Self-warning and self-repairing agent material, preparation method and application thereof

Abstract

The application belongs to the technical field of corrosion monitoring and intelligent self-repairing coating, and particularly relates to a self-warning and self-repairing electrospinning core-shell fiber coating material responding to aggregation-induced emission and a preparation method and application thereof. The material is formed in a shell-core form by a fiber shell material and a fiber core material; the fiber core material contains an aggregation-induced emission self-warning agent and a water environment self-repairing material, and the fiber shell material contains a non-Newtonian fluid polymer material. The intelligent fiber coating provided by the application has the advantages of simple preparation process, high loading rate and high repair efficiency, and has the integrated functions of self-warning and self-repairing, and has high practical value for electrospinning technology in the field of marine corrosion prevention nano coating.

Description

Technical Field

[0001] This invention belongs to the field of corrosion monitoring and intelligent self-healing coating technology, specifically a self-early warning and self-healing electrospun core-shell fiber coating material with aggregation-induced luminescence response and its preparation method and application. Background Technology

[0002] Corrosion seriously hinders the sustainable development of the national economy, posing a significant threat not only to safety and economic issues but also to the national welfare and people's livelihoods. To reduce corrosion damage, organic coatings remain the most effective, economical, and widely used method. However, due to mechanical damage and aging, these coatings eventually fail. Even at the micro- and nano-scale, coating damage inevitably compromises the integrity of the polymer matrix, leading to the initiation of underfilm corrosion. If not detected and repaired promptly, corrosion propagation can ultimately result in catastrophic structural damage, causing severe economic and safety consequences. Furthermore, defects such as pores and micro- and nano-cracks are prone to appearing during the application or curing process of organic coatings, severely shortening their service life and failing to provide long-term corrosion protection. Therefore, early monitoring and warning of corrosion and repair of micro-crack damage are of paramount importance.

[0003] Self-healing coatings are coating materials that can repair damage and restore performance with minimal or no external interference. Chinese patent CN201810934463.3 discloses a coating based on graphene nanocontainers, a self-healing coating, its preparation method, and its application. In this coating, the corrosion inhibitor loaded on the graphene nanocontainers serves as the source of the coating's repair agent. When the coating suffers mechanical damage or defects, the corrosion inhibitor released from the graphene nanocontainers coordinates with the metal substrate, adsorbing and forming a film on the metal surface, thereby achieving the coating's self-healing and anti-corrosion properties. Chinese patent CN202011177355.X provides a self-healing waterborne acrylic coating based on quinoline-based nano-metal-organic framework materials. This self-healing coating is prepared by loading zinc phosphate into the organic framework material, allowing for the gradual release of zinc phosphate molecules to promptly repair damaged areas of the coating, thus extending the steel's corrosion resistance.

[0004] The two types of coatings mentioned above only have self-healing properties and cannot monitor and warn of the corrosion and repair process of the coating in a timely manner. Furthermore, the nano-containers in the existing self-warning and self-healing coatings are complex to prepare, have low warning and repair efficiency, and cannot effectively monitor and warn of micro- and nano-cracks in the coating in an aqueous environment.

[0005] Aggregation-induced emission (AIE) response early warning materials are those whose molecules emit almost no light in solution, but whose luminescence is greatly enhanced in the aggregated state or under solid film conditions. These materials exhibit strong luminescence properties in the solid state, strong stability under ultraviolet excitation, and advantages such as high emissivity, fast response, and high sensitivity. Different wavelengths of luminescence can be regulated through flexible chemical modification. Applying AIE to coatings allows for non-destructive, visualized signal detection of crack damage, helping to prevent eventual structural failure and increase coating lifespan. However, AIE research is still in its early stages in the field of corrosion protection, and research on its application in self-healing coatings is even rarer. Summary of the Invention

[0006] The purpose of this invention is to provide a self-warning and self-healing agent material with aggregation-induced emission response, its preparation method, and its application.

