Preparation method of super-hydrophobic anticorrosive coating with self-repairing function

Abstract

The application discloses a preparation method of super-hydrophobic anti-corrosion paint with self-repairing function. Specifically, the method comprises the following steps: firstly, synthesizing microcapsules on the surface of graphene by using cyclodextrin, adding corrosion inhibitors to construct graphene loaded with corrosion inhibitors, mixing with ethanol and fluorinated modifier to construct fluorinated modified graphene loaded with corrosion inhibitors; preparing anti-corrosion paint component A by mixing fluorosilicon resin stock solution, organic solvent and fluorinated modified graphene loaded with corrosion inhibitors; preparing anti-corrosion paint component B by adding modified carbon nanotubes to fluorosilicon resin curing agent; finally, mixing anti-corrosion paint component A and anti-corrosion paint component B to prepare super-hydrophobic anti-icing paint with self-repairing function. The micron-level structure of graphene loaded with nanometer container and the hierarchical structure constructed by carbon nanotubes are utilized, meanwhile, the nanometer container can release corrosion inhibitors after acid-alkali etching, so that the damaged coating can be repaired and the anti-corrosion performance can be improved.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of grounding grid corrosion prevention, and particularly relates to a preparation method of super-hydrophobic corrosion-resistant coating with self-repairing function. BACKGROUND

[0002] The grounding grid is one of the devices that must be installed in various power facilities, and is mainly used to ensure the safety of personnel and other devices. With the rapid development of power systems towards higher voltage and larger capacity, higher requirements are put forward for the safety and reliability of system operation, and the performance requirements for the grounding grid are also higher and higher. Influenced by the national conditions, ordinary carbon steel is generally selected for the grounding grid at present in China. Such material is prone to corrosion in the soil environment, thereby reducing the performance of the grounding grid, and even unable to work normally, resulting in serious accidents.

[0003] When the surface presents the characteristics of water contact angle > 150° and rolling angle < 10°, the surface is considered to have super-hydrophobic performance, and the super-hydrophobic effect can play an anti-icing role. The water droplets cannot be wetted and stayed on the surface of the lotus leaf, which is a natural super-hydrophobic material. Research shows that there is a multi-level structure combined by micron particles and nanometer particles on the surface of the lotus leaf. The application constructs the hierarchical structure by using the micron structure of the graphene loaded with nanometer containers and the carbon nanotube. At the same time, the nanometer containers can release corrosion inhibitors after acid-base etching, repair the damaged coating and improve the corrosion resistance. SUMMARY

[0004] The application aims to provide a preparation method of super-hydrophobic corrosion-resistant coating with self-repairing function.

[0005] The application aims to provide a preparation method of super-hydrophobic corrosion-resistant coating with self-repairing function.

[0006] (1) 3-8 parts of cyclodextrin are dissolved in 10-30 parts of water according to the weight fraction, 2-5 parts of graphene are added, stirred uniformly, 1-2 parts of ammonia water are added dropwise, and stirred while adding dropwise, 15-25 parts of hydrazine hydrate are added after the dropwise addition is completed, and the above solution is placed in a 70-75℃ oil bath for reaction for 3-5h; the obtained black solution is loaded into a dialysis bag and placed in deionized water for dialysis for 1-3d, and then soaked in a corrosion inhibitor solution to obtain graphene loaded with corrosion inhibitor nanometer containers;

[0007] (2) 3-5 parts of graphene loaded with corrosion inhibitor nanometer containers are added into 30-50 parts of ethanol and 0.5-2 parts of fluorosilane modifier, fully stirred until uniformly dispersed, then ultrasonic treatment and stirring are repeated for 3-8 times, and then dried to obtain fluorinated modified graphene loaded with corrosion inhibitors;

