CN110003774B - Water-based anticorrosive paint based on carbon nano composite material and preparation method thereof - Google Patents
Water-based anticorrosive paint based on carbon nano composite material and preparation method thereof Download PDFInfo
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/08—Polyesters modified with higher fatty oils or their acids, or with natural resins or resin acids
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- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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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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- 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
- C09D5/10—Anti-corrosive paints containing metal dust
- C09D5/106—Anti-corrosive paints containing metal dust containing Zn
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
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- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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Abstract
The invention provides a water-based anticorrosive paint based on a carbon nano composite material and a preparation method thereof. The water-based anticorrosive paint based on the carbon nano composite material comprises: 20-60 parts of water-based resin emulsion, 10-30 parts of modified graphene and 5-25 parts of modified carbon nanotubes; the preparation method of the modified graphene or the modified carbon nanotube comprises the following steps: mixing graphene or carbon nanotubes with a mixed solution of sulfuric acid and nitric acid, diluting with water after dispersion, and filtering to obtain a solid; mixing the solid with water to obtain mixture, adding surfactant, dispersing, filtering to obtain insoluble substance, mixing the insoluble substance with water, and dispersing. The preparation method comprises the following steps: and mixing the aqueous resin emulsion, the modified graphene and the modified carbon nano tube, and then grinding. The application provides a waterborne anticorrosive coating based on carbon nano composite material can form compact composite structure, very big improvement the adhesive force and the mechanical strength of coating, and then improve the corrosion-resistant life-span of coating.
Description
Technical Field
The invention relates to the field of anticorrosive coatings, in particular to a water-based anticorrosive coating based on a carbon nano composite material and a preparation method thereof.
Background
The graphene composite anticorrosive paint can give consideration to excellent chemical stability, rapid conductivity, outstanding mechanical property, strong adhesive force and film forming property of polymer resin, and can synergistically improve the comprehensive performance of the paint. However, with the increasing awareness of environmental protection, the development of the original solvent-based anticorrosive paint is more and more limited. The world also puts forward more and more requirements on the anticorrosive paint, the anticorrosive paint is developing towards the direction of high performance, multifunction and environmental protection, and particularly the development of the water-based paint becomes an important development direction of the anticorrosive paint.
The originally prepared graphene and carbon nano tubes have hydrophobicity, are easy to agglomerate, are difficult to uniformly disperse in the preparation process of the water-based paint, are difficult to accurately control the concentration, and are difficult to realize the protective effect of overlapping layer by layer. Meanwhile, due to the addition of various functional materials, a coating firmly bonded with the substrate is not easy to form; the compactness and integrity of the coating itself is also affected. And due to the excellent conductivity of the graphene, the metal corrosion is accelerated once the film has slight defects, and the anti-oxidation corrosion effect can be provided only for a short time.
In the prior art, the adhesion performance and the binding force of the coating are generally improved by using a smaller amount of raw material graphene or combining a plurality of resins with a covering substrate, and the like, so that the durability of the coating is improved.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The first purpose of the invention is to provide a water-based anticorrosive coating based on a carbon nano composite material, graphene is uniformly dispersed in the coating, can be fully wetted with various materials in a system, and is combined with a carbon nano tube to form a compact composite net structure, so that the adhesive force and the mechanical strength of the system are greatly improved, and the corrosion resistance life of the coating is further prolonged.
The second purpose of the invention is to provide a preparation method of the water-based anticorrosive paint based on the carbon nano composite material, which is simple to operate, low in cost and free of pollution.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
a water-based anticorrosive paint based on a carbon nano composite material comprises the following components in parts by weight: 20-60 parts of water-based resin emulsion, 10-30 parts of modified graphene and 5-25 parts of modified carbon nanotubes;
the preparation method of the modified graphene or the modified carbon nanotube comprises the following steps:
placing graphene or carbon nano tubes into a mixed solution of sulfuric acid and nitric acid for mixing, diluting with water after first dispersion, and filtering to obtain a solid;
and mixing the solid with water to obtain a mixture, adding a surfactant, dispersing for the second time, filtering to obtain insoluble substances, mixing the insoluble substances with water, and dispersing for the third time to obtain the corresponding modified graphene or the modified carbon nanotube.
