CN111584122B - Conductive self-repairing microcapsule and preparation method and application method thereof - Google Patents

Conductive self-repairing microcapsule and preparation method and application method thereof Download PDF

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CN111584122B
CN111584122B CN202010527436.1A CN202010527436A CN111584122B CN 111584122 B CN111584122 B CN 111584122B CN 202010527436 A CN202010527436 A CN 202010527436A CN 111584122 B CN111584122 B CN 111584122B
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dispersion liquid
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core material
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CN111584122A (en
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孙志成
李芙蓉
张青青
问金月
曹梅娟
焦守政
李路海
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Beijing Institute of Graphic Communication
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    • H—ELECTRICITY
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    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/08—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances oxides
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    • C09K5/06—Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
    • C09K5/063—Materials absorbing or liberating heat during crystallisation; Heat storage materials
    • H—ELECTRICITY
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    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
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    • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
    • H01B1/026—Alloys based on copper
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    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/04—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of carbon-silicon compounds, carbon or silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
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    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
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    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
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Abstract

The invention relates to a conductive self-repairing microcapsule, a preparation method and an application method thereof, wherein the conductive self-repairing microcapsule is of a core-shell structure and comprises a polymer wall material and a core material wrapped in the polymer wall material; the core material comprises: a conductive aqueous solution, ammonium persulfate, and sodium dodecyl sulfate; the conductive aqueous solution is at least one of ferroferric oxide dispersion liquid, nano silver dispersion liquid, nano copper dispersion liquid, nano aluminum oxide dispersion liquid, poly 3, 4-ethylenedioxythiophene/polystyrene sulfonate solution, graphene oxide dispersion liquid, graphene dispersion liquid and tap water. The conductive self-repairing microcapsule is a self-repairing material which takes aqueous solution with conductive capability as a core material to coat in a high molecular polymer to form a core-shell structure. The invention takes the conductive aqueous solution as the core material, has various types, wide selectable range, low price, green and no pollution, and is superior to the conventional liquid metal and organic solvent.

Description

Conductive self-repairing microcapsule and preparation method and application method thereof
Technical Field
The invention belongs to the technical field of self-repairing microcapsules, and particularly relates to a conductive self-repairing microcapsule as well as a preparation method and an application method thereof.
Background
In the modern society, various electronic devices have become indispensable important tools in human daily life. The electronic equipment mainly comprises electronic components such as integrated circuits, transistors, electron tubes and the like and conductive circuits penetrating through the electronic components, and with the development of flexibility, light weight and high load of the electronic components, a plurality of circuits are inevitably damaged, so that the normal operation of the whole equipment is influenced, and the service efficiency and the service life of the equipment are shortened. The usual way of repair is to completely disassemble the equipment for circuit and device replacement, resulting in extended repair cycles and increased costs. The conductive self-repairing material can automatically repair a circuit or a device by utilizing the physical or chemical properties of the conductive self-repairing material under a certain condition, thereby improving the reliability of circuit operation, prolonging the service life of equipment, having certain sustainability and reducing the waste of resources and time.
The self-repairing materials reported so far mainly include metals, conductive polymers, carbon materials, and the like, which are basically solid materials, and it is difficult to implement an accurate self-repairing process for circuit damage in application. Meanwhile, the liquid conductive material is difficult to be directly applied to the conductive circuit due to the fluidity of the liquid conductive material. Therefore, the liquid self-repairing material is solidified by adopting a microcapsule technology, and the self-repairing material is released by adopting a specific method according to specific conditions, so that the conduction of a circuit can be realized.
With the gradual maturity of microcapsule technology, the development of microcapsule self-repairing composite materials is rapid, and the microcapsule self-repairing composite materials become a main way for developing self-repairing composite materials. However, the existing preparation method of the self-repairing microcapsule still has many defects, and the existing repairing material is mainly a solid metal material and is difficult to realize accurate self-repairing. In the prior art, toxic and volatile organic solvents are adopted to prepare the self-repairing microcapsules, so that the environment and the human health are seriously polluted.
Disclosure of Invention
The invention mainly aims to provide a conductive self-repairing microcapsule, a preparation method and an application method thereof, aiming at solving the technical problems that the existing repairing material is mainly a solid metal material, the accurate self-repairing is difficult to realize, toxic and volatile organic solvents are adopted, and the environment and the body health of people are seriously polluted.
The purpose of the invention and the technical problem to be solved are realized by adopting the following technical scheme. The conductive self-repairing microcapsule provided by the invention is of a core-shell structure and comprises a polymer wall material and a core material wrapped in the polymer wall material;
the core material comprises: a conductive aqueous solution, ammonium persulfate, and sodium dodecyl sulfate; wherein the mass ratio of the conductive aqueous solution to the ammonium persulfate to the sodium dodecyl sulfate is 20-30:1.5-2.6: 0.8-1.5;
the conductive aqueous solution is at least one of ferroferric oxide dispersion liquid, nano silver dispersion liquid, nano copper dispersion liquid, nano aluminum oxide dispersion liquid, poly 3, 4-ethylenedioxythiophene/polystyrene sulfonate solution, graphene oxide dispersion liquid, graphene dispersion liquid and tap water.
The object of the present invention and the technical problems solved thereby can be further achieved by the following technical measures.
Preferably, the conductive self-repairing microcapsule is a microcapsule prepared by mixing a polymer material and a polymer material, wherein the polymer material is a formaldehyde-melamine polymer or a melamine-urea-formaldehyde polymer.
Preferably, the conductive self-repairing microcapsule is a microcapsule prepared by mixing the conductive self-repairing microcapsule and the polymer wall material.
The object of the present invention and the technical problem to be solved are also achieved by the following technical means. The invention provides a preparation method of a conductive self-repairing microcapsule, which comprises the following steps:
mixing a conductive aqueous solution, ammonium persulfate and lauryl sodium sulfate to obtain a core material solution; wherein the mass ratio of the conductive aqueous solution to the ammonium persulfate to the sodium dodecyl sulfate is 20-30:1.5-2.6: 0.8-1.5;
mixing a polymer monomer with deionized water, adding triethanolamine, adjusting the pH value to 8-9, and carrying out prepolymerization reaction at 60-80 ℃ and 400-600rpm to obtain a polymer prepolymer solution;
mixing the oil phase, Span-80 and calcium stearate; and adding the core material solution and the polymer prepolymer solution, stirring to form stable W/O emulsion, carrying out in-situ polymerization reaction, and carrying out centrifugation, washing and vacuum drying to obtain the conductive self-repairing microcapsule.
The object of the present invention and the technical problems solved thereby can be further achieved by the following technical measures.
