CN111454644A - Preparation method of anticorrosive paint based on coulomb blocking effect - Google Patents
Preparation method of anticorrosive paint based on coulomb blocking effect Download PDFInfo
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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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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
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- 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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Abstract
A preparation method of an anticorrosive coating based on a coulomb blocking effect relates to a preparation method of an anticorrosive coating. The technical problem that the existing anticorrosive paint is poor in anticorrosive effect is solved. The method comprises the following steps: firstly, adding manganese chloride, pentavalent metal alkoxide and a complexing agent into distilled water for dissolving, and reacting to prepare sol; carrying out hydrothermal reaction and drying to obtain powder; secondly, adding a water-soluble polymer into the powder, drying and calcining to obtain the carbon-coated nano filler; dissolving epoxy resin in butyl acetate, adding the nano filler with the carbon coated surface, and dispersing to obtain a component A; dissolving low-molecular polyamide resin in butyl acetate, adding graphene oxide, and dispersing to obtain a component B; mixing the component A and the component B, and spraying to form a film. The anticorrosive paint prepared by the method simultaneously realizes the physical isolation and corrosion prevention for isolating oxygen and water and the electrochemical corrosion prevention for isolating an electronic passage, so that the anticorrosive performance of the paint is excellent. The invention is applied to the field of anticorrosive coatings.
Description
Technical Field
The invention relates to a preparation method of an anticorrosive paint.
Background
The corrosion of metal is an important problem to people, the corrosion prevention is always the hot direction of research, and the common corrosion prevention methods include an anode sacrificial method, a coating isolation method and the like. The coating isolation method is widely used due to low energy consumption and simple and convenient construction, and the method usually utilizes the high order or high crosslinking density of polymer molecules and added fillers to realize the isolation of oxygen and water, or adds zinc powder and other substances into the coating to ensure that the coating also has the function of anode sacrifice.
However, the existing anticorrosive paint is either electrochemical or physical anticorrosive, and the anticorrosive way is single, so the anticorrosive effect is poor.
Disclosure of Invention
The invention aims to solve the technical problem of poor anticorrosion effect of the existing anticorrosion paint, and provides a preparation method of an anticorrosion paint based on a coulomb blocking effect.
The preparation method of the anticorrosive paint based on the coulomb blocking effect comprises the following steps:
firstly, preparing the high dielectric constant inorganic nano filler:
adding manganese chloride, pentavalent metal alkoxide and a complexing agent into distilled water for dissolving, and reacting for 2-3 hours at 80-85 ℃ to prepare sol; putting the sol into a hydrothermal reaction kettle, reacting for 24-48 hours at 160-180 ℃, taking out the reactant, centrifuging for 15-20 minutes at 3500-4000 r/min, washing with distilled water, and drying to obtain powder;
secondly, a nano filler interface charge transport regulation method comprises the following steps:
adding the powder prepared in the step one into distilled water for ultrasonic dispersion, adding a water-soluble polymer until the water-soluble polymer is completely dissolved, and drying to obtain polymer-coated powder; calcining the powder coated with the polymer in a muffle furnace, heating to 200-250 ℃ for calcining for 1-2 h, then heating to 300-350 ℃ for calcining for 3-6 h, and finally heating to 450-500 ℃ for calcining for 1-2 h, and obtaining the carbon-coated nano filler after calcining;
thirdly, the preparation method of the composite coating comprises the following steps:
dissolving epoxy resin in butyl acetate, adding the carbon-coated nano filler prepared in the second step, and dispersing for 5-6 hours at 4000-4500 r/min to obtain a component A;
dissolving low-molecular polyamide resin in butyl acetate, adding multiple layers of graphene oxide, and dispersing at 4000-4500 r/min for 5-6 h to obtain a component B;
and uniformly mixing the component A and the component B, and spraying the mixture for 5-6 hours to form a film.
Further, in the step one, the pentavalent metal alkoxide is one or a mixture of two of niobium ethoxide and tantalum ethoxide.
Further, in the step one, the complexing agent is sodium citrate. The mass of the complexing agent is 0.8-1.2% of that of the manganese chloride.
