WO2018113699A1 - Method for preparing anticorrosion graphene composite coating for metal - Google Patents

Method for preparing anticorrosion graphene composite coating for metal Download PDF

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WO2018113699A1
WO2018113699A1 PCT/CN2017/117493 CN2017117493W WO2018113699A1 WO 2018113699 A1 WO2018113699 A1 WO 2018113699A1 CN 2017117493 W CN2017117493 W CN 2017117493W WO 2018113699 A1 WO2018113699 A1 WO 2018113699A1
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graphene
metal
alloy
coating
preparation
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朱英
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北京赛特石墨烯科技有限公司
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
    • B05D3/0254—After-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • 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
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • 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
    • 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
    • B05D2202/00—Metallic substrate
    • B05D2202/10—Metallic substrate based on Fe
    • 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
    • B05D2202/00—Metallic substrate
    • B05D2202/20—Metallic substrate based on light metals
    • B05D2202/25—Metallic substrate based on light metals based on Al
    • 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
    • B05D2202/00—Metallic substrate
    • B05D2202/40—Metallic substrate based on other transition elements
    • B05D2202/45—Metallic substrate based on other transition elements based on Cu

Definitions

  • the invention relates to the field of nano materials, in particular to a method for preparing a metal anticorrosive graphene composite coating.
  • Corrosion originates from the contact of air, water or other substances on the surface of the metal.
  • the commonly used anti-corrosion method is to use a protective layer of inert metal, conductive polymer, sulfhydryl monolayer, etc., but these protective layer materials have Self limit.
  • the ruthenium-based monolayer self-assembled on the metal surface cannot withstand temperatures above 100 ° C; while the polymer coating is relatively thick, which can significantly alter the physical properties of the underlying metal.
  • Graphene is a new type of carbon material with only a single atomic layer thickness, with unique structure and excellent physical and chemical properties. Due to its large specific surface area, excellent permeability resistance, high thermal stability and chemical stability, it also has great potential in the field of corrosion protection of metallic materials. Mainly due to the layered structure of graphene, which has rapid conductivity, electrons are transferred to the metal coating through graphene, and the cathode electrons do not directly occur on the metal, but directly react with the coating, thus It will reduce the dissolution of the metal and thus protect the metal.
  • Patent No. 201610148083.8 discloses a graphene anticorrosive coating for a stainless steel surface. It is made of graphite as raw material, and the graphene powder is prepared by redox method. Then, the graphene powder is freeze-dried, the graphene powder is placed in a tableting machine and pressed into a graphene film, and then the graphene film is placed on a stainless steel substrate.
  • the graphene film is broken after ion sputtering to deposit on the surface of the stainless steel to obtain a graphene anticorrosive coating.
  • Kang et al. spin-coated graphene oxide on a silicon wafer deposited with SiO 2 by self-assembly, and obtained a multilayer graphene film by heat treatment, and subjected to oxidation test on Cu and Fe substrates, covered with graphene. The metal surface is effectively protected.
  • Liu et al. applied graphene oxide to the Al surface by dipping, and reduced graphene oxide to graphene due to the activity of Al, which showed high corrosion resistance. Chen et al.
  • ion barriers can effectively prevent the electrochemical corrosion of metals in salt solutions.
  • Prasai et al. used a CVD method to prepare a graphene coating on Cu and Ni surfaces, a graphene coating on a Cu substrate to improve corrosion resistance by 7 times, and a graphene coating on a Ni substrate to increase corrosion resistance by 20 times.
  • a quantitative model of a single or multi-layer graphene film coating was established to describe its passivation mechanism.
  • S. Raman et al. studied the corrosion behavior of Cu-based graphene film coatings prepared by CVD in NaCl solution. It was found that the electrochemical corrosion of the anode and cathode currents were reduced by one to two orders of magnitude, and the AC impedance spectrum showed graphene coating. The layer significantly increases the impedance of the metal.
  • an object of the present invention is to provide a high-isolation anti-corrosion nano-coating for a metal surface, and to provide a preparation method and use of a high-efficiency anti-corrosion coating.
  • the metal anti-corrosion graphene coating of the present invention is prepared by coating a surface of a single metal or alloy with a layer of graphene, wherein the metal or alloy comprises copper, copper alloy, nickel, nickel alloy, aluminum, aluminum alloy, etc.
  • the graphene coating has a thickness of about 20 nm to 10 ⁇ m.
  • Graphene is coated on the surface of metal or alloy by interface transfer method.
  • the prepared graphene coating has the advantages of stability, high efficiency, non-toxicity, water and air insulation, and corrosion resistance. It can be widely used in ocean, land and Corrosion protection of steel used in underground industrial production environments and daily life environments.
  • the preparation method of the metal anticorrosive graphene coating of the invention comprises the following steps:
  • the graphene sheet is obtained by mechanical stripping using natural graphite as a raw material, and a graphene dispersion having a concentration of 0.1 wt% to 1 wt% is obtained;
  • the metal sheet covered with the graphene coating is treated in an inert gas atmosphere at 300 to 900 ° C for 2 to 6 hours to obtain a metal anticorrosive graphene coating.
