CN109836919B - Functionalized graphene oxide anticorrosive coating and preparation process thereof - Google Patents
Functionalized graphene oxide anticorrosive coating and preparation process thereof Download PDFInfo
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Abstract
The invention discloses a functionalized graphene oxide anticorrosive coating and a preparation process thereof, and is characterized in that: modified graphene oxide, inorganic nanoparticles, film-forming substances and the like are adopted to prepare the anticorrosive paint, and the paint is uniformly brushed on the surface of the metal to be subjected to corrosion prevention by a brushing method to form an anticorrosive coating with excellent performance. The method mainly comprises the following steps: (1) performing functional modification on the prepared graphene oxide; (2) dissolving functionalized graphene oxide in an organic solvent, and performing ultrasonic dispersion to obtain a uniform graphene oxide dispersion liquid; (3) adding inorganic nano particles for ultrasonic dispersion; (4) adding a film forming substance, stirring for a certain time, then dropping a certain amount of surface modifier and curing agent to reduce the surface energy of the coating, and removing bubbles in the solution by using a proper amount of defoaming agent; (5) stopping stirring, standing, uniformly brushing the metal plate after treatment by adopting a brushing method, and curing at room temperature to form a coating with excellent corrosion resistance. The preparation method has the advantages of simple process, convenient operation and high corrosion resistance.
Description
Technical Field
The invention belongs to the technical field of synthesis and preparation of graphene anticorrosive coatings, and relates to a functionalized graphene oxide anticorrosive coating and a preparation process thereof.
Background
The graphene has excellent conductivity, mechanical property, thermal stability and shielding effect, and can be used as a functional filler to enhance the performance of the coating. The graphene has the following advantages as an anticorrosive functional filler: (1) small size effect, nanometer small size can make it fill in the hole, defect in the coating; (2) the specific surface area is large, the graphene belongs to a lamellar structure, has a large specific surface area, can form a large barrier, and has an effect higher than that of mica flakes; (3) the barrier property is excellent, the graphene is composed of a plurality of carbon atom six-membered rings, has a stable conjugated structure, is neither hydrophilic nor oleophilic, can resist external corrosive substances from permeating to the surface of the metal, but when the coating has defects, the conductivity of the graphene promotes the metal corrosion instead. Graphene also has some disadvantages as a functional filler for corrosion protection: (1) the dispersibility of graphene is poor, and defects are easily formed in the coating; (2) electron transfer may exist between graphene and metal; (3) the compatibility of graphene with other polymers is poor; these drawbacks also limit their application in many fields. Therefore, in order to better utilize the shielding effect of graphene, it is necessary to perform functional modification on graphene. Compared with graphene, the graphene oxide has more oxygen-containing functional groups which can be just used as active sites for reaction, and the graphene oxide is functionally modified by using small molecular substances, so that the dispersibility of the graphene oxide can be improved and the graphene oxide can be uniformly distributed in a coating; on the other hand, the conductivity of the alloy can be reduced and the corrosion can be prevented by grafting p-phenylenediamine and the like through an oxygen-containing group. In addition, the addition of the inorganic nano particles can also improve the hydrophobicity and the pollution resistance of the coating, thereby improving the anticorrosion performance.
Disclosure of Invention
The invention aims to provide a functionalized graphene oxide anticorrosive coating with good dispersibility and a preparation method thereof.
The technical scheme of the invention is as follows: firstly, preparing graphene oxide by adopting an improved Hummers method, then carrying out graft modification on the graphene oxide by using p-phenylenediamine through a hydrothermal reflux method, dissolving the obtained product in a methanol solution, simultaneously adding polyvinyl butyral, silicon dioxide, titanium dioxide inorganic nano ions and polydimethylsiloxane to prepare a solution, stirring for a certain time, standing for defoaming, uniformly coating the solution on a metal plate by adopting a brush coating method, and curing the solution at room temperature for one day to obtain a coating with excellent corrosion resistance.
The main innovation points of the invention are as follows: the graphene oxide is grafted and modified by the small molecular substance to improve the dispersibility of the graphene oxide in the polymer, and then the graphene oxide is combined with inorganic nano particle silicon dioxide, titanium dioxide and the like to realize synergistic corrosion prevention, and simultaneously interacts with polydimethylsiloxane prepolymer and the like to reduce the surface energy of the coating and jointly improve the corrosion prevention performance of the coating.
The method for preparing the functionalized graphene oxide comprises the following steps: graphite powder is used as a raw material, an improved Hummers method is adopted to prepare graphene oxide, a graphene oxide aqueous solution with a certain concentration is prepared, ultrasonic dispersion is adopted for a certain time, p-phenylenediamine is added, stirring and refluxing are carried out for a certain time at a certain temperature under an alkaline condition, and finally, the functionalized graphene oxide is obtained through suction filtration, cleaning and freeze drying.
The preparation process of the functionalized graphene oxide anticorrosive paint in the method is as follows: dissolving the obtained functionalized graphene oxide in a methanol solution, and carrying out water bath ultrasound for a certain time; then adding polyvinyl butyral, silicon dioxide, titanium dioxide and polydimethylsiloxane, and continuously stirring for a long time to obtain the anticorrosive paint.
The preparation process of the functionalized graphene oxide anticorrosive coating in the method is as follows: the anticorrosive paint is brushed on the treated metal plate by a brushing method, and a coating with excellent anticorrosive performance can be obtained on the metal surface after curing for 24 hours at room temperature.
Reagents and materials used in the invention: graphite powder, potassium permanganate, sodium nitrate, concentrated sulfuric acid, dilute hydrochloric acid, hydrogen peroxide, p-phenylenediamine and ammonia water, which are analytically pure, inorganic nano-particle silicon dioxide, titanium dioxide, polyvinyl butyral, polydimethylsiloxane prepolymer and defoaming agent B-457 for oily paint.
