WO2021139227A1 - 仿生三明治防腐涂层及其制备方法与应用 - Google Patents

仿生三明治防腐涂层及其制备方法与应用 Download PDF

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WO2021139227A1
WO2021139227A1 PCT/CN2020/117977 CN2020117977W WO2021139227A1 WO 2021139227 A1 WO2021139227 A1 WO 2021139227A1 CN 2020117977 W CN2020117977 W CN 2020117977W WO 2021139227 A1 WO2021139227 A1 WO 2021139227A1
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dopamine
water
graphene
substrate
preparation
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PCT/CN2020/117977
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English (en)
French (fr)
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王立平
朱小波
刘栓
卢光明
赵海超
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中国科学院宁波材料技术与工程研究所
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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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
    • C09D5/4419—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications with polymers obtained otherwise than by polymerisation reactions only involving carbon-to-carbon unsaturated bonds
    • C09D5/443—Polyepoxides
    • C09D5/4457—Polyepoxides containing special additives, e.g. pigments, polymeric particles
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
    • C09D5/4407—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications with polymers obtained by polymerisation reactions involving only carbon-to-carbon unsaturated bonds
    • C09D5/4411—Homopolymers or copolymers of acrylates or methacrylates
    • 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
    • C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
    • C09D5/4419—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications with polymers obtained otherwise than by polymerisation reactions only involving carbon-to-carbon unsaturated bonds
    • C09D5/4465—Polyurethanes
    • 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
    • C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
    • C09D5/4419—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications with polymers obtained otherwise than by polymerisation reactions only involving carbon-to-carbon unsaturated bonds
    • C09D5/4469—Phenoplasts; Aminoplasts
    • 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
    • C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
    • C09D5/448—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications characterised by the additives used
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires

Definitions

  • the application relates to an anticorrosive coating, in particular to a biomimetic sandwich anticorrosive coating inspired by natural nacre and mussels, and a preparation method and application thereof, belonging to the technical field of anticorrosive coatings.
  • organic protective coatings are one of the most widely used and cost-effective anti-corrosion measures.
  • the water-based cathodic electrophoretic emulsion is a coating with water as the solvent, which is not only environmentally friendly (meeting the requirements of low volatile organic compound emissions), but also has ideal adhesion, and is widely used in mainstream automotive and marine coatings.
  • corrosive media H 2 O, O 2 and Cl - etc.
  • Sheet-shaped nano-fillers with high aspect ratio and capable of inhibiting the penetration and diffusion of corrosive substances, such as graphene, can effectively solve the above problems.
  • Graphene's stable SP 2 hybrid structure makes it form a physical barrier between the metal and the corrosive medium to prevent the diffusion and penetration of the medium. It is considered the thinnest known anti-corrosion layer (0.34nm).
  • graphene can effectively extend the diffusion path of corrosive media, has excellent barrier properties and good chemical stability and oxidation resistance.
  • the new heavy-duty anti-corrosion coating system modified by two-dimensional sheet materials the directional arrangement and optimization of two-dimensional sheet materials in polymer resins have always been the core technologies in this field that urgently need to be broken.
  • the main purpose of this application is to provide a bionic sandwich anticorrosive coating and a preparation method thereof to overcome the deficiencies in the prior art.
  • Another object of the present application is to provide the application of the biomimetic sandwich anticorrosive coating.
  • the embodiment of the present application provides a bionic sandwich anticorrosive coating, which includes at least two water-based resin layers covering the surface of a substrate, wherein at least one graphene barrier layer is distributed between two adjacent water-based resin layers.
  • the graphene barrier layer includes a dopamine-functionalized graphene material having a sheet structure, and the dopamine-functionalized graphene material is arranged in a manner parallel to the surface of the substrate.
  • a plurality of dopamine-functionalized graphene materials in the graphene barrier layer are arranged in parallel to form a dense structure.
  • the dopamine-functionalized graphene material is obtained by modifying graphene oxide with dopamine.
  • the embodiment of the application also provides a preparation method of the bionic sandwich anticorrosive coating, which includes:
  • the graphene oxide is modified with dopamine to obtain dopamine-functionalized graphene materials
  • Electrodeposition is used to deposit the dopamine-functionalized graphene material and water-based resin alternately on the surface of the substrate to form multiple water-based resin layers, and at least one graphene barrier layer is distributed between two adjacent water-based resin layers. And the dopamine-functionalized graphene material in the graphene barrier layer is arranged in a manner parallel to the surface of the substrate to form a dense structure, thereby obtaining a composite coating;
  • the composite coating is cured to obtain the bionic sandwich anticorrosive coating.
  • the process conditions used in the electrophoretic deposition technique include: a deposition voltage of 10 to 220V, and a deposition time of 1 to 30 minutes.
  • the process conditions adopted by the cyclic voltammetry include: the number of cycles is 1-10 times, the scanning range is 0.1-1.1V, and the scanning rate is 5-50mV/s.
  • the embodiments of the present application also provide the biomimetic sandwich anticorrosive coating prepared by the foregoing method.
  • the embodiments of the present application also provide the application of the aforementioned bionic sandwich anticorrosive coating in the field of metal anticorrosion.
  • the dopamine provided in this application can act as a binder to improve the interface compatibility and adhesion between epoxy resin and graphene;
  • the dopamine-functionalized graphene material provided by this application can be arranged parallel to the substrate between two epoxy coatings due to hydrogen bonding and electrostatic interaction;
  • the lamellar structure of the dopamine-functionalized graphene material provided by this application can form a barrier layer in the anti-corrosion coating, effectively blocking the penetration of corrosive media such as water, oxygen, and chloride ions, and fully exerting the physical isolation effect of graphene and approaching Barrier limit
  • the uniform dispersion of the dopamine-functionalized graphene material provided in the application in the anticorrosive coating can significantly extend the diffusion path of the corrosive medium
  • bionic sandwich water-based anticorrosive coating does not contain organic solvents, does not cause organic volatile emissions, and is green and environmentally friendly;
  • the electrophoretic deposition technique is simple, low cost, low energy consumption, low pollution, and has a wide range of application prospects.
  • Fig. 1a is a schematic diagram of the barrier effect of a biomimetic sandwich anticorrosive coating on water in a typical embodiment of the present application;
  • Figure 1b is a cross-sectional scanning view of the bionic sandwich anticorrosive coating described in Example 1 of the present application;
  • Figure 1c is a partial cross-sectional scanning enlarged view of the graphene layer in the biomimetic sandwich anticorrosive coating described in Example 1 of the present application;
  • Figures 2a and 2b are optical photographs of the water-based epoxy anticorrosive coating prepared in Comparative Example 1 and Example 1 of the present application after undergoing salt spray tests at different times;
  • the inventor of this case has been able to propose the technical solution of the application after long-term research and extensive practice, aiming to provide a bionic sandwich anticorrosive coating inspired by natural nacre and mussels and a preparation method thereof. It mainly includes the steps of graphene modification, electrolyte configuration, substrate pretreatment, and composite coating preparation.
  • the technical solution, its implementation process and principles will be further explained as follows.
  • One aspect of the embodiments of the present application provides a biomimetic sandwich anticorrosive coating inspired by natural nacre and mussels, which includes at least two water-based resin layers covering the surface of a substrate, wherein two adjacent water-based resin layers are distributed There is at least one graphene barrier layer, the graphene barrier layer includes a dopamine-functionalized graphene material having a sheet structure, and the dopamine-functionalized graphene material is arranged in a manner parallel to the surface of the substrate.
  • the biomimetic sandwich anticorrosive coating is composed of a water-based resin layer-different layers of graphene/dopamine-water-based resin layer.
  • the mechanism of the barrier effect of the biomimetic sandwich anticorrosive coating of this application on corrosive media is: Please refer to Figure 1a. Due to hydrogen bonding and electrostatic interaction, the dopamine-functionalized graphene material is arranged parallel to the substrate. Between the two layers of water-based resin, it is beneficial to maintain the high aspect ratio of graphene and form a "labyrinth effect".
  • the intermediate layer of graphene sandwiched between the water-based resin avoids direct contact with the metal substrate and shields galvanic corrosion, which is not only effective Extend the diffusion path of corrosive media, and can give full play to the barrier effect of graphene and approach the barrier limit, effectively hinder the penetration of corrosive media such as water, oxygen, and chloride ions, and give full play to its physical isolation effect.
  • dopamine can be used as a binder to improve the interface compatibility and adhesion between graphene and water-based resin.
  • a plurality of dopamine-functionalized graphene materials in the graphene barrier layer are arranged in parallel to form a dense structure.
  • the dopamine-functionalized graphene material is prepared by modifying graphene oxide with dopamine.
  • the preparation method of the dopamine-functionalized graphene material includes: uniformly dispersing dopamine and graphene oxide in a phosphate buffer with a pH value of 6-8 and mixing them thoroughly.
  • the mass ratio of the dopamine to the graphene oxide is 1:100-5:1.
  • the graphene oxide has a diameter of 1-50 ⁇ m and a thickness of 0.5-5 nm.
  • the dopamine-functionalized graphene material is a cationic dopamine-functionalized graphene material
  • the preparation method includes: adding dopamine and graphene oxide into a phosphate buffer solution with a pH value of 6-8 Mix well to obtain a dopamine-functionalized graphene material, and then disperse the dopamine-functionalized graphene material and acetic acid with a mass ratio of 1:1 to 1:5 in a polar solvent and stir at 20-30°C for more than 1 hour.
  • a graphene material functionalized with cationic dopamine is obtained.
  • the cationic dopamine-functionalized graphene material can be stably dispersed in an aqueous resin emulsion for 60 days without precipitation due to the presence of ammonium ions (-NH 3 + -).
  • the -NH 3 + -in the cationic dopamine-functionalized graphene can adsorb electrons and corrosive anions, cut off local galvanic corrosion, and form a dense passivation layer on the surface of the steel substrate.
  • the mass ratio of the dopamine-functionalized graphene material to acetic acid is 1:1 to 1:5.
  • the polar solvent includes any one or a combination of two or more of acetone, ethanol, N,N-dimethylformamide, ethyl acetate, chloroform, etc., but is not limited thereto.
  • the thickness of the graphene barrier layer is 1 to 5 ⁇ m.
