CN117736627A - Ceramic/fiber modified coating for steel pipe pile and preparation method and application thereof - Google Patents
Ceramic/fiber modified coating for steel pipe pile and preparation method and application thereof Download PDFInfo
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- CN117736627A CN117736627A CN202311754780.4A CN202311754780A CN117736627A CN 117736627 A CN117736627 A CN 117736627A CN 202311754780 A CN202311754780 A CN 202311754780A CN 117736627 A CN117736627 A CN 117736627A
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- 239000000919 ceramic Substances 0.000 title claims abstract description 102
- 238000000576 coating method Methods 0.000 title claims abstract description 58
- 239000011248 coating agent Substances 0.000 title claims abstract description 47
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 33
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- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000002245 particle Substances 0.000 claims abstract description 67
- 238000000034 method Methods 0.000 claims abstract description 42
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- 238000005240 physical vapour deposition Methods 0.000 claims abstract description 5
- 238000001308 synthesis method Methods 0.000 claims abstract description 4
- 239000002608 ionic liquid Substances 0.000 claims description 48
- 229920006231 aramid fiber Polymers 0.000 claims description 42
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 39
- -1 tetrafluoroborate Chemical compound 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
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- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 5
- 229960000686 benzalkonium chloride Drugs 0.000 claims description 5
- CADWTSSKOVRVJC-UHFFFAOYSA-N benzyl(dimethyl)azanium;chloride Chemical compound [Cl-].C[NH+](C)CC1=CC=CC=C1 CADWTSSKOVRVJC-UHFFFAOYSA-N 0.000 claims description 5
- 150000003233 pyrroles Chemical class 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 150000001413 amino acids Chemical class 0.000 claims description 4
- 239000002280 amphoteric surfactant Substances 0.000 claims description 4
- 125000000129 anionic group Chemical group 0.000 claims description 4
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- 125000002091 cationic group Chemical group 0.000 claims description 4
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- 229960002233 benzalkonium bromide Drugs 0.000 claims description 3
- KHSLHYAUZSPBIU-UHFFFAOYSA-M benzododecinium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 KHSLHYAUZSPBIU-UHFFFAOYSA-M 0.000 claims description 3
- 239000003595 mist Substances 0.000 claims description 3
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 claims description 2
- 239000004925 Acrylic resin Substances 0.000 claims description 2
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- 239000004952 Polyamide Substances 0.000 claims description 2
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- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 2
- 150000004982 aromatic amines Chemical class 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- 150000004665 fatty acids Chemical class 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 150000002460 imidazoles Chemical class 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 150000004714 phosphonium salts Chemical group 0.000 claims description 2
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 2
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- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 150000003512 tertiary amines Chemical class 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims 1
- 150000008064 anhydrides Chemical class 0.000 claims 1
- 230000007797 corrosion Effects 0.000 abstract description 7
- 238000005260 corrosion Methods 0.000 abstract description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 36
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 24
- 239000000243 solution Substances 0.000 description 17
- 238000012986 modification Methods 0.000 description 10
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- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
The invention discloses a ceramic/fiber modified coating for a steel pipe pile, and a preparation method and application thereof. The preparation method comprises the following steps: modifying the ceramic particles by adopting a first modifier to obtain modified ceramic particles; at least adopting any one mode 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 to grow nano-scale or micro-scale modified ceramic particles on the surface of the fiber, so as to obtain the fiber with the grown modified ceramic particles; modifying the fiber growing the modified ceramic particles by adopting a second modifier to obtain a modified fiber; and mixing the modified fiber, the resin and the curing agent, applying the mixture on the surface of a matrix, and curing the mixture to obtain the ceramic/fiber modified coating. The ceramic/fiber modified coating provided by the invention has excellent impact resistance and has good application prospect in the field of scour and corrosion resistance.
Description
Technical Field
The invention belongs to the technical field of fiber modified coatings, and particularly relates to a ceramic/fiber modified coating for a steel pipe pile, and a preparation method and application thereof.
