CN113930859A

CN113930859A - Multifunctional core-shell self-repairing electrostatic spinning material and synthesis method and application thereof

Info

Publication number: CN113930859A
Application number: CN202111270531.9A
Authority: CN
Inventors: 王巍; 曹琳; 李其原; 刘琮; 陈守刚
Original assignee: Ocean University of China
Current assignee: Ocean University of China
Priority date: 2021-10-29
Filing date: 2021-10-29
Publication date: 2022-01-14
Anticipated expiration: 2041-10-29
Also published as: CN113930859B

Abstract

The invention provides a multifunctional core-shell self-repairing electrostatic spinning material and a synthesis method and application thereof. The shell solution synthesized by the method is prepared from a shell polymer shell material, a shell material solvent and a copper source according to the mass ratio of 0.5-1.5: 2-10: 0.1-2; the nuclear solution is prepared from a nuclear material and a nuclear material solvent according to the mass ratio of 1: 5-10. And obtaining precursor nanofiber through coaxial electrostatic spinning, and performing gas phase reduction to obtain the multifunctional core-shell self-repairing electrostatic spinning material. And loading the multifunctional core-shell nanofiber into resin to obtain the photo-thermal response self-repairing coating. The invention can effectively improve the load rate, the load stability and the uniformity of the nano cuprous oxide on the surface of the polyvinyl butyral nano fiber. The invention can improve the mechanical property of the composite coating. The Q235 steel is used as a substrate for research, the combination of intrinsic self-repairing and extrinsic self-repairing is realized, the corrosion resistance is excellent, the corrosion resistance of the Q235 steel in a corrosive environment can be effectively improved, and the Q235 steel has excellent protection performance on the substrate material. Through experimental exploration on key material parts, a process route with the best performance is obtained.

Description

Multifunctional core-shell self-repairing electrostatic spinning material and synthesis method and application thereof

Technical Field

The invention relates to the technical field of synthesis of nanofibers, in particular to a multifunctional core-shell self-repairing electrostatic spinning material and a synthesis method and application thereof.

Background

Metal corrosion is one of the most serious economic loss phenomena worldwide, especially for engineering materials. In recent years, self-repairing anticorrosive coatings are hot research due to the self-repairing and excellent corrosion resistance. The repair mechanism of the self-repairing anticorrosive coating mainly comprises the steps of loading a repair agent into a nano container and dispersing the nano container into a coating. When the coating is affected by environmental change and has a damage phenomenon, the repairing agent is released from the nano container to repair the damaged coating, so that the corrosion of the metal matrix is avoided. However, the existing self-repairing anticorrosive coating still has the problems of complex synthesis process of the nano container, easy agglomeration, reduced mechanical property of the composite coating, limited self-repairing times, new defects after the repairing agent is released and the like.

The intelligent response self-repairing coating can rapidly respond to environmental changes so as to repair the coating, and becomes a research hotspot in recent years. Compared with other responses, the photo-thermal response self-repairing coating has the advantages of strong controllability, multiple repairing, short repairing time and the like. However, there are some limitations, such as high cost of the noble metal nanoparticles of the conventional photo-thermal agent and easy agglomeration and low loading rate of the photo-thermal agent in the coating.

The electrostatic spinning fiber has great potential in the aspect of loading the photothermal agent nanoparticles due to the advantages of self-assembly, high specific surface area and volume ratio, high porosity, strong mechanical property and the like. The coaxial electrostatic spinning fiber can be used as a nano container load repairing agent to realize self-repairing functionalization. However, after the repairing agent fills the cracks of the coating, a chelate formed with the base is easy to fall off, so that the coating fails and the service life of the coating is shortened.

Therefore, the invention discloses an electrostatic spinning material with low cost, photo-thermal response self-repairing, high repairing agent loading and high photo-thermal agent loading.

Disclosure of Invention

The technical task of the invention is to provide a multifunctional core-shell self-repairing electrostatic spinning material, a synthetic method and application thereof, aiming at the defects of the prior art, so that the mechanical property of a self-repairing coating is improved, and multiple repairs are realized.

