CN111548707B - Modified graphene oxide epoxy resin composite coating and preparation method thereof - Google Patents
Modified graphene oxide epoxy resin composite coating and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a modified graphene oxide epoxy resin composite coating and a preparation method thereof, and belongs to the technical field of material coatings. The coating comprises the following components: cerium oxide, ferric salt solution, epoxy resin and graphene oxide. According to the invention, firstly, graphene oxide cake materials are utilized to prepare graphene oxide dispersion liquid, then a cerium oxide-graphene oxide compound is synthesized through a hydrothermal reaction, and finally, the granular compound and a ferric salt solution are subjected to a hydrothermal reaction and are calcined at a high temperature to prepare the cerium oxide-graphene oxide composite. The preparation method has the advantages of easily available raw materials, reasonable process route, convenient operation, no pollution in the preparation process, good anticorrosive performance of the coating and the like.
Description
Technical Field
The invention relates to the technical field of material coatings, in particular to a modified graphene oxide epoxy resin composite coating and a preparation method thereof.
Background
With the progress of science and technology, the exploitation of land resources is approaching saturation, and the ocean industry is gradually rising. The ocean occupies 71 percent of area and is rich in resources, but seawater has the property of electrolyte solution, so that metal materials are easy to generate electrochemical corrosion and the reliability of metal components is reduced. Therefore, in the development process, the severe corrosive environment brings great economic loss and causes problems in various aspects of safety, ecological civilization and national civilization. In severe service environments such as marine climate environments, the corrosion resistance of epoxy resin coatings is still required to be improved.
The epoxy resin coating is one of the most widely applied anticorrosive coatings, has excellent chemical resistance, obvious barrier effect on external corrosive media, good corrosion resistance and good adhesive force on various substrates. The graphene and the graphene oxide are novel two-dimensional nanosheet layer materials, and researches show that the corrosion resistance of the coating can be greatly improved by adding a small amount of graphene into the epoxy resin coating. However, the dispersibility of graphene in the epoxy resin coating limits the contribution of graphene to the improvement of the corrosion protection performance of the coating. The surface of the graphene oxide has more oxygen-containing functional groups, so that the graphene oxide is favorable for further organic modification. The modified graphene oxide can obtain better dispersibility in the epoxy resin coating, and further effectively improves the corrosion protection performance of the coating. However, when preparing epoxy resin coatings, the filler is often not a single species. In order to obtain good barrier properties for the coating, cerium oxide, iron oxide red, graphene oxide and modified graphene oxide are often used together. In previous researches, cerium oxide and iron oxide red are generally single modified graphene oxide and are dispersed in an epoxy resin coating in a physical blending mode. Although the physical blending method can improve the corrosion resistance of the coating to some extent, the physical blending method needs to be improved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a modified graphene oxide epoxy resin composite coating and a preparation method thereof, so as to solve the problems of insufficient process and performance of an anticorrosive coating in the prior art.
In order to achieve the above object, the present invention provides the following technical solutions:
the modified graphene oxide epoxy resin composite coating comprises, by weight, 1-4 parts of cerium oxide, 4-15 parts of a ferric salt solution, 80-96 parts of epoxy resin and 1-2 parts of graphene oxide.
Further, the epoxy value of the epoxy resin is 0.48-0.55; the graphene oxide has a purity of more than 95wt%, a thickness of 1nm to 20nm, and a planar transverse dimension of 1 μm to 100 μm.
A preparation method of a modified graphene oxide epoxy resin composite coating comprises the following steps:
mixing graphene oxide dispersion liquid and Ce (NO) 3 ) 3 ·6H 2Adding O into distilled water, adjusting pH to 11-12, and performing hydrothermal reactionObtaining a nano cerium oxide particle modified graphene oxide compound;
adding the graphene oxide compound modified by the nano cerium oxide particles into an inorganic ferric salt solution, carrying out hydrothermal reaction, and drying and calcining under the condition of inert gas to obtain a modified graphene oxide composite material;
and uniformly mixing the modified graphene oxide composite material with 0.5wt.% of vinyl resin to prepare the composite coating.
