CN109627906B - Super-hydrophobic graphene anticorrosive coating with double-layer inclusion structure and preparation method thereof - Google Patents
Super-hydrophobic graphene anticorrosive coating with double-layer inclusion structure and preparation method thereof Download PDFInfo
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Abstract
A super-hydrophobic graphene anticorrosive coating with a double-layer inclusion structure and a preparation method thereof belong to the technical field of super-hydrophobic anticorrosive coatings, and can solve the problems that the structure and performance of the existing super-hydrophobic coating are unstable, the anticorrosive performance of the super-hydrophobic coating is poor, the super-hydrophobic coating cannot be prepared on a large scale, and the like. The invention comprises the following steps: firstly, synthesizing a nano particle oily dispersion liquid with low surface energy and a graphene/resin composite oily dispersion liquid with good dispersibility; and secondly, spraying the graphene/resin composite oily dispersion liquid and the nano particle oily dispersion liquid on the metal substrate in sequence to prepare the coating with the double-layer inclusion structure. Compared with the traditional super-hydrophobic anticorrosive coating, the super-hydrophobic anticorrosive coating has more excellent hydrophobic property and anticorrosive property, more stable surface structure and performance, and can be prepared in a large-scale controllable manner, thereby accelerating the engineering application of the super-hydrophobic coating in the anticorrosive field.
Description
Technical Field
The invention belongs to the technical field of super-hydrophobic anticorrosive coatings, and particularly relates to a super-hydrophobic graphene anticorrosive coating with a double-layer inclusion structure and a preparation method thereof.
Background
The super-hydrophobic coating is easy to form a gasification film on the interface between the super-hydrophobic coating and an aqueous medium in water, can effectively isolate corrosive ions in water from permeating into the coating, can prevent microorganisms from enriching on the surface of the coating, and can effectively improve the anticorrosion effect and prolong the service life of the coating, so that the super-hydrophobic coating has wide application prospect in the field of high-efficiency and long-service-life metal ocean heavy-duty anticorrosion.
Recently, research on synthesis of super-hydrophobic coatings and in the field of metal corrosion prevention has been widely carried out, and a key technology of the research is how to prepare coatings with super-hydrophobicity and high stability on metal surfaces. The construction of micro-nano coarse structure and low surface energy is two effective ways to realize super-hydrophobicity. However, it is difficult to obtain a superhydrophobic surface (contact angle) by merely manipulating and lowering the surface energy of the coated substrate<120o). In the previous research, the method is mainly applied to gold by an aqueous solution chemical method, a chemical or laser etching method, a hydrothermal method, an anodic treatment method, an electrochemical deposition method, a sol-gel method, a nano composite coating method, a template method and the likeThe surface is a coating for constructing a porous or array structure. The research shows that the coating with the porous or array structure has excellent super-hydrophobic characteristics, but the porous or array structure has large roughness and low mechanical strength, and is easy to damage under the action of the outside, so that the hydrophobic performance is reduced, and the hydrophobic coating is easy to generate cracks and defects, so that the corrosion resistance and the service life of the coating material are reduced. Therefore, how to prepare a coating with excellent superhydrophobicity and structural stability on a metal surface remains the biggest difficulty and challenge in the application of the superhydrophobic technology in the anticorrosion field. In addition, most of the preparation methods of the super-hydrophobic coatings at the early stage have the defects of expensive equipment, poor repeatability, complex process and the like, are only suitable for experimental research, and cannot be produced and prepared on a large scale. Therefore, how to develop a preparation method of the super-hydrophobic coating, which is simple to operate, can be applied in a large scale and has stable performance, is of great value and significance.
Disclosure of Invention
The invention provides a super-hydrophobic graphene anticorrosive coating with a double-layer inclusion structure and a preparation method thereof, aiming at the problem that the super-hydrophobicity, the mechanical property and the processing stability of the existing super-hydrophobic anticorrosive coating are difficult to optimize simultaneously.
