corrosion system.

Among them, when the first functional layer is subjected to pressure, it can generate a dynamic response current to disturb the transmission process of corrosive ions inside the coating, and significantly slow down the penetration of corrosive ions in the anti-corrosion system. Therefore, the anti-corrosion system can actively control the transmission process of corrosive ions inside the anti-corrosion system.

3. The embodiment of the present invention also provides an anti-corrosion coating, which contains a fluorine-containing piezoelectric material, a nucleating agent and a solvent.

The solvent is used to dissolve other materials, and it is also convenient for the anti-corrosion paint to form a coating. In the actual use process, it is generally dried and removed or slowly volatilized in a natural state. Solvents include, but are not limited to, dichloromethane, chloroform, n-hexane, butyrolactone, diethyl ether, ethyl acetate, tetrahydrofuran, dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethyl One or more of methyl acetamide, 1,3-dioxolane, toluene and xylene.

The anti-corrosion coating provided by the embodiment of the present invention is the first functional layer in the aforementioned anti-corrosion system after being dried to form a coating.

4. The embodiment of the present invention also provides a method for preparing the above-mentioned anti-corrosion system, which includes preparing the material for forming the first functional layer according to a selected ratio to form a first precursor solution; The first precursor solution is coated on the protected substrate and dried to form the first functional layer to obtain an anti-corrosion system including the first functional layer.

In some preferred embodiments, the first functional layer is a coating. The steps of forming the coating generally include: preparing the coating material into a specific form, for example, dissolving the solid coating material in a solvent, dissolving and mixing the coating material to form a liquid coating material, and then using a coating process to form the coating.

The mixing operation involved in the embodiment of the present invention may be mechanical stirring or magnetic stirring, the temperature of the coating material during mixing is 20-90° C., and the mixing time is 0.5-10 h.

Commonly used coating processes include spray gun coating method, wire bar coating method, brush coating method, roll coating, etc., which are not particularly limited in the embodiments of the present invention.

In some preferred embodiments, the first functional layer is a fluorine-containing piezoelectric material coating.

In some preferred embodiments, the fluorine-containing piezoelectric material coating is a fluorine-containing piezoelectric resin coating. The fluorine-containing piezoelectric resin coating includes but is not limited to polyvinylidene fluoride coating, vinylidene fluoride-trifluoroethylene copolymer coating, vinylidene fluoride-chlorotrifluoroethylene copolymer coating, vinylidene fluoride Ethylene-hexafluoropropylene copolymer coating and vinylidene fluoride-trifluoroethylene-chlorofluoroethylene terpolymer coating.

Among them, the preparation method of the fluorine-containing piezoelectric resin coating specifically includes: dissolving the fluorine-containing piezoelectric resin in a solvent and mixing to obtain a fluorine-containing piezoelectric resin precursor solution; and then coating the fluorine-containing piezoelectric resin precursor solution On the surface of the protected substrate, a fluorine-containing piezoelectric resin coating is formed after drying. (The fluorine-containing piezoelectric resin precursor solution here can be regarded as the aforementioned anti-corrosion coating)

Wherein, the drying can be carried out at room temperature, or can be carried out in a blast drying oven with a temperature of 25-60° C., and the drying time is 2-24 hours, which is used to remove the solvent.

Among them, the solvent includes, but is not limited to, dichloromethane, chloroform, n-hexane, butyrolactone, diethyl ether, ethyl acetate, tetrahydrofuran, dimethyl sulfoxide, N,N-dimethylformamide, N,N- One or more of dimethylacetamide, 1,3-dioxolane, toluene and xylene.

In some preferred embodiments, the fluorine-containing piezoelectric resin precursor solution further includes a nucleating agent.

Among them, nucleating agents include but are not limited to carbon nanotubes (CNT), graphene oxide (GO), silicon dioxide (SiO ₂ ), barium titanate (BaTiO ₃ ), calcium carbonate (CaCO ₃ ), mica and other nanoparticles. One or more of.

