A corrosion-resistant waterproof coating and a preparation method thereof

Abstract

The application discloses a kind of corrosion-resistant waterproof coating and preparation method thereof, it is related to protective coating technical field.The impact force generated by spraying process in the application, so that ceramic flexible fiber is embedded in the small pore or uneven place of substrate surface, and three-dimensional network structure is formed on the surface, so as to realize the corrosion resistance and waterproofness of coating, simultaneously, by acting force, promote titanium sol and metal substrate combination, reaction, and then passivate metal surface, further enhance corrosion resistance and waterproofness, then by high-temperature treatment, form nanoscale rough surface on coating, so that substrate realizes hydrophobicity, so as to enhance the corrosion resistance, waterproof effect of coating, finally, spray epoxy resin, form ultra-thin encapsulation coating, so that rough hydrophobic structure is not influenced, and then improve corrosion resistance and waterproofness.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of protective coating, in particular to a corrosion-resistant waterproof coating and a preparation method thereof. BACKGROUND

[0002] The concept of metal corrosion is generally considered to be a physical and chemical reaction between metal materials and external environment, which gradually damages and deteriorates the metal materials. Metal corrosion can be seen everywhere in our production and life. For example, rust on the outside of steel products, oxidation of steel exposed to air for a long time, and the appearance of a powdery aluminum oxide layer on aluminum utensils are all phenomena of metal corrosion. Due to the complex and diverse use environment of metal materials, environmental factors such as oxygen, temperature and humidity, and pH value can cause the failure of metal material protection; the adverse consequences caused by metal corrosion not only affect the appearance, color and strength of the metal itself, but also cause damage or scrap of instruments, tools and metal structures made of metal, which reduces their utilization efficiency, and even causes accidents and disasters in extreme cases. According to incomplete statistics, one-third of the world's steel production is scrapped due to corrosion every year, and the waste of steel caused by corrosion is as high as 10% excluding the part that can be recycled.

[0003] The structural damage, energy efficiency reduction and economic losses caused by metal corrosion are immeasurable. Therefore, more and more people pay attention to the protection methods and effects of metal corrosion. Traditional metal corrosion protection measures may have a certain negative impact on the environment. For example, using toxic substances such as chromate for passivation treatment may cause environmental pollution; on the other hand, the protection effect of traditional protection measures has great limitations, which can only provide a certain degree of protection, and the maintenance cost is high. For example, the coating may peel off, crack and other problems, which may expose the metal to the corrosion environment. However, corrosion-resistant coatings have unique advantages such as low cost, fast construction, strong corrosion resistance, etc., and are widely used in metal protection. Coating protection is a kind of liquid or solid material that can form a film on the surface of an object under certain conditions to protect, decorate or have other special functions (insulation, rust prevention, mildew prevention, heat resistance, etc.). It is a kind of coating widely used in modern industry, transportation, energy, marine engineering and other departments. However, the flexibility of the coating is crucial on the surface of some substrates that need to withstand deformation, such as the curved parts of metal pipes or the deformation areas of metal plates during processing. If the coating lacks flexibility, it is easy to crack when the substrate deforms, which can damage the protective performance of the coating and limit the application of the coating. SUMMARY

[0004] The present application relates to the technical field of protective coating, in particular to a corrosion-resistant waterproof coating and a preparation method thereof.

[0005] In order to solve the above technical problems, the application provides the following technical scheme: a preparation method of a corrosion-resistant waterproof coating, comprising the following steps:

[0006] (1) pretreating ceramic flexible fibers, then mixing the ceramic flexible fibers with titanium sol to obtain a coating;

[0007] (2) pretreating an iron plate, then spraying the coating on the surface of the iron plate, and finally performing high-temperature treatment;

[0008] (3) mixing bisphenol A epoxy resin, a promoter, an initiator, and di-tripropylene glycol diacrylate, and spraying the mixture on the plate obtained in step (2) to obtain an encapsulation layer with a thickness of 5-30 microns, and then performing ultraviolet treatment to obtain the corrosion-resistant waterproof coating;