Background
The ocean engineering equipment is in a severe environment with high temperature, high humidity and high salt fog for a long time, particularly the steel pipe pile used as the foundation of the ocean engineering equipment, and the service life of the steel pipe pile is greatly shortened under the continuous spray splashing and the scouring corrosion of seawater and sediment in a tidal range area. The coating material on the surface of the steel pipe pile is easy to receive the external force effect to generate damage such as scratch, peeling and tilting in the processes of hoisting, transporting, inserting and driving construction, bearing platform disassembly, construction ship collision and the like in the construction of the steel pipe pile, and the damage becomes a corrosion starting point in the service process of the steel pipe pile, so that the life of the clothes of the steel pipe pile is seriously reduced. The service requirements of the steel pipe pile in a spray splashing area and a tidal range area cannot be met, severe damage is caused under the continuous corrosion of dry-wet alternation and high-concentration salt mist, the safety of marine equipment is dangerous, and serious economic loss is caused. Therefore, designing and developing protective coatings for marine engineering equipment is a highly desirable problem.
Disclosure of Invention
The invention mainly aims to provide a ceramic/fiber modified coating for a steel pipe pile, and a preparation method and application thereof, so as to overcome the defects of the prior art.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a preparation method of a ceramic/fiber modified coating for a steel pipe pile, which comprises the following steps:
modifying the ceramic particles by adopting a first modifier to obtain modified ceramic particles; wherein the first modifier comprises any one or a combination of a plurality of dopamine, a surfactant and an ionic liquid;
at least adopting any one mode 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 to grow nano-scale or micro-scale modified ceramic particles on the surface of the fiber, so as to obtain the fiber with the grown modified ceramic particles;
modifying the fiber growing the modified ceramic particles by adopting a second modifier to obtain a modified fiber; wherein the second modifier comprises a surfactant and/or an ionic liquid;
and mixing the modified fiber, the resin and the curing agent, applying the mixture on the surface of a matrix, and curing the mixture to obtain the ceramic/fiber modified coating.
The embodiment of the invention also provides the ceramic/fiber modified coating for the steel pipe pile prepared by the preparation method.
The embodiment of the invention also provides application of the ceramic/fiber modified coating for the steel pipe pile in the field of marine engineering equipment protection.
Compared with the prior art, the invention has the beneficial effects that: the corrosion protection capability of the ceramic/fiber modified coating prepared by the invention is greatly improved, and the low-frequency impedance value is 10 after 30 days of service 11 Ω·cm 2 The bonding force between the coating and the metal substrate is up to 8MPa even if the coating is soaked for 10 days in a high-pressure environment, and the water absorption rate is as low as 2%, so that the excellent long-acting corrosion protection effect is reflected; meanwhile, the ceramic/fiber modified coating provided by the invention has excellent impact resistance and has good application prospect in the field of scour and corrosion resistance.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments described in the present invention, and other drawings may be obtained according to the drawings without inventive effort to those skilled in the art.
FIG. 1 is a topography of an aramid fiber of example 1 of the present invention;
FIG. 2 is a topography of a modified aramid fiber of example 1 of the invention.
Detailed Description
In view of the shortcomings of the prior art, the inventor of the present application has long studied and put forward a great deal of practice, and the technical solution of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Specifically, as one aspect of the technical scheme of the invention, the preparation method of the ceramic/fiber modified coating for the steel pipe pile comprises the following steps:
modifying the ceramic particles by adopting a first modifier to obtain modified ceramic particles; wherein the first modifier comprises any one or a combination of a plurality of dopamine, a surfactant and an ionic liquid;
at least adopting any one mode of hydrothermal method, chemical vapor deposition method, physical vapor deposition method, sol-gel method, microwave synthesis method and redox method to grow nano-scale or micro-scale modified ceramic particles on the surface of the fiber so as to obtain the fiber with the grown modified ceramic particles;
modifying the fiber growing the modified ceramic particles by adopting a second modifier to obtain a modified fiber; wherein the second modifier comprises a surfactant and/or an ionic liquid;
and mixing the modified fiber, the resin and the curing agent, applying the mixture on the surface of a matrix, and curing the mixture to obtain the ceramic/fiber modified coating.
In some preferred embodiments, the method for preparing the modified ceramic particles specifically comprises: mixing the solution containing the first modifier with ceramic particles and reacting at 60-75 ℃ for 6-48 h to obtain modified ceramic particles.
Specifically, preparing a first modifier solution (comprising dopamine, surfactant, ionic liquid and the like) with the concentration of 0.5-5 mg/ml, reacting with 100mg of ceramic particles at 60 ℃ for 6-48 h, and centrifugally washing by deionized water to obtain a product.
In some preferred embodiments, the ratio of the first modifier to ceramic particles is 40 to 200mL: 10-500 mg.
In some preferred embodiments, the modified ceramic particles have a particle size of 100 to 300nm.
