CN113122044B - Cationic dopamine-functionalized graphene water-based anticorrosive paint, and preparation method and application thereof - Google Patents
Cationic dopamine-functionalized graphene water-based anticorrosive paint, and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a cationic dopamine functionalized graphene water-based anticorrosive paint, and a preparation method and application thereof. The cationic dopamine functionalized graphene water-based anticorrosive paint comprises: the cationic dopamine-functionalized graphene material is uniformly dispersed in the aqueous resin emulsion. The preparation method of the water-based anticorrosive paint comprises the following steps: and uniformly dispersing the cationic dopamine-functionalized graphene material in the aqueous resin emulsion. The preparation method of the coating formed by the anticorrosive paint comprises the following steps: and depositing to form the anticorrosive coating on the surface of the substrate by adopting an electrophoretic deposition technology. The dopamine modified graphene greatly improves the dispersibility and stability of the dopamine modified graphene, can form a barrier layer in a coating, obviously prolongs the diffusion path of a corrosive medium, and forms a compact passivation layer on the surface of a substrate; meanwhile, the invention adopts an electrophoretic deposition technology, has the advantages of simple method, low cost, small pollution and wide application prospect.
Description
Technical Field
The invention relates to an anticorrosive coating, in particular to a cationic dopamine functionalized graphene water-based anticorrosive coating, a preparation method thereof, a preparation method and application of a corresponding coating, and belongs to the technical field of anticorrosive coatings.
Background
With the rapid development of the marine industry and its strong demand for marine resources, various marine facilities, ships and metal parts must face severe corrosion problems in the development of marine resources. Research shows that the organic protective coating is one of the most widely applied and highest cost performance anticorrosion measures except reasonable material selection. The aqueous cathodic electrophoretic emulsion is a coating taking water as a solvent, is green and environment-friendly (meets the requirement of low-volatility organic compound emission), has ideal adhesive force, and is widely applied to mainstream automobile and ship coatings. However, organic coatings are resistant to corrosive media (H)2O、O2And Cl-Etc.) have a certain permeability. Therefore, much work has been focused on improving the impermeability of organic coatings to enhance their corrosion resistance.
A plate-like nanofiller, such as graphene, having a high aspect ratio and capable of inhibiting penetration and diffusion of corrosive substances can effectively solve the above problems. Graphene stabilized SP2The hybrid structure allows it to form a physical barrier between the metal and the corrosive medium, preventing diffusion and permeation of the medium, and is considered to be the thinnest (0.34nm) known corrosion protection layer. This is achieved byIn addition, the graphene can effectively prolong the diffusion path of a corrosive medium, and has excellent barrier property and good chemical stability and oxidation resistance. However, due to van der waals forces between the plate-like nanofillers, it is easily aggregated in the polymer matrix, and thus, the preparation of well-dispersed nanofillers is key to improve the corrosion protection properties of the composite coating.
Disclosure of Invention
The invention mainly aims to provide a cationic dopamine functionalized graphene water-based anticorrosive paint and a preparation method thereof, so as to overcome the defects in the prior art.
Another object of the present invention is to provide an anticorrosive coating and a method for preparing the same.
The invention also aims to provide application of the cationic dopamine functionalized graphene water-based anticorrosive paint or anticorrosive coating.
In order to achieve the purpose, the invention adopts the following technical scheme:
the embodiment of the invention provides a cationic dopamine functionalized graphene water-based anticorrosive paint, which comprises: the cationic dopamine-functionalized graphene material is uniformly dispersed in the aqueous resin emulsion.
The embodiment of the invention also provides a preparation method of the cationic dopamine functionalized graphene water-based anticorrosive paint, which comprises the following steps:
modifying the graphene material with dopamine to obtain a dopamine-functionalized graphene material;
modifying graphene oxide with dopamine to obtain a dopamine-functionalized graphene material;
ionizing the dopamine-functionalized graphene material to obtain a cationic dopamine-functionalized graphene material;
and uniformly dispersing the cationic dopamine-functionalized graphene material in an aqueous resin emulsion to obtain the cationic dopamine-functionalized graphene aqueous anticorrosive paint.
The embodiment of the invention also provides the cationic dopamine functionalized graphene water-based anticorrosive paint prepared by the method.
The embodiment of the invention also provides a preparation method of the anticorrosive coating, which comprises the following steps:
at least enabling a substrate serving as a cathode, an anode and electrolyte to jointly construct an electrochemical reaction system, wherein the electrolyte adopts the cationic dopamine functionalized graphene water-based anticorrosive paint;
and electrifying the electrochemical reaction system by adopting an electrophoretic deposition technology, depositing on the surface of the substrate to form a compact passivation layer, and then curing to obtain the anticorrosive coating.
In some embodiments, the electrophoretic deposition technique employs process conditions that include: the deposition voltage is 10-220V, and the deposition time is 1-30 min.
Further, the curing temperature is 60-200 ℃, and the curing time is 10-30 min.