[0008] (3) 4-6 parts of carbon nanotubes are added into 30-50 parts of ethanol and 0.5-2 parts of fluorosilane modifier, and after being fully stirred to be uniformly dispersed, 3-8 times of ultrasonic treatment and stirring are repeated, and then drying is performed to obtain fluorosilane modified carbon nanotubes;

[0009] (4) 3-7 parts of fluorosilicon resin stock solution are mixed with 15-25 parts of organic solvent, and 1-3 parts of fluorosilane modified carbon nanotubes are fully stirred to be uniformly mixed to obtain anticorrosive coating component A;

[0010] (5) 1-3 parts of fluorosilicon resin curing solution are mixed with 10-20 parts of organic solvent, and 3-7 parts of graphene loaded with fluorinated modified corrosion inhibitor are fully stirred to be uniformly mixed to obtain anticorrosive coating component B;

[0011] (6) anticorrosive coating component A and anticorrosive coating component B are mixed according to a weight ratio of 1:(0.5-2) and are uniformly stirred to obtain super-hydrophobic anticorrosive coating.

[0012] The corrosion inhibitor solution is benzotriazole and / or mercaptobenzotriazole.

[0013] The fluorosilane modifier is tridecafluorooctyltriethoxysilane and / or heptadecafluorodecyltriethoxysilane.

[0014] The length of the carbon nanotubes is 5-50 μm.

[0015] The organic solvent is ethyl acetate and / or butyl acetate.

[0016] The ultrasonic treatment and stirring are 10-20 min of ultrasonic treatment followed by 10-20 min of glass rod stirring or magnetic stirring; the fully stirring is 30-50 min of glass rod stirring or magnetic stirring; and the uniform stirring is 5-10 min of glass rod stirring or magnetic stirring.

[0017] A super-hydrophobic anticorrosive coating layer with self-repairing function is prepared by spraying the above-prepared super-hydrophobic anticorrosive coating on a substrate and performing room temperature curing to obtain a super-hydrophobic anticorrosive coating layer with self-repairing function.

[0018] The substrate is one or more of metal, ceramic, glass, fiber and plastic.

[0019] The spraying coating amount is 0.02-0.05 mL / cm 2 .

[0020] The present application has the following beneficial effects: the present application utilizes the micro-scale structure of graphene loaded with nano-containers and the hierarchical structure of carbon nanotubes; at the same time, the nano-containers can release corrosion inhibitors after acid and alkali etching, repair the damaged coating and improve the anticorrosive performance. BRIEF DESCRIPTION OF DRAWINGS

[0021] Figure 1 Transmission electron microscope image of the material prepared for Example 1. DETAILED DESCRIPTION

[0022] For the purpose of promoting an understanding of the principles of the application, a thorough and complete description of the application will be presented. It is intended, however, that the application be construed as including all such embodiments and equivalents thereto.

[0023] Example 1

[0024] A preparation method of a super-hydrophobic anti-corrosion coating material with self-repairing function, comprising the following steps:

[0025] (1) 5 parts of cyclodextrin are dissolved in 20 parts of water, 4 parts of graphene is added, stirred uniformly (magnetic stirring for 8 min), 1 part of ammonia is added dropwise while stirring, after the dropwise addition is completed, 20 parts of hydrazine hydrate is added, and the above solution is placed in a 72℃ oil bath for reaction for 4h; the obtained black solution is loaded into a dialysis bag and placed in deionized water for dialysis for 2d, and then soaked in a benzotriazole solution to obtain graphene loaded with corrosion inhibitor nanoreactor;

[0026] (2) 4 parts of graphene loaded with corrosion inhibitor nanoreactor is added to 40 parts of ethanol and 1 part of tridecafluorooctyltriethoxysilane, and fully stirred (magnetic stirring for 40 min) until uniformly dispersed, then repeated 5 times of ultrasonic treatment and stirring (ultrasonic treatment for 15 min followed by magnetic stirring for 15 min), and dried to obtain fluorinated modified graphene loaded with corrosion inhibitor;