The innovation points of the invention are mainly as follows:

1. the invention takes the electrostatic spinning nano-fiber as a template, and photo-thermal agent nano-particles are uniformly modified in a nano-fiber shell layer by a gas phase reduction method, thereby solving the problem of agglomeration of the photo-thermal agent nano-particles due to surface tension. Meanwhile, the electrostatic spinning nano-fiber is used as a container to load the green environment-friendly repairing agent, so that the corrosion resistance of the coating is enhanced in many aspects.

2. By introducing photo-thermal agent nanoparticles, the multifunctional nanofiber forms a composite coating, and after the composite coating is turned on/off by multiple times of illumination, the damaged coating can still be quickly repaired, multiple times of repair can be realized, and the corrosion resistance of the coating is enhanced.

3. By introducing the multifunctional nano-fiber, the composite coating is enhanced and toughened, and the mechanical property of the coating is improved.

4. The multifunctional nano-fiber is introduced into the traditional resin coating, so that the corrosion resistance of the resin coating is improved.

The technical scheme adopted by the invention for solving the technical problems is as follows:

1. the invention provides a multifunctional core-shell self-repairing electrostatic spinning material which comprises a shell structure component A, a core structure component B coated inside the shell structure, and an organic coating layer component C:

wherein the shell structure solution is prepared by a shell polymer shell material, a shell material solvent and a copper source according to the mass ratio of 0.5-1.5: 2-10: 0.1-2;

wherein the nuclear structure solution is prepared from nuclear materials and a nuclear material solvent according to the mass ratio of 1: 5-10;

and respectively injecting the shell structure solution and the core structure solution into two solution channels of a coaxial electrostatic spinning device, and carrying out electrostatic spinning synthesis to obtain the precursor nanofiber electrostatic spinning material with the core-shell structure.

And (3) placing the precursor nanofiber in reducing gas for 12-24 hours to obtain the multifunctional core-shell self-repairing fiber electrostatic spinning material.

2. The invention also provides a synthesis method of the multifunctional core-shell self-repairing electrostatic spinning material, which comprises the following concrete implementation steps:

1) and (2) synthesizing the component A shell solution, namely weighing the polymer shell material, the shell material solvent and the copper source according to the mass ratio of 0.5-1.5: 2-10: 0.1-2, wherein the adding sequence of the medicines is as follows:

1.1) mixing the polymer shell material and the shell material solvent, and stirring for 12-48 hours at the rotating speed of 300-1000 rmp within the temperature range of 20-35 ℃;

1.2) adding a copper source, and stirring at the rotating speed of 200-500 rmp for 1-4 hours at the temperature of 20-35 ℃;

2) and B component nuclear solution synthesis, namely weighing the nuclear material and the nuclear material solvent according to the mass ratio of 1: 5-10, and stirring for 5-24 hours at the rotating speed of 300-1000 rmp within the temperature range of 20-35 ℃.

3) Fixing tin foil paper or aluminum foil paper on a roller receiver, installing an injector of a shell-core solution and a coaxial needle, and then switching on a power supply to carry out electrostatic spinning, specifically:

3.1) firstly setting a translation distance, setting the front dead point of the injection device to be zero, setting the capacity of the injector to be 5-50 mL, setting a positive voltage of 10-25 kV and a negative voltage of 2-8 kV, wherein the injection rate A component is 0.05-10 mm/min, the injection rate B component is 0.05-10 mm/min, the receiving rate is 1-20 r/min, the translation speed is 5-80 mm/min, and the receiving distance is 5-60 cm;

3.2) after spinning for 2h, a sample of the precursor nanofiber membrane can be obtained;

4) and (3) reduction treatment, namely placing the molded precursor nanofiber mat sample in a reduction atmosphere, and obtaining the treated nanofiber mat after the reduction time is 12-48 hours within the temperature range of 20-35 ℃.

Optionally, the polymer shell material is one of polyvinyl butyral, polylactic acid, polyethylene terephthalate, polycaprolactone, polyvinylidene fluoride, polybutylene terephthalate, chitin, cellulose, methyl cellulose, polyhydroxyalkanoate, polybutylene succinate, polyarylate, polyvinyl acetate, polymethyl methacrylate and polyaniline, or a mixture of the above polymers.

Optionally, the shell solvent is any one or more of methanol, acetone, ethanol, isopropanol, tetrahydrofuran, methyl butanone, methyl isobutyl ketone, methyl acetate, ethyl acetate, N-propyl acetate, N-dimethylformamide and N, N-dimethylacetamide.

