CN113930859B - Multifunctional core-shell self-repairing electrostatic spinning material and synthesis method and application thereof - Google Patents

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

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CN113930859B
CN113930859B CN202111270531.9A CN202111270531A CN113930859B CN 113930859 B CN113930859 B CN 113930859B CN 202111270531 A CN202111270531 A CN 202111270531A CN 113930859 B CN113930859 B CN 113930859B
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shell
repairing
electrostatic spinning
core
self
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CN113930859A (en
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王巍
曹琳
李其原
刘琮
陈守刚
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Ocean University of China
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    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/50—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyalcohols, polyacetals or polyketals
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    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
    • 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
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
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    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
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    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
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    • D01F8/10—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained by reactions only involving carbon-to-carbon unsaturated bonds as constituent
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    • C08K3/20—Oxides; Hydroxides
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    • C08K2003/2248—Oxides; Hydroxides of metals of copper
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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; the nuclear solution is prepared from nuclear materials and a nuclear material solvent according to the mass ratio of 1:5-10. Obtaining precursor nanofiber through coaxial electrostatic spinning, and carrying out 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 the nano-containers and dispersing the nano-containers into the coating. When the coating is affected by environmental change and damaged, the repairing agent is released from the nano container to repair the damaged coating, thereby avoiding the corrosion of the metal matrix. 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 nanofiber 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 from a shell polymer shell material, a shell material solvent and a copper source according to the mass ratio of 0.5-1.5;
wherein the nuclear structure solution is prepared by mixing 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) A, synthesizing a shell solution, namely weighing a polymer shell material, a shell material solvent and a copper source according to the mass ratio of 0.5-1.5:
1.1 Mixing the polymer shell material and the shell material solvent, and stirring at the rotating speed of 300-1000rmp within the temperature range of 20-35 ℃ for 12-48 hours;
1.2 ) then adding a copper source, and stirring at the rotating speed of 200-500rmp for 1-4 hours at the temperature of 20-35 ℃;
2) And B, synthesizing the component B, 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 300-1000rmp within the temperature range of 20-35 ℃.
3) Electrostatic spinning synthesis, namely fixing the tin foil paper or the aluminum foil paper on a roller receiver, installing a syringe of the shell-core solution and a coaxial needle, and then switching on a power supply to carry out electrostatic spinning, specifically:
3.1 Firstly setting translation distance, setting the front dead point of the injection device to be zero, using 5-50mL of injector capacity, setting positive voltage to be 10-25kV, negative voltage to be 2-8kV, setting injection rate A component to be 0.05-10mm/min, B component to be 0.05-10mm/min, receiving rate to be 1-20 r/min, translation speed to be 5-80mm/min and receiving distance to be 5-60cm;
3.2 After 2h of spinning, a sample of shaped 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 base material to be protected, and dried for 72 hours at room temperature, and finally the self-repairing anti-corrosion organic coating is obtained.
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 anticorrosion performance.
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 repairing, solves the problem that the coating cannot provide long-acting protection, and has wide application prospect and market value in the future marine anticorrosive coatings.
Drawings
FIG. 1 is a diagram of one embodiment of the present invention, a synthesized precursor PVB-Cu 2+ @ TA scanning electron microscope photograph of core-shell electrospinning;
FIG. 2 is a precursor PVB-Cu synthesized in accordance with an embodiment of the present invention 2+ A transmission electron microscope photograph of @ TA core-shell electrospinning;
FIG. 3 is a PVB-Cu composite of an embodiment of the present invention 2 Scanning electron microscope photo of O @ TA core-shell electrospinning;
FIG. 4 is a transmission electron micrograph showing the synthesized PVB-Cu according to an embodiment of the present invention 2 The 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 invention 2 O @ TA core-shell electrostatic spinning and PVB, TA and Cu 2 O-contrast infrared spectrogram;
FIG. 6 is a PVB-Cu composite of an embodiment of the present invention 2 O @ TA core-shell electrospinning and Cu 2 XRD contrast of O standard card;
FIG. 7 shows PVB/CA-Cu synthesized in accordance with example two of the present invention 2 Scanning electron microscope photo of O @ TA core-shell electrospinning;
FIG. 8 is a PVB-Cu alloy of the third embodiment of the present invention 2 O 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 shows an optical photograph and an infrared temperature imaging image of a damaged coating repaired by a PCT-10 composite coating prepared in the third embodiment of the invention after being irradiated for 200s by near-infrared laser with the power of 1.5W and the wavelength of 808 nm;
fig. 11 is an optical image of a PCT-10 composite coating prepared in the third embodiment of the present invention, which was subjected to five transverse and longitudinal scratch repair tests at the same position under irradiation of 1.5w 808nm near-infrared laser.