  • the graphene sheet has a thickness of 4 nm or less and a particle diameter of 100 to 6000 nm.
  • the dispersing agent of the graphene dispersion may be cyclopentanone, cyclohexanone, vinyl pyrrolidone, 1,3-dimethyl-2-imidazoline benzyl benzoin Acid, N,N-dimethylpropenyl ketone, N-ethyl-2-pyrrolidone, N-methylpyrrolidone, cyclohexylpyrrolidone, N-octylpyrrolidone, ethyl acetate, N-dodecylpyrrolidone , one of pyridine, dimethyl decanoate, ethanol, acetone, vinyl acetate, ethylene glycol, heptane, pentane, hexane, formamide, dimethylformamide, dimethyl sulfoxide and tetrahydrofuran Or a variety.
  • the polar solvent in the step (2) is one or more of ethanol, methanol, propanol, isopropanol, water, acetone, pyridine, acetic acid and acetonitrile.
  • the single metal may be, but not limited to, iron, copper, nickel or aluminum, etc.
  • the alloy may be, but not limited to, an iron alloy (including steel), a copper alloy, a nickel alloy, or an aluminum alloy.
  • the metal anticorrosive graphene coating obtained in the step (5) may have a thickness of from 20 nm to 10 ⁇ m.
  • the raw material of the graphene dispersion used in the present invention is graphite, the raw material is easy to obtain, and the cost is low;
  • the graphene coating of the invention adopts the interface transfer technology, the obtained graphene film is uniform, the thickness is controllable, the efficiency is high, the preparation method is simple and easy to be scaled preparation;
  • the method can transfer the graphene film to a single metal or alloy surface of any shape, without being limited by the shape of the material;
  • the graphene anti-corrosion layer is closely packed on the surface of metal or alloy, has the advantages of isolating water and air, and has strong corrosion resistance.
  • the low-frequency impedance modulus of the graphene coating is increased from 10 -2 to 10 -7 , which can be applied to the substrate. It has a more effective protection effect; and it is soaked in a strong corrosive solution for many days, the low-frequency impedance modulus is basically unchanged, showing excellent corrosion resistance stability.
  • Figure 1 is a scanning electron micrograph of a graphene coating of the present invention.
  • Figure 2 is a Bode plot of uncoated carbon steel and graphene coated carbon steel in a 0.1 mol L -1 sulfuric acid solution.
  • a carbon steel sheet covered with graphene was treated at 300 ° C for 6 hours in an argon atmosphere to obtain a corrosion-resistant graphene coating.
  • the graphene coating was observed using a scanning electron microscope, and the thickness of the graphene coating was about 100 nm. As shown in Fig. 1, it can be seen from Fig. 1 that the graphene sheets have a size of about 500 nm to 1 ⁇ m, and these graphene sheets are closely stacked. Together, a dense protective layer is formed.
  • the uncoated carbon steel and the graphene-coated carbon steel were subjected to a corrosion test in a 0.1 mol L -1 sulfuric acid solution.
  • the Bode diagram of the two is shown in Figure 2.
  • the upper line is the Bode plot of pure carbon steel and the lower line is the Bode plot of carbon steel covered with graphene. From the figure, it can be found that graphene Carbon steel has a large impedance in both the low frequency region and the high frequency region, showing a good anticorrosive effect.
  • a copper-zinc alloy sheet covered with graphene was treated at 600 ° C for 2 hours in a helium atmosphere to obtain a corrosion-resistant graphene coating.
  • the obtained graphene coating has a thickness of about 10 ⁇ m and good corrosion resistance.
  • step (2) (4) inserting the cleaned nickel rod into the solution containing the graphene layer in step (2), performing interface transfer of the film, and obtaining a uniform graphene coating on the surface of the nickel rod;
  • a nickel rod covered with graphene was treated at 400 ° C for 5 hours in an argon atmosphere to obtain a corrosion-resistant graphene coating.
  • the obtained graphene coating has a thickness of about 20 nm and good corrosion resistance.
  • step (2) (4) inserting the cleaned aluminum sheet into the solution containing the graphene layer in step (2), performing interface transfer of the film, and obtaining a uniform graphene coating on the surface of the aluminum sheet;
  • the obtained graphene coating has a thickness of about 50 nm and good corrosion resistance.

Abstract

A method for preparing an anticorrosion graphene composite coating for metal comprises the following steps: (1)using graphite as a raw material and preparing a graphene dispersion of the concentration of 0.1wt% to 1wt%; (2) dropping the graphene dispersion to the surface of a polar solvent to form a graphene thin-film layer on the surface of the polar solvent; (3) cleaning a single metal or alloy to form a hydrophilic surface; (4) inserting the cleaned single metal or alloy into a solution containing the graphene layer in step (2), and transferring the interface of the thin film, so as to obtain a graphene coating; and (5) treating a metal sheet covered with the graphene coating for 2 hours at a high temperature in an inert gas environment, so as to obtain an anticorrosion graphene coating for metal. The graphene coating is coated on the surface of a metal or alloy by using the interfacial transfer method, and the prepared graphene coating has the advantages of stability, high efficiency, non-toxicity, isolation from water and air, and the like.