Furthermore, the molar ratio of manganese element to pentavalent metal alkoxide in the manganese monochloride is (0.8-0.95): (0.05-0.2).
Further, in the second step, the water-soluble polymer is a mixture of water-soluble phenolic resin, polyvinylpyrrolidone resin and polyvinyl alcohol resin. Wherein the mass ratio of the water-soluble phenolic resin, the polyvinylpyrrolidone resin and the polyvinyl alcohol resin is (0.5-0.65): (0.2-0.35): 0.15-0.3).
Further, the mass ratio of the powder to the water-soluble polymer in the second step is 100: 5.
Furthermore, the epoxy resin in the third step is composed of E-51 resin and E-44 resin according to the mass ratio of (0.7-1) to (0-0.3).
Further, the low molecular polyamide resin in the third step is low molecular polyamide resin 650 or low molecular polyamide resin 651.
Furthermore, the mass of the nano filler in the component A in the step three is 12-19% of the mass of the epoxy resin.
Furthermore, the mass of the graphene oxide in the component B in the third step is 0.3-0.6% of the mass of the low molecular polyamide resin.
Furthermore, the mass ratio of the epoxy resin in the component A to the low-molecular polyamide resin in the component B is 100 (90-125).
The principle of the invention is as follows:
the coulomb blocking effect is to add a proper amount of conductor or semiconductor into the insulating polymer, although the introduced carriers can increase the dielectric loss of the material, the formed micro-capacitance model can differentiate the electric field, so that the breakdown field strength of the material under direct current is improved. The effect can not only improve the breakdown field intensity of the composite material, but also reduce the corrosion current flowing through the interior of the coating when the composite material is used as an anticorrosive coating, and the electrochemical anticorrosion effect is achieved while the physical isolation effect is achieved. Therefore, the dielectric property of the polymer-based composite material is reasonably regulated and controlled, and the partition of a coating conductive path can be realized by utilizing the coulomb blocking effect.
The method is characterized in that coulomb blocking effect is taken as a theoretical basis, epoxy resin and low-molecular polyamide resin are taken as matrixes, pentavalent niobium or tantalum doped modified manganese oxide powder is synthesized, a carbon layer is coated on the surface of the manganese oxide powder to serve as a component A filler, and graphene oxide serves as a component B filler, so that the anticorrosive paint is prepared. The graphene oxide and the nano filler coated with carbon on the surface have the function of adjusting the dielectric constant of the coating, so that the electrochemical corrosion resistance is enhanced, and meanwhile, the two substances also have excellent physical insulation function, so that the physical insulation corrosion resistance can be realized, and the performance of the anticorrosive coating is improved by the electrochemical corrosion resistance and the physical insulation corrosion resistance together.
The invention has the beneficial effects that:
the method simultaneously realizes the physical isolation and corrosion prevention for blocking oxygen and water and the electrochemical corrosion prevention for blocking an electronic passage, so that the prepared coating has excellent corrosion resistance.
The anticorrosive paint prepared by the method has good anticorrosive performance, and the neutral salt spray resistant time can reach 450-fold and 600 h.
The anticorrosive paint prepared by the method has excellent electrochemical corrosion resistance, and the corrosion current density is 1.9-3.2E6A/cm2。
Detailed Description
The technical solution of the present invention is not limited to the following specific embodiments, but includes any combination of the specific embodiments.
