A ceramic / fiber modified coating for steel pipe piles, its preparation method and application

Abstract

The present invention discloses a ceramic / fiber modified coating for steel pipe piles, its preparation method and application. The preparation method includes: modifying ceramic particles with a first modifier to obtain modified ceramic particles; growing the modified ceramic particles at the nanoscale or microscale on the surface of fibers by at least any one of hydrothermal method, chemical vapor deposition method, physical vapor deposition method, sol-gel method, microwave synthesis method, redox method to obtain fibers with grown modified ceramic particles; modifying the fibers with grown modified ceramic particles with a second modifier to obtain modified fibers; and mixing the modified fibers, resin and curing agent, applying them to the surface of a substrate and performing curing treatment to prepare the ceramic / fiber modified coating. The ceramic / fiber modified coating provided by the present invention has excellent impact resistance performance and has good application prospects in the field of erosion-corrosion resistance.

Description

Technical Field

[0001] The present invention belongs to the technical field of fiber modified coatings, and particularly relates to a ceramic / fiber modified coating for steel pipe piles, a preparation method thereof, and an application thereof. Background Art

[0002] Offshore engineering equipment is in a harsh environment of high temperature, high humidity, and high salt spray for a long time. Especially for steel pipe piles, which are the foundation of offshore equipment, under the continuous erosion of splashing waves and seawater and sediment in the tidal range area, the service life of steel pipe piles is greatly reduced. The coating material on the surface of steel pipe piles is prone to damage such as scratches, peeling, and warping during the construction of steel pipe piles, including hoisting, transportation, driving construction, removal of the bearing platform, and collision with construction ships. These damages will become the starting point of corrosion during their service, thus seriously reducing the service life of steel pipe piles. It cannot meet the service requirements of steel pipe piles in the splash zone and tidal range area, and will cause serious damage under the continuous corrosion of wet-dry alternation and high-concentration salt spray, endangering the safety of offshore equipment and causing serious economic losses. Therefore, designing and developing a protective coating for offshore engineering equipment is an urgent problem to be solved. Summary of the Invention

[0003] The main purpose of the present invention is to provide a ceramic / fiber modified coating for steel pipe piles, a preparation method thereof, and an application thereof, so as to overcome the deficiencies of the prior art.

[0004] To achieve the foregoing invention purpose, the technical solutions adopted by the present invention include:

[0005] An embodiment of the present invention provides a preparation method of a ceramic / fiber modified coating for steel pipe piles, which includes:

[0006] Modifying ceramic particles with a first modifier to obtain modified ceramic particles; wherein, the first modifier includes any one or a combination of dopamine, surfactant, and ionic liquid;

[0007] Growing the modified ceramic particles at the nanoscale or microscale on the surface of the fiber by at least any one of hydrothermal method, chemical vapor deposition method, physical vapor deposition method, sol-gel method, microwave synthesis method, and redox method to obtain fibers with grown modified ceramic particles;

[0008] Modifying the fibers with grown modified ceramic particles with a second modifier to obtain modified fibers; wherein, the second modifier includes surfactant and / or ionic liquid;

[0009] And, mixing the modified fibers, resin, and curing agent, applying them to the surface of the substrate and performing curing treatment to prepare a ceramic / fiber modified coating.

[0010] An embodiment of the present invention also provides a ceramic / fiber modified coating for steel pipe piles prepared by the foregoing preparation method.

[0011] An embodiment of the present invention also provides an application of the foregoing ceramic / fiber modified coating for steel pipe piles in the field of protection of offshore engineering equipment.

[0012] Compared with the prior art, the beneficial effects of the present invention are as follows: The corrosion protection ability of the ceramic / fiber modified coating prepared by the present invention is greatly improved. After 30 days of service, its low-frequency impedance value is above 10 11 Ω·cm 2 Moreover, the bonding force between the coating and the metal substrate is as high as 8 MPa even after soaking in a high-pressure environment for 10 days, and the water absorption rate is as low as 2%, demonstrating an excellent long-term corrosion protection effect; at the same time, the ceramic / fiber modified coating provided by the present invention has excellent impact resistance performance and has good application prospects in the field of erosion-corrosion resistance. BRIEF DESCRIPTION OF THE DRAWINGS

[0013] In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings required for description in the embodiments or the prior art. Obviously, the drawings in the following description are only some embodiments recorded in the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can also be obtained based on these drawings.