Preferably, in the preparation method of the conductive self-repairing microcapsule, the conductive aqueous solution is at least one of ferroferric oxide dispersion liquid, nano silver dispersion liquid, nano copper dispersion liquid, nano aluminum oxide dispersion liquid, poly 3, 4-ethylenedioxythiophene/polystyrene sulfonate solution, graphene oxide dispersion liquid, graphene dispersion liquid and tap water;
the polymer monomer is formaldehyde and melamine, or the polymer monomer is formaldehyde, melamine and urea;
the mass ratio of the oil phase, Span-80 and calcium stearate is 50-60:1.5-2: 0.05-0.15;
the oil phase comprises: at least one of liquid paraffin, gasoline and edible oil.
Preferably, the preparation method of the conductive self-repairing microcapsule further comprises:
adding an acid solution into the core material solution, adjusting the pH value to 4-5, and magnetically stirring for 20-40 min; or adding an acid solution into the W/O emulsion, adjusting the pH value to 4-5, and magnetically stirring for 20-40 min;
the acid solution is citric acid solution, acetic acid solution or dilute hydrochloric acid solution.
Preferably, in the preparation method of the conductive self-repairing microcapsule, the polymerization reaction is water-in-oil in-situ polymerization, and the reaction conditions are as follows: reacting in water bath at 60-80 ℃ for 3-4h under the conditions of 400 plus materials and 600 rpm.
The object of the present invention and the technical problem to be solved are also achieved by the following technical means. The invention provides a preparation method of a conductive self-repairing microcapsule, which comprises the following steps:
mixing a conductive aqueous solution, ammonium persulfate and lauryl sodium sulfate to obtain a core material solution; wherein the mass ratio of the conductive aqueous solution to the ammonium persulfate to the sodium dodecyl sulfate is 20-30:1.5-2.6: 0.8-1.5;
melting at least one of gelatin and acacia to obtain wall material liquid;
mixing the oil phase, Span-80 and calcium stearate to obtain water-in-oil dispersion, adding the core material solution and the wall material solution, stirring to form a stable W/O emulsion, and reacting the emulsion for 3-4h in a water bath at 20-25 ℃ and at 600rpm of 400-; and centrifuging, washing and vacuum drying to obtain the conductive self-repairing microcapsule.
The object of the present invention and the technical problems solved thereby can be further achieved by the following technical measures.
Preferably, in the preparation method of the conductive self-repairing microcapsule, the conductive aqueous solution is at least one of ferroferric oxide dispersion liquid, nano silver dispersion liquid, nano copper dispersion liquid, nano aluminum oxide dispersion liquid, graphene dispersion liquid, poly 3, 4-ethylenedioxythiophene/polystyrene sulfonate solution and tap water;
the oil phase comprises: at least one of liquid paraffin, gasoline and edible oil;
the mass ratio of the oil phase, Span-80 and calcium stearate is 50-60:1.5-2: 0.05-0.15;
the mass ratio of the core material solution to the wall material solution to the water-in-oil dispersion liquid is as follows: 14-18:25-30:50-60.
The object of the present invention and the technical problem to be solved are also achieved by the following technical means. The invention provides an application method of the conductive self-repairing microcapsule, which comprises the following steps:
the conductive self-repairing microcapsule is sealed and adsorbed on the surface of electronic equipment or a lead;
when the electronic equipment or the lead is damaged, the damaged part is pressed, and the conductive solution in the conductive self-repairing microcapsule is released to the damaged part to form a conductive path.
By the technical scheme, the conductive self-repairing microcapsule, the preparation method and the application method thereof provided by the invention at least have the following advantages:
1. the conductive self-repairing microcapsule is a self-repairing material which takes aqueous solution with conductive capability as a core material to coat in a high molecular polymer to form a core-shell structure. The invention takes the conductive aqueous solution as the core material, has various types, wide selectable range, low price, green and no pollution, and is superior to the conventional liquid metal and organic solvent.
2. The preparation method adopts a water-in-oil type in-situ polymerization method to synthesize the conductive self-repairing microcapsule which takes the conductive aqueous solution as the core material and the high molecular polymer as the shell, and is used for automatically recovering the conductivity in the damaged electronic equipment.
3. The preparation method of the invention selects non-toxic and pollution-free organic solvent as the continuous phase and the dispersed phase, therefore, the preparation process of the microcapsule is completely non-toxic.
4. The invention coats the water solution with conductive ability in the high molecular polymer as the self-repairing material, and is used in the electronic equipment or the lead, when the electronic equipment or the lead is damaged, the conductive self-repairing microcapsule is crushed, the conductive water solution is released to the damaged part, the conductive performance of the electronic equipment or the lead can be recovered in a short time, in addition, the conductive water solution has certain phase change latent heat, so the conductive self-repairing microcapsule can play the roles of reducing the self temperature of the equipment and maintaining the high-efficiency operation of the equipment when the equipment is operated for a long time.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical solutions of the present invention more clearly understood and to implement them in accordance with the contents of the description, the following detailed description is given with reference to the preferred embodiments of the present invention and the accompanying drawings.
Drawings
FIG. 1 shows a schematic diagram of a conductive self-healing microcapsule according to an embodiment of the present invention;
FIG. 2 is a schematic flow chart of a method for preparing conductive self-repairing microcapsules according to an embodiment of the present invention;
FIG. 3 is a schematic flow chart showing a method for applying the electrically conductive self-healing microcapsules according to one embodiment of the present invention;
FIG. 4 shows a schematic diagram of a test circuit of the proposed electrically conductive self-healing microcapsules of the present invention;
FIG. 5 shows a sample diagram of different classes of electrically conductive self-healing microcapsules proposed by the present invention; the conductive self-repairing microcapsule sample takes PEDOT and PSS aqueous solution as core materials; (b) the conductive self-repairing microcapsule sample takes a graphene oxide dispersion solution as a core material; (c) is Fe3O4A conductive self-repairing microcapsule sample with a dispersion solution as a core material; (d) the conductive self-repairing microcapsule sample takes tap water as a core material; (e) the conductive self-repairing microcapsule sample takes deionized water as a core material;
FIG. 6a shows an SEM image of a conductive self-repairing microcapsule with a core material of a PEDOT/PSS aqueous solution according to an embodiment of the present invention;
fig. 6b shows an SEM image of the conductive self-repairing microcapsule with the graphene oxide dispersion solution as the core material according to the embodiment of the present invention;
FIG. 6c shows Fe according to an embodiment of the present invention3O4SEM picture of conductive self-repairing microcapsule with dispersed solution as core material;
FIG. 6d shows an SEM image of a conductive self-repairing microcapsule with a core material of tap water according to one embodiment of the present invention;
fig. 6e shows an SEM image of the conductive self-repairing microcapsule with deionized water as a core material according to one embodiment of the present invention;
FIG. 7 shows an optical microscope picture of a conductive self-repairing microcapsule with PEDOT: PSS aqueous solution as a core material according to an embodiment of the present invention;
FIG. 8 shows the bearing pressure curves of the conductive self-repairing microcapsules with different conductive aqueous solutions as core materials;
FIG. 9a shows an FTIR spectrum of a conductive self-repairing microcapsule with PEDOT: PSS aqueous solution as core material according to an embodiment of the present invention;
fig. 9b shows an FTIR spectrum of the conductive self-repairing microcapsule with the graphene oxide dispersion solution as the core material according to the embodiment of the invention;
FIG. 9c shows Fe according to an embodiment of the present invention3O4An FTIR spectrogram of the conductive self-repairing microcapsule taking the dispersion solution as the core material;
FIG. 9d shows an FTIR spectrum of a conductive self-repairing microcapsule with a core material of tap water according to an embodiment of the present invention;
fig. 9e shows an FTIR spectrum of the conductive self-repairing microcapsule with deionized water as the core material according to one embodiment of the present invention;
FIG. 10 shows the melting enthalpies of conductive self-repairing microcapsules with different conductive aqueous solutions as core materials according to one embodiment of the present invention;
FIG. 11 shows the enthalpy of crystallization of conductive self-repairing microcapsules with different conductive aqueous solutions as core materials according to one embodiment of the present invention;
fig. 12 shows the thermal stability of the conductive self-repairing microcapsules with different conductive aqueous solutions as core materials according to one embodiment of the present invention.