Optionally, the copper source is any one or more of copper nitrate, copper acetate, copper chloride, copper carbonate and copper sulfate.

Optionally, the core material is any one or more of mercaptobenzothiazole, benzotriazole, tolyltriazole, phosphonocarboxylic acid, sulfonated lignin, hexadecylamine, tannic acid and oleic acid.

Optionally, the core material solvent is any one or more of methanol, acetone, ethanol, isopropanol, tetrahydrofuran, methyl butanone, methyl isobutyl ketone, methyl acetate, ethyl acetate, N-propyl acetate, N-dimethylformamide and N, N-dimethylacetamide.

Optionally, the reducing gas is any one of hydrogen, carbon monoxide, hydrogen sulfide and hydrazine hydrate vapor.

3. The invention also provides application of the multifunctional core-shell self-repairing electrostatic spinning material, wherein the synthesized electrostatic spinning material and the organic coating are mixed and proportioned according to the thickness ratio of 1: 1-20, coated on a substrate to be protected, and dried for 72 hours at room temperature to finally obtain the self-repairing anti-corrosion organic coating.

The base material to be protected is metal, can be steel material with wide application, and can also be other metal materials such as iron, copper, aluminum and the like.

Compared with the prior art, the multifunctional core-shell self-repairing electrostatic spinning material and the synthesis method and the application thereof have the beneficial effects that:

1. the invention provides a synthetic method of a multifunctional core-shell self-repairing electrostatic spinning material and a synthetic method of a photo-thermal response self-repairing coating. The synthesized core-shell nano-fiber and photo-thermal agent nano-particles are uniformly modified in the shell layer of the nano-fiber by a gas phase reduction method, so that the problem of agglomeration of the nano-particles due to surface tension is solved. Meanwhile, the nano-fiber is used as a container to load the green environment-friendly repairing agent, so that the nano-fiber has multifunctional self-repairing and anti-corrosion properties.

2. Experiments show that the multifunctional core-shell self-repairing electrostatic spinning material synthesized by the invention can improve the strength of the coating and increase the mechanical property of the coating when added into an organic coating.

3. The electrostatic spinning material can be added into an organic coating, is designed and developed into a photo-thermal self-repairing coating, realizes multiple repairs, solves the problem that the coating cannot provide long-acting protection, and has wide application prospect and market value in future marine anticorrosive coatings.

Drawings

FIG. 1 is a diagram of one embodiment of the present invention, a synthesized precursor PVB-Cu²⁺@ TA scanning electron microscope photograph of core-shell electrospinning;

FIG. 2 is a schematic representation of a synthesized precursor PVB-Cu of an embodiment of the present invention²⁺A transmission electron microscope photograph of @ TA core-shell electrospinning;

FIG. 3 is a PVB-Cu composite of an embodiment of the present invention₂A scanning electron microscope photo of O @ TA core-shell electrostatic spinning;

FIG. 4 is a transmission electron micrograph showing the synthesized PVB-Cu according to an embodiment of the present invention₂The nano particles are uniformly loaded on the O @ TA core-shell electrostatic spinning;

FIG. 5 is a drawing of a PVB-Cu composite of an embodiment of the present invention₂O @ TA core-shell staticsElectrospinning and PVB, TA, Cu₂O-contrast infrared spectrogram;

FIG. 6 is a PVB-Cu composite of an embodiment of the present invention₂O @ TA core-shell electrostatic spinning and Cu₂XRD contrast of O standard card;

FIG. 7 is a PVB/CA-Cu sample synthesized according to example two of the present invention₂A scanning electron microscope photo of O @ TA core-shell electrostatic spinning;

FIG. 8 is a PVB-Cu alloy of a third embodiment of the present invention₂O_10%EDS spectrum analysis chart of @ TA;

FIG. 9 is a stress-strain curve of a PCT-10 composite coating and a blank coating synthesized according to example III of the present invention;

FIG. 10 is an optical photograph and an infrared temperature imaging image of the repaired damaged coating of the PCT-10 composite coating prepared in the third embodiment of the invention after being irradiated for 200s by near-infrared laser with power of 1.5W and wavelength of 808 nm;

FIG. 11 is an optical image of a PCT-10 composite coating prepared in the third embodiment of the invention, which is subjected to five transverse and longitudinal scratch repair tests at the same position under the irradiation of 1.5W 808nm near infrared laser.

