CN112647139A - Corrosion inhibitor coated core-shell fiber toughened organic coating and preparation method thereof - Google Patents
Corrosion inhibitor coated core-shell fiber toughened organic coating and preparation method thereof Download PDFInfo
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
- D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D11/00—Other features of manufacture
- D01D11/06—Coating with spinning solutions or melts
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
- D01D5/30—Conjugate filaments; Spinnerette packs therefor
- D01D5/34—Core-skin structure; Spinnerette packs therefor
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- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention relates to an anti-corrosion protective film material, in particular to a corrosion inhibitor-coated core-shell fiber toughening organic coating and a preparation method thereof. The organic coating is a core-shell fiber layer and an organic resin layer which are coated with the corrosion inhibitor; wherein, the core-shell fiber layer coated with the corrosion inhibitor accounts for 5-15 wt% of the organic coating. The invention has the advantages of simple manufacture and low cost, and the coating has multiple excellent performances of high resistance, high toughness, self-repairing performance and the like, has outstanding durability and has huge application prospect in the aspect of marine corrosion protection.
Description
Technical Field
The invention relates to an anti-corrosion protective film material, in particular to a corrosion inhibitor-coated core-shell fiber toughening organic coating and a preparation method thereof.
Background
The organic coating inevitably generates cracks or defects during use, and corrosive media (such as water, chlorine ions and the like) of small molecules can reach a protected substrate through the cracks or the defects to initiate corrosion. Therefore, the toughness of the coating and the adhesive force between the coating and the substrate are improved, the probability of generating cracks on the coating can be effectively reduced, and the protective performance of the coating system is improved. Fiber toughening techniques have been widely recognized. However, the fiber and resin sandwich method is commonly adopted in the current preparation technology, on one hand, because the compatibility of the fiber and the organic resin is poor, the peeling and layering phenomena are easy to occur, and on the other hand, the adhesive force of the resin and the metal matrix is not improved, so that the toughening protection effect is not achieved, and the corrosion process is accelerated.
Disclosure of Invention
Aiming at the defects of the existing coating, the invention aims to provide a corrosion inhibitor-coated core-shell fiber toughened organic coating and a preparation method thereof.
In order to achieve the purpose of the invention, the technical route of the invention is as follows:
a core-shell fiber toughening organic coating coated with a corrosion inhibitor is characterized in that the organic coating is a core-shell fiber layer coated with the corrosion inhibitor and an organic resin layer; wherein, the core-shell fiber layer coated with the corrosion inhibitor accounts for 5-15 wt% of the organic coating, preferably 6-12 wt%.
The corrosion inhibitor is coated in the nano-fiber by the electrostatic spinning technology; wherein, the shell material of the core-shell fiber layer is polyacrylonitrile, which accounts for 90-98 wt% of the core-shell fiber layer coated with the corrosion inhibitor, and the core material is a seawater type corrosion inhibitor, which accounts for 2-10%, preferably 4-8% of the core-shell fiber layer coated with the corrosion inhibitor.
The diameter of the core-shell fiber in the core-shell fiber layer is 100-200 nm.
The organic resin layer is prepared from resin and a curing agent according to a weight ratio of 2: 1-1: 1, proportioning and mixing; wherein the organic resin is one or more of epoxy resin, acrylic resin, polyurethane resin, fluorocarbon resin and amino resin;
the curing agent is one or more of an epoxy resin curing agent, an acrylic resin curing agent, a polyurethane resin curing agent, a fluorocarbon resin curing agent and an amino resin curing agent.
A preparation method of a corrosion inhibitor-coated core-shell fiber toughening organic coating comprises the following steps:
1) core-shell fiber preparation
Performing injection spinning on the shell fiber spinning solution and the core material spinning solution respectively through an electrostatic spinning technology to obtain a corrosion inhibitor-coated core-shell fiber material;
2) preparation of organic coatings
Mixing resin and a curing agent according to a weight ratio of 2: 1-1: 1, uniformly coating the core-shell fiber material coated with the corrosion inhibitor on the core-shell fiber material, and drying to obtain the core-shell fiber toughening organic coating.