The first embodiment is as follows: the preparation method of the anticorrosive paint based on the coulomb blocking effect comprises the following steps:
firstly, preparing the high dielectric constant inorganic nano filler:
adding manganese chloride, pentavalent metal alkoxide and a complexing agent into distilled water for dissolving, and reacting for 2-3 hours at 80-85 ℃ to prepare sol; putting the sol into a hydrothermal reaction kettle, reacting for 24-48 hours at 160-180 ℃, taking out the reactant, centrifuging for 15-20 minutes at 3500-4000 r/min, washing with distilled water, and drying to obtain powder;
wherein, manganese chloride is hydrolyzed to generate manganese oxide, and the addition of pentavalent alkoxide is to carry out pentavalent doping in the manganese oxide to manufacture valence change so as to form local defects and increase the number of holes;
secondly, a nano filler interface charge transport regulation method comprises the following steps:
adding the powder prepared in the step one into distilled water for ultrasonic dispersion, adding a water-soluble polymer until the water-soluble polymer is completely dissolved, and drying to obtain polymer-coated powder; calcining the powder coated with the polymer in a muffle furnace, heating to 200-250 ℃ for calcining for 1-2 h, then heating to 300-350 ℃ for calcining for 3-6 h, and finally heating to 450-500 ℃ for calcining for 1-2 h, and obtaining the carbon-coated nano filler after calcining;
wherein the purpose of staged temperature rise is to control the decomposition process of the polymer, so that the carbon layer is more complete and compact;
the purpose of coating carbon on the surface is to form a carbon layer on the surface of the high dielectric constant powder, and the carbon layer can play a role of an electrode and amplify the function of storing charges of the high dielectric inorganic powder;
thirdly, the preparation method of the composite coating comprises the following steps:
dissolving epoxy resin in butyl acetate, adding the carbon-coated nano filler prepared in the second step, and dispersing for 5-6 hours at 4000-4500 r/min to obtain a component A;
dissolving low-molecular polyamide resin in butyl acetate, adding 5-10 layers of graphene oxide, and dispersing for 5-6 hours at 4000-4500 r/min to obtain a component B; the multilayer graphene oxide can play two roles, namely, physical isolation is realized, and water and oxygen are isolated by utilizing the good chemical stability of the graphene oxide, so that the anticorrosion function is realized; the other is that a micro-capacitance structure is formed to assist in playing a coulomb blocking effect, namely an electronic passage is isolated;
and uniformly mixing the component A and the component B, and spraying the mixture for 5-6 hours to form a film.
Wherein the component A is epoxy resin, the component B is low molecular polyamide resin, and the epoxy resin is cured at room temperature by virtue of the polyamide resin to obtain a paint film.
The second embodiment is as follows: the first difference between the present embodiment and the specific embodiment is: in the first step, the pentavalent metal alkoxide is one or a mixture of two of niobium ethoxide and tantalum ethoxide. The rest is the same as the first embodiment.
The third concrete implementation mode: the present embodiment differs from the first or second embodiment in that: in the first step, the complexing agent is sodium citrate. The other is the same as in the first or second embodiment.
The fourth concrete implementation mode: the difference between this embodiment mode and one of the first to third embodiment modes is: in the first step, the molar ratio of manganese element to pentavalent metal alkoxide is (0.8-0.95): (0.05-0.2). The others are the same as in one of the first to third embodiments.
The fifth concrete implementation mode: the difference between this embodiment and one of the first to fourth embodiments is: in the first step, the mass of the complexing agent is 0.8-1.2% of the mass of the manganese chloride. The other is the same as one of the first to fourth embodiments.
The sixth specific implementation mode: the difference between this embodiment and one of the first to fifth embodiments is: and in the second step, the water-soluble polymer is a mixture consisting of water-soluble phenolic resin, polyvinylpyrrolidone resin and polyvinyl alcohol resin. Wherein the mass ratio of the water-soluble phenolic resin, the polyvinylpyrrolidone resin and the polyvinyl alcohol resin is (0.5-0.65): (0.2-0.35): 0.15-0.3). The other is the same as one of the first to fifth embodiments.
The seventh embodiment: the difference between this embodiment and one of the first to sixth embodiments is: and in the second step, the mass ratio of the powder to the water-soluble polymer is 100: 5. The other is the same as one of the first to sixth embodiments.
The specific implementation mode is eight: the present embodiment differs from one of the first to seventh embodiments in that: the epoxy resin in the third step is composed of E-51 resin and E-44 resin according to the mass ratio of (0.7-1) to (0-0.3). The other is the same as one of the first to seventh embodiments.
The specific implementation method nine: the present embodiment differs from the first to eighth embodiments in that: the low molecular polyamide resin in the step three is low molecular polyamide resin 650 or low molecular polyamide resin 651. The rest is the same as the first to eighth embodiments.