FIG. 12 is a graph comparing the electrochemical impedance spectroscopy of a PCT-10 composite coating prepared in the third example of the invention, scratched and subjected to NIR irradiation of 1.5W 808nm in seawater, and scratched and not subjected to NIR laser irradiation;

FIG. 13 is an optical photograph and an infrared temperature imaging image of the repaired damaged coating of the PCT-5 composite coating prepared in the fourth embodiment of the present invention after being irradiated for 200s by the near infrared laser with the power of 1.5W and the wavelength of 808 nm;

FIG. 14 is an optical photograph and an infrared temperature imaging image of the damaged coating repaired by the PCT-20 composite coating prepared by the fifth embodiment of the invention after being irradiated by near-infrared laser with power of 1.5W and wavelength of 808nm for 200 s;

FIG. 15 shows an optical photograph and an infrared temperature imaging image of the repair of a damaged coating layer after the PCCT-10 composite coating layer prepared in the sixth embodiment of the invention is irradiated with near-infrared laser with a power of 1.5W and a wavelength of 808nm for 200 s;

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

The invention provides a multifunctional core-shell self-repairing electrostatic spinning material which comprises a shell structure component A, a core structure component B coated inside the shell structure, and an organic coating layer component C:

The invention also provides a synthesis method of the multifunctional core-shell self-repairing electrostatic spinning material, which comprises the following concrete implementation steps:

3) Electrostatic spinning synthesis, namely fixing the tin-foil paper or the aluminum-foil paper on a roller receiver according to a proper size, installing a coaxial needle of an injector of a shell-core solution, and then switching on a power supply to perform electrostatic spinning synthesis, specifically:

3.2) after spinning for 2h, a sample of the shaped precursor nanofiber mat can be obtained;

Wherein the polymer shell material in the step 1) is one of polyvinyl butyral, polylactic acid, polyethylene terephthalate, polycaprolactone, polyvinylidene fluoride, polybutylene terephthalate, chitin, cellulose, methyl cellulose, polyhydroxyalkanoate, polybutylene succinate, polyarylate, polyvinyl acetate, polymethyl methacrylate and polyaniline, or a mixture of the above polymers.

Wherein the shell solvent in the step 1) is any one or more of methanol, acetone, ethanol, isopropanol, tetrahydrofuran, methyl butanone, methyl isobutyl ketone, methyl acetate, ethyl acetate, N-propyl acetate, N-dimethylformamide and N, N-dimethylacetamide.

Wherein the copper source in the step 1) is any one or more of copper nitrate, copper acetate, copper chloride, copper carbonate and copper sulfate.

The core material in the step 2) is any one or more of mercaptobenzothiazole, benzotriazole, sulfonated lignin and tannic acid, and the core material solvent in the step 2) is any one or more of methanol, acetone, ethanol, isopropanol, tetrahydrofuran, methyl butanone, methyl isobutyl ketone, methyl acetate, ethyl acetate, N-propyl acetate, N-dimethylformamide and N, N-dimethylacetamide.

Wherein the reducing gas in the step 4) is any one of hydrogen, carbon monoxide, hydrogen sulfide and hydrazine hydrate steam.

The synthesized electrostatic spinning material and the organic coating C component are mixed and proportioned according to the thickness ratio of 1: 1-20, coated on the surface of a metal matrix, and dried for 72 hours at room temperature to obtain the self-repairing anticorrosive coating which is applied to the field of matrix anticorrosion.

Wherein the organic coating is any one of epoxy resin coating, polyurethane coating, alkyd resin coating and acrylic resin coating.

Example one

The invention provides a multifunctional core-shell self-repairing electrostatic spinning material which comprises a shell structure component A and a core structure component B coated in the shell structure,

the method comprises the following specific steps:

1) and (2) synthesizing a component A shell solution, namely weighing a polymer shell material, a shell material solvent and a copper source according to the mass ratio of 1:5:5:1, wherein the adding sequence of the medicines is as follows:

1.1) adding 1g of polyvinyl butyral (PVB) into a mixed solution of 5mL of ethanol and 5mL of N, N dimethylformamide, and stirring at a temperature of 25 ℃ and a rotating speed of 500rmp for 24 hours;

1.2) then adding 1g of copper nitrate, and stirring for 2 hours at the rotating speed of 300rmp at the temperature of 25 ℃;

2) b component nuclear solution synthesis:

1g of Tannic Acid (TA) was added to 10mL of ethanol solution and stirred at 25 ℃ at 500rmp for 12 hours.