[0007] To achieve the above objectives, the present invention adopts the following technical solution:

[0008] A self-warning and self-healing agent material, wherein the material is formed in the form of a shell material and a core material; the core material contains an aggregation-induced emission self-warning agent and a water environment self-healing material, and the shell material contains a non-Newtonian fluid polymer material.

[0009] The fiber core material contains an aggregation-induced emission self-warning agent and a water environment self-healing material mixed in a mass ratio of 0.05-1:5-10;

[0010] The fiber shell material is a mixture of a non-Newtonian fluid polymer material and a shell solvent in a mass ratio of 1:8-20.

[0011] The fiber shell material also contains surfactants, such as the nonionic surfactant Tween 20 or the cationic surfactant cetyltrimethylammonium bromide (CTAB). The mass ratio of surfactant to fiber shell material is 0.01-1:1, which increases the conductivity of the fiber spinning shell solution to a certain extent and inhibits "beading".

[0012] The non-Newtonian fluid polymer material is one or more of polyacrylonitrile, cellulose acetate, PCL, and PS; the shell solvent is one or more of acetone, N,N-dimethylformamide, N,N-dimethylacetamide, and dimethyl sulfoxide.

[0013] The aggregation-induced fluorescence self-warning core material is tetraphenylethylene or a derivative of tetraphenylethylene; the water environment self-healing material is a film-forming substance that can react with water or water vapor (e.g., diisocyanate) or underwater-curing epoxy resin (e.g., underwater-curing epoxy resin J40).

[0014] A method for preparing the self-warning-self-repairing agent material involves using an electrospinning device to perform coaxial spinning of the fiber shell material and the fiber core material, thereby obtaining a self-warning-self-repairing material.

[0015] Specifically:

[0016] 1) Preparation of fiber shell material: According to the above proportion, the non-Newtonian fluid polymer material is added to the shell material solvent under stirring conditions, and then stirred at 40-65℃ and 1000-5000 rpm for 1-2 hours until the non-Newtonian fluid polymer material is dissolved, thus obtaining the fiber shell material.

[0017] Alternatively, after the non-Newtonian fluid polymer material has dissolved, the surfactant can be added and stirring can continue for 3-6 hours. The mass ratio of the surfactant to the non-Newtonian fluid polymer material and the shell solvent is 0.01-1:1.

[0018] 2) Preparation of fiber core material: Aggregation-induced fluorescence self-early warning material and water environment self-repair material are mixed and magnetically stirred at room temperature for 3-6 hours;

[0019] 3) Preparation of core and shell fibers by electrospinning: Adjust the electrospinning machine, assemble and fix the coaxial needle injector, inject the fiber shell material and fiber core material at the same time, and perform coaxial spinning at room temperature to obtain the self-warning-self-healing agent material.

[0020] The spinning voltage range is controlled at 25-30kV, the negative voltage is -2.5-3.5kV, the distance from the coaxial needle nozzle to the roller receiver is 8-15cm, and the syringe volume is 3-15ml. The shell solution injection speed is 0.1-1mm / min, the core solution injection speed is 0.001-0.1mm / min, and the core structure self-warning-self-healing agent material is prepared after spinning for 4-6 hours.

[0021] An application of the aforementioned self-warning-self-healing agent material, wherein the material is used as an aggregation-induced emission response self-warning-self-healing agent material in aquatic environments for metal corrosion protection.

[0022] An aggregation-induced emission responsive water environment self-warning and self-healing coating, wherein the coating contains the aforementioned self-warning and self-healing agent material.

[0023] Specifically, the self-warning-self-healing agent material and organic coating are mixed in a mass ratio of 1:10-20, and then coated on the surface of the metal substrate. After drying at room temperature for 2-7 days, an aggregation-induced emission response self-warning-self-healing coating is obtained.

[0024] The organic coating is any one of polydimethylsiloxane coating, epoxy resin coating, or polyurethane coating.