The detailed implementation mode is ten: the present embodiment differs from one of the first to ninth embodiments in that: and step three, the mass of the nano filler in the component A is 12-19% of the mass of the epoxy resin. The other is the same as one of the first to ninth embodiments.
The concrete implementation mode eleven: the present embodiment differs from one of the first to tenth embodiments in that: and step three, the mass of the graphene oxide in the component B is 0.3-0.6% of the mass of the low molecular polyamide resin. The rest is the same as one of the first to tenth embodiments.
The specific implementation mode twelve: the present embodiment differs from one of the first to tenth embodiments in that: and step three, the mass ratio of the epoxy resin in the component A to the low-molecular polyamide resin in the component B is 100 (90-125). The rest is the same as one of the first to tenth embodiments.
The following examples are given to illustrate the present invention, and the following examples are carried out on the premise of the technical solution of the present invention, and give detailed embodiments and specific procedures, but the scope of the present invention is not limited to the following examples.
Example 1:
the preparation method of the anticorrosive paint based on the coulomb blockade effect comprises the following steps:
firstly, preparing the high dielectric constant inorganic nano filler:
adding manganese chloride, niobium ethoxide and sodium citrate into distilled water for dissolving, and reacting for 2 hours at 80 ℃ to obtain sol; putting the sol into a hydrothermal reaction kettle, reacting for 24 hours at 180 ℃, taking out the reactant, centrifuging for 15 minutes at 4000r/min, washing with distilled water, and drying to obtain powder;
secondly, a nano filler interface charge transport regulation method comprises the following steps:
adding the powder prepared in the step one into distilled water for ultrasonic dispersion, adding a water-soluble polymer until the water-soluble polymer is completely dissolved, and drying to obtain polymer-coated powder; calcining the powder coated with the polymer in a muffle furnace, heating to 200 ℃ for calcining for 1h, heating to 300 ℃ for calcining for 4h, heating to 450 ℃ for calcining for 2h, and obtaining the nano filler coated with carbon on the surface after calcining;
thirdly, the preparation method of the composite coating comprises the following steps:
dissolving epoxy resin in butyl acetate, adding the nano filler with the carbon-coated surface prepared in the second step, and dispersing for 5 hours at 4000r/min to obtain a component A;
dissolving low-molecular polyamide resin 650 in butyl acetate, adding 5-10 layers of graphene oxide, and dispersing for 5 hours at 4000r/min to obtain a component B;
the component A and the component B are uniformly mixed and sprayed into a film within 5 hours.
Further, the molar ratio of the manganese element to the niobium ethoxide in the manganese monochloride in the step is 0.9: 0.05.
In the first step, the mass of the sodium citrate is 1.0 percent of the mass of the manganese chloride.
Further, in the second step, the water-soluble polymer is a mixture of water-soluble phenolic resin, polyvinylpyrrolidone resin and polyvinyl alcohol resin. Wherein the mass ratio of the water-soluble phenolic resin to the polyvinylpyrrolidone resin to the polyvinyl alcohol resin is 0.5:0.3: 0.2.
And in the second step, the mass ratio of the powder to the water-soluble polymer is 100: 5.
Further, in the third step, the epoxy resin is composed of E-51 resin and E-44 resin according to the mass ratio of 0.8: 0.1.
Furthermore, the mass of the nano filler in the component A in the step three is 15% of the mass of the epoxy resin.
Furthermore, the mass of the graphene oxide in the component B in the step three is 0.5% of the mass of the low molecular polyamide resin.
And step three, the mass ratio of the epoxy resin in the component A to the low-molecular polyamide resin in the component B is 100: 95.