The embodiment of the invention also provides an anticorrosive coating prepared by the method.
The embodiment of the invention also provides application of the cationic dopamine functionalized graphene water-based anticorrosive coating or anticorrosive coating in the corrosion field.
Compared with the prior art, the invention has the beneficial effects that:
1) the dopamine-functionalized graphene material provided by the invention greatly improves the dispersibility and stability of graphene, and effectively inhibits the electrochemical activity of the surface of graphene;
2) the cationic dopamine functionalized graphene material provided by the invention is prepared from ammonium ions (-NH)3 +-) is stably dispersed in the aqueous resin emulsion for 60 days without precipitation;
3) the lamellar structure of the cationic dopamine functional graphene material provided by the invention can form a barrier layer in an anticorrosive coating, effectively hinders penetration of corrosive media such as water, oxygen, chloride ions and the like, and fully plays a role in physical isolation;
4) the cation dopamine functionalized graphene material provided by the invention can be uniformly dispersed in an anticorrosive coating to obviously prolong the diffusion path of an etching medium;
5) the invention provides-NH of a cationic dopamine functionalized graphene material3 +The material can adsorb electrons and corrosive anions, cut off local galvanic corrosion and form a compact passivation layer on the steel surface;
6) the cationic dopamine-functionalized graphene water-based anticorrosive paint provided by the invention does not contain an organic solvent, does not cause emission of organic volatile matters, and is green and environment-friendly;
7) the preparation method of the cationic dopamine-functionalized graphene material provided by the invention is simple, and the cationic dopamine-functionalized graphene material has excellent dispersibility and chemical stability in an aqueous emulsion;
8) the electrophoretic deposition technology in the preparation method of the anticorrosive coating provided by the invention is simple and convenient, low in cost, low in energy consumption, small in pollution and wide in application prospect.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
Fig. 1 is a photograph showing the dispersion of different amounts of cationic dopamine functionalized graphene in an aqueous epoxy emulsion according to example 1 of the present invention.
Fig. 2a to 2c are a scanning image, a transmission electron microscope photograph and an atomic force microscope image of the cationic dopamine-functionalized graphene aqueous anticorrosive coating in example 1 of the present invention, respectively.
FIGS. 3a to 3d are a surface scanning view, a cross-sectional scanning view and an internal transmission electron micrograph of the waterborne epoxy anticorrosive coating prepared in example 1 of the invention.
Fig. 4a and 4b are optical photographs of the waterborne epoxy anticorrosive coatings prepared in example 1 of the present invention and comparative example 1, respectively, after salt spray tests for different times.
Fig. 5a and 5b are electrochemical ac impedance plots of the aqueous epoxy anticorrosive coatings prepared in example 1 of the present invention and comparative example 1, respectively, immersed in 3.5 wt% NaCl (pH 7) for different periods of time.
Fig. 6a and 6b are respectively a morphology chart of corrosion products on the surface of the carbon steel obtained by removing the epoxy coating on the surface of the carbon steel after the waterborne epoxy anticorrosive coatings prepared in example 1 and comparative example 1 of the invention are soaked in 3.5 wt% NaCl (pH 7) for 90 days.
Detailed Description
In view of the defects in the prior art, the inventors of the present invention have made long-term research and extensive practice to provide a technical scheme of the present invention, and aim to provide a preparation method of a cationic dopamine-functionalized graphene water-based anticorrosive paint and a coating thereof, which mainly comprises the steps of graphene modification, graphene ionization, electrolyte preparation, substrate pretreatment, composite coating preparation, and the like. The technical solution, its implementation and principles, etc. will be further explained as follows.
One aspect of the embodiments of the present invention provides a cationic dopamine-functionalized graphene aqueous anticorrosive coating, which includes: the cationic dopamine-functionalized graphene material is uniformly dispersed in the aqueous resin emulsion.
In some preferred embodiments, the cationic dopamine-functionalized graphene material is prepared by ionizing a dopamine-functionalized graphene material.
In some preferred embodiments, the dopamine-functionalized graphene material is prepared by performing dopamine modification treatment on a graphene material.
In some preferred embodiments, the graphene oxide has a diameter of 1 to 50 μm and a thickness of 0.5 to 5 nm.
In some preferred embodiments, the cationic dopamine functionalized graphene material is due to ammonium ions (-NH)3 +-) was able to be stably dispersed in the aqueous resin emulsion for 60 days without precipitation.
In some preferred embodiments, the aqueous resin emulsion includes any one or a combination of two or more of an aqueous cathode epoxy resin, an aqueous cathode acrylic resin, an aqueous cathode polyurethane resin, an aqueous amino resin, and the like, but is not limited thereto.
In some preferred embodiments, the content of the cationic dopamine-functionalized graphene material in the cationic dopamine-functionalized graphene aqueous anticorrosive paint is 0.01-5 wt%.
Further, the solid content of the aqueous resin emulsion is 5-50 wt%.