[0025] The aggregation-induced light-emitting response water environment self-warning-self-healing coating, when the coating is damaged by cracks, the self-warning material and the self-healing material are released from the fibers at the same time. When the self-healing material comes into contact with water or water vapor, it will form a filling repair film on the metal substrate in the crack area.

[0026] The aggregation-induced emission responsive water environment self-warning and self-healing coating, as the repair film forms, restricts the movement of aggregation-induced emission molecules, which enhances radiative transitions and produces a visible fluorescence warning function, enabling real-time monitoring of the corrosion repair process.

[0027] Embodiments of the present invention also provide the use of any of the foregoing coatings or self-warning-self-healing coatings in metal corrosion protection.

[0028] Compared with the prior art, the advantages of the present invention are at least as follows:

[0029] 1) The aggregation-induced light emission response water environment self-early warning and self-healing coating provided by the present invention can simultaneously realize the crack early warning monitoring and self-healing process of the anti-corrosion coating, give full play to the dual functions of early warning and repair materials, and realize the long-term anti-corrosion performance of the coating.

[0030] 2) The aggregation-induced emission responsive water environment self-warning and self-healing coating provided by this invention, when the coating is damaged by cracks, the self-warning material and the self-healing material are released simultaneously from the fibers. When the self-healing material encounters water or water vapor, it forms a filling repair film on the metal substrate in the crack area. As the repair film forms, the movement of aggregation-induced emission molecules is restricted, which enhances radiative transitions and produces a visible fluorescence warning function, allowing for real-time monitoring of the corrosion repair process.

[0031] 3) This invention provides a method for preparing a core-shell fiber material for an aggregation-induced emission-responsive self-warning and self-healing agent for the water environment, and a method for preparing an anti-corrosion coating. Using the prepared core-shell fiber material as a nanocontainer offers advantages such as simple preparation process, high loading rate, and high repair efficiency. Furthermore, the nanofiber network is uniformly distributed in the coating, solving the problems of complex preparation processes, low loading rates, and uneven distribution in coatings associated with inorganic nanocontainers. This invention has high practical value for electrospinning technology in the field of marine anti-corrosion nanocoatings. Attached Figure Description

[0032] Figure 1 These are transmission electron microscopy (TEM) images (a) and laser confocal fluorescence microscopy (CLSM) images (b) of the core-shell fibers obtained in the embodiments of the present invention;

[0033] Figure 2 a and 2c are SEM images and corresponding UV irradiation images of the scratch locations after the fiber coating has been immersed in 3.5 wt.% NaCl solution for 120 h.

[0034] Figure 2 b and 2d are FE-SEM images and corresponding CLSM images of the scratch locations after the fiber coating has been immersed in 3.5 wt.% NaCl solution for 120 h.

[0035] Figure 2 A photo comparing the luminescence of an HDI repair film with TPE added as a warning agent and a blank repair film after the fiber coating was soaked in 3.5 wt.% NaCl solution for 120 h and then irradiated with a UV lamp at the scratched area.

[0036] Figure 3 The images show the electrochemical impedance spectroscopy (EIS) spectra of the fiber coating, including (a) the Nyquist plot and (b) the impedance modulus |Z| plot.

[0037] Figure 4 The EIS spectra of the blank coating are shown in (a) Nyquist plot and (b) impedance modulus |Z| plot.

[0038] Figure 5 Seawater immersion experiments on fiber coatings: (a) 1h (b) 60h (c) 120h;

[0039] Figure 6 Seawater immersion experiments for blank coatings: (a) 1h (b) 60h (c) 120h;

[0040] Figure 7 (a) and (b) are SEM images of the fiber morphology in the electrospun fiber shell solution with and without added surfactant, respectively. Detailed Implementation

[0041] The following examples further illustrate specific embodiments of the present invention. It should be noted that the specific embodiments described herein are merely for illustration and explanation and are not intended to limit the scope of the present invention.

