WO2021243771A1 - 一种防腐蚀体系及其制备方法、防腐蚀涂料 - Google Patents

一种防腐蚀体系及其制备方法、防腐蚀涂料 Download PDF

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WO2021243771A1
WO2021243771A1 PCT/CN2020/098227 CN2020098227W WO2021243771A1 WO 2021243771 A1 WO2021243771 A1 WO 2021243771A1 CN 2020098227 W CN2020098227 W CN 2020098227W WO 2021243771 A1 WO2021243771 A1 WO 2021243771A1
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functional layer
corrosion
fluorine
coating
corrosion system
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French (fr)
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王彬
黄俊贤
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Shenzhen Institute of Advanced Technology of CAS
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Shenzhen Institute of Advanced Technology of CAS
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    • C—CHEMISTRY; METALLURGY
    • 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
    • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C09D127/16—Homopolymers or copolymers of vinylidene fluoride
    • 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
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • 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
    • 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
    • B05D7/50—Multilayers
    • B05D7/52—Two layers
    • B05D7/54—No clear coat specified
    • B05D7/544—No clear coat specified the first layer is let to dry at least partially before applying the second layer
    • 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
    • B05D7/50—Multilayers
    • B05D7/52—Two layers
    • B05D7/54—No clear coat specified
    • B05D7/546—No clear coat specified each layer being cured, at least partially, separately
    • C—CHEMISTRY; METALLURGY
    • 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
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • 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
    • C—CHEMISTRY; METALLURGY
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F15/00—Other methods of preventing corrosion or incrustation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

Definitions

  • 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.
  • 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.
  • 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.
  • due to the hydrogen precipitation on the surface it may cause the danger of hydrogen embrittlement and overprotection.
  • 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.
  • 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.
  • 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.
  • 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.
  • the existing anti-corrosion coating technology can only function as a physical barrier and can only passively block corrosive substances.
  • only relying on its own barrier to serve in the complex seawater environment cannot form a long-term effective barrier to various 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.
  • 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.
  • the material used to form the first functional layer includes a fluorine-containing piezoelectric material, a nucleating agent, and a solvent.
  • the mass ratio of the fluorine-containing piezoelectric material to the nucleating agent is 10:1 to 200:1.
  • the fluorine-containing piezoelectric material is a fluorine-containing piezoelectric resin.
  • 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.
  • 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.
  • the material used to form the second functional layer includes epoxy resin, auxiliary agent and curing agent.
  • the auxiliary agent is a defoamer and/or a leveling agent.
  • 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:
  • 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.
  • 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 is provided.
  • 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.
  • the corrosive environment is any one of an acidic corrosive environment, an alkaline corrosive environment, a salty corrosive environment, and an aqueous corrosive 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.
  • the mass ratio of the fluorine-containing piezoelectric material to the nucleating agent is 10:1 to 200:1.
  • the fluorine-containing piezoelectric material is a fluorine-containing piezoelectric resin.
  • 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 at least one of carbon nanotubes, graphene oxide, silica nanoparticles, barium titanate nanoparticles, calcium carbonate nanoparticles, and mica nanoparticles.
  • 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.
  • 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.
  • the first functional layer 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.
  • 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.
  • the inventor of the present invention 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.
  • 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.
  • the material used to form the first functional layer includes a fluorine-containing piezoelectric material, a nucleating agent, and a solvent.
  • 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.
  • 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.
  • a fluorine-containing piezoelectric resin material such as: polyvinylidene fluoride, vinylidene fluoride-trifluoroethylene copolymer, vinylidene fluoride-chlorotrifluoroethylene copolymer, and vinylidene fluoride-trifluoroethylene copolymer.
  • 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.
  • 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.
  • 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.
  • coating materials with anti-corrosion function which is inconvenient List them here.
  • the material used to form the second functional layer includes epoxy resin, auxiliary agent and curing agent.
  • the material used to form the second functional layer further contains a defoaming agent and/or a leveling agent.
  • the ratio of the thickness of the first functional layer to the second functional layer is set to 1:1 to 1:5.
  • a fluorine-containing piezoelectric material with anti-corrosion and piezoelectricity is used as the first functional layer in the anti-corrosion system.
  • the first functional layer 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.
  • 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 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.
  • 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.
  • the anti-corrosion system can actively control the transmission process of corrosive ions inside the anti-corrosion system.
  • 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 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.
  • 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.
  • a fluorine-containing piezoelectric resin material such as: polyvinylidene fluoride, vinylidene fluoride-trifluoroethylene copolymer, vinylidene fluoride-chlorotrifluoroethylene copolymer, and vinylidene fluoride-trifluoroethylene copolymer.
  • 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.
  • 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.
  • 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.
  • 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.
  • the first functional layer is a fluorine-containing piezoelectric material coating.
  • 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.
  • 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
  • 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.
  • 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.
  • the fluorine-containing piezoelectric resin precursor solution further includes a nucleating agent.
  • 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.
  • CNT carbon nanotubes
  • GO graphene oxide
  • SiO 2 silicon dioxide
  • BaTiO 3 barium titanate
  • CaCO 3 calcium carbonate
  • 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 ( ⁇ phase) in polyvinylidene fluoride, to promote and induce the crystal phase conversion, and produce more
  • the ⁇ -phase crystallization further enhances the piezoelectric properties of the polyvinylidene fluoride resin.
  • the amount of nucleating agent can be appropriately reduced or not added.
  • 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).
  • 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.
  • 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.
  • coating materials with anti-corrosion function which is inconvenient List them here.
  • the second functional layer is an epoxy resin coating.
  • 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.
  • the temperature during drying and curing is 25-120°C, and the drying and curing time is 6-48 hours.
  • 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.
  • 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.
  • 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).
  • 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.
  • 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.
  • 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 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.
  • 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 ⁇ m.
  • 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 °C for curing for 6 hours to form a B coating with a thickness of 34.24 ⁇ m.
  • 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 7.01 ⁇ m and 34.24 ⁇ m, respectively.
  • 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.
  • 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.
  • 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 ⁇ m 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 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.
  • Figure 1 shows the potentiodynamic polarization curve spectra of the above-mentioned four anti-corrosion systems for 15 days simulation test.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 ⁇ cm -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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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. ⁇ m and 32.43 ⁇ m.
  • 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 13.66 ⁇ m.
  • 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 °C for curing for 6 hours to form a B coating with a thickness of 51.53 ⁇ m.
  • 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 13.66 ⁇ m and 51.53 ⁇ m, respectively.