The aqueous resin emulsion exists as a basic film-forming component and can be aqueous epoxy resin emulsion, aqueous polyurethane emulsion, aqueous alkyd emulsion, aqueous fluorocarbon resin emulsion, aqueous acrylic resin emulsion and the like.
The graphene has special structural characteristics of a two-dimensional lamellar structure, excellent hydrophobic property, small-size effect and the like, and excellent conductivity; the laminated structure can well form a physical isolation layer; the paint has good hydrophobicity, and can prevent water molecules from contacting with a metal matrix when added into the paint, so as to achieve the effect of corrosion prevention; the size is small, and the gap of the anticorrosive paint can be filled; good conductivity can transfer electrons lost by the metal to the surface of the coating, thereby avoiding the precipitation of the metal and reducing the electrochemical corrosion speed of the metal. The raw material of the modified graphene can be prepared by a chemical vapor deposition method or an electrochemical ultrasonic stripping method and other conventional methods.
The carbon nano tube is added into the system, so as to improve the compactness and the integrity of the coating obtained by the anticorrosive coating and form a composite reinforced coating. The carbon nano tubes and the graphene are matched and mutually staggered in the coating to form a three-dimensional net structure, and the internal combination of the coating is greatly enhanced. The raw materials of the modified carbon nano tube can be prepared by adopting a chemical vapor deposition method or physical methods such as arc discharge and the like.
The graphene and the carbon nano tube are compounded, so that the conductivity of the graphene is enhanced, electrons can be conveniently transferred in the coating, the electrochemical corrosion of the surface of the metal substrate is prevented, and in addition, the coating obtained by the coating can also prevent electrostatic accumulation.
The method comprises the following steps of treating raw materials of graphene and carbon nano tubes by using a mixed solution of sulfuric acid and nitric acid, so that the surfaces of the graphene and the carbon nano tubes are oxidized to generate carboxyl and hydrogen bonds, the hydrophilic property of the graphene and the carbon nano tubes is enhanced, and the affinity of the graphene and the carbon nano tubes with aqueous resin emulsion is improved; the purpose of continuing to use the surfactant for treatment is to coat the surfactant on the surface of the graphene or the carbon nanotube so as to form a surface membrane, separate the graphene particles or the carbon nanotubes adjacent to each other, and avoid agglomeration between the graphene and the graphene, between the carbon nanotubes and between the graphene and the carbon nanotubes under the action of steric hindrance and electrostatic repulsion.
In an alternative embodiment, the aqueous resin emulsion may be any value between 20 parts, 30 parts, 40 parts, 50 parts, 60 parts and 20 to 60 parts, the modified graphene may be any value between 10 parts, 15 parts, 20 parts, 25 parts, 30 parts and 10 to 30 parts, and the modified carbon nanotube may be any value between 5 parts, 10 parts, 15 parts, 20 parts, 25 parts and 5 to 25 parts.
Preferably, the carbon nanocomposite-based water-based anticorrosive paint further comprises, in parts by weight: 5-25 parts of zinc powder and/or aluminum powder.
The zinc powder and the aluminum powder exist as sacrificial anodes, so that the anticorrosion life of the coating can be prolonged.
In alternative embodiments, the zinc powder and/or aluminum powder may be used in any amount between 5 parts, 10 parts, 15 parts, 20 parts, 25 parts, and 5-25 parts.
More preferably, the particle size of the zinc powder and the aluminum powder is 5-30 μm, and the thickness of the scale is 0.1-0.5 μm.
The zinc powder and the aluminum powder with the scale can form a multi-layer covering structure, so that foreign matters are prevented from invading into the base material, and better protection is provided.
Preferably, the carbon nanocomposite-based water-based anticorrosive paint further comprises, in parts by weight: 5-25 parts of diluent, 0.1-5 parts of coupling agent, 0.1-5 parts of dispersing agent, 0.1-5 parts of defoaming agent, 0.1-5 parts of flatting agent, 3-10 parts of filler, 0.1-5 parts of anti-flash rust agent and 3-15 parts of pigment.