The invention adopts the following technical scheme:
the utility model provides a super hydrophobic graphene anticorrosion coating of double-deck inclusion structure, includes from outer to interior external coating and the undercoating of spraying on the metal substrate layer in proper order, wherein, the external coating is for having the nano particle assembled film of low surface energy, the undercoating is graphite alkene/resin doping complex film.
A preparation method of a super-hydrophobic graphene anticorrosive coating with a double-layer inclusion structure comprises the following steps:
first, preparation of a nanoparticle oil dispersion with low surface energy
a. Weighing 4-6 g of NaOH, dissolving in 92.5mL of deionized water to prepare a NaOH solution for later use, and weighing 2.86-4.29 g of FeCl2·4H2O and 4.864-7.296 g of FeCl3·6H2Dissolving O in 70-120 ml of deionized water, ultrasonically dispersing to form a uniform solution, and transferring to a containerHeating in a flask, when the temperature rises to 65-75 ℃, dropwise adding NaOH solution into the flask at the rate of 1 drop/second, continuing to react for 1.5h at the temperature of 65-75 ℃ after dropwise adding, cooling to 25 ℃ after the reaction is finished, ultrasonically washing the magnetic particles for a plurality of times by using deionized water to obtain magnetic particles, and ultrasonically dispersing the magnetic particles into 250-350 ml of water/ethanol solution with the volume ratio of 1:4 to obtain stable Fe3O4A dispersion liquid;
b. 250.0ml of Fe is taken3O4Adding 10ml ammonia water into the dispersion, stirring and dispersing for 1h, dropwise adding 4ml ethyl silicate in the stirring process, then stirring for 6h at 25 ℃, precipitating by magnetic adsorption, washing with ethanol and distilled water to obtain Fe3O4@SiO2Core-shell structured composite nanoparticles of Fe3O4@SiO2Ultrasonically dispersing the core-shell structure composite nano particles in 150ml of deionized water to obtain Fe3O4@SiO2A core-shell structure composite nanoparticle dispersion;
c. taking 120ml Fe3O4@SiO2Adding 1-4 g of urea, 2-6 g of cationic surfactant, 4-10 ml of 1-pentanol, 100-150 ml of cyclohexane and 10g of ethyl silicate into core-shell structure composite nanoparticle dispersion liquid in sequence, stirring and dispersing for 0.5-6h at 25 ℃ to obtain a mixed solution, transferring the mixed solution into a reaction kettle, reacting for 5h at 110-150 ℃, cooling to 25 ℃, performing magnetic adsorption precipitation, washing with water and ethanol and drying to obtain Fe3O4@SiO2/organic composite nanoparticles of Fe3O4@SiO2Dispersing organic composite nano particles in 150ml of toluene solution to obtain Fe3O4@SiO2Organic composite nano particle toluene dispersion;
d. 100ml of Fe was weighed3O4@SiO2Adding 30-50 ml of n-octyl trimethoxy siloxane into organic composite nanoparticle toluene dispersion, carrying out reflux reaction for 20-48h at 120 ℃, carrying out magnetic adsorption precipitation, and washing with toluene and xylene to obtain Fe3O4@H-SiO2Organic composite nano-particlesParticles of Fe3O4@H-SiO2Performing ultrasonic dispersion on organic composite nanoparticles in a solvent to obtain a low-surface-energy nanoparticle oily dispersion liquid with the solid content of 10.0-25.0 wt%;
secondly, preparing graphene/resin doped composite oily dispersion liquid
a. Weighing 0.1g of graphite oxide, dissolving in 50ml of deionized water, performing ultrasonic treatment at 25 ℃ for 1h to obtain a graphene oxide aqueous solution, adding 0.2-4.5 g of temperature-sensitive polymer into the solution, stirring, dissolving and dispersing at 25 ℃ for 1h to obtain a mixed solution, adding 20-50 mu l of 33% hydrazine hydrate into the mixed solution, and reacting in a water bath at 95-100 ℃ for 30min to obtain a temperature-sensitive polymer modified rGO dispersion liquid;
b. adding a nonpolar solvent into the temperature-sensitive polymer modified rGO dispersion liquid, stirring for 20 to-120 min at the temperature of 60 ℃ and the pH value of 2 to 5, standing for layering, adding anhydrous calcium chloride, soaking for 24h, and filtering to obtain a graphene nonpolar solvent dispersion liquid of 2.0mg/ml to 8.0 mg/ml;
c. adding resin into the graphene nonpolar solvent dispersion liquid, and stirring and dispersing for 1h at the rotating speed of 1500r/min in the range of 1000-;
thirdly, preparing the super-hydrophobic graphene anticorrosive coating
Uniformly spraying the graphene/resin doped composite oily dispersion liquid on the surface of a metal substrate to serve as an inner coating, putting the metal substrate into a 60-DEG C oven for 30-120 min, when the surface of the inner coating is not completely cured, uniformly spraying the low-surface-energy nano particle oily dispersion liquid on the surface of the inner coating to serve as an outer coating, and further curing to obtain the super-hydrophobic graphene anticorrosive coating with the double-layer inclusion structure.