Among them, the purpose of adding the nucleating agent is to improve the piezoelectric performance of the fluorine-containing piezoelectric resin, for example, as the crystalline nucleus of the polar crystal form (β phase) in polyvinylidene fluoride, to promote and induce the crystal phase conversion, and produce more The β-phase crystallization further enhances the piezoelectric properties of the polyvinylidene fluoride resin. For fluorine-containing piezoelectric resins with good piezoelectric properties, such as vinylidene fluoride-trifluoroethylene copolymer, the amount of nucleating agent can be appropriately reduced or not added.

In some preferred embodiments, the mass ratio of the fluorine-containing piezoelectric resin to the solvent and the nucleating agent ranges from (5-20): (30-90): (0.1-20).

In some preferred embodiments, the preparation method further includes: formulating the material for forming the second functional layer in a selected ratio to form a second precursor solution; then, coating the second precursor solution On the first functional layer, the second functional layer is formed on the first functional layer after curing to obtain an anti-corrosion system including the first functional layer and the second functional layer.

In some preferred embodiments, the second functional layer is a coating. The steps of forming the coating generally include: preparing the coating material into a specific form, for example, dissolving the solid coating material in a solvent, dissolving and mixing the coating material to form a liquid coating material, and then using a coating process to form the coating. The function of the second functional layer is to better block corrosive substances and avoid direct exposure of the first functional layer to the corrosive environment, thereby prolonging the service life of the first functional layer. There are many kinds of coating materials with anti-corrosion function, which is inconvenient List them here.

In some preferred embodiments, the second functional layer is an epoxy resin coating.

Among them, the preparation method of the epoxy resin coating specifically includes: mixing the epoxy resin with the curing agent to obtain the epoxy resin precursor solution; then coating the epoxy resin precursor solution on the first functional layer, and drying and curing Then an epoxy resin coating is formed.

Preferably, the temperature during drying and curing is 25-120°C, and the drying and curing time is 6-48 hours.

Preferably, the epoxy equivalent of the epoxy resin is 50-350 g/eq; the role of the curing agent is to enhance or control the curing reaction of the epoxy resin. For example, amine curing agents can be used. Commonly used amine curing agents include but are not limited to ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, diethylaminopropylamine, m-phenylenediamine, and polyetheramine. One or more of.

Among them, the range of the mass ratio of the curing agent to the epoxy resin is 1:(1-10), and a more preferable range is 1:(1-4).

In some preferred embodiments, the epoxy resin precursor solution also includes additives for reducing or suppressing bubble defects and improving the leveling of the coating surface. The auxiliary agent includes a defoamer and/or a leveling agent.

Among them, defoamers include, but are not limited to, long-chain alcohol defoamers, polyether defoamers, silicone defoamers, polyether modified silicone defoamers; leveling agents include but are not limited to polyether defoamers. Dimethylsiloxane, polyether polyester modified organosiloxane, alkyl modified organosiloxane.

Among them, the mass ratio of curing agent, epoxy resin and auxiliary agent ranges from 1:(1-10):(0.1-1); the mass ratio of defoamer to leveling agent in the auxiliary agent is arbitrary.

The preparation method of the above-mentioned anti-corrosion system has simple preparation process and low cost. The prepared anti-corrosion system can control the transmission process of corrosive ions inside the anti-corrosion system, and significantly slow down the penetration of corrosive ions. The anti-corrosion system provided by the embodiment of the present invention can actively control the transmission process of corrosive ions inside the anti-corrosion system.

The following examples will be combined with specific examples to illustrate the above-mentioned and preparation methods of the present invention. Those skilled in the art understand that the following examples are only specific typical examples of the above-mentioned anti-corrosion system and preparation methods of the present invention, not To limit it all.

In the embodiment of the present invention, the first functional layer is simply referred to as "A coating"; the second functional layer is simply referred to as "B coating".

