CN116396662B - Conductive anticorrosive composite coating and preparation method and application thereof - Google Patents
Conductive anticorrosive composite coating and preparation method and application thereof Download PDFInfo
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Classifications
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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
-
- 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
- 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
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/24—Electrically-conducting paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
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Abstract
The invention relates to the field of electric engineering materials, and particularly discloses a conductive anti-corrosion composite coating, a preparation method and application thereof. The conductive anticorrosive composite coating comprises the following components in parts by weight: 10-15 parts of aqueous epoxy resin emulsion, 1-5 parts of curing agent, 20-60 parts of water and 20-60 parts of amination modified graphene oxide/acidified carbon nano tube/polyaniline composite material. The composite coating has the advantages of conductivity, corrosion resistance and excellent mechanical properties, can well solve the problem of corrosion protection of the grounding grid after being used for the grounding grid, improves the corrosion resistance of the grounding grid material, ensures the stability of the grounding performance, effectively prolongs the service life of the grounding grid, ensures the long-term normal operation of power equipment, avoids production accidents, reduces maintenance and transformation cost, and further generates obvious economic benefit and social benefit.
Description
Technical Field
The invention relates to the field of electric engineering materials, and particularly discloses a conductive anti-corrosion composite coating, a preparation method and application thereof.
Background
The grounding grid for the power engineering is an important measure for maintaining the safe and reliable operation of the power system and guaranteeing the safety of personnel and equipment, however, the accident of the power system caused by the corrosion and the fracture of the grounding grid is a prominent problem of the domestic grounding grid. Aiming at the corrosion prevention problem of the grounding grid, the grounding materials adopted at home and abroad at present are steel, copper, galvanized, copper-plated, steel externally-coated corrosion-resistant conductive paint and the like, and the grounding grid with longer service life requirement can be selected to be plated with copper grounding electrode or to be coated with corrosion-resistant paint on the surface of steel. At present, a domestic electric power engineering grounding grid widely adopts hot galvanized flat steel as a grounding material, but excavation is carried out after the galvanized flat steel material is put into operation for a period of time in a region with higher corrosion intensity and larger soil alkalinity, so that the problem of serious corrosion of the galvanized flat steel material wholly or locally occurs; or copper bars or stainless steel grounding materials are adopted, the corrosion resistance is obviously improved, but the manufacturing cost is high, and the engineering investment is large.
The paint protection is a kind of anti-corrosion measure with wider application, and the application of the conductive paint in a grounding system can realize dual functions of conductivity and corrosion resistance. However, the conductive coating often has the defect that the conductive performance and the corrosion resistance or the mechanical performance cannot be simultaneously achieved, the good conductive performance requires the content of the conductive filler of the coating to be increased, the increase of the filler tends to cause the defect of the coating to be increased, and the coating practicability is seriously affected.
The conductive anticorrosive paint developed in China mainly takes additive type conductive paint as main material, and at present, a lot of metal conductive fillers are studied, such as grounding paint for a power system prepared from epoxy resin and silver powder or conductive anticorrosive paint for the electrolysis industry prepared from epoxy resin and silver-coated glass powder, and the conductive anticorrosive paint taking silver powder as main filler greatly reduces the resistivity of a matrix, but has larger filler proportion, increases the use cost and greatly influences the adhesive force of the matrix. The chemical synthesis method is adopted to silver the copper powder, or the silane coupling agent is adopted to treat the copper powder, so that the resistivity of the coating is reduced by-order of magnitude, the use cost is greatly reduced, but the doping amount of the filler mainly containing copper is still higher. Electrochemical corrosion generated when the paint is defective, which aggravates corrosion, and nickel powder type conductive anticorrosive paint is easy to oxidize and is not conductive after oxidation. The carbon conductive filler has the advantages of good conductivity, stable performance, wide sources, low price and the like, but the conductive coating formed by the traditional carbon filler has generally higher resistivity, and the conductive coating of the graphite powder has conductivity and directivity.
Therefore, providing a composite conductive anticorrosive material that combines conductive, anticorrosive and mechanical properties in order to solve the problems of the prior art is the key point of the research.
Disclosure of Invention
Aiming at the technical problems that in the prior art, the metal filler can aggravate corrosion when the paint is defective, the metal filler is not conductive after oxidation, the conductive coating of the graphite powder has directivity and the like, the invention provides the conductive anti-corrosion composite paint which has conductive, anti-corrosion and excellent mechanical properties, and after being used for a grounding grid, the composite paint can well solve the problem of corrosion protection of the grounding grid, improve the corrosion resistance of the grounding grid material, ensure the stability of the grounding performance, effectively prolong the service life of the grounding grid, ensure the long-term normal operation of power equipment, avoid the occurrence of production accidents, reduce maintenance and transformation cost, and further generate obvious economic and social benefits.
In order to further explain the technical scheme of the invention, the specific contents are as follows:
the invention provides a conductive anti-corrosion composite coating, which comprises the following components in parts by weight: 10-15 parts of aqueous epoxy resin emulsion, 1-5 parts of curing agent, 20-60 parts of water and 20-60 parts of amination modified graphene oxide/acidified carbon nano tube/polyaniline composite material.