In the first step, the cationic surfactant in step c is any one of cetyltrimethylammonium bromide, dodecyltrimethylammonium bromide, tetradecyltrimethylammonium bromide, octadecyltrimethylammonium bromide and cetylpyridinium bromide.
In the step d of the first step, the solvent is any one of propanol methyl ether, ethyl acetate and xylene.
In the second step, the temperature-sensitive polymer in the step a is any one of (methoxy) polyethylene glycol (methyl) acrylate, maleic anhydride (methyl) polyethylene glycol monoester and polyethylene glycol methyl ethyl ether methacrylate.
The nonpolar solvent in the step b of the second step is any one of xylene, toluene, cyclohexane and hexane.
In the step c of the second step, the resin is any one of epoxy resin, polyurethane resin and tetrafluoroethylene resin with the mass concentration of 30.0-45.0 wt%.
And in the third step, the further curing mode is curing for 4-8 h in a 60 ℃ oven or curing for 20h at 25 ℃.
The spraying pressure of the inner coating is 0.1MPa-0.25MPa, and the spraying thickness is 40-80 mu m; the spraying pressure of the outer coating is 0.25 MPa-0.35 MPa.
In the invention, the key point of the preparation of the low-surface-energy nanoparticle oily dispersion liquid is to obtain the low-surface-energy nanoparticles with good structural stability, and simultaneously have good stability and dispersibility in a non-polar solvent. Aiming at the requirements, compared with the traditional preparation process of the low-surface-energy nano particles, the preparation method makes some corresponding innovations and improvements in the following aspects: in the preparation process of the particles, the particle size, the structure and the dosage of the surfactant and the dispersion concentration are controlled to improve the stability and the dispersibility of the particles in a non-polar solvent; secondly, in the whole preparation process, a wet transfer method is adopted to purify and disperse the particles, so that the particles are prevented from forming secondary agglomeration in the drying process, the stability and the dispersibility of the particles in a non-polar solvent are influenced, and the particles are not beneficial to re-modification; in addition, the synthesis process is controlled, proper low-surface-energy organic molecules are selected, and the organic molecules are modified on the surfaces of the nanoparticles by a chemical grafting method, so that the stable nanoparticles with low surface energy are obtained.
The key point of the preparation of the graphene/resin doped composite oily dispersion liquid is how to uniformly disperse graphene in a non-polar solvent. In order to meet the requirements, the modified graphene can be directly transferred from a polar aqueous solution to a non-polar solvent by utilizing the solubility difference and adopting an extraction method, so that the problems that the graphene is secondarily agglomerated and is difficult to re-disperse in the traditional drying process and the traditional wet transfer process is complicated are avoided.
The key point of the preparation of the super-hydrophobic graphene anticorrosive coating is to obtain a super-hydrophobic surface with stable structure, and simultaneously, the super-hydrophobic graphene anticorrosive coating can be stably prepared in a large area. According to the traditional nano doping method, super-hydrophobicity is realized by utilizing the high roughness constructed on the surface of the coating by the high-concentration nano particles, although the method can be used for large-area preparation by adopting a spraying method, the repeated preparation stability is poor, the adhesive force between the coating and a substrate is low, the rough structure is easy to damage, the super-hydrophobicity is lost, and the application of the method is greatly limited. In order to solve the problems, the invention develops the super-hydrophobic coating with a novel structure, which not only has excellent super-hydrophobicity, mechanics and stable repeated preparation, but also can be prepared in a large area by adopting a spraying method.