  • 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 ⁇ m.
  • 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 °C for curing for 6 hours to form a B coating with a thickness of 21.61 ⁇ m.
  • 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 5.45 ⁇ m and 21.61 ⁇ m, respectively.
  • 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 ⁇ m.
  • 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 °C for curing for 6 hours to form a B coating with a thickness of 13.11 ⁇ m.
  • 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 3.74 ⁇ m and 13.11 ⁇ m, respectively.
  • the anti-corrosion system 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.

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Abstract

本发明公开了一种防腐蚀体系及其制备方法、防腐蚀涂料，该防腐蚀体系包括包覆于被保护基体上的第一功能层，所述第一功能层中包含有含氟压电材料，所述第一功能层在受力条件下能够产生动态响应电流以阻碍腐蚀性离子传输至所述被保护基体。本发明提供的防腐蚀体系能够主动调控腐蚀性离子在防腐蚀体系内部的传输过程，显著减缓腐蚀性离子在防腐蚀体系中的渗透作用。本发明进一步提供前述防腐蚀体系的制备方法和该防腐蚀体系在腐蚀性环境中的应用。本发明同时还提出一种防腐蚀涂料，该涂料干燥形成涂层后，在受力条件下能够产生动态响应电流以阻碍腐蚀性离子传输至所述被保护基体，显著减缓腐蚀性离子在涂层中的渗透作用。

Description

一种防腐蚀体系及其制备方法、防腐蚀涂料 技术领域
本发明涉及防腐蚀材料技术领域，具体涉及一种防腐蚀体系及其制备方法、防腐蚀涂料。
背景技术
长期在海洋环境中使用的舰船、采油平台等金属工程设备会面临严峻的腐蚀问题，这是因为海洋环境中存在大量的腐蚀性物质。金属腐蚀是世界性的问题，根据相关调查报告显示，世界年平均由腐蚀直接及间接造成损失可达数十亿美元，占全球国民生产总值的3.4％，而其中海洋腐蚀的损失约占总损失的三分之一。近年来我国每年因海洋腐蚀所造成的损失甚至已超过当年自然灾害损失的总和。因此，金属的腐蚀防护成为急需解决的重要问题，特别是海洋腐蚀防护的相关技术研发。
在腐蚀防护的工程领域中，常用的防腐蚀技术有：电化学阴极保护法、电化学阳极保护法、缓蚀剂保护法、开发新型耐腐蚀合金材料、金属表面保护层等。
(1)电化学阴极保护法又包括牺牲阳极的阴极保护法和强制电流阴极保护法，其基本原理在于通过阴极极化使被保护金属达到保护电位，使电化学腐蚀过程的速率降低或完全停止。此方法容易使被保护金属的电位太负，造成能源的浪费、拉升成本，而且由于表面析出氢气，可能使金属产生氢脆的危险，出现过保护现象。
(2)电化学阳极保护法指在外加阳极电流的作用下，金属在腐蚀介质中发生钝化，进而使腐蚀速率显著下降的保护方法。此方法通常应用在硫酸、有机磺酸等强氧化介质的腐蚀防护中，对于不能钝化的体系或含Cl -离子的介质中不能使用阳极保护，应用范围有限。
(3)缓蚀剂保护法是通过引入特殊的化学物质以降低金属的腐蚀速率。缓蚀剂的成分、作用机理及应用非常广泛。需要注意的是，许多性能较好的缓 蚀剂被证明对环境有不可忽视的污染作用及对生物的毒害作用，例如，已应用的含铬等缓蚀剂效果明显，但往往对生态环境毒性大，有些已被发达国家明令禁止，在缓释性能与环境负荷之间的抉择，已成为制约缓蚀剂在实际应用中的一个重大问题。
(4)开发新型耐腐蚀合金材料的关键在于掌握材料的耐腐蚀机理、各元素的耐腐蚀性能以及对合金材料的成分调配、工艺改进等。然而，金属腐蚀规律尤为复杂，在不同外界环境如不同温度、湿度、不同腐蚀介质浓度时腐蚀规律都不尽相同，因此，想在开发新型合金方面取得突破性进展，仍需要花费大量的人力与时间去进行基础性探索与研究。
(5)金属表面保护层包括金属保护层和非金属涂层，其根本目的是在金属基体表面和腐蚀介质之间引入一物理屏障，以阻止或延缓腐蚀性离子等通过扩散或渗透作用到达涂层-金属界面，造成金属腐蚀。其中金属保护层一般是通过电镀、热镀、渗镀、化学镀等方法将一种或多种惰性金属镀在被保护金属的表面，形成一层致密的金属保护层；而非金属保护层范围则更加广泛，包含有机涂层、无机涂层及复合涂层等。其中有机防腐蚀涂层由于具有操作简单、经济实用、防腐蚀性能优异等优点而被广泛应用。
上述现有防腐蚀技术各有优缺点，其中，现有的防腐蚀涂层技术只能起到物理屏障的作用，只能被动阻隔腐蚀性物质。而在成分复杂的海水环境中服役仅仅依靠自身的屏障并不能对各类腐蚀性物质形成长期有效的阻隔。
发明内容