Example 2:
the preparation method of the anticorrosive paint based on the coulomb blockade effect comprises the following steps:
firstly, preparing the high dielectric constant inorganic nano filler:
adding manganese chloride, tantalum ethoxide and sodium citrate into distilled water for dissolving, and reacting for 2 hours at 80 ℃ to obtain sol; putting the sol into a hydrothermal reaction kettle, reacting for 24 hours at 160 ℃, taking out the reactant, centrifuging for 15 minutes at 4000r/min, washing with distilled water, and drying to obtain powder;
secondly, a nano filler interface charge transport regulation method comprises the following steps:
adding the powder prepared in the step one into distilled water for ultrasonic dispersion, adding a water-soluble polymer until the water-soluble polymer is completely dissolved, and drying to obtain polymer-coated powder; calcining the powder coated with the polymer in a muffle furnace, heating to 200 ℃ for calcining for 1h, heating to 300 ℃ for calcining for 4h, and finally heating to 450 ℃ for calcining for 1h to obtain the nano filler coated with carbon on the surface after the calcining is finished;
thirdly, the preparation method of the composite coating comprises the following steps:
dissolving epoxy resin in butyl acetate, adding the nano filler with the carbon-coated surface prepared in the second step, and dispersing for 5 hours at 4000r/min to obtain a component A;
dissolving low-molecular polyamide resin 650 in butyl acetate, adding 5-10 layers of graphene oxide, and dispersing for 5 hours at 4000r/min to obtain a component B;
the component A and the component B are uniformly mixed and sprayed into a film within 5 hours.
Furthermore, the molar ratio of the manganese element to the tantalum ethoxide in the manganese monochloride in the step is 0.9: 0.1.
In the first step, the mass of the sodium citrate is 1.0 percent of the mass of the manganese chloride.
Further, in the second step, the water-soluble polymer is a mixture of water-soluble phenolic resin, polyvinylpyrrolidone resin and polyvinyl alcohol resin. Wherein the mass ratio of the water-soluble phenolic resin to the polyvinylpyrrolidone resin to the polyvinyl alcohol resin is 0.6:0.2: 0.3.
And in the second step, the mass ratio of the powder to the water-soluble polymer is 100: 5.
Further, in the third step, the epoxy resin is composed of E-51 resin and E-44 resin according to the mass ratio of 0.8: 0.3.
Furthermore, the mass of the nano filler in the component A in the third step is 18 percent of the mass of the epoxy resin.
Furthermore, the mass of the graphene oxide in the component B in the step three is 0.4% of the mass of the low molecular polyamide resin.
And step three, the mass ratio of the epoxy resin in the component A to the low-molecular polyamide resin in the component B is 100: 110.
Example 3:
the preparation method of the anticorrosive paint based on the coulomb blockade effect comprises the following steps:
firstly, preparing the high dielectric constant inorganic nano filler:
adding manganese chloride, pentavalent metal alkoxide and sodium citrate into distilled water for dissolving, and reacting for 2 hours at 85 ℃ to prepare sol; putting the sol into a hydrothermal reaction kettle, reacting for 36 hours at 180 ℃, taking out the reactant, centrifuging for 15 minutes at 4000r/min, washing with distilled water, and drying to obtain powder; the pentavalent metal alkoxide is a mixture of niobium ethoxide and tantalum ethoxide, and the molar ratio of the niobium ethoxide to the tantalum ethoxide is 1: 1;
secondly, a nano filler interface charge transport regulation method comprises the following steps:
adding the powder prepared in the step one into distilled water for ultrasonic dispersion, adding a water-soluble polymer until the water-soluble polymer is completely dissolved, and drying to obtain polymer-coated powder; calcining the powder coated with the polymer in a muffle furnace, heating to 250 ℃ for calcining for 1h, heating to 350 ℃ for calcining for 3h, and finally heating to 500 ℃ for calcining for 1h to obtain the nano filler coated with carbon on the surface after the calcining is finished;
thirdly, the preparation method of the composite coating comprises the following steps:
dissolving epoxy resin in butyl acetate, adding the nano filler with the carbon-coated surface prepared in the second step, and dispersing for 5 hours at 4000r/min to obtain a component A;
dissolving low-molecular polyamide resin 650 in butyl acetate, adding 5-10 layers of graphene oxide, and dispersing for 5 hours at 4000r/min to obtain a component B;
the component A and the component B are uniformly mixed and sprayed into a film within 5 hours.
Further, the molar ratio of the manganese element to the pentavalent metal alkoxide in the manganese monochloride in the step is 0.9: 0.1.