In some preferred embodiments, the ceramic particles include, but are not limited to, any one or a combination of more of titanium dioxide, aluminum oxide, zirconium oxide, silicon dioxide.
In some preferred embodiments, the surfactant includes any one or a combination of a cationic surfactant, an anionic surfactant, an amphoteric surfactant, a nonionic surfactant, and the like, and is not limited thereto.
Further, the cationic surfactant comprises an amino acid type cationic surfactant and/or a quaternary ammonium compound, and the amino acid type cationic surfactant comprises N-cocoyl arginine ethyl ester; the quaternary ammonium compound includes any one or a combination of a plurality of benzalkonium chloride (benzalkonium chloride), benzalkonium bromide (benzalkonium bromide), benzalkonium chloride, and the like, and is not limited thereto.
Further, the anionic surfactant includes sodium lauryl sulfate, and is not limited thereto.
Further, the amphoteric surfactant includes N-alkyl aspartic acid-b-alkyl esters, and is not limited thereto.
Further, the nonionic surfactant includes, but is not limited to, a fatty acid glyceride and/or a fatty acid sorbitan.
In some preferred embodiments, the ionic liquid includes a cationic ionic liquid and/or an anionic ionic liquid, and is not limited thereto.
Further, the cationic ionic liquid includes any one or a combination of a plurality of quaternary ammonium salt ionic liquid, quaternary phosphonium salt ionic liquid, imidazole salt ionic liquid and pyrrole salt ionic liquid, and is not limited thereto.
Further, the anionic ionic liquid includes any one or a combination of a plurality of halogen ionic liquid, tetrafluoroborate ionic liquid and hexafluorophosphate ionic liquid, and is not limited thereto.
In some preferred embodiments, the first modifier is the same as or different from the second modifier.
In some preferred embodiments, the fibers include any one of organic fibers, inorganic fibers, organic/inorganic composite fibers, and are not limited thereto.
Further, the organic fiber includes any one or a combination of more of aramid fiber, polypropylene fiber, polyester fiber, polyacrylonitrile fiber, polyphenylene sulfide fiber, and the like, and is not limited thereto.
Further, the inorganic fibers include any one or a combination of a plurality of carbon fibers, glass fibers, silicon carbide fibers, and silicon aluminum fibers, and are not limited thereto.
Further, the organic/inorganic composite fiber includes a glass fiber/carbon fiber composite fiber, and is not limited thereto.
In some preferred embodiments, the fibers have a diameter of 5 to 20 μm and a length of 1 to 10mm.
In some preferred embodiments, the morphology of the particles in the fibers of the growth-modified ceramic particles includes any one or a combination of more of spheres, polyhedrons, cones, and cuboids, and is not limited thereto.
Further, the particles grow in any one of a side of the fiber, surrounding the fiber.
In some preferred embodiments, the method for growing modified ceramic particles on the surface of a fiber by a hydrothermal method specifically comprises:
dispersing 0.01-1 g of modified ceramic particles and 0.1-10 g of fibers in 1-100 ml of modifier in deionized water, ethanol and other solvents, stirring for 6-49 hours at 60-120 ℃ in an oil bath, washing with deionized water and/or ethanol, and freeze-drying for 12-48 hours to obtain a final product.
In some preferred embodiments, the method for growing modified ceramic particles on the surface of a fiber by chemical vapor deposition specifically comprises:
and sputtering the modified ceramic particle target material for 5 to 120 minutes in a high vacuum environment with the temperature of 100 to 600 ℃ to realize the growth of ceramic particles on the surface of the fiber.
In some preferred embodiments, the method for growing nano-or micro-sized modified ceramic particles on the surface of a fiber by physical vapor deposition specifically comprises:
and sputtering the target material (modified ceramic particle target material) for 5 to 120 minutes in a high vacuum environment at 300 to 500 ℃ to realize the growth of ceramic particles on the surface of the fiber.
In some preferred embodiments, the method for growing nano-or micro-sized modified ceramic particles on the surface of a fiber by using a sol-gel method specifically comprises:
the Guan Gaixing ceramic particles (modified titanium oxide and the like) are dissolved in a proper solvent, a proper amount of acid or alkali is added into the sol, the pH value of the solution is adjusted, the sol is promoted to generate hydrolysis and gelation reaction, and then the gel is dried and heat treated, so that the ceramic particles grow on the surface of the fiber.