Description

一种金属防腐石墨烯复合涂层的制备方法Method for preparing metal anticorrosive graphene composite coating 技术领域Technical field
本发明涉及纳米材料领域，具体地，涉及一种金属防腐石墨烯复合涂层的制备方法。The invention relates to the field of nano materials, in particular to a method for preparing a metal anticorrosive graphene composite coating.
背景技术Background technique
金属腐蚀是一个非常严重的全球性问题，它对国民经济造成了直接的损失，因此，世界各国的科学家们都在努力地寻找有效的金属防护技术手段。腐蚀源于金属的表面同空气、水或其他物质发生了接触，目前普遍采用的防腐蚀方法是用惰性金属、导电聚合物、巯基的单分子层等保护层，但这些保护层材料都有其自身限制。自组装在金属表面的巯基单分子层不能耐100℃以上的温度；而聚合物涂层相对较厚，从而会显著改变下层金属的物理性质。Metal corrosion is a very serious global problem that directly causes losses to the national economy. Therefore, scientists all over the world are striving to find effective metal protection techniques. Corrosion originates from the contact of air, water or other substances on the surface of the metal. The commonly used anti-corrosion method is to use a protective layer of inert metal, conductive polymer, sulfhydryl monolayer, etc., but these protective layer materials have Self limit. The ruthenium-based monolayer self-assembled on the metal surface cannot withstand temperatures above 100 ° C; while the polymer coating is relatively thick, which can significantly alter the physical properties of the underlying metal.
石墨烯是一种仅有单原子层厚度的新型碳材料，具有独特的结构和优异的物理化学性能。由于其具有超大的比表面积、优异的抗渗透性、高的热稳定性和化学稳定性等优点，故在金属材料的防腐领域也具有非常大的潜力。主要是由于石墨烯的层状结构使得其有快速的导电性，电子会通过石墨烯传递到金属涂层上，阴极电子不会直接发生在金属上，而是直接与涂层发生反应，这样就会降低对金属的溶解，从而实现对金属的保护。专利申请号201510785643.6公开了利用PECVD方法在锆合金表面原位生长垂直石墨烯的方法，该石墨烯层提高了锆合金的耐腐蚀性能和抗磨损能力。发明专利申请号为201610148083.8的专利公开了一种用于不锈钢表面的石墨烯防腐涂层。其是以石墨为原料，通过氧化还原法制备得到石墨烯粉末，然后对石墨烯粉末进行冷冻干燥，将石墨烯粉末放在压片机中压成石墨烯薄膜，然后石墨烯薄膜放在不锈钢基底上方作为离子溅射的靶材，经离子溅射后石墨烯薄膜被打碎从而沉积在不锈钢表面，得到石墨烯防腐涂层。Kang等通过自组装的方式，将氧化石墨烯旋涂在沉积有SiO2的硅片上，经热处理还原得到多层石墨烯薄膜，在Cu和Fe的基底上进行氧化实验测试，覆盖有石墨烯的金属表面得到有效保护。Liu等采用浸渍法在Al表面涂上氧化石墨烯，由于Al的活性，将氧化石墨烯还原为石墨烯，该涂层显示出高的抗腐蚀性。Chen等利用CVD法在纯金属Cu和Cu/Ni合金表面制备的石墨烯的抗氧化性能，电化学测试发现石墨烯在保护金属表面形成透明的导电惰性薄膜涂层，能有效防止金属在多种环境下(空气、溶液中)的氧化，同时 发现石墨烯晶粒边界处会发生局部氧化，因此石墨烯的质量将是影响其抗氧化性的关键。澳大利亚的Nick Bribilis探索了石墨烯作为在Ni和Cu表面的防腐涂层的耐蚀性，先采用CVD方法在纯Ni和纯Cu表面沉积一层石墨烯，电化学研究表明，石墨烯在金属表面形成离子阻碍，能有效阻止金属在盐溶液中的电化学腐蚀。Prasai等采用CVD法在Cu和Ni表面制备石墨烯涂层，在Cu基底上生长石墨烯涂层使耐蚀性提高7倍，而在Ni基底上生长石墨烯涂层使耐蚀性提高20倍，并且建立了单层或多层石墨烯薄膜涂层的数量模型来描述其钝化机制。S.Raman等研究了CVD法制备Cu基石墨烯薄膜涂层在NaCl溶液中的腐蚀行为，发现电化学腐蚀的阳极和阴极电流都减小了1～2个数量级，交流阻抗谱显示石墨烯涂层显著提高了金属的阻抗。Graphene is a new type of carbon material with only a single atomic layer thickness, with unique structure and excellent physical and chemical properties. Due to its large specific surface area, excellent permeability resistance, high thermal stability and chemical stability, it also has great potential in the field of corrosion protection of metallic materials. Mainly due to the layered structure of graphene, which has rapid conductivity, electrons are transferred to the metal coating through graphene, and the cathode electrons do not directly occur on the metal, but directly react with the coating, thus It will reduce the dissolution of the metal and thus protect the metal. Patent Application No. 201510785643.6 discloses a method for in situ growth of vertical graphene on the surface of a zirconium alloy by a PECVD method which improves the corrosion resistance and wear resistance of the zirconium alloy. Patent No. 201610148083.8 discloses a graphene anticorrosive coating for a stainless steel surface. It is made of graphite as raw material, and the graphene powder is prepared by redox method. Then, the graphene powder is freeze-dried, the graphene powder is placed in a tableting machine and pressed into a graphene film, and then the graphene film is placed on a stainless steel substrate. As a target for ion sputtering, the graphene film is broken after ion sputtering to deposit on the surface of the stainless steel to obtain a graphene