为了解决现有的防腐蚀涂层只能起到被动阻隔腐蚀性物质的问题，本发明提供了一种具有主动调控腐蚀性离子传输功能的新型的防腐蚀体系，并进一步提供了该防腐蚀体系的制备方法。
为了达到上述发明目的，本发明提供一种防腐蚀体系，包括包覆于被保护基体上的第一功能层，所述第一功能层中包含有含氟压电材料，所述第一功能层在受力条件下能够产生动态响应电流以阻碍腐蚀性离子传输至所述被保护基体。
进一步地，用于形成所述第一功能层的材料包含有含氟压电材料、成核剂以及溶剂。
优选地，所述含氟压电材料与所述成核剂的质量比为10:1-200:1。
优选地，所述含氟压电材料为含氟压电树脂。
优选地，所述含氟压电树脂选择聚偏二氟乙烯、偏氟乙烯-三氟乙烯共聚物、偏二氟乙烯-三氟氯乙烯共聚物、偏二氟乙烯-六氟丙烯共聚物和偏氟乙烯-三氟乙烯-氯氟乙烯三元共聚物中的至少一种；所述成核剂选自碳纳米管、氧化石墨烯、二氧化硅纳米颗粒、钛酸钡纳米颗粒、碳酸钙纳米颗粒和云母纳米颗粒中的至少一种。
进一步地，所述防腐蚀体系还包括形成在所述第一功能层之上的至少一个第二功能层，所述第二功能层为防腐蚀涂层。
优选地，用于形成所述第二功能层的材料包含有环氧树脂、助剂和固化剂。
优选地，所述助剂为消泡剂和/或流平剂。
优选地，所述第一功能层与所述第二功能层的厚度之比为1:1-1:5。
本发明还提供一种上述的防腐蚀体系的制备方法，包括：
将用于形成第一功能层的材料按照选定的比例配制形成第一前驱体溶液；
将所述第一前驱体溶液涂布于被保护基体上，干燥后形成所述第一功能层，获得包含有所述第一功能层的防腐蚀体系。
优选地，所述制备方法还包括：将用于形成第二功能层的材料按照选定的比例配制形成第二前驱体溶液；
将所述第二前驱体溶液涂布于所述第一功能层之上，固化后在所述第一功能层上形成所述第二功能层，获得包含有所述第一功能层和所述第二功能层的防腐蚀体系。
基于上述的防腐蚀体系，本发明进一步提供一种该防腐蚀体系的应用，将所述防腐蚀体系应用于在腐蚀性环境中对金属基体进行防腐蚀保护。
进一步地，所述腐蚀性环境为酸性腐蚀环境、碱性腐蚀环境、盐性腐蚀环境、水性腐蚀环境中的任意一种。
进一步地，在海洋环境中，所述压力作用包括海浪拍击所述防腐蚀体系带来的压力作用、潮汐作用给所述防腐蚀体系带来的压力作用。
本发明还提供一种防腐蚀涂料，其包含有含氟压电材料、成核剂以及溶剂。
进一步地，在防腐蚀涂料中，所述含氟压电材料与所述成核剂的质量比为10:1-200:1。
进一步地，所述含氟压电材料为含氟压电树脂。
进一步地，所述含氟压电树脂选择聚偏二氟乙烯、偏氟乙烯-三氟乙烯共聚物、偏二氟乙烯-三氟氯乙烯共聚物、偏二氟乙烯-六氟丙烯共聚物和偏氟乙烯-三氟乙烯-氯氟乙烯三元共聚物中的至少一种。
进一步地，所述成核剂选自碳纳米管、氧化石墨烯、二氧化硅纳米颗粒、钛酸钡纳米颗粒、碳酸钙纳米颗粒和云母纳米颗粒中的至少一种。
进一步地，所述溶剂选自二氯甲烷、三氯甲烷、正己烷、丁内酯、乙醚、乙酸乙酯、四氢呋喃、二甲基亚砜、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、1,3-二氧杂环戊烷、甲苯和二甲苯中的中的至少一种。
相比现有技术，本发明具有如下有益效果：
本发明提供的防腐蚀体系，其创造性地提出将具有压电性的含氟压电材料作为第一功能层应用于防腐蚀体系中，第一功能层受到压力作用时，能产生动态响应电流进而扰乱腐蚀性离子在防腐蚀体系内部的传输过程，显著减缓腐蚀性离子在防腐蚀体系中的渗透作用。因此，本发明提供的防腐蚀体系能达到主动调控腐蚀性离子在防腐蚀体系内部的传输过程的效果。
本发明提供的防腐蚀体系的制备方法，其制备工艺简单，成本低廉，制备得到的防腐蚀体系能够调控腐蚀性离子在防腐蚀体系内部的传输过程，显著减缓腐蚀性离子的渗透作用。因此，上述制备方法制备得到的防腐蚀体系能达到主动调控腐蚀性离子在涂层体系内部的传输过程的效果。
附图说明
通过结合附图进行的以下描述，本发明的实施例的特点和优点将变得更加清楚，附图中：
图1为实施例一、实施例二、对比例一和对比例二4个防腐蚀体系15天模拟测试的动电位极化曲线谱图；
图2-1～图2-4分别为实施例一、实施例二、对比例一和对比例二4个防腐蚀体系15天模拟测试的奈奎斯特谱图；
图3-1～图3-4分别为实施例一、实施例二、对比例一和对比例二4个防腐蚀体系15天模拟测试的电化学阻抗谱图。
具体实施方式
以下，将参照附图来详细描述本发明的实施例。然而，可以以许多不同的形式来实施本发明，并且本发明不应该被解释为限制于这里阐述的具体实施例。相反，提供这些实施例是为了解释本发明的原理及其实际应用，从而使本领域的其他技术人员能够理解本发明的各种实施例和适合于特定预期应用的各种修改。
本发明的发明人基于现有技术中的防腐蚀涂层只能起到被动阻隔腐蚀性物质的问题，提供了一种具有主动调控腐蚀性离子传输功能的新型的防腐蚀体系，并进一步提供了该防腐蚀体系的制备方法。
1、本发明实施例提供一种防腐蚀体系，包括包覆于被保护基体上的第一功能层，所述第一功能层中包含有含氟压电材料，所述第一功能层在受力条件下能够产生动态响应电流以阻碍腐蚀性离子传输至所述被保护基体。
进一步地，用于形成所述第一功能层的材料包含有含氟压电材料、成核剂以及溶剂。
在一些优选的实施例中，所述含氟压电材料与所述成核剂的质量比为10:1-200:1。
所述含氟压电材料可以是本身含氟的压电材料，也可以是含氟材料与压电材料的混合。
其中，本身含氟的压电材料可以是含氟压电树脂材料，例如：聚偏二氟乙烯、偏氟乙烯-三氟乙烯共聚物、偏二氟乙烯-三氟氯乙烯共聚物、偏二氟乙烯-六氟丙烯共聚物和偏氟乙烯-三氟乙烯-氯氟乙烯三元共聚物中的至少一种。