The invention has the following beneficial effects:
1. the super-hydrophobic graphene anticorrosive coating with the double-layer inclusion structure provided by the invention has more excellent super-hydrophobic characteristics, and the contact angle is larger than 174 degrees, and the rolling angle is smaller than 2 degrees.
2. The super-hydrophobic graphene anticorrosive coating with the double-layer inclusion structure can be prepared in a large area by adopting a spraying method, the super-hydrophobicity mainly comes from the low surface energy of surface nano particles, the dependence on the surface roughness is small, and the repeated preparation stability of the coating is good.
3. The super-hydrophobic graphene anticorrosive coating with the double-layer inclusion structure is prepared, the curing condition of the coating is easy to control, the coating can be cured under the heating condition or at 25 ℃, and the coating is more suitable for large-scale preparation in an outdoor real environment.
4. According to the preparation method disclosed by the invention, the super-hydrophobic graphene anticorrosive coating with the double-layer inclusion structure is prepared, the nano particles are directly sprayed on the surface of the coating which is not completely dried, the particles are stably embedded on the surface of the coating along with the further solidification of the coating, the nano particles are bonded by the graphene coating, the surface particle structure is stable, a 100g weight is loaded, the parallel movement is carried out for 10cm, the cycle is carried out for 100 times, the contact angle is still larger than 160 degrees, and the excellent mechanical stability is realized.
5. The super-hydrophobic graphene anticorrosive coating with the double-layer inclusion structure has more excellent acid, alkali and salt resistance, and the contact angle is larger than 172 degrees after the coating is soaked in acid (pH = 1), alkali (pH =14) and salt (3.5wt% NaCl) for 10 days, and the electrochemical performance of the coating is hardly changed.
6. The super-hydrophobic graphene anticorrosive coating with the double-layer inclusion structure combines the good surface shielding and blocking performance of the super-hydrophobic coating and the internal blocking and diffusing performance of the graphene coating, completely combines the unique performances of the super-hydrophobic coating and the graphene coating, enables the composite coating to have more excellent anticorrosive performance, and has the corrosion current of 1.4 multiplied by 10 in 3.5wt% of NaCl aqueous solution-11A/cm2The corrosion rate is 1.6X 10-7mm/year, polarization resistance of 7.9 × 104MΩ·cm2。
Drawings
FIG. 1 is a schematic structural view of a coating of the present invention, wherein: 1-a metal substrate; 2-a resin; 3-graphene; 4-low surface energy nanoparticles;
FIG. 2 shows highly dispersed Fe prepared in example 1 of the present invention3O4And Fe3O4@H-SiO2XRD pattern of/CTAB nano particle, a is high dispersion Fe3O4XRD pattern of (b) is Fe3O4@H-SiO2XRD pattern of/CTAB nanoparticles;
FIG. 3 is a diagram of a super-hydrophobic graphene anticorrosive coating prepared in example 2 of the present invention;
FIG. 4 shows Fe prepared in the examples of the present invention3O4@H-SiO2SEM image of/CTAB nanoparticles, wherein A is Fe of the silane-modified fibrous core-shell structure of example 13O4@H-SiO2SEM image of/CTAB nanoparticles, B being Fe of the silane-modified, fibrous core-shell structure of example 23O4@H-SiO2SEM image of/CTAB nanoparticles;
FIG. 5 is an SEM image of an ultrahydrophobic graphene anticorrosive coating of example 3 of the present invention;
FIG. 6 is a physical diagram of the mechanical stability of the superhydrophobic graphene anticorrosive coating of embodiment 4 of the invention;
fig. 7 is a graph showing the change of the impedance modulus of the super-hydrophobic graphene anticorrosive coating of example 3 of the present invention when the super-hydrophobic graphene anticorrosive coating is soaked in a solution with pH =1 for 10 days.