Compared with the prior art, the invention provides the conductive anticorrosive composite coating, and the inventor bonds and composites the amination modified graphene oxide with the acidified carbon nano tube and the polyaniline, and effectively improves the dispersion performance, the anticorrosive performance and the conductive performance of the coating by utilizing the synergistic effect of the three materials. The amination modified graphene oxide can effectively improve the shielding performance of the composite coating, effectively block small molecules such as water, oxygen and the like from penetrating, and polyaniline can be used as an effective nano wedge to expand the interlayer spacing of graphene oxide sheets, so that the graphene oxide can be better dispersed in the coating, and the metal surface can be passivated and is not easy to corrode; the carbon nano tube can improve the conductivity of the coating, strengthen the mechanical strength and the corrosion resistance of the coating, and bond polyaniline and amination modified graphene oxide on the surface after acidizing and modifying the coating, so that the problem of poor dispersibility of the carbon nano tube and the polyaniline is solved, and the conductivity of the composite coating is further improved; polyaniline forms in-situ polymerization on the surfaces of the amination modified graphene oxide and the acidified carbon nano tube and uniformly covers the surfaces of the amination modified graphene oxide and the acidified carbon nano tube, so that the polyaniline is prevented from agglomerating, and the corrosion resistance of the polyaniline composite material can be effectively improved. The conductive anticorrosive composite coating prepared by the method utilizes the synergistic effect of the amination modified graphene oxide, the acidified carbon nano tube and the polyaniline, effectively improves the dispersion performance of the coating, greatly improves the anticorrosive performance and the conductive performance of the coating, has excellent mechanical property and longer service life.
Preferably, the curing agent is any one of p-hydroxybenzenesulfonic acid, diethylenetriamine or polyamide resin.
Preferably, the preparation method of the amination modified graphene oxide/acidified carbon nano tube/polyaniline composite material comprises the following steps:
step a, dissolving graphene oxide in dimethylformamide, dispersing uniformly, adding diethylenetriamine, mixing uniformly, reacting at 50-80 ℃, filtering, and drying to obtain amination modified graphene oxide;
step b, dispersing the carbon nano tubes in a mixed acid solution, stirring and reacting at the temperature of 55-75 ℃, adding deionized water after the reaction is finished, filtering, and drying to obtain acidified carbon nano tubes;
c, dispersing the amination modified graphene oxide and the acidification carbon nano tube in deionized water respectively to obtain a modified graphene oxide dispersion liquid and a carbon nano tube dispersion liquid; uniformly mixing the modified graphene oxide dispersion liquid and the carbon nanotube dispersion liquid to obtain a mixed dispersion liquid;
step d, regulating the pH value of the mixed dispersion liquid to be 1-1.5, and adding aniline and (NH) step by step 4 ) 2 S 2 O 8 And (3) reacting the solution at the temperature of 0-5 ℃, filtering and drying after the reaction is finished to obtain the amination modified graphene oxide/acidified carbon nano tube/polyaniline composite material.
Preferably, in the step a, the mass ratio of the graphene oxide to the dimethylformamide is 1:20-30.
Preferably, in the step a, the mass ratio of the graphene oxide to the diethylenetriamine is 1-1.2:25-35.
Preferably, in the step b, the mixed acid solution is concentrated sulfuric acid and concentrated nitric acid with a volume ratio of 2-4:1.
Preferably, in the step b, the mass concentration of the carbon nanotube dispersion liquid is 1.5mg/mL-3mg/mL.
Preferably, in the step b, the volume ratio of the deionized water to the mixed acid solution is 2-5:1.
Preferably, in step b, the particle size of the resulting acidified carbon nanotubes is less than 0.25 μm.
Preferably, in the step c, the mass ratio of the amination modified graphene oxide, the acidification carbon nano tube and the aniline is 1-1.1:2-5:1-1.1.
Preferably, in the step d, the pH is adjusted by adopting a hydrochloric acid solution with the mass concentration of 35-40%.
Preferably, in step d, the (NH 4 ) 2 S 2 O 8 The concentration of the solution is 0.9mol/L to 1.0mol/L.
Preferably, in step d, the aniline is reacted with (NH) 4 ) 2 S 2 O 8 The molar ratio of (2) is 1:1-1.2.
Preferably, in step a, the reaction time is from 10h to 15h.
Preferably, in step b, the reaction time is 3h to 6h.
Preferably, in step d, the reaction time is from 5h to 8h.
The invention provides a preparation method of the conductive anti-corrosion composite coating, which comprises the following steps:
firstly, weighing components except for the amination modified graphene oxide/acidified carbon nano tube/polyaniline composite material according to a designed proportion, and uniformly mixing the weighed components to obtain a first mixture;
and step two, adding the amination modified graphene oxide/acidified carbon nano tube/polyaniline composite material into the first mixture, and uniformly mixing to obtain the conductive anti-corrosion composite coating.
The third aspect of the invention provides a conductive anti-corrosion composite coating, which comprises the conductive anti-corrosion composite coating.
The fourth aspect of the invention provides a preparation method of the conductive anti-corrosion composite coating, comprising the following steps: and coating the conductive anticorrosive composite coating on the surface of a metal matrix, and heating and curing to obtain the conductive anticorrosive composite coating.
Preferably, the metal matrix is any one of Q235 steel or galvanized steel.
Preferably, the thickness of the coating is 0.5mm to 1mm.
Preferably, the temperature of the heat curing is 50 ℃ to 70 ℃.