Detailed Description
To further illustrate the technical means and effects of the present invention adopted to achieve the predetermined objects, the following detailed description of the conductive self-repairing microcapsules, the preparation method thereof, the application method thereof, the specific implementation modes, the structures, the characteristics and the effects thereof according to the present invention will be provided with reference to the accompanying drawings and the preferred embodiments. In the following description, different "one embodiment" or "an embodiment" refers to not necessarily the same embodiment. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments.
As shown in fig. 1, the conductive self-repairing microcapsule 4 according to an embodiment of the present invention has a core-shell structure, and includes a polymer wall material 41 and a core material 42 wrapped inside the polymer wall material 41, that is, the polymer wall material 41 wraps the core material 42; the core material 42 includes: the conductive aqueous solution, the ammonium persulfate and the sodium dodecyl sulfate are mixed according to the mass ratio of 20-30:1.5-2.6:0.8-1.5, preferably 25:2.5: 1. The conductive aqueous solution is at least one of ferroferric oxide dispersion liquid, nano silver dispersion liquid, nano copper dispersion liquid, nano aluminum oxide dispersion liquid, poly 3, 4-ethylenedioxythiophene/polystyrene sulfonate solution (PEDOT: PSS), graphene oxide dispersion liquid, graphene dispersion liquid and tap water. Correspondingly, the conductive material 421 contained in the core material 42 includes at least one of ferroferric oxide, nano silver, nano copper, nano aluminum oxide, poly 3, 4-ethylenedioxythiophene/polystyrene sulfonate, graphene oxide, graphene and tap water.
In the present embodiment, the polymer wall material satisfies the following conditions: the solution before polymerization is dissolved in water, is not dissolved in water or oil after polymerization, and does not react with the core material and the solvent.
Sodium dodecyl sulfate as emulsifier for emulsifying the conductive aqueous solution to form small-ball-like droplets, and adding ammonium persulfate to form H+The ammonium persulfate plays a stabilizing role, so that the formed liquid drops are more stable and do not agglomerate, the emulsion drops are more stable, the shape is more complete, and the emulsion drops are not easy to break or deform.
In some embodiments, the polymer wall material 41 is formaldehyde-melamine polymer or melamine-urea-formaldehyde polymer.
In other embodiments, the polymer wall material 41 is at least one of gelatin and gum arabic.
The invention provides a preparation method of a conductive self-repairing microcapsule, which is a preparation method for organic polymers as high molecular wall materials, and specifically comprises the following steps:
step 1, mixing conductive aqueous solution and ammonium persulfate ((NH)4)2S2O8) And Sodium Dodecyl Sulfate (SDS) were added to the beaker and magnetically stirred for 30min to obtain a core material solution.
In some embodiments, the core material solution is adjusted to a pH of 4-5 with an acid solution, preferably 10% citric acid.
In some embodiments, the conductive aqueous solution is at least one of ferroferric oxide dispersion, nano silver dispersion, nano copper dispersion, nano alumina dispersion, poly 3, 4-ethylenedioxythiophene/polystyrene sulfonate solution (PEDOT: PSS), graphene oxide dispersion, graphene dispersion, and tap water. Correspondingly, the conductive material 21 contained in the core material 2 includes at least one of ferroferric oxide, nano silver, nano copper, nano aluminum oxide, poly 3, 4-ethylenedioxythiophene/polystyrene sulfonate, graphene oxide, graphene and tap water.
In the step 1, sodium dodecyl sulfate is used as an emulsifier to play a role in emulsifying the conductive aqueous solution, so that the conductive aqueous solution forms droplets like small balls, and ammonium persulfate is added to form H in the solution+The ammonium persulfate plays a stabilizing role, so that the formed liquid drops are more stable and do not agglomerate, the emulsion drops are more stable, the shape is more complete, and the emulsion drops are not easy to break or deform.
Step 2, mixing a polymer monomer with deionized water, adding 10% triethanolamine, adjusting the pH value to 8-9, and carrying out a prepolymerization reaction to obtain a polymer prepolymer solution; the polymer monomer is formaldehyde and melamine, or the polymer monomer is formaldehyde, melamine and urea. When the polymer monomers are formaldehyde and melamine, the mass ratio of the formaldehyde to the melamine to the deionized water is 2-3:0.5-1.5: 7-10.
The reason why the reaction system has a pH of 8 to 9 by adding triethanolamine in step 2 is that the reaction prepolymer is stable only when the pH is 8 to 9, and a polymer prepolymer is formed.
Taking formaldehyde and melamine as monomers as an example, carrying out prepolymerization reaction for 20-40min at the temperature of 60-80 ℃ and the rotation speed of 400-600rpm to obtain a melamine-formaldehyde prepolymer solution; the mass ratio of the formaldehyde to the melamine to the deionized water is 2-3:0.5-1.5: 7-10. Preferably 2.5:1.25: 10.
Step 3, adding the oil phase, Span-80 and calcium stearate into a flask, and then mechanically stirring the flask in a water bath at the temperature of 60-80 ℃ for 50-70 min; the oil phase comprises: at least one of liquid paraffin, gasoline and edible oil.
In some embodiments, the mass ratio of the oil phase, Span-80, and calcium stearate is from 50-60:1.5-2: 0.05-0.15; preferably, 55:1.5: 0.07.
The oil phase is used for dispersing the core material aqueous solution, Span-80 and calcium stearate provide dispersion conditions, Span-80 has an emulsifying effect and is a water-in-oil emulsifier, and the calcium stearate has a stabilizing effect.
And 3, mechanically stirring by using a water bath to promote the mixing of the oil phase liquid and provide stable reaction conditions for the step 4.
