CN114940851A - Rare earth modified graphene/water-based epoxy resin coating and preparation and coating methods thereof - Google Patents
Rare earth modified graphene/water-based epoxy resin coating and preparation and coating methods thereof Download PDFInfo
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- CN114940851A CN114940851A CN202210633855.2A CN202210633855A CN114940851A CN 114940851 A CN114940851 A CN 114940851A CN 202210633855 A CN202210633855 A CN 202210633855A CN 114940851 A CN114940851 A CN 114940851A
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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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- 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
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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Abstract
The invention discloses a rare earth modified graphene/water-based epoxy resin coating and a preparation method and a coating method thereof, belonging to the technical field of functional coatings, wherein the coating specifically comprises the following raw materials: the coating comprises water-based epoxy resin, rare earth modified graphene, a curing agent, a dispersing agent and deionized water. The preparation method specifically comprises the following steps: adding the rare earth modified graphene and a dispersing agent into deionized water, stirring and ultrasonically mixing the rare earth modified graphene and the water-based epoxy resin uniformly, then adding a curing agent, stirring uniformly again, standing and defoaming until the viscosity is 15-20 s, and thus obtaining the rare earth modified graphene/water-based epoxy resin coating. In addition, the coating provided by the invention is sprayed on the surface of a substrate by using an air spray gun. The invention reduces the harm of the coating solvent to operators and the pollution to the environment from the source, greatly improves the corrosion resistance of the epoxy coating, has uniform coating thickness, high coating surface quality and wide adaptability to the coating and a matrix.
Description
Technical Field
The invention relates to the technical field of functional coatings, in particular to a rare earth modified graphene/water-based epoxy resin coating and a preparation method and a coating method thereof.
Background
Corrosion is one of the failure modes of materials, has concealment, universality and spontaneity, is easy to cause catastrophic accidents, and causes huge economic loss. By selecting reasonable anticorrosion measures, the corrosion of the material can be effectively slowed down, and the protection cost is reduced by 15-35%. Coating protection is the mainstream anticorrosion means at present. The epoxy resin has excellent adhesive force, chemical resistance and stability, and is a film forming substance commonly used in anticorrosive coatings. However, the environment-friendly water-based epoxy coating takes water as a dispersion medium, the surface drying time of the coating is long, the adhesion force between coating layers is poor, the hydrophilicity of the coating is increased by the residual hydrophilic groups in the coating, and finally the flash corrosion and the corrosion resistance of the coating are reduced.
Graphene is the thinnest two-dimensional nano material in the prior art, has excellent physical and chemical properties, is often used as a nano filler to be introduced into a coating, and can improve the corrosion resistance of a coating due to a small-size effect, a two-dimensional lamellar structure and hydrophobicity. The nature and lamellar structure of carbon element in the graphene are favorable for improving the adhesive force of the coating and the matrix and avoiding peeling and cracking of the coating. Meanwhile, the graphene has excellent electrical conductivity, thermal conductivity and mechanical property, and is beneficial to improving the comprehensive performance of the coating. However, graphene sheets are easily agglomerated due to van der waals forces, and are difficult to uniformly disperse in a coating, and the agglomerated graphene in the coating may rather accelerate corrosion of the coating.
Therefore, how to provide an environment-friendly graphene/epoxy resin coating capable of greatly improving the corrosion resistance and durability of the coating is a technical problem to be solved by those skilled in the art.
Disclosure of Invention
The invention aims to provide a rare earth modified graphene/water-based epoxy resin coating with good corrosion resistance and durability, and a preparation method and a coating method thereof.
In order to achieve the purpose, the invention provides the following scheme:
the rare earth modified graphene/water-based epoxy resin coating comprises the following raw materials in parts by weight: 40-50 parts of water-based epoxy resin, 0.15-0.8 part of rare earth modified graphene, 20-25 parts of curing agent, 0.01-0.07 part of dispersing agent and 24-39 parts of deionized water.