  • the thickness of the water-based resin layer is 2-20 ⁇ m.
  • the material of the water-based resin layer includes any one or a combination of two or more of water-based cathode epoxy resin, water-based cathode acrylic resin, water-based cathode polyurethane resin, and water-based amino resin, but is not limited thereto.
  • the thickness of the bionic sandwich anticorrosive coating is 5-50 ⁇ m.
  • Another aspect of the embodiments of the present application provides a method for preparing a biomimetic sandwich anticorrosive coating including: first depositing a layer of water-based resin on the surface of the substrate using electrophoretic deposition technology; then depositing different layers of graphite by cyclic voltammetry En/dopamine; Finally, a layer of water-based resin is deposited by electrophoretic deposition technology.
  • the preparation method includes:
  • the graphene oxide is modified with dopamine to obtain dopamine-functionalized graphene materials
  • Electrodeposition is used to deposit the dopamine-functionalized graphene material and water-based resin alternately on the surface of the substrate to form multiple water-based resin layers, and at least one graphene barrier layer is distributed between two adjacent water-based resin layers. And the dopamine-functionalized graphene material in the graphene barrier layer is arranged in a manner parallel to the surface of the substrate to form a dense structure, thereby obtaining a composite coating;
  • the composite coating is cured to obtain the bionic sandwich anticorrosive coating.
  • the preparation method specifically includes: uniformly dispersing dopamine and graphene oxide in a phosphate buffer solution with a pH of 6 to 8 and mixing them thoroughly to prevent the oxidative self-polymerization of dopamine and obtain dopamine functionalization Graphene material.
  • the purpose of the phosphate buffer is to prevent the oxidative self-polymerization of dopamine.
  • the mass ratio of the dopamine to the graphene oxide is 1:100-5:1.
  • the graphene oxide has a diameter of 1-50 ⁇ m and a thickness of 0.5-5 nm.
  • the mixing temperature range is 10-70°C, and the time is 0.5-24h.
  • the dopamine-functionalized graphene material is a cationic dopamine-functionalized graphene material
  • the preparation method includes: adding dopamine and graphene oxide into a phosphate buffer solution with a pH value of 6-8 Mix well to obtain a dopamine-functionalized graphene material, and then disperse the dopamine-functionalized graphene material and acetic acid with a mass ratio of 1:1 to 1:5 in a polar solvent and stir at 20-30°C for more than 1 hour.
  • a graphene material functionalized with cationic dopamine is obtained.
  • the mass ratio of the dopamine-functionalized graphene material to acetic acid is 1:1 to 1:5.
  • the mass ratio of the dopamine-functionalized graphene material to the polar solvent is 1:10 to 1:100.
  • the polar solvent includes any one or a combination of two or more of acetone, ethanol, N,N-dimethylformamide, ethyl acetate, chloroform, etc., but is not limited thereto.
  • the preparation method specifically includes:
  • At least the anode, the substrate as the cathode and the aqueous resin emulsion as the electrolyte are used to construct an electrochemical reaction system;
  • the electrochemical reaction system is energized, and the water-based resin is deposited on the surface of the substrate by electrophoretic deposition to form a water-based resin layer.
  • the process conditions adopted by the electrophoretic deposition technique include: a deposition voltage of 10 to 220V, and a deposition time of 1 to 30 minutes.
  • the water-based resin emulsion includes any one or a combination of two or more of water-based cathode epoxy resin, water-based cathode acrylic resin, water-based cathode polyurethane resin, and water-based amino resin, but is not limited thereto.
  • the solid content of the aqueous resin emulsion is 5-50%.
  • the water-based resin layer is directly deposited on the surface of the substrate, or at least one water-based resin layer and at least one graphene barrier layer are sequentially deposited on the surface of the substrate in advance.
  • the thickness of the water-based resin layer is 2-20 ⁇ m.
  • the preparation method specifically includes:
  • a substrate with at least one water-based resin layer on the surface is used as a cathode, and an electrochemical reaction system is constructed together with an anode and an electrolyte containing dopamine-functionalized graphene materials;
  • the electrochemical reaction system is energized, and the dopamine-functionalized graphene material is deposited on the surface of the water-based resin layer by cyclic voltammetry, thereby forming the graphene barrier layer.
  • the process conditions adopted by the cyclic voltammetry include: the number of cycles is 1-10 times, the scanning range is 0.1-1.1V, and the scanning rate is 5-50mV/s.
  • the preparation method specifically includes:
  • the anode, the substrate as the cathode, and the aqueous resin emulsion as the electrolyte are used to construct an electrochemical reaction system, and then the electrochemical reaction system is energized, and the aqueous resin is deposited on the surface of the substrate by electrophoretic deposition to form Water-based resin layer;
  • a substrate with a water-based resin layer on its surface is used as a cathode, and an electrochemical reaction system is constructed together with the anode and the electrolyte containing dopamine-functionalized graphene materials, and then the electrochemical reaction system is energized, and the electrochemical reaction system is energized through cycling.
  • Anfa deposits a graphene material functionalized with dopamine on the surface of the water-based resin layer, thereby forming the graphene barrier layer;
  • the thickness of the graphene barrier layer is 1 to 5 ⁇ m.
  • the curing temperature is 60-200°C, and the time is 10-30 min.
  • the thickness of the bionic sandwich anticorrosive coating is 5-50 ⁇ m.
  • the preparation method further includes: pre-treating the substrate before performing electrophoretic deposition; wherein, the pre-processing includes: sanding the substrate with 100-2000 mesh sandpaper, followed by ultrasonic cleaning for 5-30 minutes, and then Dry treatment.
  • the preparation method of a biomimetic sandwich anticorrosive coating of the present application includes the following steps:
  • the deposition voltage is 10 ⁇ 220V
  • the deposition time is 1 ⁇ 30min
  • the number of cycles It is 1-10 times
  • the scanning range is 0.1-1.1V
  • the scanning rate is 20mv/s.
  • Another aspect of the embodiments of the present application also provides a biomimetic sandwich anticorrosive coating prepared by the foregoing method.
  • the thickness of the bionic sandwich anticorrosive coating is 5-50 ⁇ m.
  • Another aspect of the embodiments of the present application also provides the application of the aforementioned biomimetic sandwich anticorrosive coating in the field of metal anticorrosion.
  • this application prepares the biomimetic sandwich anticorrosive coating through electrophoretic deposition technology and cyclic voltammetry.
  • dopamine acts as a binder to improve the interface compatibility and adhesion between epoxy resin and graphene.
  • the dopamine-functionalized graphene material is arranged parallel to the substrate between the two water-based resin layers.
  • the intermediate layer of graphene sandwiched between the water-based resin layers avoids direct contact with the metal substrate and shields galvanic corrosion, and fully exerts the barrier effect of graphene and approaches the barrier limit, effectively blocking corrosive media such as water, oxygen, and chloride ions. Wait for penetration to give full play to its physical isolation effect.
  • the parallel arrangement of dopamine-functionalized graphene materials in the coating can significantly extend the diffusion path of corrosive media.
  • the water-based dopamine-modified graphene/resin does not contain organic solvents, does not cause organic volatile emissions, and is environmentally friendly.
  • the preparation method of the dopamine-modified graphene material provided by this application is simple.
  • the electrophoretic deposition technology adopted in this application has simple methods, low cost, low energy consumption, and low pollution, and has a wide range of application prospects.
  • a method for preparing a bionic sandwich waterborne epoxy anticorrosive coating includes the following steps:
  • Graphene modification Add dopamine and graphene oxide with a mass ratio of 1:1 into a phosphate buffer solution with a pH of 6.7 and mix uniformly.
  • the mixing temperature is 25°C and the mixing time is 10 hours.
  • Steel sheet pretreatment Grind the steel sheet with a size of 3 ⁇ 3cm 2 on 600 and 1200 grit sandpaper, ultrasonically clean it with ethanol for 20 minutes, and finally dry it with nitrogen.
  • Preparation of composite coating use a steel sheet as a cathode and a copper sheet of the same size as an anode, immersed in 100g of an aqueous epoxy emulsion with a solid content of 25%; deposit the aqueous resin on the surface of the substrate by controlling the deposition voltage and deposition time; Deposit different layers of graphene/dopamine materials on the surface of the coating by cyclic voltammetry; finally, use electrophoretic deposition technology to deposit another layer of water-based anticorrosive coating on the surface of the coating; where the deposition voltage is 30V, and the deposition time 8min; The number of cycles is 10, the scanning range is 0.1-1.1V, and the scanning rate is 20mv/s.
  • FIGs 1b-1c are cross-sectional scanning views of the bionic sandwich anticorrosive coating in this embodiment. It can be seen from Figure 1b that the graphene material is arranged between the two epoxy coatings parallel to the substrate. This is conducive to maintaining the high aspect ratio of graphene and forming a "labyrinth effect", thereby giving full play to its physical isolation effect, effectively blocking the penetration of corrosive media such as water, oxygen, and chloride ions, and significantly extending the diffusion path of corrosive media.
  • dopamine can act as a binder to improve the interface compatibility and adhesion between epoxy resin and graphene.
  • a method for preparing a bionic sandwich water-based acrylic anticorrosive coating includes the following steps:
  • Graphene modification Add dopamine and graphene oxide with a mass ratio of 1:100 into a phosphate buffer solution with a pH of 8 and mix uniformly.
  • the mixing temperature is 10°C and the mixing time is 24h.
  • Steel sheet pretreatment Grind the steel sheet with a size of 1 ⁇ 1cm 2 on 100 or 1000 grit sandpaper, ultrasonically clean it with ethanol for 5 minutes, and finally dry it with nitrogen.
  • Preparation of composite coating use a steel sheet as a cathode and a copper sheet of the same size as an anode, immerse in 100g of an aqueous acrylic emulsion with a solid content of 5%; deposit the aqueous resin on the surface of the substrate by controlling the deposition voltage and deposition time; then pass Cyclic voltammetry deposits different layers of graphene/dopamine materials on the surface of the above coating; finally, using electrophoretic deposition technology, another layer of water-based anticorrosive coating is deposited on the surface of the above coating; the deposition voltage is 10V, and the deposition time is 30min ; The number of cycles is 1, the scanning range is 0.1-1.1V, and the scanning rate is 5mv/s.