The conductive anticorrosive composite coating provided by the invention comprises a matrix and a conductive anticorrosive composite coating, wherein the conductive anticorrosive composite coating is prepared by taking epoxy resin emulsion with a dispersion medium being water as film-forming resin and adding assistants such as an amination modified graphene oxide/acidified carbon nano tube/polyaniline composite material, a curing agent and the like. The composite coating has the advantages of conductivity, corrosion resistance and excellent mechanical properties, can well solve the problem of corrosion protection of the grounding grid after being used for the grounding grid, improves the corrosion resistance of the grounding grid material, ensures the stability of the grounding performance, effectively prolongs the service life of the grounding grid, ensures the long-term normal operation of power equipment, avoids production accidents, reduces maintenance and transformation cost, and further generates obvious economic benefit and social benefit.
Drawings
FIG. 1 is a polarization graph of examples 1-3 and comparative examples 1-3;
FIG. 2 shows photographs (500 h) of salt spray tests of example 3 and comparative examples 1 to 4, wherein (a) is example 3, (b) is comparative example 1, (c) is comparative example 2, (d) is comparative example 3, and (e) is comparative example 4.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The embodiment provides a conductive anti-corrosion composite coating, which comprises the following specific contents:
the conductive anticorrosive composite coating comprises a substrate and a conductive anticorrosive composite coating, wherein the conductive anticorrosive composite coating comprises the following components in parts by weight: 10 parts of aqueous epoxy resin emulsion, 3 parts of p-hydroxybenzenesulfonic acid, 40 parts of water and 40 parts of amination modified graphene oxide/acidified carbon nano tube/polyaniline composite material.
Dissolving 1.8g of graphene oxide in 36g of dimethylformamide, carrying out ultrasonic treatment until the graphene oxide is uniformly dispersed, adding 45g of diethylenetriamine, carrying out ultrasonic treatment again for 2 hours to uniformly mix the graphene oxide, reacting for 10 hours at 60 ℃, filtering, and drying a solid filter material at 50 ℃ for 8 hours to obtain the amination modified graphene oxide;
dispersing 0.6g of carbon nano tubes in a mixed acid solution (225 mL of concentrated sulfuric acid and 75mL of concentrated nitric acid), carrying out ultrasonic treatment for 1h to uniformly mix the carbon nano tubes, stirring the mixed acid solution at the temperature of 55 ℃ for 4h, adding 800mL of deionized water for dilution after the reaction is finished, filtering the mixed acid solution by using a polytetrafluoroethylene film with the pore diameter of 0.20 mu m, and drying the solid filter at the temperature of 55 ℃ for 8h to obtain acidified carbon nano tubes;
dispersing 0.8g of the amination modified graphene oxide in 8mL of deionized water, and carrying out ultrasonic treatment for 1h to uniformly disperse the amination modified graphene oxide to obtain modified graphene oxide dispersion liquid; dispersing 1.6g of acidified carbon nano tubes in 35mL of deionized water, carrying out ultrasonic treatment for 1h to uniformly disperse the acidified carbon nano tubes to obtain a carbon nano tube dispersion liquid, and mixing the dispersion liquid to obtain a mixed dispersion liquid;
adding 36% hydrochloric acid solution into the mixed dispersion liquid, regulating the pH value to 1.2, adding 0.8g of aniline into the mixed dispersion liquid at the temperature of 2 ℃, stirring and reacting for 1h, dissolving 2.1g of ammonium persulfate into 10mL of deionized water, adding the same into the mixed dispersion liquid, reacting for 6h at the temperature of 0 ℃, filtering after the reaction is finished, and drying the solid filter material at the temperature of 60 ℃ for 10h to obtain the amination modified graphene oxide/acidified carbon nano tube/polyaniline composite material;
and fifthly, weighing components except the amination modified graphene oxide/acidified carbon nano tube/polyaniline composite material according to a designed proportion, uniformly mixing to obtain a first mixture, adding the amination modified graphene oxide/acidified carbon nano tube/polyaniline composite material into the first mixture, and uniformly mixing to obtain the conductive anti-corrosion composite coating.
And step six, coating the conductive anti-corrosion composite coating on the surface of the metal matrix Q235 steel by using a brush coating method, wherein the thickness of the coating is 0.5mm, and heating and curing the coating at 50 ℃ to obtain the conductive anti-corrosion composite coating.
Example 2
The embodiment provides a conductive anti-corrosion composite coating, which comprises the following specific contents:
the conductive anticorrosive composite coating comprises a substrate and a conductive anticorrosive composite coating, wherein the conductive anticorrosive composite coating comprises the following components in parts by weight: 12 parts of aqueous epoxy resin emulsion, 4 parts of diethylenetriamine, 45 parts of water and 45 parts of amination modified graphene oxide/acidified carbon nano tube/polyaniline composite material.
