CN110358395B - Graphene-based corrosion-resistant coating and preparation method thereof - Google Patents
Graphene-based corrosion-resistant coating and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a graphene-based corrosion-resistant coating and a preparation method thereof, and relates to the technical field of metal surface treatment. The preparation method comprises the steps of firstly reacting graphene oxide with 3-aminopropyltriethoxysilane and chloroacetic acid to prepare modified graphene, then preparing modified silicon dioxide from carboxylated mesoporous silicon dioxide, potassium tetratitanate and polypyrrole, finally mixing the modified graphene with the modified silicon dioxide, adding acrylic emulsion, a film-forming assistant and water to prepare the corrosion-resistant coating, coating the corrosion-resistant coating on the surface of a pretreated metal matrix, and drying to obtain the graphene-based corrosion-resistant coating. The graphene-based corrosion-resistant coating prepared by the invention has excellent corrosion resistance and good coating fastness.
Description
Technical Field
The invention relates to the technical field of metal surface treatment, in particular to a graphene-based corrosion-resistant coating and a preparation method thereof.
Background
The metal corrosion brings huge economic loss and social harm to human beings, the importance of metal corrosion prevention is increasingly prominent along with the development of industry and science and technology, wherein the coating technology is most convenient and economic, and therefore, the metal corrosion prevention method plays an increasingly important role in national economic construction. The traditional anticorrosive coating is usually solvent-based coating, contains a large amount of volatile organic compounds, and a considerable part of the coating contains toxic substances such as tin, lead or chromium, which brings serious pollution to the environment and harms the health of human beings. Therefore, the development of the aqueous corrosion-resistant coating material becomes the pursuit target of researchers in the field of metal protection, and has profound strategic significance and wide application prospect.
The graphene serving as a single-layer sheet two-dimensional nanomaterial formed by sp hybridized orbits of carbon atoms has excellent mechanical property, transparency, flexibility, hydrophobicity, chemical stability and excellent thermal conductivity and electron mobility, and the sheet structure of the graphene can effectively prevent oxygen, water, ions and electrons from passing through the graphene, so that the graphene is very suitable for being used as a coating material, especially for metal protection in severe environments such as oceans, saline alkali and the like. However, it is very difficult to fix graphene directly to the surface of a metal substrate, and it is difficult to stably disperse graphene in water or an organic solvent, and graphene has poor compatibility with other materials, and is easily laminated. Therefore, it is necessary to modify graphene to improve its dispersibility in water or an organic solvent and compatibility with other materials.
Disclosure of Invention
The invention aims to provide a graphene-based corrosion-resistant coating and a preparation method thereof, and aims to solve the problems in the prior art.
In order to achieve the purpose, the invention provides the following technical scheme:
the graphene-based corrosion-resistant coating is characterized by mainly comprising the following raw material components in parts by weight: 12-20 parts of modified graphene, 30-60 parts of aqueous acrylic emulsion, 2-3 parts of film forming auxiliary agent and 20-30 parts of water.
The graphene-based corrosion-resistant coating is characterized by further comprising the following raw material components in parts by weight: 10-15 parts of modified silicon dioxide.
For optimization, the solid content of the water-based acrylic emulsion is 45-55%, and the film-forming assistant is a mixture of decaglycol ester and 1, 2-propylene glycol according to a mass ratio of 1:1, mixing the mixture.
Preferably, the modified graphene is obtained by treating graphene oxide with 3-aminopropyltriethoxysilane and chloroacetic acid.
Preferably, the modified silica is prepared from carboxylated mesoporous silica, potassium tetratitanate and polypyrrole.
As optimization, the graphene-based corrosion-resistant coating mainly comprises the following raw material components in parts by weight: 20 parts of modified graphene, 60 parts of aqueous acrylic emulsion, 3 parts of film-forming aid, 20 parts of water and 15 parts of modified silicon dioxide.
As optimization, the preparation method of the corrosion-resistant coating based on the graphene mainly comprises the following preparation steps:
(1) mixing graphene oxide with 3-aminopropyltriethoxysilane, and reacting with chloroacetic acid to obtain modified graphene;
(2) mixing titanium dioxide and potassium carbonate, grinding, calcining, washing and drying to obtain potassium tetratitanate, mixing the potassium tetratitanate and ethyl orthosilicate, adding a pore-forming agent, stirring and reacting under an alkaline condition, and calcining to obtain modified silicon dioxide;
(3) mixing the modified graphene obtained in the step (1) with the modified silicon dioxide obtained in the step (2), adding a mixed dispersion liquid of 3-aminopropyltriethoxysilane and succinic anhydride, stirring for reaction, filtering to obtain a mixture, mixing the mixture with a pyrrole ethanol solution, filtering, mixing with a hydrochloric acid solution of ferric trichloride, filtering, washing, and drying to obtain a blank;
(4) mixing the blank obtained in the step (3) with a water-based acrylic emulsion; adding water and a film-forming assistant, and stirring and mixing to obtain the graphene corrosion-resistant coating;
(5) smearing the graphene corrosion-resistant coating obtained in the step (4) on the surface of a metal substrate, and drying to obtain a graphene-based corrosion-resistant coating;
(6) and (4) performing index analysis on the graphene-based corrosion-resistant coating obtained in the step (5).