[0014] Figure 1 It is the morphology diagram of aramid fiber in Embodiment 1 of the present invention;

[0015] Figure 2 It is the morphology diagram of modified aramid fiber in Embodiment 1 of the present invention. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0016] In view of the defects of the prior art, the inventors of this case have proposed the technical solution of the present invention through long-term research and a large number of practices. The following will clearly and completely describe the technical solution of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts fall within the protection scope of the present invention.

[0017] Specifically, as an aspect of the technical solution of the present invention, a preparation method of a ceramic / fiber modified coating for steel pipe piles includes:

[0018] Modifying ceramic particles with a first modifier to obtain modified ceramic particles; wherein, the first modifier includes any one or a combination of dopamine, surfactant, and ionic liquid;

[0019] At least one of a hydrothermal method, a chemical vapor deposition method, a physical vapor deposition method, a sol-gel method, a microwave synthesis method, and a redox method is used to grow nano-scale or micro-scale modified ceramic particles on the fiber surface to obtain fibers having grown modified ceramic particles;

[0020] Modifying the fibers of the grown modified ceramic particles with a second modifier to obtain modified fibers; wherein the second modifier comprises a surfactant and / or an ionic liquid;

[0021] Furthermore, the modified fiber, resin and curing agent are mixed, applied to the surface of a substrate and cured to obtain a ceramic / fiber modified coating.

[0022] In some preferred embodiments, the method for preparing the modified ceramic particles specifically comprises: mixing a solution containing a first modifier with ceramic particles and reacting the mixture at 60-75° C. for 6-48 hours to obtain modified ceramic particles.

[0023] Specifically, a first modifier solution (including dopamine, surfactant, ionic liquid, etc.) with a concentration of 0.5-5 mg / ml is prepared, reacted with 100 mg of ceramic particles at 60° C. for 6-48 hours, and washed by centrifugation with deionized water to obtain a product.

[0024] In some preferred embodiments, the ratio of the first modifier to the ceramic particles is 40-200 mL: 10-500 mg.

[0025] In some preferred embodiments, the modified ceramic particles have a particle size of 100-300 nm.

[0026] In some preferred embodiments, the ceramic particles include any one or more combinations of titanium dioxide, aluminum oxide, zirconium oxide, and silicon dioxide, but are not limited thereto.

[0027] In some preferred embodiments, the surfactant includes any one or more combinations of cationic surfactants, anionic surfactants, amphoteric surfactants, and nonionic surfactants, but is not limited thereto.

[0028] Furthermore, the cationic surfactant includes an amino acid type cationic surfactant and / or a quaternary ammonium compound, the amino acid type cationic surfactant includes N-cocoyl arginine ethyl ester; the quaternary ammonium compound includes any one or more combinations of benzalkonium chloride (chlorhexidine), benzalkonium bromide (chlorhexidine), and benzalkonium chloride, and is not limited thereto.

[0029] Furthermore, the anionic surfactant includes sodium lauryl sulfate, but is not limited thereto.

[0030] Further, the amphoteric surfactant includes, but is not limited to, N-alkyl aspartic acid-b-alkyl ester.

[0031] Further, the non-ionic surfactant includes, but is not limited to, fatty acid glyceride and / or sorbitan fatty acid ester.

[0032] In some preferred embodiments, the ionic liquid includes, but is not limited to, cationic ionic liquid and / or anionic ionic liquid.

[0033] Further, the cationic ionic liquid includes any one or a combination of more than one of quaternary ammonium salt ionic liquid, quaternary phosphonium salt ionic liquid, imidazole salt ionic liquid, pyrrole salt ionic liquid, and the like, and is not limited thereto.

[0034] Further, the anionic ionic liquid includes any one or a combination of more than one of halogen ionic liquid, tetrafluoroborate ionic liquid, hexafluorophosphate ionic liquid, and the like, and is not limited thereto.

[0035] In some preferred embodiments, the first modifier is the same as or different from the second modifier.

[0036] In some preferred embodiments, the fiber includes any one of organic fiber, inorganic fiber, and organic / inorganic composite fiber, and is not limited thereto.