FIG. 12 is an electrochemical impedance spectroscopy contrast diagram of a PCT-10 composite coating prepared in the third embodiment of the invention, scratched and subjected to NIR irradiation of 1.5W 808nm in seawater, and scratched without NIR laser irradiation;
FIG. 13 is an optical photograph and an infrared temperature imaging image of a damaged coating repaired by a PCT-5 composite coating prepared according to a fourth embodiment of the invention after being irradiated for 200s by near-infrared laser with a power of 1.5W and a wavelength of 808 nm;
FIG. 14 is an optical photograph and an infrared temperature imaging image of a damaged coating repaired by irradiating PCT-20 composite coating prepared in the fifth embodiment of the invention with near infrared laser light having a power of 1.5W and a wavelength of 808nm for 200 s;
FIG. 15 is an optical photograph and an infrared temperature imaging image of a damaged coating repaired by irradiating a PCCT-10 composite coating prepared according to a sixth embodiment of the invention with near-infrared laser having 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 obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to 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:
wherein the shell structure solution 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;
wherein the nuclear structure solution is prepared by mixing 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.
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) A, synthesizing a shell solution, namely weighing a polymer shell material, a shell material solvent and a copper source according to the mass ratio of 0.5-1.5:
1.1 Mixing the polymer shell material and the shell material solvent, and stirring at the rotating speed of 300-1000rmp within the temperature range of 20-35 ℃ for 12-48 hours;
1.2 ) then adding a copper source, and stirring at the rotating speed of 200-500rmp for 1-4 hours at the temperature of 20-35 ℃;
2) And B, synthesizing the component B, 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 300-1000rmp within the temperature range of 20-35 ℃.
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:
3.1 Firstly setting translation distance, setting the front dead point of the injection device to be zero, using 5-50mL of injector capacity, setting positive voltage to be 10-25kV, negative voltage to be 2-8kV, setting injection rate A component to be 0.05-10mm/min, B component to be 0.05-10mm/min, receiving rate to be 1-20 r/min, translation speed to be 5-80mm/min and receiving distance to be 5-60cm;
3.2 After 2h of spinning, a sample of shaped precursor nanofiber mat 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 ℃.
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) A, synthesizing a component shell solution, namely weighing a polymer shell material, a shell material solvent and a copper source according to the mass ratio of 1:
1.1 5mL of ethanol and 5mL of N, N-dimethylformamide, 1g of polyvinyl butyral (PVB) was added and the mixture was stirred at a temperature of 25 ℃ and a rotation speed of 500rmp for 24 hours;
1.2 Then 1g of copper nitrate is added, and the mixture is stirred for 2 hours at the rotating speed of 300rmp within the temperature of 25 ℃;
2) B component nuclear solution synthesis:
1g of Tannic Acid (TA) was added to 10mL of ethanol solution, and the mixture was stirred at a temperature of 25 ℃ and a rpm of 500rmp for 12 hours.
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:
3.1 Firstly setting translation distance, setting the front dead point of the injection device to be zero, using 10mL of injector capacity, setting positive voltage to be 15kV and negative voltage to be 3kV, setting injection rate A component to be 5mm/min, B component to be 2mm/min, receiving rate to be 10 r/min, translation speed to be 20mm/min and receiving distance to be 30cm;
3.2 After 2h of spinning, the shaped precursor PVB-Cu is obtained 2+ @ TA nanofiber film samples;
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 C 2 O @ TA nanofiber mat.
The obtained nanofibers were subjected to characterization tests:
the above-mentioned precursor PVB-Cu 2+ Scanning electron micrograph of @ TA nanofiber As shown in FIG. 1, the surface of the precursor fiberSmooth, uniform in morphology, and about 748 nm average diameter.
