CN111690279A - Preparation method of polydopamine-doped graphene corrosion-resistant coating - Google Patents

Preparation method of polydopamine-doped graphene corrosion-resistant coating Download PDF

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Publication number
CN111690279A
CN111690279A CN202010421579.4A CN202010421579A CN111690279A CN 111690279 A CN111690279 A CN 111690279A CN 202010421579 A CN202010421579 A CN 202010421579A CN 111690279 A CN111690279 A CN 111690279A
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graphene
polydopamine
solution
composite coating
dopamine
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王飞
郑志强
黄平
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Xian Jiaotong University
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Xian Jiaotong University
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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
    • C09D5/08—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
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • 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
    • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
    • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • 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

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

The invention discloses a preparation method of a polydopamine pDA doped graphene GR corrosion-resistant coating. The composite coating is characterized in that graphene is uniformly dispersed in polydopamine to form the composite coating and has strong corrosion resistance. The realization mode is as follows: the poly-dopamine-graphene composite coating is prepared by coating graphene in a poly-dopamine film generated by oxidation autopolymerization of dopamine. In the coating system, the structural defect repair of the graphene is realized by utilizing the structural similarity of polydopamine and the graphene; the characteristic that polydopamine is insulated per se is utilized to isolate graphene from a metal matrix so as to inhibit galvanic corrosion reaction. The composite coating is simple to prepare, environment-friendly, capable of being prepared on the surface of a sample in any shape, and capable of realizing large-scale production.