[0037] Further, the organic fiber includes any one or a combination of more than one of aramid fiber, polypropylene fiber, polyester fiber, polyacrylonitrile fiber, polyphenylene sulfide fiber, and the like, and is not limited thereto.

[0038] Further, the inorganic fiber includes any one or a combination of more than one of carbon fiber, glass fiber, silicon carbide fiber, silicon oxyaluminum fiber, and the like, and is not limited thereto.

[0039] Further, the organic / inorganic composite fiber includes, but is not limited to, glass fiber / carbon fiber composite fiber.

[0040] In some preferred embodiments, the diameter of the fiber is 5 - 20 μm, and the length is 1 - 10 mm.

[0041] In some preferred embodiments, the morphology of the particles in the fiber with growth-modified ceramic particles includes any one or a combination of more than one of spherical, polyhedral, conical, and cuboid, and is not limited thereto.

[0042] Further, the particles grow in any one of the ways of on one side of the fiber, surrounding the fiber, and around the fiber.

[0043] In some preferred embodiments, the method for growing modified ceramic particles on the fiber surface by hydrothermal method specifically includes:

[0044] Disperse 0.01 - 1 g of modified ceramic particles and 0.1 - 10 g of fibers in 1 - 100 ml of modifier in solvents such as deionized water and ethanol, stir at 60 - 120 °C in an oil bath for 6 - 49 hours, and finally wash with deionized water and / or ethanol, and freeze-dry for 12 - 48 hours to obtain the final product.

[0045] In some preferred embodiments, the method for growing modified ceramic particles on the fiber surface by chemical vapor deposition method specifically includes:

[0046] In a high-vacuum environment at 100 - 600 °C, using a modified ceramic particle target, sputter for 5 - 120 minutes to achieve the growth of ceramic particles on the fiber surface.

[0047] In some preferred embodiments, the method for growing nano-scale or micro-scale modified ceramic particles on the fiber surface by physical vapor deposition method specifically includes:

[0048] In a high-vacuum environment at 300 - 500 °C, using a target target (modified ceramic particle target), sputter for 5 - 120 minutes to achieve the growth of ceramic particles on the fiber surface.

[0049] In some preferred embodiments, the method for growing nano-scale or micro-scale modified ceramic particles on the fiber surface by sol-gel method specifically includes:

[0050] Dissolve relevant modified ceramic particles (such as modified titanium oxide) in an appropriate solvent, add an appropriate amount of acid or base to the sol, adjust the pH of the solution, promote the hydrolysis and gelation reactions of the sol, and then dry and heat-treat the gel to achieve the growth of ceramic particles on the fiber surface.

[0051] In some preferred embodiments, the method for growing nano-scale or micro-scale modified ceramic particles on the fiber surface by microwave synthesis method specifically includes:

[0052] Mix the ceramic particles and fibers in a mass ratio, and achieve the growth of ceramic particles on the fiber surface by controlling the frequency of electromagnetic radiation.

[0053] In some preferred embodiments, the method for growing nano-scale or micro-scale modified ceramic particles on the fiber surface by redox method specifically includes:

[0054] Directly reduce the ceramic particles, and under the action of a reducing agent (such as hydrogen, sodium borohydride, ammonia, sodium hydroxide, etc.), achieve the growth of modified ceramic particles on the fiber surface.

[0055] In some preferred embodiments, the method for preparing the modified fiber comprises: dispersing the fiber for growing modified ceramic particles and a second modifier in a solvent, stirring and reacting at 60-120 °C for 6-48 h, and then performing washing and freeze-drying treatments to obtain the modified fiber.

[0056] Further, the dosage ratio of the fiber for growing modified ceramic particles to the second modifier is 0.01-1 g: 1-100 ml.

[0057] Further, the solvent includes deionized water and / or ethanol, and is not limited thereto.

[0058] For example: 0.01-1 g of the fiber for growing modified ceramic particles and 1-100 ml of the modifier are dispersed in solvents such as deionized water and ethanol, stirred at 60-120 °C in an oil bath for 6-48 hours, and finally washed with deionized water and / or ethanol and freeze-dried for 12-48 hours to obtain the final product.

