CN112375459A - Graphene/water-based epoxy zinc-rich coating with high corrosion resistance and strong adhesive force and preparation method thereof - Google Patents
Graphene/water-based epoxy zinc-rich coating with high corrosion resistance and strong adhesive force and preparation method thereof Download PDFInfo
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- CN112375459A CN112375459A CN202011318093.4A CN202011318093A CN112375459A CN 112375459 A CN112375459 A CN 112375459A CN 202011318093 A CN202011318093 A CN 202011318093A CN 112375459 A CN112375459 A CN 112375459A
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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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- 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
- C09D5/10—Anti-corrosive paints containing metal dust
- C09D5/106—Anti-corrosive paints containing metal dust containing Zn
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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
- C09D7/60—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
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0893—Zinc
Abstract
The invention discloses a high-corrosion-resistance and strong-adhesion graphene/water-based epoxy zinc-rich coating which is composed of a component A and a component B, wherein the component A comprises the following components in parts by mass: 0.3-1.5 parts of modified graphene, 5-25 parts of deionized water, 20-75 parts of waterborne epoxy resin and 0.3-1 part of a base material wetting agent, wherein the component B comprises the following components in parts by mass: 40-70 parts of zinc powder, 15-30 parts of ethylene glycol monobutyl ether and 10-25 parts of water-based epoxy resin curing agent; the high-corrosion-resistance and strong-adhesion graphene/water-based epoxy zinc-rich coating takes graphene oxide as a precursor, the graphene oxide is grafted and reduced by adopting polyethyleneimine, the graphene oxide and the water-based epoxy resin are uniformly and alternately combined to a uniform system through stirring and shearing actions, and the high-corrosion-resistance and strong-adhesion anticorrosive coating is obtained by further stirring the graphene oxide/water-based epoxy zinc-rich coating with zinc powder and ethylene glycol monobutyl ether mixed in a water-based epoxy resin curing agent component.
Description
Technical Field
The invention relates to the technical field of cosmetics, in particular to a graphene/water-based epoxy zinc-rich coating with high corrosion resistance and strong adhesive force and a preparation method thereof.
Background
Corrosion is a common problem of metal materials, which not only causes huge resource consumption and aggravates environmental pollution, but also causes personnel safety problems due to structural damage, and causes huge social and economic losses. The coating is one of the important means for preventing corrosion of steel. Unlike conventional coatings, zinc-rich coatings provide effective cathodic protection for steel substrates even in the presence of minor mechanical damage, and are therefore widely used in marine, industrial, and other heavy-duty corrosive environments. The water-based zinc-rich paint has good development prospect because no toxic and harmful waste water and waste gas are discharged in the coating process. To ensure that the zinc-rich coating provides excellent cathodic protection, the dry film zinc content of the coating is often as high as 80 wt.% or more to ensure that the zinc powder particles complete an electron transport circuit with each other and with the metal substrate. However, high zinc powder content results in increased porosity of the coating after spraying, poor flatness and poor adhesion to the metal substrate.
The graphene is a monoatomic layer of graphite flakes having a structure represented by sp2The hybridized carbon atoms are arranged closely to form a two-dimensional honeycomb crystal structure. The zinc-rich coating has excellent optical, mechanical, electrical and thermal properties, and has large specific surface area and impermeability, so that the zinc-rich coating is considered to be a novel two-dimensional nano material which can replace part of zinc powder and improve the corrosion resistance of the zinc-rich coating. However, graphene is very prone to agglomeration due to its high specific surface area and strong van der waals forces between its layers. In addition, graphene as an inert material has limited compatibility with aqueous organic resins, which greatly limits the application of graphene in aqueous organic zinc-rich coatings. Therefore, the compatibility of graphene in aqueous organic resin is improved, the graphene is uniformly dispersed in the resin, and the method has great practical benefits for improving the comprehensive performance of the graphene on a zinc-rich coating, particularly improving the cathode protection performance of zinc powder particles.
Disclosure of Invention
In order to overcome the existing problems, the invention aims to provide the graphene/water-based epoxy zinc-rich anticorrosive paint which has the properties of good stability, high corrosion resistance, strong adhesion and the like.