Description

Preparation method of polydopamine-doped graphene corrosion-resistant coating
Technical Field
The invention relates to the field of functional materials, in particular to a preparation method of a polydopamine-doped graphene corrosion-resistant coating.
Background
In social production and life, metal materials are used as main structural materials, and the metal materials are required to be capable of bearing the corrosion of the external environment and still maintain the original mechanical properties. Research shows that the failure mode of metal materials in nature is mainly fracture and corrosion failure. Statistically, the annual economic loss in the united states due to corrosion failure of metallic materials is $ 2000 billion. Therefore, the corrosion failure of the metal material brings great economic and resource waste for the country. Therefore, the strengthening of the corrosion resistance of the metal material has great significance.
Graphene has received attention from a number of researchers since its discovery. The graphene is formed by the SP of carbon atoms2The two-dimensional material with honeycomb carbon six-ring structure formed by hybridization mode has a single-layer thickness of only 0.335 nm, and is the material with the thinnest thickness currently known. In addition to the honeycomb layered structure where carbon atoms are linked to each other with sigma bonds to form hexagonal rings, the pz orbital of each carbon atom perpendicular to the plane of the sheet can form a large pi bond throughout the layer (similar to a benzene ring). This special carbon six-membered ring structure gives graphene a series of excellent properties, such as conductivity: the electron mobility of graphene can exceed 15000cm at room temperature2V.s, optical property that the light absorption rate of single-layer graphene is only 2.3 percent, the light transmittance can reach 97.7 percent, and the thermal conductivity is that the thermal conductivity of the graphene at room temperature is about 5 × 103W/(m.K), which is more than 10 times that of copper under the same conditions; mechanical properties: lee et al measured the strength of single-layer graphene under an atomic force microscope by a nanoindentation method to be about 130GPa, the Young modulus of the single-layer graphene reaches 1.1TPa, and the graphene is a material with the highest known strength at present; chemical stability: the graphene has a carbon six-membered ring structure, and the surface of the graphene has no chemical functional group, so that the graphene is inert in chemical property. Therefore, graphene is used as a reinforcing phase in a large amount of research to improve the physicochemical properties of the matrix.
At present, a great deal of research is carried out on the mechanical property and the corrosion resistance of a graphene reinforced metal matrix, and the result shows that the hexabasic structure with extremely tiny pore diameter of graphene is the main factor for inhibiting the diffusion of a corrosion medium. However, all currently prepared graphene has structural defects (grain boundaries, point defects, and the like), which weaken the corrosion protection performance of graphene. Therefore, the structure of graphene needs to be repaired to improve the corrosion protection performance of graphene. In addition, studies have also found that galvanic corrosion reactions that exist between graphene and the metal matrix promote metal corrosion, leading to failure of the corrosion protection of graphene. Therefore, aiming at the application of graphene in the field of metal corrosion prevention, repairing the structural defects of graphene and inhibiting galvanic corrosion are two problems which need to be solved urgently.
Disclosure of Invention
In order to solve the existing problems, the invention provides a preparation method of a polydopamine-doped graphene composite coating, and in the coating system, the structural defect repair of graphene is realized by utilizing the structural similarity of polydopamine and graphene; the characteristic that polydopamine is insulated per se is utilized to isolate graphene from a metal matrix so as to inhibit galvanic corrosion reaction. In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a polydopamine-doped graphene corrosion-resistant coating is disclosed, wherein graphene is uniformly distributed in polydopamine to form a composite coating:
firstly, dispersing graphene into deionized water, wherein the concentration of the graphene is 0.1-2g/L, carrying out ultrasonic oscillation for 30-60 minutes, and then carrying out magnetic stirring for 30-60 minutes to realize preliminary dispersion of the graphene. Tris (Tris hydroxymethyl aminomethane) was then added to the graphene aqueous solution, maintaining its concentration at 10 mmol/L. Adjusting the pH value of the solution to stabilize the pH value at 7.5-9. Dopamine is added to the solution to maintain its concentration at 0.1-2 g/L. Immersing the copper foil into the solution, placing the solution in an environment of 15-35 ℃ for reaction for 3-24 hours, and simultaneously stirring the solution continuously and slowly by adopting magnetic stirring.
The graphene sheets used have a size of 1-1000 μm2The number of the layers is 1-10.
The pH value of the solution is adjusted by using common dilute hydrochloric acid, dilute sulfuric acid, sodium hydroxide, ammonia water and other solutions to ensure that the pH value is stabilized at 7.5-9.
The thickness of the prepared polydopamine-doped graphene composite coating is 1-15 nm.
The graphene used includes Graphene (GR), Graphene Oxide (GO), Reduced Graphene Oxide (RGO).
The invention has the following advantages:
1. and repairing the structural defect of the graphene by utilizing the structural similarity of the polydopamine and the graphene.
2. The characteristic that polydopamine is insulated by itself is utilized to inhibit galvanic corrosion reaction between graphene and a metal matrix.
3. The composite coating has simple preparation process and is environment-friendly.
4. The composite coating has excellent corrosion resistance.
5. The poly-dopamine-doped graphene composite coating prepared by the method can be prepared on the surface of a sample in any shape.
Drawings
Fig. 1 is a TEM photograph of a poly-dopamine doped graphene composite coating, wherein (a) is a pure poly-dopamine layer, and (b) is a poly-dopamine doped graphene composite coating;
fig. 2 shows the results of spectrum testing of the polydopamine-doped graphene composite coating, wherein (a) is a raman spectrum and (b) is an ultraviolet absorption spectrum;
FIG. 3 electrochemical performance test results-impedance spectra.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific examples, but the present invention is not limited thereto.
Example 1
The TEM test result of the polydopamine-coated graphene composite coating is shown in FIG. 1, and the result shows that graphene is distributed in polydopamine to successfully prepare the polydopamine-coated graphene composite coating; the coating spectrum test result is shown in fig. 2, and the result shows that the poly-dopamine repairs the structural defects of the graphene through pi-pi conjugation; the corrosion resistance test result of the coating is shown in fig. 3, and the result shows that the galvanic corrosion reaction is inhibited, and the polydopamine-coated graphene composite coating has excellent corrosion resistance. The specific implementation steps are as follows:
firstly, dispersing graphene into deionized water, wherein the concentration of the graphene is 1g/L, carrying out ultrasonic oscillation for 30 minutes, and then carrying out magnetic stirring for 30 minutes to realize preliminary dispersion of the graphene. Tris (Tris hydroxymethyl aminomethane) was then added to the graphene aqueous solution, maintaining its concentration at 10 mmol/L. And ammonia water is adopted to adjust the pH value of the solution, so that the pH value is stabilized to about 8.5. Dopamine was added to the solution to maintain a concentration of 1 g/L. Immersing a copper foil (1cm multiplied by 0.2cm) into the solution, placing the solution in an environment with the temperature of 25 ℃ for reaction for 12 hours, and meanwhile, continuously and slowly stirring by adopting magnetic stirring to prepare the polydopamine-coated graphene composite coating on the surface of the copper foil, wherein the thickness of the polydopamine-coated graphene composite coating is about 5 nm.
Example 2
Firstly, dispersing graphene into deionized water, controlling the concentration of the graphene to be 1g/L, carrying out ultrasonic oscillation for 30 minutes, and then carrying out magnetic stirring for 30 minutes. Tris (Tris hydroxymethyl aminomethane) was then added to the graphene aqueous solution, maintaining its concentration at 10 mmol/L. And (3) adjusting the pH value of the solution by adopting a sodium hydroxide solution to stabilize the pH value to about 8.5. Dopamine was added to the solution to maintain a concentration of 0.5 g/L. Immersing a copper foil (1cm multiplied by 0.2cm) into the solution, placing the solution in an environment with the temperature of 20 ℃ for reacting for 6 hours, and meanwhile, continuously and slowly stirring by adopting magnetic stirring to prepare the polydopamine-coated graphene composite coating with the thickness of about 2 nm.
Example 3
Dispersing graphene into deionized water, wherein the concentration of the graphene is 1g/L, ultrasonically oscillating for 60 minutes, and then magnetically stirring for 60 minutes to realize preliminary dispersion of the graphene. Tris (Tris hydroxymethyl aminomethane) was then added to the graphene aqueous solution, maintaining its concentration at 10 mmol/L. The pH value of the solution is adjusted by using a sodium hydroxide solution, so that the pH value is stabilized to be about 8. Dopamine was added to the solution, maintaining the concentration of dopamine at 2 g/L. Immersing a copper foil (1cm multiplied by 0.2cm) into the solution, placing the solution in an environment with the temperature of 30 ℃ for reacting for 18 hours, and continuously and slowly stirring the solution by adopting magnetic stirring, namely forming a polydopamine-coated graphene composite coating on the surface of the copper foil, wherein the thickness of the coating is about 10 nm.