[0009] The preparation method of the ceramic flexible fibers is as follows: 10wt% polyvinylpyrrolidone-ethanol solution, 1mol / L nitric acid solution, and vinyltrimethylsilane are mixed, stirred at 500rpm for 4-8h, ultrasonicated at 21kHz for 10-30min, zirconium n-butoxide, aluminum n-butoxide, and acetic acid are added, and stirred for another 1h, spinning treatment is performed at a needle diameter of 0.6mm and a rate of 2000-4000m / min, and finally, the temperature is raised to 600℃ at a rate of 1℃ / min under an argon atmosphere, the temperature is kept for 2h, the temperature is then raised to 900-1200℃ at a rate of 5℃ / min, and the temperature is kept for 1h, and the ceramic flexible fibers are obtained; the mass ratio of the 10wt% polyvinylpyrrolidone-ethanol solution, the 1mol / L nitric acid solution, the vinyltrimethylsilane, the zirconium n-butoxide, the aluminum n-butoxide, and the acetic acid is 5:1.5:1.5:3:3:4.

[0010] Further, the length of the ceramic flexible fibers in step (1) is 0.05-0.2mm.

[0011] Further, the specific steps of the pretreatment in step (1) are as follows: a low-temperature ammonia gas plasma process is used, and the process parameters are as follows: a temperature of 100-200℃, a gas pressure of 80-100MPa, a power of 700-800W, and a time of 40-80min.

[0012] Further, the mass ratio of the ceramic flexible fibers to the titanium sol in step (1) is 1:50-100.

[0013] Further, the specific steps of the pretreatment in step (2) are as follows: first, sandpaper with a mesh size of 80-120 is used to polish the iron plate, then the iron plate is washed with anhydrous ethanol for 5 times, and finally, the iron plate is treated with 10wt% sodium hydroxide solution under ultrasonic conditions at 21kHz for 15min, and dried at 60℃ for 4h.

[0014] Further, the pressure of the spraying in step (2) is 11-25MPa, the running speed is 20-60m / s, and the spraying angle is 30-80°.

[0015] Further, the temperature of the high-temperature treatment in step (2) is 400-700 DEG C, and the time is 30-50 min.

[0016] Further, the ultraviolet treatment condition in step (3) is that the wavelength is 310-395 nm, the intensity is 40-100 mW / cm 2 , the temperature is 80 DEG C, and the time is 5-30 s.

[0017] Further, the mass ratio of the bisphenol A epoxy resin, the accelerator, the initiator, and the tripropylene glycol dipropylene glycol diacrylate in step (3) is 50:0.2:0.2-0.6:5-15.

[0018] Compared with the prior art, the achieved beneficial effects are:

[0019] The ceramic flexible fiber is first activated and pretreated in the application, so that the fiber surface has polar groups such as amino groups, and then the fiber is compounded with titanium sol, and the impact force generated by the spraying process makes the fiber material play a mechanical anchoring role on the metal base material, part of the fiber can be embedded in the small pores or uneven places on the surface of the base material, and a three-dimensional network structure is formed on the surface, thereby preventing the penetration of corrosive media, and the amino groups on the surface of the fiber can form amide bonds with the active groups on the surface of the base material, thereby enhancing the adhesion between the coating and the base material, thereby realizing the corrosion resistance and water resistance of the coating, and at the same time, the force promotes the combination and reaction of the sol and the free radicals on the surface of the metal base material, thereby forming a stable complex, passivating the metal surface, and further enhancing the corrosion resistance and water resistance.

[0020] Secondly, by high-temperature treatment, nano-titanium dioxide is generated on the surface of the fiber and inside the coating, and then by forming a nano-scale rough surface, the base material realizes hydrophobicity, thereby greatly improving the corrosion resistance and water resistance of the coating, and finally, the epoxy resin monomer is sprayed, and under the conditions of ultraviolet and initiation, polymerization is carried out to form an ultra-thin encapsulation coating, so that the rough and hydrophobic structure is not affected, thereby further improving the corrosion resistance and water resistance of the coating. DETAILED DESCRIPTION

[0021] The technical solutions in the embodiments of the application will be clearly and completely described below with reference to the embodiments of the application. Obviously, the described embodiments are only a part of the embodiments of the application, rather than all the embodiments of the application. Based on the embodiments in the application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the application.