Detailed Description
Example 1
A preparation method of a super-hydrophobic graphene anticorrosive coating with a double-layer inclusion structure comprises the following steps:
first, preparation of a nanoparticle oil dispersion with low surface energy
a. 5g of NaOH was weighed and dissolved in 92.5mL of deionized water to prepare a homogeneous solution for use. 3.5g of ferrous chloride tetrahydrate (FeCl) was weighed2·4H2O) and 6.5g of iron chloride hexahydrate (FeCl)3·6H2O), dissolving in deionized water, transferring to a flask after ultrasonic dispersion to a uniform solution, starting to dropwise add NaOH solution when the temperature reaches 65-75 ℃, the dropwise adding rate is 1 drop/second, reacting for 1.5h after the dropwise addition is finished, cooling to 25 ℃ after the reaction is finished, ultrasonically washing with deionized water for multiple times, and finally ultrasonically dispersing magnetic particles in a water/ethanol solution (V)Water (W)/VEthanolIn =1:4), stable Fe is prepared3O4Dispersion (8.0 mg/ml);
b. at 250.0ml Fe3O410ml of ammonia water is added into the dispersion liquid, the mixture is stirred and dispersed for 1 hour, 4ml of ethyl silicate is added dropwise during stirring, then the mixture is stirred and reacted for 6 hours at 25 ℃, the reaction solution is removed through magnetic adsorption precipitation, and the mixture is washed clean by ethanol and distilled water. Finally, Fe3O4@SiO2Ultrasonically dispersing the core-shell structure composite nano particles in an aqueous solution to obtain Fe3O4@SiO2Core-shell structure composite nanoparticle dispersion (16.7 mg/ml);
c. at 120ml Fe3O4@SiO2Adding 2.5g of urea, 4g of hexadecyl trimethyl ammonium bromide, 7ml of 1-pentanol, 100l of cyclohexane and 10g of ethyl silicate into the core-shell structure composite nanoparticle dispersion liquid in sequence, and stirring and dividing at 25 DEG CDispersing for 2h, transferring the mixed solution into a reaction kettle, reacting for 5h at 130 ℃, cooling to 25 ℃, fully washing the precipitate with water and ethanol through magnetic adsorption, and drying to obtain Fe3O4@SiO2Dispersing organic composite nano particles in a toluene solution to prepare Fe3O4@SiO2CTAB nanoparticle toluene dispersion (0.2 g/ml);
d. in 100ml Fe3O4@SiO2Adding 35ml of n-octyl trimethoxy siloxane into the organic composite nanoparticle toluene dispersion, then carrying out reflux reaction for 30 hours at 120 ℃, using magnetic adsorption to precipitate, and fully washing with toluene and xylene. Mixing Fe3O4@H-SiO2Performing ultrasonic dispersion on CTAB nano particles in dimethylbenzene to obtain oily low-surface-energy nano particle dispersion liquid with the solid content of 15.0 wt%;
secondly, preparing graphene/resin doped composite oily dispersion liquid
a. Weighing 0.1g of graphite oxide, dissolving the graphite oxide in 50ml of deionized water, performing ultrasonic treatment at 25 ℃ for 1.0h to obtain a graphene oxide aqueous solution, adding 0.5g of temperature-sensitive polymer (methoxy) polyethylene glycol (methyl) acrylate, stirring at normal temperature, dissolving and dispersing for 1.0h, adding 35 mu l of hydrazine hydrate (33%), performing water bath reaction at 95 ℃ for 30.0min, and after the reaction is finished, changing the color of the solution from brown to black to obtain a (methoxy) polyethylene glycol (methyl) acrylate modified rGO dispersion liquid;
b. adding nonpolar solvent xylene into the (methoxyl) polyethylene glycol (methyl) acrylate modified rGO aqueous solution, mechanically and electrically stirring for 60min at the temperature of 60.0 ℃ and under the condition of pH =3, and standing for layering. Adding a water removing agent, namely anhydrous calcium chloride, soaking for 24 hours, and filtering to obtain a graphene nonpolar solvent dispersion liquid (2.0 mg-8.0 mg/ml);
c. adding epoxy resin (with the solid content of 40 wt%) into a graphene nonpolar solvent, and dispersing for 1.0h under high-speed electric stirring (1000 revolutions per minute) to obtain a graphene/resin doped composite oily dispersion liquid with the solid content of 1 wt%;
thirdly, preparing the super-hydrophobic graphene anticorrosive coating
Uniformly spraying the graphene/resin doped composite oily dispersion liquid on the surface of a metal substrate to serve as an inner coating, placing the metal substrate in a 60.0 ℃ drying oven for 1h under the spraying pressure of 0.1MPa, uniformly spraying the low-surface-energy nano particle oily dispersion liquid on the surface of the inner coating to serve as an outer coating when the surface of the inner coating is not completely cured, placing the metal substrate in the 60.0 ℃ drying oven for curing for 6h under the spraying pressure of 0.3MPa, and thus obtaining the super-hydrophobic graphene anticorrosive coating with the double-layer inclusion structure.