[0042] This invention utilizes coaxial electrospinning technology to prepare a core-shell fiber nanofiber network filler with dual functions of fluorescence early warning response and self-healing in aquatic environments. This filler is then uniformly dispersed in a coating, using the core-shell fiber material as the reinforcing phase and a polymer organic coating as the matrix phase, resulting in an intelligent early warning and repair coating with excellent corrosion resistance. When cracks appear in the coating, on one hand, both the early warning and self-healing materials are released from the fibers. The self-healing material reacts with water or water vapor to form a film-forming film on the metal substrate in the cracked area. On the other hand, the aggregation-induced emission material released from the fibers, along with the reaction of the repair film, restricts the movement of aggregation-induced emission molecules, enhancing radiative transitions and producing a visible fluorescence early warning function. This achieves fluorescence early warning monitoring of the cracked area of ​​the coating, enabling real-time monitoring of the corrosion repair process. The intelligent fiber coating provided by this invention has a simple preparation process, high loading rate and repair efficiency, and integrates self-early warning and self-healing functions, making it highly practical for electrospinning technology in the field of marine anti-corrosion nanocoatings.

[0043] Example 1

[0044] Agglomeration-induced emission response water environment self-early warning and self-healing agent material, which consists of two structures: shell and core.

[0045] The specific implementation steps are as follows:

[0046] 1) Preparation of fiber shell material: PAN coaxial fibers were prepared using a 10 wt.% polyacrylonitrile (PAN) solution as the spinning solution.

[0047] Specifically, 2.5g of PAN powder and 0.05g of cationic surfactant cetyltrimethylammonium bromide (CTAB) were dissolved in 22.5g of NN-dimethylformamide DMF to prepare a 10wt.% polyacrylonitrile (PAN) spinning shell solution. The solution was heated in a water bath at 45°C and magnetically stirred for 6 hours until completely dissolved.

[0048] 2) Preparation of fiber core material: Dissolve 0.1g of tetraphenylethylene (TPE) in 5g of diisocyanate (HDI), stir magnetically at 40°C for 3 hours, and then spin for later use.

[0049] 3) Preparation of electrospun core shell fiber: Adjust the parameters of the electrospinning machine, assemble and fix the coaxial needle injector, and spin at room temperature to obtain the water environment self-warning-self-repair agent material;

[0050] Specifically:

[0051] The spinning voltage range was controlled at 25kV, with a negative voltage of -3.5kV. The distance from the coaxial needle nozzle to the roller receiver was 10cm, and the syringe volume used was 10ml. The shell solution injection rate was 0.3mm / min, and the core solution injection rate was 0.005mm / min. After 6 hours of spinning, a core-shell structured water environment self-warning and self-healing agent material was prepared.

[0052] 4) Weigh 5g of the above-prepared water environment self-warning-self-repairing agent material and spread it evenly on the surface of Q235 metal substrate to form a fiber membrane. Then weigh 50g of epoxy resin coating (the epoxy resin coating is commercially available, which is made by mixing the main agent and the auxiliary agent in a mass ratio of 3:1) and coat it on the fiber membrane. Dry it at room temperature for 5 days to obtain the aggregation-induced light emission response self-warning-self-repairing coating.

[0053] The self-warning-self-healing agent material prepared above was characterized (see [reference]). Figure 1 ), Figure 1 a is a TEM image of the obtained core-shell fiber, which shows that the fiber surface is smooth and has no beaded structure. The size of a single fiber is about 216 nm, of which the core size is 160 nm. The thickness of the fiber membrane is 100 μm, and the thickness of the composite coating is 160 μm. Figure 1 b is the CLSM diagram corresponding to the core and shell fibers, showing the fiber shell structure, core structure, and overall structure in red, green, and yellow respectively.