所述成核剂可以选自碳纳米管、氧化石墨烯、二氧化硅纳米颗粒、钛酸钡纳米颗粒、碳酸钙纳米颗粒和云母纳米颗粒中的至少一种。
所述溶剂用于溶解其他形成第一功能层的材料，在制备过程中一般会被干燥去除。溶剂包括但不限于二氯甲烷、三氯甲烷、正己烷、丁内酯、乙醚、乙酸乙酯、四氢呋喃、二甲基亚砜、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、1,3-二氧杂环戊烷、甲苯和二甲苯中的一种或多种。
在一些优选的实施例中，所述第一功能层为含氟压电树脂涂层。含氟压电树脂涂层包括但不限于聚偏二氟乙烯涂层、偏氟乙烯-三氟乙烯共聚物涂层、偏二氟乙烯-三氟氯乙烯共聚物涂层、偏二氟乙烯-六氟丙烯共聚物涂层和偏氟乙烯-三氟乙烯-氯氟乙烯三元共聚物涂层。
在一些优选的实施例中，还在第一功能层之上设有至少一个具有防腐蚀功能的第二功能层。第二功能层的作用是为了更好地阻隔腐蚀性物质，避免第一功能层直接暴露于腐蚀环境中，进而延长第一功能层的使用寿命，具有防腐蚀功能的涂层材料种类繁多，不便在此一一列举。
在一些优选的实施例中，用于形成所述第二功能层的材料包含有环氧树脂、助剂和固化剂。
在一些优选的实施例中，用于形成所述第二功能层的材料还包含有消泡剂和/或流平剂。
在一些优选的实施例中，为了进一步保护第一功能层，将第一功能层与第二功能层的厚度之比设置为1:1-1:5。
本发明实施例提供的防腐蚀体系，将具有防腐蚀性、压电性的含氟压电材料作为第一功能层应用于防腐蚀体系中，第一功能层受到压力作用时，能产生动态响应电流进而扰乱腐蚀性离子在防腐蚀体系内部的传输过程，显著减缓腐蚀性离子在防腐蚀体系中的渗透作用。因此，本发明提供的防腐蚀体系能主动调控腐蚀性离子在涂层体系内部的传输过程。
更具体的防腐蚀机理在于：含氟压电材料中的氟原子与金属表面所存在的羟基(FeOOH)之间存在氢键作用。氟原子通过氢键作用紧密而有序的排布在金属基体-防腐蚀体系界面，而氟原子本身又具负电性，可排斥阴离子，使海水中的腐蚀性离子(主要是活性阴离子，例如Cl -)不易到达金属基体-防腐蚀体系界面；配合含氟压电材料所产生的响应电流，可扰乱腐蚀性离子的传输过程，以达到阻止腐蚀性离子的目的。
本发明另一些实施例提供的防腐蚀体系，将具有防腐蚀性、压电性的压电材料作为第一功能层应用于防腐蚀体系中，并进一步在所述防腐蚀压电涂层上增设具有防腐蚀功能的第二功能层。第二功能层可以帮助更好地阻隔腐蚀性物质，避免第一功能层直接暴露于腐蚀环境中，进而延长第一功能层的使用寿命。
2、本发明实施例还提供上述防腐蚀体系的应用：当防腐蚀体系的应用环境处于海洋领域时，所述被保护基体为金属基体，通常是舰船、采油平台等金属工程设备。而所述第一功能层覆盖的区域一般是有可能被应用环境中腐蚀性物质接触的区域，第一功能层可以全面覆盖这些区域，也可以选择性覆盖，具体的覆盖范围需要根据实际需求和要求进行选择，故不便对此在本发明进行限制。
海洋环境中的压力作用包括但不限于海浪拍击所述防腐蚀体系带来的压力作用、潮汐作用给所述防腐蚀体系带来的压力作用。
其中，第一功能层受到压力作用时，能产生动态响应电流进而扰乱腐蚀性离子在涂层内部的传输过程，显著减缓腐蚀性离子在防腐蚀体系中的渗透作用。因此防腐蚀体系能主动调控腐蚀性离子在防腐蚀体系内部的传输过程。
3、本发明的实施方案还提供了一种防腐蚀涂料，该防腐蚀涂料包含有含氟压电材料、成核剂以及溶剂。
在一些优选的实施例中，所述含氟压电材料与所述成核剂的质量比为10:1-200:1。
所述含氟压电材料可以是本身含氟的压电材料，也可以是含氟材料与压电材料的混合。
其中，本身含氟的压电材料可以是含氟压电树脂材料，例如：聚偏二氟乙烯、偏氟乙烯-三氟乙烯共聚物、偏二氟乙烯-三氟氯乙烯共聚物、偏二氟乙烯-六氟丙烯共聚物和偏氟乙烯-三氟乙烯-氯氟乙烯三元共聚物中的至少一种。
所述成核剂可以选自碳纳米管、氧化石墨烯、二氧化硅纳米颗粒、钛酸钡纳米颗粒、碳酸钙纳米颗粒和云母纳米颗粒中的至少一种。
所述溶剂用于溶解其他材料，也便于使防腐蚀涂料形成涂层，在实际使用过程中一般会被干燥去除或在自然状态下缓慢挥发掉。溶剂包括但不限于二氯甲烷、三氯甲烷、正己烷、丁内酯、乙醚、乙酸乙酯、四氢呋喃、二甲基亚砜、 N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、1,3-二氧杂环戊烷、甲苯和二甲苯中的一种或多种。
本发明实施例提供的防腐蚀涂料，在干燥形成涂层后，即为前述防腐蚀体系中的第一功能层。
4、本发明的实施例还提供了一种上述的防腐蚀体系的制备方法，包括将用于形成第一功能层的材料按照选定的比例配制形成第一前驱体溶液；然后，将所述第一前驱体溶液涂布于被保护基体上，干燥后形成所述第一功能层，获得包含有所述第一功能层的防腐蚀体系。
在一些优选的实施例中，第一功能层为涂层。涂层形成的步骤一般包括：将涂层原料制成特定的形式，例如，将固态的涂层原料溶于溶剂，溶解并混合后形成液态的涂层原料，然后采用涂布工艺形成涂层。
本发明实施例中涉及的混合操作可以是机械搅拌或磁力搅拌，混合时涂层原料的温度为20-90℃，混合的时间为0.5-10h。
常用的涂布工艺有喷漆枪涂布法、线棒涂布法、毛刷涂布法及滚涂等，本发明的实施例中对此不做特别限制。
在一些优选的实施例中，所述第一功能层为含氟压电材料涂层。