In another aspect of the embodiments of the present invention, a preparation method of a cationic dopamine-functionalized graphene aqueous anticorrosive coating includes:
modifying graphene oxide with dopamine to obtain a dopamine-functionalized graphene material;
ionizing the dopamine-functionalized graphene material to obtain a cationic dopamine-functionalized graphene material;
and uniformly dispersing the cationic dopamine-functionalized graphene material in an aqueous resin emulsion to obtain the cationic dopamine-functionalized graphene aqueous anticorrosive paint.
In some preferred embodiments, the preparation method specifically comprises: adding dopamine and graphene oxide into a buffer solution with the pH value of 8.5, stirring at room temperature for 12-24 hours to obtain a dopamine-functionalized graphene material, and then drying in vacuum at 20-80 ℃.
Further, the mass ratio of the dopamine to the graphene oxide is 1: 100-5: 1.
in some preferred embodiments, the preparation method comprises: mixing the components in a mass ratio of 1: 1-1: 5, mixing and dispersing the dopamine-functionalized graphene material and acetic acid in a polar solvent, stirring for 1-5 hours at 20-30 ℃ to obtain a cationic dopamine-functionalized graphene material, and then drying in vacuum at 20-80 ℃.
Further, the mass ratio of the dopamine-functionalized graphene material to the polar solvent is 1: 10-1: 100.
further, the polar solvent may include any one or a combination of two or more of acetone, ethanol, N-dimethylformamide, ethyl acetate, chloroform, and the like, but is not limited thereto.
Further, the dopamine-functionalized graphene material can be stably dispersed in an aqueous resin emulsion for 60 days without precipitation.
In some preferred embodiments, the preparation method specifically comprises: and uniformly dispersing the cationic dopamine-functionalized graphene material in an aqueous resin emulsion, and performing ultrasonic dispersion for 5-120 min to obtain the cationic dopamine-functionalized graphene aqueous anticorrosive paint.
In some preferred embodiments, the aqueous resin emulsion includes any one or a combination of two or more of an aqueous cathode epoxy resin, an aqueous cathode acrylic resin, an aqueous cathode polyurethane resin, an aqueous amino resin, and the like, but is not limited thereto.
Further, the solid content of the aqueous resin emulsion is 5-50%.
In another aspect of the embodiment of the invention, the cationic dopamine-functionalized graphene water-based anticorrosive paint prepared by the method is also provided.
Further, the content of the cationic dopamine-functionalized graphene material in the cationic dopamine-functionalized graphene water-based anticorrosive paint is 0.01-5 wt%.
Another aspect of an embodiment of the present invention also provides a method for preparing an anticorrosive coating, including:
providing a substrate;
and depositing the dopamine-functionalized graphene water-based anticorrosive coating on the surface of the substrate by adopting an electrophoretic deposition technology.
In some preferred embodiments, the preparation method specifically comprises:
at least enabling a substrate serving as a cathode, an anode and electrolyte to jointly construct an electrochemical reaction system, wherein the electrolyte adopts the cationic dopamine functionalized graphene water-based anticorrosive paint;
and electrifying the electrochemical reaction system by adopting an electrophoretic deposition technology, depositing on the surface of the substrate to form a compact passivation layer, and then curing to obtain the anticorrosive coating.
In some preferred embodiments, the electrophoretic deposition technique employs process conditions that include: the deposition voltage is 10-220V, and the deposition time is 1-30 min.
In some preferred embodiments, the curing temperature is 60-200 ℃ and the curing time is 10-30 min.
Further, the preparation method further comprises the following steps: before electrophoretic deposition, preprocessing a substrate; wherein the pre-processing comprises: and (3) polishing the substrate by using 100-2000-mesh sand paper, then ultrasonically cleaning for 5-30 min, and drying.
Further, the thickness of the anticorrosive coating is 5-50 μm.
In some more typical embodiments, the preparation method of the cationic dopamine-functionalized graphene aqueous anticorrosive coating comprises the following steps:
(1) modifying graphene: mixing the components in a mass ratio of 1: 100-5: adding the dopamine and graphene oxide of 1 into a buffer solution with the pH value of 8.5, stirring for 12-24 hours at room temperature to obtain a dopamine-functionalized graphene material, and then drying in vacuum at 20-80 ℃ to obtain powder.
(2) Graphene ionization: mixing the components in a mass ratio of 1: 1-1: 5, mixing and dispersing the dopamine-functionalized graphene material and acetic acid in a polar solvent, stirring for 1-5 hours at 20-30 ℃ to obtain a cationic dopamine-functionalized graphene material, and then drying in vacuum at 20-80 ℃ to obtain powder; the mass ratio of the dopamine-functionalized graphene material to the polar solvent is 1: 10-1: 100, respectively; the polar solvent is one or a mixture of more than two of acetone, ethanol, N-dimethylformamide, ethyl acetate, trichloromethane and the like.