The shell fiber spinning solution is prepared by dissolving polyacrylonitrile in an organic solvent, and stirring the dissolved solution at 20-28 ℃ and 20-30% of humidity; wherein, the adding amount of polyacrylonitrile is 6-10%, preferably 6-8%;
the core material spinning solution is prepared by dissolving a seawater corrosion inhibitor in an organic solvent, wherein the addition amount of the seawater corrosion inhibitor is 6-10%.
The organic solvent is one or a mixture of N, N-dimethylformamide, dimethylacetamide, dimethyl sulfoxide, ethyl acetate and tetrahydrofuran.
The electrostatic spinning technology comprises the steps of respectively extracting shell fiber spinning solution and core material spinning solution into injectors, respectively fixing the injectors on two different injection pumps of an electrostatic coaxial spinning machine, and well connecting a coaxial needle with a positive power supply and a negative power supply; adjusting spinning voltage at 15kV-30kV, temperature at 20-28 deg.C, and humidity at 20% -30%, and spinning for 40 min; wherein the shell fiber spinning solution is 0.2-1.0mm/min, and the core material spinning solution is 0.02-0.10 mm/min.
The core-shell fiber toughening organic coating is applied to being used as a metal anticorrosive coating.
Further, the core-shell fiber coated with the corrosion inhibitor is directly formed on the metal matrix to be protected, and then the core-shell fiber layer of the metal matrix is coated with the organic resin layer to form the organic coating, so that the organic coating protects the metal matrix.
The core-shell fiber toughened organic coating is applied to metal substrates which are easy to corrode, chemical equipment and major industrial metal equipment and is used as an anti-corrosion protective film material.
The metal is a steel pile, an oil pipeline, chemical equipment, a ship or ocean platform metal equipment.
Compared with the prior art, the invention has the following beneficial effects:
the invention utilizes the excellent mechanical property of the nano fiber and adds the nano fiber into the resin, so that the defect of the resin as a brittle material is effectively improved, the mechanical strength of the resin is obviously enhanced, and the nano fiber further has more excellent protection effect on a metal matrix. The core-shell fiber layer in the organic coating can seal micropores generated in the manufacturing process of the coating, cut off a transmission channel of a corrosive medium and further enhance the protective performance of the material. The corrosion inhibitor is wrapped in the fiber, and when the coating is damaged or cracked, the corrosion inhibitor is released, so that the coating at the defect part has a secondary protection and repair effect, and the protective performance of the resin coating is further improved. In addition, the fiber has good compatibility with organic resin due to the addition of the fiber, and new pores and interface defects are not brought to the organic resin due to the dispersion problem, so that the organic resin and the organic resin achieve better synergistic effect. Compared with other common resin coatings, the coating has the advantages of good adhesive force, water resistance, salt water permeation resistance, simple process, low cost, excellent anticorrosion effect and strong protection capability after being cured into a film.
Drawings
FIG. 1 is SEM images of polyacrylonitrile fibers with different concentrations, wherein (a) the polyacrylonitrile fibers with the concentration of 6 percent, (b) the polyacrylonitrile fibers with the concentration of 10 percent, and (c) the polyacrylonitrile fibers with the concentration of 12 percent are provided in the embodiment of the present invention;
FIG. 2 is a TEM image of a core-shell structure of a corrosion inhibitor coated with polyacrylonitrile fibers, provided by an embodiment of the present invention;
FIG. 3 is a schematic diagram showing the comparison of tensile strengths of a core-shell fiber toughened organic composite coating of polyacrylonitrile, core-shell fibers and a pure epoxy resin coating provided by an embodiment of the present invention;
FIG. 4 shows a composite coating/carbon steel interface morphology (a) and a pure epoxy coating/carbon steel interface morphology (b) provided by an embodiment of the present invention;
FIG. 5 is a diagram of a Baud of the modulus value of a polyacrylonitrile core-shell fiber epoxy resin composite coating/carbon steel system containing corrosion inhibitor according to an embodiment of the present invention;
FIG. 6 is a diagram of the mode value Baud of a polyacrylonitrile core-shell fiber epoxy resin composite coating/carbon steel system without corrosion inhibitor according to an embodiment of the present invention;
FIG. 7 is a mode number Baud plot of a pure epoxy coating/carbon steel system provided by an embodiment of the present invention;
fig. 8 is a baud chart of the modulus values of bare carbon steel according to an embodiment of the present invention.