[0027] (3) 5 parts of carbon nanotube (length of 25μm) is added to 40 parts of ethanol and 1 part of tridecafluorooctyltriethoxysilane, and fully stirred (magnetic stirring for 40 min) until uniformly dispersed, then repeated 5 times of ultrasonic treatment and stirring (ultrasonic treatment for 15 min followed by magnetic stirring for 15 min), and dried to obtain fluorosilane modified carbon nanotube;

[0028] (4) 5 parts of fluorosilicon resin stock solution is mixed with 20 parts of ethyl acetate, and fully stirred (magnetic stirring for 40 min) with 2 parts of fluorosilane modified carbon nanotube until uniformly mixed to obtain anti-corrosion coating component A;

[0029] (5) 2 parts of fluorosilicon resin curing solution is mixed with 15 parts of ethyl acetate, and fully stirred (magnetic stirring for 40 min) with 5 parts of fluorinated modified graphene loaded with corrosion inhibitor until uniformly mixed to obtain anti-corrosion coating component B;

[0030] (6) Anti-corrosion coating component A and anti-corrosion coating component B are mixed in a weight ratio of 1:1 and stirred uniformly (magnetic stirring for 8 min) to obtain a super-hydrophobic anti-corrosion coating material.

[0031] A super-hydrophobic anti-corrosion coating with self-repairing function is prepared by spraying the prepared super-hydrophobic anti-corrosion coating on a stainless steel substrate, and curing at room temperature to obtain a super-hydrophobic anti-corrosion coating with self-repairing function; the spraying coating amount is 0.03 mL / cm 2 .

[0032] Example 2

[0033] A preparation method of a super-hydrophobic anti-corrosion coating with self-repairing function, comprising the following steps:

[0034] (1) According to the weight fraction, 3 parts of cyclodextrin are dissolved in 12 parts of water, 2 parts of graphene are added, stirred uniformly (magnetic stirring for 5 min), 1 part of ammonia water is added dropwise, and stirred while adding, after the dropwise addition is completed, 15 parts of hydrazine hydrate is added, the above solution is placed in an oil bath at 70℃ for reaction for 5h; the obtained black solution is loaded into a dialysis bag and placed in deionized water for dialysis for 1d, and then soaked in a mercapto benzothiazole solution to obtain graphene loaded with inhibitor nanoreactor;

[0035] (2) 3 parts of graphene loaded with inhibitor nanoreactor are added to 30 parts of ethanol and 0.5 parts of heptadecafluorodecyl triethoxysilane, and fully stirred (magnetic stirring for 30 min) until uniformly dispersed, then repeated 3 times of ultrasonic treatment and stirring (ultrasonic treatment for 10 min followed by magnetic stirring for 10 min), and dried to obtain fluorinated modified graphene loaded with inhibitor;

[0036] (3) 4 parts of carbon nanotubes (length of 15 μm) are added to 30 parts of ethanol and 0.5 parts of heptadecafluorodecyl triethoxysilane, and fully stirred (magnetic stirring for 30 min) until uniformly dispersed, then repeated 3 times of ultrasonic treatment and stirring (ultrasonic treatment for 10 min followed by magnetic stirring for 10 min), and dried to obtain fluorosilane modified carbon nanotubes;

[0037] (4) 3 parts of fluorosilicon resin stock solution are mixed with 15 parts of butyl acetate, and 1 part of fluorosilane modified carbon nanotubes is fully stirred (magnetic stirring for 30 min) until uniformly mixed to obtain anti-corrosion coating component A;

[0038] (5) 1 part of fluorosilicon resin curing liquid is mixed with 10 parts of butyl acetate, and 3 parts of fluorinated modified graphene loaded with inhibitor is fully stirred (magnetic stirring for 30 min) until uniformly mixed to obtain anti-corrosion coating component B;

[0039] (6) Anti-corrosion coating component A and anti-corrosion coating component B are mixed according to a weight ratio of 1:0.5 and stirred uniformly (magnetic stirring for 5 min) to obtain a super-hydrophobic anti-corrosion coating.