anticorrosive coating. Kang et al. spin-coated graphene oxide on a silicon wafer deposited with SiO 2 by self-assembly, and obtained a multilayer graphene film by heat treatment, and subjected to oxidation test on Cu and Fe substrates, covered with graphene. The metal surface is effectively protected. Liu et al. applied graphene oxide to the Al surface by dipping, and reduced graphene oxide to graphene due to the activity of Al, which showed high corrosion resistance. Chen et al. The oxidation resistance of graphene prepared on the surface of pure metal Cu and Cu/Ni alloy by CVD method. Electrochemical tests show that graphene forms a transparent conductive inert film coating on the surface of protective metal, which can effectively prevent metal in various kinds. Oxidation in the environment (air, solution), and local oxidation occurs at the grain boundaries of the graphene, so the quality of graphene will be the key to affect its oxidation resistance. Australia's Nick Bribilis explored the corrosion resistance of graphene as an anti-corrosion coating on Ni and Cu surfaces. First, a layer of graphene was deposited on the surface of pure Ni and pure Cu by CVD. Electrochemical studies showed that graphene was on the metal surface. The formation of ion barriers can effectively prevent the electrochemical corrosion of metals in salt solutions. Prasai et al. used a CVD method to prepare a graphene coating on Cu and Ni surfaces, a graphene coating on a Cu substrate to improve corrosion resistance by 7 times, and a graphene coating on a Ni substrate to increase corrosion resistance by 20 times. And a quantitative model of a single or multi-layer graphene film coating was established to describe its passivation mechanism. S. Raman et al. studied the corrosion behavior of Cu-based graphene film coatings prepared by CVD in NaCl solution. It was found that the electrochemical corrosion of the anode and cathode currents were reduced by one to two orders of magnitude, and the AC impedance spectrum showed graphene coating. The layer significantly increases the impedance of the metal.
综上所述，目前金属表面石墨烯涂层主要的制备方法是CVD法和氧化还原法，但是这些方法都难以实现大规模制备大面积的无缺陷石墨烯薄膜，仍然是制约其在金属防腐领域的发展的瓶颈。In summary, the main preparation methods of graphene coating on metal surface are CVD method and redox method, but these methods are difficult to realize large-scale preparation of large-area defect-free graphene film, which still restricts its in the field of metal anti-corrosion. The bottleneck of development.
发明内容Summary of the invention
针对上述技术问题，本发明的目的在于提供一种用于金属表面的高隔绝防腐纳米涂层，同时提供高效防腐涂层的制备方法及用途。In view of the above technical problems, an object of the present invention is to provide a high-isolation anti-corrosion nano-coating for a metal surface, and to provide a preparation method and use of a high-efficiency anti-corrosion coating.
本发明的金属防腐石墨烯涂层的制备方法，是在单一金属或合金的表面覆盖一层石墨烯，其中所述的金属或合金包括铜、铜合金、镍、镍合金、铝、铝合金等；所述的石墨烯涂层的厚度约为20nm-10μm。用界面转移方法将石墨烯涂覆在金属或合金表面，制备的石墨烯涂层具有稳定、高效、无毒、隔绝水和空气等优点，实现抗腐蚀的作用，可广泛应用于海洋、陆地以及地下工业生产环境和日常生活环境中使用的钢材等的腐蚀防护。The metal anti-corrosion graphene coating of the present invention is prepared by coating a surface of a single metal or alloy with a layer of graphene, wherein the metal or alloy comprises copper, copper alloy, nickel, nickel alloy, aluminum, aluminum alloy, etc. The graphene coating has a thickness of about 20 nm to 10 μm. Graphene is coated on the surface of metal or alloy by interface transfer method. The prepared graphene coating has the advantages of stability, high efficiency, non-toxicity, water and air insulation, and corrosion resistance. It can be widely used in ocean, land and Corrosion protection of steel used in underground industrial production environments and daily life environments.