[0022] In order to more clearly illustrate the method provided by the application, the following embodiments are used for detailed description, and the test methods of various indexes of the corrosion-resistant and waterproof coating prepared in the following embodiments are as follows:

[0023] Water resistance: The hydrophobic effect test was performed on the same size of examples and comparative examples, and the water contact angle of the fabric was tested by OCA15EC type contact angle measuring instrument, the drop size was 8 μl, and the drop rate was 2 μl / s.

[0024] Corrosion resistance: The same size of examples and comparative examples were taken for acid and alkali resistance test, and the sample was immersed in 30wt% sulfuric acid solution and 10wt% sodium hydroxide solution respectively for 7 days, and the change was observed.

[0025] Example 1

[0026] (1) 10wt% polyvinylpyrrolidone-ethanol solution, 1mol / L nitric acid solution, vinyltrimethylsilane were mixed, stirred at 500 rpm for 4h, ultrasonic at 21 kHz for 10 min, zirconium n-butanol, aluminum n-butanol, acetic acid were added, and stirred for 1h, and then the spinning treatment was performed, the needle diameter was 0.6mm, the rate was 2000m / min, finally, the temperature was increased to 600℃ at 1℃ / min under argon atmosphere, and then the temperature was increased to 900-1200℃ at 5℃ / min, and the temperature was kept for 1h, and ceramic flexible fiber was obtained; the mass ratio of 10wt% polyvinylpyrrolidone-ethanol solution, 1mol / L nitric acid solution, vinyltrimethylsilane, zirconium n-butanol, aluminum n-butanol, acetic acid was 5:1.5:1.5:3:3:4; the ceramic flexible fiber was pretreated by low temperature ammonia plasma process, the process parameters were: temperature 100℃, pressure 80MPa, power 700W, time 40min, and then mixed with titanium sol to obtain coating; the mass ratio of the ceramic flexible fiber and the titanium sol was 1:50; the length of the ceramic flexible fiber was 0.05mm; the type of the titanium sol was SS-TA10W;

[0027] (2) The iron plate was pretreated: first polished with 80 mesh sandpaper, then washed with anhydrous ethanol for 5 times, finally treated with 10wt% sodium hydroxide solution under 21 kHz ultrasonic condition for 15min, and dried at 60℃ for 4h, then the surface of the plate was sprayed with the coating, the spraying pressure was 11MPa, the running speed was 20m / s, the spraying angle was 30°, and finally high temperature treatment was performed, the temperature was 400℃, and the time was 30min;

[0028] (3) Bisphenol A epoxy resin, accelerator, initiator, tripropyleneglycol diacrylate were mixed and sprayed on the plate obtained by step (2) to obtain a packaging layer with a thickness of 5μm, and then treated by ultraviolet, the condition parameters were: wavelength 310nm, intensity 40mW / cm 2, temperature is 80℃, time is 5s, corrosion-resistant waterproof coating is obtained; the mass ratio of bisphenol A epoxy resin, accelerator, initiator, tripropyleneglycol diacrylate is 50:0.2:0.2:5; the accelerator is benzophenone; the initiator is OMNICAT 550.

[0029] Example 2

[0030] (1) 10wt% polyvinylpyrrolidone-ethanol solution, 1mol / L nitric acid solution, vinyltrimethylsilane are mixed, stirred at 500rpm for 6h, ultrasonic at 21kHz for 20min, zirconium n-butyl alcohol, aluminum n-butyl alcohol, acetic acid are added, stirred for 1h, spinning treatment is carried out, the needle diameter is 0.6mm, the rate is 3000m / min, finally, it is heated to 600℃ at 1℃ / min under argon atmosphere, keeps warm for 2h, then heated to 1000℃ at 5℃ / min, keeps warm for 1h, ceramic flexible fiber is obtained; the mass ratio of 10wt% polyvinylpyrrolidone-ethanol solution, 1mol / L nitric acid solution, vinyltrimethylsilane, zirconium n-butyl alcohol, aluminum n-butyl alcohol, acetic acid is 5:1.5:1.5:3:3:4; the ceramic flexible fiber is pretreated by low-temperature ammonia plasma process, the process parameters are: temperature is 150℃, gas pressure is 90MPa, power is 750W, time is 60min, then mixed with titanium sol, coating is obtained; the mass ratio of the ceramic flexible fiber and titanium sol is 1:80; the length of the ceramic flexible fiber is 0.12mm; the model of the titanium sol is SS-TA10W;