Preferably, the preparation method of the rare earth modified graphene comprises the following steps:
1) adding cerium chloride heptahydrate into the graphene oxide dispersion liquid, stirring and standing, reacting at 120-180 ℃ for 12-24 h, cooling to room temperature after the reaction is finished, and then sequentially washing solid products in the reaction liquid to be neutral, freezing and drying to obtain a rare earth modified graphene precursor;
the preparation method of the graphene oxide dispersion liquid comprises the following steps: mixing graphene oxide and water according to a mass ratio of 1:500, and performing ultrasonic treatment for 1h under the condition of an ultrasonic power of 80W to obtain a graphene oxide dispersion liquid.
2) Subjecting the rare earth modified graphene precursor to N 2 And heating to 500-900 ℃ in the atmosphere, and reducing for 0.5-2 h to obtain the rare earth modified graphene powder.
Has the advantages that: according to the invention, rare earth is utilized to modify graphene, so that a layer of rare earth oxide is attached to the surface of the graphene, then the rare earth modified graphene is introduced into the epoxy coating as a nano filler, and the epoxy coating is coated in an air spraying manner, so that the corrosion resistance and durability of the water-based epoxy coating can be greatly improved.
Preferably, the mass concentration of the graphene oxide dispersion liquid in the step 1) is 2 mg/ml;
the mass ratio of the graphene oxide to the cerium chloride heptahydrate is 1: (1-3);
the standing is performed at room temperature for 12-24 hours;
the freezing is carried out at the temperature of-70 to-50 ℃ for 1 to 4 hours;
the drying is freeze drying for 48h under the condition that the vacuum degree is less than 10 Pa.
Has the advantages that: according to the invention, rare earth element ions can be fully adsorbed on the surface of the graphene oxide by adopting a stirring and standing method, and the graphene can be kept in a high dispersion state in the freeze drying process, so that stacking caused by the van der Waals force between sheets is avoided.
Preferably, N is defined in step 2) 2 The flow rate is 1-3 m 3 /h；
The heating rate is 7 ℃/min.
Has the advantages that: the invention is in the presence of high purity N 2 And calcining the graphene precursor in the atmosphere. The surface of the graphene can be uniformly loaded with rare earth oxide (cerium oxide) grains with uniform sizes, and the O element in the cerium oxide is completely derived from the graphene oxide, so that excessive growth and aggregation of the cerium oxide are effectively prevented.
Preferably, the epoxy resin is anionic water-dispersible bisphenol A epoxy resin emulsion, has an epoxy value of 0.125-0.25, and is a mixture of polyethylene glycol, epoxy resin, propylene glycol butyl ether, n-butyl alcohol and deionized water.
Has the advantages that: according to the invention, the waterborne epoxy resin emulsion purchased from Jitian chemical industry Limited company in Shenzhen city is used for preparing the waterborne coating, so that the content of VOC in the coating is reduced, and the step of waterborne coating is realized.
Preferably, the curing agent is a non-ionic waterborne epoxy curing agent and does not include a free surfactant, including dibutyltin dilaurate.
Has the advantages that: the epoxy resin curing agent has high environmental stability, good compatibility with the epoxy resin and excellent curing performance.
Preferably, the dispersant is a non-ionic aqueous wetting dispersant comprising dioctyl sodium sulfosuccinate.
Has the advantages that: according to the invention, the wetting dispersant is used to reduce the surface tension of the coating, enhance the wetting effect between the graphene and the coating and improve the dispersion efficiency of the graphene.
The waterborne epoxy resin, the curing agent and the dispersing agent used in the invention are respectively waterborne epoxy resin emulsion F0704, waterborne epoxy curing agent F0705 and wetting dispersing agent OT-75 provided by Shenzhen Jitian chemical Co., Ltd.
A preparation method of a rare earth modified graphene/water-based epoxy resin coating is characterized by comprising the following steps:
(1) adding the rare earth modified graphene and a dispersing agent into deionized water, and stirring and performing ultrasonic treatment to obtain a graphene dispersion liquid;
(2) and stirring and ultrasonically mixing the graphene dispersion liquid and the water-based epoxy resin uniformly, adding a curing agent, stirring uniformly again, standing and defoaming until the viscosity is 15-20 s, and thus obtaining the rare earth modified graphene/water-based epoxy resin coating.
Wherein the viscosity of the coating is measured by a coating-4 viscometer at the room temperature of 25-30 ℃.