在一些优选的实施例中，所述含氟压电材料涂层为含氟压电树脂涂层。所述含氟压电树脂涂层包括但不限于聚偏二氟乙烯涂层、偏氟乙烯-三氟乙烯共聚物涂层、偏二氟乙烯-三氟氯乙烯共聚物涂层、偏二氟乙烯-六氟丙烯共聚物涂层和偏氟乙烯-三氟乙烯-氯氟乙烯三元共聚物涂层。
其中，含氟压电树脂涂层的制备方法具体包括：将含氟压电树脂溶于溶剂中，混合后得到含氟压电树脂前驱体溶液；然后将含氟压电树脂前驱体溶液涂覆在被保护基体表面，干燥后形成含氟压电树脂涂层。(此处的含氟压电树脂前驱体溶液即可看作是前述的防腐蚀涂料)
其中，干燥可以是室温下进行干燥，也可以是温度为25-60℃的鼓风干燥箱进行干燥，干燥时间为2-24h，用于除去溶剂。
其中，溶剂包括但不限于二氯甲烷、三氯甲烷、正己烷、丁内酯、乙醚、乙酸乙酯、四氢呋喃、二甲基亚砜、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、1,3-二氧杂环戊烷、甲苯和二甲苯中的一种或多种。
在一些优选的实施例中，所述含氟压电树脂前驱体溶液中还包括成核剂。
其中，成核剂包括但不限于碳纳米管(CNT)、氧化石墨烯(GO)、二氧化硅(SiO 2)钛酸钡(BaTiO 3)、碳酸钙(CaCO 3)、云母等纳米颗粒中的一种或多种。
其中，成核剂加入的目的是提升含氟压电树脂的压电性能，如作为聚偏二氟乙烯中极性晶型(β相)的结晶核，促进并诱导晶相转换，生成更多的β相结晶进而提升聚偏二氟乙烯树脂的压电性能。而对于本身压电性能较好的含氟压电树脂如偏氟乙烯-三氟乙烯共聚物等，成核剂用量可适当减少或不进行添加。
在一些优选的实施例中，含氟压电树脂与溶剂以及成核剂的质量比的范围为(5-20):(30-90):(0.1-20)。
在一些优选的实施例中，所述制备方法还包括：将用于形成第二功能层的材料按照选定的比例配制形成第二前驱体溶液；然后，将所述第二前驱体溶液涂布于所述第一功能层之上，固化后在所述第一功能层上形成所述第二功能层，获得包含有所述第一功能层和所述第二功能层的防腐蚀体系。
在一些优选的实施例中，第二功能层为涂层。涂层形成的步骤一般包括：将涂层原料制成特定的形式，例如，将固态的涂层原料溶于溶剂，溶解并混合后形成液态的涂层原料，然后采用涂布工艺形成涂层。第二功能层的作用是为了更好地阻隔腐蚀性物质，避免第一功能层直接暴露于腐蚀环境中，进而延长第一功能层的使用寿命，具有防腐蚀功能的涂层材料种类繁多，不便在此一一列举。
在一些优选的实施例中，第二功能层为环氧树脂涂层。
其中，环氧树脂涂层的制备方法具体包括：将环氧树脂与固化剂混合，得到环氧树脂前驱体溶液；然后将环氧树脂前驱体溶液涂覆在第一功能层之上，干燥固化后形成环氧树脂涂层。
优选地，干燥固化时的温度25-120℃，干燥固化时间为6-48h。
优选地，环氧树脂的环氧当量为50-350g/eq；固化剂的作用在于增进或控制环氧树脂的固化反应，其种类繁多，不便在此一一列举。例如，可以采用胺 类固化剂，常用的胺类固化剂包括但不限于乙二胺、己二胺、二乙烯三胺、三乙烯四胺、二乙氨基丙胺、间苯二胺、聚醚胺中的一种或多种。
其中，固化剂与环氧树脂的质量之比的范围为1:(1-10)，进一步优选的范围为1:(1-4)。
在一些优选的实施例中，环氧树脂前驱体溶液中还包括助剂，用于减少或抑制气泡缺陷、提升涂层表面的流平性。该助剂包括消泡剂和/或流平剂。
其中，消泡剂包括但不限于长链醇型消泡剂、聚醚型消泡剂、有机硅型消泡剂、聚醚改性有机硅型消泡剂；流平剂包括但不限于聚二甲基硅氧烷、聚醚聚酯改性有机硅氧烷、烷基改性有机硅氧烷。
其中，固化剂、环氧树脂以及助剂的质量之比的范围为1:(1-10):(0.1-1)；助剂中消泡剂与流平剂的质量之比是任意的。
如上所述的防腐蚀体系的制备方法，其制备工艺简单，成本低廉，制备得到的防腐蚀体系能够调控腐蚀性离子在防腐蚀体系内部的传输过程，显著减缓腐蚀性离子的渗透作用。本发明实施例提供的防腐蚀体系能主动调控腐蚀性离子在防腐蚀体系内部的传输过程。
以下将结合具体的实施例来说明本发明的上述及其制备方法，本领域技术人员所理解的是，下述实施例仅是本发明上述防腐蚀体系及其制备方法的具体典型示例，而不用于限制其全部。
在本发明的实施例中，第一功能层简称为“A涂层”；第二功能层简称为“B涂层”。
本发明实施例的耐酸碱性测试是根据《GB1763-79漆膜耐化学试剂性测定法》，将各实施例和对比例中前驱体溶液成膜后分别浸泡在5wt％硫酸水溶液中30天、浸泡在5wt％氢氧化钠水溶液中30天，观察涂层和被保护的金属材料表面是否出现生锈、气泡、裂痕、脱落等现象。
本发明实施例的耐盐水性测试是根据《GB1763-79漆膜耐化学试剂性测定法》，将各实施例和对比例中前驱体溶液成膜后，将试板的2/3面积浸入3wt％氯化钠水溶液中，按产品规定时间取出并检查观察膜层和被涂覆的金属材料表面是否出现生锈、气泡、裂痕、脱落等现象。
本发明实施例的耐水性测试是根据《GB/T1733-93漆膜耐水性测定法》，将各实施例和对比例中前驱体溶液成膜后，在23±2℃的水中浸泡45天，观察膜层和被涂覆的金属材料表面是否出现生锈、气泡、裂痕、脱落等现象。
实施例一
按质量计算，称取10份聚偏二氟乙烯压电树脂，然后加入90份二甲基亚砜溶剂，在60℃加热条件下搅拌2h至混合均匀。然后停止加热，加入二氧化硅成核剂0.5份，继续搅拌1h，得到A前驱体溶液。
取Q235碳钢基体，先分别经200目、400目、800目、1000目、1500目砂纸逐级打磨，然后分别在乙醇、丙酮中进行30min的超声洗涤，用氮气将基体表面吹干。