3.1) firstly setting a translation distance, setting a front dead point of the injection device to be zero, setting the capacity of the injector to be 10mL, setting a positive voltage to be 15kV and a negative voltage to be 3kV, setting an injection rate A component to be 5mm/min, a B component to be 2mm/min, a receiving rate to be 10 r/min, a translation speed to be 20mm/min and a receiving distance to be 30cm;

3.2) after spinning for 2h, a shaped precursor PVB-Cu is obtained²⁺@ TA nanofiber membrane sample;

4) reduction treatment, namely placing the molded precursor nanofiber mat sample in hydrazine hydrate vapor atmosphere, and obtaining treated PVB-Cu after 16 hours of reduction time within the temperature range of 25 DEG C₂O @ TA nanofiber mat.

The obtained nanofibers were subjected to characterization tests:

the above-mentioned precursor PVB-Cu²⁺The scanning electron micrograph of the @ TA nanofiber is shown in figure 1, and the precursor fiber has a smooth surface, uniform morphology and an average diameter of about 748 nm.

Precursor PVB-Cu²⁺The TEM photograph of the @ TA nanofiber is shown in FIG. 2, the core structure of the nanofiber can be obviously observed, and TEM indicates that the repairing agent is successfully coated in the nanofiber.

PVB-Cu synthesized as described above₂A scanning electron micrograph of the O @ TA nanofibers is shown in FIG. 3, comparing the precursor fibers, PVB-Cu₂The O @ TA nano fiber has a rough surface and is uniformly distributed with tree-like protrusions, and the average diameter of the nano fiber is about 861 nm.

PVB-Cu₂A projection electron microscope photograph of the O @ TA nanofiber is shown in figure 4, the nanofiber is in an obvious coaxial core-shell structure, and Cu is uniformly and densely distributed on the surface of the nanofiber₂O nanoparticles, Cu₂The O nano-particles have uniform particle size, and the average particle size is about 19 nm.

Synthetic PVB-Cu₂The infrared spectrum of the O @ TA nanofiber is shown in FIG. 5. The infrared spectrum shows that the repairing agent TA is successfully coated in the PVB nuclear shell nano fiber, and the PVB-Cu₂The spectra of the O @ TA nanofibers all showed some characteristic peaks for the PVB molecules. 2937 cm⁻¹And 2868 cm⁻¹The characteristic peaks at (A) each represent-CH₃and-CH₂Is present. C-O-C stretching vibration is generally 1132 cm⁻¹And 959 cm⁻¹Nearby, 3200 and 3500 cm in FIG. 5⁻¹The broad peak between is the result of-OH stretching vibration. 1660 cm⁻¹The peak at (a) is due to carbonyl (C = O) stretching vibration of TA. The characteristic peak of C = O in the core-shell nanofibers shifts to low wavenumbers due to the reduced hydrogen bonding between the PVB molecules (-OH) and TA (C = O).

Synthetic PVB-Cu₂O @ TA core-shell electrostatic spinning and Cu₂XRD contrast of O standard card is shown in FIG. 6, PVB-Cu₂The O @ TA nano fiber has diffraction peaks at 36.42 degrees, 42.30 degrees and 61.34 degrees, and corresponds to Cu₂O nanoparticles of (111), (200) and (220), indicating Cu₂And the O nano-particles grow on the surface of the PVB shell layer. The XRD pattern of the PVB shell layer has a broad peak at 20 degrees. PVB is an organic polymer material, and the PVB peak in an XRD spectrogram is amorphous. Cu was confirmed by comparison with a card (JCPDS number 05-0667)₂The O NPs have been supported on nanofibers.