(3) Electrolyte preparation: the cationic dopamine functionalized graphene material is uniformly dispersed in the aqueous resin emulsion, and can be dispersed by ultrasonic for 5-120 min.
(4) Steel sheet pretreatment:the size of the particles is (1-10) × (1-10) cm2The steel sheet is polished on 100-2000-mesh sand paper, then ultrasonically cleaned for 5-30 min by using ethanol, and finally dried by using nitrogen.
(5) Preparing a composite coating: the method comprises the steps of taking a steel sheet as a cathode, taking copper sheets with the same size as an anode, immersing the steel sheet into electrolyte, and depositing a dopamine-functionalized graphene water-based anticorrosive coating on the surface of a substrate by controlling deposition voltage and deposition time, wherein the deposition voltage is 10-220V, and the deposition time is 1-30 min.
(6) Preparing an anticorrosive coating: and curing the coating obtained by electrodeposition in a drying oven for 10-30 min, wherein the curing temperature is 60-200 ℃ so as to remove the water solvent in the emulsion on the surface of the substrate.
Another aspect of an embodiment of the present invention also provides an anticorrosive coating prepared by the foregoing method.
Further, the thickness of the anticorrosive coating is 5-50 μm.
In another aspect of the embodiment of the invention, the application of the cationic dopamine functionalized graphene water-based anticorrosive paint or anticorrosive coating in the corrosion field is also provided.
In conclusion, the dopamine functionalized graphene anticorrosive coating is deposited by an electrophoretic deposition technology after grinding and ethanol cleaning are carried out on steel serving as a substrate. The dopamine functionalized graphene oxide greatly improves the dispersibility and stability of graphene and effectively inhibits the electrochemical activity of the surface of the graphene. Cationic dopamine functionalized graphene is prepared from ammonium ions (-NH)3 +-) was stable dispersed in the aqueous emulsion for 60 days without precipitation. The lamellar structure of the graphene can form a barrier layer in the coating, effectively prevent corrosive media such as water, oxygen, chloride ions and the like from permeating, and fully play the role of physical isolation. The uniform dispersion of graphene in the coating can significantly prolong the corrosive medium diffusion path. -NH in cationic dopamine functionalized graphene3 +The steel can adsorb electrons and corrosive anions, cut off local galvanic corrosion and form a compact passivation layer on the surface of a steel matrix. The aqueous dopamine modified graphene/resin does not contain organic solvent, and does not bring organic volatile matterDischarge and environmental protection. The dopamine modified graphene material provided by the invention is simple in preparation method, and has excellent dispersibility and chemical stability in an aqueous emulsion. The electrophoretic deposition technology adopted by the invention has the advantages of simple method, low cost, low energy consumption, small pollution and wide application prospect.
The embodiment of the invention also provides application of the cationic dopamine functionalized graphene water-based anticorrosive coating in the corrosion field.
The technical solutions in the embodiments of the present invention are clearly and completely described below with reference to the specific embodiments and the accompanying drawings, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A preparation method of a cationic dopamine functionalized graphene water-based epoxy anticorrosive paint and a coating thereof comprises the following steps:
1. modifying graphene: the mass ratio is 3: mixing dopamine and graphene oxide of 1 in a buffer solution with the pH value of 8.5, stirring for 24 hours at room temperature to obtain dopamine-functionalized graphene, and then drying the obtained dopamine-functionalized graphene in vacuum at 40 ℃ to form powder.
2. Graphene ionization: dispersing 0.5g of dried dopamine reduced graphene oxide and 1.35g of acetic acid in 20mL of acetone solution, stirring at 28 ℃ for 3h to obtain cationic dopamine functionalized graphene, and then drying in vacuum at 40 ℃ to obtain powder.
3. Electrolyte preparation: 0.5g of ionized dopamine reduced graphene oxide is dispersed in 100g of aqueous cathode epoxy resin emulsion with the solid content of 15 percent, and the mixture is subjected to ultrasonic dispersion for 30 min.
4. Steel sheet pretreatment: the size of the sample is 3 x 3cm2The steel sheets are respectively polished on 400, 800 and 1200-mesh sand paper, ultrasonically cleaned for 20min by ethanol, and finally dried by nitrogen.
5. Preparing a composite coating: and immersing a steel sheet serving as a cathode and a copper sheet with the same size serving as an anode into electrolyte, and depositing the dopamine modified graphene/resin composite coating on the surface of the substrate by controlling the deposition voltage and the deposition time, wherein the deposition voltage is 60V, and the deposition time is 5 min.
6. Preparing an anticorrosive coating: curing the coating obtained by electrodeposition in a drying oven for 20min, wherein the curing temperature is 150 ℃ so as to remove the water solvent in the emulsion on the surface of the substrate; the thickness of the prepared anticorrosive coating is 25 mu m.