Drawings
FIG. 1 is a diagram of the corrosion prevention mechanism for preparing a coating.
Fig. 2 is a nyquist plot for different contents of modified graphene oxide anti-corrosive coatings.
Fig. 3 is a graph of corrosion rates of modified graphene oxide anti-corrosive coatings at different contents.
Detailed Description
The present invention will be described in detail with reference to specific examples.
Example 1: an improved Hummers method is adopted, graphite powder is used as a raw material, and graphene oxide dispersion liquid is prepared. Preparing 100 ml of 0.4% graphene oxide solution, performing ultrasonic treatment at 500W for 30 minutes, adding 3.0 g of p-phenylenediamine, stirring and refluxing for 3 hours at 95 ℃ under an alkaline condition, performing suction filtration, respectively washing three to five times with water and ethanol, and performing freeze drying for 24 hours to obtain modified graphene oxide; placing 16mg of modified graphene oxide into 20ml of methanol solution, carrying out ultrasonic dispersion in water bath for 1 hour, then adding 2.0g of silicon dioxide, 0.5g of titanium dioxide, 2.0g of polyvinyl butyral and 0.16g of polydimethylsiloxane prepolymer, carrying out magnetic stirring for 20 hours, then adding a defoaming agent B-457, stirring for 30 minutes again, standing for 1 hour to remove bubbles to obtain an anticorrosive coating with the modified graphene oxide content of 0.8%, brushing the anticorrosive coating on a treated metal plate, and curing for 1 day at room temperature to obtain a coating with excellent anticorrosive performance on the surface of metal.
Example 2: an improved Hummers method is adopted, graphite powder is used as a raw material, and graphene oxide dispersion liquid is prepared. Preparing 100 ml of 0.4% graphene oxide solution, performing ultrasonic treatment at 500W for 30 minutes, adding 3.0 g of p-toluidine, stirring and refluxing for 3 hours at 95 ℃ under an alkaline condition, performing suction filtration, respectively washing three to five times with water and ethanol, and performing freeze drying for 24 hours to obtain modified graphene oxide; 20mg of modified graphene oxide is placed into 20ml of ethylene glycol solution, the modified graphene oxide is dispersed in water bath for 1 hour in an ultrasonic mode, then 2.0g of silicon dioxide, 0.5g of titanium dioxide, 2.0g of epoxy resin and 0.16g of methacrylic acid are added, magnetic stirring is carried out for 20 hours, then a self-emulsifying defoaming agent is added, stirring is carried out for 30 minutes, standing is carried out for 1 hour to remove air bubbles, an anticorrosive coating with the modified graphene oxide content of 1.0% is obtained, the anticorrosive coating is coated on a treated metal plate, and after the coating is solidified for 1 day at room temperature, a coating with excellent anticorrosive performance can be obtained on the surface of the metal.
Claims (6)
1. A preparation method of a functionalized graphene oxide anticorrosive coating is characterized by comprising the following steps: the method mainly comprises the following steps:
step 1: performing functional modification on graphene oxide by adopting a hydrothermal reflux method, grafting p-phenylenediamine, gamma-methacryloxypropyltrimethoxysilane and p-toluidine on the graphene oxide to obtain functional graphene oxide, and dispersing the functional graphene oxide into an organic solvent to obtain a graphene oxide dispersion liquid;
step 2: adding inorganic nanoparticles into the graphene oxide dispersion liquid obtained in the step (1) for ultrasonic dispersion for 0.5-2 hours; then adding a film forming substance, stirring for 12-48 hours, adding a surface modifier and an oily coating defoamer during stirring, and stirring for a certain time; standing for a period of time after stirring is finished, uniformly coating the metal plate on which the treatment is carried out by using a brush coating method, and curing for one day at room temperature to obtain a coating with good corrosion resistance; the anticorrosive coating comprises the following components in percentage by mass:
the film forming material comprises polyvinyl butyral, phenolic resin and epoxy resin.
2. The method of claim 1, wherein: the organic solvent comprises methanol, glycol and N-N-dimethylformamide.
3. The method of claim 1, wherein: the inorganic nanoparticles comprise silicon dioxide, and the content of the silicon dioxide is 4-12%.
4. The method of claim 1, wherein: the inorganic nano particles comprise titanium dioxide and account for 1-3%.
5. The method of claim 1, wherein: the surface modifier comprises polydimethylsiloxane prepolymer, methacrylic acid and cinnamic acid.
6. The method of claim 1, wherein: the oil paint defoaming agent comprises high-carbon alcohol and a self-emulsifying defoaming agent.
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| CN112676129A (en) * | 2019-10-18 | 2021-04-20 | 天津工业大学 | Graphene anticorrosive coating with layer assembly structure and preparation process thereof |
| CN110760252B (en) * | 2019-11-08 | 2021-06-22 | 珠海格力绿色再生资源有限公司 | Functional coating and preparation method and application thereof |
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| CN113755076A (en) * | 2021-09-30 | 2021-12-07 | 南通大学 | Preparation method of aromatic diamine modified graphene oxide epoxy resin coating |
| CN113956746B (en) * | 2021-11-02 | 2022-11-29 | 国科广化韶关新材料研究院 | Water-based epoxy group anticorrosive paint containing composite functionalized modified graphene oxide and preparation method and application thereof |
| CN115926574A (en) * | 2022-12-12 | 2023-04-07 | 南通尔东金属科技有限公司 | Hardware surface anti-corrosion treatment process |
| CN116622270B (en) * | 2023-04-07 | 2024-03-22 | 江南大学 | Modified graphene antirust anticorrosive paint and preparation method thereof |
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