  • a preparation method of a bionic sandwich waterborne polyurethane anticorrosive coating includes the following steps:
  • Graphene modification Add dopamine and graphene oxide with a mass ratio of 5:1 into a phosphate buffer solution with a pH of 6 and mix uniformly.
  • the mixing temperature is 35°C and the mixing time is 15h.
  • steel sheet pretreatment the steel sheet with a size of 10 ⁇ 10cm 2 is polished on 200, 800, and 2000 grit sandpaper, ultrasonically cleaned with ethanol for 30 minutes, and finally dried with nitrogen.
  • Preparation of composite coating use steel sheet as cathode and copper sheet of the same size as anode, immerse in 100g waterborne polyurethane emulsion with a solid content of 50%; deposit waterborne resin on the substrate surface by controlling the deposition voltage and deposition time; then pass Cyclic voltammetry deposits different layers of graphene/dopamine materials on the surface of the above coating; finally, using electrophoretic deposition technology, another layer of water-based anticorrosive coating is deposited on the surface of the above coating; the deposition voltage is 220V, and the deposition time is 1min ; The number of cycles is 5, the scanning range is 0.1-1.1V, and the scanning rate is 50mv/s.
  • a preparation method of a bionic sandwich water-based amino anticorrosive coating includes the following steps:
  • Graphene modification Add dopamine and graphene oxide with a mass ratio of 3:1 into a phosphate buffer solution with a pH of 7 and mix uniformly.
  • the mixing temperature is 70°C and the mixing time is 0.5h.
  • Steel sheet pretreatment Grind the steel sheet with a size of 5 ⁇ 5cm 2 on 600 and 1500 grit sandpaper, ultrasonically clean it with ethanol for 15 minutes, and finally dry it with nitrogen.
  • Preparation of composite coating use a steel sheet as a cathode and a copper sheet of the same size as an anode, immerse in 100g of an aqueous amino emulsion with a solid content of 20%; deposit the aqueous resin on the substrate surface by controlling the deposition voltage and deposition time; then pass Cyclic voltammetry deposits different layers of graphene/dopamine materials on the surface of the above coating; finally, using electrophoretic deposition technology, another layer of water-based anticorrosive coating is deposited on the surface of the above coating; the deposition voltage is 100V, and the deposition time is 15min ; The number of cycles is 3, the scan range is 0.1 ⁇ 1.1V, and the scan rate is 10 mv/s.
  • Example 1 5.25 ⁇ 10 10 1.30 ⁇ 10 9
  • Example 2 2.42 ⁇ 10 9 9.54 ⁇ 10 7
  • Example 3 1.32 ⁇ 10 10 7.25 ⁇ 10 8
  • Example 4 5.21 ⁇ 10 10 4.41 ⁇ 10 9
  • a method for preparing a bionic sandwich waterborne epoxy anticorrosive coating includes the following steps:
  • Graphene modification Add dopamine and graphene oxide with a mass ratio of 2:1 into a phosphate buffer solution with a pH of 6.5 and mix uniformly. The mixing temperature is 55°C and the mixing time is 8 hours to obtain dopamine functionalized. Graphene, and then the resulting dopamine-functionalized graphene is vacuum dried at 40°C into powder.
  • Graphene ionization Disperse 0.5g of dried dopamine-reduced graphene oxide and 1.35g of acetic acid in 20mL acetone solution, stir at 28°C for 3h to obtain cationic dopamine functionalized graphene, and then vacuum dry it at 40°C. powder.
  • Steel sheet pretreatment Grind the steel sheet with a size of 3 ⁇ 3cm 2 on 600 and 1200 grit sandpaper, ultrasonically clean it with ethanol for 20 minutes, and finally dry it with nitrogen.
  • Preparation of composite coating use a steel sheet as a cathode and a copper sheet of the same size as an anode, immersed in 100g of an aqueous epoxy emulsion with a solid content of 25%; deposit the aqueous resin on the surface of the substrate by controlling the deposition voltage and deposition time; then Deposit different layers of graphene/dopamine materials on the surface of the coating by cyclic voltammetry; finally, use electrophoretic deposition technology to deposit another layer of water-based anticorrosive coating on the surface of the coating; where the deposition voltage is 50V, and the deposition time 10min; The number of cycles is 8, the scanning range is 0.1-1.1V, and the scanning rate is 30mv/s.
  • biomimetic sandwich anticorrosive coating curing the coating obtained above in a drying oven for 15 minutes, where the curing temperature is 150°C to remove the water solvent in the emulsion on the substrate surface, and the prepared anticorrosive coating has a thickness of 25 ⁇ m.
  • a method for preparing a bionic sandwich water-based acrylic anticorrosive coating includes the following steps:
  • Graphene modification Add dopamine and graphene oxide with a mass ratio of 1:1 into a phosphate buffer solution with a pH of 8 and mix uniformly. The mixing temperature is 20°C and the mixing time is 24h to obtain dopamine-functionalized Graphene, and then the resulting dopamine-functionalized graphene is vacuum dried at 40°C into powder.
  • Graphene ionization Take 0.5g of dried dopamine-reduced graphene oxide and 0.5g of acetic acid and disperse it in 12.5mL ethanol solution, stir at 20°C for 1h to obtain cationic dopamine functionalized graphene, and then vacuum dry it at 20°C Into a powder.
  • Steel sheet pretreatment Grind the steel sheet with a size of 1 ⁇ 1cm 2 on 100 or 1000 grit sandpaper, ultrasonically clean it with ethanol for 5 minutes, and finally dry it with nitrogen.
  • Preparation of composite coating use steel sheet as cathode and copper sheet of the same size as anode, immerse in 100g water-based acrylic emulsion with a solid content of 5%; deposit water-based resin on the substrate surface by controlling the deposition voltage and deposition time; then pass Cyclic voltammetry is used to deposit different layers of graphene/dopamine materials on the surface of the above coating; finally, an electrophoretic deposition technique is used to deposit another water-based anticorrosive coating on the surface of the above coating; the deposition voltage is 10V, and the deposition time is 20min ; The number of cycles is 2, the scanning range is 0.1-1.1V, and the scanning rate is 15mv/s.
  • biomimetic sandwich anticorrosive coating curing the coating obtained above in a drying oven for 20 minutes, wherein the curing temperature is 180°C to remove the water solvent in the emulsion on the substrate surface, and the prepared anticorrosive coating has a thickness of 10 ⁇ m.
  • a preparation method of a bionic sandwich waterborne polyurethane anticorrosive coating includes the following steps:
  • Graphene modification Add dopamine and graphene oxide with a mass ratio of 4:1 into a phosphate buffer solution with a pH of 6 and mix uniformly. The mixing temperature is 45°C and the mixing time is 15h to obtain dopamine functionalized. Graphene, and then the resulting dopamine-functionalized graphene is vacuum dried at 80°C into a powder.
  • Graphene ionization Take 0.5g of dried dopamine-reduced graphene oxide and 2.5g of acetic acid and disperse it in 125mL ethyl acetate solution, stir at 30°C for 5h to obtain cationic dopamine functionalized graphene, then vacuum at 80°C Dried into powder.
  • Steel sheet pretreatment The steel sheet with a size of 10 ⁇ 10cm 2 is polished on 200, 800, and 2000 grit sandpaper, then ultrasonically cleaned with ethanol for 30 minutes, and finally dried with nitrogen.
  • Preparation of composite coating use a steel sheet as a cathode and a copper sheet of the same size as an anode, immersed in 100g of an aqueous polyurethane emulsion with a solid content of 50%; deposit the aqueous resin on the surface of the substrate by controlling the deposition voltage and deposition time; then pass Cyclic voltammetry deposits different layers of graphene/dopamine materials on the surface of the above coating; finally, using electrophoretic deposition technology, another layer of water-based anticorrosive coating is deposited on the surface of the above coating; the deposition voltage is 220V, and the deposition time is 1min ; The number of cycles is 6, the scanning range is 0.1-1.1V, and the scanning rate is 40mv/s.
  • the coating obtained above was cured in a drying oven for 30 minutes, where the curing temperature was 80°C to remove the water solvent in the emulsion on the substrate surface.
  • the prepared anticorrosive coating had a thickness of 30 ⁇ m.
  • a preparation method of a bionic sandwich water-based amino anticorrosive coating includes the following steps:
  • Graphene modification Add dopamine and graphene oxide with a mass ratio of 3:1 into a phosphate buffer solution with a pH of 7 and mix uniformly. The mixing temperature is 60°C and the mixing time is 1h to obtain dopamine-functionalized Graphene, and then the resulting dopamine-functionalized graphene is vacuum dried at 40°C into powder.
  • Graphene ionization Take 0.5g of dried dopamine-reduced graphene oxide and 1g of acetic acid solution and disperse it in 50mL N,N-dimethylformamide solution, stir for 2h at 24°C to obtain cationic dopamine functionalized graphene. It was then vacuum dried at 40°C into a powder.
  • Steel sheet pretreatment Grind the steel sheet with a size of 5 ⁇ 5cm 2 on 600 and 1500 grit sandpaper, ultrasonically clean it with ethanol for 15 minutes, and finally dry it with nitrogen.
  • Preparation of composite coating use a steel sheet as the cathode and a copper sheet of the same size as the anode, and immerse it in 100g of an aqueous amino emulsion with a solid content of 20%; deposit the aqueous resin on the surface of the substrate by controlling the deposition voltage and deposition time; then pass Cyclic voltammetry deposits different layers of graphene/dopamine materials on the surface of the above coating; finally, using electrophoretic deposition technology, another layer of water-based anticorrosive coating is deposited on the surface of the above coating; the deposition voltage is 100V, and the deposition time is 15min ; The number of cycles is 5, the scanning range is 0.1-1.1V, and the scanning rate is 10mv/s.
  • biomimetic sandwich anticorrosive coating curing the coating obtained above in a drying oven for 15 minutes, wherein the curing temperature is 120°C to remove the water solvent in the emulsion on the substrate surface, and the prepared anticorrosive coating has a thickness of 20 ⁇ m.