The preparation sequence of the step 1, the step 2 and the step 3 is not in sequence, and different solutions are respectively prepared for standby use in the subsequent steps.
Step 4, adding the solution obtained in the step 1 and the solution obtained in the step 2 into the flask obtained in the step 3, wherein the mass ratio of the core material solution to the wall material solution to the water-in-oil dispersion liquid is as follows: 14-18:25-30:50-60, stirring at high speed for 10min to form stable W/O emulsion, and carrying out water-in-oil in-situ polymerization under the reaction conditions of: reacting in water bath at 60-80 ℃ for 3-4h under the conditions of 400 plus materials and 600 rpm. Preferably, the reaction is carried out in a water bath at 70 ℃ for 3.5h under the condition of 500 rpm. The water bath reaction makes the reaction more uniform, and the produced capsules are more uniform and complete.
In some embodiments, citric acid is added to the W/O emulsion, the pH is adjusted to 4-5, and magnetic stirring is performed for 20-40 min.
Adding an acid solution, preferably 10% citric acid, into the core material solution obtained in the step 1, or adding an acid solution, preferably 10% citric acid, into the W/O emulsion obtained in the step 4, and selecting one step to add, wherein the specific steps are as follows:
adding an acid solution into the core material solution, adjusting the pH value to 4-5, and magnetically stirring for 20-40 min; or adding an acid solution into the W/O emulsion, adjusting the pH value to 4-5, and magnetically stirring for 20-40 min.
The purpose of adjusting the pH value to 4-5 by using an acid solution is to provide reaction conditions for polymerization reaction, a prepolymer generated by a formaldehyde-melamine solution in an alkaline environment is dissolved in water, a polymer which is insoluble in water and oil is generated by further reaction under an acidic condition, and a wall material coated with a conductive aqueous solution is generated and can be separated from an oil phase.
In the step 4, the conductive aqueous solution is an aqueous solution, the conductive aqueous solution is added into an oil phase, the oil phase is used for dispersing the core material aqueous solution, Span-80 and calcium stearate provide conditions for dispersion, and Span-80 has emulsification and calcium stearate has stabilization effects. Under the combined action of Span-80 and calcium stearate, the conductive aqueous solution is dispersed in an oil phase in a droplet shape by high-speed stirring, the Span-80 and the calcium stearate are insoluble in water, and the prepolymer is slightly soluble in water and insoluble in oil, so that the prepolymer is gathered on the surface of the droplet of the conductive aqueous solution to form a stable W/O emulsion, and the self-repairing microcapsule mixed solution is obtained by in-situ polymerization.
When the solution obtained in the step 1 and the solution obtained in the step 2 are added in the step 3, the adding sequence is not sequential, and the adding sequence can be added simultaneously.
And 5, centrifuging and washing the solution obtained after the reaction in the step 4, and drying the obtained product under the vacuum condition of 40-60 ℃, preferably 50 ℃ to obtain the self-repairing microcapsule taking the conductive aqueous solution as the core material.
The conductive self-repairing microcapsule obtained by the embodiment is of a core-shell structure, and comprises a polymer wall material and a core material wrapped inside the polymer wall material, wherein the polymer wall material is used as a shell, the core material is used as a core, and the core material comprises: a conductive aqueous solution, ammonium persulfate, and sodium dodecyl sulfate; the conductive aqueous solution is at least one of ferroferric oxide dispersion liquid, nano silver dispersion liquid, nano copper dispersion liquid, nano aluminum oxide dispersion liquid, poly 3, 4-ethylenedioxythiophene/polystyrene sulfonate solution (PEDOT: PSS), graphene oxide dispersion liquid, graphene dispersion liquid and tap water, so that the core material 2 contains a conductive substance 21, and the conductive substance 21 comprises at least one of ferroferric oxide, nano silver, nano copper, nano aluminum oxide, poly 3, 4-ethylenedioxythiophene/polystyrene sulfonate, graphene oxide, graphene and tap water. The Span-80 and the calcium stearate are positioned on the surface of the core material, and the Span-80 and the calcium stearate are also wrapped in the polymer during polymerization, but the Span-80 and the calcium stearate are small in amount and dispersed in the polymer.
Another embodiment of the present invention provides a method for preparing a conductive self-repairing microcapsule, which is a method for preparing a polymer wall material from at least one of gelatin and gum arabic, and specifically includes the following steps:
step 1, adding a conductive aqueous solution, ammonium persulfate and Sodium Dodecyl Sulfate (SDS) into a beaker, and magnetically stirring for 30min to obtain a core material solution.
In some embodiments, the mass ratio of the aqueous conducting solution, ammonium persulfate and sodium dodecyl sulfate is 20-30:1.5-2.6:0.8-1.5, preferably 25:2.5: 1.
In some embodiments, the conductive aqueous solution is at least one of ferroferric oxide dispersion, nano silver dispersion, nano copper dispersion, nano alumina dispersion, poly 3, 4-ethylenedioxythiophene/polystyrene sulfonate solution (PEDOT: PSS), graphene oxide dispersion, graphene dispersion, and tap water. Correspondingly, the conductive material 21 contained in the core material 2 includes at least one of ferroferric oxide, nano silver, nano copper, nano aluminum oxide, poly 3, 4-ethylenedioxythiophene/polystyrene sulfonate, graphene oxide, graphene and tap water.
In the step 1, sodium dodecyl sulfate is used as an emulsifier to play a role in emulsifying the conductive aqueous solution, so that the conductive aqueous solution forms droplets like small balls, and ammonium persulfate is added to form H in the solution+The ammonium persulfate plays a stabilizing role, so that the formed liquid drops are more stable and do not agglomerate, the emulsion drops are more stable, the shape is more complete, and the emulsion drops are not easy to break or deform.
And 2, putting at least one of gelatin and Arabic gum in normal-temperature water, absorbing water for 0.5-1 hour to expand, heating to 60-80 ℃ through a hot water bath (indirectly isolated from water), and stirring until the gelatin is completely melted.
Step 3, adding the oil phase, Span-80 and calcium stearate into a flask, and then mechanically stirring the flask in a water bath at the temperature of 20-25 ℃ for 50-70 min; the oil phase comprises: at least one of liquid paraffin, gasoline and edible oil.
In some embodiments, the mass ratio of the oil phase, Span-80, and calcium stearate is from 50-60:1.5-2: 0.05-0.15; preferably, 55:1.5: 0.07.
The oil phase is used for dispersing the core material aqueous solution, Span-80 and calcium stearate provide dispersion conditions, Span-80 has an emulsifying effect and is a water-in-oil emulsifier, and the calcium stearate has a stabilizing effect.
The temperature is controlled at 20-25 deg.C to facilitate the later solidification of gelatin and acacia.