[0059] In some preferred embodiments, the preparation method specifically comprises:

[0060] Uniformly mixing the modified fiber and the resin, and then adding a curing agent for mixing to obtain a mixed material;

[0061] And applying the mixed material to the surface of the substrate and curing at 25-80 °C for 48-96 h to prepare a ceramic / fiber modified coating.

[0062] Further, the mass ratio of the modified fiber, the resin and the curing agent is 0.01-1: 50-90: 10-50.

[0063] Further, the resin includes any one or a combination of more than one of epoxy resin, acrylic resin, polyurethane, polyimide, and is not limited thereto.

[0064] Further, the curing agent includes any one or a combination of more than one of aliphatic amine, cycloaliphatic amine, aromatic amine, polyamide, acid anhydride, resin type, tertiary amine, and is not limited thereto.

[0065] Further, the substrate includes a steel pipe pile, and is not limited thereto.

[0066] In the present invention, ceramic particles are modified by dopamine monomers, surfactants, ionic liquids, etc. to achieve compatibility and lattice matching with fibers; and then ionic liquids and surfactant-modified fibers are used to improve the interfacial compatibility between fibers and resins and the impact resistance of composite materials.

[0067] Another aspect of the embodiments of the present invention further provides a ceramic / fiber modified coating for a steel pipe pile prepared by the foregoing preparation method.

[0068] Furthermore, the thickness of the ceramic / fiber modified coating is 50 to 1000 μm.

[0069] Furthermore, after the ceramic / fiber modified coating is immersed in brine for 30 days, the low-frequency impedance modulus of the coating is above 10 11 Ω·cm 2 and the bonding strength between the coating and the metal substrate is as high as 8 MPa.

[0070] Another aspect of the embodiments of the present invention also provides an application of the aforementioned ceramic / fiber modified coating for steel pipe piles in the field of protection of offshore engineering equipment.

[0071] Furthermore, the offshore engineering equipment includes steel pipe piles in a harsh environment of high temperature, high humidity and high salt spray.

[0072] The technical solutions of the present invention will be further described in detail below in conjunction with several preferred embodiments and the accompanying drawings. These embodiments are implemented on the premise of the technical solutions of the invention, and detailed implementation manners and specific operation processes are given. However, the protection scope of the present invention is not limited to the following embodiments.

[0073] In the following embodiments, the experimental materials used can be obtained from conventional biochemical reagent companies without special instructions.

[0074] Example 1

[0075] (1) Dopamine-modified titanium dioxide

[0076] Add a 2 mg / ml dopamine solution to an 8 mM tris buffer solution, then add 200 mg of titanium dioxide, adjust the pH to 8.5 with NaOH·HCl, soak for 6 h, ultrasonically clean the soaked sample with deionized water for 15 minutes, and dry it with N2 to obtain dopamine-modified titanium dioxide;

[0077] (2) Hydrothermal method to grow nanoscale dopamine-modified titanium dioxide on the surface of aramid fibers

[0078] Surface alkalize the aramid fibers with a NaOH solution for 12 h, then soak 100 mg of dopamine-modified titanium dioxide and 400 mg of the NaOH-treated aramid fibers in deionized water or ethanol solvent, and react in a hydrothermal reaction kettle at 80 °C for 12 h to achieve the successful growth of dopamine-modified titanium dioxide on the surface of the aramid.

[0079] (3) Preparation of modified aramid fibers

[0080] Surface modification was carried out on aramid fibers by growing nanoscale dopamine-modified titanium dioxide on the surface using imidazolium salt ions; the aramid fibers were hydrothermally modified using 2 mg / ml of imidazolium salt ions, specifically reacting at 120 °C for 24 h, and finally washing with deionized water to obtain aramid fibers with dopamine-modified titanium dioxide grown on the surface modified with imidazolium, that is, modified aramid fibers. The morphological diagrams of the aramid fibers before and after modification are respectively as shown in Figure 1 , Figure 2 .

[0081] (4) Preparation of ceramic / fiber modified coating

[0082] 0.5 g of modified aramid fibers was added to 80 g of epoxy resin, and stirred in a blender at a speed of 80 r / min for 20 min to mix evenly. Then 19.5 g of curing agent was added and stirred for 20 min. The defoaming process was carried out in a vacuum drying oven, and the obtained material was coated on the steel pipe pile and cured at room temperature for 60 h to form a ceramic / fiber modified coating with a thickness of 100 μm.