Fig. 1 is a photograph of the dispersion of different amounts of cationic dopamine functionalized graphene in the aqueous epoxy emulsion according to the present embodiment. It can be seen from fig. 1 that the cationic dopamine functionalized graphene is stably dispersed in the aqueous epoxy emulsion without precipitation. The method shows that the dispersion and stability of the graphene oxide modified by dopamine are greatly improved. Fig. 2a to 2c are a scanning view, a transmission electron microscope photograph and an atomic force microscope image of the cationic dopamine-functionalized graphene aqueous anticorrosive coating in this embodiment, respectively. From fig. 2a to fig. 2c, it can be seen that the dopamine-modified graphene oxide still has a good lamellar structure, which is beneficial to maintaining a high aspect ratio of graphene, so as to fully exert its physical isolation effect, effectively hinder penetration of corrosive media such as water, oxygen, chloride ions and the like, and significantly prolong a corrosive media diffusion path. FIGS. 3a to 3d are a surface scanning view, a cross-sectional scanning view and an internal transmission electron microscope photograph of the waterborne epoxy anticorrosive coating prepared in the embodiment. The graphene is arranged in the coating in parallel to the substrate, so that the interaction between the graphene and the electrolyte can be fully exerted, a labyrinth effect is formed, and the graphene has a better physical barrier effect and corrosion resistance.
Example 2
A preparation method of a cationic dopamine functionalized graphene water-based acrylic acid anticorrosive paint and a coating thereof comprises the following steps:
1. modifying graphene: the mass ratio is 1: 100 parts of dopamine and graphene oxide are mixed in a buffer solution with the pH value of 8.5 and stirred for 12 hours at room temperature to obtain dopamine-functionalized graphene, and then the obtained dopamine-functionalized graphene is dried in vacuum at the temperature of 20 ℃ to form powder.
2. Graphene ionization: dispersing 0.5g of dried dopamine reduced graphene oxide and 0.5g of acetic acid in 12.5mL of ethanol solution, stirring for 1h at 20 ℃ to obtain cationic dopamine functionalized graphene, and then drying in vacuum at 20 ℃ to obtain powder.
3. Electrolyte preparation: 0.01g of ionized dopamine reduced graphene oxide is dispersed in 100g of aqueous cathode acrylic resin emulsion with the solid content of 5%, and ultrasonic dispersion is carried out for 5 min.
4. Steel sheet pretreatment: the size of the sample is 1 x 1cm2The steel sheets are respectively polished on 100, 600 and 1600-mesh sand paper, ultrasonically cleaned for 5min by ethanol, and finally dried by nitrogen.
5. Preparing a composite coating: and immersing a steel sheet serving as a cathode and a copper sheet with the same size serving as an anode into electrolyte, and depositing the dopamine modified graphene/resin composite coating on the surface of the substrate by controlling the deposition voltage and the deposition time, wherein the deposition voltage is 10V, and the deposition time is 30 min.
6. Preparing an anticorrosive coating: curing the coating obtained by electrodeposition in a drying oven for 10min, wherein the curing temperature is 200 ℃ so as to remove the water solvent in the emulsion on the surface of the substrate; the thickness of the prepared anticorrosive coating is 5 mu m.
Example 3
A preparation method of a cationic dopamine functionalized graphene waterborne polyurethane anticorrosive paint and a coating thereof comprises the following steps:
1. modifying graphene: the mass ratio is 5: mixing dopamine and graphene oxide of 1 in a buffer solution with the pH value of 8.5, stirring for 18h at room temperature to obtain dopamine-functionalized graphene, and then drying the obtained dopamine-functionalized graphene in vacuum at 80 ℃ to obtain powder.
2. Graphene ionization: dispersing 0.5g of dried dopamine reduced graphene oxide and 2.5g of acetic acid in 125mL of ethyl acetate solution, stirring for 5 hours at 30 ℃ to obtain cationic dopamine functionalized graphene, and then drying in vacuum at 80 ℃ to obtain powder.
3. Electrolyte preparation: 5g of ionized dopamine reduced graphene oxide is dispersed in 100g of aqueous cathode polyurethane resin emulsion with the solid content of 50%, and ultrasonic dispersion is carried out for 120 min.
4. Steel sheet pretreatment: the size of the sample is 10 x 10cm2The steel sheets are respectively polished on 200, 800 and 1000-mesh sand paper, ultrasonically cleaned for 30min by ethanol, and finally dried by nitrogen.
5. Preparing a composite coating: and immersing a steel sheet serving as a cathode and a copper sheet with the same size serving as an anode into electrolyte, and depositing the dopamine modified graphene/resin composite coating on the surface of the substrate by controlling the deposition voltage and the deposition time, wherein the deposition voltage is 220V, and the deposition time is 1 min.
6. Preparing an anticorrosive coating: curing the coating obtained by electrodeposition in a drying oven for 30min, wherein the curing temperature is 60 ℃ so as to remove the water solvent in the emulsion on the surface of the substrate; the thickness of the prepared anticorrosive coating is 50 mu m.