In alternative embodiments, the diluent may be used in an amount of any value between 5 parts, 10 parts, 15 parts, 20 parts, 25 parts and 5 to 25 parts, the coupling agent may be used in an amount of any value between 0.1 parts, 0.5 parts, 1 part, 2 parts, 3 parts, 4 parts, 5 parts and 0.1 to 5 parts, the dispersant may be used in an amount of any value between 0.1 parts, 0.5 parts, 1 part, 2 parts, 3 parts, 4 parts, 5 parts and 0.1 to 5 parts, the defoamer may be used in an amount of any value between 0.1 parts, 0.5 parts, 1 part, 2 parts, 3 parts, 4 parts, 5 parts and 0.1 to 5 parts, the leveling agent may be used in an amount of any value between 0.1 parts, 0.5 parts, 1 part, 2 parts, 3 parts, 4 parts, 5 parts and 0.1 to 5 parts, and the filler may be used in an amount of any value between 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts and 10 parts, the flash rust inhibitor may be used in an amount of any of 0.1 parts, 0.5 parts, 1 part, 2 parts, 3 parts, 4 parts, 5 parts and 0.1 to 5 parts, and the pigment may be used in an amount of any of 3 parts, 4 parts, 5 parts, 6 parts, 8 parts, 10 parts, 12 parts, 14 parts, 15 parts and 3 to 15 parts.
The use of the diluent, the coupling agent, the dispersing agent, the defoaming agent, the leveling agent, the flash rust inhibitor and the filler can improve the uniformity of the coating and the viscosity of the coating, so that the obtained coating is more uniform, is not easy to generate bubbles and local defects and has higher strength; but also can prevent the surface coating from rusting when the surface coating is not dried.
The diluent can adopt reagents such as deionized water or ethylene glycol diglycidyl ether; as the coupling agent, there can be used, for example, a carboxylated phosphate ester or a silane coupling agent; the filler may be selected from agents such as talc, heavy calcium carbonate or zinc stearate; the dispersing agent can adopt reagents such as polycarboxylate ether, polyvinyl alcohol or fluorine silicon compound, the defoaming agent can adopt reagents such as organic polyether ester, mineral oil or polyalcohol, the leveling agent can adopt reagents such as organic silicon leveling agent or fluorocarbon, and the anti-flash rust agent can adopt reagents such as sodium molybdate, organic high molecular amine or alkynediol.
The above agents used for the diluents, coupling agents, dispersants, defoamers, leveling agents, fillers, flash rust inhibitors and pigments are only illustrative and are not to be construed as limiting the present application.
Preferably, the sheet diameter of the graphene is 1-50 μm, and the number of layers is 1-20; the diameter of the carbon nano tube is 1-100nm, and the length of the carbon nano tube is 5-200 mu m.
The preference for graphene and carbon nanotubes helps to further improve the uniformity, stability, strength and corrosion life of the coatings obtained using the coatings.
Preferably, the volume ratio of the sulfuric acid to the nitric acid is 1-3: 1.
Concentrated sulfuric acid and concentrated nitric acid are preferably used for sulfuric acid and nitric acid, the oxidation process and the oxidation degree of the surfaces of the graphene and the carbon nano tubes are controlled by the control of the proportion, and then the effect of subsequent treatment by using a surfactant is controlled, so that the graphene and the carbon nano tubes can be well compatible and compounded with the aqueous resin emulsion. The optimal volume ratio of sulfuric acid to nitric acid is 2: 1.
Preferably, the temperature of the first dispersion is 40-80 ℃, and the time is 4.5-7.5 h; the time for the second dispersion is 9-15 h; the time for the third dispersion is 1.5-2.5 h.
The control of the dispersion temperature and the dispersion time is to ensure the control of the modification process of the graphene and the carbon nano tube and to ensure better modification effect. The dispersion can be carried out by ultrasonic dispersion or other mechanical stirring, and ultrasonic dispersion is preferred.
Preferably, the surfactant is one or more of sodium dodecylbenzene sulfonate, sodium dodecylbenzene sulfonate and Triton X-100, and the amount of the surfactant is 2-6% of the total mass of the mixture.