The technical scheme of the invention is as follows:
the graphene/water-based epoxy zinc-rich coating with high corrosion resistance and strong adhesive force is composed of a component A and a component B, wherein the component A comprises the following components in parts by mass: 0.3-1.5 parts of modified graphene, 5-25 parts of deionized water, 20-75 parts of water-based epoxy resin and 0.3-1 part of a base material wetting agent, wherein the modified graphene is polymer-grafted graphene oxide obtained by grafting and reducing graphene oxide by polyethyleneimine in an alkaline environment, and the component B comprises the following components in parts by mass: 40-70 parts of zinc powder, 15-30 parts of ethylene glycol monobutyl ether and 10-25 parts of water-based epoxy resin curing agent.
A preparation method of a graphene/water-based epoxy zinc-rich coating with high corrosion resistance and strong adhesive force comprises the following steps:
(2) dispersing 1-5 parts of graphene oxide in 1000 parts of deionized water by mass, adjusting the pH value to be alkaline, adding 3-12 parts of polyethyleneimine, heating to 60-80 ℃, stirring and reacting for 2-6h, after the reaction is finished, performing suction filtration, washing and drying by using deionized water to obtain the graphene oxide grafted and reduced by the polyethyleneimine, namely modified graphene;
(2) dispersing 0.3-1.5 parts by mass of the modified graphene obtained in the step (1) into 5-25 parts by mass of deionized water, and stirring and mixing with 20-75 parts by mass of waterborne epoxy resin and 0.3-1 part by mass of a base material wetting agent to obtain a coating A component;
(3) according to the mass parts, 40-70 parts of zinc powder, 15-30 parts of ethylene glycol monobutyl ether and 10-25 parts of waterborne epoxy resin curing agent are stirred and mixed to be used as a coating B component; and finally, stirring, mixing and dispersing the components A and B uniformly to obtain the graphene/water-based epoxy zinc-rich coating with high corrosion resistance and strong adhesive force.
Preferably, the graphene oxide is single-layer or multi-layer graphene oxide prepared by a modified Hummers method; the surface of the graphene oxide contains a large number of oxygen-containing functional groups such as epoxy groups, hydroxyl groups, carboxyl groups and the like;
preferably, the dispersion mode of dispersing 0.3-1.5 parts of modified graphene in 300-1000 parts of deionized water is ultrasonic dispersion, and the dispersion time is 1 h.
Preferably, the pH is adjusted to be alkaline, wherein the alkaline value is 8-12.
Preferably, the polyethyleneimine has the structure:
when the value of n is too small, the steric hindrance effect of polyethyleneimine is not strong after the polyethyleneimine is grafted on the graphene oxide, so that van der waals force between graphene sheet layers cannot be effectively prevented, and the dispersibility of the modified graphene in the aqueous resin is not high, which is not beneficial to the improvement of the coating performance; when the value of n is too large, the molecular weight of polyethyleneimine is too large, and due to too large steric hindrance, the polyethyleneimine cannot be effectively grafted to graphene oxide, so that the modified graphene is not high in dispersibility in water-based resin and is not beneficial to the improvement of the performance of the coating; in addition, polyethyleneimine is originally a non-conductive high polymer material, and polyethyleneimine with an excessively large molecular weight is added, so that the conductivity of modified graphene is not facilitated, and the improvement of the cathode protection performance of zinc powder is not facilitated. Preferably, the value of n is preferably between 400 and 600, and at this time, the steric hindrance of the polyethyleneimine is optimal, so that the polyethyleneimine can be effectively grafted to the surface of the graphene oxide and can also block van der waals force between graphene sheet layers, so that the modified graphene is fully dispersed in the aqueous resin, and the conductivity of the modified graphene can be effectively retained, thereby facilitating the improvement of the performance of the coating.
Preferably, the mixture is stirred and mixed with 20-60 parts of the waterborne epoxy resin and 0.3-1 part of the base material wetting agent, and the stirring speed is 500-1200 rev/min.
Preferably, the zinc powder is in the shape of a flake or a sphere.