Precursor PVB-Cu 2+ 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 above 2 Scanning electron micrographs of O @ TA nanofibers are shown in FIG. 3, comparing the precursor fiber, PVB-Cu 2 The O @ TA nano fiber has rough surface and evenly distributed bark-like protrusions, and the average diameter of the nano fiber is about 861 nm.
PVB-Cu 2 A projection electron micrograph of the O @ TA nanofiber is shown in FIG. 4, the nanofiber has an obvious coaxial core-shell structure, and Cu is uniformly and densely distributed on the surface of the nanofiber 2 O nanoparticles, cu 2 The O nanoparticles are uniform in size and have an average particle size of about 19 nm.
Synthetic PVB-Cu 2 The 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-Cu 2 There are some characteristic peaks of PVB molecules on the spectrogram of O @ TA nano fiber. 2937 cm of −1 And 2868 cm −1 The characteristic peaks at (A) respectively represent-CH 3 and-CH 2 Is present. C-O-C stretching vibration is generally 1132 cm −1 And 959 cm −1 Adjacent, 3200-3500 cm in FIG. 5 −1 The broad peak between is the result of-OH stretching vibration. 1660 cm −1 The 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-Cu 2 O @ TA core-shell electrospinning and Cu 2 XRD contrast of O standard card is shown in FIG. 6, PVB-Cu 2 Diffraction peaks of the O @ TA nanofiber at 36.42 degrees, 42.30 degrees and 61.34 degrees correspond to Cu 2 (111), (200) and (220) of O nanoparticles, indicating Cu 2 And 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 high molecular material, and the XRD spectrogram contains PVBThe peak is amorphous. The confirmation of Cu was made by comparison with a card (JCPDS No. 05-0667) 2 The O NPs have been supported on nanofibers.
Example two
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) A component A is prepared by weighing a polymer shell material, a shell material solvent and a copper source according to the mass ratio of 1:
1.1 0.5g of polyvinyl butyral (PVB) and 0.5g of methylcellulose (CA) were added to 10mL of ethanol and stirred at a temperature of 25 ℃ and a rotational speed of 500rmp for 24 hours;
1.2 Then 1g of copper nitrate is added, and the mixture is stirred for 2 hours at the rotating speed of 300rmp within 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) 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:
3.1 Firstly setting translation distance, setting the front dead point of the injection device to be zero, using 10mL of injector capacity, setting positive voltage to be 20kV and negative voltage to be 5kV, setting injection rate A component to be 10mm/min, B component to be 5mm/min, receiving rate to be 6 r/min, translation speed to be 20mm/min and receiving distance to be 35cm;
3.2 After 2h of spinning, a sample of shaped precursor nanofiber membrane can be obtained;
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 C 2 O @ TA nanofiber mat.
The nanofibers obtained above were subjected to characterization tests:
PVB/CA-Cu synthesized as described above 2 The scanning electron micrograph of the O @ TA nanofiber is shown in FIG. 7, the nanofiber surface is rough, and many protrusions prove that Cu is on the nanofiber surface 2 And forming O nanoparticles.
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) A component A is prepared by weighing a polymer shell material, a shell material solvent and a copper source according to the mass ratio of 1:
1.1 5mL of ethanol and 5mL of N, N-dimethylformamide, 1g of polyvinyl butyral (PVB) was added and the mixture was stirred at a temperature of 25 ℃ and a rotation speed of 500rmp for 24 hours;
1.2 After that 1g of copper nitrate was added to the solution and stirred at a speed of 300rmp for 2 hours at a 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) 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 the shell-core solution, and then switching on a power supply to carry out electrostatic spinning synthesis, specifically:
3.1 Firstly setting translation distance, setting the front dead point of the injection device to be zero, using 10mL of injector capacity, setting positive voltage to be 15kV and negative voltage to be 3kV, setting injection rate A component to be 5mm/min, B component to be 2mm/min, receiving rate to be 10 r/min, translation speed to be 20mm/min and receiving distance to be 30cm;
3.2 After 2h of spinning, 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 C 2 O@TANanofiber mat named PVB-Cu 2 O 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-Cu 2 O 10% @ TA for example, EDS spectroscopy is shown in FIG. 8. The elemental mapping shows PVB-Cu 2 O and Cu element distribution on the surface of the O @ TA nano fiber, which proves that Cu exists on the surface of the PVB nano fiber shell 2 And O NPs. The EDS spectrum shows the relative contents of elements, namely the C content is 69.91%, the O content is 11.99% and the Cu content is 18.10%. The ratio of Cu to O is about 2:1 because except for Cu 2 The PVB outside the ONPs also contains a small amount of O element. Wherein C, O is the main element composition of PVB, and the Cu and O elements are from Cu 2 And O NPs. Therefore, C, O, cu and other main elements conform to PVB-Cu 2 O @ 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.