High dispersion of Fe from FIG. 23O4And Fe3O4@H-SiO2XRD pattern of CTAB nano particle shows that Fe is highly dispersed3O4The characteristic diffraction peak of XRD of (1) appears at 2θ=18.2 °, 29.9 °, 35.4 °, 37.1 °, 43.0 °, 53.3 °, 56.9 °, 62.6 °, and 74.1 ° for Fe3O4The (111), (220), (311), (400), (422), (511), (440), and (533) crystal planes of (c).
Fe3O4@H-SiO2XRD of/CTAB nanoparticles at 2θOccurrence of SiO =21.5 °2The amorphous diffraction peak of the Fe-based nano-material well indicates the core-shell structure Fe3O4@H-SiO2Successful preparation of CTAB nanoparticles.
Example 2
3.5g of iron chloride tetrahydrate (FeCl) in the first step of example 12·4H2O) to 4.0g ferrous chloride tetrahydrate (FeCl)2·4H2O). 3g of urea and 5g of cetyltrimethylammonium bromide were changed to 2g of urea and 4g of tetradecyltrimethylammonium bromide, 35ml of n-octyltrimethoxysilane was changed to 45ml of n-octyltrimethoxysilane, and the procedure was otherwise the same as in example 1.
Fig. 3 shows that the superhydrophobic graphene anticorrosive coating prepared by the present example has low surface energy nanoparticles uniformly loaded on the surface of the coating, and it can be seen from the figure that water drops show excellent and stable contact angles at multiple positions on the surface of the composite coating, thus proving that the superhydrophobic coating prepared by the process has excellent performance and stable structure. As can be seen from FIG. 3, the contact angle of the superhydrophobic graphene anticorrosive coating reaches 174 + -1.5 deg.
As can be seen from fig. 4, the size of the nanoparticles is reduced.
Example 3
0.35g of temperature-sensitive polymer (methoxy) polyethylene glycol (meth) acrylate in the second step of example 1 was changed to 1g of temperature-sensitive polymer maleic anhydride (meth) polyethylene glycol monoester. 35 μ l hydrazine hydrate (33%) was changed to 50 μ l hydrazine hydrate (33%).
The rest of the procedure was the same as in example 1.
As can be seen from FIG. 5, the silane-modified fibrous core-shell structure Fe3O4/H-SiO2The CTAB nano particles are uniformly embedded on the surface of the coating, so that the obtained coating has excellent structural stability and performance stability.
As can be seen from FIG. 7, the coating still has a modulus of resistance of 10 after 10 days of immersion8Ω/cm2And no obvious change appears, which indicates that the coating can stably exist in a strong acid environment.
Example 4
In the second step of example 1, the solid content of the epoxy resin was changed from 40wt% to 30wt%, and the graphene/resin composite oily dispersion liquid having a solid content of 1wt% was changed to a graphene/resin composite oily dispersion liquid having a solid content of 1.5 wt%.