Preferably, 40-70 parts of zinc powder, 15-30 parts of ethylene glycol monobutyl ether and 10-25 parts of waterborne epoxy resin curing agent are stirred and mixed to form the coating B component, and the stirring speed is 3000-6000 rev/min.
Preferably, the waterborne epoxy resin comprises at least one of bisphenol A waterborne epoxy resin, and the waterborne epoxy resin curing agent is selected from at least one of polyamide or phenolic aldehyde amine or cardanol waterborne epoxy resin curing agent.
Preferably, the substrate wetting agent is selected from one of TEGO Twin 4100 or SURFYNOL 104E, TEGO Twin 4100 is a silicone gemini surfactant, and SURFYNOL 104E is an acetylenic diol Germini nonionic surfactant.
Compared with the prior art, the invention has the following beneficial effects:
(1) the modified graphene of the graphene/water-based epoxy zinc-rich coating with high corrosion resistance and strong adhesive force has good compatibility with water-based epoxy resin, and the coating does not generate a layering phenomenon after standing for 30 days; the adhesive force of a coating prepared by the coating reaches 0 level; after 7 days of salt fog with 5% NaCl solution, the red rust at the scratch is less compared with the coating without the added graphene oxide; the coating is soaked in NaCl solution with the mass concentration of 3.5% for 66 days, the impedance value of the coating is 4 orders of magnitude higher than that of the coating without the modified graphene, and the coating shows excellent corrosion resistance.
(2) The selected polyethyleneimine is a water-soluble high-molecular polymer with a large amount of-NH on the surface2The amino group of the polyethyleneimine is mainly bonded with carboxyl on the surface of the graphene oxide to form an amido bond, and the huge steric hindrance of the amido bond can effectively prevent the graphene from agglomerating due to van der Waals force, so that the graphene oxide can be better dispersed in the aqueous epoxy resin; meanwhile, the polyethyleneimine is used as a reducing agent to reduce redundant oxygen-containing functional groups on the graphene oxide, so that the graphene oxide recovers the conductivity, and therefore, the graphene oxide with good conductivity is uniformly dispersed in the coating, stacked layer by layer and combined in the pores of the coating network structure in an interpenetration manner to form a uniform and compact conductive network structure, which is beneficial to improving the cathode protection performance of the zinc powder; on the other hand, the redundant-NH 2 of the polyethyleneimine can be in cross-linking combination with the oxygen-containing functional group of the waterborne epoxy resin, so that the polyethyleneimine, the graphene oxide and the waterborne epoxy resin are combined into a whole, the compactness of the coating is effectively improved, and the corrosion resistance and the adhesive force of the coating are further improved.
(3) The preparation method of the anticorrosive coating is simple and convenient, graphene oxide is used as a precursor, polyethyleneimine is used for grafting modification in an alkaline environment, the polyethyleneimine is used as a reducing agent to reduce redundant oxygen-containing functional groups on the graphene oxide to obtain the polyethyleneimine grafted reduced graphene oxide, namely modified graphene, the modified graphene is uniformly and alternately combined into aqueous epoxy resin through stirring and shearing effects to achieve a uniform system, and the modified graphene is further stirred with an aqueous epoxy resin curing agent component mixed with zinc powder and ethylene glycol monobutyl ether to prepare the anticorrosive coating with high corrosion resistance and strong adhesive force.
Drawings
FIG. 1 is a digital photograph of a coating A prepared in example 1 and comparative example 1 after being left for 15 days;
FIG. 2 is a Nyquist plot of the coatings prepared in example 1 and comparative example 1 after 66 days of 3.5% NaCl immersion.
FIG. 3 is a macroscopic surface view of the scratched neutral salt spray coating prepared in example 1 and comparative example 1 for 7 days.
Detailed Description
In order that the invention may be more fully understood, reference is now made to the following examples. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. These embodiments are provided so that this disclosure will be thorough and complete.
Example 1
(1) Dispersing 1 part of graphene oxide in 300 parts of deionized water by mass, ultrasonically dispersing for 1h, adjusting the pH value to 8, adding 3 parts of polyethyleneimine with the n value of 50, heating to 60 ℃, stirring for reaction for 2h, after the reaction is finished, performing suction filtration by using deionized water, washing, and drying to obtain the polyethyleneimine grafted reduced graphene oxide, hereinafter referred to as modified graphene.