[0054] Then, the performance of the above-mentioned aggregation-induced emission response self-early warning and self-healing coating was tested:

[0055] Specifically, samples with aggregation-induced emission response self-warning and self-healing coatings were artificially scratched and then immersed in 3.5 wt.% NaCl solution for 120 hours. The scratched areas were then irradiated with ultraviolet light and observed under a laser confocal fluorescence microscope (see [link to study]). Figure 2 ).

[0056] from Figure 2 In (a), a distinct blue light was observed in the scratched area after soaking for 120 hours. Figure 2 (b) shows a fluorescence image taken under CLSM, confirming the self-warning function of the fiber coating. The coating with scratches was observed using scanning electron microscopy. Figure 2 (c), Figure 2 (d) is Figure 2 (c) SEM image of a magnified local area shows that broken fiber morphology appears in the scratched area of ​​the coating. The fibers release the repair agents HDI and TPE to form a protective layer, which acts as a barrier against corrosive media in seawater. Since TPE is integrated with HDI as a repair agent, the appearance of blue fluorescence also indicates the successful formation of the repair film. Figure 2(e) is a comparison photograph of the luminescence of the HDI repair film with added warning agent TPE and the blank repair film under ultraviolet light irradiation, which also proves the luminescence effect of the fluorescent warning agent.

[0057] Example 2

[0058] A self-early warning and self-healing agent material for water environment with aggregation-induced light emission response, which consists of a shell and core structure.

[0059] The specific implementation steps are as follows:

[0060] 2) Preparation of fiber shell material: 3.0 g of cellulose acetate (CA) powder and 0.08 g of nonionic surfactant Tween 20 were dissolved in 22.0 g of acetone and N,N-dimethylacetamide (2:1 (V / V)) to prepare a 12 wt.% CA spinning shell solution. The solution was heated in a water bath at 40 °C and magnetically stirred for 4 hours until completely dissolved.

[0061] 2) Preparation of fiber core material: Dissolve 0.1g of tetraphenylethylene (TPE) in 5g of water-curing epoxy resin, stir magnetically at room temperature for 4 hours, and then spin it for later use.

[0062] 3) Preparation of electrospun core-shell fiber: Adjust the parameters of the electrospinning machine, assemble and fix the coaxial needle injector, and prepare the water environment self-early warning-self-healing agent material by spinning at room temperature;

[0063] Specifically: the spinning voltage range was controlled at 29kV, the negative voltage was -3.0kV, the distance from the coaxial needle nozzle to the roller receiver was 13cm, and the syringe volume used was 8ml. The shell solution injection speed was 0.1mm / min, the core solution injection speed was 0.002mm / min, and a core-shell structured water environment self-warning-self-healing agent material was prepared after 5 hours of spinning.

[0064] 4) Weigh 3g of the above-prepared water environment self-warning-self-repairing agent material and spread it evenly on the surface of Q235 metal substrate to form a fiber membrane. Then weigh 30g of epoxy resin coating (the epoxy resin coating is commercially available, which is made by mixing epoxy resin main agent coating and curing agent material in a mass ratio of 10:1) and apply it to the fiber membrane. First, dry it in a 75℃ oven for 2 hours, and then dry it at room temperature for 2 days to obtain the self-warning-self-repairing coating.

[0065] Meanwhile, 30g of epoxy resin coating (mixed evenly according to the mass ratio of epoxy resin main agent coating to curing agent material of 10:1) was weighed and directly coated onto the metal substrate. After drying in an oven at 75℃ for 2 hours, it was then dried at room temperature for 2 days to obtain a blank coating control sample.

[0066] Electrochemical impedance spectroscopy (EIS) characterization was performed on the coated samples:

[0067] Electrochemical evaluation was performed using a PGSTAT302N Metrohm Autolab (Utrecht, Netherlands) electrochemical workstation, employing a traditional three-electrode system with a platinum electrode as the counter electrode and saturated calomel (Hg₂Cl₂) as the reference electrode. The voltage amplitude was 10 mV, and the frequency range was 10 mV. -2 -10 5 Hz.