为实现上述目的，本发明的金属防腐石墨烯涂层的制备方法的具体工艺步骤如下：In order to achieve the above object, the specific process steps of the method for preparing the metal anticorrosive graphene coating of the present invention are as follows:
本发明的金属防腐石墨烯涂层的制备方法，包括以下步骤：The preparation method of the metal anticorrosive graphene coating of the invention comprises the following steps:
(1)优选以天然石墨为原料通过机械剥层的方法得到是石墨烯片，并制得浓度为0.1wt％-1wt％的石墨烯分散液；(1) Preferably, the graphene sheet is obtained by mechanical stripping using natural graphite as a raw material, and a graphene dispersion having a concentration of 0.1 wt% to 1 wt% is obtained;
(2)将步骤(1)所述石墨烯分散液滴加在极性溶剂表面，在极性溶剂表面形成一层均匀的石墨烯薄膜层；(2) adding the graphene dispersion droplets in the step (1) to the surface of the polar solvent to form a uniform graphene film layer on the surface of the polar solvent;
(3)将单金属或合金进行清洗，去除金属表面的油污，使其形成亲水的表面；(3) cleaning a single metal or alloy to remove oil on the metal surface to form a hydrophilic surface;
(4)将清洗后的单金属或合金***到步骤(2)含石墨烯薄膜层的溶液中，进行薄膜的界面转移，在单金属或合金表面得到均匀的石墨烯涂层； (4) inserting the cleaned single metal or alloy into the solution containing the graphene film layer in the step (2), performing interface transfer of the film, and obtaining a uniform graphene coating on the surface of the single metal or alloy;
(5)将覆盖有石墨烯涂层的金属片在惰性气体环境中、在300-900℃下处理2-6小时，得到金属防腐石墨烯涂层。(5) The metal sheet covered with the graphene coating is treated in an inert gas atmosphere at 300 to 900 ° C for 2 to 6 hours to obtain a metal anticorrosive graphene coating.
根据本发明的制备方法，作为优选地，所述石墨烯片的厚度小于等于4nm，粒径为100-6000nm。According to the production method of the present invention, preferably, the graphene sheet has a thickness of 4 nm or less and a particle diameter of 100 to 6000 nm.
根据本发明的制备方法，作为优选地，所述石墨烯分散液的分散剂可以是环戊酮、环己酮、乙烯基吡咯烷酮、1,3-二甲基-2-咪唑啉苯甲基安息香酸、N,N-二甲基丙烯基脲酮、N-乙基-2-吡咯烷酮、N-甲基吡咯烷酮、环己基吡咯烷酮、N-辛基吡咯烷酮、乙酸乙酯、N-十二烷基吡咯烷酮、吡啶、酞酸二甲酯、乙醇、丙酮、乙酸乙烯酯、乙二醇、庚烷、戊烷、己烷、甲酰胺、二甲基甲酰胺、二甲基亚砜和四氢呋喃中的一种或多种。According to the preparation method of the present invention, preferably, the dispersing agent of the graphene dispersion may be cyclopentanone, cyclohexanone, vinyl pyrrolidone, 1,3-dimethyl-2-imidazoline benzyl benzoin Acid, N,N-dimethylpropenyl ketone, N-ethyl-2-pyrrolidone, N-methylpyrrolidone, cyclohexylpyrrolidone, N-octylpyrrolidone, ethyl acetate, N-dodecylpyrrolidone , one of pyridine, dimethyl decanoate, ethanol, acetone, vinyl acetate, ethylene glycol, heptane, pentane, hexane, formamide, dimethylformamide, dimethyl sulfoxide and tetrahydrofuran Or a variety.
作为优选地，步骤(2)所述极性溶剂是乙醇、甲醇、丙醇、异丙醇、水、丙酮、吡啶、乙酸和乙腈中的一种或多种。Preferably, the polar solvent in the step (2) is one or more of ethanol, methanol, propanol, isopropanol, water, acetone, pyridine, acetic acid and acetonitrile.
根据本发明的制备方法，优选使用单金属片或合金片。所述单金属可以为但不限于铁、铜、镍或铝等，所述合金可以为但不限于铁合金(包括钢)、铜合金、镍合金或铝合金等。According to the production method of the present invention, it is preferred to use a single metal sheet or an alloy sheet. The single metal may be, but not limited to, iron, copper, nickel or aluminum, etc., and the alloy may be, but not limited to, an iron alloy (including steel), a copper alloy, a nickel alloy, or an aluminum alloy.
根据本发明的制备方法，其中，步骤(5)得到的金属防腐石墨烯涂层的厚度可以达到20nm-10μm。According to the preparation method of the present invention, the metal anticorrosive graphene coating obtained in the step (5) may have a thickness of from 20 nm to 10 μm.
本发明的金属防腐石墨烯复合涂层的制备方法，与现有技术相比，具有以下优点：The preparation method of the metal anticorrosive graphene composite coating of the invention has the following advantages compared with the prior art:
(1)本发明采用的石墨烯分散液的原料是石墨，原料易得，成本低廉；(1) The raw material of the graphene dispersion used in the present invention is graphite, the raw material is easy to obtain, and the cost is low;
(2)本发明的石墨烯涂层采用界面转移技术，所得的石墨烯薄膜均匀，厚度可控，效率高，制备方法简单易于规模化制备；(2) The graphene coating of the invention adopts the interface transfer technology, the obtained graphene film is uniform, the thickness is controllable, the efficiency is high, the preparation method is simple and easy to be scaled preparation;
(3)该方法可将石墨烯薄膜转移到任何形状的单一金属或合金表面，不受材料形状的限制；(3) The method can transfer the graphene film to a single metal or alloy surface of any shape, without being limited by the shape of the material;
(4)石墨烯防腐层在金属或合金表面堆积紧密，具有隔绝水和空气等优点，耐腐蚀性能强，石墨烯涂层的低频阻抗模值从10-2提高到10-7，能对基体起到更有效的保护作用；且在强腐蚀性溶液中浸泡多天，低频阻抗模值基本不变，显示出优异的耐腐蚀稳定性。(4) The graphene anti-corrosion layer is closely packed on the surface of metal or alloy, has the advantages of isolating water and air, and has strong corrosion resistance. The low-frequency impedance modulus of the graphene coating is increased from 10 -2 to 10 -7 , which can be applied to the substrate. It has a more effective protection effect; and it is soaked in a strong corrosive solution for many days, the low-frequency impedance modulus is basically unchanged, showing excellent corrosion resistance stability.