Further, the graphene oxide and Ce (NO) 3 ) 3 ·6H 2The molar ratio of O is: 1: 1-4; the molar ratio of the graphene oxide to the inorganic salt is 1: 4-15.
Further, the hydrothermal reaction temperature for preparing the graphene oxide compound is 170-200 ℃, and the reaction time is 22-24 hours; the hydrothermal reaction temperature for preparing the modified graphene oxide composite material is 100-150 ℃, and the reaction time is 11-14 h; the calcination temperature of the drying calcination is 370-500 ℃, and the time is 2-4 hours; the inert gas is nitrogen, neon, argon or xenon.
Further, the inorganic ferric salt solution is one or a mixture of ferrous chloride, ferrous acetate or ferrous sulfate.
Further, the molar concentration of the inorganic salt iron solution is 0.01-0.04 mol/L; the solvent of the inorganic salt iron solution is water, dimethyl amide or absolute ethyl alcohol.
Further, the preparation method of the graphene oxide dispersion liquid comprises the following steps:
boiling the dialysis bag in dialysate, and washing with distilled water for several times;
boiling the washed dialysis bag in EDTA.2Na solution;
dissolving the graphite oxide slurry in distilled water, performing ultrasonic treatment, filling the solution into a cooled dialysis bag, putting the dialysis bag into the distilled water, performing magnetic stirring, and performing ultrasonic stripping to obtain the graphene oxide dispersion liquid.
Further, the dialyzate was prepared by adding 10g of sodium hydrogencarbonate and 186.6mg of disodium ethylenediaminetetraacetate to 500ml of distilled water and stirring them well.
Further, the ultrasonic time of the graphite oxide slurry after being dissolved in distilled water is 30-40 min, and the magnetic stirring time is 3-4 d; the temperature of ultrasonic stripping is 0-5 ℃; the time of ultrasonic stripping is 30-40 min, and the number of ultrasonic stripping is 3-4.
Compared with the prior art, the invention has the following beneficial effects:
due to the pinning structure of the lamella and the lamella, the bonding property of the cerium oxide nanosheet and the graphene oxide lamella is better, the diffusion path of a corrosive medium in the coating is more complex, the transition element iron has electric activity, the reaction site is provided by the cerium oxide modified graphene oxide, the electric conductivity accelerates the electron transmission, the coating is compact in structure, no obvious agglomeration phenomenon exists, and the coating has good corrosion resistance.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
(1) To 500ml of distilled water was added 10g of sodium bicarbonate (NaHCO)3) And 186.6mg disodium ethylene diamine tetraacetate (EDTA.2Na), stirring uniformly to prepare dialysate, placing the dialysis bag in the dialysate to boil for 15 min, then washing the dialysis bag with distilled water for multiple times, placing the washed dialysis bag in 1 mmol/L EDTA.2Na solution (PH =8.0) to boil for 10 min;
(2) dissolving a proper amount of graphite oxide slurry in distilled water, performing ultrasonic treatment for 30min, then putting the graphite oxide slurry into a cooled dialysis bag, and magnetically stirring the graphite oxide slurry in a beaker filled with distilled water for 3 d. Finally, carrying out ultrasonic stripping for 3 times in total for 30min under the condition of 0 ℃ by using an ultrasonic cell disruptor to obtain a graphene oxide dispersion liquid;
(3) weighing 10ml of graphene oxide dispersion liquid, placing the graphene oxide dispersion liquid in a beaker, adding 160ml of distilled water, placing the mixture in an oven, and drying the mixture for 5 hours to obtain the solid content of 9mg/ml;
(4) measuring 8.9mlAdding 160ml of distilled water into the solution obtained in the step (3), stirring, performing ultrasonic dispersion at 30 ℃ for 30min, taking out, and adding 0.403mg of cerium nitrate hexahydrate (Ce (NO) 3 ) 3 ·6H 2 O) is dissolved in distilled water, magnetic stirring is carried out for 30min, and 4ml of ammonia water is slowly added to lead the PH to reach 11-12;
(5) and (3) placing the mixed solution into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, performing suction filtration after reacting for 24 hours at the temperature of 200 ℃, washing with ethanol, drying in an oven at the temperature of 60 ℃ for 8 hours, and finally grinding to obtain the cerium oxide modified graphene oxide particles.