[0031] (2) the iron plate is pretreated: first polished with 100 mesh sandpaper, then washed with anhydrous ethanol for 5 times, finally, 10wt% sodium hydroxide solution is used to treat the surface of the iron plate under the condition of ultrasonic at 21kHz for 15min, dried at 60℃ for 4h, then the coating is sprayed on the surface of the iron plate, the spraying pressure is 18MPa, the running speed is 40m / s, the spraying angle is 50°, finally, high-temperature treatment is carried out, the temperature is 550℃, the time is 40min;

[0032] (3) bisphenol A epoxy resin, accelerator, initiator, tripropyleneglycol diacrylate are mixed and sprayed on the plate obtained by step (2) to obtain an encapsulation layer with a thickness of 17μm, which is treated by ultraviolet, the condition parameters are: wavelength is 365nm, intensity is 70mW / cm 2 , temperature is 80℃, time is 18s, corrosion-resistant waterproof coating is obtained; the mass ratio of bisphenol A epoxy resin, accelerator, initiator, tripropyleneglycol diacrylate is 50:0.2:0.4:10; the accelerator is benzophenone; the initiator is OMNICAT 550.

[0033] Example 3

[0034] (1) 10wt% polyvinylpyrrolidone-ethanol solution, 1 mol / L nitric acid solution, vinyltrimethylsilane were mixed, stirred at 500 rpm for 8 h, ultrasonic at 21 kHz for 10-30 min, zirconium n-butyl alcohol, aluminum n-butyl alcohol, acetic acid were added, and stirred for 1 h, and then the spinning treatment was carried out, the needle diameter was 0.6 mm, the rate was 4000 m / min, finally, the temperature was raised to 600℃ at 1℃ / min under argon atmosphere, and then the temperature was kept for 2 h, and then the temperature was raised to 1200℃ at 5℃ / min, and then the temperature was kept for 1 h, and then ceramic flexible fiber was obtained; the mass ratio of the 10wt% polyvinylpyrrolidone-ethanol solution, 1 mol / L nitric acid solution, vinyltrimethylsilane, zirconium n-butyl alcohol, aluminum n-butyl alcohol, acetic acid was 5:1.5:1.5:3:3:4; the ceramic flexible fiber was pretreated by low-temperature ammonia plasma process, the process parameters were: temperature 200℃, gas pressure 100 MPa, power 800 W, time 80 min, and then mixed with titanium sol to obtain a coating; the mass ratio of the ceramic flexible fiber and the titanium sol was 1:50-100; the length of the ceramic flexible fiber was 0.2 mm; the model of the titanium sol was SS-TA10W;

[0035] (2) The iron plate was pretreated: first polished with 120 grit sandpaper, then washed with anhydrous ethanol for 5 times, finally treated with 10wt% sodium hydroxide solution under 21 kHz ultrasonic condition for 15 min, and dried at 60℃ for 4 h, then the surface of the plate was sprayed with the coating, the spraying pressure was 25 MPa, the running speed was 60 m / s, the spraying angle was 80°, and finally high temperature treatment was carried out, the temperature was 700℃, and the time was 50 min;

[0036] (3) Bisphenol A epoxy resin, accelerator, initiator, dipropylene glycol diacrylate were mixed and sprayed on the plate obtained by step (2) to obtain a packaging layer with a thickness of 30 μm, and then the packaging layer was treated by ultraviolet, the condition parameters were: wavelength 395 nm, intensity 100 mW / cm 2 , temperature 80℃, time 30 s, and then a corrosion-resistant and waterproof coating was obtained; the mass ratio of the bisphenol A epoxy resin, the accelerator, the initiator, and the dipropylene glycol diacrylate was 50:0.2:0.6:15; the accelerator was benzophenone; the initiator was OMNICAT 550.