(2) And (2) dispersing 0.6 part by mass of the modified graphene obtained in the step (1) into 5 parts by mass of deionized water, adding 30 parts by mass of Vast waterborne epoxy resin 6520 and 0.3 part by mass of TEGO Twin 4100, and stirring for 15min at a speed of 500rev/min to obtain a coating A component.
(3) In parts by mass, 40 parts of zinc powder, 15 parts of ethylene glycol monobutyl ether and 10 parts of a Vast waterborne epoxy resin curing agent 8538 are stirred for 30min through 4000rev/min and are uniformly mixed to be used as a coating B component; when in use, the mixture is stirred for 15min and uniformly mixed by adopting 500 rev/min; and finally, stirring, mixing and dispersing the coating A component and the coating B component uniformly to obtain the coating 1.
Example 2
(1) Dispersing 1 part of graphene oxide in 500 parts of deionized water by mass, ultrasonically dispersing for 1h, adjusting the pH value to 8, adding 3 parts of polyethyleneimine with the n value of 500, heating to 60 ℃, and stirring for reacting for 2 h. And after the reaction is finished, performing suction filtration by using deionized water, washing and drying to obtain the polyethyleneimine grafted reduced graphene oxide, which is hereinafter referred to as modified graphene.
(2) Dispersing 0.6 part of the modified graphene obtained in the step (1) into 5 parts of deionized water in parts by mass, adding 6520 parts of water-based epoxy resin and 0.3 part of SURFYNOL 104E, and stirring for 15min at 800rev/min to obtain a coating A component.
(3) According to the mass parts, 40 parts of zinc powder, 15 parts of ethylene glycol monobutyl ether and 10 parts of waterborne epoxy resin curing agent 6870 are stirred for 30min through 6000rev/min and are uniformly mixed to serve as a coating B component; when in use, the mixture is stirred for 15min and uniformly mixed by adopting 800 rev/min; and finally, stirring, mixing and dispersing the coating A component and the coating B component uniformly to obtain the coating 2.
Example 3
(1) Dispersing 3 parts of graphene oxide in 800 parts of deionized water by mass, ultrasonically dispersing for 1h, adjusting the pH value to 9, adding 8 parts of polyethyleneimine with the n value of 600, heating to 70 ℃, and stirring for reacting for 4 h. And after the reaction is finished, performing suction filtration by using deionized water, washing and drying to obtain the polyethyleneimine grafted reduced graphene oxide, which is hereinafter referred to as modified graphene.
(2) Dispersing 1.5 parts by mass of the modified graphene obtained in the step (1) into 25 parts by mass of deionized water, adding 75 parts by mass of waterborne epoxy resin 3540 and 0.3 part by mass of TEGO Twin 4100, and stirring for 15min at a speed of 500rev/min to obtain a coating A component.
(3) By mass, 60 parts of zinc powder, 25 parts of ethylene glycol monobutyl ether and 25 parts of waterborne epoxy resin curing agent 8538 are mixed. Stirring for 30min and uniformly mixing at 6000rev/min to obtain a component B of the coating; when in use, the mixture is stirred for 15min and uniformly mixed by adopting 800 rev/min; and finally, stirring, mixing and dispersing the coating A component and the coating B component uniformly to obtain the coating 3.
Example 4
(1) Dispersing 3 parts of graphene oxide in 800 parts of deionized water by mass, ultrasonically dispersing for 1h, adjusting the pH value to 9, adding 8 parts of polyethyleneimine with the n value of 1000, heating to 80 ℃, and stirring for reacting for 4 h. And after the reaction is finished, performing suction filtration by using deionized water, washing and drying to obtain the polyethyleneimine grafted reduced graphene oxide, which is hereinafter referred to as modified graphene.
(2) Dispersing 1 part of modified graphene obtained in the step (1) into 20 parts of deionized water, adding 60 parts of water-based epoxy resin 6520 and 1 part of TEGO Twin 4100, and stirring for 15min at a speed of 500rev/min to obtain a coating A component.