Example two

the method comprises the following specific steps:

1.1) adding 0.5g of polyvinyl butyral (PVB) and 0.5g of methyl Cellulose (CA) into 10mL of ethanol, and stirring at 25 ℃ and 500rmp for 24 hours;

2) b component nuclear solution synthesis:

3.1) firstly setting a translation distance, setting a front dead point of the injection device to be zero, setting the capacity of the injector to be 10mL, setting a positive voltage to be 20kV and a negative voltage to be 5kV, setting an injection rate A component to be 10mm/min, a B component to be 5mm/min, a receiving rate to be 6 r/min, a translation speed to be 20mm/min and a receiving distance to be 35cm;

4) reduction treatment, namely placing the molded precursor nanofiber mat sample in hydrazine hydrate vapor atmosphere, and obtaining treated PVB/CA-Cu after 16 hours of reduction time within the temperature range of 25 DEG C₂O @ TA nanofiber mat.

The obtained nanofibers were subjected to characterization tests:

PVB/CA-Cu synthesized as described above₂A scanning electron micrograph of the O @ TA nanofiber is shown in FIG. 7, the nanofiber surface is rough, and a plurality of protrusions prove that Cu is on the nanofiber surface₂And forming O nano particles.

EXAMPLE III

The invention provides a multifunctional core-shell self-repairing electrostatic spinning material and a synthesis method of a photo-thermal response self-repairing coating, wherein the multifunctional core-shell self-repairing electrostatic spinning material comprises a shell structure component A, a core structure component B and an organic coating component C, wherein the core structure component B is coated inside the shell structure;

the method comprises the following specific steps:

1.2) then adding 1g of copper nitrate into the solution, and stirring at the rotating speed of 300rmp for 2 hours at the temperature of 25 ℃;

2) b component nuclear solution synthesis:

adding 1g of Tannic Acid (TA) into 10mL of ethanol solution, and stirring at 25 ℃ and 500rmp for 12 hours;

3.2) after spinning for 2h, a precursor nanofiber mat sample can be obtained;

4) reduction treatment, namely placing the precursor nanofiber mat sample in hydrazine hydrate vapor atmosphere, and obtaining treated PVB-Cu after 16 hours of reduction time at the temperature of 25 DEG C₂O @ TA nanofiber mat named PVB-Cu₂O_10%@TA。

5) The synthesized electrostatic spinning material is respectively mixed and proportioned with acrylic resin as the component C of the organic coating according to the thickness ratio of 1:4 to prepare the obtained composite coating, which is named as PCT-10.

6) And (3) coating PCT-10 on the surface of the electrode, and drying at room temperature for 72 hours to prepare the photo-thermal self-repairing coating electrode.

And (3) carrying out performance test on the obtained composite coating:

with PVB-Cu₂O_10%@ TA is an example, and the EDS spectrum analysis thereof is shown in FIG. 8. The elemental mapping shows PVB-Cu₂The distribution of O and Cu elements on the surface of the O @ TA nano fiber proves that Cu exists on the surface of the PVB nano fiber shell₂And O NPs. The EDS spectrum shows that the relative contents of elements, namely C content of 69.91%, O content of 11.99% and Cu content of 18.10%. The ratio of Cu to O is about 2:1 because Cu is removed₂The PVB outside the ONPs also contains a small amount of O element. Wherein C, O is the main element composition of PVB, and the elements Cu and O are from Cu₂And O NPs. Therefore, C, O, Cu and the like are the main elements in accordance with PVB-Cu₂O @ TA.

A comparison of the stress-strain curves of the synthesized PCT-10 composite coating and the blank coating is shown in fig. 9. Compared with a blank acrylic resin coating, the maximum stress and the tensile strength of the PCT-10 composite coating are respectively 2.04 MPa and 2.68 MPa. The maximum stress of the composite coating is 1.8 times that of the blank coating, and the tensile strength of the composite coating is 2 times that of the blank coating. The addition of the nanofibers results in a composite coating with higher tensile strength.

Optical photographs and infrared temperature imaging images of the repair of the damaged coating after the synthesized PCT-10 composite coating is irradiated by NIR laser with the wavelength of 1.5W 808nm for 200s are shown in FIG. 10. PCT-10 showed excellent photo-thermal self-healing performance within 200 s. When the composite coating is scratched, the destructive force may cause a temporary change in the chain direction and local deformation around the cracked portion. PVB-Cu₂After the O @ TA nano fiber is irradiated by near infrared laser, light is converted into heat, the composite coating is locally heated, and recombination and conformation of molecules or covalent bonds are initiated, so that cracks can be repaired. The infrared imaging image of fig. 9 shows that heat is mainly distributed near the irradiated site by NIR laser irradiation, and the photothermal conversion process is limited to the damaged region.