The preferable surfactant is one or more of sodium dodecyl benzene sulfonate, sodium dodecyl sulfonate and Triton X-100, so that the thickness of a diaphragm formed after the graphene and the carbon nano tube are coated by the surfactant and the size of formed steric hindrance are controlled, and the effect of solving the agglomeration problem is better.
Optionally, the carbon nanocomposite-based water-based anticorrosive paint further includes, in parts by weight: 1-15 parts of a curing agent.
In alternative embodiments, the curing agent may be used in an amount of 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, and any value between 1 and 15 parts.
The water-based anticorrosive paint based on the carbon nano composite material can be prepared by dividing a curing agent and other components into two parts according to needs and premixing the two parts when in use. The curing agent can adopt reagents such as a waterborne modified amine epoxy curing agent, a waterborne polyurethane curing agent and the like. The agents used in the curing agent are given by way of illustration only and are not to be construed as limiting the present application.
The preparation method of the water-based anticorrosive paint based on the carbon nano composite material comprises the following steps:
and mixing the aqueous resin emulsion, the modified graphene and the modified carbon nano tube, and then grinding.
The grinding time is preferably 1.5 to 2.5 hours. When the diluent, the coupling agent, the dispersing agent, the defoaming agent, the leveling agent, the filler, the pigment, the flash rust prevention agent and the zinc powder or the aluminum powder are used, the diluent and the aqueous resin emulsion are mixed, then the dispersing agent, the coupling agent, the flash rust prevention agent, the defoaming agent, the leveling agent and the pigment are added one by one under the stirring state, the zinc powder and/or the aluminum powder are added, then the modified graphene and the modified carbon nano tube are added, and finally the filler is added and packaged for later use. The curing agent may be added after the addition of the dispersant or may be temporarily premixed at the time of use.
Compared with the prior art, the invention has the beneficial effects that:
(1) the modified graphene and the modified carbon nano tube have strong hydrophilicity and are dispersed in the coating more uniformly;
(2) the modified graphene and the modified carbon nano tube are matched and are mutually staggered in the coating to form a three-dimensional net structure, and the internal combination of the coating is greatly enhanced;
(3) the compactness and integrity of a coating obtained by using the water-based anticorrosive coating based on the carbon nano composite material are improved, so that the corrosion resistance life of the coating is prolonged;
(4) the preparation method is simple, low in cost, green, environment-friendly and pollution-free.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
Preparing modified graphene and modified carbon nanotubes:
placing graphene with the sheet diameter of 5 micrometers and 10 layers into a mixed solution of sulfuric acid and nitric acid, wherein the ratio of the sulfuric acid to the nitric acid is 2:1, performing ultrasonic dispersion for about 6 hours at the temperature of 60 ℃; then diluting with water and filtering; putting the solid obtained by filtering into deionized water to obtain a mixture, adding sodium dodecyl sulfate accounting for 5% of the total mass of the mixture, and performing ultrasonic dispersion for 12 hours; filtering, adding deionized water, and continuing ultrasonic dispersion for 2 hours to obtain the modified graphene.
Putting a carbon nano tube with the diameter of 2 nanometers and the length of 50 micrometers into a mixed solution of sulfuric acid and nitric acid, wherein the ratio of the sulfuric acid to the nitric acid is 2:1, performing ultrasonic dispersion for about 6 hours at the temperature of 60 ℃; then diluting with water and filtering; putting the solid obtained by filtering into deionized water to obtain a mixture, adding sodium dodecyl sulfate accounting for 5% of the total mass of the mixture, and performing ultrasonic dispersion for 12 hours; filtering, adding deionized water, and continuing ultrasonic dispersion for 2h to obtain the modified carbon nanotube.
Preparing raw materials in parts by weight:
and taking 20 parts of waterborne epoxy resin emulsion, 10 parts of modified graphene and 5 parts of modified carbon nanotubes for later use.
Preparing a water-based anticorrosive paint based on a carbon nano composite material:
and mixing the aqueous epoxy resin emulsion, the modified graphene and the modified carbon nano tube, adding a proper amount of curing agent, and grinding for 2 hours to obtain the aqueous anticorrosive paint based on the carbon nano composite material.