(3) 50 parts of zinc powder, 20 parts of ethylene glycol monobutyl ether and 15 parts of waterborne epoxy resin curing agent 6870 are uniformly mixed by stirring for 30min at 4000rev/min to serve as a coating B component; when in use, the mixture is stirred for 15min and uniformly mixed by adopting 500 rev/min; and finally, stirring, mixing and dispersing the coating A component and the coating B component uniformly to obtain the coating 4.
The paint A component and the paint B component in the embodiments 1 to 4 of the invention are mixed according to the mass ratio of 1: 1, the coating prepared by the mass ratio has the best film-forming property.
Comparative example 1
Comparative example 1 differs from example 1 in that: the method for grafting and reducing graphene oxide without adding polyethyleneimine comprises the following steps
(1) Taking 30 parts by mass of Vast waterborne epoxy resin 6520 and 0.3 part by mass of TEGO Twin 4100, and stirring for 15min at 500rev/min to obtain a coating A component.
(2) In parts by mass, 40 parts of zinc powder, 15 parts of ethylene glycol monobutyl ether and 10 parts of a Vast waterborne epoxy resin curing agent 8538 are stirred for 30min through 4000rev/min and are uniformly mixed to be used as a coating B component; when in use, the A, B components are stirred for 15min and mixed evenly by adopting 500rev/min to obtain the comparative paint.
The anticorrosive coatings obtained in the above examples and comparative examples were subjected to the following performance tests:
and (3) testing the adhesive force: a check test was performed on the surface of the coating using a hundred check knife to characterize the adhesion of the coating in accordance with GB/T9286-1998 requirements.
EIS test: a three-electrode system is adopted, and a coating is taken as a working electrode (the working area is 9 cm)2) The saturated calomel electrode is used as a reference electrode, the platinum electrode is used as an auxiliary electrode, the solution is 3.5 percent NaCl solution, and the frequency range is as follows: 0.01-100000 Hz; the amplitude was 15 mV.
And (3) salt spray testing: according to the requirements of GB 10125-1997. An "X" mark was left on the coating tested and the panel was placed in a salt spray cabinet at a temperature of (35. + -. 2 ℃ C.) and a spray rate of 1mL/(80 cm)2) The corrosion solution is 5% NaCl solution, and salt spray is continuously carried out day and night.
The compatibility and the dispersion performance of the modified graphene prepared by the invention and the waterborne epoxy resin are represented by a sedimentation test. As can be seen from fig. 1, after standing for 15 days, example 1 has changed to a uniform black color, while comparative example 1 still maintains a milky white color, which indicates that the polyethyleneimine-grafted modified reduced graphene oxide has been reduced, and in addition, the polyethyleneimine-grafted modified reduced graphene oxide has good compatibility with the aqueous epoxy resin, and can be uniformly dispersed in the aqueous epoxy resin, and after standing for 15 days, no delamination still occurs in example 1.
The adhesion of the coatings prepared in the examples and comparative examples was characterized by an adhesion test. The test results show that the adhesion of the coating coatings prepared in examples 1-4 with the modified graphene is kept at 0 level. The adhesion of the coating prepared in comparative example 1 without the modified graphene is grade 1, which shows that the addition of the modified graphene is beneficial to the increase of the adhesion of the coating.
The electrochemical properties of the coating coatings prepared in the examples and comparative examples were evaluated by EIS testing, in which the low frequency end (| Z! Y0.01Hz) The resistance value can be used as an index for judging the corrosion resistance of the coating. As can be seen from FIG. 2, after 66 days of immersion, the low frequency end (| Z! Y circuitry of comparative example 10.01Hz) The impedance value is reduced to 5641 omega cm2While the low frequency end (| Z! Y circuitry of embodiment 10.01Hz) The impedance value is 7.87 multiplied by 107Ω·cm2Much higher than in comparative example 1. On one hand, the polyethyleneimine graft modified reduced graphene oxide with a sheet structure can be distributed in the coating, so that the path length of corrosive media diffusing in the coating is increased, the corrosion process of a matrix is delayed, and simultaneously-NH on the surface of the coating2The epoxy resin and an epoxy group of the epoxy resin are subjected to crosslinking reaction, so that the curing degree and compactness of the coating are further improved, and the corrosion resistance of the coating is improved; on the other hand, the modified graphene oxide is partially reduced, has certain conductivity, increases the electrical contact between zinc powder particles in the coating and the steel matrix, and even if corrosive media invade the steel matrix, the zinc powder particles can provide cathode protection for the steel matrix, and the matrix is not corroded, so that the corrosion resistance of the coating is improved.