Example 4
A preparation method of a cationic dopamine functionalized graphene water-based amino anticorrosive paint and a coating thereof comprises the following steps:
1. modifying graphene: the mass ratio is 1: mixing dopamine and graphene oxide of 1 in a buffer solution with the pH value of 8.5, stirring for 20 hours at room temperature to obtain dopamine-functionalized graphene, and then drying the obtained dopamine-functionalized graphene in vacuum at 40 ℃ to form powder.
2. Graphene ionization: dispersing 0.5g of dried dopamine reduced graphene oxide and 1g of acetic acid solution in 50mL of N, N-dimethylformamide solution, stirring at 24 ℃ for 2h to obtain cationic dopamine functionalized graphene, and then drying in vacuum at 40 ℃ to obtain powder.
3. Electrolyte preparation: 1g of ionized dopamine reduced graphene oxide is dispersed in 100g of aqueous amino resin emulsion with the solid content of 20 percent, and ultrasonic dispersion is carried out for 60 min.
4. Steel sheet pretreatment: the size of the sample is 5 x 5cm2The steel sheets are respectively polished on 100, 600 and 2000-mesh sand paper, ultrasonically cleaned for 15min by ethanol, and finally dried by nitrogen.
5. Preparing a composite coating: and immersing a steel sheet serving as a cathode and a copper sheet with the same size serving as an anode into electrolyte, and depositing the dopamine modified graphene/resin composite coating on the surface of the substrate by controlling the deposition voltage and the deposition time, wherein the deposition voltage is 100V, and the deposition time is 15 min.
6. Preparing an anticorrosive coating: curing the coating obtained by electrodeposition in a drying oven for 15min, wherein the curing temperature is 100 ℃ so as to remove the water solvent in the emulsion on the surface of the substrate; the thickness of the prepared anticorrosive coating is 30 mu m.
Examples 1-4 coatings prepared were soaked in 3.5 wt% NaCl (pH 7) for various periods of time with the following low frequency impedance modulus values:
| coating layer | Low frequency impedance modulus (omega cm) after soaking for 1d2) | After soaking for 35d, the low-frequency impedance modulus is omega cm2 |
| Example 1 | 4.79×1010 | 7.08×109 |
| Example 2 | 2.38×109 | 6.45×108 |
| Example 3 | 1.21×1010 | 4.33×109 |
| Example 4 | 5.13×1010 | 8.32×109 |
Comparative example 1
An anticorrosive coating and a preparation method thereof, comprising the following steps:
1. steel sheet pretreatment: the size of the sample is 3 x 3cm2The steel sheets are respectively polished on 400, 800 and 1200-mesh sand paper, ultrasonically cleaned for 20min by ethanol, and finally dried by nitrogen.
2. Preparing a composite coating: and (3) taking a steel sheet as a cathode and a copper sheet with the same size as an anode, immersing the steel sheet into 100g of aqueous emulsion with the solid content of 15%, and depositing a coating on the surface of the substrate by controlling the deposition voltage and the deposition time, wherein the deposition voltage is 60V, and the deposition time is 5 min.
3. Preparing an anticorrosive coating: curing the coating obtained by electrodeposition in a drying oven for 20min, wherein the curing temperature is 150 ℃ so as to remove the water solvent in the emulsion on the surface of the substrate; the coating thickness prepared was 25 μm.
Fig. 4a and 4b are optical photographs of the waterborne epoxy anticorrosive coatings prepared in example 1 and comparative example 1 after salt spray tests for different times. From the pictures after 240 hours salt spray testing, it can be seen that the pure EP coating is rust-covered around the scratch and some rust spots appear in the undamaged areas. The surface of the dopamine-functionalized graphene anticorrosive coating is intact, and only rust is generated around scratches. After 480 hours of salt spray test, the pure EP coating is almost completely covered by rust, and black spots appear around scratches of the dopamine functionalized graphene anticorrosive coating, but the surface is kept intact. The result shows that the dopamine-functionalized graphene is added to improve the corrosion resistance of the epoxy coating.
Fig. 5a and 5b are graphs of electrochemical ac impedance of the aqueous epoxy anticorrosive coatings prepared in example 1 and comparative example 1 soaked in 3.5 wt% NaCl (pH 7) for various times. Also, as can be seen from the figure, the initial low frequency impedance modulus of the pure EP coating is 4.07X 109Ωcm2After 35 days of immersion, the temperature dropped sharply to 9.1X 107Ωcm2And is reduced by two orders of magnitude. This indicates that corrosive media have penetrated into the coated substrate through the defects, resulting in a reduction in the corrosion resistance of the coating. And the initial low-frequency impedance modulus of the dopamine-functionalized graphene anticorrosive coating is 4.79 multiplied by 1010Ωcm2Still as high as 7.08X 10 after 35 days of immersion9Ωcm2. The reason is that the sheet structure of the graphene can form a barrier layer in the coating, effectively block the permeation of corrosive media such as water, oxygen, chloride ions and the like, and fully play the role of physical insulation. And the uniform dispersion of the graphene in the coating can obviously prolong the diffusion path of the corrosive medium. Furthermore, -NH in dopamine modified graphene3 +The steel can adsorb electrons and corrosive anions, cut off local galvanic corrosion and form a compact passivation layer on the surface of the steel.