In some preferred embodiments, the method for growing nano-or micro-sized modified ceramic particles on the surface of a fiber using microwave synthesis specifically comprises:
ceramic particles and fibers are mixed according to the mass ratio, and the growth of the ceramic particles on the surfaces of the fibers is realized by regulating and controlling the frequency of electromagnetic radiation.
In some preferred embodiments, the method for growing nano-or micro-sized modified ceramic particles on the surface of a fiber using a redox process specifically comprises:
the ceramic particles are directly reduced, and the fiber surface growth modified ceramic particles are realized under the action of reducing agents (such as hydrogen, sodium borohydride, ammonia, sodium hydroxide and the like).
In some preferred embodiments, the method of making the modified fiber comprises: dispersing the fiber growing the modified ceramic particles and the second modifier in a solvent, stirring and reacting for 6-48 h at 60-120 ℃, and then washing and freeze drying to obtain the modified fiber.
Further, the dosage ratio of the fiber of the growth modified ceramic particles to the second modifier is 0.01-1 g:1-100 ml.
Further, the solvent includes deionized water and/or ethanol, and is not limited thereto.
For example: dispersing 0.01-1 g of fiber with growth modified ceramic particles and 1-100 ml of modifier in deionized water, ethanol and other solvents, stirring for 6-48 hours at 60-120 ℃ in an oil bath, washing with deionized water and/or ethanol, and freeze-drying for 12-48 hours to obtain a final product.
In some preferred embodiments, the preparation method specifically comprises:
uniformly mixing the modified fiber with resin, and then adding a curing agent for mixing to obtain a mixed material;
and applying the mixed material to the surface of a substrate and curing the mixed material at 25-80 ℃ for 48-96 hours to prepare the ceramic/fiber modified coating.
Further, the mass ratio of the modified fiber, the resin and the curing agent is 0.01-1:50-90:10-50.
Further, the resin includes any one or a combination of more of epoxy resin, acrylic resin, polyurethane, polyimide, and is not limited thereto.
Further, the curing agent includes any one or more of aliphatic amine, alicyclic amine, aromatic amine, polyamide, acid anhydride, resin, tertiary amine, and the like, and is not limited thereto.
Further, the matrix includes a steel pipe pile, and is not limited thereto.
According to the invention, the compatibility and lattice matching with fibers are realized by modifying ceramic particles through dopamine monomers, surfactants, ionic liquids and the like; and then the interface compatibility between the fiber and the resin is improved by utilizing ionic liquid, surfactant modified fiber and the like, and the impact resistance of the composite material is improved.
Another aspect of the embodiment of the invention also provides a ceramic/fiber modified coating for the steel pipe pile prepared by the preparation method.
Further, the thickness of the ceramic/fiber modified coating is 50-1000 μm.
Further, the ceramic/fiber modified coating has a low frequency impedance modulus of 10 after being soaked in 30 days of saline water 11 Ω·cm 2 The bonding strength of the coating/metal substrate is as high as 8MPa.
The invention also provides an application of the ceramic/fiber modified coating for the steel pipe pile in the field of marine engineering equipment protection.
Further, the marine engineering equipment comprises steel pipe piles in a severe environment with high temperature, high humidity and high salt mist.
The technical scheme of the present invention is further described in detail below with reference to several preferred embodiments and the accompanying drawings, and the embodiments are implemented on the premise of the technical scheme of the present invention, and detailed implementation manners and specific operation processes are given, but the protection scope of the present invention is not limited to the following embodiments.
The experimental materials used in the examples described below, unless otherwise specified, were all commercially available from conventional biochemicals.
Example 1
(1) Dopamine modified titanium dioxide
Adding 2mg/ml of dopamine solution into 8mM tris buffer solution, adding 200mg of titanium dioxide, adjusting the pH to 8.5 by using NaOH and HCl, soaking for 6 hours, ultrasonically cleaning the soaked sample by using deionized water for 15 minutes, and drying by using N2 to obtain dopamine-modified titanium dioxide;
(2) Nanometer dopamine modified titanium dioxide grown on surface of aramid fiber by hydrothermal method
And (3) carrying out surface alkalization treatment on the aramid fiber for 12 hours by using an NaOH solution, soaking 100mg of dopamine-modified titanium dioxide and 400mg of NaOH-treated aramid fiber in deionized water or an ethanol solvent, and reacting for 12 hours at 80 ℃ by using a hydrothermal reaction kettle to realize successful growth of the dopamine-modified titanium dioxide on the surface of the aramid fiber.