采用刷涂法将制备好的A前驱体溶液均匀涂在金属表面，然后放置在50℃的鼓风干燥箱中2h除去溶剂，制备形成了A涂层，测得膜厚为7.01μm。
按质量计算，称取50份双酚A二缩水甘油醚，20份聚醚胺D230，常温下搅拌均匀，然后加入1份聚醚改性聚硅氧烷消泡剂，0.5份聚丙烯酸含氟酯流平剂，继续搅拌至均匀。然后置于真空干燥箱中除泡10min，得到B前驱体溶液。
采用线棒涂布法将B前驱体溶液均匀涂在A涂层之上，然后将其放在鼓风干燥箱中100℃条件下固化6h，制备形成了B涂层，厚度为34.24μm。
本实施例制备获得的防腐蚀体系包括：Q235碳钢基体，涂覆于Q235碳钢基体上的A涂层，以及涂覆于A涂层上的B涂层，A涂层与B涂层的厚度分别为7.01μm和34.24μm。
对上述防腐蚀体系进行海洋环境腐蚀的模拟测试：将防腐蚀体系静置浸泡在3.5wt％氯化钠的水溶液中，在固定间隔时间(1、3、5、7、10、15天)取出样品并进行各项电化学性能测试。
实施例二
本实施例的防腐蚀体系及其制备方法与实施例一的相同，但模拟测试方法不同，不同之处在于：将样品固定在充满3.5wt％氯化钠水溶液的容器中，将容器放置在往复式振荡器上反复震荡，以此模拟真实海洋环境中的海浪对金属基体的拍打等压力作用。
对比例一
本实施例的制备方法与实施例一中B涂层的制备方法相同，仅在Q235碳钢基体上形成厚度为40μm的单一环氧树脂涂层。
本实施例制备获得的防腐蚀体系包括：Q235碳钢基体，涂覆于Q235碳钢基体上的B涂层。
对上述防腐蚀体系进行与实施例一相同的海洋环境腐蚀的模拟测试。
对比例二
本实施例的制备方法与对比例一的相同，海洋环境腐蚀的模拟测试方法与实施例二相同。
测试结果分析
将上述实施例一、实施例二、对比例一和对比例二中经模拟测试的4个防腐蚀体系进行电化学性能和耐腐蚀性能测试。
图1分别为上述4个防腐蚀体系的15天模拟测试的动电位极化曲线谱图。
在动电位极化曲线谱图中，通常腐蚀电流I corr越低、腐蚀电位E corr越高代表涂层对金属基体的防腐蚀效果越好。从图中可以看出，经过15天的模拟测试，实施例一、实施例二的各项电化学数据表现比两个对比例好，而对比例一、对比例二均显示出较差的耐腐蚀性能，其中对比例二的腐蚀电流I corr、腐蚀电位E corr、腐蚀速率CR分别为1.94×10 -9A·cm -2、-246mV、2.25×10 -5mm·year -1；与实施例一比较，实施例二的I corr减小、E corr增大、CR减小，分别达到了7.85×10 -10A·cm -2、-189mV、9.13×10 -6mm·year -1，说明防腐蚀体系在模拟海浪拍击环境下的防腐蚀性能比静置浸泡情况下的表现更好，外力作用所产生的动态响应电流有效地扰乱了腐蚀性离子对防腐蚀体系的渗透，显著提升了防腐蚀体系的耐腐蚀性能。
图2-1～图2-4依次为实施例一、实施例二、对比例一、对比例二各自的防腐蚀体系的15天模拟测试的奈奎斯特谱图。
从图中可以看出，四个防腐蚀体系的阻抗弧半径均随模拟测试时间的增长而逐渐减小，即防腐蚀性能逐渐降低。在开始进行模拟测试时，四个防腐蚀体系状态完好，均显示出最大的阻抗弧；在模拟测试的第五天，除了实施例二外， 其他三个防腐蚀体系的阻抗弧半径发生了大幅减小，说明腐蚀性离子开始渗透进防腐蚀体系的涂层并在涂层内扩散，防腐蚀性能开始受到影响。而纵观整个模拟测试过程，实施例二的防腐蚀体系仅略受影响，阻抗弧半径缓慢随时间减小，表现出对腐蚀性离子的良好阻隔功能。
图3-1～图3-4依次为实施例一、实施例二、对比例一、对比例二各自的防腐蚀体系的15天模拟测试的电化学阻抗谱图，其中，时间轴的单位为：天。
在电化学阻抗谱中，通常以0.01Hz处的阻抗值来评价涂层的防腐蚀性能。可以看到，在开始进行测试时，四个防腐蚀体系的阻抗值相差不大；在整个模拟测试过程中，四个防腐蚀体系在0.01Hz处的阻抗均有逐渐降低的现象，说明防腐蚀性能呈降低趋势。在测试初期(1-5天)，四个防腐蚀体系的阻抗值下降相对平稳；在测试后期(7-15天)，由于腐蚀性离子的渗透，实施例一和两个对比例的阻抗值降低有加快趋势，而实施例二的阻抗值仍相对比较稳定，并在测试周期结束后显示出最高的阻抗值，达到3.172.42×10 8Ωcm -1，表明实施例二的防腐蚀体系具有优异的防腐蚀性能。
将各实施例及对比例的电化学数据及耐腐蚀性能数据列入表1，其中，I corr、E corr、CR、Z 0.01Hz分别代表腐蚀电流、腐蚀电位、腐蚀速率以及0.01Hz处的阻抗值，“+”表示没有观察到起泡、开裂、生锈、脱落等现象。
表1各实施例及对比例的电化学数据及耐腐蚀性能数据
Figure PCTCN2020098227-appb-000001
经过15天的浸泡/震荡测试发现：(1)实施例二的防腐蚀体系在震荡条件下表现出最低的腐蚀电流I corr与腐蚀速率CR以及最高的腐蚀电位E corr；(2)包含含氟压电树脂涂层的防腐蚀体系的腐蚀速率CR均低于不包含含氟压电树脂涂层的防腐蚀体系；(3)实施例一和实施例二的结果说明，包含含氟压电树脂涂层的防腐蚀体系即使在静置浸泡情况下也具有优异防腐蚀性能。
通过长期的耐酸碱、盐水、水测试后，包含含氟压电树脂涂层的防腐蚀体系没有出现开裂、起泡、脱落等现象；不包含含氟压电树脂涂层的防腐蚀体系耐酸性较差。
从上述测试数据谱图可以看出，本发明实施例一和实施例二中的防腐蚀体系的动电位极化曲线和交流电化学阻抗测试均显示出更优异的防腐蚀效果；双层的防腐蚀体系(即实施例二的防腐蚀体系)在模拟海浪拍击环境下的防腐蚀性能比静置浸泡情况(即实施例一的模拟测试条件)下的表现更好，而对比例一和对比例二中的防腐蚀体系是单一的环氧树脂涂层，它们不论在静置还是震荡环境下防腐蚀性能均劣化很快。