Fig. 6a and 6b are respectively a morphology chart of corrosion products on the surface of the carbon steel obtained by removing the epoxy coating on the surface of the carbon steel after the waterborne epoxy anticorrosive coatings prepared in example 1 and comparative example 1 of the invention are soaked in 3.5 wt% NaCl (pH 7) for 90 days. It can be seen from the figure that the corrosion products on the surface of the dopamine-functionalized graphene anticorrosive coating carbon steel are greatly reduced compared with the corrosion products on the surface of the pure epoxy coating carbon steel, and the dopamine-functionalized graphene anticorrosive coating carbon steel shows excellent corrosion resistance.
Comparative example 2
A preparation method of a dopamine functionalized graphene water-based epoxy anticorrosive paint and a coating thereof comprises the following steps:
1. modifying graphene: the mass ratio is 3: mixing dopamine and graphene oxide of 1 in a buffer solution with the pH value of 8.5, stirring for 24 hours at room temperature to obtain dopamine-functionalized graphene, and then drying the obtained dopamine-functionalized graphene in vacuum at 40 ℃ to form powder.
2. Electrolyte preparation: 0.5g of dopamine reduced graphene oxide is taken to be dispersed in 100g of aqueous epoxy resin emulsion with the solid content of 15 percent, and ultrasonic dispersion is carried out for 30 min.
3. Steel sheet pretreatment: the size of the sample is 3 x 3cm2Respectively polishing the steel sheets on 400, 800 and 1200-mesh sand paper, and then performing ultrasonic polishing by using ethanolCleaning with sound for 20min, and blow-drying with nitrogen gas.
4. Preparing a composite coating: and immersing a steel sheet serving as a cathode and a copper sheet with the same size serving as an anode into electrolyte, and depositing the dopamine modified graphene/resin composite coating on the surface of the substrate by controlling the deposition voltage and the deposition time, wherein the deposition voltage is 60V, and the deposition time is 5 min.
5. Preparing an anticorrosive coating: curing the coating obtained by electrodeposition in a drying oven for 20min, wherein the curing temperature is 150 ℃ so as to remove the water solvent in the emulsion on the surface of the substrate; the thickness of the prepared anticorrosive coating is 24.8 mu m.
In the comparative example, because the dopamine functionalized graphene is electronegative, the dopamine functionalized graphene cannot be deposited on the surface of cathode carbon steel under the action of an electric field, and the prepared coating has the corrosion resistance similar to that of a pure epoxy resin coating.
Comparative example 3
This comparative example is essentially the same as example 1, except that step 5 is: directly spin-coating the electrolyte prepared in the step (3) on the surface of the steel sheet; and (5) performing the operation of the step (6).
In the comparative example, the composite coating obtained by spin coating is thinner and less dense than the composite coating obtained by electrodeposition, so the corrosion resistance of the composite coating obtained by spin coating is much lower than that of a pure epoxy coating obtained by electrodeposition.
In conclusion, the dopamine modified graphene/resin composite coating is deposited by an electrophoretic deposition technology after grinding and ethanol cleaning are carried out on steel serving as a substrate. The graphene oxide modified by dopamine greatly improves the dispersibility and stability of graphene and effectively inhibits the electrochemical activity of the surface of graphene. Cationic dopamine modified graphene is caused by ammonium ions (-NH)3 +-) was stable dispersed in the aqueous emulsion for 60 days without precipitation. The lamellar structure of the graphene can form a barrier layer in the coating, effectively prevent corrosive media such as water, oxygen, chloride ions and the like from permeating, and fully play the role of physical isolation. The uniform dispersion of graphene in the coating can significantly prolong the corrosive medium diffusion path. -NH in cationic dopamine modified graphene3 +The steel can adsorb electrons and corrosive anions, cut off local galvanic corrosion and form a compact passivation layer on the surface of the steel. The aqueous dopamine modified graphene/resin does not contain an organic solvent, does not cause emission of organic volatile matters, and is green and environment-friendly. The dopamine modified graphene provided by the invention is simple in preparation method, and has excellent dispersibility and chemical stability in an aqueous emulsion. The electrophoretic deposition technology has the advantages of simple method, low cost, low energy consumption, small pollution and wide application prospect.
The aspects, embodiments, features and examples of the present invention should be considered as illustrative in all respects and not intended to be limiting of the invention, the scope of which is defined only by the claims. Other embodiments, modifications, and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed invention.
The use of headings and chapters in this disclosure is not meant to limit the disclosure; each section may apply to any aspect, embodiment, or feature of the disclosure.