[0083] Comparative Example 1

[0084] The method was the same as that in Example 1, except that titanium dioxide was directly grown on the surface of the aramid fibers; specifically including:

[0085] (1) Growing nanoscale titanium dioxide on the surface of aramid fibers by hydrothermal method (obtaining aramid fibers with titanium dioxide grown)

[0086] The surface of the aramid fibers was alkalized with NaOH solution for 12 h, and then 100 mg of titanium dioxide and 400 mg of aramid fibers treated with NaOH were immersed in deionized water or ethanol solvent, and reacted in a hydrothermal reaction kettle at 80 °C for 12 h to achieve the successful growth of titanium dioxide on the surface of the aramid.

[0087] (2) Preparation of ceramic / fiber modified coating

[0088] 0.5 g of aramid fibers with titanium dioxide grown was added to 80 g of epoxy resin, and stirred in a blender at a speed of 80 r / min for 20 min to mix evenly. Then 19.5 g of curing agent was added and stirred for 20 min. The defoaming process was carried out in a vacuum drying oven, and the obtained material was coated on the steel pipe pile and cured at room temperature for 60 h to form a ceramic / fiber modified coating with a thickness of 100 μm.

[0089] Comparative Example 2

[0090] The method was the same as that in Example 1, except that titanium dioxide was not modified; specifically including:

[0091] (1) Growing nanoscale titanium dioxide on the surface of aramid fibers by hydrothermal method

[0092] The aramid fibers were subjected to surface alkalization treatment with NaOH solution for 12 h. Then, 100 mg of titanium dioxide and the aramid fibers treated with 400 mg of NaOH were immersed in deionized water or ethanol solvent, and reacted in a hydrothermal reaction kettle at 80 °C for 12 h to achieve the successful growth of titanium dioxide on the surface of aramid fibers.

[0093] (2) Preparation of modified aramid fibers

[0094] The surface of the aramid fibers with nanoscale dopamine-modified titanium dioxide grown on them was modified using imidazolium salt ions; the hydrothermal modification was carried out using 2 mg / ml of imidazolium salt ions, specifically reacting at 120 °C for 24 h, and finally washing with deionized water to obtain the aramid fibers with imidazole-modified surface and dopamine-modified titanium dioxide grown on them, that is, the modified aramid fibers.

[0095] (3) Preparation of ceramic / fiber modified coating

[0096] 0.5 g of the modified aramid fibers was added to 80 g of epoxy resin, and stirred in a blender at a speed of 80 r / min for 20 min to mix evenly. Then, 19.5 g of curing agent was added and stirred for 20 min. The defoaming process was carried out in a vacuum drying oven, and the obtained material was coated on the steel pipe pile and cured at room temperature for 60 h to form a ceramic / fiber modified coating with a thickness of 100 μm.

[0097] Comparative Example 3

[0098] The method was the same as that in Example 1, except that the aramid fibers with grown modified titanium dioxide were not further modified; specifically including:

[0099] (1) Dopamine-modified titanium dioxide

[0100] 2 mg / ml of dopamine solution was added to 8 mM tris buffer solution, then 200 mg of titanium dioxide was added, and the pH was adjusted to 8.5 using NaOH·HCl, and soaked for 6 h. The soaked sample was ultrasonically cleaned with deionized water for 15 minutes and dried with N2 to obtain dopamine-modified titanium dioxide.

[0101] (2) Hydrothermal growth of dopamine-modified titanium dioxide on the surface of aramid fibers

[0102] The aramid fibers were subjected to surface alkalization treatment with NaOH solution for 12 h. Then, 100 mg of the dopamine-modified titanium dioxide and the aramid fibers treated with 400 mg of NaOH were immersed in deionized water or ethanol solvent, and reacted in a hydrothermal reaction kettle at 80 °C for 12 h to achieve the successful growth of dopamine-modified titanium dioxide on the surface of aramid fibers.

[0103] (3) Preparation of ceramic / fiber modified coating

[0104] Add 0.5 g of aramid fiber modified with growth dopamine and titanium dioxide to 80 g of epoxy resin, stir evenly at a speed of 80 r / min in a blender for 20 min, then add 19.5 g of curing agent and stir for 20 min. Carry out the defoaming process in a vacuum drying oven, coat the obtained material on a steel pipe pile, and cure at room temperature for 60 h to form a ceramic / fiber modified coating with a thickness of 100 μm.