Has the advantages that: the modified graphene is premixed with the wetting dispersant and then mixed with the epoxy resin. The method can effectively disperse the modified graphene in the coating, reduce the dispersion time and improve the dispersion efficiency. Meanwhile, the proportion of the deionized water to the resin can meet the coating viscosity required by an air spray gun with the caliber of 0.18mm, so that the coating can be uniformly coated on the surface of a substrate.
Preferably, the stirring speed in the steps (1) and (2) is 800-1500 r/min, and the stirring time is 15-30 min;
the ultrasonic power is 80W, and the ultrasonic time is 30-60 min.
Has the beneficial effects that: according to the invention, the graphene and the resin coating can be fully mixed under the process conditions by combining magnetic stirring and ultrasonic dispersion.
The coating method of the rare earth modified graphene/water-based epoxy resin coating is characterized in that the rare earth modified graphene/water-based epoxy resin coating is sprayed on the surface of a matrix by using an air spray gun, and then the matrix is placed for 48 hours at the temperature of 20-25 ℃.
Preferably, the substrate comprises steel plate, aluminum alloy plate or concrete; wherein the steel plate is a Q235 steel plate, and the aluminum alloy plate is a 6061 aluminum alloy plate;
the air spray gun is 0.18mm in aperture, 0.2-0.3 MPa in gas pressure, 15-25 cm away from the surface of the matrix, the spraying angle is 80-90 degrees, and the spraying speed is 3-5 cm/s.
Has the beneficial effects that: the coating obtained by the spraying method has good quality and high coating efficiency, is beneficial to obtaining the hydrophobic coating, and further improves the water resistance and corrosion resistance of the coating.
The invention discloses the following technical effects:
the invention adopts the water-based epoxy resin coating, and reduces the harm of the coating solvent to operators and the pollution to the environment from the source. In addition, rare earth elements are adopted to modify graphene and serve as important components of the coating, and the corrosion resistance of the epoxy coating is greatly improved by utilizing the small size, the lamellar structure and the hydrophobicity of the graphene. When a matrix is corroded, rare earth cations can be released from the rare earth oxide loaded on the surface of the graphene, a passivation layer is formed between the coating and the metal, and the corrosion of the matrix is reduced. In addition, the invention adopts air spraying to prepare the coating, the coating thickness is uniform, the coating surface quality is high, the coating efficiency is high, and the adaptability to the coating and the matrix is wide.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without inventive exercise.
Fig. 1 is a microphotograph and a microscopic characterization of rare earth modified graphene obtained in example 1 of the present disclosure; the material comprises (a) a rare earth modified graphene powder macroscopic picture, (b) an X-ray diffraction pattern of the rare earth modified graphene, (c) a transmission electron microscope picture of the rare earth modified graphene, and (d) an electron diffraction pattern of a middle-magnification part of the rare earth modified graphene;
FIG. 2 is a photomicrograph of the coating; wherein, (a) is the epoxy resin coating in comparative example 1, and (b) is the rare earth modified graphene epoxy coating obtained in example 1 of the invention;
FIG. 3 is a photomicrograph of a coating applied to a Q235 steel sheet; wherein (a) is the epoxy resin coating in comparative example 1, and (b) is the rare earth modified graphene/waterborne epoxy resin coating obtained in example 1;
FIG. 4 is a drawing showing the microscopic morphology of a coating applied to a Q235 steel sheet; wherein, (a), (a1) and (a2) are surface and cross-sectional scanning pictures of the epoxy resin paint coating in comparative example 1, and (b), (b1) and (b2) are surface and cross-sectional scanning pictures of the rare earth modified graphene/water-based epoxy resin paint coating obtained in example 1;
FIG. 5 is a graph showing the corrosion resistance of the rare earth modified graphene/water-based epoxy resin coating obtained in example 1 coated on a Q235 steel plate; wherein (a) is the polarization curve of the coating, and (b) is the electrochemical impedance spectrum of the coating;
FIG. 6 is a photomicrograph of a coating applied to 6061 aluminum alloy sheet; wherein, (a) is an epoxy resin coating, and (b) is the rare earth modified graphene/waterborne epoxy resin coating obtained in example 1;
FIG. 7 is a drawing showing the microscopic morphology of the rare earth-modified graphene/waterborne epoxy coating obtained in example 1 coated on a 6061 aluminum alloy plate; wherein, (a), (b1) and (a2) are surface and cross-sectional scanning pictures of the epoxy resin paint coating, and (b), (b1) and (b2) are surface and cross-sectional scanning pictures of the rare earth modified graphene/waterborne epoxy resin paint coating;
FIG. 8 is a graph showing the corrosion resistance of a rare earth-modified graphene/waterborne epoxy resin coating layer obtained in example 1 coated on a 6061 aluminum alloy plate; wherein (a) is the polarization curve of the coating, and (b) is the electrochemical impedance spectrum of the coating;
FIG. 9 is a transmission electron microscope photograph of the surface micro-morphology of the rare earth-modified graphene/waterborne epoxy resin coating layer obtained in example 1 on concrete; wherein (a) is 1 μm; (b) is 500 nm; (c) is 200 nm.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, 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.