[0040] An ultrahydrophobic anticorrosion coating with self-repairing function is prepared by spraying the prepared ultrahydrophobic anticorrosion coating on a ceramic substrate, and curing at room temperature to obtain an ultrahydrophobic anticorrosion coating with self-repairing function; the spraying coating amount is 0.02 mL / cm 2 .

[0041] Example 3

[0042] A preparation method of an ultrahydrophobic anticorrosion coating with self-repairing function, comprising the following steps:

[0043] (1) According to the weight fraction, 8 parts of cyclodextrin is dissolved in 30 parts of water, 5 parts of graphene is added, stirred uniformly (glass rod stirring for 10 min), 2 parts of ammonia is added dropwise, stirring while adding, after the dropwise addition is completed, 25 parts of hydrazine hydrate is added, the above solution is placed in an oil bath at 75℃ for reaction for 5h; the obtained black solution is loaded into a dialysis bag and placed in deionized water for dialysis for 3d, and then soaked in benzotriazole to obtain graphene loaded with inhibitor nanoreservoir;

[0044] (2) 5 parts of graphene loaded with inhibitor nanoreservoir is added to 50 parts of ethanol and 2 parts of tridecafluorooctyltriethoxysilane, and fully stirred (glass rod stirring for 50 min) until uniformly dispersed, then repeated 8 times of ultrasonic treatment and stirring (ultrasonic treatment for 18 min followed by glass rod stirring for 18 min), and dried to obtain fluorinated modified graphene loaded with inhibitor;

[0045] (3) 6 parts of carbon nanotube (length of 50μm) is added to 50 parts of ethanol and 2 parts of tridecafluorooctyltriethoxysilane, and fully stirred (glass rod stirring for 50 min) until uniformly dispersed, then repeated 8 times of ultrasonic treatment and stirring (ultrasonic treatment for 18 min followed by glass rod stirring for 18 min), and dried to obtain fluorosilane modified carbon nanotube;

[0046] (4) 7 parts of fluorosilicon resin stock solution is mixed with 25 parts of ethyl acetate, and 3 parts of fluorosilane modified carbon nanotube is fully stirred (glass rod stirring for 50 min) until uniformly mixed to obtain anticorrosion coating component A;

[0047] (5) 3 parts of fluorosilicon resin curing solution is mixed with 20 parts of ethyl acetate, and 7 parts of fluorinated modified graphene loaded with inhibitor is fully stirred (glass rod stirring for 50 min) until uniformly mixed to obtain anticorrosion coating component B;

[0048] (6) Anticorrosion coating component A and anticorrosion coating component B are mixed according to a weight ratio of 1:2 and stirred uniformly (glass rod stirring for 10 min) to obtain an ultrahydrophobic anticorrosion coating.

[0049] An ultrahydrophobic anticorrosion coating with self-repairing function is prepared by spraying the prepared ultrahydrophobic anticorrosion coating on a glass substrate, and curing at room temperature to obtain an ultrahydrophobic anticorrosion coating with self-repairing function; the spraying coating amount is 0.05 mL / cm 2 .

[0050] Example 4

[0051] A preparation method of an ultrahydrophobic anticorrosion coating with self-repairing function, comprising the following steps:

[0052] (1) According to the weight fraction, 7 parts of cyclodextrin is dissolved in 18 parts of water, 3 parts of graphene is added, stirred uniformly (magnetic stirring for 7 min), 1.5 parts of ammonia water is added dropwise, stirring while adding, after the dropwise addition is completed, 18 parts of hydrazine hydrate is added, and the above solution is placed in an oil bath at 74℃ for reaction for 4h; the obtained black solution is loaded into a dialysis bag and placed in deionized water for dialysis for 1d, and then soaked in a benzotriazole solution to obtain graphene loaded with inhibitor nanoreactor;