As optimization, the preparation method of the corrosion-resistant coating based on the graphene mainly comprises the following preparation steps:
(1) mixing graphene oxide and water according to a mass ratio of 1: mixing 100-1: 120, performing ultrasonic dispersion to obtain a graphene oxide dispersion liquid, mixing the graphene oxide dispersion liquid and 3-aminopropyltriethoxysilane in a mass ratio of 50: 1-60: 1 in a beaker, stirring for reaction, adding chloroacetic acid which is 0.1-0.2 times of the residue of the graphene oxide dispersion liquid into the beaker, stirring for reaction, filtering, and drying;
(2) mixing titanium dioxide and potassium carbonate according to a molar ratio of 4:1.2, grinding to obtain mixed powder, calcining the mixed powder at the temperature of 800 ℃ for 24 hours, obtaining pretreated potassium tetratitanate, washing the pretreated potassium tetratitanate for 2 times by using hydrochloric acid with the mass fraction of 12 percent, then washing the potassium tetratitanate for 3 times by using deionized water, drying the washed pretreated potassium tetratitanate for 3 hours at the temperature of 80 ℃ to obtain potassium tetratitanate, mixing the potassium tetratitanate and tetraethoxysilane in a flask according to the mass ratio of 1:3, adding water with the mass of 30 times that of the potassium tetratitanate and hexadecyl trimethyl ammonium bromide with the mass of 1-2 times that of the potassium tetratitanate into the flask, adjusting the pH value of the materials in the flask to 10-11, stirring and reacting, filtering to obtain a modified silicon dioxide blank, calcining the modified silicon dioxide blank for 5 hours at the temperature of 500 ℃, and discharging;
(3) mixing the substance obtained in the step (1) with the substance obtained in the step (2) according to a mass ratio of 2: 1-3: 1, mixing the mixture in a three-neck flask, adding water which is 4-5 times the mass of the substance obtained in the step (1) and a mixed dispersion liquid of 3-aminopropyltriethoxysilane and succinic anhydride which is 8-10 times the mass of the substance obtained in the step (1) into the three-neck flask, stirring for reaction, filtering to obtain a mixture, mixing the mixture and a pyrrole ethanol solution with the mass fraction of 20% according to the mass ratio of 1:20, stirring for mixing, filtering to obtain a filter cake, mixing the filter cake and a hydrochloric acid solution of ferric trichloride according to the mass ratio of 1:15, stirring for reaction, filtering to obtain a pretreated blank, and drying the pretreated blank at the temperature of 80 ℃ for 2 hours;
(4) mixing the substance obtained in the step (3) and acrylic emulsion in a stirrer according to the mass ratio of 1:2, adding a film-forming aid which is 0.01 time of the mass of the substance obtained in the step (3) and water which is 0.8 time of the mass of the substance obtained in the step (3) into the stirrer, and stirring and mixing;
(5) coating the material obtained in the step (4) on the surface of a pretreated metal substrate by a coating thickness of 50 microns, and drying at the temperature of 60 ℃ for 12-36 hours to obtain a graphene-based corrosion-resistant coating;
(6) and (4) performing index analysis on the graphene-based corrosion-resistant coating obtained in the step (5).
Optimally, the preparation method of the mixed dispersion liquid of 3-aminopropyltriethoxysilane and succinic anhydride in the step (3) comprises the steps of mixing 3-aminopropyltriethoxysilane and succinic anhydride according to the mass ratio of 1:2, adding dimethyl sulfoxide 12-18 times of the mass of the 3-aminopropyltriethoxysilane, and stirring and mixing to obtain the mixed dispersion liquid of the 3-aminopropyltriethoxysilane and succinic anhydride.
And (3) optimally, mixing ferric trichloride and hydrochloric acid with the mass fraction of 12% according to the mass ratio of 1:50 to obtain the hydrochloric acid solution of ferric trichloride.
Preferably, the step (5) of pretreating the metal substrate is to wash the metal plate with ethanol and acetone respectively for 3 times to obtain the pretreated metal substrate, wherein the metal plate is any one of a steel plate and a copper plate.