(5)可广泛应用于海洋、陆地以及地下工业生产环境和日常生活环境中使用的钢材等的腐蚀防护。 (5) It can be widely used for corrosion protection of steel materials used in marine, land, and underground industrial production environments and daily life environments.
附图说明DRAWINGS
图1为本发明石墨烯涂层的扫描电镜图。Figure 1 is a scanning electron micrograph of a graphene coating of the present invention.
图2为无涂层碳钢和有石墨烯涂层的碳钢在0.1mol L-1的硫酸溶液中的波特(Bode)图对比。Figure 2 is a Bode plot of uncoated carbon steel and graphene coated carbon steel in a 0.1 mol L -1 sulfuric acid solution.
具体实施方式detailed description
下面结合实施例对本发明技术方案予以进一步的说明。The technical solution of the present invention will be further described below in conjunction with the embodiments.
实施例1Example 1
制备金属防腐石墨烯涂层：Preparation of metal anticorrosive graphene coating:
(1)以天然石墨为原料，通过机械剥层的方法得到浓度为0.1wt％石墨烯环戊酮分散液，其中石墨烯片的厚度3nm，粒径为1000nm；(1) using natural graphite as a raw material, by mechanical stripping method to obtain a concentration of 0.1 wt% graphene cyclopentanone dispersion, wherein the graphene sheet has a thickness of 3 nm and a particle diameter of 1000 nm;
(2)将步骤(2)的石墨烯分散滴加在乙醇表面，在极性溶剂表面形成一层均匀的石墨烯薄膜；(2) adding the graphene dispersion of the step (2) to the surface of the ethanol to form a uniform graphene film on the surface of the polar solvent;
(3)将碳钢片进行清洗，去除表面的油污，使其形成亲水的表面；(3) cleaning the carbon steel sheet to remove oil on the surface to form a hydrophilic surface;
(4)将清洗后的碳钢片***到步骤(2)含石墨烯层的溶液中，进行薄膜的界面转移，在碳钢表面得到均匀的石墨烯涂层；(4) inserting the cleaned carbon steel sheet into the solution containing the graphene layer in the step (2), performing interface transfer of the film, and obtaining a uniform graphene coating on the surface of the carbon steel;
(5)将覆盖有是石墨烯的碳钢片在氩气环境中在300℃下处理6小时，得到耐腐蚀的石墨烯涂层。(5) A carbon steel sheet covered with graphene was treated at 300 ° C for 6 hours in an argon atmosphere to obtain a corrosion-resistant graphene coating.
使用扫面电镜观察石墨烯涂层，所述石墨烯涂层厚度在100nm左右，如图1所示，从图1可以看出，石墨烯片尺寸约为500nm-1μm，这些石墨烯片紧密堆叠在一起，形成致密保护层。The graphene coating was observed using a scanning electron microscope, and the thickness of the graphene coating was about 100 nm. As shown in Fig. 1, it can be seen from Fig. 1 that the graphene sheets have a size of about 500 nm to 1 μm, and these graphene sheets are closely stacked. Together, a dense protective layer is formed.
将未涂层的碳钢和制作的有石墨烯涂层的碳钢在0.1mol L-1的硫酸溶液中，，进行腐蚀试验。二者的波特(Bode)图对比如图2所示，上线为纯碳钢的波特图、下线为覆盖有石墨烯的碳钢的波特图，从图中可以发现，石墨烯的碳钢在低频区和高频区都具有较大的阻抗，显示出较好的防腐效果。The uncoated carbon steel and the graphene-coated carbon steel were subjected to a corrosion test in a 0.1 mol L -1 sulfuric acid solution. The Bode diagram of the two is shown in Figure 2. The upper line is the Bode plot of pure carbon steel and the lower line is the Bode plot of carbon steel covered with graphene. From the figure, it can be found that graphene Carbon steel has a large impedance in both the low frequency region and the high frequency region, showing a good anticorrosive effect.