[0037] Comparative Example 1

[0038] The difference between Comparative Example 1 and Example 2 is that step (1) is different, and step (1) is changed to: 10wt% polyvinylpyrrolidone-ethanol solution, 1mol / L nitric acid solution, vinyltrimethylsilane are mixed, stirred at 500rpm for 6h, ultrasonic at 21kHz for 20min, zirconium n-butyl alcohol, aluminum n-butyl alcohol, acetic acid are added, and stirred for 1h, and the spinning treatment is carried out, the needle diameter is 0.6mm, the rate is 3000m / min, finally, the temperature is increased to 600℃ at 1℃ / min under argon atmosphere, and the temperature is kept for 2h, then the temperature is increased to 1000℃ at 5℃ / min, and the temperature is kept for 1h, to obtain the ceramic flexible fiber; the mass ratio of the 10wt% polyvinylpyrrolidone-ethanol solution, 1mol / L nitric acid solution, vinyltrimethylsilane, zirconium n-butyl alcohol, aluminum n-butyl alcohol, acetic acid is 5:1.5:1.5:3:3:4; the ceramic flexible fiber is pretreated by using low-temperature ammonia plasma process, and the process parameters are: temperature is 150℃, gas pressure is 90MPa, power is 750W, and time is 60min, then mixed with ethanol to obtain the coating; the mass ratio of the ceramic flexible fiber and ethanol is 1:80; the length of the ceramic flexible fiber is 0.12mm; the rest of the steps are the same as Example 2.

[0039] Comparative Example 2

[0040] The difference between Comparative Example 2 and Example 2 is that there is no step (1), and step (2) is changed to: the iron plate is pretreated: first polished with 100 mesh sandpaper, then washed with anhydrous ethanol for 5 times, finally treated with 10wt% sodium hydroxide solution under 21kHz ultrasonic condition for 15min, and dried at 60℃ for 4h, then the titanium sol is sprayed on the surface, the spraying pressure is 18MPa, the running speed is 40m / s, the spraying angle is 50°, and finally high temperature treatment is carried out, the temperature is 550℃, and the time is 40min; the type of the titanium sol is SS-TA10W; the rest of the steps are the same as Example 2.

[0041] Comparative Example 3

[0042] The difference between Comparative Example 3 and Example 2 is that there is no step (3); the rest of the steps are the same as Example 2.

[0043] Effect Example

[0044] The performance analysis results of the corrosion-resistant and waterproof coating layer using Examples 1 to 3 and Comparative Examples 1 to 3 of the application are given in the following Table 1.

[0045] Table 1

[0046]

[0047] From the comparison of the experimental results of the examples and the comparative examples in Table 1, it can be found that, in the present application, the ceramic flexible fiber is first activated and pretreated, so that the fiber surface is provided with polar groups such as amino groups, and then compounded with titanium sol, so that the impact force generated by the spraying process makes the fiber material play a mechanical anchoring role on the metal substrate, part of the fiber can be embedded in the small pores or uneven places on the surface of the substrate, and form a three-dimensional network structure on the surface, thereby preventing the penetration of corrosive media, and the amino groups on the surface of the fiber can form amide bonds with the active groups on the surface of the substrate, thereby enhancing the adhesion between the coating and the substrate, so as to realize the corrosion resistance and water resistance of the coating, at the same time, the action force promotes the combination and reaction of the sol and the free radicals on the surface of the metal substrate, thereby forming a stable complex, passivating the metal surface, and further enhancing the corrosion resistance and water resistance, then through high temperature treatment, nano titanium dioxide is generated on the surface of the fiber and in the coating, thereby forming a nano-scale rough surface, so that the substrate realizes hydrophobicity, thereby greatly improving the corrosion resistance and water resistance of the coating, finally, the epoxy resin monomer is sprayed, and under the conditions of ultraviolet and initiation, polymerization is carried out to form an ultra-thin encapsulation coating, so that the rough and hydrophobic structure is not affected, thereby further improving the corrosion resistance and water resistance of the coating.