Adding the solution obtained in the step (1) and the solution obtained in the step (2) into the flask obtained in the step (3), wherein the mass ratio of the core material solution to the wall material solution to the water-in-oil dispersion liquid is as follows: 14-18:25-30:50-60, stirring at high speed for 10-20min to form stable W/O emulsion, centrifuging and washing the solution after reaction in water bath at 20-25 ℃ and at 600rpm of 400-.
The conductive self-repairing microcapsule obtained by the embodiment is of a core-shell structure, and comprises a polymer wall material and a core material wrapped in the polymer wall material, wherein at least one wall material of gelatin and Arabic gum is taken as a shell, the core material is taken as a core, and the core material comprises: a conductive aqueous solution, ammonium persulfate, and sodium dodecyl sulfate; the conductive aqueous solution is at least one of ferroferric oxide dispersion liquid, nano silver dispersion liquid, nano copper dispersion liquid, nano aluminum oxide dispersion liquid, poly 3, 4-ethylenedioxythiophene/polystyrene sulfonate solution (PEDOT: PSS), graphene oxide dispersion liquid, graphene dispersion liquid and tap water, so that the core material 2 contains a conductive substance 21, and the conductive substance 21 comprises at least one of ferroferric oxide, nano silver, nano copper, nano aluminum oxide, poly 3, 4-ethylenedioxythiophene/polystyrene sulfonate, graphene oxide, graphene and tap water. The Span-80 and the calcium stearate are positioned on the surface of the core material, and the Span-80 and the calcium stearate are also wrapped when the colloid is solidified, but the Span-80 and the calcium stearate are small in amount and are dispersed in the colloid.
One embodiment of the present invention further provides an application method of the conductive self-repairing microcapsule, which specifically includes the following steps:
the conductive self-repairing microcapsule is sealed and adsorbed on the surface of electronic equipment or a lead;
when the equipment normally operates, the equipment generates a large amount of heat to influence the operating efficiency of the machine due to long-time power consumption, and the conductive self-repairing microcapsules attached to the equipment absorb the heat generated by the equipment, so that the temperature of the equipment is maintained, and the high-efficiency operation of the equipment is maintained.
When electronic equipment or a lead is damaged, the damaged part is pressed, the conductive solution in the conductive self-repairing microcapsule is released to the damaged part, the short circuit of the equipment is repaired, and a conductive path is formed to ensure the normal operation of the equipment.
As shown in fig. 3, the bulb 2 is connected with two wires 1 and 3 as an example to test the effect of the conductive self-repairing microcapsules, the conductive self-repairing microcapsules are arranged on the inner surfaces of the wires 1 and 3, when the power supply is switched on, the bulb 2 is on, and the conductive self-repairing microcapsules can absorb heat generated by the wires 1 and 3 to maintain the temperature of the wires; when the wire 1 is broken at the position a, 11 is a partial enlarged view including the broken position a of 1, a1 is an enlarged view of a, b is an enlarged view of a1 in longitudinal section, a conductive self-repairing microcapsule 4 is arranged on b, b1 is a schematic view when the conductive self-repairing microcapsule 4 is pressed, after the conductive self-repairing microcapsule 4 is broken, the conductive self-repairing microcapsule is filled at the broken position of the wire 1 so as to repair the broken position of the wire 1, b2 is a schematic view of the broken position of the wire 1 after repair, 11 ' is a schematic view after 11 repair, c is a reduced view of b2, c1 is a reduced view of c, 11 ' is a partial enlarged view of 1 ' and 1 ' is a schematic view after 1 repair, the wire 1 ' repaired by the conductive self-repairing microcapsule 4 realizes the conduction of the wire, and the bulb can be brightened again.
The present invention will be further described with reference to the following specific examples, which should not be construed as limiting the scope of the invention, but rather as providing those skilled in the art with certain insubstantial modifications and adaptations of the invention based on the teachings of the invention set forth herein.
In the following examples of the present invention, all reagents used are commercially available unless otherwise specified.
Example 1
As shown in fig. 2, a method for preparing a conductive self-repairing microcapsule specifically comprises the following steps:
s1, emulsification:
s11, mixing 25g of conductive aqueous solution and 2.5g of (NH)4)2S2O8And 1g SDS into a 100mL beaker, and the solution in the beaker was magnetically stirred for 30min to obtain a core material solution containing a conductive substance, H+And SDS;
s12, adding 50g of oil phase, 1.5g of Span-80 and 0.05g of calcium stearate into a 250mL flask; placing the flask containing the solutions in 70 deg.C water bath, mechanically stirring for 60min to obtain water-in-oil dispersion, and dispersing Span-80 and calcium stearate in liquid paraffin;
s13, adding the core material solution obtained in the step S11 into the flask obtained in the step S12, and stirring at a high speed for 10min to form a stable W/O emulsion; at this time, the core material solution was uniformly dispersed in the oil phase in the form of droplets, Span-80 and 0.05g of calcium stearate were dispersed on the surface of the droplets;
s2, adding wall materials:
s21, adding 5.15g of formaldehyde, 2.35g of melamine and 19.5g of deionized water into a round-bottom flask, and adjusting the pH value of the solution to 8-9 by using 10% triethanolamine; then stirring the round-bottom flask containing the solution at 70 ℃ and 500rpm for reaction for 30min to obtain a melamine-formaldehyde prepolymer solution;
s22, adding the melamine-formaldehyde prepolymer solution obtained in the step S21 into the flask obtained in the step S13, stirring at a high speed for 10min, and uniformly gathering the melamine-formaldehyde prepolymer on the surface of the liquid drops of the core material solution;
s3, polymerization:
and (3) adding citric acid into the step (S22), adjusting the pH value to 4-5, magnetically stirring for 20-40min, carrying out water-in-oil type in-situ polymerization in a water bath at 70 ℃ and at 500rpm, and finishing the polymerization after 3.5h to obtain the conductive self-repairing microcapsule 1 taking the conductive aqueous solution as a core material and the melamine-formaldehyde polymer as a shell.
Example 2
(1) 30g of PEDOT, PSS solution (poly 3, 4-ethylenedioxythiophene/polystyrene sulfonate solution), 3g (NH)4)2S2O8And 1.5g SDS were added to a 100mL beaker, and the solution in the beaker was magnetically stirred for 30min to obtain a core material solution; adjusting the core material solution to 4-5% by using 10% citric acid;
(2) adding 5.5g of formaldehyde, 2.4g of melamine and 20g of deionized water into a round-bottom flask, and adjusting the pH value of the solution to 8-9 by using 10% triethanolamine; then stirring the round-bottom flask containing the solution at 65 ℃ and 450rpm for 25min to react to obtain a melamine-formaldehyde prepolymer solution;
(3) 60g of liquid paraffin, 2g of Span-80 and 0.1g of calcium stearate are added to a 250mL flask; placing the flask containing the solutions in 65 deg.C water bath, and mechanically stirring for 35 min; adding the core material solution obtained in the step (1) and the prepolymer solution obtained in the step (2) into a 250mL flask, and stirring at a high speed for 10min to form a stable W/O emulsion; stirring the emulsion for reaction for 3 hours in water bath at 65 ℃ and at 450 rpm;
(4) and (4) centrifuging and washing the solution reacted in the step (3), and drying the obtained product at 40 ℃ under a vacuum condition to obtain the self-repairing microcapsule 2 taking the PEDOT (Poly ethylene glycol Ether-styrene) PSS solution as a core material.