  • An anticorrosive coating and a preparation method thereof including the following steps:
  • Steel sheet pretreatment Grind the steel sheet with a size of 3 ⁇ 3cm 2 on 600 and 1200 grit sandpaper respectively, and ultrasonically clean it with ethanol for 20 minutes, and finally dry it with nitrogen.
  • Preparation of composite coating take the steel sheet as the cathode and the copper sheet of the same size as the anode, immerse it in 100g of an aqueous epoxy emulsion with a solid content of 25%, and deposit for 10 minutes at a deposition voltage of 30V; then take it out and wash it with deionized water. Then, in 100 g of an aqueous emulsion with a solid content of 25%, deposit at 30V for 10 minutes.
  • Steel sheet pretreatment Grind the steel sheet with a size of 3 ⁇ 3cm 2 on 600 and 1200 grit sandpaper respectively, and ultrasonically clean it with ethanol for 20 minutes, and finally dry it with nitrogen.
  • Preparation of composite coating take the steel sheet as the cathode and the copper sheet of the same size as the anode, immerse it in 100g of an aqueous epoxy emulsion with a solid content of 25%, and deposit for 10 minutes at a deposition voltage of 30V; then take it out and wash it with deionized water. Then, by cyclic voltammetry, different layers of graphene/dopamine materials are deposited on the surface of the coating, the number of cycles is 10, the scanning range is 0.1-1.1V, and the scanning rate is 20mv/s.
  • the prepared coating also showed good corrosion resistance at the initial stage due to the coverage of the graphene layer. However, since no epoxy resin was added on the surface and the thickness of the coating was reduced compared with Comparative Example 1, the resistance It is lower than Comparative Example 2. However, since the coverage of the graphene layer can effectively enhance the penetration resistance of the coating and delay the penetration of corrosive media, the coating prepared in Comparative Example 2 has a lower corrosion rate than the coating prepared in Comparative Example 1, but the effect Still not as good as Example 1.
  • Figures 2a and 2b are optical photographs of the aqueous epoxy anticorrosive coatings prepared in Comparative Example 1 and Example 1 after salt spray tests at different times.
  • Figure 2a after a 120h test on the pure EP coating, the scratches are almost completely covered by rust.
  • Figure 2b After 240h of testing, the corrosion around the scratches further spread out, and corrosion spots appeared on the surface of the coating, indicating that the corrosive medium has reached the substrate, resulting in steel corrosion.
  • the corrosion of the coating became more and more serious, and bubbles appeared on the surface of the coating, indicating that the coating began to fall off and there was almost no protective effect.
  • Figure 2b for the modified coating, the surface of the coating remained intact after 480 hours of salt spray test.
  • the multilayer graphene sheet can fill the defects in a single graphene sheet, which is more conducive to the impermeability of graphene and enhances the barrier effect of the biomimetic sandwich coating, and further extends the diffusion path of corrosive substances to make The modified coating exhibits excellent anti-corrosion properties.
  • the initial low-frequency impedance modulus of the pure EP coating is 4.11 ⁇ 10 9 ⁇ cm 2
  • after 90 days of immersion it drops sharply to 6.44 ⁇ 10 6 ⁇ cm 2 , a decrease of 3 orders of magnitude.
  • This indicates that the corrosive medium has penetrated into the coated substrate through the defect, resulting in a decrease in the corrosion resistance of the coating. It can be seen from Fig.
  • the initial low-frequency impedance modulus of the graphene anticorrosive coating after dopamine functionalization is 5.25 ⁇ 10 10 ⁇ cm 2 , which is still as high as 1.30 ⁇ 10 9 ⁇ cm 2 after being immersed for 90 days.
  • This is due to the layer structure of graphene that can form a barrier layer in the coating, which effectively prevents the penetration of corrosive media such as water, oxygen, and chloride ions, and gives full play to its physical isolation effect.
  • the uniform dispersion of graphene in the coating can significantly extend the diffusion path of the corrosive medium.
  • the intermediate layer of graphene sandwiched between epoxy avoids direct contact with the metal substrate and shields galvanic corrosion.
  • this application uses steel as a substrate, after polishing and ethanol cleaning, a biomimetic sandwich anticorrosive coating is prepared by electrophoretic deposition technology and cyclic voltammetry.