An optical photograph and an infrared temperature imaging image of the repaired damaged coating of the synthesized PCT-10 composite coating after 1.5W 808nm NIR laser irradiation 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 causes a temporary change in the chain direction and local deformation around the cracked portion. PVB-Cu 2 After 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. FIG. 9 is a schematic view of an infrared spectrometerThe image shows that heat is mainly distributed near the irradiated part through NIR laser irradiation, and the photothermal conversion process is limited to the damaged area.
An optical image of a 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) show one to five scratch repair processes, respectively. After the coating is scratched for many times, 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 plot of the blank coating, PCT-10 composite coating after scratching, and with and without NIR laser irradiation of fig. 12, 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 Laser The composite coating has good protection effect on Q235.
Example four
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) A, synthesizing a component shell solution, namely weighing a polymer shell material, a shell material solvent and a copper source according to the mass ratio of 1:
1.1 5mL of ethanol and 5mL of N, N-dimethylformamide, 1g of polyvinyl butyral (PVB) was added and the mixture was stirred at a temperature of 25 ℃ and a rotation speed of 500rmp for 24 hours;
1.2 0.5g of copper nitrate was then added to the solution and stirred at a speed of 300rmp for 2 hours at a 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) 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:
3.1 Firstly setting translation distance, setting the front dead point of the injection device to be zero, using 10mL of injector capacity, setting positive voltage to be 15kV and negative voltage to be 3kV, setting injection rate A component to be 5mm/min, B component to be 2mm/min, receiving rate to be 10 r/min, translation speed to be 20mm/min and receiving distance to be 30cm;
3.2 After 2h of spinning, 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 C 2 O @ TA nanofiber mat. Designated PVB-Cu 2 O 5% @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-5.
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 PCT-5 composite coating after 1.5W 808nm NIR laser irradiation for 200s 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 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) A component A is prepared by weighing a polymer shell material, a shell material solvent and a copper source according to the mass ratio of 1:
1.1 5mL of ethanol and 5mL of N, N-dimethylformamide were added with 1g of polyvinyl butyral (PVB) and stirred at a temperature of 25 ℃ and a rotation speed of 500rmp for 24 hours;
1.2 2.0g of copper nitrate are then added to the solution and stirred at a speed of 300rmp for 2 hours at a temperature of 25 ℃;
2) B component nuclear solution synthesis:
1g of Tannic Acid (TA) was added to 10mL of ethanol solution, and the mixture was stirred at a temperature of 25 ℃ and a rpm of 500rmp for 12 hours.
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:
3.1 Firstly setting translation distance, setting the front dead point of the injection device to be zero, using 10mL of injector capacity, setting positive voltage to be 15kV and negative voltage to be 3kV, setting injection rate A component to be 5mm/min, B component to be 2mm/min, receiving rate to be 10 r/min, translation speed to be 20mm/min and receiving distance to be 30cm;
3.2 After 2h of spinning, 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 C 2 O @ TA nanofiber mat. Is named PVB-Cu 2 O 20% @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-20.
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 PCT-20 composite coating after 1.5W 808nm NIR laser irradiation for 200s are shown in FIG. 14. PCT-20 exhibits excellent photo-thermal self-healing properties within 200 s.
Example six
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) A component A is prepared by weighing a polymer shell material, a shell material solvent and a copper source according to the mass ratio of 1:
1.1 0.5g of polyvinyl butyral (PVB), 0.5g of methylcellulose (CA) are added to 10mL of ethanol and stirred at a temperature of 25 ℃ and a rotational speed of 500rmp for 24 hours;
1.2 After that 1g of copper nitrate was added to the solution and stirred at a speed of 300rmp for 2 hours at a temperature of 25 ℃;
2) B component nuclear solution synthesis:
1g of Tannic Acid (TA) was added to 10mL of ethanol solution, and the mixture was stirred at a temperature of 25 ℃ and a rpm of 500rmp for 12 hours.