Compared with the prior art, the invention has the beneficial effects that: according to the preparation method, the modified graphene and the modified silicon dioxide are added in the preparation of the graphene-based corrosion-resistant coating, firstly, after the graphene is modified, carboxyl groups are arranged on the surface of the graphene, and the graphene can be uniformly distributed in a product after being added into the product, so that the corrosion resistance of the product is improved, and the connection of 3-aminopropyltriethoxysilane and the modified silicon dioxide can be improved on the surface of the graphene after the graphene is modified, so that the density of the coating is improved, and the corrosion resistance of the product is further improved; secondly, after the silicon dioxide is modified, the silicon dioxide can be adsorbed on the surface of potassium tetratitanate and can form a laminated anticorrosive layer after being connected with the modified graphene under the action of 3-aminopropyltriethoxysilane, so that the density of a coating is improved, the corrosion resistance of a product is further improved, and the silicon dioxide in the modified silicon dioxide contains a mesoporous structure and can adsorb polypyrrole in the mesopores of the modified silicon dioxide after modification treatment, so that the corrosion resistance of the product is further improved.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to 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 more clearly illustrate the method provided by the present invention, the following examples are used to illustrate the method for testing each index of the graphene-based corrosion-resistant coating prepared in the following examples as follows:
acid corrosion resistance: the graphene-based corrosion-resistant coatings obtained in the examples and the comparative products were placed in 10% sulfuric acid and soaked for 200 hours, and then the surface phenomena of the graphene-based corrosion-resistant coatings obtained in the examples and the comparative products were observed.
Alkali corrosion resistance: the graphene-based corrosion-resistant coatings obtained in the examples and the comparative products were placed in a 10% sodium hydroxide solution and soaked for 200 hours, and then the surface phenomena of the graphene-based corrosion-resistant coatings obtained in the examples and the comparative products were observed.
Impact strength: the graphene-based corrosion resistant coatings obtained in the examples and the comparative products were tested according to GB 1732.
Example 1
The graphene-based corrosion-resistant coating mainly comprises the following raw material components in parts by weight: 20 parts of modified graphene, 60 parts of aqueous acrylic emulsion, 3 parts of film-forming aid, 20 parts of water and 15 parts of modified silicon dioxide.
A preparation method of a graphene-based corrosion-resistant coating mainly comprises the following preparation steps:
(1) mixing graphene oxide and water according to a mass ratio of 1: 100, performing ultrasonic dispersion for 60min under the condition of 55kHz to obtain a graphene oxide dispersion liquid, mixing the graphene oxide dispersion liquid and 3-aminopropyltriethoxysilane according to the mass ratio of 50:1 in a beaker, stirring and reacting for 4h under the conditions of 60 ℃ and 300r/min, adding chloroacetic acid 0.2 times of slag materials of the graphene oxide dispersion liquid into the beaker, stirring and reacting for 5h under the conditions of 45 ℃ and 280r/min, filtering to obtain a modified graphene blank, and drying the modified graphene blank for 2h under the condition of 80 ℃;
(2) mixing titanium dioxide and potassium carbonate in a grinding machine according to a molar ratio of 4:1.2, grinding for 3 hours to obtain mixed powder, calcining the mixed powder at 800 ℃ for 24 hours to obtain pretreated potassium tetratitanate, washing the pretreated potassium tetratitanate with hydrochloric acid with the mass fraction of 12% for 2 times, washing with deionized water for 3 times, drying the washed pretreated potassium tetratitanate at 80 ℃ for 3 hours to obtain potassium tetratitanate, mixing the potassium tetratitanate and ethyl orthosilicate according to the mass ratio of 1:3 in a flask, adding water with the mass of 30 times that of the potassium tetratitanate and hexadecyl trimethyl ammonium bromide with the mass of 1.5 times that of the potassium tetratitanate into the flask, adjusting the pH of materials in the flask to 10 by ammonia water with the mass fraction of 15%, stirring and reacting for 8 hours at 40 ℃ and the rotating speed of 240r/min, filtering, obtaining a modified silicon dioxide blank, calcining the modified silicon dioxide blank for 5 hours at the temperature of 500 ℃, and discharging;
(3) mixing the substance obtained in the step (1) with the substance obtained in the step (2) according to a mass ratio of 3:1 is mixed in a three-neck flask, water with the mass 4 times that of the substance obtained in the step (1) and mixed dispersion liquid of 3-aminopropyltriethoxysilane and succinic anhydride with the mass 10 times that of the substance obtained in the step (1) are added into the three-neck flask, and after stirring and reaction are carried out for 5 hours under the conditions that the temperature is 40 ℃ and the rotating speed is 260r/min, filtering to obtain a mixture, mixing the mixture with 20% pyrrole ethanol solution according to the mass ratio of 1:20, stirring and mixing for 25min under the conditions that the temperature is 38 ℃ and the rotating speed is 280r/min, filtering to obtain a filter cake, mixing the filter cake with hydrochloric acid solution of ferric trichloride according to the mass ratio of 1:15, stirring and reacting for 40min under the conditions that the temperature is 45 ℃ and the rotating speed is 280r/min, filtering to obtain a pretreated blank, and drying the pretreated blank for 2 hours at the temperature of 80 ℃;
(4) mixing the substance obtained in the step (3) and acrylic emulsion in a stirrer according to the mass ratio of 1:2, adding a film-forming aid which is 0.01 time of the mass of the substance obtained in the step (3) and water which is 0.8 time of the mass of the substance obtained in the step (3) into the stirrer, and stirring and mixing for 60min under the conditions that the temperature is 40 ℃ and the rotating speed is 300 r/min;
(5) coating the material obtained in the step (4) on the surface of a pretreated metal substrate by a coating thickness of 50 microns, and drying for 20 hours at the temperature of 60 ℃ to obtain the graphene-based corrosion-resistant coating;
(6) and (4) performing index analysis on the graphene-based corrosion-resistant coating obtained in the step (5).