Detailed Description
The following examples are presented to further illustrate embodiments of the present invention, and it should be understood that the embodiments described herein are for purposes of illustration and explanation only and are not intended to limit the invention.
The core-shell fiber material prepared by the invention not only has good toughening function on organic resin, but also can provide enough storage space to coat enough corrosion inhibitor, and when the coating is damaged or cracked, the corrosion inhibitor is released, so that the coating at the defect part is secondarily repaired, and the matrix is continuously protected. In addition, the selected high molecular polymer is used as a shell material of the fiber and is directly deposited on the surface of the metal matrix by adopting a classical spinning technology, so that the high molecular polymer can be perfectly combined with organic resin, and plays multiple protection roles of toughening, self-repairing, corrosion prevention and the like.
Example 1
1) Preparing an electrostatic spinning solution:
weighing 4g of polyacrylonitrile, adding the polyacrylonitrile into a beaker containing 33.3g of N, N-methylformamide solvent for mixing, and placing the beaker on a magnetic stirrer for stirring for 24 hours at the temperature of 20-25 ℃ and the humidity of 20-30% at room temperature to obtain shell material spinning solution;
weighing 3g of benzotriazole corrosion inhibitor, dissolving the benzotriazole corrosion inhibitor by adopting N, N-methylformamide, and carrying out ultrasonic treatment for 10-15 minutes to obtain a core material spinning solution;
and finally, respectively pumping the shell material spinning solution and the core material spinning solution into a syringe to start to prepare the nano-fiber.
2) Preparing corrosion inhibitor nano-fibers coated on carbon steel:
fixing two injectors filled with shell material spinning solution and core material spinning solution on two different injection pumps of an electrostatic coaxial spinning machine respectively, connecting a coaxial needle with a positive power supply and a negative power supply, covering a collector with an aluminum foil paper, and fixing metal matrix carbon steel on the aluminum foil paper; adjusting the spinning voltage to 15kV-30kV, the pushing speed of a shell material spinning solution injection pump to be 0.8mm/min, the pushing speed of a core material spinning solution to be 0.08mm/min, the temperature to be 20-28 ℃ and the humidity to be 20-30%; the spinning time is 40-60 minutes; namely coating the carbon steel with the corrosion inhibitor nano-fiber in a shell-core mode.
3) Preparing a core-shell fiber toughening organic coating:
taking the carbon steel covered with the nanofiber layer down from the aluminum-foil paper, and drying in a drying oven at 50-60 ℃ for 20-30 min; and preparing an epoxy resin coating in the period, wherein the resin and the curing agent in the epoxy resin coating are proportioned according to the weight ratio of 2:1, uniformly coating the nano-fiber film obtained by drying on a glass rod for three times, and placing the nano-fiber film in a drying oven at 60 ℃ for 48 hours to finally obtain the core-shell fiber toughening organic coating containing different polyacrylonitrile.