In the third step of example 1, the spraying pressure of the graphene/resin composite oily dispersion was changed to 0.2 MPa, the spraying pressure of the nanoparticle oily dispersion was changed to 0.35MPa, and the curing mode was changed to curing at 25 ℃.
The rest of the procedure was the same as in example 1.
Fig. 6 shows that the super-hydrophobic graphene anticorrosive coating prepared by the coating preparation process of the present application has excellent mechanical stability, and the super-hydrophobic graphene anticorrosive coating surface has excellent mechanical stability, and is loaded with 100g of weight on the coating surface, moves 10cm each time, and shows excellent and stable super-hydrophobic performance after 100 times (10 m) of cyclic movement. As can be seen from fig. 6, the coating exhibits very good mechanical stability and still has very high superhydrophobic performance during rubbing.
Claims (8)
1. The utility model provides a preparation method of super hydrophobic graphene anticorrosive coating of double-deck inclusion structure, includes undercoating and the external coating of spraying on the metal substrate from inside to outside in proper order, and wherein, the undercoating is graphite alkene/resin doping composite oil dispersion, and the external coating is the nano particle oil dispersion of low surface energy, its characterized in that: the preparation method comprises the following steps:
first, preparation of a nanoparticle oil dispersion with low surface energy
a. Weighing 4-6 g of NaOH, dissolving in 92.5mL of deionized water to prepare a NaOH solution for later use, and weighing 2.86-4.29 g of FeCl2·4H2O and 4.864-7.296 g of FeCl3·6H2Dissolving O in 70-120 mL of deionized water, ultrasonically dispersing into a uniform solution, transferring the solution into a flask for heating, when the temperature rises to 65-75 ℃, dropwise adding NaOH solution into the flask at the rate of 1 drop per second, continuing to react for 1.5 hours at the temperature of 65-75 ℃ after dropwise adding is finished, cooling to 25 ℃ after the reaction is finished, ultrasonically washing the solution for a plurality of times by using the deionized water to obtain magnetic particles, ultrasonically dispersing the magnetic particles into 250-350 mL of water/ethanol solution with the volume ratio of 1:4 to obtain stable Fe3O4A dispersion liquid;
b. 250.0mL of Fe was taken3O4Adding 10mL of ammonia water into the dispersion, stirring and dispersing for 1h, dropwise adding 4mL of ethyl silicate during stirring, stirring for 6h at 25 ℃, performing magnetic adsorption precipitation, washing with ethanol and distilled water to obtain Fe3O4@SiO2Core-shell structured composite nanoparticles of Fe3O4@SiO2Ultrasonically dispersing the core-shell structure composite nano particles in 150mL of deionized water to obtain Fe3O4@SiO2A core-shell structure composite nanoparticle dispersion;
c. take 120mLFe3O4@SiO2Adding 1-4 g of urea, 2-6 g of cationic surfactant, 4-10 mL of 1-pentanol, 100-150 mL of cyclohexane and 10g of ethyl silicate into core-shell structure composite nanoparticle dispersion liquid in sequence, stirring and dispersing for 0.5-6h at 25 ℃ to obtain a mixed solution, transferring the mixed solution to a reverse sideReacting in a kettle at 110-150 ℃ for 5h, cooling to 25 ℃, performing magnetic adsorption precipitation, washing with water and ethanol, and drying to obtain Fe3O4@SiO2/organic composite nanoparticles of Fe3O4@SiO2Dispersing organic composite nano particles in 150mL of toluene solution to obtain Fe3O4@SiO2Organic composite nano particle toluene dispersion;
d. 100mL of Fe was weighed3O4@SiO2Adding 30-50 mL of n-octyl trimethoxy siloxane into organic composite nanoparticle toluene dispersion, carrying out reflux reaction for 20-48h at 120 ℃, carrying out magnetic adsorption precipitation, and washing with toluene and xylene to obtain Fe3O4@H-SiO2/organic composite nanoparticles of Fe3O4@H-SiO2Performing ultrasonic dispersion on organic composite nanoparticles in a solvent to obtain a low-surface-energy nanoparticle oily dispersion liquid with the solid content of 10.0-25.0 wt%;