In the first step, the mass of the sodium citrate is 0.8-1.2% of the mass of the manganese chloride.
Further, in the second step, the water-soluble polymer is a mixture of water-soluble phenolic resin, polyvinylpyrrolidone resin and polyvinyl alcohol resin. Wherein the mass ratio of the water-soluble phenolic resin to the polyvinylpyrrolidone resin to the polyvinyl alcohol resin is 0.5:0.3: 0.2.
And in the second step, the mass ratio of the powder to the water-soluble polymer is 100: 5.
Further, in the third step, the epoxy resin is composed of E-51 resin and E-44 resin according to the mass ratio of 0.8: 0.1.
Furthermore, the mass of the nano filler in the component A in the step three is 15% of the mass of the epoxy resin.
Furthermore, the mass of the graphene oxide in the component B in the step three is 0.5% of the mass of the low molecular polyamide resin.
And step three, the mass ratio of the epoxy resin in the component A to the low-molecular polyamide resin in the component B is 100: 120.
Example 4:
the preparation method of the anticorrosive paint based on the coulomb blockade effect comprises the following steps:
firstly, preparing the high dielectric constant inorganic nano filler:
adding manganese chloride, niobium ethoxide and sodium citrate into distilled water for dissolving, and reacting for 2 hours at 80 ℃ to obtain sol; putting the sol into a hydrothermal reaction kettle, reacting for 24 hours at 160 ℃, taking out the reactant, centrifuging for 15 minutes at 4000r/min, washing with distilled water, and drying to obtain powder;
secondly, a nano filler interface charge transport regulation method comprises the following steps:
adding the powder prepared in the step one into distilled water for ultrasonic dispersion, adding a water-soluble polymer until the water-soluble polymer is completely dissolved, and drying to obtain polymer-coated powder; calcining the powder coated with the polymer in a muffle furnace, heating to 200 ℃ for calcining for 1h, heating to 300 ℃ for calcining for 3h, and finally heating to 450 ℃ for calcining for 1h to obtain the nano filler coated with carbon on the surface after the calcining is finished;
thirdly, the preparation method of the composite coating comprises the following steps:
dissolving epoxy resin in butyl acetate, adding the nano filler with the carbon-coated surface prepared in the second step, and dispersing for 5 hours at 4000r/min to obtain a component A;
dissolving low-molecular polyamide resin 650 in butyl acetate, adding 5-10 layers of graphene oxide, and dispersing for 5 hours at 4000r/min to obtain a component B;
the component A and the component B are uniformly mixed and sprayed into a film within 5 hours.
Further, the molar ratio of the manganese element to the niobium ethoxide in the manganese monochloride in the step is 0.9: 0.1.
In the first step, the mass of the sodium citrate is 1.0 percent of the mass of the manganese chloride.
Further, in the second step, the water-soluble polymer is a mixture of water-soluble phenolic resin, polyvinylpyrrolidone resin and polyvinyl alcohol resin. Wherein the mass ratio of the water-soluble phenolic resin to the polyvinylpyrrolidone resin to the polyvinyl alcohol resin is 0.5:0.3: 0.2.
And in the second step, the mass ratio of the powder to the water-soluble polymer is 100: 5.
Further, the epoxy resin in the third step is E-51 resin.
Furthermore, the mass of the nano filler in the component A in the third step is 18 percent of the mass of the epoxy resin.
Furthermore, the mass of the graphene oxide in the component B in the step three is 0.3% of the mass of the low molecular polyamide resin.
And step three, the mass ratio of the epoxy resin in the component A to the low-molecular polyamide resin in the component B is 100: 125.
The paint prepared in the above example was tested for corrosion resistance, the test results are shown in table 1, and the test method is as follows:
neutral salt spray test: and (3) performing a salt spray resistance test on the composite anticorrosive paint film according to the national standard GB/T6461-2002.
Corrosion current and corrosion potential testing: corrosion rate of the corrosive medium was tested using an SCE (saturated calomel) type reference electrode in a NaCl solution at a concentration of 3 wt.%. The surface area of the paint film was 1cm2, the test parameters were-0.2V (vs. OCP) for the initial potential, 0.2V for the final potential and a potential sweep rate of 2 mV/s.