Dissolving 1.9g of graphene oxide in 40g of dimethylformamide, carrying out ultrasonic treatment until the graphene oxide is uniformly dispersed, adding 50g of diethylenetriamine, carrying out ultrasonic treatment again for 2 hours to uniformly mix the graphene oxide, reacting for 10 hours at 70 ℃, filtering, and drying a solid filter material at 50 ℃ for 8 hours to obtain the amination modified graphene oxide;
dispersing 0.8g of carbon nano tubes in a mixed acid solution (230 mL of concentrated sulfuric acid and 75mL of concentrated nitric acid), carrying out ultrasonic treatment for 1h to uniformly mix the carbon nano tubes, stirring the mixed acid solution at 50 ℃ for reaction for 6h, diluting the mixed acid solution with 750mL of deionized water after the reaction is finished, filtering the mixed acid solution with a polytetrafluoroethylene film with the pore diameter of 0.20 mu m, and drying a solid filter at 60 ℃ for 9h to obtain acidified carbon nano tubes;
dispersing 1g of the amination modified graphene oxide in 10mL of deionized water, and carrying out ultrasonic treatment for 1h to uniformly disperse the amination modified graphene oxide to obtain modified graphene oxide dispersion liquid; dispersing 3g of acidified carbon nano tubes in 40mL of deionized water, carrying out ultrasonic treatment for 1h to uniformly disperse the acidified carbon nano tubes to obtain carbon nano tube dispersion liquid, and mixing the dispersion liquid to obtain mixed dispersion liquid;
adding a hydrochloric acid solution with the mass concentration of 38% into the mixed dispersion liquid, regulating the pH value to 1.2, adding 0.8g of aniline into the mixed dispersion liquid at the temperature of 2 ℃, stirring and reacting for 1h, dissolving 2.2g of ammonium persulfate into 10mL of deionized water, adding the same into the mixed dispersion liquid, reacting for 6h at the temperature of 0 ℃, filtering after the reaction is finished, and drying a solid filter material at the temperature of 65 ℃ for 10h to obtain the amination modified graphene oxide/acidified carbon nano tube/polyaniline composite material;
and fifthly, weighing components except the amination modified graphene oxide/acidified carbon nano tube/polyaniline composite material according to a designed proportion, uniformly mixing to obtain a first mixture, adding the amination modified graphene oxide/acidified carbon nano tube/polyaniline composite material into the first mixture, and uniformly mixing to obtain the conductive anti-corrosion composite coating.
And step six, coating the conductive anti-corrosion composite coating on the surface of the metal matrix Q235 steel by using a brush coating method, wherein the thickness of the coating is 0.7mm, and heating and curing the coating at 55 ℃ to obtain the conductive anti-corrosion composite coating.
Example 3
The embodiment provides a conductive anti-corrosion composite coating, which comprises the following specific contents:
the conductive anticorrosive composite coating comprises a substrate and a conductive anticorrosive composite coating, wherein the conductive anticorrosive composite coating comprises the following components in parts by weight: 15 parts of aqueous epoxy resin emulsion, 4 parts of diethylenetriamine, 40 parts of water and 40 parts of amination modified graphene oxide/acidified carbon nano tube/polyaniline composite material.
Dissolving 2g of graphene oxide in 40g of dimethylformamide, carrying out ultrasonic treatment until the graphene oxide is uniformly dispersed, adding 50g of diethylenetriamine, carrying out ultrasonic treatment again for 2 hours to uniformly mix the graphene oxide, reacting for 10 hours at 75 ℃, filtering, and drying a solid filter material at 55 ℃ for 8 hours to obtain the amination modified graphene oxide;
dispersing 0.8g of carbon nano tubes in a mixed acid solution (250 mL of concentrated sulfuric acid and 75mL of concentrated nitric acid), carrying out ultrasonic treatment for 2 hours to uniformly mix the carbon nano tubes, stirring the mixed acid solution at 65 ℃ for reaction for 5 hours, diluting the mixed acid solution with 800mL of deionized water after the reaction is finished, filtering the mixed acid solution with a polytetrafluoroethylene film with the pore diameter of 0.25 mu m, and drying a solid filter at 55 ℃ for 10 hours to obtain acidified carbon nano tubes;
dispersing 1.2g of the amination modified graphene oxide in 10mL of deionized water, and carrying out ultrasonic treatment for 1h to uniformly disperse the amination modified graphene oxide to obtain modified graphene oxide dispersion liquid; dispersing 4g of acidified carbon nano tubes in 45mL of deionized water, carrying out ultrasonic treatment for 1h to uniformly disperse the acidified carbon nano tubes to obtain carbon nano tube dispersion liquid, and mixing the dispersion liquid to obtain mixed dispersion liquid;
adding a hydrochloric acid solution with the mass concentration of 38% into the mixed dispersion liquid, regulating the pH value to 1.2, adding 1g of aniline into the mixed dispersion liquid at the temperature of 2 ℃, stirring and reacting for 1h, dissolving 2.3g of ammonium persulfate into 11mL of deionized water, adding the same into the mixed dispersion liquid, reacting for 6h at the temperature of 0 ℃, filtering after the reaction is finished, and drying a solid filter material at the temperature of 65 ℃ for 10h to obtain the amination modified graphene oxide/acidified carbon nano tube/polyaniline composite material;
and fifthly, weighing components except the amination modified graphene oxide/acidified carbon nano tube/polyaniline composite material according to a designed proportion, uniformly mixing to obtain a first mixture, adding the amination modified graphene oxide/acidified carbon nano tube/polyaniline composite material into the first mixture, and uniformly mixing to obtain the conductive anti-corrosion composite coating.
And step six, coating the conductive anticorrosive composite coating on the surface of the galvanized steel of the metal matrix by using a brush coating method, wherein the thickness of the coating is 0.7mm, and heating and curing the coating at 60 ℃ to obtain the conductive anticorrosive composite coating.