Optimally, the preparation method of the mixed dispersion liquid of 3-aminopropyltriethoxysilane and succinic anhydride in the step (3) comprises the steps of mixing 3-aminopropyltriethoxysilane and succinic anhydride according to the mass ratio of 1:2, adding dimethyl sulfoxide 12-18 times of the mass of the 3-aminopropyltriethoxysilane, and stirring and mixing to obtain the mixed dispersion liquid of the 3-aminopropyltriethoxysilane and succinic anhydride.
And (3) optimally, mixing ferric trichloride and hydrochloric acid with the mass fraction of 12% according to the mass ratio of 1:50 to obtain the hydrochloric acid solution of ferric trichloride.
And (5) optimally, the step of pretreating the metal substrate is to respectively wash the metal plate for 3 times by using ethanol and acetone to obtain the pretreated metal substrate, wherein the metal plate is a steel plate.
Example 2
The graphene-based corrosion-resistant coating mainly comprises the following raw material components in parts by weight: 20 parts of graphene, 60 parts of aqueous acrylic emulsion, 3 parts of film-forming aid, 20 parts of water and 15 parts of modified silicon dioxide.
A preparation method of a graphene-based corrosion-resistant coating mainly comprises the following preparation steps:
(1) mixing titanium dioxide and potassium carbonate in a grinding machine according to a molar ratio of 4:1.2, grinding for 3 hours to obtain mixed powder, calcining the mixed powder at 800 ℃ for 24 hours to obtain pretreated potassium tetratitanate, washing the pretreated potassium tetratitanate with hydrochloric acid with the mass fraction of 12% for 2 times, washing with deionized water for 3 times, drying the washed pretreated potassium tetratitanate at 80 ℃ for 3 hours to obtain potassium tetratitanate, mixing the potassium tetratitanate and ethyl orthosilicate according to the mass ratio of 1:3 in a flask, adding water with the mass of 30 times that of the potassium tetratitanate and hexadecyl trimethyl ammonium bromide with the mass of 1.5 times that of the potassium tetratitanate into the flask, adjusting the pH of materials in the flask to 10 by ammonia water with the mass fraction of 15%, stirring and reacting for 8 hours at 40 ℃ and the rotating speed of 240r/min, filtering, obtaining a modified silicon dioxide blank, calcining the modified silicon dioxide blank for 5 hours at the temperature of 500 ℃, and discharging;
(2) and (3) mixing graphene with the substance obtained in the step (2) according to a mass ratio of 3:1, mixing the mixture and a pyrrole ethanol solution with the mass fraction of 20% according to the mass ratio of 1:20, stirring and mixing the mixture and the pyrrole ethanol solution with the mass fraction of 20% at the temperature of 40 ℃ and the rotation speed of 280r/min for 25min, filtering to obtain a filter cake, mixing the filter cake and a hydrochloric acid solution of ferric trichloride according to the mass ratio of 1:15, stirring and reacting at the temperature of 45 ℃ and the rotation speed of 280r/min for 40min, filtering to obtain a pretreated blank, and drying the pretreated blank at the temperature of 80 ℃ for 2 h;
(3) mixing the substance obtained in the step (2) and acrylic emulsion in a stirrer according to the mass ratio of 1:2, adding a film-forming aid which is 0.01 time of the mass of the substance obtained in the step (2) and water which is 0.8 time of the mass of the substance obtained in the step (2) into the stirrer, and stirring and mixing for 60min under the conditions that the temperature is 40 ℃ and the rotating speed is 300 r/min;
(4) coating the material obtained in the step (3) on the surface of a pretreated metal substrate by a coating thickness of 50 microns, and drying for 20 hours at the temperature of 60 ℃ to obtain the graphene-based corrosion-resistant coating;
(5) and (4) performing index analysis on the graphene-based corrosion-resistant coating obtained in the step (4).
Optimally, the preparation method of the mixed dispersion liquid of 3-aminopropyltriethoxysilane and succinic anhydride in the step (2) comprises the steps of mixing 3-aminopropyltriethoxysilane and succinic anhydride according to the mass ratio of 1:2, adding dimethyl sulfoxide 12-18 times of the mass of the 3-aminopropyltriethoxysilane, and stirring and mixing to obtain the mixed dispersion liquid of the 3-aminopropyltriethoxysilane and succinic anhydride.
And (3) optimally, the hydrochloric acid solution of ferric trichloride in the step (2) is obtained by mixing ferric trichloride and hydrochloric acid with the mass fraction of 12% according to the mass ratio of 1: 50.