In order to make the aforementioned objects, features and advantages of the present invention more comprehensible, the present invention is described in detail with reference to the accompanying drawings and the detailed description thereof.
Example 1
A preparation method of a rare earth modified graphene/water-based epoxy resin coating comprises the following steps:
(1) preparing rare earth modified graphene:
(11) mixing graphene oxide and water according to a mass ratio of 1:500, and performing ultrasonic treatment for 1h under the condition of an ultrasonic power of 80W to obtain a graphene oxide dispersion liquid; adding cerium chloride heptahydrate with the mass being 2 times that of the graphene oxide into the graphene oxide dispersion liquid, magnetically stirring for 3 hours at the stirring speed of 900r/min at room temperature, standing for 24 hours, and transferring into a hydrothermal reaction kettle for reaction for 12 hours at the temperature of 120 ℃;
(12) after the hydrothermal reaction is finished, cooling to room temperature, then carrying out vacuum filtration, washing the obtained solid with deionized water for 5 times until the solid is neutral, then freezing the solid in an environment at the temperature of 70 ℃ below zero for 2 hours, and then drying the solid for 48 hours under the condition of a vacuum degree of 1Pa to obtain a rare earth modified graphene precursor;
(13) placing the graphene precursor at a flow of 2m 3 N of/h 2 Heating to 750 ℃ at a heating rate of 7 ℃/min in the atmosphere, and reducing for 1h to obtain rare earth modified graphene powder;
as shown in fig. 1, the rare earth modified graphene prepared in example 1 is a black powder, and cerium oxide particles are uniformly loaded on a graphene sheet layer;
(2) preparing a coating:
(21) mixing rare earth modified graphene, a wetting dispersant and deionized water according to a mass ratio of 1: 0.05: 95, mixing, magnetically stirring at 800r/min for 30min, and performing ultrasonic treatment at 80W for 1h to obtain a rare earth modified graphene dispersion liquid;
(22) adding the rare earth modified graphene dispersion liquid into a water-based epoxy resin emulsion, wherein the mass ratio of the rare earth modified graphene to the water-based epoxy resin emulsion is 0.015:2, then carrying out magnetic stirring at the speed of 1000r/min for 30min, then carrying out ultrasonic treatment at the ultrasonic power of 80W for 30min, then adding a curing agent according to the mass ratio of the water-based epoxy resin emulsion to the curing agent of 2:1, carrying out magnetic stirring at the speed of 1200r/min for 15min, standing for defoaming until the viscosity is measured by a coating-4 viscometer at the room temperature of 25-30 ℃ for 15-20 s, and thus obtaining the rare earth modified graphene/water-based epoxy resin coating;
as shown in figure 2, the prepared coating is milky white, and the rare earth modified graphene epoxy coating is gray black.