实施例三
按质量计算，称取20份压电树脂：偏氟乙烯-三氟乙烯共聚物，加入80份溶剂：1,3-二氧杂环戊烷，在45℃加热条件下搅拌1h至混合均匀。然后停止加热，加入0.1份氧化石墨烯，继续搅拌1h，得到A前驱体溶液。
取不锈钢基体，先分别经200目、400目、800目、1000目、1500目、2000目砂纸逐级打磨，然后用氧化铝及碳化硅微粉磨料进行抛光处理，用乙醇反复清洗后在丙酮中进行30min超声洗涤，随后用氩气将不锈钢基体表面吹干，密封保存。
采用喷涂法将制备好的A前驱体溶液均匀喷在不锈钢基体的表面，然后放置在70℃的鼓风干燥箱中30min除去溶剂，制备形成了A涂层。
称取65份邻苯二甲酸二缩水甘油酯，30份偏苯三酸酐，常温下搅拌均匀，然后加入异辛醇消泡剂1份，聚乙烯醇缩丁醛流平剂1份，继续搅拌至均匀；然后放置于真空干燥箱中除泡20min，得到B前驱体溶液。
采用线棒涂布法将B前驱体溶液均匀涂在A涂层之上，将试样放在鼓风干燥箱中130℃固化6h，制备形成了B涂层。
本实施例制备获得的防腐蚀体系包括：不锈钢基体，涂覆于不锈钢基体上的A涂层，以及涂覆于A涂层上的B涂层，A涂层与B涂层的厚度分别为15.30μm和32.43μm。
实施例四
按质量计算，称取15份偏二氟乙烯-三氟氯乙烯共聚物压电树脂，然后加入85份N,N-二甲基乙酰胺溶剂，在70℃加热条件下搅拌2h至混合均匀。然后停止加热，加入氧化石墨烯成核剂1份，继续搅拌1h，得到A前驱体溶液。
取Q195碳钢基体，先分别经200目、400目、800目、1000目、1500目砂纸逐级打磨，然后分别在乙醇、丙酮中进行30min的超声洗涤，用氮气将基体表面吹干，置入真空箱中待用。
采用刷涂法将制备好的A前驱体溶液均匀涂在金属表面，然后放置在50℃的鼓风干燥箱中2h除去溶剂，制备形成了A涂层，测得膜厚为13.66μm。
按质量计算，称取90份E-51型树脂，10份二乙烯三胺固化剂，常温下搅拌均匀，然后加入0.5份二甲基硅油消泡剂，0.5份醋丁纤维素流平剂，继续搅拌至均匀。然后置于真空干燥箱中除泡15min，得到B前驱体溶液。
采用线棒涂布法将B前驱体溶液均匀涂在A涂层之上，然后将其放在鼓风干燥箱中50℃条件下固化6h，制备形成了B涂层，厚度为51.53μm。
本实施例制备获得的防腐蚀体系包括：Q195碳钢基体，涂覆于Q195碳钢基体上的A涂层，以及涂覆于A涂层上的B涂层，A涂层与B涂层的厚度分别为13.66μm和51.53μm。
实施例五
按质量计算，称取25份偏二氟乙烯-六氟丙烯共聚物压电树脂，然后加入75份N,N-二甲基甲酰胺溶剂，在70℃加热条件下搅拌1h至混合均匀。然后停止加热，加入碳纳米管成核剂0.5份，继续搅拌1h，得到A前驱体溶液。
取Q195碳钢基体，先分别经200目、400目、800目、1000目、1500目砂纸逐级打磨，然后分别在乙醇、丙酮中进行30min的超声洗涤，用氮气将基体表面吹干，置入真空箱中待用。
采用刷涂法将制备好的A前驱体溶液均匀涂在金属表面，然后放置在50℃的鼓风干燥箱中2h除去溶剂，制备形成了A涂层，测得膜厚为5.45μm。
按质量计算，称取80份E-44型树脂，20份二乙氨基丙胺固化剂，常温下搅拌均匀，然后加入0.5份矿物油消泡剂，1份异佛尔酮流平剂，继续搅拌至均匀。然后置于真空干燥箱中除泡15min，得到B前驱体溶液。
采用线棒涂布法将B前驱体溶液均匀涂在A涂层之上，然后将其放在鼓风干燥箱中50℃条件下固化6h，制备形成了B涂层，厚度为21.61μm。
本实施例制备获得的防腐蚀体系包括：Q195碳钢基体，涂覆于Q195碳钢基体上的A涂层，以及涂覆于A涂层上的B涂层，A涂层与B涂层的厚度分别为5.45μm和21.61μm。
实施例六
按质量计算，称取10份偏氟乙烯-三氟乙烯-氯氟乙烯三元共聚物压电树脂，然后加入90份N-甲基吡咯烷酮溶剂，在75℃加热条件下搅拌1h至混合均匀。然后停止加热，加入二氧化硅纳米粒0.1份，继续搅拌1h，得到A前驱体溶液。
取Q215碳钢基体，先分别经200目、400目、800目、1000目、1500目、2000目砂纸逐级打磨，然后用氧化铝及碳化硅微粉磨料进行抛光处理，用乙醇反复清洗后在丙酮中进行30min超声洗涤，随后用氩气将不锈钢基体表面吹干，置入真空箱中待用。
采用喷涂法将制备好的A前驱体溶液均匀喷涂在金属表面，然后放置在60℃的鼓风干燥箱中2h除去溶剂，制备形成了A涂层，测得膜厚为3.74μm。
按质量计算，称取75份双(2,3-环氧基环戊基)醚树脂，25份甲基环己烯四酸二酐固化剂，常温下搅拌均匀，然后加入1份异聚丙烯酸酯流平剂，继续搅拌至均匀。然后置于真空干燥箱中除泡25min，得到B前驱体溶液。
采用线棒涂布法将B前驱体溶液均匀涂在A涂层之上，然后将其放在鼓风干燥箱中50℃条件下固化6h，制备形成了B涂层，厚度为13.11μm。
本实施例制备获得的防腐蚀体系包括：Q215碳钢基体，涂覆于Q215碳钢基体上的A涂层，以及涂覆于A涂层上的B涂层，A涂层与B涂层的厚度分别为3.74μm和13.11μm。
将实施例四～实施例六防腐蚀体系的耐腐蚀性能数据列入表2，其中，“+”表示没有观察到起泡、开裂、生锈、脱落等现象。
表2实施例四～实施例六的耐腐蚀性能数据
Figure PCTCN2020098227-appb-000002