An optical image of the PCT-10 composite coating subjected to five scratch repair tests at the same position under 1.5W 808nm NIR laser irradiation is shown in fig. 11, where fig. 11 (a-d) shows one to five scratch repair processes, respectively. After the coating is scratched for many times, the self-repairing can still be realized through NIR irradiation, which shows that the composite coating has good multiple self-repairing performance.

Electrochemical impedance analysis testing of electrodes modified with different coatings is shown in figure 12. As can be seen from the Nyquist comparison of the blank coating, the PCT-10 composite coating after scratching, and without NIR laser irradiation, the three curves are semicircular above the solid axis. The arc sizes of the capacitive reactance in the figure are arranged as blank coating < PCT-10_Laser. It can be seen that the sample with the modified PCT-10 coating has a larger capacitive arc radius than the unmodified blank sample, and after NIR laser irradiation, the capacitive arc becomes larger, and after laser irradiation, the PCT-10 coating has a larger capacitive arc radius than the unmodified blank sample_LaserThe composite coating has good protection effect on Q235.

Example four

the method comprises the following specific steps:

1.2) then adding 0.5g of copper nitrate into the solution, and stirring at the rotating speed of 300rmp for 2 hours at the temperature of 25 ℃;

2) b component nuclear solution synthesis:

3.2) after spinning for 2h, a precursor nanofiber mat sample can be obtained;

4) reduction treatment, namely placing the precursor nanofiber mat sample in hydrazine hydrate vapor atmosphere, and obtaining treated PVB-Cu after 16 hours of reduction time at the temperature of 25 DEG C₂O @ TA nanofiber mat. Designated PVB-Cu₂O_5%@TA。

5) And (3) respectively mixing and proportioning the synthesized electrostatic spinning material and acrylic resin as the component C of the organic coating according to the thickness ratio of 1:4 to prepare the obtained composite coating, which is named as PCT-5.

And (3) carrying out performance test on the obtained composite coating:

optical photographs and infrared temperature imaging images of the repair of the damaged coating after 1.5W 808nm NIR laser irradiation for 200s of the synthesized PCT-5 composite coating are shown in FIG. 13. The PCT-5 coating has the function of generating photo-thermal conversion and cannot completely repair scratches.

EXAMPLE five

the method comprises the following specific steps:

1.2) then adding 2.0g of copper nitrate into the solution, and stirring at the rotating speed of 300rmp for 2 hours at the temperature of 25 ℃;

2) b component nuclear solution synthesis:

3.2) after spinning for 2h, a precursor nanofiber mat sample can be obtained;

4) reduction treatment, namely placing the precursor nanofiber mat sample in hydrazine hydrate vapor atmosphere, and obtaining treated PVB-Cu after 16 hours of reduction time at the temperature of 25 DEG C₂O @ TA nanofiber mat. Designated PVB-Cu₂O_20%@TA。

5) And (3) respectively mixing and proportioning the synthesized electrostatic spinning material and acrylic resin as the component C of the organic coating according to the thickness ratio of 1:4 to prepare the obtained composite coating, which is named as PCT-20.

And (3) carrying out performance test on the obtained composite coating:

optical photographs and infrared temperature imaging images of the repair of the damaged coating after 1.5W 808nm NIR laser irradiation for 200s of the synthesized PCT-20 composite coating are shown in FIG. 14. PCT-20 exhibits excellent photo-thermal self-healing properties within 200 s.

EXAMPLE six

the method comprises the following specific steps:

2) b component nuclear solution synthesis:

3.2) after spinning for 2h, a precursor nanofiber mat sample can be obtained;

4) reduction treatment, namely placing the precursor nanofiber mat sample in hydrazine hydrate vapor atmosphere, and obtaining treated PVB/CA-Cu after 16 hours of reduction time at the temperature of 25 DEG C₂O @ TA nanofiber mat.

5) The synthesized electrostatic spinning material is respectively mixed and proportioned with acrylic resin as the component C of the organic coating according to the thickness ratio of 1:4 to prepare the composite coating which is named PCCT-10.