(6) Dissolving ferrous acetate in distilled water, stirring until the ferrous acetate is completely dissolved to obtain 500ml of 0.01mol/L ferrous acetate solution, adding the cerium oxide modified graphene oxide particles, and stirring to obtain a stable suspension;
(7) placing the suspension in a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, reacting for 14h at 120 ℃, cooling to room temperature after the reaction is finished, washing with water and performing suction filtration to obtain a compound;
(8) calcining the compound obtained in the step 7 at a high temperature of 400 ℃ for 2 hours in an inert atmosphere to obtain a modified graphene oxide compound, and uniformly mixing the modified graphene oxide compound with 0.5wt.% of vinyl resin to obtain a composite coating;
the salt spray test and the electrochemical test were performed on the cerium oxide and iron red modified graphene oxide resin composite coating, and the obtained results are listed in table 1.
Example 2
(1) To 500ml of distilled water was added 10g of sodium bicarbonate (NaHCO)3) And 186.6mg disodium ethylene diamine tetraacetate (EDTA.2Na), stirring uniformly to prepare dialysate, placing the dialysis bag in the dialysate to boil for 15 min, then washing the dialysis bag with distilled water for multiple times, placing the washed dialysis bag in 1 mmol/L EDTA.2Na solution (PH =8.0) to boil for 10 min;
(2) dissolving a proper amount of graphite oxide slurry in distilled water, performing ultrasonic treatment for 40min, then putting the graphite oxide slurry into a cooled dialysis bag, and magnetically stirring the graphite oxide slurry in a beaker filled with distilled water for 3 d. Finally, carrying out ultrasonic stripping for 4 times in total for 40min under the condition of 5 ℃ by using an ultrasonic cell disruptor to obtain a graphene oxide dispersion liquid;
(3) weighing 10ml of graphene oxide dispersion liquid, placing the graphene oxide dispersion liquid in a beaker, adding 160ml of distilled water, placing the mixture in an oven, and drying the mixture for 5 hours to obtain the solid content of 9mg/ml;
(4) measuring 8.9ml of the solution obtained in the step (3), adding 160ml of distilled water, stirring, ultrasonically dispersing at 30 ℃ for 30min, taking out, and adding 0.807mg of cerium nitrate hexahydrate (Ce (NO) 3 ) 3 ·6H 2 O) is dissolved in distilled water, magnetic stirring is carried out for 30min, and 4ml of ammonia water is slowly added to lead the PH to reach 11-12;
(5) and (3) placing the mixed solution into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, performing suction filtration after reacting for 23 h at 170 ℃, washing with ethanol, drying in an oven at 60 ℃ for 8h, and finally grinding to obtain the cerium oxide modified graphene oxide particles.
(6) Dissolving ferrous acetate in distilled water, stirring until the ferrous acetate is completely dissolved to obtain 500ml of 0.01mol/L ferrous acetate solution, adding the cerium oxide modified graphene oxide particles, and stirring to obtain a stable suspension;
(7) placing the suspension in a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, reacting for 13 h at 130 ℃, cooling to room temperature after the reaction is finished, washing with water and performing suction filtration to obtain a compound;
(8) calcining the compound obtained in the step 7 at a high temperature of 400 ℃ for 2 hours in an inert atmosphere to obtain a modified graphene oxide compound, and uniformly mixing the modified graphene oxide compound with 0.5wt.% of vinyl resin to obtain a composite coating;
the salt spray test and the electrochemical test were performed on the cerium oxide and iron red modified graphene oxide resin composite coating, and the obtained results are listed in table 1.