(3) Preparation of modified aramid fibers
The surface of aramid fiber is modified by nanometer dopamine modified titanium dioxide grown on the surface of aramid fiber by utilizing imidazolium ions; the imidazole salt ion with the concentration of 2mg/ml is utilized to carry out hydrothermal modification, specifically, the reaction is carried out for 24 hours at the temperature of 120 ℃, and finally, deionized water is utilized to wash, so that the dopamine modified titanium dioxide grown on the surface of the imidazole modified aramid fiber, namely the modified aramid fiber, is obtained. Wherein the morphology diagrams before and after the modification of the aramid fiber are respectively shown in fig. 1 and fig. 2.
(4) Preparation of ceramic/fiber modified coatings
Adding 0.5g of modified aramid fiber into 80g of epoxy resin, stirring at the speed of 80r/min for 20min and uniformly mixing, then adding 19.5g of curing agent and stirring for 20min, performing a defoaming process in a vacuum drying box, coating the obtained material on a steel pipe pile, and curing at room temperature for 60h to form a ceramic/fiber modified coating with the thickness of 100 mu m.
Comparative example 1
The method is the same as in example 1, except that titanium dioxide is directly grown on the surface of the aramid fiber; the method specifically comprises the following steps:
(1) Nanometer titanium dioxide grows on the surface of the aramid fiber by a hydrothermal method (the aramid fiber growing titanium dioxide is prepared)
And (3) carrying out surface alkalization treatment on the aramid fiber by using an NaOH solution for 12 hours, soaking 100mg of titanium dioxide and 400mg of the aramid fiber subjected to NaOH treatment in deionized water or an ethanol solvent, and reacting for 12 hours at 80 ℃ by using a hydrothermal reaction kettle to realize successful growth of the titanium dioxide on the surface of the aramid fiber.
(2) Preparation of ceramic/fiber modified coatings
Adding 0.5g of aramid fiber with titanium dioxide grown into 80g of epoxy resin, stirring at a speed of 80r/min for 20min to mix uniformly, adding 19.5g of curing agent, stirring for 20min, performing a defoaming process in a vacuum drying oven, coating the obtained material on a steel pipe pile, and curing at room temperature for 60h to form a ceramic/fiber modified coating with a thickness of 100 mu m.
Comparative example 2
The process is the same as in example 1 except that the titanium dioxide is not modified; the method specifically comprises the following steps:
(1) Nanometer titanium dioxide grows on surface of aramid fiber by hydrothermal method
And (3) carrying out surface alkalization treatment on the aramid fiber by using an NaOH solution for 12 hours, soaking 100mg of titanium dioxide and 400mg of the aramid fiber subjected to NaOH treatment in deionized water or an ethanol solvent, and reacting for 12 hours at 80 ℃ by using a hydrothermal reaction kettle to realize successful growth of the titanium dioxide on the surface of the aramid fiber.
(2) Preparation of modified aramid fibers
The surface of aramid fiber is modified by nanometer dopamine modified titanium dioxide grown on the surface of aramid fiber by utilizing imidazolium ions; the imidazole salt ion with the concentration of 2mg/ml is utilized to carry out hydrothermal modification, specifically, the reaction is carried out for 24 hours at the temperature of 120 ℃, and finally, deionized water is utilized to wash, so that the dopamine modified titanium dioxide grown on the surface of the imidazole modified aramid fiber, namely the modified aramid fiber, is obtained.
(3) Preparation of ceramic/fiber modified coatings
Adding 0.5g of modified aramid fiber into 80g of epoxy resin, stirring at the speed of 80r/min for 20min and uniformly mixing, then adding 19.5g of curing agent and stirring for 20min, performing a defoaming process in a vacuum drying box, coating the obtained material on a steel pipe pile, and curing at room temperature for 60h to form a ceramic/fiber modified coating with the thickness of 100 mu m.
Comparative example 3
The process was the same as in example 1 except that the aramid fiber of the growth-modified titanium dioxide was not continuously modified; the method specifically comprises the following steps:
(1) Dopamine modified titanium dioxide
Adding 2mg/ml of dopamine solution into 8mM tris buffer solution, adding 200mg of titanium dioxide, adjusting the pH to 8.5 by using NaOH and HCl, soaking for 6 hours, ultrasonically cleaning the soaked sample by using deionized water for 15 minutes, and drying by using N2 to obtain the dopamine-modified titanium dioxide.