And (3) carrying out performance test on the core-shell fiber toughening organic coating prepared by the method:
1) scanning Electron Micrographs (SEM) of nanofibers at different concentrations:
each sample was subjected to gold spraying treatment, and surface observation was performed under a scanning electron microscope. (see FIG. 1)
As can be seen from the scanning electron micrograph of the sample in fig. 1, wherein (a) is polyacrylonitrile nanofibers with a concentration of 6%, wherein the fibers are distributed very uniformly, the diameter distribution of each fiber is relatively uniform, and the microstructure is ideal and relatively smooth; (b) the polyacrylonitrile nano-fiber with the concentration of 10 percent is shown in the figure, the surface is disordered and unclear, and floccules are generated, because the concentration of the spinning solution (shell) is increased to cause macromolecular agglomeration and cannot be completely elongated under the action of an electric field, so that the fibers are unevenly distributed and have non-uniform diameters, and the corrosion inhibitor flows out because some fibers are broken; the graph (c) shows that the polyacrylonitrile nano-fiber with the concentration of 12 percent cannot be drawn into a fibrous shape by the electric field intensity along with the continuous increase of the concentration of the spinning solution (shell), and a series of bead structures with different sizes, also called polymer beads, are generated, so that the fiber surface is intricate and complex, the distribution is disordered, and the diameters are completely non-uniform. Therefore, the form of the polyacrylonitrile spinning solution with the concentration of 6 percent is better than that of other samples.
2) Transmission Electron Micrograph (TEM) of nanofibres coated corrosion inhibitor containing polyacrylonitrile with concentration of 6%:
the sample was placed under a transmission electron microscope and the internal structure thereof was observed (see fig. 2).
As can be seen from the image observed by the transmission electron microscope in FIG. 2, the polyacrylonitrile nano-fiber has a good core-shell structure, the interior is a hollow structure, and the benzotriazole corrosion inhibitor is partially embedded into the nano-fiber; the polyacrylonitrile nano-fiber has brighter color under a transmission electron microscope, the benzotriazole has darker color under the transmission electron microscope, and the benzotriazole corrosion inhibitor is successfully coated in the polyacrylonitrile nano-fiber through an electrostatic spinning technology.
3) Comparison of tensile strength of organic coating:
fixing the two ends of each sample and the tin foil paper on a tensile testing machine, slowly applying tensile stress, gradually increasing the tensile stress along with the increase of time until the sample is broken, and recording the tensile stress value and the tensile distance of the sample (see figure 3); in the above examples, core-shell fiber toughened organic composite coating (composite coating) containing 6% polyacrylonitrile, core-shell fiber (prepared according to step 2 described in the above examples) formed corrosion inhibitor nanofiber layer in a shell-core form on tin foil paper, and pure epoxy resin coating were obtained for each sample.
From the comparison of the figures, it is found that the tensile strength of the epoxy sample is high, but since the epoxy is a brittle material, the sample suddenly breaks when the pure epoxy coating reaches the maximum tensile stress. After a certain amount of nano fibers are added into the epoxy resin, the maximum tensile strength of the sample is improved, and the tensile distance is improved at the same time; when the sample reaches the maximum stretching amount, the sample does not break immediately, but gradually breaks after following 1mm, which shows that the mechanical property of the epoxy resin is obviously improved by the nanofiber, and the brittle property of the epoxy resin is improved, so that the metal matrix is more comprehensively protected by the nanofiber.
4) Comparison of coating and substrate adhesion Properties
The interface between the polyacrylonitrile core-shell fiber toughened organic composite coating and the carbon steel is observed on the surface under a scanning electron microscope, and the figure 4(a) shows.
The interface of the pure epoxy coating with the carbon steel was also surface observed under a scanning electron microscope, see fig. 4 (b).
As can be seen from the scanning electron microscope image, the organic composite coating and the interface of the metal matrix can be perfectly combined, no stripping and no air hole exist, the adhesive force is good, and the invasion of erosive particles to the surface of the matrix is not facilitated. And a certain pore exists between the pure epoxy coating and the metal matrix interface, so that the pure epoxy coating cannot be perfectly combined, and the metal matrix cannot be well protected.
5) Electrochemical impedance testing of different coatings:
the core-shell fiber toughened organic coating (added with corrosion inhibitor)/carbon steel obtained in the above example, and the composite coating (prepared according to the description of the above example only without adding corrosion inhibitor)/carbon steel, pure carbon steel and pure epoxy coating/carbon steel systems are respectively fixed outside an electrolytic cell, NaCl solution with the concentration of 3.5% is used as electrolyte,the saturated calomel electrode is used as a reference electrode, the carbon rod is used as a counter electrode, the test amplitude is 20mV, and the test frequency is 10 mV-2-105Hz, the coating electrochemical impedance test was performed at different soaking times using a parttatp 4000+ electrochemical workstation.