Example 3
(1) To 500ml of distilled water was added 10g of sodium bicarbonate (NaHCO)3) And 186.6mg disodium ethylene diamine tetraacetate (EDTA.2Na), stirring well to prepare dialysate, placing the dialysis bag in the dialysate to boil for 15 min, and washing with distilled water for several times to dialyzeAfter the bag, the washed dialysis bag is put into a 1 mmol/L EDTA.2Na solution (PH =8.0) and boiled for 10 min;
(2) dissolving a proper amount of graphite oxide slurry in distilled water, performing ultrasonic treatment for 30min, then putting the graphite oxide slurry into a cooled dialysis bag, and magnetically stirring the graphite oxide slurry in a beaker filled with distilled water for 4 d. Finally, carrying out ultrasonic stripping for 4 times in total for 40min under the condition of 3 ℃ by using an ultrasonic cell disruptor to obtain a graphene oxide dispersion liquid;
(3) weighing 10ml of graphene oxide dispersion liquid, placing the graphene oxide dispersion liquid in a beaker, adding 160ml of distilled water, placing the mixture in an oven, and drying the mixture for 5 hours to obtain the solid content of 9mg/ml;
(4) measuring 8.9ml of the solution obtained in the step (3), adding 160ml of distilled water, stirring, ultrasonically dispersing at 30 ℃ for 30min, taking out, and adding 0.201mg of cerium nitrate hexahydrate (Ce (NO) 3 ) 3 ·6H 2 O) is dissolved in distilled water, magnetic stirring is carried out for 30min, and 4ml of ammonia water is slowly added to lead the PH to reach 11-12;
(5) and (3) placing the mixed solution into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, performing suction filtration after reacting for 24 hours at 190 ℃, washing with ethanol, drying in an oven at 60 ℃ for 8 hours, and finally grinding to obtain the cerium oxide modified graphene oxide particles.
(6) Dissolving ferrous chloride in absolute ethyl alcohol, stirring until the ferrous chloride is completely dissolved to obtain 500ml of 0.02mol/L ferrous acetate solution, adding the cerium oxide modified graphene oxide particles, and stirring to obtain a stable suspension;
(7) placing the suspension in a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, reacting for 12 h at 120 ℃, cooling to room temperature after the reaction is finished, washing with water and performing suction filtration to obtain a compound;
(8) calcining the compound obtained in the step 7 at 450 ℃ for 2h under an inert atmosphere to obtain a modified graphene oxide compound, and uniformly mixing the modified graphene oxide compound with 0.5wt.% of vinyl resin to obtain a composite coating;
the salt spray test and the electrochemical test were performed on the cerium oxide and iron red modified graphene oxide resin composite coating, and the obtained results are listed in table 1.
Example 4
(1) To 500ml of distilled water was added 10g of sodium bicarbonate (NaHCO)3) And 186.6mg disodium ethylene diamine tetraacetate (EDTA.2Na), stirring uniformly to prepare dialysate, placing the dialysis bag in the dialysate to boil for 15 min, then washing the dialysis bag with distilled water for multiple times, placing the washed dialysis bag in 1 mmol/L EDTA.2Na solution (PH =8.0) to boil for 10 min;
(2) dissolving a proper amount of graphite oxide slurry in distilled water, performing ultrasonic treatment for 40min, then putting the graphite oxide slurry into a cooled dialysis bag, and magnetically stirring the graphite oxide slurry in a beaker filled with distilled water for 3 d. Finally, carrying out ultrasonic stripping for 3 times in total for 35min under the condition of 2 ℃ by using an ultrasonic cell disruptor to obtain a graphene oxide dispersion liquid;
(3) weighing 10ml of graphene oxide dispersion liquid, placing the graphene oxide dispersion liquid in a beaker, adding 160ml of distilled water, placing the mixture in an oven, and drying the mixture for 5 hours to obtain the solid content of 9mg/ml;
(4) measuring 8.9ml of the solution obtained in the step (3), adding 160ml of distilled water, stirring, ultrasonically dispersing at 30 ℃ for 30min, taking out, and adding 0.807mg of cerium nitrate hexahydrate (Ce (NO) 3 ) 3 ·6H 2 O) is dissolved in distilled water, magnetic stirring is carried out for 30min, and 4ml of ammonia water is slowly added to lead the PH to reach 11-12;
(5) and (3) placing the mixed solution into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, performing suction filtration after reacting for 22 h at 200 ℃, washing with ethanol, drying in an oven at 60 ℃ for 8h, and finally grinding to obtain the cerium oxide modified graphene oxide particles.