A preparation method of a rare earth modified graphene/water-based epoxy resin coating comprises the following steps:
taking a Q235 steel plate as a steel substrate, polishing the steel plate by using 1200# abrasive paper until the surface roughness is 6.068 mu m, ultrasonically cleaning the steel plate for 15min by using alcohol under the condition of the ultrasonic power of 80W, and spraying and cleaning the rare earth modified graphene/water-based epoxy resin coating on the surface of the cleaned steel substrate by using an air spray gun. Wherein the air pressure of the air spray gun with the aperture of 0.18mm is 0.3MPa, the distance from the surface of a spraying matrix is 20cm, the angle is 80-90 degrees, and the spraying speed is 4 cm/s. Followed by curing at 25 ℃ for 24 h.
Example 2
The coating method of the rare earth modified graphene/water-based epoxy resin coating is different from that of the embodiment 1 in that:
in step (3), a 6061 aluminum alloy sheet was used as an aluminum substrate instead of a steel substrate, and 1200# sandpaper was used for grinding to a surface roughness of 7.672 μm.
Example 3
The difference between the coating method of the rare earth modified graphene/water-based epoxy resin coating and the coating method of the embodiment 1 is that:
replacing the copper matrix in the step (3) with a concrete material;
and comprises the following steps:
the concrete material was treated with a wire brush to remove surface crystals and loose materials before use, and then the alkalinity of the base material was neutralized with 5% zinc sulfate and water. And then, polishing the coated surface by using No. 240 sand paper, washing by using water flow, and drying for later use. The water content of the concrete base material before coating is less than 8 percent, and the pH value is less than 8. And (3) spraying by using an air spray gun, wherein the air pressure of the air spray gun is 0.3MPa, the distance from the air spray gun to the surface of the sprayed substrate is 20cm, the angle is 80-90 degrees, the spraying speed is 4cm/s, and then the substrate is cured for 24 hours at the room temperature of 25 ℃. The surface micro-topography of the rare earth modified graphene/waterborne epoxy resin coating on the concrete is shown in fig. 9.
Example 4
The coating method of the rare earth modified graphene/water-based epoxy resin coating is different from that of the embodiment 1 in that:
in the step (1), the mass ratio of the graphene oxide to the cerium chloride heptahydrate is 1: 1.
Example 5
The coating method of the rare earth modified graphene/water-based epoxy resin coating is different from that of the embodiment 1 in that:
in the step (1), the mass ratio of the graphene oxide to the cerium chloride heptahydrate is 1: 3. After cerium chloride heptahydrate was added to the graphene oxide dispersion, it was magnetically stirred at a stirring speed of 1000r/min for 3 h.
Example 6
The coating method of the rare earth modified graphene/water-based epoxy resin coating is different from that of the embodiment 1 in that:
in the step (2), the preparation ratio of the coating is that the mass ratio of the rare earth modified graphene to the epoxy resin emulsion is 0.0075: 2.
Example 7
The coating method of the rare earth modified graphene/water-based epoxy resin coating is different from that of the embodiment 1 in that:
in the step (2), the preparation ratio of the coating is that the mass ratio of the rare earth modified graphene to the epoxy resin emulsion is 0.04: 2.
In the step (3), after the rare earth modified graphene dispersion liquid and the epoxy resin emulsion are mixed, magnetically stirring for 15min at the speed of 1200 r/min; after the curing agent is added, the mixture is magnetically stirred for 15min at the speed of 1500 r/min.
Comparative example 1
The preparation method of the water-based epoxy resin coating is different from the preparation method of the example 1 in that: rare earth modified graphene is not included.
Comparative example 2
The preparation method of the rare earth modified graphene composite coating is different from that of the embodiment 1 in that: the coating is prepared by adopting a wire bar coater, and the method specifically comprises the following steps:
the specification of the wire bar coater is that the thread depth is 100 mu m, and the coating process is to drop a proper amount of coating on the surface of the substrate and uniformly scrape in a single direction and a single time.
Comparative example 3
The preparation method of the water-based epoxy resin coating is different from the preparation method of the example 1 in that: the preparation method does not comprise rare earth modified graphene, and adopts a wire bar coater to prepare the coating, and specifically comprises the following steps:
the specification of the wire bar coater is that the thread depth is 100 mu m, and the coating process is to drop a proper amount of coating on the surface of the substrate and uniformly scrape in a single direction and a single time.