(2) Dopamine modified titanium dioxide grown on surface of aramid fiber by hydrothermal method
And (3) carrying out surface alkalization treatment on the aramid fiber for 12 hours by using an NaOH solution, soaking 100mg of dopamine-modified titanium dioxide and 400mg of NaOH-treated aramid fiber in deionized water or an ethanol solvent, and reacting for 12 hours at 80 ℃ by using a hydrothermal reaction kettle to realize successful growth of the dopamine-modified titanium dioxide on the surface of the aramid fiber.
(3) Preparation of ceramic/fiber modified coatings
Adding 0.5g of aramid fiber for growing dopamine-modified titanium dioxide into 80g of epoxy resin, stirring for 20min at the speed of 80r/min in a stirrer, uniformly mixing, adding 19.5g of curing agent, stirring for 20min, performing a defoaming process in a vacuum drying oven, coating the obtained material on a steel pipe pile, and curing at room temperature for 60h to form a ceramic/fiber modified coating with the thickness of 100 mu m.
Comparative example 4
The method is the same as in example 1, except that the modified aramid fiber is directly replaced by aramid fiber and titanium dioxide particles, and specifically comprises the following steps:
preparation of ceramic/fiber modified coatings
Adding 0.5g of aramid fiber and 0.05g of titanium dioxide particles into 80g of epoxy resin, stirring for 20min at the speed of 80r/min in a stirrer, uniformly mixing, adding 19.45g of curing agent, stirring for 20min, performing a defoaming process in a vacuum drying oven, coating the obtained material on a steel pipe pile, and curing at room temperature for 60h to form the ceramic/fiber modified coating.
Example 2
(1) Sodium lauryl sulfate modified titanium dioxide
Adding 200mg of titanium dioxide into 4mg/ml sodium laurylsulfate, reacting at 60 ℃ for 6 hours, and ultrasonically cleaning the soaked sample with deionized water for 15 minutes to obtain sodium laurylsulfate modified titanium dioxide;
(2) Chemical vapor deposition method for growing micron-sized sodium laurylsulfate modified titanium dioxide on carbon fiber surface
In a high vacuum environment at 350 ℃, sodium lauryl sulfate modified titanium dioxide is used as a target material, and sputtering is carried out for 60 minutes, so that micron-sized sodium lauryl sulfate modified titanium dioxide can be grown on the surface of the carbon fiber;
(3) Preparation of modified carbon fibers
The surface modification is carried out on the nano sodium lauryl sulfate modified growth modified titanium dioxide grown on the surface of the carbon fiber by utilizing imidazole salt ions; the imidazole salt ion with the concentration of 2mg/ml is utilized to carry out hydrothermal modification, specifically, the reaction is carried out for 24 hours at the temperature of 120 ℃, and finally deionized water is utilized to wash, so as to obtain the modified titanium dioxide with the modified growth of sodium lauryl sulfate on the surface of the carbon fiber modified by imidazole.
(4) Preparation of ceramic/fiber modified coatings
Adding 0.5g of modified carbon fiber into 80g of epoxy resin, stirring at the speed of 80r/min for 20min and uniformly mixing, then adding 19.5g of curing agent and stirring for 20min, performing a defoaming process in a vacuum drying oven, coating the obtained material on a steel pipe pile, and curing at room temperature for 60h to form the ceramic/fiber modified coating.
Example 3
(1) Ionic liquid modified titanium dioxide
200mg of titanium dioxide is added into 3mg/ml of quaternary ammonium salt ionic liquid, the reaction is carried out for 6 hours at 60 ℃, and the soaked sample is ultrasonically cleaned by deionized water for 15 minutes, thus obtaining the quaternary ammonium salt ionic liquid modified titanium dioxide;
(2) Nanometer level ion liquid modified titanium dioxide grown on aramid fiber surface by sol-gel method
Dissolving quaternary ammonium salt ionic liquid modified titanium dioxide in proper deionized water/ethanol mixed solution, adding proper amount of NaOH into sol, regulating pH of the solution to promote sol to undergo hydrolysis and gelation reaction, and drying and heat-treating the gel to realize growth of ceramic particles on the surface of fiber
(3) Preparation of modified glass fiber/carbon fiber composite fiber
The method comprises the steps of (1) carrying out surface modification on the nano-scale quaternary ammonium salt ionic liquid modified titanium dioxide grown on the surface of glass/carbon fiber by utilizing pyrrole salt ionic liquid; the glass fiber/carbon fiber composite fiber of the growth modified titanium dioxide is obtained by carrying out hydrothermal modification on the pyrrole salt ionic liquid with the concentration of 2mg/ml, specifically reacting for 24 hours at 120 ℃, and finally washing the pyrrole salt ionic liquid with deionized water.