通过长期的耐酸碱、盐水、水测试后，上述包含含氟压电树脂涂层的防腐蚀体系均没有出现开裂、起泡、脱落等现象。
通过上述实施例可以得知，本发明实施例提供的防腐蚀体系，将具有防腐蚀性、压电性的含氟压电树脂材料作为A涂层应用于防腐蚀体系中，当受到压力作用时，A涂层能产生动态响应电流进而扰乱腐蚀性离子在防腐蚀体系内部的传输过程，显著减缓腐蚀性离子在防腐蚀体系中的渗透作用，达到了主动调控腐蚀性离子在防腐蚀体系内部的传输过程的效果。
虽然已经参照特定实施例示出并描述了本发明，但是本领域的技术人员将理解：在不脱离由权利要求及其等同物限定的本发明的精神和范围的情况下，可在此进行形式和细节上的各种变化。

Claims (20)

  1. 一种防腐蚀体系，其中，包括包覆于被保护基体上的第一功能层，所述第一功能层中包含有含氟压电材料，所述第一功能层在受力条件下能够产生动态响应电流以阻碍腐蚀性离子传输至所述被保护基体。
  2. 根据权利要求1所述的防腐蚀体系，其中，用于形成所述第一功能层的材料包含有含氟压电材料、成核剂以及溶剂。
  3. 根据权利要求2所述的防腐蚀体系，其中，其中，所述含氟压电材料与所述成核剂的质量比为10:1-200:1。
  4. 根据权利要求2所述的防腐蚀体系，其中，所述含氟压电材料为含氟压电树脂。
  5. 根据权利要求4所述的防腐蚀体系，其中，所述含氟压电树脂选择聚偏二氟乙烯、偏氟乙烯-三氟乙烯共聚物、偏二氟乙烯-三氟氯乙烯共聚物、偏二氟乙烯-六氟丙烯共聚物和偏氟乙烯-三氟乙烯-氯氟乙烯三元共聚物中的至少一种；所述成核剂选自碳纳米管、氧化石墨烯、二氧化硅纳米颗粒、钛酸钡纳米颗粒、碳酸钙纳米颗粒和云母纳米颗粒中的至少一种。
  6. 根据权利要求2所述的防腐蚀体系，其中，所述防腐蚀体系还包括形成在所述第一功能层之上的至少一个第二功能层，所述第二功能层为防腐蚀涂层。
  7. 根据权利要求6所述的防腐蚀体系，其中，用于形成所述第二功能层的材料包含有环氧树脂、助剂和固化剂。
  8. 根据权利要求7所述的防腐蚀体系，其中，用于形成所述第二功能层的材料，所述固化剂、所述环氧树脂以及所述助剂之间的质量之比的范围为1:(1-10):(0.1-1)。
  9. 一种防腐蚀体系的制备方法，其中，包括：
    将用于形成第一功能层的材料按照选定的比例配制形成第一前驱体溶液；
    将所述第一前驱体溶液涂布于被保护基体上，干燥后形成所述第一功能层，获得包含有所述第一功能层的防腐蚀体系；
    其中，所述用于形成第一功能层的材料包含有含氟压电材料，所述第一功能层在受力条件下能够产生动态响应电流以阻碍腐蚀性离子传输至所述被保护基体。
  10. 根据权利要求9所述的防腐蚀体系的制备方法，其中，所述用于形成所述第一功能层的材料包含有含氟压电材料、成核剂以及溶剂。
  11. 根据权利要求10所述的防腐蚀体系的制备方法，其中，其中，所述含氟压电材料与所述成核剂的质量比为10:1-200:1。
  12. 根据权利要求10所述的防腐蚀体系的制备方法，其中，所述含氟压电材料为含氟压电树脂。
  13. 根据权利要求12所述的防腐蚀体系的制备方法，其中，所述含氟压电树脂选择聚偏二氟乙烯、偏氟乙烯-三氟乙烯共聚物、偏二氟乙烯-三氟氯乙烯共聚物、偏二氟乙烯-六氟丙烯共聚物和偏氟乙烯-三氟乙烯-氯氟乙烯三元共聚物中的至少一种；所述成核剂选自碳纳米管、氧化石墨烯、二氧化硅纳米颗粒、钛酸钡纳米颗粒、碳酸钙纳米颗粒和云母纳米颗粒中的至少一种。
  14. 根据权利要求9所述的防腐蚀体系的制备方法，其中，所述制备方法还包括：在所述第一功能层制备形成第二功能层，所述第二功能层为防腐蚀涂层；所述在所述第一功能层制备形成第二功能层具体包括：
    将用于形成第二功能层的材料按照选定的比例配制形成第二前驱体溶液；
    将所述第二前驱体溶液涂布于所述第一功能层之上，固化后在所述第一功能层上形成所述第二功能层，获得包含有所述第一功能层和所述第二功能层的防腐蚀体系。
  15. 根据权利要求14所述的防腐蚀体系的制备方法，其中，所述用于形成所述第二功能层的材料包含有环氧树脂、助剂和固化剂。
  16. 根据权利要求15所述的防腐蚀体系的制备方法，其中，用于形成所述第二功能层的材料，所述固化剂、所述环氧树脂以及所述助剂之间的质量之比的范围为1:(1-10):(0.1-1)。
  17. 一种防腐蚀涂料，其中，所述防腐蚀涂料包含有含氟压电材料、成核剂以及溶剂。
  18. 根据权利要求17所述的防腐蚀涂料，其中，所述含氟压电材料与所述成核剂的质量比为10:1-200:1。
  19. 根据权利要求17所述的防腐蚀涂料，其中，所述含氟压电材料为含氟压电树脂。
  20. 根据权利要求19所述的防腐蚀涂料，其中，所述含氟压电树脂选择聚偏二氟乙烯、偏氟乙烯-三氟乙烯共聚物、偏二氟乙烯-三氟氯乙烯共聚物、偏二氟乙烯-六氟丙烯共聚物和偏氟乙烯-三氟乙烯-氯氟乙烯三元共聚物中的至少一种；所述成核剂选自碳纳米管、氧化石墨烯、二氧化硅纳米颗粒、钛酸钡纳米颗粒、碳酸钙纳米颗粒和云母纳米颗粒中的至少一种；所述溶剂选自二氯甲烷、三氯甲烷、正己烷、丁内酯、乙醚、乙酸乙酯、四氢呋喃、二甲基亚砜、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、1,3-二氧杂环戊烷、甲苯和二甲苯中的中的至少一种。
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