  • dopamine acts as a binder to improve the interface compatibility and adhesion between epoxy resin and graphene.
  • the dopamine-functionalized graphene material is arranged parallel to the substrate between the two water-based resin layers.
  • the intermediate layer of graphene sandwiched between the water-based resin layers avoids direct contact with the metal substrate and shields galvanic corrosion, and fully exerts the barrier effect of graphene and approaches the barrier limit, effectively blocking corrosive media such as water, oxygen, and chloride ions.
  • the parallel arrangement of dopamine-functionalized graphene materials in the coating can significantly extend the diffusion path of corrosive media.
  • the water-based dopamine-modified graphene/resin does not contain organic solvents, does not cause organic volatile emissions, and is environmentally friendly.
  • the preparation method of the dopamine-modified graphene material provided in this application is simple.
  • the electrophoretic deposition technology adopted in this application has simple methods, low cost, low energy consumption, and low pollution, and has a wide range of application prospects.
  • composition taught in the present application is also basically The above is composed of or consists of the described components, and the process taught in this application is basically composed of the described process steps or a set of described process steps.

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Abstract

一种仿生三明治防腐涂层及其制备方法与应用。所述仿生三明治防腐涂层包括覆设于基底表面的至少两个水性树脂层，其中相邻两个水性树脂层之间分布有至少一个石墨烯阻隔层，所述石墨烯阻隔层包括具有片层结构的多巴胺功能化的石墨烯材料，并且所述多巴胺功能化的石墨烯材料以平行于基底表面的方式排列。所述制备方法包括：采用电泳沉积技术及循环伏安法，在基底表面依次沉积水性树脂层、石墨烯阻隔层及水性树脂层。由于氢键和静电相互作用，石墨烯材料平行排列在两层水性树脂层之间，不仅可以有效延长腐蚀介质扩散路径，而且可以充分发挥石墨烯的阻隔作用并逼近阻隔极限；同时制备方法简便、成本低廉、污染性小。

Description

[根据细则37.2由ISA制定的发明名称]　仿生三明治防腐涂层及其制备方法与应用 技术领域
本申请涉及一种防腐涂层，尤其涉及一种受天然珍珠层和贻贝启发的仿生三明治防腐涂层及其制备方法与应用，属于防腐涂层技术领域。
背景技术
随着海洋产业的快速发展及其对海洋资源的强烈需求，各种海洋设施、船舶和金属部件在海洋资源开发中必须面临严峻的腐蚀问题。研究表明，除合理选材外，有机防护涂层是应用最广泛、性价比最高的防腐措施之一。其中，水性阴极电泳乳液是以水为溶剂的涂料，不仅绿色环保(满足低挥发性有机化合物排放的要求)，而且具有理想的附着力，广泛用于主流汽车和船舶涂料中。然而，腐蚀性介质(H 2O、O 2和Cl -等)对有机涂层有一定的渗透性。因此，大量工作集中在改善有机涂层的不渗透性以增强其耐腐蚀性。
具有高纵横比和能抑制腐蚀性物质渗透和扩散的片状纳米填料，如石墨烯可以有效解决上述问题。石墨烯稳定的SP 2杂化结构使其在金属与腐蚀介质间形成物理阻隔层，阻止介质扩散和渗透，被认为是已知最薄的防腐层(0.34nm)。此外，石墨烯能有效延长腐蚀介质的扩散路径，具有优异的阻隔性能和良好的化学稳定性和抗氧化性能。其中在二维片层材料改性新型重防腐涂层体系中，二维片层材料在高分子树脂中的定向排布与优化调控问题一直是该领域急需突破的核心技术。
发明内容
本申请的主要目的在于提供一种仿生三明治防腐涂层及其制备方法，以克服现有技术中的不足。
本申请的另一目的在于提供所述仿生三明治防腐涂层的应用。
为实现上述发明目的，本申请采用了如下技术方案：
本申请实施例提供了一种仿生三明治防腐涂层，其包括覆设于基底表面的至少两个水性树脂层，其中相邻两个水性树脂层之间分布有至少一个石墨烯阻隔层，所述石墨烯阻隔层包 括具有片层结构的多巴胺功能化的石墨烯材料，并且所述多巴胺功能化的石墨烯材料以平行于基底表面的方式排列。
在一些实施例中，所述石墨烯阻隔层内的多个多巴胺功能化的石墨烯材料平行排列形成致密结构。
在一些实施例中，所述多巴胺功能化的石墨烯材料是氧化石墨烯经多巴胺改性处理制得的。
本申请实施例还提供了一种仿生三明治防腐涂层的制备方法，其包括：
以多巴胺对氧化石墨烯进行改性处理，获得多巴胺功能化的石墨烯材料；
采用电沉积法将所述多巴胺功能化的石墨烯材料、水性树脂交替沉积在基底表面，形成多个水性树脂层，并使其中相邻两个水性树脂层之间分布至少一个石墨烯阻隔层，且使所述石墨烯阻隔层中的多巴胺功能化的石墨烯材料以平行于基底表面的方式排列形成致密结构，从而获得复合涂层；
使所述复合涂层固化，获得所述仿生三明治防腐涂层。
在一些实施例中，所述电泳沉积技术采用的工艺条件包括：沉积电压为10～220V，沉积时间为1～30min。
进一步地，所述循环伏安法采用的工艺条件包括：循环次数为1～10次，扫描范围0.1～1.1V，扫描速率为5～50mV/s。
本申请实施例还提供了由前述方法制备的仿生三明治防腐涂层。
本申请实施例还提供了前述仿生三明治防腐涂层在金属防腐领域中的应用。
与现有技术相比，本申请的有益效果至少在于：
1)本申请提供的多巴胺功能化的石墨烯材料有效地抑制了石墨烯表面的电化学活性；
2)本申请提供的多巴胺能充当粘结剂以改善环氧树脂和石墨烯之间的界面相容性和粘附力；
3)本申请提供的多巴胺功能化的石墨烯材料由于氢键和静电相互作用，能平行于基材排列在两个环氧涂层之间；
4)本申请提供的多巴胺功能化石墨烯材料的片层结构在防腐涂层中能形成阻隔层，有效阻碍腐蚀性介质如水、氧气、氯离子等渗透，充分发挥石墨烯的物理隔绝作用并逼近阻隔极限；
5)本申请提供的多巴胺功能化石墨烯材料在防腐涂层中的均匀分散能显著延长腐蚀介质扩散路径；
6)本申请提供的仿生三明治防腐涂层的中间层石墨烯阻隔层避免了与金属基底的直接接触，屏蔽了电偶腐蚀；
7)本申请提供的仿生三明治水性防腐涂层不含有机溶剂，不会带来有机挥发物排放，绿色环保；
8)本申请提供的防腐涂层的制备方法中电泳沉积技术方法简便、成本低廉、能耗低、污染性小，有广泛的应用前景。
附图说明
为了更清楚地说明本申请实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本申请中记载的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
图1a是本申请一典型实施例中仿生三明治防腐涂层对水的阻隔作用的原理示意图；
图1b是本申请实施例1中所述仿生三明治防腐涂层的断面扫描图；
图1c是本申请实施例1中所述仿生三明治防腐涂层中石墨烯层的局部断面扫描放大图；
图2a和图2b分别是本申请对比例1和实施例1所制备的水性环氧防腐涂层经不同时间盐雾试验后的光学照片；
图3a和图3b分别是本申请对比例1和实施例1所制备的水性环氧防腐涂层在3.5wt％NaCl(pH值＝7)中浸泡不同时间的电化学交流阻抗图；
图4a和图4b分别是本申请对比例1和实施例1所制备的水性环氧防腐涂层在3.5wt％NaCl(pH值＝7)中浸泡90天后去除碳钢表面环氧涂层得到的碳钢表面腐蚀产物形貌图。
具体实施方式
鉴于现有技术中的不足，本案发明人经长期研究和大量实践，得以提出本申请的技术方案，旨在提供一种受天然珍珠层和贻贝启发的仿生三明治防腐涂层及其制备方法，主要包括石墨烯改性、电解液配置、基底预处理、复合涂层制备等步骤。如下将对该技术方案、其实施过程及原理等作进一步的解释说明。
本申请实施例的一个方面提供的一种受天然珍珠层和贻贝启发的仿生三明治防腐涂层包括覆设于基底表面的至少两个水性树脂层，其中相邻两个水性树脂层之间分布有至少一个石墨烯阻隔层，所述石墨烯阻隔层包括具有片层结构的多巴胺功能化的石墨烯材料，并且所述 多巴胺功能化的石墨烯材料以平行于基底表面的方式排列。
在一些优选实施例中，所述仿生三明治防腐涂层由水性树脂层-不同层数的石墨烯/多巴胺-水性树脂层组成。
本申请的仿生三明治防腐涂层对腐蚀性介质(例如水)的阻隔作用的机理在于：请参阅图1a所示，由于氢键和静电相互作用，多巴胺功能化的石墨烯材料平行于基底排列在两层水性树脂之间，有利于保持石墨烯的高纵横比，形成“迷宫效应”，夹在水性树脂之间的中间层石墨烯避免与金属基底直接接触而屏蔽了电偶腐蚀，不仅可以有效延长腐蚀介质扩散路径，而且可以充分发挥石墨烯的阻隔作用并逼近阻隔极限，有效阻碍腐蚀性介质如水、氧气、氯离子等渗透，充分发挥其物理隔绝作用。此外，多巴胺可以作为粘结剂改善石墨烯和水性树脂之间的界面相容性和粘附力。