The acid and alkali resistance test of the examples of the present invention is based on the "GB1763-79 Chemical Reagent Resistance Test Method for Paint Films". The precursor solutions in the examples and comparative examples were respectively immersed in a 5wt% sulfuric acid aqueous solution for 30 days after forming a film. , Soak in a 5wt% sodium hydroxide aqueous solution for 30 days, observe whether the coating and the surface of the metal material to be protected appear rust, bubbles, cracks, peeling, etc.

The salt water resistance test of the examples of the present invention is based on the "GB1763-79 Chemical Reagent Resistance Test Method for Paint Films". After the precursor solutions in the examples and comparative examples are formed into a film, 2/3 of the test plate is immersed in 3wt. In% sodium chloride aqueous solution, take it out according to the specified time of the product and check to observe whether the film layer and the surface of the coated metal material appear rust, bubbles, cracks, peeling, etc.

The water resistance test of the examples of the present invention is based on the "GB/T1733-93 Paint Film Water Resistance Test Method". After the precursor solutions in the examples and comparative examples are formed into a film, they are immersed in water at 23±2°C for 45 days. Observe whether rust, bubbles, cracks, peeling, etc. appear on the surface of the film and the coated metal material.

Example one

Calculated by mass, weigh 10 parts of polyvinylidene fluoride piezoelectric resin, then add 90 parts of dimethyl sulfoxide solvent, and stir for 2 hours under heating at 60°C until the mixture is uniform. Then stop heating, add 0.5 part of silica nucleating agent, continue to stir for 1h, and obtain A precursor solution.

Take the Q235 carbon steel substrate and polish it step by step with 200 mesh, 400 mesh, 800 mesh, 1000 mesh, and 1500 mesh sandpaper, and then perform ultrasonic washing in ethanol and acetone for 30 minutes, and dry the surface of the substrate with nitrogen.

The prepared A precursor solution was evenly coated on the metal surface by brushing method, and then placed in a blast drying oven at 50° C. for 2 hours to remove the solvent to form an A coating. The measured film thickness was 7.01 μm.

Calculate by mass, weigh 50 parts of bisphenol A diglycidyl ether, 20 parts of polyetheramine D230, stir evenly at room temperature, then add 1 part of polyether modified polysiloxane defoamer, 0.5 part of polyacrylic acid containing fluorine Ester leveling agent, continue to stir until uniform. Then it was placed in a vacuum drying oven to defoam for 10 minutes to obtain a B precursor solution.

The B precursor solution was evenly coated on the A coating by the wire rod coating method, and then it was placed in a blast drying oven at 100 ℃ for curing for 6 hours to form a B coating with a thickness of 34.24 μm.

The anti-corrosion system prepared in this embodiment includes: Q235 carbon steel substrate, A coating coated on Q235 carbon steel substrate, and B coating coated on A coating, A coating and B coating The thicknesses are 7.01μm and 34.24μm, respectively.

Carry out the marine environment corrosion simulation test for the above-mentioned anti-corrosion system: the anti-corrosion system is immersed in a 3.5wt% sodium chloride aqueous solution and taken out at fixed intervals (1, 3, 5, 7, 10, 15 days) Samples and conduct various electrochemical performance tests.

Example two

The anti-corrosion system of this embodiment and its preparation method are the same as those of the first embodiment, but the simulation test method is different. The difference is that the sample is fixed in a container filled with 3.5wt% sodium chloride aqueous solution, and the container is placed in a reciprocating manner. The oscillator repeatedly oscillates to simulate the pressure effect of waves hitting the metal substrate in the real ocean environment.

Comparative example one

The preparation method of this embodiment is the same as the preparation method of the B coating in the first embodiment, and only a single epoxy resin coating with a thickness of 40 μm is formed on the Q235 carbon steel substrate.

The anti-corrosion system prepared in this embodiment includes: a Q235 carbon steel substrate and a B coating coated on the Q235 carbon steel substrate.