Example 2
Preparing modified graphene and modified carbon nanotubes:
placing graphene with the sheet diameter of 1 micron and 20 layers into a mixed solution of sulfuric acid and nitric acid, wherein the ratio of the sulfuric acid to the nitric acid is 1: 1, performing ultrasonic dispersion for about 4.5 hours at the temperature of 40 ℃; then diluting with water and filtering; putting the solid obtained by filtering into deionized water to obtain a mixture, adding sodium dodecyl sulfate accounting for 2% of the total mass of the mixture, and performing ultrasonic dispersion for 15 hours; filtering, adding deionized water, and continuing ultrasonic dispersion for 1.5h to obtain the modified graphene.
Putting carbon nano tubes with the diameter of 100 nanometers and the length of 5 micrometers into a mixed solution of sulfuric acid and nitric acid, wherein the ratio of the sulfuric acid to the nitric acid is 3:1, performing ultrasonic dispersion for about 7.5 hours at the temperature of 80 ℃; then diluting with water and filtering; putting the solid obtained by filtering into deionized water to obtain a mixture, adding sodium dodecyl benzene sulfonate accounting for 6% of the total mass of the mixture, and performing ultrasonic dispersion for 9 hours; filtering, adding deionized water, and continuing ultrasonic dispersion for 1.5h to obtain the modified carbon nanotube.
Preparing raw materials in parts by weight:
60 parts of aqueous polyurethane emulsion, 20 parts of modified graphene and 10 parts of modified carbon nano tube, 15 parts of zinc powder and aluminum powder, 25 parts of diluent, 0.1 part of coupling agent, 0.1 part of dispersing agent, 15 parts of curing agent, 5 parts of defoaming agent, 0.1 part of flatting agent, 10 parts of filler, 0.1 part of anti-flash rust agent and 15 parts of pigment for later use.
The zinc powder and the aluminum powder are flaky, the average grain diameter is 5-30um, and the thickness of the flake is 0.1-0.5 um.
Preparing a water-based anticorrosive paint based on a carbon nano composite material:
uniformly mixing a diluent and the aqueous polyurethane emulsion, then adding a dispersing agent, a curing agent, a coupling agent, an anti-flash rust agent, a defoaming agent, a leveling agent and a pigment one by one under a stirring state, then adding zinc powder and aluminum powder, then adding modified graphene and modified carbon nanotubes, finally adding a filler, and grinding for 2 hours to obtain the aqueous anticorrosive paint based on the carbon nanocomposite.
Example 3
Preparing modified graphene and modified carbon nanotubes:
placing graphene with the sheet diameter of 50 micrometers and 1 layer in a mixed solution of sulfuric acid and nitric acid, wherein the ratio of the sulfuric acid to the nitric acid is 3:1, performing ultrasonic dispersion for about 7.5 hours at the temperature of 80 ℃; then diluting with water and filtering; putting the solid obtained by filtering into deionized water to obtain a mixture, adding sodium dodecyl benzene sulfonate accounting for 6% of the total mass of the mixture, and performing ultrasonic dispersion for 9 hours; filtering, adding deionized water, and continuing ultrasonic dispersion for 2.5h to obtain the modified graphene.
Putting a carbon nano tube with the diameter of 1 nanometer and the length of 200 micrometers into a mixed solution of sulfuric acid and nitric acid, wherein the ratio of the sulfuric acid to the nitric acid is 1: 1, performing ultrasonic dispersion for about 4.5 hours at the temperature of 40 ℃; then diluting with water and filtering; putting the solid obtained by filtering into deionized water to obtain a mixture, adding sodium dodecyl benzene sulfonate accounting for 2% of the total mass of the mixture, and performing ultrasonic dispersion for 15 hours; filtering, adding deionized water, and continuing ultrasonic dispersion for 2.5h to obtain the modified carbon nanotube.