[0105] Comparative Example 4

[0106] The method is the same as that of Example 1, except that aramid fiber and titanium dioxide particles are directly used instead of modified aramid fiber. Specifically, it includes:

[0107] Prepare a ceramic / fiber modified coating

[0108] Add 0.5 g of aramid fiber and 0.05 g of titanium dioxide particles to 80 g of epoxy resin, stir evenly at a speed of 80 r / min in a blender for 20 min, then add 19.45 g of curing agent and stir for 20 min. Carry out the defoaming process in a vacuum drying oven, coat the obtained material on a steel pipe pile, and cure at room temperature for 60 h to form a ceramic / fiber modified coating.

[0109] Example 2

[0110] (1) Sodium lauryl sulfate modified titanium dioxide

[0111] Add 200 mg of titanium dioxide to 4 mg / ml of sodium lauryl sulfate, react at 60 °C for 6 h, and ultrasonically clean the soaked sample with deionized water for 15 minutes to obtain sodium lauryl sulfate modified titanium dioxide;

[0112] (2) Chemical vapor deposition method to grow micron-sized sodium lauryl sulfate modified titanium dioxide on the surface of carbon fiber

[0113] In a high-vacuum environment at 350 °C, using sodium lauryl sulfate modified titanium dioxide as a target, sputter for 60 minutes to achieve the growth of micron-sized sodium lauryl sulfate modified titanium dioxide on the surface of carbon fiber;

[0114] (3) Prepare modified carbon fiber

[0115] Use imidazolium salt ions to modify the surface of carbon fiber grown with nano-sized sodium lauryl sulfate modified and grown modified titanium dioxide; perform hydrothermal modification on it with 2 mg / ml of imidazolium salt ions, specifically react at 120 °C for 24 h, and finally wash with deionized water to obtain carbon fiber modified with imidazole and grown with sodium lauryl sulfate modified and grown modified titanium dioxide on the surface.

[0116] (4) Prepare a ceramic / fiber modified coating

[0117] Add 0.5 g of modified carbon fiber to 80 g of epoxy resin, stir evenly at a speed of 80 r / min in a blender for 20 min, then add 19.5 g of curing agent and stir for 20 min. Carry out the defoaming process in a vacuum drying oven, coat the obtained material on the steel pipe pile, and cure at room temperature for 60 h to form a ceramic / fiber modified coating.

[0118] Example 3

[0119] (1) Ionic liquid modified titanium dioxide

[0120] Add 200 mg of titanium dioxide to a 3 mg / ml quaternary ammonium salt ionic liquid, react at 60 °C for 6 h, and ultrasonically clean the soaked sample with deionized water for 15 minutes to obtain quaternary ammonium salt ionic liquid modified titanium dioxide;

[0121] (2) Growing nanoscale ionic liquid modified titanium dioxide on the surface of aramid fiber by sol-gel method

[0122] Dissolve the quaternary ammonium salt ionic liquid modified titanium dioxide in an appropriate deionized water / ethanol mixed solution, add an appropriate amount of NaOH to the sol, adjust the pH of the solution, and promote the hydrolysis and gelation reactions of the sol. Then dry and heat-treat the gel to achieve the growth of ceramic particles on the fiber surface

[0123] (3) Prepare modified glass fiber / carbon fiber composite fiber

[0124] Use pyrrole salt ionic liquid to modify the surface of the glass / carbon fiber growing nanoscale quaternary ammonium salt ionic liquid modified titanium dioxide; carry out hydrothermal modification on it with a 2 mg / ml pyrrole salt ionic liquid, specifically react at 120 °C for 24 h, and finally wash with deionized water to obtain a pyrrole salt ionic liquid modified glass fiber / carbon fiber composite fiber with pyrrole salt ionic liquid modified growing titanium dioxide.

[0125] (4) Prepare ceramic / fiber modified coating

[0126] Add 0.5 g of modified glass fiber / carbon fiber composite fiber to 80 g of epoxy resin, stir evenly at a speed of 80 r / min in a blender for 20 min, then add 19.5 g of curing agent and stir for 20 min. Carry out the defoaming process in a vacuum drying oven, coat the obtained material on the steel pipe pile, and cure at room temperature for 60 h to form a ceramic / fiber modified coating.