And (4) as an optimization, the step of pretreating the metal substrate is to respectively wash the metal plate for 3 times by using ethanol and acetone to obtain the pretreated metal substrate, wherein the metal plate is a steel plate.
Example 3
The graphene-based corrosion-resistant coating mainly comprises the following raw material components in parts by weight: 20 parts of modified graphene, 60 parts of aqueous acrylic emulsion, 3 parts of film-forming aid, 20 parts of water and 15 parts of modified silicon dioxide.
A preparation method of a graphene-based corrosion-resistant coating mainly comprises the following preparation steps:
(1) mixing graphene oxide and water according to a mass ratio of 1: 100, performing ultrasonic dispersion for 60min under the condition of 55kHz to obtain a graphene oxide dispersion liquid, mixing the graphene oxide dispersion liquid and 3-aminopropyltriethoxysilane according to the mass ratio of 50:1 in a beaker, stirring and reacting for 4h under the conditions of 60 ℃ and 300r/min, adding chloroacetic acid 0.2 times of slag materials of the graphene oxide dispersion liquid into the beaker, stirring and reacting for 5h under the conditions of 45 ℃ and 280r/min, filtering to obtain a modified graphene blank, and drying the modified graphene blank for 2h under the condition of 80 ℃;
(2) adding tetraethoxysilane into a flask, adding water with the mass 30 times that of the tetraethoxysilane and hexadecyl trimethyl ammonium bromide with the mass 1.5 times that of the tetraethoxysilane into the flask, adjusting the pH of the materials in the flask to 10 by using ammonia water with the mass fraction of 15%, stirring and reacting for 8 hours at the temperature of 40 ℃ and the rotating speed of 240r/min, filtering to obtain a silicon dioxide blank, calcining the silicon dioxide blank for 5 hours at the temperature of 500 ℃, and discharging;
(3) mixing the substance obtained in the step (1) with the substance obtained in the step (2) according to a mass ratio of 3:1 is mixed in a three-neck flask, water with the mass 4 times that of the substance obtained in the step (1) and mixed dispersion liquid of 3-aminopropyltriethoxysilane and succinic anhydride with the mass 10 times that of the substance obtained in the step (1) are added into the three-neck flask, and after stirring and reaction are carried out for 5 hours under the conditions that the temperature is 40 ℃ and the rotating speed is 260r/min, filtering to obtain a mixture, mixing the mixture with 20% pyrrole ethanol solution according to the mass ratio of 1:20, stirring and mixing for 25min under the conditions that the temperature is 38 ℃ and the rotating speed is 280r/min, filtering to obtain a filter cake, mixing the filter cake with hydrochloric acid solution of ferric trichloride according to the mass ratio of 1:15, stirring and reacting for 40min under the conditions that the temperature is 45 ℃ and the rotating speed is 280r/min, filtering to obtain a pretreated blank, and drying the pretreated blank for 2 hours at the temperature of 80 ℃;
(4) mixing the substance obtained in the step (3) and acrylic emulsion in a stirrer according to the mass ratio of 1:2, adding a film-forming aid which is 0.01 time of the mass of the substance obtained in the step (3) and water which is 0.8 time of the mass of the substance obtained in the step (3) into the stirrer, and stirring and mixing for 60min under the conditions that the temperature is 40 ℃ and the rotating speed is 300 r/min;
(5) coating the material obtained in the step (4) on the surface of a pretreated metal substrate by a coating thickness of 50 microns, and drying for 20 hours at the temperature of 60 ℃ to obtain the graphene-based corrosion-resistant coating;
(6) and (4) performing index analysis on the graphene-based corrosion-resistant coating obtained in the step (5).
Optimally, the preparation method of the mixed dispersion liquid of 3-aminopropyltriethoxysilane and succinic anhydride in the step (3) comprises the steps of mixing 3-aminopropyltriethoxysilane and succinic anhydride according to the mass ratio of 1:2, adding dimethyl sulfoxide 12-18 times of the mass of the 3-aminopropyltriethoxysilane, and stirring and mixing to obtain the mixed dispersion liquid of the 3-aminopropyltriethoxysilane and succinic anhydride.
And (3) optimally, mixing ferric trichloride and hydrochloric acid with the mass fraction of 12% according to the mass ratio of 1:50 to obtain the hydrochloric acid solution of ferric trichloride.
And (5) optimally, the step of pretreating the metal substrate is to respectively wash the metal plate for 3 times by using ethanol and acetone to obtain the pretreated metal substrate, wherein the metal plate is a steel plate.
Example 4
The graphene-based corrosion-resistant coating mainly comprises the following raw material components in parts by weight: 20 parts of modified graphene, 60 parts of aqueous acrylic emulsion, 3 parts of film-forming aid, 20 parts of water and 15 parts of modified silicon dioxide.