As shown in the comparison of electrochemical impedance spectrograms of different coating/carbon steel systems of figures 5 to 8, which are soaked in 3.5 wt.% NaCl solution for 0 to 15 days, the surface of the pure carbon steel has no corrosion resistance, and the system impedance is only 103Ω·cm2After the pure epoxy resin is coated, the impedance of the system is improved to 105Ω·cm2(ii) a After the nano-fiber without being coated with the corrosion inhibitor is added into the epoxy resin, the system impedance is only improved to 107Ω·cm2After the nano-fiber coated with the corrosion inhibitor is added into the epoxy resin, the system impedance is improved to 108Ω·cm2. After the core-shell fiber toughened organic coating is soaked for 15 days, the core-shell fiber toughened organic coating still has certain anticorrosion performance, other coatings begin to be stripped, and the metal matrix is almost completely corroded. It is generally accepted that the system impedance is higher than 106Ω·cm2Has a certain protection capability which is lower than 106Ω·cm2Then has no protective capability, higher than 108Ω·cm2Thus having excellent protective performance. Therefore, the protective effect of the core-shell fiber toughened organic coating is more obvious, and the protective time is more durable.
Example 2
The difference from example 1 is that the substrate is replaced by a titanium alloy:
1) preparing an electrostatic spinning solution:
weighing 2g of polyacrylonitrile, adding the weighed polyacrylonitrile into a beaker containing 33.3g of N, N-methylformamide solvent for mixing, and placing the mixture on a magnetic stirrer for stirring for 24 hours at the room temperature of 20-25 ℃ and the humidity of 20-30%. Obtaining a shell material spinning solution; weighing 2.5g of benzotriazole corrosion inhibitor, adding the benzotriazole corrosion inhibitor into a beaker containing N, N-methylformamide solvent, and carrying out ultrasonic treatment for 10-15 minutes to obtain a core material spinning solution; and finally, respectively drawing the shell material and the core material into a syringe to start to prepare the nano-fiber.
2) Preparing corrosion inhibitor nano-fibers coated on the titanium alloy:
fixing two injectors filled with spinning solution (shell) and spinning solution (core) on two different injection pumps of an electrostatic coaxial spinning machine respectively, connecting a coaxial needle with a positive power supply and a negative power supply, covering an aluminum foil paper on a collector, and fixing a metal matrix titanium alloy on the aluminum foil paper; adjusting spinning voltage to 18kV-25kV, pushing speed of the injection pump to be 1.0mm/min of spinning solution (shell), 0.10mm/min of spinning solution (core), temperature to 20-28 ℃, and humidity to 20-30%; the spinning time is 40-60 minutes.
3) Preparing a core-shell fiber toughening organic coating:
taking the titanium alloy covered with the nanofiber layer down from the aluminum-foil paper, and drying in a drying oven at 50-60 ℃ for 20-30 min; preparing an epoxy resin coating during the preparation, wherein the weight ratio of resin to curing agent is 2: 1-1: 1, uniformly coating the obtained nanofiber membrane on a glass rod, brushing for three times, and placing the nanofiber membrane in a 60 ℃ oven for 48 hours to finally obtain the core-shell fiber toughening organic coating.
The obtained corrosion inhibitor-coated core-shell fiber toughened organic coating film obtained by the electrostatic spinning technology has the advantages of improved compactness, more uniform thickness and composition, more excellent conformity with a metal matrix, and improved original brittleness of pure epoxy resin; the embedding of the corrosion inhibitor is further integral corrosion resistance, and the metal matrix is more excellent in protection.
It should be understood that various changes, substitutions, combinations and alterations can be made by those skilled in the art without departing from the scope of the invention as defined by the appended claims.
Claims (10)
1. A core-shell fiber toughening organic coating coated with a corrosion inhibitor is characterized in that the organic coating is a core-shell fiber layer coated with the corrosion inhibitor and an organic resin layer; wherein, the core-shell fiber layer coated with the corrosion inhibitor accounts for 5-15 wt% of the organic coating.