(6) Dissolving ferrous chloride in absolute ethyl alcohol, stirring until the ferrous chloride is completely dissolved to obtain 500ml of 0.02mol/L ferrous acetate solution, adding the cerium oxide modified graphene oxide particles, and stirring to obtain a stable suspension;
(7) placing the suspension in a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, reacting for 14h at 100 ℃, cooling to room temperature after the reaction is finished, washing with water and performing suction filtration to obtain a compound;
(8) calcining the compound obtained in the step 7 at 450 ℃ for 2h under an inert atmosphere to obtain a modified graphene oxide compound, and uniformly mixing the modified graphene oxide compound with 0.5wt.% of vinyl resin to obtain a composite coating;
the salt spray test and the electrochemical test were performed on the cerium oxide and iron red modified graphene oxide resin composite coating, and the obtained results are listed in table 1.
Example 5
(1) To 500ml of distilled water was added 10g of sodium bicarbonate (NaHCO)3) And 186.6mg disodium ethylene diamine tetraacetate (EDTA.2Na), stirring uniformly to prepare dialysate, placing the dialysis bag in the dialysate to boil for 15 min, then washing the dialysis bag with distilled water for multiple times, placing the washed dialysis bag in 1 mmol/L EDTA.2Na solution (PH =8.0) to boil for 10 min;
(2) dissolving a proper amount of graphite oxide slurry in distilled water, performing ultrasonic treatment for 35min, then putting the graphite oxide slurry into a cooled dialysis bag, and magnetically stirring the graphite oxide slurry in a beaker filled with distilled water for 3 d. Finally, carrying out ultrasonic stripping for 30min for 4 times under the condition of 0 ℃ by using an ultrasonic cell disruptor to obtain a graphene oxide dispersion liquid;
(3) weighing 10ml of graphene oxide dispersion liquid, placing the graphene oxide dispersion liquid in a beaker, adding 160ml of distilled water, placing the mixture in an oven, and drying the mixture for 5 hours to obtain the solid content of 9mg/ml;
(4) measuring 8.9ml of the solution obtained in the step (3), adding 160ml of distilled water, stirring, performing ultrasonic dispersion at 30 ℃ for 30min, taking out, and adding 0.403mg of cerium nitrate hexahydrate (Ce (NO) 3 ) 3 ·6H 2 O) is dissolved in distilled water, magnetic stirring is carried out for 30min, and 4ml of ammonia water is slowly added to lead the PH to reach 11-12;
(5) and (3) placing the mixed solution into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, performing suction filtration after reacting for 22 h at 170 ℃, washing with ethanol, drying in an oven at 60 ℃ for 8h, and finally grinding to obtain the cerium oxide modified graphene oxide particles.