Comparative example 1
The comparative example provides a conductive and corrosion-resistant composite coating, and the comparative example is different from example 3 in that the amination modified graphene oxide is replaced by graphene oxide with the same mass part, and the specific contents are as follows:
the conductive anticorrosive composite coating comprises a substrate and a conductive anticorrosive composite coating, wherein the conductive anticorrosive composite coating comprises the following components in parts by weight: 15 parts of aqueous epoxy resin emulsion, 4 parts of diethylenetriamine, 40 parts of water and 40 parts of graphene oxide/acidified carbon nano tube/polyaniline composite material.
Dispersing 0.8g of carbon nano tubes in a mixed acid solution (250 mL of concentrated sulfuric acid and 75mL of concentrated nitric acid), carrying out ultrasonic treatment for 2 hours to uniformly mix the carbon nano tubes, stirring the mixed acid solution at 65 ℃ for reaction for 5 hours, diluting the mixed acid solution with 800mL of deionized water after the reaction is finished, filtering the mixed acid solution with a polytetrafluoroethylene film with the pore diameter of 0.25 mu m, and drying a solid filter at 55 ℃ for 10 hours to obtain acidified carbon nano tubes;
dispersing 1.2g of graphene oxide in 10mL of deionized water, and carrying out ultrasonic treatment for 1h to uniformly disperse the graphene oxide to obtain graphene oxide dispersion liquid; dispersing 4g of acidified carbon nano tubes in 45mL of deionized water, carrying out ultrasonic treatment for 1h to uniformly disperse the acidified carbon nano tubes to obtain carbon nano tube dispersion liquid, and mixing the dispersion liquid to obtain mixed dispersion liquid;
adding a hydrochloric acid solution with the mass concentration of 38% into the mixed dispersion liquid, regulating the pH value to 1.2, adding 1g of aniline into the mixed dispersion liquid at the temperature of 2 ℃, stirring and reacting for 1h, dissolving 2.3g of ammonium persulfate into 11mL of deionized water, adding the same into the mixed dispersion liquid, reacting for 6h at the temperature of 0 ℃, filtering after the reaction is finished, and drying a solid filter material at the temperature of 65 ℃ for 10h to obtain the graphene oxide/acidified carbon nano tube/polyaniline composite material;
and step four, weighing components except the graphene oxide/acidified carbon nano tube/polyaniline composite material according to a designed proportion, uniformly mixing to obtain a first mixture, adding the graphene oxide/acidified carbon nano tube/polyaniline composite material into the first mixture, and uniformly mixing to obtain the conductive anticorrosive composite coating.
And fifthly, coating the conductive anti-corrosion composite coating on the surface of the galvanized steel of the metal matrix by using a brush coating method, wherein the thickness of the coating is 0.7mm, and heating and curing the coating at 60 ℃ to obtain the conductive anti-corrosion composite coating.
Comparative example 2
The comparative example provides a conductive corrosion-resistant composite coating, and the comparative example is different from example 3 in that the acidified carbon nanotubes are replaced by the carbon nanotubes with the same mass portion, and the specific contents are as follows:
the conductive anticorrosive composite coating comprises a substrate and a conductive anticorrosive composite coating, wherein the conductive anticorrosive composite coating comprises the following components in parts by weight: 15 parts of aqueous epoxy resin emulsion, 4 parts of diethylenetriamine, 40 parts of water and 40 parts of amination modified graphene oxide/carbon nano tube/polyaniline composite material.
Dissolving 2g of graphene oxide in 40g of dimethylformamide, carrying out ultrasonic treatment until the graphene oxide is uniformly dispersed, adding 50g of diethylenetriamine, carrying out ultrasonic treatment again for 2 hours to uniformly mix the graphene oxide, reacting for 10 hours at 75 ℃, filtering, and drying a solid filter material at 55 ℃ for 8 hours to obtain the amination modified graphene oxide;
dispersing 1.2g of the amination modified graphene oxide in 10mL of deionized water, and carrying out ultrasonic treatment for 1h to uniformly disperse the amination modified graphene oxide to obtain modified graphene oxide dispersion liquid; dispersing 4g of carbon nano tubes in 45mL of deionized water, carrying out ultrasonic treatment for 1h to uniformly disperse the carbon nano tubes to obtain carbon nano tube dispersion liquid, and mixing the dispersion liquid to obtain mixed dispersion liquid;
adding a hydrochloric acid solution with the mass concentration of 38% into the mixed dispersion liquid, regulating the pH value to 1.2, adding 1g of aniline into the mixed dispersion liquid at the temperature of 2 ℃, stirring and reacting for 1h, dissolving 2.3g of ammonium persulfate into 11mL of deionized water, adding the same into the mixed dispersion liquid, reacting for 6h at the temperature of 0 ℃, filtering after the reaction is finished, and drying a solid filter material at the temperature of 65 ℃ for 10h to obtain the amination modified graphene oxide/carbon nano tube/polyaniline composite material;
and fifthly, weighing components except the amination modified graphene oxide/carbon nano tube/polyaniline composite material according to a designed proportion, uniformly mixing to obtain a first mixture, adding the amination modified graphene oxide/carbon nano tube/polyaniline composite material into the first mixture, and uniformly mixing to obtain the conductive anticorrosive composite coating.