(4) Preparation of ceramic/fiber modified coatings
Adding 0.5g of modified glass fiber/carbon fiber composite fiber into 80g of epoxy resin, stirring for 20min at the speed of 80r/min in a stirrer, uniformly mixing, adding 19.5g of curing agent, stirring for 20min, performing a defoaming process in a vacuum drying oven, coating the obtained material on a steel pipe pile, and curing for 60h at room temperature to form the ceramic/fiber modified coating.
Example 4
(1) Ionic liquid modified titanium dioxide
200mg of titanium dioxide is added into 3mg/ml of quaternary ammonium salt ionic liquid, the reaction is carried out for 6 hours at 60 ℃, and the soaked sample is ultrasonically cleaned by deionized water for 15 minutes, thus obtaining the quaternary ammonium salt ionic liquid modified titanium dioxide;
(2) Microwave synthesis process of growing nanometer level ion liquid modified titania on polypropylene fiber surface
The quaternary ammonium salt ionic liquid modified titanium dioxide and polypropylene fibers are mixed according to the mass ratio of 2:1, and the nano-scale quaternary ammonium salt ionic liquid modified titanium dioxide grows on the surfaces of the polypropylene fibers by regulating and controlling electromagnetic radiation frequency (100 GHz);
(3) Preparation of modified Polypropylene fibers
The surface modification is carried out on the nano-scale quaternary ammonium salt ionic liquid modified titanium dioxide grown on the surface of the polypropylene fiber by using N-cocoyl arginine ethyl ester; the modified titanium dioxide is prepared by carrying out hydrothermal modification on N-cocoyl arginine ethyl ester with the concentration of 2mg/ml, specifically reacting for 24 hours at the temperature of 120 ℃, and finally washing with deionized water to obtain the polypropylene fiber growth quaternary ammonium salt ionic liquid modified growth modified titanium dioxide of the N-cocoyl arginine ethyl ester.
(4) Preparation of ceramic/fiber modified coatings
Adding 0.5g of modified polypropylene fiber into 80g of epoxy resin, stirring at the speed of 80r/min for 20min and uniformly mixing, then adding 19.5g of curing agent and stirring for 20min, performing a defoaming process in a vacuum drying oven, coating the obtained material on a steel pipe pile, and curing at room temperature for 60h to form the ceramic/fiber modified coating.
The coatings of examples 1-4 and comparative examples 1-4 were tested and the results are shown in Table 1, wherein 3.5wt% NaCl solution was used for the soaking.
TABLE 1 test results for the coatings in examples 1-4 and comparative examples 1-4
In addition, the inventors have conducted experiments with other materials, process operations, and process conditions as described in this specification with reference to the foregoing examples, and have all obtained desirable results.
It should be understood that the technical solution of the present invention is not limited to the above specific embodiments, and all technical modifications made according to the technical solution of the present invention without departing from the spirit of the present invention and the scope of the claims are within the scope of the present invention.
Claims (10)
1. The preparation method of the ceramic/fiber modified coating for the steel pipe pile is characterized by comprising the following steps of:
modifying the ceramic particles by adopting a first modifier to obtain modified ceramic particles; wherein the first modifier comprises any one or a combination of a plurality of dopamine, a surfactant and an ionic liquid;
at least adopting any one mode 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 to grow nano-scale or micro-scale modified ceramic particles on the surface of the fiber, so as to obtain the fiber with the grown modified ceramic particles;
modifying the fiber growing the modified ceramic particles by adopting a second modifier to obtain a modified fiber; wherein the second modifier comprises a surfactant and/or an ionic liquid;
and mixing the modified fiber, the resin and the curing agent, applying the mixture on the surface of a matrix, and curing the mixture to obtain the ceramic/fiber modified coating.
2. The preparation method according to claim 1, wherein the preparation method of the modified ceramic particles specifically comprises: mixing the solution containing the first modifier with ceramic particles and reacting at 60-75 ℃ for 6-48 hours to obtain modified ceramic particles;
and/or the dosage ratio of the first modifier to the ceramic particles is 40-200 mL:10-500 mg;
and/or the particle size of the modified ceramic particles is 100-300nm.