在一些优选实施例中，所述石墨烯阻隔层内的多个多巴胺功能化的石墨烯材料平行排列形成致密结构。
在一些优选实施例中，所述多巴胺功能化的石墨烯材料是氧化石墨烯经多巴胺改性处理制得的。
在一些优选实施例中，所述多巴胺功能化的石墨烯材料的制备方法包括：将多巴胺和氧化石墨烯均匀分散在pH值＝6～8的磷酸盐缓冲液中并充分混合。
进一步地，所述多巴胺与氧化石墨烯的质量比为1：100～5：1。
在一些优选实施例中，所述氧化石墨烯的直径为1～50μm，厚度为0.5～5nm。
在一些优选实施例中，所述多巴胺功能化的石墨烯材料是阳离子多巴胺功能化的石墨烯材料，且制备方法包括：将多巴胺、氧化石墨烯加入pH值＝6～8的磷酸盐缓冲溶液中充分混合，获得多巴胺功能化的石墨烯材料，再将质量比为1：1～1：5的多巴胺功能化的石墨烯材料与乙酸分散于极性溶剂中并于20～30℃搅拌1h以上，获得阳离子多巴胺功能化的石墨烯材料。
在一些优选实施例中，所述阳离子多巴胺功能化的石墨烯材料由于铵根离子(-NH 3 +-)的存在能够稳定分散在水性树脂乳液中60天而不产生沉淀。阳离子多巴胺功能化石墨烯中的-NH 3 +-能吸附电子和腐蚀性阴离子，切断局部电偶腐蚀，在钢基体表面形成致密钝化层。
进一步地，所述多巴胺功能化的石墨烯材料与乙酸的质量比为1：1～1：5。
进一步地，所述极性溶剂包括丙酮、乙醇、N，N-二甲基甲酰胺、乙酸乙酯、三氯甲烷等中的任意一种或两种以上的组合，但不限于此。
进一步地，所述石墨烯阻隔层的厚度为1～5μm。
进一步地，所述水性树脂层的厚度为2～20μm。
进一步地，所述水性树脂层的材质包括水性阴极环氧树脂、水性阴极丙烯酸树脂、水性阴极聚氨酯树脂、水性氨基树脂等中的任意一种或两种以上的组合，但不限于此。
在一些优选实施例中，所述仿生三明治防腐涂层的厚度为5～50μm。
本申请实施例的另一个方面提供的一种仿生三明治防腐涂层的制备方法包括：采用电泳沉积技术，在基底表面先沉积一层水性树脂层；然后通过循环伏安法沉积不同层数的石墨烯/多巴胺；最后再通过电泳沉积技术沉积一层水性树脂层。
在一些优选实施例中，所述制备方法包括：
以多巴胺对氧化石墨烯进行改性处理，获得多巴胺功能化的石墨烯材料；
采用电沉积法将所述多巴胺功能化的石墨烯材料、水性树脂交替沉积在基底表面，形成多个水性树脂层，并使其中相邻两个水性树脂层之间分布至少一个石墨烯阻隔层，且使所述石墨烯阻隔层中的多巴胺功能化的石墨烯材料以平行于基底表面的方式排列形成致密结构，从而获得复合涂层；
使所述复合涂层固化，获得所述仿生三明治防腐涂层。
在一些优选实施例中，所述制备方法具体包括：将多巴胺、氧化石墨烯均匀分散在pH值为6～8的磷酸盐缓冲溶液中并充分混合，以防止多巴胺氧化自聚合，获得多巴胺功能化的石墨烯材料。其中，所述磷酸盐缓冲液的目的是防止多巴胺氧化自聚合。
进一步地，所述多巴胺与氧化石墨烯的质量比为1：100～5：1。
进一步地，所述氧化石墨烯的直径为1～50μm，厚度为0.5～5nm。
进一步地，所述混合温度范围为10～70℃，时间为0.5～24h。
在一些优选实施例中，所述多巴胺功能化的石墨烯材料是阳离子多巴胺功能化的石墨烯材料，且制备方法包括：将多巴胺、氧化石墨烯加入pH值＝6～8的磷酸盐缓冲溶液中充分混合，获得多巴胺功能化的石墨烯材料，再将质量比为1：1～1：5的多巴胺功能化的石墨烯材料与乙酸分散于极性溶剂中并于20～30℃搅拌1h以上，获得阳离子多巴胺功能化的石墨烯材料。
进一步地，所述多巴胺功能化的石墨烯材料与乙酸的质量比为1：1～1：5。
进一步地，所述多巴胺功能化的石墨烯材料与极性溶剂的质量比为1：10～1：100。
进一步地，所述极性溶剂包括丙酮、乙醇、N，N-二甲基甲酰胺、乙酸乙酯、三氯甲烷等中的任意一种或两种以上的组合，但不限于此。
在一些优选实施例中，所述制备方法具体包括：
提供基底；
至少以阳极、作为阴极的基底和作为电解液的水性树脂乳液共同构建电化学反应体系；
向所述电化学反应体系通电，以电泳沉积方式使水性树脂在所述基底表面沉积，形成水性树脂层。
在一些优选实施例中，所述电泳沉积技术采用的工艺条件包括：沉积电压为10～220V，沉积时间为1～30min。
在一些优选实施例中，所述水性树脂乳液包括水性阴极环氧树脂、水性阴极丙烯酸树脂、水性阴极聚氨酯树脂、水性氨基树脂等中的任意一种或两种以上的组合，但不限于此。
进一步地，所述水性树脂乳液的固含量为5～50％。
在一些优选实施例中，所述水性树脂层直接沉积在所述基底表面，或者，所述基底表面预先依次沉积有至少一层水性树脂层和至少一层石墨烯阻隔层。
进一步地，所述水性树脂层的厚度为2～20μm。
在一些优选实施例中，所述制备方法具体包括：
以表面结合有至少一层水性树脂层的基底作为阴极，并与阳极、含有多巴胺功能化的石墨烯材料的电解液共同构建电化学反应体系；
向所述电化学反应体系通电，通过循环伏安法使多巴胺功能化的石墨烯材料沉积在所述水性树脂层表面，从而形成所述石墨烯阻隔层。
进一步地，所述循环伏安法采用的工艺条件包括：循环次数为1～10次，扫描范围0.1～1.1V，扫描速率为5～50mV/s。
在一些更为优选的实施例中，所述制备方法具体包括：
(1)以阳极、作为阴极的基底和作为电解液的水性树脂乳液共同构建电化学反应体系，再向所述电化学反应体系通电，以电泳沉积方式使水性树脂在所述基底表面沉积，形成水性树脂层；
(2)以表面结合有水性树脂层的基底作为阴极，并与阳极、含有多巴胺功能化的石墨烯材料的电解液共同构建电化学反应体系，再向所述电化学反应体系通电，通过循环伏安法使多巴胺功能化的石墨烯材料沉积在所述水性树脂层表面，从而形成所述石墨烯阻隔层；
(3)以表面结合有石墨烯阻隔层的基底作为阴极，并与阳极和作为电解液的水性树脂乳液共同构建电化学反应体系，再向所述电化学反应体系通电，以电泳沉积方式使水性树脂在所述石墨烯阻隔层上沉积，形成水性树脂层；
重复步骤(1)-(3)的操作一次或多次，获得所述复合涂层。
进一步地，所述石墨烯阻隔层的厚度为1～5μm。
在一些优选实施例中，所述固化的温度为60～200℃，时间为10～30min。
进一步地，所述仿生三明治防腐涂层的厚度为5～50μm。
进一步地，所述制备方法还包括：在进行电泳沉积之前，先对基底进行预处理；其中，所述预处理包括：采用100～2000目砂纸对基底进行打磨，之后超声清洗5～30min，再干燥处理。
在一些更为典型的具体实施案例之中，本申请的一种仿生三明治防腐涂层的制备方法包括如下步骤：
(1)石墨烯改性：将质量比为1：100～5：1的多巴胺和氧化石墨烯加入pH值为6～8的磷酸盐缓冲溶液中。
(2)钢片预处理：将尺寸为(1～10)×(1～10)cm 2的钢片在100～2000目砂纸上打磨后用乙醇超声清洗5～30min，最后用氮气吹干。
(3)复合涂层制备：将钢片作为阴极，相同尺寸的铜片作为阳极，浸入电解液中；通过控制沉积电压和沉积时间在基底表面沉积水性树脂；然后通过循环伏安法在上述涂层表面沉积不同层数的石墨烯/多巴胺材料；最后，采用电泳沉积技术，在上述涂层表面再沉积一层水性防腐涂层；其中沉积电压为10～220V，沉积时间1～30min；循环次数为1～10次，扫描范围0.1～1.1V，扫描速率为20mv/s。
(4)仿生三明治防腐涂层制备：将上述得到的涂层在干燥箱中固化10～30min，其中固化温度为60～200℃，以去除基底表面乳液中的水溶剂。
本申请实施例的另一个方面还提供了由前述方法制备的仿生三明治防腐涂层。
进一步地，所述仿生三明治防腐涂层的厚度为5～50μm。
本申请实施例的另一个方面还提供了前述仿生三明治防腐涂层于金属防腐领域中的应用。
综上所述，本申请通过电泳沉积技术和循环伏安法制备仿生三明治防腐涂层。其中多巴胺充当粘结剂以改善环氧树脂和石墨烯之间的界面相容性和粘附力。此外，由于氢键和静电相互作用，多巴胺功能化的石墨烯材料平行于基材排列在两个水性树脂层之间。夹在水性树脂层之间的中间层石墨烯避免与金属基底直接接触而屏蔽了电偶腐蚀，且充分发挥了石墨烯的阻隔作用并逼近阻隔极限，有效阻碍腐蚀性介质如水、氧气、氯离子等渗透，充分发挥其物理隔绝作用。多巴胺功能化的石墨烯材料在涂层中的平行排列能显著延长腐蚀介质扩散路径。水性多巴胺改性石墨烯/树脂不含有机溶剂，不会带来有机挥发物排放，绿色环保。本申 请提供的多巴胺改性石墨烯材料制备方法简单。本申请采用的电泳沉积技术方法简便、成本低廉、能耗低、污染性小，有广泛的应用前景。
下面通过具体实施例及附图，对本申请实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本申请一部分实施例，而不是全部的实施例。基于本申请中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本申请保护的范围。
实施例1
一种仿生三明治水性环氧防腐涂层的制备方法，包括如下步骤：
1.石墨烯改性：将质量比为1：1的多巴胺和氧化石墨烯加入pH值为6.7的磷酸盐缓冲溶液中均匀混合，混合温度为25℃，混合时间为10h。
2.钢片预处理：将尺寸为3×3cm 2的钢片在600、1200目砂纸上打磨后用乙醇超声清洗20min，最后用氮气吹干。
3.复合涂层制备：将钢片作为阴极，相同尺寸的铜片作为阳极，浸入100g固含量为25％的水性环氧乳液中；通过控制沉积电压和沉积时间在基底表面沉积水性树脂；然后通过循环伏安法在上述涂层表面沉积不同层数的石墨烯/多巴胺材料；最后，采用电泳沉积技术，在上述涂层表面再沉积一层水性防腐涂层；其中沉积电压为30V，沉积时间8min；循环次数为10次，扫描范围0.1～1.1V，扫描速率为20mv/s。
4.仿生三明治防腐涂层制备：将上述得到的涂层在干燥箱中固化15min，其中固化温度为160℃，以去除基底表面乳液中的水溶剂，所制备的防腐涂层厚度为23.5μm。
图1b-图1c是本实施例中所述仿生三明治防腐涂层的断面扫描图。从图1b中可以看出，石墨烯材料平行于基底排列在两个环氧涂层之间。这有利于保持石墨烯的高纵横比，形成“迷宫效应”，从而充分发挥其物理隔绝作用，有效阻碍腐蚀性介质如水、氧气、氯离子等渗透，显著延长腐蚀介质扩散路径。此外，多巴胺可以充当粘结剂以改善环氧树脂和石墨烯之间的界面相容性和粘附力。
实施例2
一种仿生三明治水性丙烯酸防腐涂层的制备方法，包括如下步骤：
1.石墨烯改性：将质量比为1：100的多巴胺和氧化石墨烯加入pH值为8的磷酸盐缓冲溶液中均匀混合，混合温度为10℃，混合时间为24h。