The technical effects are as follows:
the water-based epoxy resin coating in the comparative example 1 and the rare earth modified graphene/water-based epoxy resin coating in the example 1 are sprayed by an air spray gun with the caliber of 0.18mm, the gas pressure is 0.2-0.3 MPa, the distance from the surface of the matrix is 15-25 cm, the spraying angle is 80-90 degrees, and the spraying speed is 3-5 cm/s. Followed by curing at 25 ℃ for 24 h.
Comparative examples 2 and 3 used a 100 μm gauge wire bar applicator for single direction, single pass application. Followed by curing at 25 ℃ for 24 h.
1. The cured coating on the Q235 steel plate is shown in FIG. 3, the epoxy resin paint coating obtained in comparative example 1 is transparent, and the paint coating obtained in example 1 is uniformly black. With reference to fig. 4 to 5, the corrosion resistance ratio of the coating on the surface of the Q235 steel plate in example 1 and comparative examples 1 to 3 is shown in table 1.
TABLE 1
| Test specimen | Ecorr(V) | Icorr(μA/cm -2 ) | CR(mm/year) | |Z|0.01Hz(Ω·cm 2 ) |
| Q235 steel plate | -0.596 | 66.278 | 7.445×10 -1 | -- |
| Comparative example 1 | -0.514 | 5.520 | 6.600×10 -2 | 3.467×10 4 |
| Comparative example 2 | -0.486 | 0.492 | 5.889×10 -3 | 3.186×10 5 |
| Comparative example 3 | -0.543 | 1.155 | 1.382×10 -2 | 2.967×10 5 |
| Example 1 | -0.332 | 0.013 | 1.565×10 -4 | 1.023×10 6 |
2. FIG. 6 shows the cured coating on 6061 aluminum alloy plate, the coating of epoxy resin paint obtained in comparative example 1 is transparent, and the coating obtained in example 2 is uniformly black on the surface of aluminum alloy. With reference to fig. 7 to 8, the corrosion resistance ratio of the 6061 aluminum alloy plate surface coating of the example 2 and the comparative examples 1 to 3 is shown in table 2.
TABLE 2
3. The corrosion resistance ratio of the rare earth modified graphene/water-based epoxy resin coating obtained in example 3 to the epoxy resin coating obtained in comparative example 1 on the concrete surface coating is shown in table 3.
TABLE 3
The data show that compared with the epoxy resin coating, the rare earth modified graphene/water-based epoxy resin coating provided by the invention greatly improves the corrosion resistance of the coating and can effectively reduce the corrosion of a matrix.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.
Claims (10)
1. The rare earth modified graphene/water-based epoxy resin coating is characterized by comprising the following raw materials in parts by weight: 40-50 parts of water-based epoxy resin, 0.15-0.8 part of rare earth modified graphene, 20-25 parts of curing agent, 0.01-0.07 part of dispersing agent and 24-39 parts of deionized water.
2. The rare earth modified graphene/water-based epoxy resin coating as claimed in claim 1, wherein the preparation method of the rare earth modified graphene comprises the following steps:
1) adding cerium chloride heptahydrate into the graphene oxide dispersion liquid, stirring and standing, reacting at 120-180 ℃ for 12-24 h, cooling to room temperature after the reaction is finished, and then sequentially washing solid products in the reaction liquid to be neutral, freezing and drying to obtain a rare earth modified graphene precursor;
2) subjecting the rare earth modified graphene precursor to N 2 Heating to 500-900 ℃ in the atmosphere, and reducing for 0.5-2 h to obtain the rare earth modified graphene powder.
3. The rare earth modified graphene/waterborne epoxy resin coating according to claim 2, wherein the mass concentration of the graphene oxide dispersion liquid in the step 1) is 2 mg/ml;
the mass ratio of the graphene oxide to the cerium chloride heptahydrate is 1 (1-3);
the standing is performed at room temperature for 12-24 hours;
the freezing is carried out at the temperature of-70 to-50 ℃ for 1 to 4 hours;
the drying is freeze drying for 48h under the condition that the vacuum degree is less than 10 Pa.
4. The rare earth modified graphene/waterborne epoxy resin coating of claim 2, wherein the N in step 2) 2 The flow rate is 1-3 m 3 /h；
The heating rate is 7 ℃/min.