Example 3
A preparation method of a conductive self-repairing microcapsule specifically comprises the following steps:
(1) 20g of the ferroferric oxide dispersion and 1g of (NH)4)2S2O8And 1.5g SDS were added to a 100mL beaker, and the solution in the beaker was magnetically stirred for 20min to obtain a core material solution;
(2) adding 6g of formaldehyde, 3g of melamine and 25g of deionized water into a round-bottom flask, and adjusting the pH value of the solution to 8-9 by using 10% triethanolamine; then stirring the round-bottom flask containing the solution at 60 ℃ and 700rpm for 40min to obtain a melamine-formaldehyde prepolymer solution;
(3) 70g of liquid paraffin, 2g of Span-80 and 0.1g of calcium stearate are added to a 250mL flask; placing the flask containing the solutions in a water bath at 60 deg.C, and mechanically stirring for 45 min; adding the core material solution obtained in the step (1) and the prepolymer solution obtained in the step (2) into a 250mL flask, and stirring at a high speed for 8min to form a stable W/O emulsion; stirring the emulsion for reaction for 3 hours in water bath at 60 ℃ and at 550 rpm;
(4) and (4) centrifuging and washing the solution reacted in the step (3), and drying the obtained product at 50 ℃ under a vacuum condition to obtain the self-repairing microcapsule 3 taking the ferroferric oxide dispersion liquid as the core material.
Example 4
A preparation method of a conductive self-repairing microcapsule specifically comprises the following steps:
(1) 23g of graphene oxide dispersion and 2g of (NH)4)2S2O8And 1.5g SDS were added to a 100mL beaker, and the solution in the beaker was magnetically stirred for 40min to obtain a core material solution;
(2) adding 5g of formaldehyde, 1.5g of melamine, 0.5g of urea and 17g of deionized water into a round-bottom flask, and adjusting the pH value of the solution to 8-9 by using 10% triethanolamine; then stirring the round-bottom flask containing the solution at 68 ℃ and 400rpm for reaction for 30min to obtain a melamine-formaldehyde-urea prepolymer solution;
(3) 45g of liquid paraffin, 1.2g of Span-80 and 0.08g of calcium stearate were put into a 250mL flask, and the flask containing these solutions was placed in a 70 ℃ water bath and mechanically stirred for 60 min. Adding the core material solution obtained in the step (1) and the prepolymer solution obtained in the step (2) into a 250mL flask, stirring at a high speed for 12min to form a stable W/O emulsion, and stirring and reacting the emulsion for 3.2h under the conditions of water bath at 68 ℃ and 600 rpm;
(4) and (4) centrifuging and washing the solution reacted in the step (3), and drying the obtained product at 45 ℃ under a vacuum condition to obtain the self-repairing microcapsule 4 taking the graphene oxide dispersion solution as a core material.
Example 5
A preparation method of a conductive self-repairing microcapsule specifically comprises the following steps:
(1) 20g of graphene oxide dispersion liquid, 5g of ferroferric oxide dispersion liquid, and 2.5g of (NH)4)2S2O8Adding 1.2g of SDS into a 100mL beaker, and magnetically stirring the solution in the beaker for 25min to obtain a core material solution;
(2) adding 6.3g of formaldehyde, 3.3g of melamine and 35g of deionized water into a round-bottom flask, and adjusting the pH value of the solution to 8-9 by using 10% triethanolamine; then stirring the round-bottom flask containing the solution at 64 ℃ and 500rpm for 25min to obtain a melamine-formaldehyde prepolymer solution;
(3) adding 55g of liquid paraffin, 2g of Span-80 and 0.1g of calcium stearate into a 250mL flask, and mechanically stirring the flask containing the solutions in a 64 ℃ water bath for 60 min; adding the core material solution obtained in the step (1) and the prepolymer solution obtained in the step (2) into a 250mL flask, stirring at a high speed for 10min to form a stable W/O emulsion, and stirring the emulsion for reaction for 3.2h under the conditions of 64 ℃ water bath and 550 rpm;
(4) and (4) centrifuging and washing the solution reacted in the step (3), and drying the obtained product at 50 ℃ under a vacuum condition to obtain the self-repairing microcapsule 5 taking the graphene oxide dispersion liquid and the ferroferric oxide dispersion liquid as core materials.
Example 6
A preparation method of a conductive self-repairing microcapsule specifically comprises the following steps:
(1) the PEDOT, PSS solution, ferroferric oxide dispersion liquid and (NH) are mixed4)2S2O8Adding SDS into a 100mL beaker according to the mass ratio of 23:2:2.5:1, and magnetically stirring the solution in the beaker for 30min to obtain a core material solution;
(2) adding 5.2g of formaldehyde, 2g of melamine, 0.4 g of urea and 20g of deionized water into a round-bottom flask, and adjusting the pH value of the solution to 8-9 by using 10% triethanolamine; then reacting the round-bottom flask containing the solution for 30min at 70 ℃ and 480rpm to obtain a melamine-formaldehyde prepolymer solution;
(3) 55g of liquid paraffin, 1.7g of Span-80, and 0.06g of calcium stearate were charged into a 250mL flask. Placing the flask containing the solutions in 70 deg.C water bath, and mechanically stirring for 50 min; and (3) adding the core material solution obtained in the step (1) and the prepolymer solution obtained in the step (2) into a 250mL flask, and stirring at a high speed for 10min to form a stable W/O emulsion. Stirring the emulsion in a water bath at 70 ℃ and 550rpm for reaction for 2.5 h;
(4) and (4) centrifuging and washing the solution reacted in the step (3), and drying the products at 50 ℃ under a vacuum condition to obtain the self-repairing microcapsule 6 taking the PEDOT, the PSS solution and the ferroferric oxide dispersion liquid as core materials.
Example 7
A preparation method of a conductive self-repairing microcapsule specifically comprises the following steps:
(1) PSS solution, graphene oxide dispersion liquid and (NH)4)2S2O8Adding SDS into a 100mL beaker according to the mass ratio of 18:7:2.5:1, and magnetically stirring the solution in the beaker for 30min to obtain a core material solution;
(2) adding 5.5g of formaldehyde, 2.1g of melamine and 21g of deionized water into a round-bottom flask, and adjusting the pH value of the solution to 8-9 by using 10% triethanolamine; then stirring the solution-containing flask at 68 ℃ and 650rpm for reaction for 30min to obtain a melamine-formaldehyde prepolymer solution;
(3) adding 47g of liquid paraffin, 1.2g of Span-80 and 0.04g of calcium stearate into a 250mL flask, and mechanically stirring the flask containing the solutions in a 68 ℃ water bath for 60 min; adding the core material solution obtained in the step (1) and the prepolymer solution obtained in the step (2) into a 250mL flask, stirring at a high speed for 10min to form a stable W/O emulsion, and stirring the emulsion for reaction for 3.3h under the conditions of water bath at 68 ℃ and 650 rpm;
(4) and (4) centrifuging and washing the solution reacted in the step (3), and drying the obtained product at 50 ℃ under a vacuum condition to obtain the self-repairing microcapsule 7 taking the PEDOT, the PSS solution and the graphene oxide dispersion liquid as core materials.