And step six, coating the conductive anticorrosive composite coating on the surface of the galvanized steel of the metal matrix by using a brush coating method, wherein the thickness of the coating is 0.7mm, and heating and curing the coating at 60 ℃ to obtain the conductive anticorrosive composite coating.
Comparative example 3
The comparative example provides a conductive corrosion-resistant composite coating, and the comparative example is different from the example 3 in that the amination modified graphene oxide/acidified carbon nano tube/polyaniline composite material is replaced by the amination modified graphene oxide/acidified carbon nano tube composite material with the same mass portion, and the specific contents are as follows:
the conductive anticorrosive composite coating comprises a substrate and a conductive anticorrosive composite coating, wherein the conductive anticorrosive composite coating comprises the following components in parts by weight: 15 parts of aqueous epoxy resin emulsion, 4 parts of diethylenetriamine, 40 parts of water and 40 parts of amination modified graphene oxide/acidified carbon nano tube composite material.
Dissolving 2g of graphene oxide in 40g of dimethylformamide, carrying out ultrasonic treatment until the graphene oxide is uniformly dispersed, adding 50g of diethylenetriamine, carrying out ultrasonic treatment again for 2 hours to uniformly mix the graphene oxide, reacting for 10 hours at 75 ℃, filtering, and drying a solid filter material at 55 ℃ for 8 hours to obtain amino modified graphene oxide;
dispersing 0.8g of carbon nano tubes in a mixed acid solution (250 mL of concentrated sulfuric acid and 75mL of concentrated nitric acid), carrying out ultrasonic treatment for 2 hours to uniformly mix the carbon nano tubes, stirring the mixed acid solution at 65 ℃ for reaction for 5 hours, diluting the mixed acid solution with 800mL of deionized water after the reaction is finished, filtering the mixed acid solution with a polytetrafluoroethylene film with the pore diameter of 0.25 mu m, and drying a solid filter at 55 ℃ for 10 hours to obtain acidified carbon nano tubes;
dispersing 1.2g of the amination modified graphene oxide in 10mL of deionized water, and carrying out ultrasonic treatment for 1h to uniformly disperse the amination modified graphene oxide to obtain modified graphene oxide dispersion liquid; dispersing 4g of acidified carbon nano tubes in 45mL of deionized water, carrying out ultrasonic treatment for 1h to uniformly disperse the acidified carbon nano tubes to obtain carbon nano tube dispersion liquid, and mixing the dispersion liquid to obtain an amination modified graphene oxide/acidified carbon nano tube composite material;
and step four, weighing components except the amination modified graphene oxide/acidified carbon nano tube composite material according to a designed proportion, uniformly mixing to obtain a first mixture, adding the amination modified graphene oxide/acidified carbon nano tube composite material into the first mixture, and uniformly mixing to obtain the conductive anticorrosive composite coating.
And fifthly, coating the conductive anti-corrosion composite coating on the surface of the galvanized steel of the metal matrix by using a brush coating method, wherein the thickness of the coating is 0.7mm, and heating and curing the coating at 60 ℃ to obtain the conductive anti-corrosion composite coating.
Comparative example 4
The comparative example provides a coating prepared from a coating of a commercially available aqueous epoxy resin emulsion (model BSE 7001), which comprises the following specific contents:
the preparation method comprises the steps of weighing BSE7001 aqueous epoxy resin emulsion, diethylenetriamine and water according to the design proportion of the embodiment 3, uniformly mixing to obtain mixed emulsion, coating the mixed emulsion on the surface of the galvanized steel of the metal substrate by using a brush coating method, wherein the coating thickness is 0.8mm, and heating and curing at 50 ℃ to obtain the conductive anti-corrosion composite coating.
Performance testing
To further illustrate the technical effect of the present invention, the conductive corrosion protection composite coatings provided in examples 1-3 and comparative examples 1-3 (wherein the salt spray test is the sample provided in example 3 and comparative examples 1-4) were tested as follows:
(1) Polarization curve: polarization curve determination using electrochemical workstation (model: interface 1000) with three electrode arrangement. Wherein the three-electrode system is a carbon steel test piece coated by the prepared composite coating (the exposed surface area of the test piece is 1 cm) by taking an Ag/AgCl electrode as a reference electrode, a Pt electrode as an auxiliary electrode and a working electrode 2 ) The experimental medium was an aqueous solution of NaCl at 3.5% by mass and the scan rate was 0.5mV/s, and the results are shown in Table 1 and FIG. 1.
(2) Volume resistivity: according to the specification of the electric power industry standard of the people's republic of China, namely the technical condition of the conductive anti-corrosion coating for electric power engineering grounding, the volume resistivity of the coating is measured according to the in-line four-probe method in the standard GB/T1551-2009. And taking the conductive anticorrosive paint for grounding, and carrying out cubic forming of the coating blocks according to the coating process requirement. The sample specification is that the dimension in any direction is not less than 3cm, the volume is not less than 125cm, and the number of the samples is 3. The test was performed at room temperature using a four-probe nonmetallic resistivity tester with a probe pitch of 1mm in the center area of the sample surface. The average value of 3 samples was used as the room temperature resistivity of the conductive anticorrosive paint for grounding, and the results are shown in table 2.
(3) Adhesion measurement: the adhesion of the composite coating was determined by the cross-hatch test of paint and varnish according to GB/T9286-1998, the cross-hatch test of paint film of paint and varnish, and the results are shown in Table 2.