According to the national standard GB/T6739-2006, a pencil hardness tester of Shanghai modern environmental engineering technology division Limited division is used for testing the hardness of the paint film.
The paint films were subjected to adhesion tests using a finish QFZ paint film adhesion tester according to the national standard GB/T1720-1979.
TABLE 1
Claims (10)
1. The preparation method of the anticorrosive paint based on the coulomb blocking effect is characterized by comprising the following steps:
firstly, adding manganese chloride, pentavalent metal alkoxide and a complexing agent into distilled water for dissolving, and reacting for 2-3 hours at 80-85 ℃ to prepare sol; putting the sol into a hydrothermal reaction kettle, reacting for 24-48 hours at 160-180 ℃, taking out the reactant, centrifuging for 15-20 minutes at 3500-4000 r/min, washing with distilled water, and drying to obtain powder;
secondly, adding the powder prepared in the first step into distilled water for ultrasonic dispersion, adding a water-soluble polymer until the water-soluble polymer is completely dissolved, and drying to obtain polymer-coated powder; calcining the powder coated with the polymer in a muffle furnace, heating to 200-250 ℃ for calcining for 1-2 h, then heating to 300-350 ℃ for calcining for 3-6 h, and finally heating to 450-500 ℃ for calcining for 1-2 h, and obtaining the carbon-coated nano filler after calcining;
dissolving epoxy resin in butyl acetate, adding the carbon-coated nano filler prepared in the step two, and dispersing for 5-6 hours at 4000-4500 r/min to obtain a component A;
dissolving low-molecular polyamide resin in butyl acetate, adding multiple layers of graphene oxide, and dispersing at 4000-4500 r/min for 5-6 h to obtain a component B;
and uniformly mixing the component A and the component B, and spraying the mixture for 5-6 hours to form a film.
2. The method for preparing the coulomb blockade-based anticorrosive paint according to claim 1, wherein the pentavalent metal alkoxide in step one is one or a mixture of two of niobium ethoxide and tantalum ethoxide.
3. The method for preparing an anticorrosive paint based on coulomb blockade as claimed in claim 1 or 2, wherein the molar ratio of manganese element to pentavalent metal alkoxide in the manganese chloride in the step one is (0.8-0.95): (0.05-0.2).
4. The method for preparing an anticorrosive paint based on coulomb blockade as claimed in claim 3, wherein the mass of the complexing agent in the first step is 0.8-1.2% of the mass of manganese chloride.
5. The method for preparing an anticorrosive paint based on coulomb blockade according to claim 1, 2 or 4, wherein the water-soluble polymer in step two is a mixture of water-soluble phenolic resin, polyvinylpyrrolidone resin and polyvinyl alcohol resin; wherein the mass ratio of the water-soluble phenolic resin, the polyvinylpyrrolidone resin and the polyvinyl alcohol resin is (0.5-0.65): (0.2-0.35): 0.15-0.3).
6. The method for preparing an anticorrosive paint based on coulomb blockade as claimed in claim 1, wherein the epoxy resin in step three is composed of E-51 resin and E-44 resin by mass ratio (0.7-1): 0-0.3).
7. The method for preparing an anticorrosive coating based on coulomb blockade according to claim 1 or 6, characterized in that the low molecular polyamide resin in step three is low molecular polyamide resin 650 or low molecular polyamide resin 651.
8. The method for preparing the anti-corrosive paint based on the coulomb blockade effect according to the claim 1, characterized in that the nanometer filler in the component A in the step three accounts for 12 to 19 percent of the weight of the epoxy resin.
9. The method for preparing an anticorrosive paint based on coulomb blockade according to claim 1, wherein the mass of graphene oxide in the component B in the step three is 0.3-0.6% of the mass of the low molecular polyamide resin.
10. The method for preparing an anticorrosive paint based on coulomb blockade as claimed in claim 1, 8 or 9, wherein the mass ratio of the epoxy resin in the component A to the low molecular polyamide resin in the component B is 100 (90-125).
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