[0127] Example 4

[0128] (1) Ionic liquid modified titanium dioxide

[0129] Add 200 mg of titanium dioxide to the quaternary ammonium salt ionic liquid at 3 mg / ml, react at 60 °C for 6 h, and ultrasonically clean the soaked sample with deionized water for 15 minutes to obtain quaternary ammonium salt ionic liquid-modified titanium dioxide;

[0130] (2) Microwave synthesis method to grow nanoscale ionic liquid-modified titanium dioxide on the surface of polypropylene fibers

[0131] Mix the quaternary ammonium salt ionic liquid-modified titanium dioxide and polypropylene fibers at a mass ratio of 2:1, and grow nanoscale quaternary ammonium salt ionic liquid-modified titanium dioxide on the surface of polypropylene fibers by regulating the electromagnetic radiation frequency (100 GHz);

[0132] (3) Prepare modified polypropylene fibers

[0133] Surface-modify the nanoscale quaternary ammonium salt ionic liquid-modified titanium dioxide grown on the surface of polypropylene fibers with N-cocoyl arginine ethyl ester; perform hydrothermal modification on it with 2 mg / ml of N-cocoyl arginine ethyl ester, specifically react at 120 °C for 24 h, and finally wash with deionized water to obtain polypropylene fibers with N-cocoyl arginine ethyl ester growing quaternary ammonium salt ionic liquid-modified and grown modified titanium dioxide.

[0134] (4) Prepare a ceramic / fiber modified coating

[0135] Add 0.5 g of modified polypropylene fibers to 80 g of epoxy resin, stir evenly at a speed of 80 r / min in a blender for 20 min, then add 19.5 g of curing agent and stir for 20 min. Perform a defoaming process in a vacuum drying oven, coat the obtained material on a steel pipe pile, and cure at room temperature for 60 h to form a ceramic / fiber modified coating.

[0136] Test the coatings of Examples 1-4 and Comparative Examples 1-4, and the results are shown in Table 1, where the immersion is carried out with a 3.5 wt% NaCl solution.

[0137] Table 1 Test results of the coatings in Examples 1-4 and Comparative Examples 1-4

[0138]

[0139]

[0140] In addition, the inventors of this case also referred to the foregoing examples, conducted tests with other raw materials, process operations, and process conditions described in this specification, and all obtained relatively ideal results.

[0141] It should be understood that the technical solution of the present invention is not limited to the limitations of the above specific embodiments. Any technical deformation made according to the technical solution of the present invention without departing from the gist of the present invention and the scope protected by the claims falls within the protection scope of the present invention.

Claims

1. A preparation method of a ceramic / fiber modified coating for steel pipe piles, characterized in that, Comprising: Modifying ceramic particles with a first modifier to obtain modified ceramic particles; wherein, the first modifier is selected from any one or a combination of dopamine, surfactant, ionic liquid; Growing the modified ceramic particles at the nanoscale or microscale on the fiber surface by at least one of hydrothermal method, chemical vapor deposition method, physical vapor deposition method, sol-gel method, microwave synthesis method, redox method to obtain a fiber with grown modified ceramic particles; Modifying the fiber with the grown modified ceramic particles with a second modifier to obtain a modified fiber; wherein, the second modifier is selected from surfactant and / or ionic liquid; And, mixing the modified fiber, resin, and curing agent, applying them to the surface of the substrate and performing a curing treatment to prepare a ceramic / fiber modified coating.

2. The preparation method according to claim 1, wherein The preparation method of the modified ceramic particles specifically includes: mixing a solution containing the first modifier with the ceramic particles and reacting at 60-75 °C for 6-48 h to obtain the modified ceramic particles.

3. The preparation method according to claim 1, characterized in that: The dosage ratio of the first modifier to the ceramic particles is 40-200 mL: 10-500 mg.

4. The preparation method according to claim 1, characterized in that: The particle size of the modified ceramic particles is 100-300 nm.

5. The preparation method according to claim 1, characterized in that: The ceramic particles are selected from any one or a combination of titanium dioxide, alumina, zirconia, silica.