3. The method of manufacturing according to claim 1, characterized in that: the ceramic particles comprise any one or a combination of a plurality of titanium dioxide, aluminum oxide, zirconium oxide and silicon dioxide;
and/or the surfactant comprises any one or a combination of a plurality of cationic surfactants, anionic surfactants, amphoteric surfactants and nonionic surfactants; preferably, the cationic surfactant comprises an amino acid type cationic surfactant and/or a quaternary ammonium compound, and the amino acid type cationic surfactant comprises N-cocoyl arginine ethyl ester; the quaternary ammonium compound comprises any one or a combination of a plurality of benzalkonium chloride, benzalkonium bromide and benzalkonium chloride; preferably, the anionic surfactant comprises sodium lauryl sulfate; preferably, the amphoteric surfactant comprises an N-alkyl aspartic acid-b-alkyl ester; preferably, the nonionic surfactant comprises a fatty acid glyceride and/or a fatty acid sorbitan;
and/or the ionic liquid comprises a cationic ionic liquid and/or an anionic ionic liquid; preferably, the cationic ionic liquid comprises any one or a combination of a plurality of quaternary ammonium salt ionic liquid, quaternary phosphonium salt ionic liquid, imidazole salt ionic liquid and pyrrole salt ionic liquid; preferably, the anionic ionic liquid comprises any one or a combination of a plurality of halogen ionic liquid, tetrafluoroborate ionic liquid and hexafluorophosphate ionic liquid;
and/or the first modifier is the same as or different from the second modifier.
4. The method of manufacturing according to claim 1, characterized in that: the fiber comprises any one of organic fiber, inorganic fiber and organic/inorganic composite fiber; preferably, the organic fiber comprises any one or a combination of more than one of aramid fiber, polypropylene fiber, polyester fiber, polyacrylonitrile fiber and polyphenylene sulfide fiber; preferably, the inorganic fibers comprise any one or a combination of a plurality of carbon fibers, glass fibers, silicon carbide fibers and silica-alumina fibers; preferably, the organic/inorganic composite fiber includes a glass fiber/carbon fiber composite fiber;
and/or the fibers have a diameter of 5-20 μm and a length of 1-10mm.
5. The method of manufacturing according to claim 1, characterized in that: the morphology of the particles in the fiber of the growth modified ceramic particles comprises any one or a combination of a plurality of spherical, polyhedral, conical and cuboid; preferably, the particles grow on one side of the fiber or around the fiber.
6. The preparation method according to claim 1, wherein the preparation method of the modified fiber specifically comprises: dispersing the fiber growing the modified ceramic particles and the second modifier in a solvent, stirring and reacting for 6-48 hours at 60-120 ℃, and then washing and freeze drying to obtain the modified fiber;
preferably, the dosage ratio of the fiber of the growth modified ceramic particles to the second modifier is 0.01-1 g:1-100 ml; preferably, the solvent comprises deionized water and/or ethanol.
7. The preparation method according to claim 1, characterized in that it comprises in particular:
uniformly mixing the modified fiber with resin, and then adding a curing agent for mixing to obtain a mixed material;
and applying the mixed material to the surface of a substrate and curing the mixed material at 25-80 ℃ for 48-96 hours to prepare the ceramic/fiber modified coating.
8. The method of manufacturing according to claim 7, wherein: the mass ratio of the modified fiber to the resin to the curing agent is 0.01-1:50-90:10-50;
and/or the resin comprises any one or a combination of a plurality of epoxy resin, acrylic resin, polyurethane and polyimide; and/or the curing agent comprises any one or a combination of more of aliphatic amine, alicyclic amine, aromatic amine, polyamide, anhydride, resin and tertiary amine; and/or the matrix comprises a steel pipe pile.
9. A ceramic/fiber-modified coating for a steel pipe pile produced by the production method according to any one of claims 1 to 8;
preferably, the thickness of the ceramic/fiber modified coating is 50-1000 μm; preferably, the ceramic/fiber modified coating has a low frequency impedance modulus of 10 after 30 days of salt water soaking 11 Ω·cm 2 The above.
10. Use of the ceramic/fiber modified coating for steel pipe piles of claim 9 in the field of marine engineering equipment protection; preferably, the marine engineering equipment comprises steel pipe piles in a severe environment with high temperature, high humidity and high salt mist.
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