[0068] Depend on Figure 3 To obtain the electrochemical impedance spectroscopy (EIS) spectrum of the obtained fiber coating, compare it with the blank coating without fibers. Figure 4 It can be seen that the impedance arc radius in the Nyquist plot of the fiber composite coating remains within 10h. 7 The magnitude of the difference indicates that the scratched coating still possesses excellent protective capabilities due to the formation of a self-healing film in the scratched area. A comparison with the blank coating shows that... Figure 3-7 In (a), the impedance arc radius of the Nyquist plot has decreased to 10 after 1 hour. 5 The order of magnitude decreased to 10 in 10 hours. 4 The magnitude indicates that the blank coating loses its protective ability after being scratched or damaged.

[0069] Figure 3 (b) shows the trend of the impedance magnitude |Z| over time at a frequency of 0.01Hz, with |Z| being 35302.6kΩ·cm in the first hour. 2 At the 10th hour, the impedance modulus was 13740.7 kΩ·cm. 2 blank coating in Figure 4 In (b), the first h|Z| is 162.2 kΩ·cm. 2 At the 10th hour, the impedance modulus was 40.42 kΩ·cm. 2 The comparison shows that the impedance modulus |Z| of the fiber coating at a frequency of 0.01Hz is 2-3 orders of magnitude higher, indicating that the repair agent of the core and shell fibers in the damaged coating plays an effective role in repairing the cracked area, and the self-healing film can resist the erosion of corrosive media over time.

[0070] Blank coated specimens and fiber-coated specimens were subjected to seawater immersion experiments. The experiments were conducted under natural conditions for 120 hours. The average temperature at the experimental site during the experiment was 25.3℃, and the average humidity was greater than 70%. The morphology of the fiber coating before and after seawater immersion is shown below. Figure 5As shown. After 1 hour of immersion, no obvious corrosion products were observed at the scratches, demonstrating self-healing properties. After 120 hours of immersion, a small amount of corrosion products appeared at the scratches on the fiber coating, but the self-healing film still provided protection. The morphology of the blank epoxy resin coating before and after immersion is shown in the figure. Figure 6 As shown, the blank coating peeled off the carbon steel substrate from the scratch, and yellow corrosion products appeared. After 120 hours of immersion, the corrosion intensified, the coating peeled off more rapidly, the scratched area increased significantly, and the yellow corrosion products increased, indicating that the blank coating has no self-healing ability.

[0071] Example 3

[0072] A self-early warning and self-healing agent material for water environment with aggregation-induced light emission response, which consists of a shell and core structure.

[0073] The specific implementation steps are as follows:

[0074] 3) Preparation of fiber shell material: Dissolve 3.0g of cellulose acetate (CA) powder in 22.0g of acetone and N,N-dimethylacetamide (2:1 (V / V)) to prepare a 12wt.% CA spinning shell solution. Heat in a water bath at 40℃ and stir magnetically for 4 hours until completely dissolved.

[0075] 2) Preparation of fiber core material: Dissolve 0.1g of tetraphenylethylene (TPE) in 5g of water-curing epoxy resin, stir magnetically at room temperature for 4 hours, and then spin it for later use.

[0076] 3) Preparation of electrospun core-shell fiber: Adjust the parameters of the electrospinning machine, assemble and fix the coaxial needle injector, and prepare the water environment self-early warning-self-healing agent material by spinning at room temperature;

[0077] Specifically: the spinning voltage range was controlled at 29kV, the negative voltage was -3.0kV, the distance from the coaxial needle nozzle to the roller receiver was 13cm, and the syringe volume used was 8ml. The shell solution injection speed was 0.1mm / min, the core solution injection speed was 0.002mm / min, and a core-shell structured water environment self-warning-self-healing agent material was prepared after 5 hours of spinning.