(6) Dissolving ferrous sulfate in dimethyl amide, stirring until the ferrous sulfate is completely dissolved to obtain 500ml of 0.04mol/L ferrous acetate solution, adding the cerium oxide modified graphene oxide particles, and stirring to obtain a stable suspension;
(7) placing the suspension in a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, reacting for 11 h at 130 ℃, cooling to room temperature after the reaction is finished, washing with water and performing suction filtration to obtain a compound;
(8) calcining the compound obtained in the step 7 at 370 ℃ for 3h under an inert atmosphere to obtain a modified graphene oxide compound, and uniformly mixing the modified graphene oxide compound with 0.5wt.% of vinyl resin to obtain a composite coating;
the salt spray test and the electrochemical test were performed on the cerium oxide and iron red modified graphene oxide resin composite coating, and the obtained results are listed in table 1.
Example 6
(1) To 500ml of distilled water was added 10g of sodium bicarbonate (NaHCO)3) And 186.6mg disodium ethylene diamine tetraacetate (EDTA.2Na), stirring uniformly to prepare dialysate, placing the dialysis bag in the dialysate to boil for 15 min, then washing the dialysis bag with distilled water for multiple times, placing the washed dialysis bag in 1 mmol/L EDTA.2Na solution (PH =8.0) to boil for 10 min;
(2) dissolving a proper amount of graphite oxide slurry in distilled water, performing ultrasonic treatment for 40min, then putting the graphite oxide slurry into a cooled dialysis bag, and magnetically stirring the graphite oxide slurry in a beaker filled with distilled water for 4 d. Finally, carrying out ultrasonic stripping for 3 times in total for 35min under the condition of 5 ℃ by using an ultrasonic cell disruptor to obtain a graphene oxide dispersion liquid;
(3) weighing 10ml of graphene oxide dispersion liquid, placing the graphene oxide dispersion liquid in a beaker, adding 160ml of distilled water, placing the mixture in an oven, and drying the mixture for 5 hours to obtain the solid content of 9mg/ml;
(4) measuring 8.9ml of the solution obtained in the step (3), adding 160ml of distilled water, stirring, performing ultrasonic dispersion at 30 ℃ for 30min, taking out, and adding 0.201mg of cerium nitrate hexahydrate (Ce (NO) 3 ) 3 ·6H 2 O) is dissolved in distilled water, magnetic stirring is carried out for 30min, and 4ml of ammonia water is slowly added to lead the PH to reach 11-12;
(5) and (3) placing the mixed solution into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, performing suction filtration after reacting for 24 hours at 190 ℃, washing with ethanol, drying in an oven at 60 ℃ for 8 hours, and finally grinding to obtain the cerium oxide modified graphene oxide particles.
(6) Dissolving ferrous sulfate in dimethyl amide, stirring until the ferrous sulfate is completely dissolved to obtain 500ml of 0.04mol/L ferrous acetate solution, adding the cerium oxide modified graphene oxide particles, and stirring to obtain a stable suspension;
(7) placing the suspension in a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, reacting for 13 h at 150 ℃, cooling to room temperature after the reaction is finished, washing with water and performing suction filtration to obtain a compound;
(8) calcining the compound obtained in the step 7 at a high temperature of 500 ℃ for 4 hours in an inert atmosphere to obtain a modified graphene oxide compound, and uniformly mixing the modified graphene oxide compound with 0.5wt.% of vinyl resin to obtain a composite coating;
the cerium oxide and iron oxide red modified graphene oxide resin composite coating is subjected to an adhesion test, a salt spray test and an electrochemical test, and the obtained results are listed in table 1.
Table 1 modified graphene oxide resin composite coating test results
| Cerium oxide mg | Salt iron solution | The concentration of the solution is mol/L | Adhesion test MPa | Salt spray test d | Resistance omega | |
| Example 1 | 0.403 | Ferrous acetate | 0.05 | 13.77 | 149 | 0.5 |
| Example 2 | 0.807 | Ferrous acetate | 0.05 | 7.12 | 142 | 0.4 |
| Example 3 | 0.201 | Ferrous chloride | 0.08 | 11.43 | 103 | 0.1 |
| Example 4 | 0.807 | Ferrous chloride | 0.08 | 6.31 | 97 | 0.2 |
| Example 5 | 0.201 | Ferrous sulfate | 0.1 | 12.49 | 135 | 0.1 |
| Example 6 | 0.201 | Ferrous sulfate | 0.1 | 7.06 | 128 | 0.1 |
As can be seen from table 1, when the molar ratio of graphene oxide to cerium oxide is 1: 2, when the ferric salt solution is ferrous acetate, the coating has the best corrosion resistance.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and improvements can be made without departing from the principle of the present invention, and these modifications and improvements should also be construed as the protection scope of the present invention.