Preparing raw materials in parts by weight:
taking 40 parts of aqueous fluorocarbon resin emulsion, 30 parts of modified graphene, 25 parts of modified carbon nano tubes, 5 parts of zinc powder, 5 parts of diluent, 5 parts of coupling agent, 5 parts of dispersing agent, 1 part of curing agent, 0.1 part of defoaming agent, 5 parts of flatting agent, 3 parts of filler, 5 parts of flash rust inhibitor and 3 parts of pigment for later use.
The flaky zinc powder has an average particle size of 5-30um and a flake thickness of 0.1-0.5 um.
Preparing a water-based anticorrosive paint based on a carbon nano composite material:
the water-based anticorrosive coating based on the carbon nano composite material is prepared by uniformly mixing a diluent and a water-based fluorocarbon resin emulsion, then adding a dispersing agent, a curing agent, a coupling agent, an anti-flash rust agent, a defoaming agent, a leveling agent and a pigment one by one under a stirring state, then adding zinc powder and aluminum powder, then adding modified graphene and modified carbon nano tubes, finally adding a filler, and grinding for 2.5 hours.
Example 4
Preparing modified graphene and modified carbon nanotubes:
placing graphene with the sheet diameter of 20 micrometers and 5 layers into a mixed solution of sulfuric acid and nitric acid, wherein the ratio of the sulfuric acid to the nitric acid is 2:1, performing ultrasonic dispersion for about 6 hours at the temperature of 60 ℃; then diluting with water and filtering; putting the solid obtained by filtering into deionized water to obtain a mixture, adding sodium dodecyl benzene sulfonate accounting for 4% of the total mass of the mixture, and performing ultrasonic dispersion for 12 hours; filtering, adding deionized water, and continuing ultrasonic dispersion for 2 hours to obtain the modified graphene.
Putting carbon nano tubes with the diameter of 20 nanometers and the length of 100 micrometers into a mixed solution of sulfuric acid and nitric acid, wherein the ratio of the sulfuric acid to the nitric acid is 2:1, performing ultrasonic dispersion for about 6 hours at the temperature of 60 ℃; then diluting with water and filtering; putting the solid obtained by filtering into deionized water to obtain a mixture, adding sodium dodecyl benzene sulfonate accounting for 4% of the total mass of the mixture, and performing ultrasonic dispersion for 12 hours; filtering, adding deionized water, and continuing ultrasonic dispersion for 2h to obtain the modified carbon nanotube.
Preparing raw materials in parts by weight:
50 parts of water-based alkyd emulsion, 15 parts of modified graphene, 20 parts of modified carbon nano tube, 25 parts of aluminum powder, 15 parts of diluent, 2 parts of coupling agent, 3 parts of dispersing agent, 10 parts of curing agent, 2 parts of defoaming agent, 4 parts of flatting agent, 5 parts of filler, 4 parts of flash rust inhibitor and 5 parts of pigment are taken for later use.
The scale-shaped aluminum powder has an average particle diameter of 5-30um and a scale thickness of 0.1-0.5 um.
Preparing a water-based anticorrosive paint based on a carbon nano composite material:
the preparation method comprises the steps of uniformly mixing a diluent and the water-based alkyd emulsion, then adding a dispersing agent, a coupling agent, an anti-flash rust agent, a defoaming agent, a leveling agent and a pigment one by one under a stirring state, then adding zinc powder and aluminum powder, then adding modified graphene and modified carbon nano tubes, finally adding a filler, and grinding for 2 hours to obtain the component A.
And respectively packaging the component A and the curing agent, and temporarily mixing the component A and the curing agent when in use to obtain the water-based anticorrosive paint based on the carbon nano composite material.
Comparative example 1
The difference from example 4 is that graphene is not modified.
Comparative example 2
The difference from example 4 is that the carbon nanotubes were not modified.
Comparative example 3
The difference from example 4 is that neither graphene nor carbon nanotubes are modified.
Comparative example 4
The difference from example 4 is that modified carbon nanotubes were not added.