6. The preparation method according to claim 1, characterized in that: The surfactant is selected from any one or a combination of cationic surfactants, anionic surfactants, amphoteric surfactants, nonionic surfactants; wherein, the cationic surfactant is selected from amino acid-based cationic surfactants and / or quaternary ammonium compounds, the amino acid-based cationic surfactant is selected from N-cocoyl arginine ethyl ester; the quaternary ammonium compounds are selected from any one or a combination of benzalkonium chloride, benzalkonium bromide, benzyl chloride ammonium; the anionic surfactant is selected from sodium lauryl sulfate; the amphoteric surfactant is selected from N-alkyl aspartic acid-b-alkyl ester; the nonionic surfactant is selected from fatty acid glycerides and / or sorbitan fatty acid esters.

7. The preparation method according to claim 1, characterized in that: The ionic liquid is selected from cationic ionic liquids and / or anionic ionic liquids; wherein, the cationic ionic liquid is selected from any one or a combination of quaternary ammonium salt ionic liquids, quaternary phosphonium salt ionic liquids, imidazole salt ionic liquids, pyrrole salt ionic liquids; the anionic ionic liquid is selected from any one or a combination of halogen ionic liquids, tetrafluoroborate ionic liquids, hexafluorophosphate ionic liquids.

8. The preparation method according to claim 1, characterized in that: The first modifier and the second modifier are the same or different.

9. The preparation method according to claim 1, characterized in that: The fiber is selected from any one of organic fibers, inorganic fibers, organic / inorganic composite fibers; wherein, the organic fibers are selected from any one or a combination of aramid fibers, polypropylene fibers, polyester fibers, polyacrylonitrile fibers, polyphenylene sulfide fibers; the inorganic fibers are selected from any one or a combination of carbon fibers, glass fibers, silicon carbide fibers, silicon oxyaluminum fibers; the organic / inorganic composite fibers are selected from glass fiber / carbon fiber composite fibers.

10. The preparation method according to claim 1, characterized in that: The diameter of the fiber is 5-20 μm and the length is 1-10 mm.

11. According to the preparation method described in claim 1, characterized in that: The morphology of the particles in the fibers of the growth-modified ceramic particles is selected from any one or a combination of spherical, conical, and cuboid; the particles grow on one side of the fiber or around the fiber.

12. The preparation method according to claim 1, characterized in that, The preparation method of the modified fiber specifically includes: dispersing the fiber of the growth-modified ceramic particles and a second modifier in a solvent, and stirring and reacting at 60-120 °C for 6-48 h, and then washing and freeze-drying to obtain the modified fiber; Among them, the dosage ratio of the fiber of the growth-modified ceramic particles to the second modifier is 0.01-1 g: 1-100 ml; the solvent is selected from deionized water and / or ethanol.

13. The preparation method according to claim 1, wherein, Specifically include: Uniformly mixing the modified fiber and the resin, and then adding a curing agent to mix to obtain a mixed material; And applying the mixed material to the surface of the substrate and curing at 25-80 °C for 48-96 h to prepare a ceramic / fiber modified coating.

14. The preparation method according to claim 13, wherein: The mass ratio of the modified fiber, the resin and the curing agent is 0.01-1: 50-90: 10-50.

15. The preparation method according to claim 13, characterized in that: The resin is selected from any one or a combination of epoxy resin, acrylic resin, polyurethane, and polyimide.

16. The preparation method according to claim 13, characterized in that: The curing agent is selected from any one or a combination of aliphatic amines, cycloaliphatic amines, aromatic amines, polyamides, acid anhydrides, and tertiary amines.

17. The preparation method according to claim 13, wherein: The substrate is selected from steel pipe piles.

18. A ceramic / fiber modified coating for a steel pipe pile prepared by the preparation method according to any one of claims 1-17.

19. The ceramic / fiber modified coating for steel pipe piles according to claim 18, characterized in that: The thickness of the ceramic / fiber modified coating is 50-1000 μm.

20. The ceramic / fiber modified coating for steel pipe piles according to claim 18, characterized in that: After the ceramic / fiber modified coating is immersed in salt water for 30 days, the low-frequency impedance modulus of the coating is at 10 11 Ω·cm 2 or above.

21. Application of the ceramic / fiber modified coating for a steel pipe pile according to any one of claims 18-20 in the field of protection of marine engineering equipment.

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