Claims (5)

1. A preparation method of a polydopamine-doped graphene corrosion-resistant coating is characterized by comprising the following steps: the graphene is uniformly distributed in the polydopamine to form a composite coating:
firstly, dispersing graphene into deionized water, wherein the concentration of the graphene is 0.1-2g/L, carrying out ultrasonic oscillation for 30-60 minutes, then carrying out magnetic stirring for 30-60 minutes to realize primary dispersion on the graphene, then adding Tris and Tris into a graphene aqueous solution, keeping the concentration of the Tris at 10mmol/L, adjusting the pH value of the solution to 7.5-9, adding dopamine into the solution, keeping the concentration of the dopamine at 0.1-2g/L, immersing a copper foil into the solution, placing the solution in an environment at 15-35 ℃ for reaction for 3-24 hours, and meanwhile, carrying out magnetic stirring continuously and slowly.
2. The method of claim 1, wherein: the graphene used is 1-1000 μm in size2The number of the layers is 1-10.
3. The method of claim 1, wherein: the pH value of the solution is adjusted by adopting common dilute hydrochloric acid, dilute sulfuric acid, sodium hydroxide and ammonia water solution to ensure that the pH value reaches 7.5-9.
4. The method of claim 1, wherein: the thickness of the prepared polydopamine-doped graphene composite coating is 1-15 nm.
5. The method of claim 1, wherein: the adopted graphene comprises graphene GR, graphene oxide GO and reduced graphene oxide RGO.
CN202010421579.4A 2020-05-18 2020-05-18 Preparation method of polydopamine-doped graphene corrosion-resistant coating Pending CN111690279A (en)