Example 8
A preparation method of a conductive self-repairing microcapsule specifically comprises the following steps:
(1) 16g of PEDOT PSS solution, 5g of graphene oxide dispersion, 4g of tap water, 2.5g of (NH)4)2S2O8Adding 1g of SDS into a 100mL beaker, and magnetically stirring the solution in the beaker for 30min to obtain a core material solution;
(2) 5.1g of formaldehyde and 2.2 g of melamine are reacted in a flask containing the solution at 67 ℃ and 5000rpm for 30min to obtain a melamine-formaldehyde prepolymer solution. 49g of liquid paraffin, 1.4g of Span-80, and 0.07g of calcium stearate were charged into a 250mL flask. The flask with these solutions was placed in a 67 ℃ water bath and mechanically stirred for 55 min. The core material solution and the prepolymer solution were added to a 250mL flask and stirred at high speed for 10min to form a stable W/O emulsion. Stirring the emulsion for reaction for 3.2h in a water bath at 67 ℃ and at 500 rpm;
(3) and (4) centrifuging and washing the solution reacted in the step (3), and drying the obtained product at 50 ℃ under a vacuum condition to obtain the self-repairing microcapsule 8 taking the PEDOT, the PSS solution and the graphene oxide dispersion liquid as core materials.
Example 9
A preparation method of a conductive self-repairing microcapsule specifically comprises the following steps:
(1) 25g of graphene oxide dispersion and 2.5g of (NH)4)2S2O8And 1g of Sodium Dodecyl Sulfate (SDS) were added to a 100mL beaker, and the solution in the beaker was magnetically stirred for 30min to obtain a core material solution;
(2) putting gelatin in normal temperature water for 0.5-1h, absorbing water to swell, heating to 70 deg.C by hot water bath (indirect water isolation), and stirring until completely melting to obtain gelatin solution;
(3) adding 56g of liquid paraffin, 1.7g of Span-80 and 0.06g of calcium stearate into a 250mL flask, and mechanically stirring the flask containing the solution in a water bath at 20-25 ℃ for 60 min;
(4) adding the solution obtained in the step (1) and the gelatin solution obtained in the step (2) into a 250mL flask, stirring at a high speed for 10min to form a stable W/O emulsion, and stirring and reacting the emulsion for 4h under the conditions of water bath at 20-25 ℃ and 500 rpm.
(5) And (4) centrifuging and washing the solution reacted in the step (4), and drying the obtained product at 20 ℃ under a vacuum condition to obtain the self-repairing microcapsule 9 taking the graphene oxide dispersion liquid as a core material.
Comparative example
In comparison with example 2, No (NH) was added4)2S2O8And others areWith any change, no microcapsules could be formed.
Selecting conductive self-repairing microcapsule samples taking different types of aqueous solutions as core materials for testing, and showing a sample diagram of the conductive self-repairing microcapsules of different types in fig. 5, wherein (a) the conductive self-repairing microcapsule samples taking PEDOT and PSS aqueous solutions as core materials; (b) the conductive self-repairing microcapsule sample takes a graphene oxide dispersion solution as a core material; (c) is Fe3O4A conductive self-repairing microcapsule sample with a dispersion solution as a core material; (d) the conductive self-repairing microcapsule sample takes tap water as a core material; (e) the conductive self-repairing microcapsule sample takes deionized water as a core material; table 1 shows the particle size distribution of the self-repairing microcapsules of different conductive aqueous solutions, and the thermogravimetric curves of the microcapsules of conductive aqueous solutions, as shown in fig. 10, 11 and 12, the distribution is the melting enthalpy, crystallization enthalpy and thermal stability of the conductive self-repairing microcapsules using different conductive aqueous solutions as core materials.
TABLE 1 particle size distribution of self-repairing microcapsules of different conductive aqueous solutions
Particle size (μm) D10 D50 D90 MZa PDIb
PEDOT:PSS-MPCMs 9.070 18.166 32.576 19.509 1.294
GO-MPCMs 20.793 36.98 60.625 38.672 1.077
Fe3O4-MPCMs 8.347 15.423 25.931 16.201 1.140
Tap water-MPCMs 7.720 14.797 25.988 15.823 1.235
Deionized Water-MPCMs 4.974 9.385 15.874 9.895 1.161
Note: in table 1, a is the average particle size; b is the dispersion of particle size.
As can be seen from Table 1, the conductive self-repairing microcapsule obtained by the invention has uniform particle size.
In order to verify the repair capability of the microcapsules, the conductive self-repair microcapsules are adhered to copper foil, then the copper foil is adhered to a glass slide, the glass slide with the attached copper foil is used for replacing a section of conducting wire to connect a small bulb and a voltage-stabilizing direct-current power supply to form a series circuit, as shown in fig. 4, the schematic diagram of the test circuit of the conductive self-repair microcapsules comprises a bulb 5, a conducting wire 6 and a power supply 7, and the conducting wire 6 is provided with a glass slide 8 with the attached copper foil. When the power is turned on, the circuit is turned on, and the lamp 5 is turned on. Then, the glass slide 8 of the copper foil is scratched by a knife to form an open circuit, and the bulb 5 is turned off. The microcapsules are then attached to the wound and crushed using a force greater than 14N, the circuit re-completes the circuit and the light bulb 5 re-illuminates. The PEDOT, PSS aqueous solution microcapsule and Fe can be found from the repair circuit formed by the self-repairing microcapsule taking different conductive aqueous solutions as core materials3O4The dispersion solution microcapsule, the graphene oxide dispersion solution microcapsule and the tap water microcapsule can lighten the bulb again. But the de-ionized water microcapsules did not light the bulb. Because the de-ionized water microcapsules contain a core material that is nearly non-conductive. Table 2 shows the conductivity of the self-repairing microcapsules with different conductive aqueous solutions as core materials. Table 3 shows the bearing capacity of the self-repairing microcapsules of different conductive aqueous solutions, and fig. 8 shows the bearing capacity curve of the conductive self-repairing microcapsules using different conductive aqueous solutions as the core material. FIGS. 6a to 6e show that a PEDOT/PSS aqueous solution is used as a core material, a graphene oxide dispersion solution is used as a core material, and Fe is used as a core material3O4SEM image of conductive self-repairing microcapsule with dispersed solution as core material, tap water as core material and deionized water as core material; FIG. 7 shows an optical microscope picture of a conductive self-repairing microcapsule with PEDOT: PSS aqueous solution as a core material; FIGS. 9a to 9e show that a PEDOT/PSS aqueous solution is used as a core material, a graphene oxide dispersion solution is used as a core material, and Fe is used as a core material3O4And an FTIR spectrum of the conductive self-repairing microcapsule with the dispersion solution as a core material, tap water as a core material and deionized water as a core material.