A preparation method of a graphene-based corrosion-resistant coating mainly comprises the following preparation steps:
(1) mixing graphene oxide and water according to a mass ratio of 1: 100, performing ultrasonic dispersion for 60min under the condition of 55kHz to obtain a graphene oxide dispersion liquid, mixing the graphene oxide dispersion liquid and 3-aminopropyltriethoxysilane according to the mass ratio of 50:1 in a beaker, stirring and reacting for 4h under the conditions of 60 ℃ and 300r/min, adding chloroacetic acid 0.2 times of slag materials of the graphene oxide dispersion liquid into the beaker, stirring and reacting for 5h under the conditions of 45 ℃ and 280r/min, filtering to obtain a modified graphene blank, and drying the modified graphene blank for 2h under the condition of 80 ℃;
(2) mixing titanium dioxide and potassium carbonate in a grinding machine according to a molar ratio of 4:1.2, grinding for 3 hours to obtain mixed powder, calcining the mixed powder at 800 ℃ for 24 hours to obtain pretreated potassium tetratitanate, washing the pretreated potassium tetratitanate with hydrochloric acid with the mass fraction of 12% for 2 times, washing with deionized water for 3 times, drying the washed pretreated potassium tetratitanate at 80 ℃ for 3 hours to obtain potassium tetratitanate, mixing the potassium tetratitanate and ethyl orthosilicate according to the mass ratio of 1:3 in a flask, adding water with the mass of 30 times that of the potassium tetratitanate and hexadecyl trimethyl ammonium bromide with the mass of 1.5 times that of the potassium tetratitanate into the flask, adjusting the pH of materials in the flask to 10 by ammonia water with the mass fraction of 15%, stirring and reacting for 8 hours at 40 ℃ and the rotating speed of 240r/min, filtering, obtaining a modified silicon dioxide blank, calcining the modified silicon dioxide blank for 5 hours at the temperature of 500 ℃, and discharging;
(3) mixing the substance obtained in the step (1) with the substance obtained in the step (2) according to a mass ratio of 3:1, mixing the mixture in a three-neck flask, adding water 4 times the mass of the substance obtained in the step (1) and a mixed dispersion of 3-aminopropyltriethoxysilane and succinic anhydride 10 times the mass of the substance obtained in the step (1) into the three-neck flask, stirring and reacting for 5 hours at the temperature of 40 ℃ and the rotating speed of 260r/min, filtering, removing filtrate, and drying for 2 hours at the temperature of 80 ℃;
(4) mixing the substance obtained in the step (3) and acrylic emulsion in a stirrer according to the mass ratio of 1:2, adding a film-forming aid which is 0.01 time of the mass of the substance obtained in the step (3) and water which is 0.8 time of the mass of the substance obtained in the step (3) into the stirrer, and stirring and mixing for 60min under the conditions that the temperature is 40 ℃ and the rotating speed is 300 r/min;
(5) coating the material obtained in the step (4) on the surface of a pretreated metal substrate by a coating thickness of 50 microns, and drying for 20 hours at the temperature of 60 ℃ to obtain the graphene-based corrosion-resistant coating;
(6) and (4) performing index analysis on the graphene-based corrosion-resistant coating obtained in the step (5).
Optimally, the preparation method of the mixed dispersion liquid of 3-aminopropyltriethoxysilane and succinic anhydride in the step (3) comprises the steps of mixing 3-aminopropyltriethoxysilane and succinic anhydride according to the mass ratio of 1:2, adding dimethyl sulfoxide 12-18 times of the mass of the 3-aminopropyltriethoxysilane, and stirring and mixing to obtain the mixed dispersion liquid of the 3-aminopropyltriethoxysilane and succinic anhydride.
And (5) optimally, the step of pretreating the metal substrate is to respectively wash the metal plate for 3 times by using ethanol and acetone to obtain the pretreated metal substrate, wherein the metal plate is a steel plate.
Comparative example
The graphene-based corrosion-resistant coating mainly comprises the following raw material components in parts by weight: 20 parts of graphene, 60 parts of aqueous acrylic emulsion, 3 parts of film-forming aid, 20 parts of water and 15 parts of silicon dioxide.