The same marine environment corrosion simulation test as in Example 1 was performed on the above-mentioned anti-corrosion system.

Comparative example two

The preparation method of this embodiment is the same as that of Comparative Example 1, and the simulation test method of marine environment corrosion is the same as that of Example 2.

Test result analysis

The electrochemical performance and corrosion resistance performance of the four anti-corrosion systems that were simulated in the foregoing Example 1, Example 2, Comparative Example 1, and Comparative Example 2 were tested.

Figure 1 shows the potentiodynamic polarization curve spectra of the above-mentioned four anti-corrosion systems for 15 days simulation test.

In the spectrum of the potential polarization curve, generally, _{the lower the corrosion current I corr and the} higher the corrosion potential E _{corr, the} better the anti-corrosion effect of the coating on the metal substrate. It can be seen from the figure that after 15 days of simulation test, the electrochemical data of Example 1 and Example 2 performed better than the two comparative examples, while Comparative Example 1 and Comparative Example 2 both showed poor resistance. Corrosion performance, in which the corrosion current I _corr , corrosion potential E _corr and corrosion rate CR ^{of Comparative Example 2 were 1.94×10 -9} A·cm ^-2 , -246 mV, 2.25×10 ^-5 mm·year ^{-1, respectively} ; In comparison with example 1, I _corr decreased, E _corr increased, and CR decreased ^{in Example 2, reaching 7.85×10 -10} A·cm ^-2 , -189 mV, and 9.13×10 ^-6 mm·year ^-1 , respectively. It shows that the anti-corrosion performance of the anti-corrosion system in the simulated sea wave slap environment is better than that of the static immersion. The dynamic response current generated by the external force effectively disrupts the penetration of corrosive ions into the anti-corrosion system and significantly improves Improve the corrosion resistance of the anti-corrosion system.

Figures 2-1 to 2-4 are the Nyquist spectra of the 15-day simulation test of the anti-corrosion system of Example 1, Example 2, Comparative Example 1, and Comparative Example 2 in sequence.

It can be seen from the figure that the impedance arc radii of the four anti-corrosion systems all gradually decrease with the increase of the simulation test time, that is, the anti-corrosion performance gradually decreases. At the beginning of the simulation test, the four anti-corrosion systems were in good condition and all showed the largest impedance arc; on the fifth day of the simulation test, except for Example 2, the impedance arc radii of the other three anti-corrosion systems experienced significant changes. Decrease, indicating that corrosive ions begin to penetrate into the coating of the anti-corrosion system and diffuse in the coating, and the anti-corrosion performance begins to be affected. Throughout the entire simulation test process, the anti-corrosion system of Example 2 is only slightly affected, and the impedance arc radius decreases slowly with time, showing a good barrier function to corrosive ions.

Figures 3-1 to Figure 3-4 are the electrochemical impedance spectra of the 15-day simulation test of the anti-corrosion system of Example 1, Example 2, Comparative Example 1, and Comparative Example 2, in which the unit of the time axis is :sky.

In electrochemical impedance spectroscopy, the resistance value at 0.01 Hz is usually used to evaluate the corrosion resistance of the coating. It can be seen that at the beginning of the test, the impedance values of the four anti-corrosion systems are not much different; during the entire simulation test, the impedance of the four anti-corrosion systems at 0.01 Hz gradually decreases, indicating that the anti-corrosion system Performance is decreasing. In the early stage of the test (1-5 days), the impedance values of the four anti-corrosion systems decreased relatively smoothly; in the later stage of the test (7-15 days), due to the penetration of corrosive ions, the impedance values of Example 1 and the two comparative examples The decrease has a tendency to accelerate, and the impedance value of Example 2 is still relatively stable, and after the end of the test period, it shows the highest impedance value, reaching 3.172.42×10 ⁸ Ωcm ^-1 , indicating that the anti-corrosion system of Example 2 has Excellent anti-corrosion performance.