[0053] (2) 3 parts of graphene loaded with inhibitor nanoreactor is added to 35 parts of ethanol and 2 parts of tridecafluorooctyltriethoxysilane, and fully stirred (magnetic stirring for 32 min) until uniformly dispersed, then repeated 5 times of ultrasonic treatment and stirring (ultrasonic treatment for 12 min followed by magnetic stirring for 15 min), and dried to obtain fluorinated modified graphene loaded with inhibitor;

[0054] (3) 4 parts of carbon nanotube (length of 28μm) is added to 45 parts of ethanol and 1 part of heptadecafluorodecyltriethoxysilane, and fully stirred (magnetic stirring for 32 min) until uniformly dispersed, then repeated 6 times of ultrasonic treatment and stirring (ultrasonic treatment for 12 min followed by magnetic stirring for 15 min), and dried to obtain fluorosilane modified carbon nanotube;

[0055] (4) 4 parts of fluorosilicon resin stock solution is mixed with 18 parts of ethyl acetate, and fully stirred (magnetic stirring for 32 min) with 1 part of fluorosilane modified carbon nanotube until uniformly mixed to obtain anticorrosion coating component A;

[0056] (5) 1 part of fluorosilicon resin curing solution is mixed with 12 parts of butyl acetate, and fully stirred (magnetic stirring for 32 min) with 4 parts of fluorinated modified graphene loaded with inhibitor until uniformly mixed to obtain anticorrosion coating component B;

[0057] (6) Anticorrosion coating component A and anticorrosion coating component B are mixed according to a weight ratio of 1:1.5 and stirred uniformly (magnetic stirring for 32 min) to obtain an ultrahydrophobic anticorrosion coating.

[0058] A kind of super-hydrophobic anticorrosive coating with self-repairing function, the super-hydrophobic anticorrosive coating prepared above is sprayed on plastic substrate, and self-repairing function super-hydrophobic anticorrosive coating is obtained by room temperature curing;The spraying coating amount of the coating is 0.03 mL / cm 2 .

[0059] Experimental example:

[0060] The material prepared in example 1 is observed in electron microscope, as shown in Figure 1 .

[0061] After the sample in example 1 is placed in different pH value (pH 1, 3, 5, 7, 9, 11, 13) solution for 24 hours, the contact angle and rolling angle are determined by 《GB / T30447-2013 Nano film contact angle measurement method》, and the determination results are shown in table 1:

[0062] Table 1 contact angle and rolling angle of sample in example 1 after being placed in different pH value solution for 24 hours

[0063] pH value 1 3 5 7 9 11 13 contact angle 152° 154° 155° 165° 162° 161° 158° rolling angle 9° 5° 4° 2° 3° 4° 8°

[0064] As can be seen from table 1, under the condition of pH=7, neutral, the contact angle of the material is maximum, the rolling angle is minimum, and the performance of the material is best.

[0065] The polarization current of commercially available pure Q235 steel and the sample prepared in example 1-4 is determined, as shown in table 2, and the polarization current value of the coating of the application is improved.

[0066] Table 2 polarization current comparison of different examples

[0067] sample pure Q235 steel Example 1 Example 2 Example 3 Example 4 polarization current (A) 0.0009 0.000016 0.000012 0.000014 0.000011

[0068] The above examples only express several embodiments of the present application, and the description is more specific and detailed, but it cannot be understood as the limitation of the scope of the patent. It should be pointed out that for ordinary skilled in the art, without departing from the concept of the present application, a number of variations and improvements can be made, which belong to the protection scope of the present application. Therefore, the protection scope of the patent of the present application should be subject to the appended claims.