5. The rare earth modified graphene/waterborne epoxy resin coating as claimed in claim 1, wherein the epoxy resin is an anionic water-dispersible bisphenol A epoxy resin emulsion, and the epoxy value is 0.125-0.25.
6. The rare earth modified graphene/waterborne epoxy resin coating according to claim 1, wherein the curing agent is a non-ionic waterborne epoxy curing agent and does not include a free surfactant;
the curing agent comprises dibutyltin dilaurate;
the dispersant is a non-ionic aqueous wetting dispersant and comprises dioctyl sodium sulfosuccinate.
7. The preparation method of the rare earth modified graphene/water-based epoxy resin coating as claimed in any one of claims 1 to 6, characterized by comprising the following steps:
(1) adding the rare earth modified graphene and a dispersing agent into deionized water, and stirring and performing ultrasonic treatment to obtain a graphene dispersion liquid;
(2) and stirring and ultrasonically mixing the graphene dispersion liquid and the water-based epoxy resin uniformly, adding a curing agent, stirring uniformly again, standing and defoaming until the viscosity is 15-20 s, and thus obtaining the rare earth modified graphene/water-based epoxy resin coating.
8. The preparation method of the rare earth modified graphene/water-based epoxy resin coating according to claim 7, wherein the stirring speed in the steps (1) and (2) is 800-1500 r/min, and the stirring time is 15-30 min;
the ultrasonic power is 80W, and the ultrasonic time is 30-60 min.
9. The method for coating the rare earth modified graphene/waterborne epoxy resin coating according to any one of claims 1 to 6, wherein the rare earth modified graphene/waterborne epoxy resin coating is sprayed on the surface of a substrate by an air spray gun, and then is placed at 20-25 ℃ for 48 hours.
10. The coating method of the rare earth modified graphene/water-based epoxy resin coating according to claim 9, wherein the substrate comprises a steel plate, an aluminum alloy plate or concrete;
the caliber of the air spray gun is 0.18mm, the air pressure is 0.2-0.3 MPa, the distance between the air spray gun and the surface of the substrate is 15-25 cm, the spraying angle is 80-90 degrees, and the spraying speed is 3-5 cm/s.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115124874A (en) * | 2022-09-01 | 2022-09-30 | 广东合胜实业股份有限公司 | Back water surface anti-permeability coating and preparation method thereof |
| CN115926586A (en) * | 2023-02-01 | 2023-04-07 | 天津大学 | Epoxy heat-conducting anticorrosive paint and preparation method thereof |
| CN116285594A (en) * | 2023-05-09 | 2023-06-23 | 鞠慧 | Environment-friendly paint and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115011202A (en) * | 2022-06-14 | 2022-09-06 | 安徽登王化工有限公司 | Water-based epoxy resin coating based on modified graphite and preparation method thereof |
-
2022
- 2022-06-07 CN CN202210633855.2A patent/CN114940851A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115011202A (en) * | 2022-06-14 | 2022-09-06 | 安徽登王化工有限公司 | Water-based epoxy resin coating based on modified graphite and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 钱颖: "Enhanced functional properties of CeO2 modified graphene/epoxy nanocomposite coating through interface engineering", vol. 409, pages 2 * |
| 魏爱敏: "建筑装饰材料", 北京理工大学出版社, pages: 162 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115124874A (en) * | 2022-09-01 | 2022-09-30 | 广东合胜实业股份有限公司 | Back water surface anti-permeability coating and preparation method thereof |
| CN115926586A (en) * | 2023-02-01 | 2023-04-07 | 天津大学 | Epoxy heat-conducting anticorrosive paint and preparation method thereof |
| CN115926586B (en) * | 2023-02-01 | 2023-08-18 | 天津大学 | Epoxy heat-conducting anticorrosive paint and preparation method thereof |
| CN116285594A (en) * | 2023-05-09 | 2023-06-23 | 鞠慧 | Environment-friendly paint and preparation method thereof |
| CN116285594B (en) * | 2023-05-09 | 2024-05-14 | 玉森林(北京)生态环保科技有限公司 | Environment-friendly paint and preparation method thereof |
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