The electrochemical data and corrosion resistance data of each example and comparative example are listed in Table 1. Among them, I _corr , E _corr , CR, Z _0.01Hz represent corrosion current, corrosion potential, corrosion rate, and impedance at 0.01Hz, respectively Value, "+" means that no blistering, cracking, rusting, peeling, etc. are observed.

Table 1 Electrochemical data and corrosion resistance data of each embodiment and comparative example

After 15 days of immersion/oscillation test, it was found that: (1) the anti-corrosion system of Example 2 exhibits the lowest corrosion current I _corr and corrosion rate CR and the highest corrosion potential E _corr under shaking conditions; (2) contains fluorine The corrosion rate CR of the anti-corrosion system of the piezoelectric resin coating is lower than that of the anti-corrosion system without the fluorine-containing piezoelectric resin coating; (3) The results of the first and second embodiments show that the fluorine-containing piezoelectric resin is included The coating's anti-corrosion system has excellent anti-corrosion performance even in the case of standing immersion.

After long-term resistance to acid, alkali, salt water, and water, the anti-corrosion system containing the fluorine-containing piezoelectric resin coating did not show cracks, blisters, or shedding; the anti-corrosion system that does not contain the fluorine-containing piezoelectric resin coating is acid resistant Poor sex.

It can be seen from the above test data spectrum that the potential polarization curve and AC electrochemical impedance test of the anti-corrosion system in Example 1 and Example 2 of the present invention both show more excellent anti-corrosion effects; double-layer anti-corrosion The anti-corrosion performance of the system (i.e. the anti-corrosion system of Example 2) under the simulated sea wave slap environment is better than that under the static immersion condition (i.e. the simulated test conditions of Example 1), while the comparative example 1 and the comparative example The second anti-corrosion system is a single epoxy resin coating, and their anti-corrosion performance deteriorates quickly regardless of whether it is left standing or in a shock environment.

Example three

According to mass calculation, weigh 20 parts of piezoelectric resin: vinylidene fluoride-trifluoroethylene copolymer, add 80 parts of solvent: 1,3-dioxolane, and stir for 1 hour under heating conditions at 45°C until the mixture is uniform. Then the heating was stopped, 0.1 part of graphene oxide was added, and stirring was continued for 1 h to obtain the A precursor solution.

Take the stainless steel substrate and polish it step by step with 200 mesh, 400 mesh, 800 mesh, 1000 mesh, 1500 mesh, 2000 mesh sandpaper, and then polish it with alumina and silicon carbide micro-powder abrasives. After repeated cleaning with ethanol, it is in acetone. Carry out ultrasonic washing for 30 minutes, and then use argon to dry the surface of the stainless steel substrate and keep it sealed.

The prepared A precursor solution was sprayed uniformly on the surface of the stainless steel substrate by spraying method, and then placed in a blast drying oven at 70°C for 30 minutes to remove the solvent, and the A coating was prepared.

Weigh 65 parts of phthalic acid diglycidyl ester and 30 parts of trimellitic anhydride. Stir evenly at room temperature, then add 1 part of isooctyl alcohol defoamer, 1 part of polyvinyl butyral leveling agent, and continue to stir until uniform; Then it was placed in a vacuum drying oven to defoam for 20 minutes to obtain a B precursor solution.

The B precursor solution was evenly coated on the A coating by the wire rod coating method, and the sample was cured in a blast drying oven at 130°C for 6 hours to prepare the B coating.

The anti-corrosion system prepared in this embodiment includes: a stainless steel substrate, an A coating coated on the stainless steel substrate, and a B coating coated on the A coating. The thickness of the A coating and the B coating are 15.30, respectively. μm and 32.43μm.

Embodiment four

Calculated by mass, weigh 15 parts of vinylidene fluoride-chlorotrifluoroethylene copolymer piezoelectric resin, then add 85 parts of N,N-dimethylacetamide solvent, and stir for 2h under heating conditions at 70°C until the mixture is uniform. Then stop heating, add 1 part of graphene oxide nucleating agent, and continue to stir for 1 h to obtain A precursor solution.