实施例2Example 2
制备金属防腐石墨烯涂层：Preparation of metal anticorrosive graphene coating:
(1)以天然石墨为原料，通过机械剥层的方法得到浓度为1wt％石墨烯乙酸乙酯分散液，其中石墨烯片的厚度4nm，粒径为6000nm；(1) using natural graphite as a raw material, by mechanical stripping method to obtain a concentration of 1 wt% graphene ethyl acetate dispersion, wherein the graphene sheet has a thickness of 4 nm and a particle diameter of 6000 nm;
(2)将步骤(2)的石墨烯分散滴加在水表面，在极性溶剂表面形成一层均匀的石墨烯薄膜； (2) adding the graphene dispersion of the step (2) to the surface of the water to form a uniform graphene film on the surface of the polar solvent;
(3)将铜锌合金片进行清洗，去除表面的油污，使其形成亲水的表面；(3) cleaning the copper-zinc alloy sheet to remove oil on the surface to form a hydrophilic surface;
(4)将清洗后的铜锌合金片***到步骤(2)含石墨烯层的溶液中，进行薄膜的界面转移，在铜锌合金片表面得到均匀的石墨烯涂层；(4) inserting the cleaned copper-zinc alloy sheet into the solution containing the graphene layer in the step (2), performing interface transfer of the film, and obtaining a uniform graphene coating on the surface of the copper-zinc alloy sheet;
(5)将覆盖有是石墨烯的铜锌合金片在氦气环境中在600℃下处理2小时，得到耐腐蚀的石墨烯涂层。(5) A copper-zinc alloy sheet covered with graphene was treated at 600 ° C for 2 hours in a helium atmosphere to obtain a corrosion-resistant graphene coating.
所制得的石墨烯涂层厚度在10μm左右，耐腐蚀性能良好。The obtained graphene coating has a thickness of about 10 μm and good corrosion resistance.
实施例3Example 3
制备金属防腐石墨烯涂层：Preparation of metal anticorrosive graphene coating:
(1)以天然石墨为原料，通过机械剥层的方法得到浓度为0.5wt％石墨烯丙酮分散液，其中石墨烯片的厚度1nm，粒径为100nm；(1) using natural graphite as a raw material, by mechanical stripping method to obtain a concentration of 0.5 wt% graphene acetone dispersion, wherein the graphene sheet has a thickness of 1 nm and a particle diameter of 100 nm;
(2)将步骤(2)的石墨烯分散滴加在丙酮表面，在极性溶剂表面形成一层均匀的石墨烯薄膜；(2) adding the graphene dispersion of the step (2) to the surface of the acetone to form a uniform graphene film on the surface of the polar solvent;
(3)将镍棒进行清洗，去除表面的油污，使其形成亲水的表面；(3) cleaning the nickel rod to remove oil on the surface to form a hydrophilic surface;
(4)将清洗后的镍棒***到步骤(2)含石墨烯层的溶液中，进行薄膜的界面转移，在镍棒表面得到均匀的石墨烯涂层；(4) inserting the cleaned nickel rod into the solution containing the graphene layer in step (2), performing interface transfer of the film, and obtaining a uniform graphene coating on the surface of the nickel rod;
(5)将覆盖有是石墨烯的镍棒在氩气环境中在400℃下处理5小时，得到耐腐蚀的石墨烯涂层。(5) A nickel rod covered with graphene was treated at 400 ° C for 5 hours in an argon atmosphere to obtain a corrosion-resistant graphene coating.
所制得的石墨烯涂层厚度在20nm左右，耐腐蚀性能良好。The obtained graphene coating has a thickness of about 20 nm and good corrosion resistance.
实施例4Example 4
制备金属防腐石墨烯涂层：Preparation of metal anticorrosive graphene coating:
(1)以天然石墨为原料，通过机械剥层的方法得到浓度为0.8wt％石墨烯四氢呋喃分散液，其中石墨烯片的厚度2nm，粒径为500nm；(1) using natural graphite as a raw material, by mechanical stripping method to obtain a concentration of 0.8 wt% graphene tetrahydrofuran dispersion, wherein the graphene sheet has a thickness of 2 nm and a particle diameter of 500 nm;
(2)将步骤(2)的石墨烯分散滴加在乙酸表面，在极性溶剂表面形成一层均匀的石墨烯薄膜；(2) adding the graphene dispersion of the step (2) to the surface of the acetic acid to form a uniform graphene film on the surface of the polar solvent;
(3)将铝片进行清洗，去除表面的油污，使其形成亲水的表面；(3) cleaning the aluminum sheet to remove oil on the surface to form a hydrophilic surface;
(4)将清洗后的铝片***到步骤(2)含石墨烯层的溶液中，进行薄膜的界面转移，在铝片表面得到均匀的石墨烯涂层；(4) inserting the cleaned aluminum sheet into the solution containing the graphene layer in step (2), performing interface transfer of the film, and obtaining a uniform graphene coating on the surface of the aluminum sheet;
(5)将覆盖有是石墨烯的铝片在氩气环境中在900℃下处理2小时，得到耐腐蚀的石墨烯涂层。(5) An aluminum sheet covered with graphene was treated at 900 ° C for 2 hours in an argon atmosphere to obtain a corrosion-resistant graphene coating.
所制得的石墨烯涂层厚度在50nm左右，耐腐蚀性能良好。The obtained graphene coating has a thickness of about 50 nm and good corrosion resistance.
当然，本发明还可以有多种实施例，在不背离本发明精神及其实质的情况下，熟悉本领域的技术人员可根据本发明的公开做出各种相应的改变和变形，但这些相 应的改变和变形都应属于本发明的权利要求的保护范围。 The invention may, of course, be embodied in various other modifications and changes without departing from the spirit and scope of the invention. All changes and modifications are intended to fall within the scope of the appended claims.