Claims (8)
1. A preparation method of a modified graphene oxide epoxy resin composite coating is characterized by comprising the following steps:
mixing graphene oxide dispersion liquid and Ce (NO) 3 ) 3 ·6H 2Adding O into distilled water, adjusting the pH value to 11-12, and performing hydrothermal reaction to obtain a nano cerium oxide particle modified graphene oxide compound;
adding the graphene oxide compound modified by the nano cerium oxide particles into an inorganic ferric salt solution, carrying out hydrothermal reaction, and drying and calcining under the condition of inert gas to obtain a modified graphene oxide composite material;
uniformly mixing the modified graphene oxide composite material with 0.5wt.% of epoxy resin containing vinyl to prepare a composite coating;
the mol ratio of the graphene oxide to the inorganic salt iron is 1: 4-15;
the mol ratio of the graphene oxide to the cerium oxide is 1: 2, the inorganic ferric salt solution is ferrous acetate solution.
2. The preparation method of the modified graphene oxide epoxy resin composite coating according to claim 1, wherein the hydrothermal reaction temperature for preparing the graphene oxide composite is 170-200 ℃, and the reaction time is 22-24 h; the hydrothermal reaction temperature for preparing the modified graphene oxide composite material is 100-150 ℃, and the reaction time is 11-14 h; the calcination temperature of the drying calcination is 370-500 ℃, and the time is 2-4 hours; the inert gas is nitrogen, neon, argon or xenon.
3. The preparation method of the modified graphene oxide epoxy resin composite coating according to claim 1, wherein the molar concentration of the inorganic ferric salt solution is 0.01-0.04 mol/L; the solvent of the inorganic salt iron solution is water, dimethyl amide or absolute ethyl alcohol.
4. The preparation method of the modified graphene oxide epoxy resin composite coating according to claim 1, wherein the preparation method of the graphene oxide dispersion liquid comprises the following steps:
boiling the dialysis bag in dialysate, and washing with distilled water for several times;
boiling the washed dialysis bag in EDTA.2Na solution;
dissolving the graphite oxide slurry in distilled water, performing ultrasonic treatment, filling the solution into a cooled dialysis bag, putting the dialysis bag into the distilled water, performing magnetic stirring, and performing ultrasonic stripping to obtain the graphene oxide dispersion liquid.
5. The preparation method of the modified graphene oxide epoxy resin composite coating according to claim 4, wherein the dialysate is obtained by adding 10g of sodium bicarbonate and 186.6mg of disodium ethylene diamine tetraacetate into 500ml of distilled water and uniformly stirring.
6. The preparation method of the modified graphene oxide epoxy resin composite coating according to claim 4, wherein the ultrasonic time of the graphite oxide slurry after being dissolved in distilled water is 30-40 min, and the magnetic stirring time is 3-4 d; the temperature of ultrasonic stripping is 0-5 ℃; the time of ultrasonic stripping is 30-40 min, and the number of ultrasonic stripping is 3-4.
7. The preparation method of the modified graphene oxide epoxy resin composite coating according to claim 1, wherein the epoxy value of the epoxy resin is 0.48-0.55; the graphene oxide has a purity of more than 95wt%, a thickness of 1nm to 20nm, and a planar transverse dimension of 1 μm to 100 μm.
8. A modified graphene oxide epoxy resin composite coating prepared according to the preparation method of any one of claims 1 to 7.
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