And (3) carrying out performance test on the obtained composite coating:

an optical photograph and an infrared temperature imaging image of the repaired damaged coating of the synthesized PCCT-10 composite coating after 1.5W 808nm NIR laser irradiation for 200s are shown in FIG. 15. PCCT-10 exhibits excellent photothermal self-repair performance within 200 s.

While the preferred embodiments of the present application have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all alterations and modifications as fall within the scope of the application.

It will be apparent to those skilled in the art that various changes and modifications may be made in the present application without departing from the spirit and scope of the application. Thus, if such modifications and variations of the present application fall within the scope of the claims of the present application and their equivalents, the present application is intended to include such modifications and variations as well.

In addition to the technical features described in the specification, the technology is known to those skilled in the art.

Claims

1. A multifunctional nuclear shell self-repairing electrostatic spinning material and a synthetic method and application thereof are characterized in that: comprises a core-shell nanofiber shell structure and a core structure coated inside the shell structure,

respectively injecting the shell solution and the core solution into two solution channels of a coaxial electrostatic spinning device, carrying out electrostatic spinning to obtain a precursor nanofiber electrostatic spinning material with a core-shell structure,

and (3) placing the precursor nanofiber in reducing gas for 12-24 hours to obtain the multifunctional core-shell fiber self-repairing electrostatic spinning material.

2. A multifunctional nuclear shell self-repairing electrostatic spinning material and a synthetic method and application thereof are characterized by comprising the following concrete implementation steps:

2) b component nuclear solution synthesis, weighing nuclear material and nuclear material solvent according to the mass ratio of 1: 5-10, stirring for 5-24 hours at the rotating speed of 300-1000 rmp within the temperature range of 20-35 ℃,

3. The method for synthesizing the multifunctional core-shell self-repairing electrospun material as claimed in claim 2, wherein in the step 1), the polymer shell material is one of polyvinyl butyral, polylactic acid, polyethylene terephthalate, polycaprolactone, polyvinylidene fluoride, polybutylene terephthalate, chitin, cellulose, methyl cellulose, polyhydroxyalkanoate, polybutylene succinate, polyarylate, polyvinyl acetate, polymethyl methacrylate and polyaniline, or a mixture of the above polymers.

4. The method for synthesizing the multifunctional core-shell self-repairing electrospinning material according to claim 2 or 3, wherein the shell solvent in step 1) is any one or more of methanol, acetone, ethanol, isopropanol, tetrahydrofuran, methyl butanone, methyl isobutyl ketone, methyl acetate, ethyl acetate, N-propyl acetate, N-dimethylformamide, and N, N-dimethylacetamide.

5. The method for synthesizing the multifunctional core-shell self-repairing electrospun material as claimed in claim 2 or 3, wherein the copper source in step 1) is any one or more of copper nitrate, copper acetate, copper chloride, copper carbonate and copper sulfate.

6. The method for synthesizing the multifunctional core-shell self-repairing electrostatic spinning material according to claim 2 or 3, characterized in that the core material in the step 2) is any one or more of mercaptobenzothiazole, benzotriazole, tolyltriazole, phosphonocarboxylic acid, sulfonated lignin, hexadecylamine, tannic acid and oleic acid, and the core material solvent in the step 2) is any one or more of methanol, acetone, ethanol, isopropanol, tetrahydrofuran, methyl butanone, methyl isobutyl ketone, methyl acetate, ethyl acetate, N-propyl acetate, N-dimethylformamide and N, N-dimethylacetamide.

7. The synthesis method of the multifunctional core-shell self-repairing electrospinning material according to claim 2 or 3, wherein the reducing gas in step 4) is any one of hydrogen, carbon monoxide, hydrogen sulfide and hydrazine hydrate vapor.

8. The application of the multifunctional core-shell self-repairing electrostatic spinning material is characterized in that the electrostatic spinning material synthesized in the claim 1 and an organic coating are mixed and proportioned according to the thickness ratio of 1: 1-20, coated on the surface of a matrix, and dried for 72 hours at room temperature to obtain the photo-thermal response self-repairing anticorrosive coating.

9. The application of the multifunctional core-shell self-repairing electrospun material as claimed in claim 8, wherein the organic coating is any one of an epoxy resin coating, a polyurethane coating, an alkyd resin coating and an acrylic resin coating.