[0048] It will be apparent to those skilled in the art that the application is not limited to the details of the above-described exemplary embodiments, and can be implemented in other specific forms without departing from the spirit or essential characteristics of the application. Therefore, the embodiments should be regarded as exemplary and non-limiting, and the scope of the application is defined by the appended claims rather than the above description, and all changes falling within the meaning and scope of the equivalent elements of the claims are intended to be included in the application. Any mark in the claims should not be regarded as limiting the involved claims.

Claims

1. A method for preparing a corrosion-resistant and waterproof coating, characterized in that, Includes the following steps: (1) The ceramic flexible fiber is pretreated and then mixed with titanium sol to obtain a coating. (2) The iron plate is pretreated, then the coating is sprayed onto its surface, and finally it is subjected to high temperature treatment; (3) Mix bisphenol A epoxy resin, accelerator, initiator and tripropylene glycol diacrylate and spray it onto the board obtained in step (2) to obtain an encapsulation layer with a thickness of 5 to 30 μm. After ultraviolet treatment, a corrosion-resistant and waterproof coating is obtained. The method for preparing the ceramic flexible fiber is as follows: 10wt% polyvinylpyrrolidone-ethanol solution, 1mol / L nitric acid solution, and vinyltrimethylsilane are mixed and stirred at 500rpm for 4-8h, ultrasonicated at 21kHz for 10-30min, zirconium n-butoxide, aluminum n-butoxide, and acetic acid are added, and the mixture is stirred for another 1h. Spinning is then performed with a needle diameter of 0.6mm and a spinning speed of 2000-4000m / min. Finally, the temperature is increased to 600℃ at 1℃ / min under an argon atmosphere and held for 2h, then increased to 900-1200℃ at 5℃ / min and held for 1h to obtain the fiber. The mass ratio of the 10wt% polyvinylpyrrolidone-ethanol solution, 1mol / L nitric acid solution, vinyltrimethylsilane, zirconium n-butoxide, aluminum n-butoxide, and acetic acid is 5:1.5:1.5:3:3:

4.

2. The method for preparing a corrosion-resistant and waterproof coating according to claim 1, characterized in that, The length of the ceramic flexible fiber in step (1) is 0.05 to 0.2 mm.

3. The method for preparing a corrosion-resistant and waterproof coating according to claim 1, characterized in that, The specific steps of the pretreatment in step (1) are as follows: a low-temperature ammonia plasma process is adopted, and the process parameters are: temperature of 100-200℃, gas pressure of 80-100MPa, power of 700-800W, and time of 40-80min.

4. The method for preparing a corrosion-resistant and waterproof coating according to claim 1, characterized in that, The mass ratio of ceramic flexible fiber to titanium sol in step (1) is 1:50 to 100.

5. The method for preparing a corrosion-resistant and waterproof coating according to claim 1, characterized in that, The specific steps of the pretreatment in step (2) are as follows: first, polish with 80-120 grit sandpaper, then rinse with anhydrous ethanol 5 times, and finally treat with 10wt% sodium hydroxide solution under 21kHz ultrasonic conditions for 15 minutes and dry at 60℃ for 4 hours.

6. The method for preparing a corrosion-resistant and waterproof coating according to claim 1, characterized in that, The spraying pressure in step (2) is 11-25 MPa, the operating speed is 20-60 m / s, and the spraying angle is 30-80°.

7. The method for preparing a corrosion-resistant and waterproof coating according to claim 1, characterized in that, The high-temperature treatment in step (2) is performed at a temperature of 400–700°C for 30–50 minutes.

8. The method for preparing a corrosion-resistant and waterproof coating according to claim 1, characterized in that, The ultraviolet treatment conditions in step (3) are: wavelength 310–395 nm and intensity 40–100 mW / cm. 2 The temperature is 80℃ and the time is 5 to 30 seconds.

9. The method for preparing a corrosion-resistant and waterproof coating according to claim 1, characterized in that, The mass ratio of bisphenol A epoxy resin, accelerator, initiator and tripropylene glycol diacrylate in step (3) is 50:0.2:0.2~0.6:5~15.

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