(4) Hardness measurement: the pencil hardness of the coating was measured by a pencil hardness tester according to GB/T6739-2006, paint film hardness measured by the paint and varnish pencil method, and the results are shown in Table 2.
(5) Flexibility measurement: according to GB/T6742-2007 color paint and varnish bending test: the cylindrical axis specifies the flexibility of the coating as measured by a bending tester, and the results are shown in Table 2.
(6) Salt spray test: the salt spray resistance of the composite coating was tested in a salt spray test box according to GB/T1771-2007 determination of neutral salt spray resistance of paints and varnishes, and the results are shown in FIG. 2.
TABLE 1 polarization curve fitting data for conductive corrosion resistant composite coatings provided in examples 1-3 and comparative examples 1-3
| Project | I corr (A/cm 2 ) | E(V) | C R (mm/year) | R P (Ω) |
| Example 1 | 3.78×10 -8 | -0.356 | 2.92×10 -4 | 1.71×10 7 |
| Example 2 | 1.38×10 -8 | -0.321 | 1.67×10 -4 | 4.60×10 7 |
| Example 3 | 1.30×10 -8 | -0.306 | 1.01×10 -4 | 7.75×10 7 |
| Comparative example 1 | 1.41×10 -7 | -0.596 | 1.09×10 -3 | 9.63×10 6 |
| Comparative example 2 | 1.18×10 -7 | -0.556 | 9.13×10 -4 | 5.24×10 6 |
| Comparative example 3 | 8.76×10 -7 | -1.310 | 2.32×10 -2 | 2.74×10 5 |
I in Table 1 corr (A/cm 2 ) For corrosion current density, E (V) is corrosion potential, C R (mm/year) is the corrosion rate, R P (Ω) is polarization resistance. As can be seen from Table 1 and FIG. 1, compared with comparative examples 1-3, the conductive anticorrosive composite coating provided in examples 1-3 has reduced corrosion current density and corrosion rate, increased corrosion potential and polarization resistance, and shows that the aminated modified graphene oxide/acidified carbon nanotube bonded composite polyaniline ternary composite conductive anticorrosive coating provided by the invention has better protection effect on metals. The corrosion current density of examples 1-3 was reduced by 1 order of magnitude compared to comparative examples 1-3, and correspondingly, the corrosion rate was also reduced by 1-2 orders of magnitude. The conductive corrosion-resistant composite coating provided by the invention can be proved to be capable of more effectively delaying the corrosion of metal. And, according to the calculation, the polarization resistance R of the conductive anti-corrosion composite coating provided in the embodiment 3 is obtained p Is 7.75X10 7 Ω·cm 2 While the polarization resistance R of the conductive anticorrosive composite coating provided in comparative example 3 p Is 2.7X10 5 Ω·cm 2 Indicating that the amination is modified to be graphene/carbon nano tubeCompared with the amination modified graphene/carbon nano tube composite material, the polyaniline composite material has more excellent performance, and the polarization resistance of the polyaniline composite material is increased by 282 times due to the fact that the modified bonding composite polyaniline, so that the corrosion resistance of the composite epoxy coating is obviously enhanced.
TABLE 2 volume resistivity and mechanical property test data for the conductive corrosion resistant composite coatings provided in examples 1-3 and comparative examples 1-3
Table 2 shows the volume resistivity and mechanical property test data of the conductive corrosion-resistant composite coatings provided in examples 1-3 and comparative examples 1-3. It can be seen that the acidified carbon nanotubes and the modified graphene in the conductive anti-corrosion composite coating provided in the comparative example 3 can reduce the volume resistivity of the composite coating, while the volume resistivity of the conductive anti-corrosion composite coating provided in the comparative examples 1 and 2 is increased after the carbon nanotubes and the graphene are not modified and the polyaniline is compounded, on one hand, the carbon nanotubes and the graphene are not modified, the conductivity is relatively weak, and on the other hand, the polyaniline is used as a conductive polymer material, is easy to agglomerate, and the conductivity is also weak compared with the carbon nanotubes and the graphene. According to the embodiment of the invention, graphene is modified, the carbon nano tube is acidified, and then the composite polyaniline is bonded to obtain the conductive anti-corrosion composite coating, so that not only is the dispersibility of polyaniline improved, but also the anti-corrosion performance of the composite coating is improved, and the exertion of the conductive performance of the acidified carbon nano tube and the modified graphene is ensured, so that the volume resistivity of the composite coating is reduced, the comprehensive performance is improved, and the technical requirements of the conductive anti-corrosion material for grounding are met.
In addition, the conductive and corrosion-resistant composite coating provided by the embodiments 1-3 of the invention ensures that the conductive and corrosion-resistant properties are improved and simultaneously gives consideration to the mechanical properties of the composite coating. The addition of graphene oxide, carbon nanotubes and polyaniline can increase the hardness of the composite material, but too high a hardness can affect the flexibility of the composite material. Polyaniline has inductive coupling effect with metal surface, but polyaniline is easy to agglomerate to influence the performance. The amination modified graphene oxide/acidified carbon nano tube/polyaniline composite material is well dispersed in epoxy resin emulsion, so that the adhesive force of the conductive anti-corrosion composite coating is improved to 0 level, the hardness is kept at 2H, the flexibility reaches 5mm, and the requirements of power construction application are met.