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Cited By (10)

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Publication number Priority date Publication date Assignee Title
CN112300697A (en) * 2020-11-17 2021-02-02 中山大学 Preparation method and application of modified anticorrosive super-hydrophobic integrated coating
CN112624096A (en) * 2020-12-23 2021-04-09 西安交通大学 Graphene surface dispersibility modification method
CN112680106A (en) * 2020-12-22 2021-04-20 清华大学 Mussel protein-graphene composite coating and method for carrying out surface treatment on metal material
CN113088117A (en) * 2021-03-31 2021-07-09 杭州佳杭新材料科技有限公司 Preparation method of graphene composite anticorrosive coating
CN113308693A (en) * 2021-04-30 2021-08-27 江苏龙山管件有限公司 High-strength corrosion-resistant stainless steel pipe fitting and machining process thereof
CN113823460A (en) * 2021-10-29 2021-12-21 盐城师范学院 Preparation method of silver nanowire transparent conductive film
CN114456711A (en) * 2021-12-15 2022-05-10 浙江亚厦装饰股份有限公司 Chromium-free Dacromet coating liquid and preparation method and application thereof
CN114471185A (en) * 2020-10-27 2022-05-13 山东海科创新研究院有限公司 Surface-modified PVDF anti-fouling hydrophilic membrane and one-step preparation process and application thereof
CN114601962A (en) * 2020-12-09 2022-06-10 上海交通大学 Polydopamine-graphene composite coating on surface of biomedical magnesium alloy and preparation thereof
CN116535931A (en) * 2023-05-08 2023-08-04 广州特种承压设备检测研究院 Water-based epoxy resin anticorrosive paint and preparation method and application thereof

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114471185A (en) * 2020-10-27 2022-05-13 山东海科创新研究院有限公司 Surface-modified PVDF anti-fouling hydrophilic membrane and one-step preparation process and application thereof
CN112300697A (en) * 2020-11-17 2021-02-02 中山大学 Preparation method and application of modified anticorrosive super-hydrophobic integrated coating
CN114601962A (en) * 2020-12-09 2022-06-10 上海交通大学 Polydopamine-graphene composite coating on surface of biomedical magnesium alloy and preparation thereof
CN112680106A (en) * 2020-12-22 2021-04-20 清华大学 Mussel protein-graphene composite coating and method for carrying out surface treatment on metal material
CN112624096A (en) * 2020-12-23 2021-04-09 西安交通大学 Graphene surface dispersibility modification method
CN113088117A (en) * 2021-03-31 2021-07-09 杭州佳杭新材料科技有限公司 Preparation method of graphene composite anticorrosive coating
CN113308693A (en) * 2021-04-30 2021-08-27 江苏龙山管件有限公司 High-strength corrosion-resistant stainless steel pipe fitting and machining process thereof
CN113823460A (en) * 2021-10-29 2021-12-21 盐城师范学院 Preparation method of silver nanowire transparent conductive film
CN113823460B (en) * 2021-10-29 2024-04-16 盐城师范学院 Preparation method of silver nanowire transparent conductive film
CN114456711A (en) * 2021-12-15 2022-05-10 浙江亚厦装饰股份有限公司 Chromium-free Dacromet coating liquid and preparation method and application thereof
CN114456711B (en) * 2021-12-15 2023-03-10 浙江亚厦装饰股份有限公司 Chromium-free Dacromet coating liquid and preparation method and application thereof
CN116535931A (en) * 2023-05-08 2023-08-04 广州特种承压设备检测研究院 Water-based epoxy resin anticorrosive paint and preparation method and application thereof

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