Take the Q195 carbon steel substrate, first polish it with 200 mesh, 400 mesh, 800 mesh, 1000 mesh, 1500 mesh sandpaper, and then perform ultrasonic washing in ethanol and acetone for 30 minutes. Dry the surface of the substrate with nitrogen. Put it into the vacuum box for later use.

The prepared A precursor solution was evenly coated on the metal surface by brushing method, and then placed in a blast drying oven at 50°C for 2 hours to remove the solvent, and the A coating was prepared. The measured film thickness was 13.66μm.

Calculate by mass, weigh out 90 parts of E-51 resin, 10 parts of diethylene triamine curing agent, stir evenly at room temperature, then add 0.5 part of dimethyl silicone oil defoamer, 0.5 part of cellulose acetate and butyl cellulose leveling agent, Continue to stir until uniform. Then it was placed in a vacuum drying oven to defoam for 15 minutes to obtain a B precursor solution.

The B precursor solution was evenly coated on the A coating by the wire rod coating method, and then it was placed in a blast drying oven at 50 ℃ for curing for 6 hours to form a B coating with a thickness of 51.53 μm.

The anti-corrosion system prepared in this embodiment includes: Q195 carbon steel substrate, A coating coated on Q195 carbon steel substrate, and B coating coated on A coating, A coating and B coating The thickness is 13.66μm and 51.53μm, respectively.

Embodiment five

Calculated by mass, weigh 25 parts of vinylidene fluoride-hexafluoropropylene copolymer piezoelectric resin, and then add 75 parts of N,N-dimethylformamide solvent, and stir at 70°C for 1 hour until the mixture is uniform. Then, the heating was stopped, 0.5 part of the carbon nanotube nucleating agent was added, and stirring was continued for 1 hour to obtain the A precursor solution.

The prepared A precursor solution was evenly coated on the metal surface by brush coating, and then placed in a blast drying oven at 50° C. for 2 hours to remove the solvent, and the A coating was prepared. The measured film thickness was 5.45 μm.

Calculate by mass, weigh out 80 parts of E-44 resin, 20 parts of diethylaminopropylamine curing agent, stir evenly at room temperature, then add 0.5 part of mineral oil defoamer, 1 part of isophorone leveling agent, and continue to stir To uniform. Then it was placed in a vacuum drying oven to defoam for 15 minutes to obtain a B precursor solution.

The B precursor solution was evenly coated on the A coating by the wire rod coating method, and then it was placed in a blast drying oven at 50 ℃ for curing for 6 hours to form a B coating with a thickness of 21.61 μm.

The anti-corrosion system prepared in this embodiment includes: Q195 carbon steel substrate, A coating coated on Q195 carbon steel substrate, and B coating coated on A coating, A coating and B coating The thickness is 5.45μm and 21.61μm, respectively.

Example Six

According to mass calculation, weigh 10 parts of vinylidene fluoride-trifluoroethylene-chlorofluoroethylene terpolymer piezoelectric resin, and then add 90 parts of N-methylpyrrolidone solvent, and stir for 1h under heating conditions of 75°C until the mixture is uniform. Then stop heating, add 0.1 part of silica nanoparticles, continue to stir for 1 hour to obtain A precursor solution.

Take the Q215 carbon steel substrate, first polish it with 200 mesh, 400 mesh, 800 mesh, 1000 mesh, 1500 mesh, 2000 mesh sandpaper, and then polish it with alumina and silicon carbide micro-powder abrasives, and clean it repeatedly with ethanol. Carry out ultrasonic washing in acetone for 30 minutes, then dry the surface of the stainless steel substrate with argon gas, and put it in a vacuum box for later use.