The cathodic protection performance of the coatings prepared in example 1 and comparative example 1 was characterized using a neutral scratch test. As can be seen from fig. 3, the coating prepared in comparative example 1 had red rust width at the scratch which far exceeded the scratch width and was partially peeled off without having a cathodic protection effect, whereas the coating prepared in example 1 had only slight red rust at the scratch and did not develop red rust. Meaning that the coating now provides better cathodic protection of the steel substrate at the scratch, slowing the corrosion of the exposed substrate. The polyethyleneimine is grafted, modified and reduced to reduce the graphene oxide, so that the conductivity of the graphene oxide is recovered, and the cathode protection performance of the zinc powder is improved. In addition, the excessive-NH 2 is cross-linked with the epoxy resin and the oxygen-containing functional group on the substrate to form a new chemical bond, so that the corrosion medium is difficult to diffuse at the scratch position, and the corrosion resistance of the coating is improved.
The dispersing effects of paints 1 to 4 prepared in examples 1 to 4 were compared by a settling experiment as shown in table 1 below:
| standing for 60 days | |
| Coating 1 | Slightly delaminated |
| Paint 2 | Not layering |
| Coating 3 | Not layering |
| Coating 4 | Not layering |
EIS test for comparing the corrosion resistance of the coatings prepared in examples 1 to 4 after soaking in 3.5% NaCl for 66 days, and combining with FIG. 2, the obtained low frequency end (| Z | Y |)0.01Hz) The impedance values are as follows in table 2:
| corrosion resistance of coating | |
| Example 1 | 7.87×107Ω·cm2 |
| Example 2 | 3.92×106Ω·cm2 |
| Example 3 | 2.35×106Ω·cm2 |
| Example 4 | 7.85×105Ω·cm2 |
From the results in tables 1 and 2, the resistance of example 1 is good, but the dispersion effect is not as good as that of examples 2-4, and the dispersion effect of example 4 is good, but the resistance value is not as good as that of examples 1-3, and is mainly influenced by the selection of the n value of polyethyleneimine, and the n value is preferably 400-600, so that the coating is ensured to have excellent dispersion effect and good corrosion resistance of the coating, and has more remarkable practical benefit for improving the cathodic protection performance of zinc powder particles.
The embodiments of the present invention are not limited to the above-mentioned embodiments, and any other changes and simplifications which do not depart from the spirit of the present invention should be construed as equivalents thereof, and all such changes and simplifications are encompassed by the scope of the present invention.
Claims (10)
1. The graphene/water-based epoxy zinc-rich coating with high corrosion resistance and strong adhesive force is characterized by consisting of a component A and a component B, wherein the component A comprises the following components in parts by mass: 0.3-1.5 parts of modified graphene, 5-25 parts of deionized water, 20-75 parts of water-based epoxy resin and 0.3-1 part of a base material wetting agent, wherein the modified graphene is polymer-grafted graphene oxide obtained by grafting and reducing graphene oxide by polyethyleneimine in an alkaline environment, and the component B comprises the following components in parts by mass: 40-70 parts of zinc powder, 15-30 parts of ethylene glycol monobutyl ether and 10-25 parts of water-based epoxy resin curing agent.