secondly, preparing graphene/resin doped composite oily dispersion liquid
a. Weighing 0.1g of graphite oxide, dissolving in 50mL of deionized water, performing ultrasonic treatment at 25 ℃ for 1h to obtain a graphene oxide aqueous solution, adding 0.2-4.5 g of temperature-sensitive polymer into the solution, stirring, dissolving and dispersing at 25 ℃ for 1h to obtain a mixed solution, adding 20-50 mu L of 33% hydrazine hydrate into the mixed solution, and reacting in a water bath at 95-100 ℃ for 30min to obtain a temperature-sensitive polymer modified rGO dispersion liquid;
b. adding a non-polar solvent into the temperature-sensitive polymer modified rGO dispersion liquid, stirring for 20-120 min at 60 ℃ and pH of 2-5, standing for layering, adding anhydrous calcium chloride, soaking for 24h, and filtering to obtain 2.0-8.0 mg/mL graphene non-polar solvent dispersion liquid;
c. adding resin into the graphene nonpolar solvent dispersion liquid, and stirring and dispersing for 1h at the rotating speed of 1000-1500r/min to obtain 0.5-1.5 wt% graphene/resin doped composite oily dispersion liquid;
thirdly, preparing the super-hydrophobic graphene anticorrosive coating
Uniformly spraying the graphene/resin doped composite oily dispersion liquid on the surface of a metal substrate to serve as an inner coating, putting the metal substrate into a 60-DEG C oven for 30-120 min, when the surface of the inner coating is not completely cured, uniformly spraying the low-surface-energy nano particle oily dispersion liquid on the surface of the inner coating to serve as an outer coating, and further curing to obtain the super-hydrophobic graphene anticorrosive coating with the double-layer inclusion structure.
2. The preparation method of the super-hydrophobic graphene anticorrosive coating with the double-layer inclusion structure according to claim 1, is characterized in that: in the first step, the cationic surfactant in step c is any one of cetyltrimethylammonium bromide, dodecyltrimethylammonium bromide, tetradecyltrimethylammonium bromide, octadecyltrimethylammonium bromide and cetylpyridinium bromide.
3. The preparation method of the super-hydrophobic graphene anticorrosive coating with the double-layer inclusion structure according to claim 1, is characterized in that: in the step d of the first step, the solvent is any one of propylene glycol methyl ether, ethyl acetate and xylene.
4. The preparation method of the super-hydrophobic graphene anticorrosive coating with the double-layer inclusion structure according to claim 1, is characterized in that: in the second step, the temperature-sensitive polymer in the step a is any one of (methoxy) polyethylene glycol (methyl) acrylate, maleic anhydride (methyl) polyethylene glycol monoester and polyethylene glycol methyl ethyl ether methacrylate.
5. The preparation method of the super-hydrophobic graphene anticorrosive coating with the double-layer inclusion structure according to claim 1, is characterized in that: the nonpolar solvent in the step b of the second step is any one of xylene, toluene, cyclohexane and hexane.
6. The preparation method of the super-hydrophobic graphene anticorrosive coating with the double-layer inclusion structure according to claim 1, is characterized in that: in the step c of the second step, the resin is any one of epoxy resin, polyurethane resin and tetrafluoroethylene resin with the mass concentration of 30.0-45.0 wt%.
7. The preparation method of the super-hydrophobic graphene anticorrosive coating with the double-layer inclusion structure according to claim 1, is characterized in that: and in the third step, the further curing mode is curing for 4-8 h in a 60 ℃ oven or curing for 20h at 25 ℃.
8. The preparation method of the super-hydrophobic graphene anticorrosive coating with the double-layer inclusion structure according to claim 1, is characterized in that: in the third step, the spraying pressure of the inner coating is 0.1MPa-0.25MPa, and the spraying thickness is 40-80 mu m; the spraying pressure of the outer coating is 0.25 MPa-0.35 MPa.
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