2.钢片预处理：将尺寸为1×1cm 2的钢片在100、1000目砂纸上打磨后用乙醇超声清洗5min，最后用氮气吹干。
3.复合涂层制备：将钢片作为阴极，相同尺寸的铜片作为阳极，浸入100g固含量为5％的水性丙烯酸乳液中；通过控制沉积电压和沉积时间在基底表面沉积水性树脂；然后通过循环伏安法在上述涂层表面沉积不同层数的石墨烯/多巴胺材料；最后，采用电泳沉积技术，在上述涂层表面再沉积一层水性防腐涂层；其中沉积电压为10V，沉积时间30min；循环次数为1次，扫描范围0.1～1.1V，扫描速率为5mv/s。
4.仿生三明治防腐涂层制备：将上述得到的涂层在干燥箱中固化10min，其中固化温度为200℃，以去除基底表面乳液中的水溶剂，所制备的防腐涂层厚度为5μm。
实施例3
一种仿生三明治水性聚氨酯防腐涂层的制备方法，包括如下步骤：
1.石墨烯改性：将质量比为5：1的多巴胺和氧化石墨烯加入pH值为6的磷酸盐缓冲溶液中均匀混合，混合温度为35℃，混合时间为15h。
2.钢片预处理：将尺寸为10×10cm 2的钢片在200、800、2000目砂纸上打磨后用乙醇超声清洗30min，最后用氮气吹干。
3.复合涂层制备：将钢片作为阴极，相同尺寸的铜片作为阳极，浸入100g固含量为50％的水性聚氨酯乳液中；通过控制沉积电压和沉积时间在基底表面沉积水性树脂；然后通过循环伏安法在上述涂层表面沉积不同层数的石墨烯/多巴胺材料；最后，采用电泳沉积技术，在上述涂层表面再沉积一层水性防腐涂层；其中沉积电压为220V，沉积时间1min；循环次数为5次，扫描范围0.1～1.1V，扫描速率为50mv/s。
4.仿生三明治防腐涂层制备：将上述得到的涂层在干燥箱中固化30min，其中固化温度为60℃，以去除基底表面乳液中的水溶剂，所制备的防腐涂层厚度为50μm。
实施例4
一种仿生三明治水性氨基防腐涂层的制备方法，包括如下步骤：
1.石墨烯改性：将质量比为3：1的多巴胺和氧化石墨烯加入pH值为7的磷酸盐缓冲溶液中均匀混合，混合温度为70℃，混合时间为0.5h。
2.钢片预处理：将尺寸为5×5cm 2的钢片在600、1500目砂纸上打磨后用乙醇超声清洗15min，最后用氮气吹干。
3.复合涂层制备：将钢片作为阴极，相同尺寸的铜片作为阳极，浸入100g固含量为20％的水性氨基乳液中；通过控制沉积电压和沉积时间在基底表面沉积水性树脂；然后通过循环伏安法在上述涂层表面沉积不同层数的石墨烯/多巴胺材料；最后，采用电泳沉积技术，在上述涂层表面再沉积一层水性防腐涂层；其中沉积电压为100V，沉积时间15min；循环次数为 3次，扫描范围0.1～1.1V，扫描速率为10mv/s。
4.仿生三明治防腐涂层制备：将上述得到的涂层在干燥箱中固化15min，其中固化温度为100℃，以去除基底表面乳液中的水溶剂，所制备的防腐涂层厚度为30μm。
本申请实施例1-4所制备涂层在3.5wt％NaCl(pH值＝7)中浸泡不同时间的低频阻抗模量值如下：
涂层 浸泡1d后低频阻抗模量(Ωcm 2) 浸泡90d后低频阻抗模量(Ωcm 2)
实施例1 5.25×10 10 1.30×10 9
实施例2 2.42×10 9 9.54×10 7
实施例3 1.32×10 10 7.25×10 8
实施例4 5.21×10 10 4.41×10 9
实施例5
一种仿生三明治水性环氧防腐涂层的制备方法，包括如下步骤：
1.石墨烯改性：将质量比为2：1的多巴胺和氧化石墨烯加入pH值为6.5的磷酸盐缓冲溶液中均匀混合，混合温度为55℃，混合时间为8h，获得多巴胺功能化的石墨烯，然后将得到的多巴胺功能化的石墨烯在40℃下真空干燥成粉末。
2.石墨烯离子化：取0.5g干燥后的多巴胺还原氧化石墨烯和1.35g乙酸分散在20mL丙酮溶液中，28℃搅拌3h，获得阳离子多巴胺功能化石墨烯，然后在40℃下真空干燥成粉末。
3.钢片预处理：将尺寸为3×3cm 2的钢片在600、1200目砂纸上打磨后用乙醇超声清洗20min，最后用氮气吹干。
4.复合涂层制备：将钢片作为阴极，相同尺寸的铜片作为阳极，浸入100g固含量为25％的水性环氧乳液中；通过控制沉积电压和沉积时间在基底表面沉积水性树脂；然后通过循环伏安法在上述涂层表面沉积不同层数的石墨烯/多巴胺材料；最后，采用电泳沉积技术，在上述涂层表面再沉积一层水性防腐涂层；其中沉积电压为50V，沉积时间10min；循环次数为8次，扫描范围0.1～1.1V，扫描速率为30mv/s。
5.仿生三明治防腐涂层制备：将上述得到的涂层在干燥箱中固化15min，其中固化温度为150℃，以去除基底表面乳液中的水溶剂，所制备的防腐涂层厚度为25μm。
实施例6
一种仿生三明治水性丙烯酸防腐涂层的制备方法，包括如下步骤：
1.石墨烯改性：将质量比为1：1的多巴胺和氧化石墨烯加入pH值为8的磷酸盐缓冲溶液中均匀混合，混合温度为20℃，混合时间为24h，获得多巴胺功能化的石墨烯，然后将得到的多巴胺功能化的石墨烯在40℃下真空干燥成粉末。
2.石墨烯离子化：取0.5g干燥后的多巴胺还原氧化石墨烯和0.5g乙酸分散在12.5mL乙醇溶液中，20℃搅拌1h，获得阳离子多巴胺功能化石墨烯，然后在20℃下真空干燥成粉末。
3.钢片预处理：将尺寸为1×1cm 2的钢片在100、1000目砂纸上打磨后用乙醇超声清洗5min，最后用氮气吹干。
4.复合涂层制备：将钢片作为阴极，相同尺寸的铜片作为阳极，浸入100g固含量为5％的水性丙烯酸乳液中；通过控制沉积电压和沉积时间在基底表面沉积水性树脂；然后通过循环伏安法在上述涂层表面沉积不同层数的石墨烯/多巴胺材料；最后，采用电泳沉积技术，在上述涂层表面再沉积一层水性防腐涂层；其中沉积电压为10V，沉积时间20min；循环次数为2次，扫描范围0.1～1.1V，扫描速率为15mv/s。
5.仿生三明治防腐涂层制备：将上述得到的涂层在干燥箱中固化20min，其中固化温度为180℃，以去除基底表面乳液中的水溶剂，所制备的防腐涂层厚度为10μm。
实施例7
一种仿生三明治水性聚氨酯防腐涂层的制备方法，包括如下步骤：
1.石墨烯改性：将质量比为4：1的多巴胺和氧化石墨烯加入pH值为6的磷酸盐缓冲溶液中均匀混合，混合温度为45℃，混合时间为15h，获得多巴胺功能化的石墨烯，然后将得到的多巴胺功能化的石墨烯在80℃下真空干燥成粉末。
2.石墨烯离子化：取0.5g干燥后的多巴胺还原氧化石墨烯和2.5g乙酸分散在125mL乙酸乙酯溶液中，30℃搅拌5h，获得阳离子多巴胺功能化石墨烯，然后在80℃下真空干燥成粉末。
3.钢片预处理：将尺寸为10×10cm 2的钢片在200、800、2000目砂纸上打磨后用乙醇超声清洗30min，最后用氮气吹干。
4.复合涂层制备：将钢片作为阴极，相同尺寸的铜片作为阳极，浸入100g固含量为50％的水性聚氨酯乳液中；通过控制沉积电压和沉积时间在基底表面沉积水性树脂；然后通过循环伏安法在上述涂层表面沉积不同层数的石墨烯/多巴胺材料；最后，采用电泳沉积技术，在上述涂层表面再沉积一层水性防腐涂层；其中沉积电压为220V，沉积时间1min；循环次数为6次，扫描范围0.1～1.1V，扫描速率为40mv/s。
5.仿生三明治防腐涂层制备：将上述得到的涂层在干燥箱中固化30min，其中固化温度 为80℃，以去除基底表面乳液中的水溶剂，所制备的防腐涂层厚度为30μm。
实施例8
一种仿生三明治水性氨基防腐涂层的制备方法，包括如下步骤：
1.石墨烯改性：将质量比为3：1的多巴胺和氧化石墨烯加入pH值为7的磷酸盐缓冲溶液中均匀混合，混合温度为60℃，混合时间为1h，获得多巴胺功能化的石墨烯，然后将得到的多巴胺功能化的石墨烯在40℃下真空干燥成粉末。
2.石墨烯离子化：取0.5g干燥后的多巴胺还原氧化石墨烯和1g乙酸溶液分散在50mL N,N-二甲基甲酰胺溶液中，24℃搅拌2h，获得阳离子多巴胺功能化石墨烯，然后在40℃下真空干燥成粉末。
3.钢片预处理：将尺寸为5×5cm 2的钢片在600、1500目砂纸上打磨后用乙醇超声清洗15min，最后用氮气吹干。
4.复合涂层制备：将钢片作为阴极，相同尺寸的铜片作为阳极，浸入100g固含量为20％的水性氨基乳液中；通过控制沉积电压和沉积时间在基底表面沉积水性树脂；然后通过循环伏安法在上述涂层表面沉积不同层数的石墨烯/多巴胺材料；最后，采用电泳沉积技术，在上述涂层表面再沉积一层水性防腐涂层；其中沉积电压为100V，沉积时间15min；循环次数为5次，扫描范围0.1～1.1V，扫描速率为10mv/s。
5.仿生三明治防腐涂层制备：将上述得到的涂层在干燥箱中固化15min，其中固化温度为120℃，以去除基底表面乳液中的水溶剂，所制备的防腐涂层厚度为20μm。
对比例1
一种防腐涂层及其制备方法，包括如下步骤：
1.钢片预处理：将尺寸为3×3cm 2的钢片分别在600、1200目砂纸上打磨后用乙醇超声清洗20min，最后用氮气吹干。
2.复合涂层制备：将钢片作为阴极，相同尺寸的铜片作为阳极，浸入100g固含量为25％的水性环氧乳液中，沉积电压30V下沉积10min；然后取出用去离子水清洗，再在100g固含量为25％的水性乳液中，30V下沉积10min。
3.防腐涂层制备：将上述得到的涂层在干燥箱中固化15min，其中固化温度为160℃，以去除基底表面乳液中的水溶剂，所制备的防腐涂层厚度为23.5μm。
对比例2
1.钢片预处理：将尺寸为3×3cm 2的钢片分别在600、1200目砂纸上打磨后用乙醇超声清洗20min，最后用氮气吹干。
2.复合涂层制备：将钢片作为阴极，相同尺寸的铜片作为阳极，浸入100g固含量为25％的水性环氧乳液中，沉积电压30V下沉积10min；然后取出用去离子水清洗，然后通过循环伏安法在上述涂层表面沉积不同层数的石墨烯/多巴胺材料，循环次数为10次，扫描范围0.1～1.1V，扫描速率为20mv/s。
3.防腐涂层制备：将上述得到的涂层在干燥箱中固化15min，其中固化温度为160℃，以去除基底表面乳液中的水溶剂，所制备的防腐涂层厚度为14.5μm。
所制备的涂层由于石墨烯层的覆盖，在初期同样表现出较好的抗腐蚀性能，但由于表面未增加一层环氧树脂，且涂层厚度较对比例1有所减小，故阻抗较对比例2低。然而，由于石墨烯层的覆盖能有效增强涂层的抗渗透性和延时腐蚀性介质的渗透，故对比例2制备的涂层较对比例1制备的涂层腐蚀速率有所降低，但效果仍不如实施例1。
图2a和图2b是对比例1和实施例1所制备的水性环氧防腐涂层经不同时间盐雾试验后的光学照片。如图2a所示，对纯EP涂层进行了120h测试后，划痕周围几乎完全被锈覆盖。经过240h的测试后，划痕周围的腐蚀进一步向外扩散，并且在涂层表面出现腐蚀点，表明腐蚀性介质已经到达基材，从而导致钢腐蚀。480小时试验后，涂层腐蚀变得越来越严重，并且在涂层表面上出现气泡，表明涂层开始脱落，几乎没有保护作用。如图2b所示，对于改性后的涂层，盐雾测试480小时后，涂层表面保持完整。这是因为多层石墨烯片可以填充单个石墨烯片中的缺陷，这更有利于发挥石墨烯的不渗透性并增强仿生三明治涂层的阻隔作用，并进一步延长腐蚀性物质的扩散路径，使改性后的涂层展示出优异的防腐性能。