[0078] 4) Weigh 3g of the above-prepared water environment self-warning-self-repairing agent material and spread it evenly on the surface of Q235 metal substrate to form a fiber membrane. Then weigh 30g of epoxy resin coating (the epoxy resin coating is commercially available, which is made by uniformly mixing epoxy resin main agent coating and curing agent material in a mass ratio of 10:1) and coat it on the fiber membrane. First, dry it in an oven at 75℃ for 2 hours, and then dry it at room temperature for 2 days to obtain the self-warning-self-repairing coating. This serves as a control example of electrospinning shell solution without the addition of surfactant.

[0079] FE-SEM testing revealed that the fiber surface in the shell solution without added surfactants easily exhibited a beaded structure, with uneven fiber size and a rough surface. Figure 7 (a); while the fiber surface morphology with added surfactant is good, smooth and without beaded structure, see Figure 7 (b) It can be seen that the addition of surfactants in the electrospinning shell solution has an important influence on fiber formation.

[0080] It should be understood from the foregoing that those skilled in the art, under the guidance of this invention, can make various modifications such as substitutions and simple combinations without departing from the scope of protection of the claims of this invention. The scope of protection of this invention shall be determined by the claims.

Claims

1. A self-warning-self-healing agent material, characterized in that: The material is formed by a fiber shell material and a fiber core material; the fiber core material contains aggregation-induced light-emitting self-warning agent and water environment self-healing material, and the fiber shell material contains non-Newtonian fluid polymer material. The non-Newtonian fluid polymer material is one or more of polyacrylonitrile, cellulose acetate, PCL, and PS; the shell material solvent is one or more of acetone, N,N-dimethylformamide, N,N-dimethylacetamide, and dimethyl sulfoxide. The aggregation-induced emission self-warning agent is tetraphenylethylene or a derivative of tetraphenylethylene; the water environment self-healing material is a film-forming substance that can react with water or water vapor or an underwater curing epoxy resin. The fiber core material contains an aggregation-induced emission self-warning agent and a water environment self-healing material mixed in a mass ratio of 0.05-1:5-10; The fiber shell material is a mixture of a non-Newtonian fluid polymer material and a shell solvent in a mass ratio of 1:8-20. The fiber shell material also contains a surfactant, and the mass ratio of the surfactant to the fiber shell material is 0.01-1:

1.

2. A method for preparing the self-early warning and self-healing agent material according to claim 1, characterized in that: The fiber shell material and fiber core material are coaxially spun using an electrospinning device to obtain a material with self-early warning and self-repair capabilities.

3. The preparation method of the self-early warning-self-healing agent material according to claim 2, characterized in that: 1) Preparation of fiber shell material: According to the above proportion, the non-Newtonian fluid polymer material is added to the shell material solvent under stirring conditions, and then stirred at 40-65℃ and 1000-5000 rpm for 1-2 h until the non-Newtonian fluid polymer material is dissolved, thus obtaining the fiber shell material. Alternatively, after the non-Newtonian fluid polymer material has dissolved, the surfactant can be added and stirring can continue for 3-6 hours, wherein the mass ratio of the surfactant to the non-Newtonian fluid polymer material and the shell solvent is 0.01-1:

1. 2) Preparation of fiber core material: Aggregation-induced emission self-warning agent is mixed with water environment self-healing material and magnetically stirred at room temperature for 3-6 h; 3) Preparation of core and shell fibers by electrospinning: Adjust the electrospinning machine, assemble and fix the coaxial needle injector, inject the fiber shell material and fiber core material at the same time, and perform coaxial spinning at room temperature to obtain the self-warning-self-repairing agent material for application in metal corrosion protection.

4. The application of the self-warning-self-healing agent material according to claim 1, characterized in that: The material is used as a self-early warning and self-healing agent for water environments that respond to aggregation-induced emission.

5. A self-early warning and self-healing coating for aquatic environments with aggregation-induced emission response, characterized in that: The coating contains the self-warning and self-healing agent material as described in claim 1.

Images