Throughout this specification, where a composition is described as having, containing, or comprising specific components or where a process is described as having, containing, or comprising specific process steps, it is contemplated that the composition of the present teachings also consist essentially of, or consist of, the recited components, and the process of the present teachings also consist essentially of, or consist of, the recited process steps.
Unless specifically stated otherwise, use of the terms "comprising", "including", "having" or "having" is generally to be understood as open-ended and not limiting.
It should be understood that the order of steps or the order in which particular actions are performed is not critical, so long as the teachings of the invention remain operable. Further, two or more steps or actions may be performed simultaneously.
In addition, the inventors of the present invention have also made experiments with other materials, process operations, and process conditions described in the present specification with reference to the above examples, and have obtained preferable results.
While the invention has been described with reference to illustrative embodiments, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from its scope. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims. Moreover, unless specifically stated any use of the terms first, second, etc. do not denote any order or importance, but rather the terms first, second, etc. are used to distinguish one element from another.
Claims (12)
1. A preparation method of a cationic dopamine functionalized graphene water-based anticorrosive paint is characterized by comprising the following steps:
modifying graphene oxide with dopamine to obtain a dopamine-functionalized graphene material;
mixing the components in a mass ratio of 1: 1-1: 5, mixing and dispersing the dopamine-functionalized graphene material and acetic acid in a polar solvent, stirring for 1-5 hours at 20-30 ℃ to obtain a cationic dopamine-functionalized graphene material, and then drying in vacuum at 20-80 ℃; the mass ratio of the dopamine-functionalized graphene material to the polar solvent is 1: 10-1: 100, the polar solvent is selected from any one or the combination of more than two of acetone, ethanol, N-dimethylformamide, ethyl acetate and trichloromethane;
uniformly dispersing the cationic dopamine-functionalized graphene material in an aqueous resin emulsion to obtain a cationic dopamine-functionalized graphene aqueous anticorrosive paint;
the cationic dopamine functionalized graphene water-based anticorrosive paint comprises: the cationic dopamine-functionalized graphene material is uniformly dispersed in the aqueous resin emulsion, the cationic dopamine-functionalized graphene material can be stably dispersed in the aqueous resin emulsion for 60 days without generating precipitation, and the content of the cationic dopamine-functionalized graphene material in the aqueous anticorrosive coating is 0.01-5 wt%.
2. The production method according to claim 1, characterized by comprising: adding dopamine and graphene oxide into a buffer solution with the pH value of 8.5, stirring at room temperature for 12-24 hours to obtain a dopamine-functionalized graphene material, and then drying in vacuum at 20-80 ℃.
3. The method of claim 2, wherein: the mass ratio of the dopamine to the graphene oxide is 1: 100-5: 1.
4. the method of claim 2, wherein: the diameter of the graphene oxide is 1-50 mu m, and the thickness of the graphene oxide is 0.5-5 nm.
5. The production method according to claim 1, characterized by comprising: and uniformly dispersing the cationic dopamine-functionalized graphene material in an aqueous resin emulsion, and performing ultrasonic dispersion for 5-120 min to obtain the cationic dopamine-functionalized graphene aqueous anticorrosive paint.
6. The method of claim 5, wherein: the aqueous resin emulsion is selected from any one or the combination of more than two of aqueous cathode epoxy resin, aqueous cathode acrylic resin, aqueous cathode polyurethane resin and aqueous amino resin.
7. The method of claim 5, wherein: the solid content of the aqueous resin emulsion is 5-50%.
8. A method for preparing an anticorrosive coating, characterized by comprising:
at least enabling a substrate serving as a cathode, an anode and an electrolyte to jointly construct an electrochemical reaction system, wherein the electrolyte adopts the cationic dopamine-functionalized graphene water-based anticorrosive paint prepared by the preparation method of any one of claims 1-7;
electrifying the electrochemical reaction system by adopting an electrophoretic deposition technology, depositing a compact passivation layer on the surface of the substrate, and then curing to obtain the anticorrosive coating, wherein the electrophoretic deposition technology adopts the process conditions comprising: the deposition voltage is 10-220V, the deposition time is 1-30 min, the curing temperature is 60-200 ℃, and the curing time is 10-30 min.
9. The method of manufacturing according to claim 8, further comprising: before electrophoretic deposition, preprocessing a substrate; the pretreatment comprises the following steps: and (3) polishing the substrate by using 100-2000-mesh sand paper, then ultrasonically cleaning for 5-30 min, and drying.
10. An anti-corrosion coating prepared by the method of any one of claims 8 to 9.
11. The corrosion protective coating of claim 10, wherein: the thickness of the anticorrosive coating is 5-50 mu m.
12. Use of the cationic dopamine-functionalized graphene aqueous anticorrosive coating prepared by the preparation method according to any one of claims 1 to 7 or the anticorrosive coating according to any one of claims 10 to 11 in the field of corrosion protection.
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