The prepared A precursor solution was uniformly sprayed on the metal surface by spraying method, and then placed in a blast drying oven at 60° C. for 2 hours to remove the solvent, and an A coating was prepared. The measured film thickness was 3.74 μm.

Calculate by mass, weigh out 75 parts of bis(2,3-epoxycyclopentyl) ether resin, 25 parts of methylcyclohexenetetracarboxylic dianhydride curing agent, stir evenly at room temperature, and then add 1 part of heteropolyacrylic acid Ester leveling agent, continue to stir until uniform. Then it was placed in a vacuum drying oven to defoam for 25 minutes to obtain a B precursor solution.

The B precursor solution was uniformly coated on the A coating by the wire rod coating method, and then it was placed in a blast drying oven at 50 ℃ for curing for 6 hours to form a B coating with a thickness of 13.11 μm.

The anti-corrosion system prepared in this embodiment includes: Q215 carbon steel substrate, A coating coated on Q215 carbon steel substrate, and B coating coated on A coating, A coating and B coating The thickness is 3.74μm and 13.11μm, respectively.

The corrosion resistance data of the anti-corrosion system of Example 4 to Example 6 are listed in Table 2, where "+" means that no blistering, cracking, rusting, peeling, etc. are observed.

Table 2 Corrosion resistance data of Example 4 to Example 6

After long-term resistance to acid and alkali, salt water, and water, none of the anti-corrosion systems containing fluorine-containing piezoelectric resin coatings showed cracks, blisters, or shedding.

It can be known from the above embodiments that the anti-corrosion system provided by the embodiments of the present invention uses a fluorine-containing piezoelectric resin material with anti-corrosion and piezoelectricity as the A coating applied to the anti-corrosion system. , A coating can generate a dynamic response current to disturb the transmission process of corrosive ions in the anti-corrosion system, significantly slow down the penetration of corrosive ions in the anti-corrosion system, and achieve active control of the corrosive ions in the anti-corrosion system. The effect of the transmission process.

Although the present invention has been illustrated and described with reference to specific embodiments, those skilled in the art will understand that forms and forms can be made here without departing from the spirit and scope of the present invention defined by the claims and their equivalents. Various changes in details.

Claims

An anti-corrosion system, which includes a first functional layer coated on a protected substrate, the first functional layer contains a fluorine-containing piezoelectric material, and the first functional layer can produce Dynamic response to current to hinder the transmission of corrosive ions to the protected substrate.
The anti-corrosion system according to claim 1, wherein the material used to form the first functional layer includes a fluorine-containing piezoelectric material, a nucleating agent, and a solvent.
The anti-corrosion system according to claim 2, wherein the mass ratio of the fluorine-containing piezoelectric material to the nucleating agent is 10:1 to 200:1.
The anti-corrosion system according to claim 2, wherein the fluorine-containing piezoelectric material is a fluorine-containing piezoelectric resin.
The anti-corrosion system according to claim 4, wherein the fluorine-containing piezoelectric resin is selected from polyvinylidene fluoride, vinylidene fluoride-trifluoroethylene copolymer, vinylidene fluoride-chlorotrifluoroethylene copolymer, and vinylidene fluoride-trifluoroethylene copolymer. At least one of vinylidene fluoride-hexafluoropropylene copolymer and vinylidene fluoride-trifluoroethylene-chlorofluoroethylene terpolymer; the nucleating agent is selected from carbon nanotubes, graphene oxide, silicon dioxide nano At least one of particles, barium titanate nanoparticles, calcium carbonate nanoparticles, and mica nanoparticles.
The anti-corrosion system according to claim 2, wherein the anti-corrosion system further comprises at least one second functional layer formed on the first functional layer, and the second functional layer is an anti-corrosion coating.
The anti-corrosion system according to claim 6, wherein the material used to form the second functional layer includes epoxy resin, auxiliary agent and curing agent.
The anti-corrosion system according to claim 7, wherein the mass ratio of the material used to form the second functional layer, the curing agent, the epoxy resin, and the auxiliary agent is in the range of 1. :(1-10):(0.1-1).
A preparation method of an anti-corrosion system, which includes:

Preparing the material used to form the first functional layer according to a selected ratio to form a first precursor solution;

Coating the first precursor solution on the substrate to be protected, and forming the first functional layer after drying to obtain an anti-corrosion system including the first functional layer;

Wherein, the material used to form the first functional layer includes a fluorine-containing piezoelectric material, and the first functional layer can generate a dynamic response current under a force condition to hinder the transmission of corrosive ions to the protected substrate.
The method for preparing an anti-corrosion system according to claim 9, wherein the material used to form the first functional layer includes a fluorine-containing piezoelectric material, a nucleating agent, and a solvent.
The method for preparing an anti-corrosion system according to claim 10, wherein the mass ratio of the fluorine-containing piezoelectric material to the nucleating agent is 10:1 to 200:1.
The method for preparing an anti-corrosion system according to claim 10, wherein the fluorine-containing piezoelectric material is a fluorine-containing piezoelectric resin.
The method for preparing an anti-corrosion system according to claim 12, wherein the fluorine-containing piezoelectric resin is selected from polyvinylidene fluoride, vinylidene fluoride-trifluoroethylene copolymer, and vinylidene fluoride-chlorotrifluoroethylene copolymer At least one of vinylidene fluoride-hexafluoropropylene copolymer and vinylidene fluoride-trifluoroethylene-chlorofluoroethylene terpolymer; the nucleating agent is selected from carbon nanotubes, graphene oxide, two At least one of silicon oxide nanoparticles, barium titanate nanoparticles, calcium carbonate nanoparticles, and mica nanoparticles.
The preparation method of the anti-corrosion system according to claim 9, wherein the preparation method further comprises: preparing and forming a second functional layer on the first functional layer, the second functional layer being an anti-corrosion coating; The preparation of the first functional layer to form the second functional layer specifically includes:

The material used to form the second functional layer is formulated in a selected ratio to form a second precursor solution;

The second precursor solution is coated on the first functional layer, and after curing, the second functional layer is formed on the first functional layer to obtain the first functional layer and the first functional layer. Anti-corrosion system for the second functional layer.
The method for preparing an anti-corrosion system according to claim 14, wherein the material used to form the second functional layer comprises epoxy resin, auxiliary agent and curing agent.
The preparation method of the anti-corrosion system according to claim 15, wherein the material used to form the second functional layer, the mass ratio of the curing agent, the epoxy resin and the auxiliary agent The range is 1:(1-10):(0.1-1).
An anti-corrosion paint, wherein the anti-corrosion paint contains a fluorine-containing piezoelectric material, a nucleating agent and a solvent.
The anti-corrosion coating according to claim 17, wherein the mass ratio of the fluorine-containing piezoelectric material to the nucleating agent is 10:1 to 200:1.
The anticorrosive paint according to claim 17, wherein the fluorine-containing piezoelectric material is a fluorine-containing piezoelectric resin.
The anti-corrosion coating according to claim 19, wherein the fluorine-containing piezoelectric resin is selected from polyvinylidene fluoride, vinylidene fluoride-trifluoroethylene copolymer, vinylidene fluoride-chlorotrifluoroethylene copolymer, and vinylidene fluoride-trifluoroethylene copolymer. At least one of vinylidene fluoride-hexafluoropropylene copolymer and vinylidene fluoride-trifluoroethylene-chlorofluoroethylene terpolymer; the nucleating agent is selected from carbon nanotubes, graphene oxide, silicon dioxide nano At least one of particles, barium titanate nanoparticles, calcium carbonate nanoparticles and mica nanoparticles; the solvent is selected from dichloromethane, chloroform, n-hexane, butyrolactone, diethyl ether, ethyl acetate, tetrahydrofuran, At least one of dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, 1,3-dioxolane, toluene, and xylene.