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:
3.1 Firstly setting translation distance, setting the front dead point of the injection device to be zero, using 10mL of injector capacity, setting positive voltage to be 20kV and negative voltage to be 5kV, setting injection rate A component to be 10mm/min, B component to be 5mm/min, receiving rate to be 6 r/min, translation speed to be 20mm/min and receiving distance to be 35cm;
3.2 After 2h of spinning, 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 C 2 O @ 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 prepared 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 after the synthesized PCCT-10 composite coating is irradiated by NIR laser at 1.5W 808nm for 200s are shown in figure 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 the preferred embodiment and all changes and modifications that fall within the scope of the present 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 (4)

1. A synthetic method of a multifunctional core-shell self-repairing electrostatic spinning material is characterized by comprising the following steps: the nano-fiber core-shell structure comprises a core-shell nano-fiber shell structure and a core structure coated inside the shell structure;
wherein the shell structure solution 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;
wherein the nuclear structure solution is prepared by mixing nuclear materials and a nuclear material solvent according to the mass ratio of 1:5-10;
respectively injecting the shell solution and the core solution into two solution channels of a coaxial electrostatic spinning device, and carrying out electrostatic spinning to obtain a precursor nanofiber electrostatic spinning material with a core-shell structure;
putting the precursor nano-fiber in hydrazine hydrate reducing gas for 12-24 hours to obtain the multifunctional nuclear shell fiber self-repairing electrostatic spinning material;
wherein the polymer shell material is one or more 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; the shell 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;
wherein the copper source is any one or more of copper nitrate, copper acetate, copper chloride, copper carbonate and copper sulfate;
wherein the core material is one or more of mercaptobenzothiazole, benzotriazole, tolyltriazole, phosphonocarboxylic acid, sulfonated lignin, hexadecylamine, tannic acid and oleic acid; 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.
2. The synthesis method of the multifunctional core-shell self-repairing electrostatic spinning material according to claim 1, characterized by comprising the following concrete implementation steps:
1) A, synthesizing a shell solution, namely weighing a polymer shell material, a shell material solvent and a copper source according to the mass ratio of 0.5-1.5:
1.1 Mixing the polymer shell material and the shell material solvent, and stirring at the rotating speed of 300-1000rmp for 12-48 hours at the temperature of 20-35 ℃;
1.2 Adding copper source, stirring at 200-500rmp for 1-4 hr at 20-35 deg.C;
2) B, synthesizing a component nuclear solution, namely weighing nuclear materials and a nuclear material solvent according to the mass ratio of 1:5-10, and stirring for 5-24 hours at the rotating speed of 300-1000rmp within the temperature range of 20-35 ℃;
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:
3.1 Firstly setting translation distance, setting the front dead point of the injection device to be zero, using 5-50mL of injector capacity, setting positive voltage to be 10-25kV, negative voltage to be 2-8kV, setting injection rate A component to be 0.05-10mm/min, B component to be 0.05-10mm/min, receiving rate to be 1-20 r/min, translation speed to be 5-80mm/min and receiving distance to be 5-60cm;
3.2 After 2h of spinning, a sample of shaped precursor nanofiber mat can be obtained;
4) And (3) reduction treatment, namely, placing the molded precursor nanofiber mat sample in a reduction atmosphere at the temperature of between 20 and 35 ℃ for 12 to 48 hours to obtain the treated nanofiber mat.
3. The application of the multifunctional core-shell self-repairing electrostatic spinning material is characterized in that the electrostatic spinning material synthesized according to the method in claim 2 and an organic coating are coated on the surface of a substrate according to the thickness ratio of 1:1-20, and the coating is dried for 72 hours at room temperature to obtain the photo-thermal response self-repairing anticorrosive coating.
4. The application of the multifunctional core-shell self-repairing electrospun material as claimed in claim 3, wherein the organic coating is any one of an epoxy resin coating, a polyurethane coating, an alkyd resin coating and an acrylic resin coating.
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