2. The preparation method of the graphene/water-based epoxy zinc-rich coating with high corrosion resistance and strong adhesion as claimed in claim 1, is characterized by comprising the following steps:
(1) dispersing 1-5 parts of graphene oxide in 1000 parts of deionized water by mass, adjusting the pH value to be alkaline, adding 3-12 parts of polyethyleneimine, heating to 60-80 ℃, stirring and reacting for 2-6 hours, after the reaction is finished, performing suction filtration by using deionized water, washing, and drying to obtain the polyethyleneimine grafted reduced graphene oxide, namely modified graphene;
(2) dispersing 0.3-1.5 parts by mass of the modified graphene obtained in the step (1) into 5-25 parts by mass of deionized water, and stirring and mixing with 20-75 parts by mass of waterborne epoxy resin and 0.3-1 part by mass of a base material wetting agent to obtain a coating A component;
(3) according to the mass parts, 40-70 parts of zinc powder, 15-30 parts of ethylene glycol monobutyl ether and 10-25 parts of waterborne epoxy resin curing agent are stirred and mixed to be used as a coating B component; and finally, stirring, mixing and dispersing the A, B component uniformly to obtain the graphene/water-based epoxy zinc-rich coating with high corrosion resistance and strong adhesive force.
3. The high-corrosion-resistance and strong-adhesion graphene/water-based epoxy zinc-rich coating according to claim 1, wherein the graphene oxide is single-layer or multi-layer graphene oxide prepared by a modified Hummers method.
4. The graphene/waterborne epoxy zinc-rich coating with high corrosion resistance and strong adhesion force according to claim 1, wherein the polyethyleneimine has a structure as follows:
wherein, the value of n is 50 to 1000.
5. The graphene/waterborne epoxy zinc-rich coating with high corrosion resistance and strong adhesion force according to claim 4, wherein the value of n of the polyethyleneimine is 400-600.
6. The graphene/waterborne epoxy zinc rich coating with high corrosion resistance and strong adhesion according to claim 1, wherein the waterborne epoxy resin comprises at least one of bisphenol A waterborne epoxy resin.
7. The graphene/waterborne epoxy zinc-rich paint with high corrosion resistance and strong adhesion according to claim 1, wherein the waterborne epoxy resin curing agent is at least one selected from polyamide, phenolic amine and cardanol waterborne epoxy resin curing agent.
8. The high corrosion resistant, high adhesion graphene/waterborne zinc-rich epoxy coating of claim 1, wherein the substrate wetting agent is selected from one of TEGO Twin 4100 or SURFYNOL 104E.
9. The graphene/waterborne epoxy zinc-rich coating with high corrosion resistance and strong adhesion of claim 1, wherein the zinc powder is in the shape of a flake or a sphere.
10. The preparation method of the graphene/waterborne epoxy zinc-rich coating with high corrosion resistance and strong adhesion according to claim 2, wherein the pH value is adjusted to be 8-12.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113583545A (en) * | 2021-09-13 | 2021-11-02 | 安徽大学 | Amination GO/cyclodextrin modified waterborne epoxy resin anticorrosive paint |
| CN113583544A (en) * | 2021-07-29 | 2021-11-02 | 安徽大学 | Aminated GO/sulfonated polyaniline modified waterborne epoxy resin anticorrosive paint |
| CN113930158A (en) * | 2021-10-15 | 2022-01-14 | 中国铁路设计集团有限公司 | Modified epoxy resin, preparation method thereof, epoxy resin emulsion and anticorrosive paint |
| CN114133831A (en) * | 2021-12-28 | 2022-03-04 | 南昌航空大学 | Graphene oxide water-based epoxy coating and preparation method thereof |
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| CN113583544B (en) * | 2021-07-29 | 2022-06-21 | 安徽大学 | Aminated GO/sulfonated polyaniline modified waterborne epoxy resin anticorrosive paint |
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| CN113583545B (en) * | 2021-09-13 | 2022-06-21 | 安徽大学 | Amination GO/cyclodextrin modified waterborne epoxy resin anticorrosive paint |
| CN113930158A (en) * | 2021-10-15 | 2022-01-14 | 中国铁路设计集团有限公司 | Modified epoxy resin, preparation method thereof, epoxy resin emulsion and anticorrosive paint |
| CN114133831A (en) * | 2021-12-28 | 2022-03-04 | 南昌航空大学 | Graphene oxide water-based epoxy coating and preparation method thereof |
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