2. The corrosion inhibitor-coated core-shell fiber toughened organic coating according to claim 1, wherein the corrosion inhibitor is coated in the nanofibers by an electrospinning technique; wherein, the shell material of the core-shell fiber layer is polyacrylonitrile, which accounts for 90-98 wt% of the core-shell fiber layer coated with the corrosion inhibitor, and the core material is a seawater type corrosion inhibitor, which accounts for 2-10% of the core-shell fiber layer coated with the corrosion inhibitor.
3. The corrosion inhibitor-coated core-shell fiber toughened organic coating as claimed in claim 2, wherein the diameter of the core-shell fiber in the core-shell fiber layer is 100-200 nm.
4. The corrosion inhibitor-coated core-shell fiber toughened organic coating as claimed in claim 1, wherein the organic resin layer is a mixture of resin and curing agent in a weight ratio of 2: 1-1: 1, proportioning and mixing; wherein the organic resin is one or more of epoxy resin, acrylic resin, polyurethane resin, fluorocarbon resin and amino resin;
the curing agent is one or more of an epoxy resin curing agent, an acrylic resin curing agent, a polyurethane resin curing agent, a fluorocarbon resin curing agent and an amino resin curing agent.
5. A preparation method of the corrosion inhibitor-coated core-shell fiber toughened organic coating of claim 1, which is characterized by comprising the following steps:
1) core-shell fiber preparation
Performing injection spinning on the shell fiber spinning solution and the core material spinning solution respectively through an electrostatic spinning technology to obtain a corrosion inhibitor-coated core-shell fiber material;
2) preparation of organic coatings
Mixing resin and a curing agent according to a weight ratio of 2: 1-1: 1, uniformly coating the core-shell fiber material coated with the corrosion inhibitor on the core-shell fiber material, and drying to obtain the core-shell fiber toughening organic coating.
6. The preparation method of the corrosion inhibitor-coated core-shell fiber toughened organic coating, according to claim 5, is characterized in that: the shell fiber spinning solution is prepared by dissolving polyacrylonitrile in an organic solvent, and stirring the dissolved solution at 20-28 ℃ and 20-30% of humidity; wherein, the addition amount of polyacrylonitrile is 6-10%;
the core material spinning solution is prepared by dissolving a seawater corrosion inhibitor in an organic solvent, wherein the addition amount of the seawater corrosion inhibitor is 6-10%.
7. The preparation method of the corrosion inhibitor-coated core-shell fiber toughened organic coating according to claim 6, characterized in that: the organic solvent is one or a mixture of N, N-dimethylformamide, dimethylacetamide, dimethyl sulfoxide, ethyl acetate and tetrahydrofuran.
8. The preparation method of the corrosion inhibitor-coated core-shell fiber toughened organic coating, according to claim 5, is characterized in that: the electrostatic spinning technology comprises the steps of respectively extracting shell fiber spinning solution and core material spinning solution into injectors, respectively fixing the injectors on two different injection pumps of an electrostatic coaxial spinning machine, and well connecting a coaxial needle with a positive power supply and a negative power supply; adjusting spinning voltage at 15kV-30kV, temperature at 20-28 deg.C, and humidity at 20% -30%, and spinning for 40 min; wherein the shell fiber spinning solution is 0.2-1.0mm/min, and the core material spinning solution is 0.02-0.10 mm/min.
9. The use of the corrosion inhibitor-coated core-shell fiber toughened organic coating according to claim 1, wherein: the core-shell fiber toughening organic coating is applied to being used as a metal anticorrosive coating.
10. The use of the corrosion inhibitor-coated core-shell fiber toughened organic coating according to claim 9, wherein: the core-shell fiber coated with the corrosion inhibitor is directly formed on a metal matrix to be protected, and then an organic resin layer is coated on the core-shell fiber layer of the metal matrix to form an organic coating so as to protect the metal matrix.
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