A preparation method of a graphene-based corrosion-resistant coating mainly comprises the following preparation steps:
(1) adding tetraethoxysilane into a flask, adding water with the mass 30 times that of the tetraethoxysilane and hexadecyl trimethyl ammonium bromide with the mass 1.5 times that of the tetraethoxysilane into the flask, adjusting the pH of the materials in the flask to 10 by using ammonia water with the mass fraction of 15%, stirring and reacting for 8 hours at the temperature of 40 ℃ and the rotating speed of 240r/min, filtering to obtain a silicon dioxide blank, calcining the silicon dioxide blank for 5 hours at the temperature of 500 ℃, and discharging;
(2) mixing graphene and the substance obtained in the step (1) according to a mass ratio of 3:1, mixing the mixture in a three-neck flask, adding water 4 times the mass of graphene and a mixed dispersion of 3-aminopropyltriethoxysilane and succinic anhydride 10 times the mass of graphene into the three-neck flask, stirring and reacting for 5 hours at the temperature of 40 ℃ and the rotating speed of 260r/min, filtering, removing filtrate, and drying for 2 hours at the temperature of 80 ℃;
(3) mixing the substance obtained in the step (2) and acrylic emulsion in a stirrer according to the mass ratio of 1:2, adding a film-forming aid which is 0.01 time of the mass of the substance obtained in the step (2) and water which is 0.8 time of the mass of the substance obtained in the step (2) into the stirrer, and stirring and mixing for 60min under the conditions that the temperature is 40 ℃ and the rotating speed is 300 r/min;
(4) coating the material obtained in the step (3) on the surface of a pretreated metal substrate by a coating thickness of 50 microns, and drying for 20 hours at the temperature of 60 ℃ to obtain the graphene-based corrosion-resistant coating;
(5) and (4) performing index analysis on the graphene-based corrosion-resistant coating obtained in the step (4).
Optimally, the preparation method of the mixed dispersion liquid of 3-aminopropyltriethoxysilane and succinic anhydride in the step (2) comprises the steps of mixing 3-aminopropyltriethoxysilane and succinic anhydride according to the mass ratio of 1:2, adding dimethyl sulfoxide 12-18 times of the mass of the 3-aminopropyltriethoxysilane, and stirring and mixing to obtain the mixed dispersion liquid of the 3-aminopropyltriethoxysilane and succinic anhydride.
And (4) as an optimization, the step of pretreating the metal substrate is to respectively wash the metal plate for 3 times by using ethanol and acetone to obtain the pretreated metal substrate, wherein the metal plate is a steel plate.
Examples of effects
Table 1 below gives the analysis results of the acid corrosion resistance, alkali corrosion resistance, and impact strength of the graphene-based corrosion-resistant coatings using examples 1 to 4 of the present invention and the comparative example.
TABLE 1
| Resistance to acid corrosion | Resistance to alkali corrosion | Impact strength (Kg/cm) | |
| Example 1 | Surface smoothing | Surface smoothing | 260 |
| Example 2 | The surface has a few cracks | The surface has a few cracks | 240 |
| Example 3 | Surface cracking and bubbling | Surface cracking and bubbling | 235 |
| Example 4 | Obvious rust spots on the surface | Obvious rust spots on the surface | 225 |
| Comparative example | Has more rust spots on the surface | Has more rust spots on the surface | 180 |
As can be seen from the comparison of the experimental data of example 1 and the comparative example in table 1, after the modified graphene and the silicon dioxide modified by potassium tetratitanate and polypyrrole are used in the preparation of the graphene-based corrosion-resistant coating, the acid and alkali corrosion resistance of the graphene-based corrosion-resistant coating can be greatly improved, and the product has good strength; from the comparison of the experimental data of the embodiment 1 and the embodiment 2, it can be found that when the modified graphene is not added to the product, the graphene cannot generate a lamination effect with the modified silicon dioxide, and the graphene cannot be uniformly dispersed in the product, so that the acid-base corrosion resistance of the product is reduced, and from the comparison of the experimental data of the embodiment 1, the embodiment 3 and the embodiment 4, when the silicon dioxide modified by potassium tetratitanate and polypyrrole is not added to the product, the dense corrosion-resistant coating cannot be formed in the product, so that the acid-base corrosion resistance of the product is greatly influenced.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (6)
1. The graphene-based corrosion-resistant coating is characterized by mainly comprising the following raw material components in parts by weight: 12-20 parts of modified graphene, 30-60 parts of aqueous acrylic emulsion, 2-3 parts of film forming auxiliary agent and 20-30 parts of water; the graphene-based corrosion-resistant coating also comprises the following raw material components in parts by weight: 10-15 parts of modified silicon dioxide; the solid content of the water-based acrylic emulsion is 45-55%, and the film-forming assistant is composed of glycol decaether and 1, 2-propylene glycol according to a mass ratio of 1:1 mixing the mixture;
the preparation method of the graphene-based corrosion-resistant coating comprises the following steps:
(1) mixing graphene oxide with 3-aminopropyltriethoxysilane, and reacting with chloroacetic acid to obtain modified graphene;
(2) mixing titanium dioxide and potassium carbonate, grinding, calcining, washing and drying to obtain potassium tetratitanate, mixing the potassium tetratitanate and ethyl orthosilicate, adding a pore-forming agent, stirring and reacting under an alkaline condition, and calcining to obtain modified silicon dioxide;
(3) mixing the modified graphene obtained in the step (1) with the modified silicon dioxide obtained in the step (2), adding a mixed dispersion liquid of 3-aminopropyltriethoxysilane and succinic anhydride, stirring for reaction, filtering to obtain a mixture, mixing the mixture with a pyrrole ethanol solution, filtering, mixing with a hydrochloric acid solution of ferric trichloride, filtering, washing, and drying to obtain a blank;
(4) mixing the blank obtained in the step (3) with a water-based acrylic emulsion; adding water and a film-forming assistant, and stirring and mixing to obtain the graphene corrosion-resistant coating;
(5) smearing the graphene corrosion-resistant coating obtained in the step (4) on the surface of a pretreated metal substrate, and drying to obtain a graphene-based corrosion-resistant coating;
(6) and (4) performing index analysis on the graphene-based corrosion-resistant coating obtained in the step (5).