The anticorrosive coatings obtained in examples 1 to 4 and comparative examples 1 to 4 were applied to the same base material, and the maximum corrosion resistance time was measured by the salt spray test according to GB/T1771-91 "measurement of neutral salt spray resistance of colored and clear paints", and the results are shown in Table 1 below:
TABLE 1 test results of maximum Corrosion resistance time
As can be seen from table 1 above, the addition of the modified carbon nanotubes can effectively increase the maximum corrosion resistance time of the anticorrosive coating and increase the corrosion resistance life of the coating; compared with the untreated graphene and carbon nano tubes, the performance of the prepared anticorrosive paint is greatly improved.
The water-based anticorrosive coating based on the carbon nano composite material is more uniform in dispersion, the internal combination of the obtained coating is greatly enhanced, the compactness and the integrity of the coating are improved, and the corrosion resistance and the service life are long; the preparation method is simple, low in cost, green, environment-friendly and pollution-free.
While particular embodiments of the present invention have been illustrated and described, it would be obvious that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.
Claims (3)
1. The water-based anticorrosive paint based on the carbon nano composite material is characterized by comprising the following components in parts by weight: 20-60 parts of water-based resin emulsion, 10-30 parts of modified graphene, 5-25 parts of modified carbon nano tube, 5-25 parts of diluent, 0.1-5 parts of coupling agent, 0.1-5 parts of dispersing agent, 0.1-5 parts of defoaming agent, 0.1-5 parts of flatting agent, 3-10 parts of filler, 0.1-5 parts of anti-flash rust agent, 3-15 parts of pigment and 5-25 parts of zinc powder and/or aluminum powder; the particle size of the zinc powder and the aluminum powder is 5-30 mu m, and the thickness of the scale is 0.1-0.5 mu m;
the preparation method of the modified graphene or the modified carbon nanotube comprises the following steps:
mixing graphene or carbon nanotubes with a mixed solution of sulfuric acid and nitric acid, diluting with water after first dispersion, and filtering to obtain a solid; the sheet diameter of the graphene is 1-50 mu m, and the number of layers is 1-20; the diameter of the carbon nano tube is 1-100nm, and the length of the carbon nano tube is 5-200 mu m; the volume ratio of the sulfuric acid to the nitric acid is 1-3: 1;
mixing the solid with water to obtain a mixture, adding a surfactant, dispersing for the second time, filtering to obtain insoluble substances, mixing the insoluble substances with water, and dispersing for the third time to obtain the corresponding modified graphene or the modified carbon nanotube;
the surfactant is one or more of sodium dodecyl benzene sulfonate, sodium dodecyl sulfonate and Triton X-100, and the dosage of the surfactant is 2-6% of the total mass of the mixture; the temperature of the first dispersion is 40-80 ℃, and the time is 4.5-7.5 h; the time for the second dispersion is 9-15 h; the time for the third dispersion is 1.5-2.5 h.
2. The carbon nanocomposite-based water-based anticorrosive paint according to claim 1, further comprising, in parts by weight: 1-15 parts of a curing agent.
3. The preparation method of the carbon nanocomposite-based water-based anticorrosive paint according to claim 1, characterized by comprising the steps of:
mixing a diluent and an aqueous resin emulsion, then adding a dispersing agent, a coupling agent, an anti-flash rust agent, a defoaming agent, a leveling agent and a pigment one by one under a stirring state, then adding zinc powder and/or aluminum powder, then adding modified graphene and modified carbon nano tubes, finally adding a filler and packaging for later use.
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| US11021614B1 (en) * | 2020-03-10 | 2021-06-01 | Tesla Nanocoatings, Inc. | Self-stratifying coatings |
| CN112430419A (en) * | 2020-11-30 | 2021-03-02 | 长沙理工大学 | Large-pipe-diameter inner-covering composite hydrophobic coating and preparation method thereof |
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| CN114958146B (en) * | 2022-06-30 | 2023-03-17 | 北京理工大学珠海学院 | Anticorrosive composite material containing modified carbon nano tube and preparation method thereof |
| CN115418143A (en) * | 2022-09-23 | 2022-12-02 | 青岛中氟氟碳材料有限公司 | Water-based fluorocarbon coating for surface of aluminum veneer and preparation method thereof |
| CN116640499B (en) * | 2023-06-12 | 2023-11-17 | 东营海瑞宝新材料有限公司 | Polyurea waterproof composition and preparation method thereof |
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