Fig. 2 is a photograph of a salt spray test 500h of the composite coatings provided in example 3 and comparative examples 1-4. In order to observe the metal corrosion diffusion under the coating, scratch treatment is carried out on the surface of the coating. At 500h of salt spray test, the coating of comparative example 4 had very severe corrosion diffusion and the coating had substantially lost its protective effect. The coating of comparative example 3, after being added with the amination modified graphene oxide and the acidification carbon nano tube, plays a role in blocking, so that corrosive medium and corrosive ion penetrating coating are prevented from reaching the metal surface to a certain extent, the protective performance is improved, and the composite coating of comparative example 1 and comparative example 2 further improves the corrosion resistance due to the passivation effect of polyaniline on the metal surface. The composite coating provided by the embodiment 3 of the invention fully plays the synergistic effect of the modified graphene, the acidified carbon nano tube and the bonded polyaniline, enhances the barrier, conductive and passivation properties of the composite coating, and only slightly corrodes the scratch part when a salt spray test is carried out for 500 hours, so that the metal is protected for a long time.
Claims (9)
1. The conductive anticorrosive composite paint is characterized in that: comprises the following components in parts by weight: 10-15 parts of aqueous epoxy resin emulsion, 1-5 parts of curing agent, 20-60 parts of water and 20-60 parts of amination modified graphene oxide/acidified carbon nano tube/polyaniline composite material;
the preparation method of the amination modified graphene oxide/acidified carbon nano tube/polyaniline composite material comprises the following steps:
step a, dissolving graphene oxide in dimethylformamide, dispersing uniformly, adding diethylenetriamine, mixing uniformly, reacting at 50-80 ℃, filtering, and drying to obtain amination modified graphene oxide;
step b, dispersing the carbon nano tubes in a mixed acid solution, stirring and reacting at the temperature of 55-75 ℃, adding deionized water after the reaction is finished, filtering, and drying to obtain acidified carbon nano tubes;
c, dispersing the amination modified graphene oxide and the acidification carbon nano tube in deionized water respectively to obtain a modified graphene oxide dispersion liquid and a carbon nano tube dispersion liquid; uniformly mixing the modified graphene oxide dispersion liquid and the carbon nanotube dispersion liquid to obtain a mixed dispersion liquid;
step d, regulating the pH value of the mixed dispersion liquid to be 1-1.5, and adding aniline and (NH) step by step 4 ) 2 S 2 O 8 And (3) reacting the solution at the temperature of 0-5 ℃, filtering and drying after the reaction is finished to obtain the amination modified graphene oxide/acidified carbon nano tube/polyaniline composite material.
2. The conductive corrosion resistant composite coating of claim 1, wherein: the curing agent is any one of p-hydroxybenzenesulfonic acid, diethylenetriamine or polyamide resin.
3. The conductive corrosion resistant composite coating of claim 1, wherein: in the step a, the mass ratio of the graphene oxide to the dimethylformamide is 1:20-30; and/or
In the step a, the mass ratio of the graphene oxide to the diethylenetriamine is 1-1.2:25-35; and/or
In the step b, the mixed acid solution is concentrated sulfuric acid and concentrated nitric acid with the volume ratio of 2-4:1; and/or
In the step b, the mass concentration of the carbon nanotube dispersion liquid is 1.5mg/mL-3mg/mL.
4. The conductive corrosion resistant composite coating of claim 1, wherein: in the step b, the volume ratio of the deionized water to the mixed acid solution is 2-5:1; and/or
In the step b, the particle size of the obtained acidified carbon nanotubes is less than 0.25 mu m; and/or
In the step c, the mass ratio of the amination modified graphene oxide, the acidification carbon nano tube and the aniline is 1-1.1:2-5:1-1.1; and/or
In step d, the (NH) 4 ) 2 S 2 O 8 The concentration of the solution is 0.9mol/L-1.0mol/L; and/or
In step d, the aniline is reacted with (NH) 4 ) 2 S 2 O 8 The molar ratio of (2) is 1:1-1.2.
5. The conductive corrosion resistant composite coating of claim 1, wherein: in the step a, the reaction time is 10-15 h; and/or
In the step b, the reaction time is 3-6 h; and/or
In step d, the reaction time is 5-8 h.
6. The method for preparing the conductive anticorrosive composite coating according to any one of claims 1 to 5, which is characterized in that: the method comprises the following steps:
firstly, weighing components except for the amination modified graphene oxide/acidified carbon nano tube/polyaniline composite material according to a designed proportion, and uniformly mixing the weighed components to obtain a first mixture;
and step two, adding the amination modified graphene oxide/acidified carbon nano tube/polyaniline composite material into the first mixture, and uniformly mixing to obtain the conductive anti-corrosion composite coating.
7. The utility model provides a conductive anticorrosive composite coating which characterized in that: a conductive corrosion resistant composite coating comprising any one of claims 1-5.
8. The method for preparing the conductive anti-corrosion composite coating according to claim 7, which is characterized in that: the method comprises the following steps: and coating the conductive anticorrosive composite coating on the surface of a metal matrix, and heating and curing to obtain the conductive anticorrosive composite coating.
9. The method for preparing the conductive anti-corrosion composite coating according to claim 8, wherein: the metal matrix is any one of Q235 steel or galvanized steel; and/or
The thickness of the coating is 0.5mm-1mm.
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