Claims

1. A method for preparing a superhydrophobic anticorrosive coating having a self-repairing function, characterized by, The method comprises the following steps: (1) according to the weight fraction, 3-8 parts of cyclodextrin is dissolved in 10-30 parts of water, 2-5 parts of graphene is added, and 1-2 parts of ammonia water is added dropwise while stirring, 15-25 parts of hydrazine hydrate is added after the dropwise addition is completed, the solution added with hydrazine hydrate is placed in an oil bath at 70-75℃ for reaction for 3-5 hours to obtain a black solution; the obtained black solution is loaded into a dialysis bag and placed in deionized water for dialysis for 1-3 days, and then immersed in an inhibitor solution to obtain graphene loaded with inhibitor nanoreactor; The inhibitor solution is benzotriazole and / or mercaptobenzothiazole; (2) 3-5 parts of graphene loaded with inhibitor nanoreactor is added into 30-50 parts of ethanol and 0.5-2 parts of fluoroalkylsilane modifier, and after being fully stirred and uniformly dispersed, ultrasonic treatment and stirring are repeated for 3-8 times, and then drying is performed to obtain graphene loaded with inhibitor nanoreactor and modified by fluoroalkylsilane; (3) 4-6 parts of carbon nanotube is added into 30-50 parts of ethanol and 0.5-2 parts of fluoroalkylsilane modifier, and after being fully stirred and uniformly dispersed, ultrasonic treatment and stirring are repeated for 3-8 times, and then drying is performed to obtain carbon nanotube modified by fluoroalkylsilane; the length of the carbon nanotube is 5-50 μm; (4) 3-7 parts of fluoroalkylsilane resin stock solution is mixed with 15-25 parts of organic solvent, and 1-3 parts of carbon nanotube modified by fluoroalkylsilane is fully stirred and uniformly mixed to obtain anticorrosive coating component A; (5) 1-3 parts of fluoroalkylsilane resin curing solution is mixed with 10-20 parts of organic solvent, and 3-7 parts of graphene loaded with inhibitor nanoreactor and modified by fluoroalkylsilane is fully stirred and uniformly mixed to obtain anticorrosive coating component B; (6) anticorrosive coating component A and anticorrosive coating component B are mixed according to a weight ratio of 1:(0.5-2) and are uniformly stirred to obtain super-hydrophobic anticorrosive coating.

2. according to the preparation method of the super hydrophobic anti-corrosion coating with self-repairing function of claim 1, it is characterized in that, The fluoroalkylsilane modifier is tridecafluorooctyltriethoxysilane and / or heptadecafluorodecyltriethoxysilane.

3. according to the preparation method of the super hydrophobic anti-corrosion coating with self-repairing function of claim 1, it is characterized in that, The organic solvent is ethyl acetate and / or butyl acetate.

4. The method of claim 1, wherein the self-repairing superhydrophobic anticorrosion coating is prepared by the following steps: (1) preparing a solution of a hydrophobic material and a hydrophilic material; (2) mixing the solution with a polymer solution; (3) coating the mixture on a substrate; and (4) drying the mixture. The ultrasonic treatment and stirring are ultrasonic treatment for 10-20 minutes and glass rod stirring or magnetic stirring for 10-20 minutes; the fully stirring is glass rod stirring or magnetic stirring for 30-50 minutes; and the uniformly stirring is glass rod stirring or magnetic stirring for 5-10 minutes.

5. A superhydrophobic anti-corrosion coating with self-repairing function, characterized in that, The super-hydrophobic anticorrosive coating prepared in claim 1 is sprayed on a substrate, and a super-hydrophobic anticorrosive coating layer with self-repairing function is obtained after room temperature curing.

6. The superhydrophobic anti-corrosion coating with self-repairing function according to claim 5, characterized in that, The substrate is one or more of metal, ceramic, glass, fiber and plastic.

7. The superhydrophobic anti-corrosion coating with self-repairing function according to claim 5, characterized in that, The sprayed coating amount is 0.02-0.05 mL / cm 2 .

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