图3a和图3b是对比例1和实施例1所制备的水性环氧防腐涂层在3.5wt％NaCl(pH值＝7)中浸泡不同时间的电化学交流阻抗图。同样，从图3a中可以看出，纯EP涂层的初始低频阻抗模量为4.11×10 9Ωcm 2，浸入90天后，急剧下降至6.44×10 6Ωcm 2，降低了3个数量级。这表明腐蚀性介质已通过缺陷渗透到涂层基材中，导致涂层的耐腐蚀性降低。而从图3b可以看出，多巴胺功能化后的石墨烯防腐涂层的初始低频阻抗模量为5.25×10 10Ωcm 2，在浸入90天后仍高达1.30×10 9Ωcm 2。这归因于石墨烯的片层结构在涂层中能形成阻隔层，有效阻碍腐蚀性介质如水、氧气、氯离子等渗透，充分发挥其物理隔绝作用。而且石墨烯在涂层中的均匀分散能显著延长腐蚀介质扩散路径。此外，夹在环氧之间的中间层石墨烯避免与金属基底直接接触而屏蔽了电偶腐蚀。
图4a和图4b分别是本申请对比例1和实施例1所制备的水性环氧防腐涂层在3.5wt％NaCl(pH值＝7)中浸泡90天后去除碳钢表面环氧涂层得到的碳钢表面腐蚀产物形貌图。从图中可以看出多巴胺功能化后的石墨烯防腐涂层碳钢表面的腐蚀产物(图4b)较纯环氧涂层 碳钢表面的腐蚀产物(图4a)大大减少，表现出优异的耐腐蚀性能。
综上所述，本申请以钢为基底，经打磨处理和乙醇清洗后，通过电泳沉积技术和循环伏安法制备仿生三明治防腐涂层。其中多巴胺充当粘结剂以改善环氧树脂和石墨烯之间的界面相容性和粘附力。此外，由于氢键和静电相互作用，多巴胺功能化的石墨烯材料平行于基材排列在两个水性树脂层之间。夹在水性树脂层之间的中间层石墨烯避免与金属基底直接接触而屏蔽了电偶腐蚀，且充分发挥了石墨烯的阻隔作用并逼近阻隔极限，有效阻碍腐蚀性介质如水、氧气、氯离子等渗透，充分发挥其物理隔绝作用。多巴胺功能化的石墨烯材料在涂层中的平行排列能显著延长腐蚀介质扩散路径。水性多巴胺改性石墨烯/树脂不含有机溶剂，不会带来有机挥发物排放，绿色环保。本申请提供的多巴胺改性石墨烯材料制备方法简单。本申请采用的电泳沉积技术方法简便、成本低廉、能耗低、污染性小，有广泛的应用前景。
本申请的各方面、实施例、特征及实例应视为在所有方面为说明性的且不打算限制本申请，本申请的范围仅由权利要求书界定。在不背离所主张的本申请的精神及范围的情况下，所属领域的技术人员将明了其它实施例、修改及使用。
在本申请案中标题及章节的使用不意味着限制本申请；每一章节可应用于本申请的任何方面、实施例或特征。
在本申请案通篇中，在将组合物描述为具有、包含或包括特定组份之处或者在将过程描述为具有、包含或包括特定过程步骤之处，预期本申请教示的组合物也基本上由所叙述组份组成或由所叙述组份组成，且本申请教示的过程也基本上由所叙述过程步骤组成或由所叙述过程步骤组组成。
除非另外具体陈述，否则术语“包含(include、includes、including)”、“具有(have、has或having)”的使用通常应理解为开放式的且不具限制性。
应理解，各步骤的次序或执行特定动作的次序并非十分重要，只要本申请教示保持可操作即可。此外，可同时进行两个或两个以上步骤或动作。
此外，本案发明人还参照前述实施例，以本说明书述及的其它原料、工艺操作、工艺条件进行了试验，并均获得了较为理想的结果。
尽管已参考说明性实施例描述了本申请，但所属领域的技术人员将理解，在不背离本申请的精神及范围的情况下可做出各种其它改变、省略及/或添加且可用实质等效物替代所述实施例的元件。另外，可在不背离本申请的范围的情况下做出许多修改以使特定情形或材料适应本申请的教示。因此，本文并不打算将本申请限制于用于执行本申请的所揭示特定实施例，而是打算使本申请将包含归属于所附权利要求书的范围内的所有实施例。此外，除非具体陈 述，否则术语第一、第二等的任何使用不表示任何次序或重要性，而是使用术语第一、第二等来区分一个元素与另一元素。

Claims (10)

  1. 一种仿生三明治防腐涂层，其特征在于包括覆设于基底表面的至少两个水性树脂层，其中相邻两个水性树脂层之间分布有至少一个石墨烯阻隔层，所述石墨烯阻隔层包括具有片层结构的多巴胺功能化的石墨烯材料，并且所述多巴胺功能化的石墨烯材料以平行于基底表面的方式排列。
  2. 根据权利要求1所述的仿生三明治防腐涂层，其特征在于：
    所述石墨烯阻隔层内的多个多巴胺功能化的石墨烯材料平行排列形成致密结构；
    和/或，所述多巴胺功能化的石墨烯材料是氧化石墨烯经多巴胺改性处理制得的；
    优选的，所述多巴胺功能化的石墨烯材料的制备方法包括：将多巴胺和氧化石墨烯均匀分散在pH值＝6～8的磷酸盐缓冲液中并充分混合；优选的，所述氧化石墨烯的直径为1～50μm，厚度为0.5～5nm；优选的，所述多巴胺与氧化石墨烯的质量比为1：100～5：1；
    优选的，所述多巴胺功能化的石墨烯材料是阳离子多巴胺功能化的石墨烯材料，且制备方法包括：将多巴胺、氧化石墨烯加入pH值＝6～8的磷酸盐缓冲溶液中充分混合，获得多巴胺功能化的石墨烯材料，再将质量比为1：1～1：5的多巴胺功能化的石墨烯材料与乙酸分散于极性溶剂中并于20～30℃搅拌1h以上，获得阳离子多巴胺功能化的石墨烯材料；优选的，所述多巴胺功能化的石墨烯材料与乙酸的质量比为1：1～1：5；优选的，所述极性溶剂包括丙酮、乙醇、N，N-二甲基甲酰胺、乙酸乙酯、三氯甲烷中的任意一种或两种以上的组合。
  3. 根据权利要求1所述的仿生三明治防腐涂层，其特征在于：所述石墨烯阻隔层的厚度为1～5μm；和/或，所述水性树脂层的厚度为2～20μm；和/或，所述水性树脂层的材质包括水性阴极环氧树脂、水性阴极丙烯酸树脂、水性阴极聚氨酯树脂、水性氨基树脂中的任意一种或两种以上的组合；和/或，所述仿生三明治防腐涂层的厚度为5～50μm。
  4. 一种仿生三明治防腐涂层的制备方法，其特征在于包括：
    以多巴胺对氧化石墨烯进行改性处理，获得多巴胺功能化的石墨烯材料；
    采用电沉积法将所述多巴胺功能化的石墨烯材料、水性树脂交替沉积在基底表面，形成多个水性树脂层，并使其中相邻两个水性树脂层之间分布至少一个石墨烯阻隔层，且使所述石墨烯阻隔层中的多巴胺功能化的石墨烯材料以平行于基底表面的方式排列形成致密结构，从而获得复合涂层；
    使所述复合涂层固化，获得所述仿生三明治防腐涂层。
  5. 根据权利要求4所述的制备方法，其特征在于包括：将多巴胺、氧化石墨烯加入pH值为6～8的磷酸盐缓冲溶液中并充分混合，获得多巴胺功能化的石墨烯材料；优选的，所述多巴胺与氧化石墨烯的质量比为1：100～5：1；优选的，所述氧化石墨烯的直径为1～50μm，厚度为0.5～5nm；优选的，所述混合的温度为10～70℃，时间为0.5～24h。
    优选的，所述多巴胺功能化的石墨烯材料是阳离子多巴胺功能化的石墨烯材料，且制备方法包括：将多巴胺、氧化石墨烯加入pH值＝6～8的磷酸盐缓冲溶液中充分混合，获得多巴胺功能化的石墨烯材料，再将质量比为1：1～1：5的多巴胺功能化的石墨烯材料与乙酸分散于极性溶剂中并于20～30℃搅拌1h以上，获得阳离子多巴胺功能化的石墨烯材料；优选的，所述多巴胺功能化的石墨烯材料与乙酸的质量比为1：1～1：5；优选的，所述极性溶剂包括丙酮、乙醇、N，N-二甲基甲酰胺、乙酸乙酯、三氯甲烷中的任意一种或两种以上的组合。
  6. 根据权利要求4所述的制备方法，其特征在于具体包括：
    至少以阳极、作为阴极的基底和作为电解液的水性树脂乳液共同构建电化学反应体系；
    向所述电化学反应体系通电，以电泳沉积方式使水性树脂在所述基底表面沉积，形成水性树脂层；
    优选的，所述电泳沉积技术采用的工艺条件包括：沉积电压为10～220V，沉积时间为1～30min；
    优选的，所述水性树脂乳液包括水性阴极环氧树脂、水性阴极丙烯酸树脂、水性阴极聚氨酯树脂、水性氨基树脂中的任意一种或两种以上的组合；优选的，所述水性树脂乳液的固含量为5～50％；
    优选的，所述水性树脂层直接沉积在所述基底表面，或者，所述基底表面预先依次沉积有至少一层水性树脂层和至少一层石墨烯阻隔层；
    和/或，所述水性树脂层的厚度为2～20μm。
  7. 根据权利要求4或5所述的制备方法，其特征在于具体包括：
    以表面结合有至少一层水性树脂层的基底作为阴极，并与阳极、含有多巴胺功能化的石墨烯材料的电解液共同构建电化学反应体系；
    向所述电化学反应体系通电，通过循环伏安法使多巴胺功能化的石墨烯材料沉积在所述水性树脂层表面，从而形成所述石墨烯阻隔层；
    优选的，所述循环伏安法采用的工艺条件包括：循环次数为1～10次，扫描范围0.1～1.1V，扫描速率为5～50mV/s；
    优选的，所述制备方法具体包括：
    (1)以阳极、作为阴极的基底和作为电解液的水性树脂乳液共同构建电化学反应体系，再向所述电化学反应体系通电，以电泳沉积方式使水性树脂在所述基底表面沉积，形成水性树脂层；
    (2)以表面结合有水性树脂层的基底作为阴极，并与阳极、含有多巴胺功能化的石墨烯材料的电解液共同构建电化学反应体系，再向所述电化学反应体系通电，通过循环伏安法使多巴胺功能化的石墨烯材料沉积在所述水性树脂层表面，从而形成所述石墨烯阻隔层；
    (3)以表面结合有石墨烯阻隔层的基底作为阴极，并与阳极和作为电解液的水性树脂乳液共同构建电化学反应体系，再向所述电化学反应体系通电，以电泳沉积方式使水性树脂在所述石墨烯阻隔层上沉积，形成水性树脂层；
    重复步骤(1)-(3)的操作一次或多次，获得所述复合涂层。
  8. 根据权利要求4所述的制备方法，其特征在于：所述固化的温度为60～200℃，时间为10～30min；和/或，所述仿生三明治防腐涂层的厚度为5～50μm；
    和/或，所述制备方法还包括：在进行电泳沉积之前，先对基底进行预处理；优选的，所述预处理包括：采用100～2000目砂纸对基底进行打磨，之后超声清洗5～30min，再干燥处理。
  9. 由权利要求4-8中任一项所述方法制备的仿生三明治防腐涂层。
  10. 权利要求1-3、9中任一项所述的仿生三明治防腐涂层于金属防腐领域中的应用。
PCT/CN2020/117977 2020-01-10 2020-09-27 仿生三明治防腐涂层及其制备方法与应用 WO2021139227A1 (zh)

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