Claims (9)

  1. 一种金属防腐石墨烯复合涂层的制备方法，包括以下步骤：A method for preparing a metal anticorrosive graphene composite coating comprises the following steps:
    (1)以石墨为原料通过机械剥层的方法得到石墨烯片，并制得浓度为0.1wt％-1wt％的石墨烯分散液；(1) obtaining a graphene sheet by mechanical stripping using graphite as a raw material, and preparing a graphene dispersion having a concentration of 0.1 wt% to 1 wt%;
    (2)将步骤(1)所述石墨烯分散液滴加在极性溶剂表面，在极性溶剂表面形成一层石墨烯薄膜层；(2) adding the graphene dispersion droplets in the step (1) to the surface of the polar solvent to form a layer of graphene film on the surface of the polar solvent;
    (3)将单金属或合金进行清洗，去除金属表面的油污，使其形成亲水的表面；(3) cleaning a single metal or alloy to remove oil on the metal surface to form a hydrophilic surface;
    (4)将清洗后的单金属或合金***到步骤(2)含石墨烯薄膜层的溶液中，进行薄膜的界面转移，在单金属或合金表面得到石墨烯涂层；(4) inserting the cleaned single metal or alloy into the solution containing the graphene film layer in the step (2), performing interface transfer of the film, and obtaining a graphene coating on the surface of the single metal or alloy;
    (5)将覆盖有石墨烯涂层的金属片在惰性气体环境中、在300-900℃下处理2-6小时，得到金属防腐石墨烯复合涂层。(5) The metal sheet covered with the graphene coating is treated in an inert gas atmosphere at 300-900 ° C for 2-6 hours to obtain a metal anticorrosive graphene composite coating.
  2. 根据权利要求1所述的制备方法，其特征在于，所述石墨为天然石墨。The preparation method according to claim 1, wherein the graphite is natural graphite.
  3. 根据权利要求1或2所述的制备方法，其特征在于，所述石墨烯片的厚度小于等于4nm，粒径为100-6000nm。The production method according to claim 1 or 2, wherein the graphene sheet has a thickness of 4 nm or less and a particle diameter of 100 to 6000 nm.
  4. 根据权利要求1所述的制备方法，其特征在于，所述石墨烯分散液的分散剂是环戊酮、环己酮、乙烯基吡咯烷酮、1,3-二甲基-2-咪唑啉苯甲基安息香酸、N,N-二甲基丙烯基脲酮、N-乙基-2-吡咯烷酮、N-甲基吡咯烷酮、环己基吡咯烷酮、N-辛基吡咯烷酮、乙酸乙酯、N-十二烷基吡咯烷酮、吡啶、酞酸二甲酯、乙醇、丙酮、乙酸乙烯酯、乙二醇、庚烷、戊烷、己烷、甲酰胺、二甲基甲酰胺、二甲基亚砜和四氢呋喃中的一种或多种。The preparation method according to claim 1, wherein the dispersing agent of the graphene dispersion is cyclopentanone, cyclohexanone, vinyl pyrrolidone, 1,3-dimethyl-2-imidazoline benzene Kean acid, N,N-dimethylpropenyl ketone, N-ethyl-2-pyrrolidone, N-methylpyrrolidone, cyclohexyl pyrrolidone, N-octylpyrrolidone, ethyl acetate, N-dodecane Of pyrrolidone, pyridine, dimethyl phthalate, ethanol, acetone, vinyl acetate, ethylene glycol, heptane, pentane, hexane, formamide, dimethylformamide, dimethyl sulfoxide and tetrahydrofuran One or more.
  5. 根据权利要求1所述的制备方法，其特征在于，步骤(2)所述极性溶剂是乙醇、甲醇、丙醇、异丙醇、水、丙酮、吡啶、乙酸和乙腈中的一种或多种。The preparation method according to claim 1, wherein the polar solvent in the step (2) is one or more of ethanol, methanol, propanol, isopropanol, water, acetone, pyridine, acetic acid and acetonitrile. Kind.
  6. 根据权利要求1所述的制备方法，其特征在于，所述单金属或合金为片状。The method according to claim 1, wherein the single metal or alloy is in the form of a sheet.
  7. 根据权利要求1或6所述的制备方法，其特征在于，所述单金属为铁、铜、镍或铝，所述合金为铁合金、铜合金、镍合金或铝合金。The preparation method according to claim 1 or 6, wherein the single metal is iron, copper, nickel or aluminum, and the alloy is an iron alloy, a copper alloy, a nickel alloy or an aluminum alloy.
  8. 根据权利要求1所述的制备方法，其特征在于，步骤(5)得到的金属防腐石墨烯涂层的厚度为20nm-10μm。The preparation method according to claim 1, wherein the metal anticorrosive graphene coating layer obtained in the step (5) has a thickness of from 20 nm to 10 μm.
  9. 根据权利要求1所述的制备方法，其特征在于，步骤(2)在极性溶剂表面形成一层均匀的石墨烯薄膜层；步骤(4)在单金属或合金表面得到均匀的石墨烯涂层。 The preparation method according to claim 1, wherein the step (2) forms a uniform graphene film layer on the surface of the polar solvent; and the step (4) obtains a uniform graphene coating on the surface of the single metal or alloy. .
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