TABLE 2 conductivity of self-repairing microcapsules with different conductive aqueous solutions as core materials
Figure BDA0002534132010000201
TABLE 3 pressure-bearing capacity of self-repairing microcapsules with different conductive aqueous solutions as core materials
Kind of conductive aqueous solution Initial burst value (N) Total rupture number (N)
PEDOT:PSS-MPCMs 12.307 14.478
GO-MPCMs 12.789 15.685
Fe3O4-MPCMs 11.824 14.961
Tap water-MPCMs 11.100 13.754
Deionized Water-MPCMs 10.617 13.513
As can be seen from Table 2, the aqueous solution of PEDOT and PSS was used as a core material, the dispersion solution of graphene oxide was used as a core material, and Fe was used as a core material3O4The conductive self-repairing microcapsule taking the disperse solution as the core material and taking tap water as the core material has better conductivity, particularly, the conductive self-repairing microcapsule taking the PEDOT/PSS aqueous solution as the core material has the best conductivity, and the conductive self-repairing microcapsule taking the deionized water as the core material has small conductivity and is almost non-conductive.
As can be seen from Table 3, the self-repairing microcapsules prepared by the invention and taking different conductive aqueous solutions as core materials have a certain withstand voltage value, but when the withstand voltage value reaches a certain value, the self-repairing microcapsules can be broken, and then the conductive aqueous solutions in the microcapsules are released.
As can be seen from fig. 6a to 6e, the self-repairing microcapsules with different conductive aqueous solutions as core materials are spherical.
As can be seen from FIG. 7, the conductive self-repairing microcapsule with PEDOT/PSS aqueous solution as core material is spherical under an optical microscope and has uniform size.
From the infrared analysis shown in fig. 9a to 9e and the thermal analysis shown in fig. 10 to 12, it can be seen that the polymeric wall material of the conductive self-repairing microcapsule encapsulates the conductive aqueous solution.
In the foregoing embodiments, the descriptions of the respective embodiments have respective emphasis, and for parts that are not described in detail in a certain embodiment, reference may be made to related descriptions of other embodiments.
It will be appreciated that the relevant features of the devices described above may be referred to one another. In addition, "first", "second", and the like in the above embodiments are for distinguishing the embodiments, and do not represent merits of the embodiments.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (5)

1. A preparation method of a conductive self-repairing microcapsule is characterized by comprising the following steps:
mixing a conductive aqueous solution, ammonium persulfate and lauryl sodium sulfate to obtain a core material solution; wherein the mass ratio of the conductive aqueous solution to the ammonium persulfate to the sodium dodecyl sulfate is 20-30:1.5-2.6: 0.8-1.5;
mixing a polymer monomer with deionized water, adding triethanolamine, adjusting the pH value to 8-9, and carrying out prepolymerization reaction at 60-80 ℃ and 400-600rpm to obtain a polymer prepolymer solution;
mixing the oil phase, Span-80 and calcium stearate; adding the core material solution and the polymer prepolymer solution, stirring to form stable W/O emulsion, carrying out in-situ polymerization reaction, and carrying out centrifugation, washing and vacuum drying to obtain the conductive self-repairing microcapsule;
the conductive aqueous solution is at least one of ferroferric oxide dispersion liquid, nano silver dispersion liquid, nano copper dispersion liquid, nano aluminum oxide dispersion liquid, poly 3, 4-ethylenedioxythiophene/polystyrene sulfonate solution, graphene oxide dispersion liquid, graphene dispersion liquid and tap water;
the polymer monomer is formaldehyde and melamine, or the polymer monomer is formaldehyde, melamine and urea;
the mass ratio of the oil phase, Span-80 and calcium stearate is 50-60:1.5-2: 0.05-0.15;
the oil phase comprises: at least one of liquid paraffin, gasoline and edible oil.
2. The method for preparing the conductive self-repairing microcapsule according to claim 1, further comprising: adding an acid solution into the core material solution, adjusting the pH value to 4-5, and magnetically stirring for 20-40 min; or the like, or, alternatively,
adding an acid solution into the W/O emulsion, adjusting the pH value to 4-5, and magnetically stirring for 20-40 min;
the acid solution is citric acid solution, acetic acid solution or dilute hydrochloric acid solution.
3. The preparation method of the conductive self-repairing microcapsule according to claim 1,
the polymerization reaction is water-in-oil in-situ polymerization, and the reaction conditions are as follows: reacting in water bath at 60-80 ℃ for 3-4h under the conditions of 400 plus materials and 600 rpm.
4. A preparation method of a conductive self-repairing microcapsule is characterized by comprising the following steps:
mixing a conductive aqueous solution, ammonium persulfate and lauryl sodium sulfate to obtain a core material solution; wherein the mass ratio of the conductive aqueous solution to the ammonium persulfate to the sodium dodecyl sulfate is 20-30:1.5-2.6: 0.8-1.5;
melting at least one of gelatin and acacia to obtain wall material liquid;
mixing the oil phase, Span-80 and calcium stearate to obtain water-in-oil dispersion, adding the core material solution and the wall material solution, stirring to form a stable W/O emulsion, and reacting the emulsion for 3-4h in a water bath at 20-25 ℃ and at 600rpm of 400-; centrifuging, washing and vacuum drying to obtain the conductive self-repairing microcapsule;
the conductive aqueous solution is at least one of ferroferric oxide dispersion liquid, nano silver dispersion liquid, nano copper dispersion liquid, nano aluminum oxide dispersion liquid, graphene dispersion liquid, poly 3, 4-ethylenedioxythiophene/polystyrene sulfonate solution and tap water;
the oil phase comprises: at least one of liquid paraffin, gasoline and edible oil;
the mass ratio of the oil phase, Span-80 and calcium stearate is 50-60:1.5-2: 0.05-0.15;
the mass ratio of the core material solution to the wall material solution to the water-in-oil dispersion liquid is as follows: 14-18:25-30:50-60.
5. The application method of the conductive self-repairing microcapsule prepared by the preparation method of any one of claims 1-4 is characterized by comprising the following steps:
the conductive self-repairing microcapsule is sealed and adsorbed on the surface of electronic equipment or a lead;
when the electronic equipment or the lead is damaged, the damaged part is pressed, and the conductive solution in the conductive self-repairing microcapsule is released to the damaged part to form a conductive path.
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