2. The graphene-based corrosion-resistant coating according to claim 1, wherein the graphene-based corrosion-resistant coating mainly comprises the following raw material components in parts by weight: 20 parts of modified graphene, 60 parts of aqueous acrylic emulsion, 3 parts of film-forming aid, 20 parts of water and 15 parts of modified silicon dioxide.
3. A preparation method of a graphene-based corrosion-resistant coating is characterized by mainly comprising the following preparation steps:
(1) mixing graphene oxide and water according to a mass ratio of 1: 100-1: 120, performing ultrasonic dispersion to obtain a graphene oxide dispersion liquid, mixing the graphene oxide dispersion liquid and 3-aminopropyltriethoxysilane in a mass ratio of 50: 1-60: 1 in a beaker, stirring for reaction, adding chloroacetic acid in an amount which is 0.1-0.2 times that of a residue material of the graphene oxide dispersion liquid into the beaker, stirring for reaction, filtering, and drying;
(2) mixing titanium dioxide and potassium carbonate according to a molar ratio of 4:1.2, grinding to obtain mixed powder, calcining the mixed powder at the temperature of 800 ℃ for 24 hours to obtain pretreated potassium tetratitanate, washing the pretreated potassium tetratitanate with hydrochloric acid with the mass fraction of 12% for 2 times, washing with deionized water for 3 times, drying the washed pretreated potassium tetratitanate at the temperature of 80 ℃ for 3 hours to obtain potassium tetratitanate, mixing the potassium tetratitanate and tetraethoxysilane according to the mass ratio of 1:3 in a flask, adding water which is 30 times of the mass of the potassium tetratitanate and hexadecyl trimethyl ammonium bromide which is 1-2 times of the mass of the potassium tetratitanate into the flask, adjusting the pH of materials in the flask to 10-11, stirring and reacting, filtering to obtain a modified silicon dioxide blank, calcining the modified silicon dioxide blank at the temperature of 500 ℃ for 5 hours, discharging;
(3) mixing the substance obtained in the step (1) and the substance obtained in the step (2) in a three-neck flask according to a mass ratio of 2: 1-3: 1, adding water 4-5 times the mass of the substance obtained in the step (1) and mixed dispersion liquid of 3-aminopropyltriethoxysilane and succinic anhydride 8-10 times the mass of the substance obtained in the step (1) into the three-neck flask, stirring and reacting, filtering to obtain a mixture, mixing the mixture and a pyrrole ethanol solution with a mass fraction of 20% according to a mass ratio of 1:20, stirring and mixing, filtering to obtain a filter cake, mixing the filter cake and a hydrochloric acid solution of ferric trichloride according to a mass ratio of 1:15, stirring and reacting, filtering to obtain a pretreated blank, and drying the pretreated blank at a temperature of 80 ℃ for 2 hours;
(4) mixing the substance obtained in the step (3) and acrylic emulsion in a stirrer according to the mass ratio of 1:2, adding a film-forming aid which is 0.01 time of the mass of the substance obtained in the step (3) and water which is 0.8 time of the mass of the substance obtained in the step (3) into the stirrer, and stirring and mixing;
(5) coating the material obtained in the step (4) on the surface of a pretreated metal substrate by a coating thickness of 50 microns, and drying at the temperature of 60 ℃ for 12-36 hours to obtain a graphene-based corrosion-resistant coating;
(6) and (4) performing index analysis on the graphene-based corrosion-resistant coating obtained in the step (5).
4. The preparation method of the graphene-based corrosion-resistant coating according to claim 3, wherein the preparation method of the mixed dispersion of 3-aminopropyltriethoxysilane and succinic anhydride in the step (3) comprises mixing 3-aminopropyltriethoxysilane and succinic anhydride in a mass ratio of 1:2, adding 12-18 times of dimethyl sulfoxide by mass of 3-aminopropyltriethoxysilane, and stirring and mixing to obtain the mixed dispersion of 3-aminopropyltriethoxysilane and succinic anhydride.
5. The preparation method of the graphene-based corrosion-resistant coating according to claim 3, wherein the hydrochloric acid solution of ferric trichloride in the step (3) is obtained by mixing ferric trichloride and hydrochloric acid with a mass fraction of 12% in a mass ratio of 1: 50.
6. The method for preparing the graphene-based corrosion-resistant coating according to claim 3, wherein the pretreating of the metal substrate in the step (5) comprises washing a metal plate with ethanol and acetone respectively for 3 times to obtain the pretreated metal substrate, wherein the metal plate is any one of a steel plate and a copper plate.
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