CN113046852B - Coaxial device and method for preparing core-shell hollow structure - Google Patents
Coaxial device and method for preparing core-shell hollow structure Download PDFInfo
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- CN113046852B CN113046852B CN202110307726.XA CN202110307726A CN113046852B CN 113046852 B CN113046852 B CN 113046852B CN 202110307726 A CN202110307726 A CN 202110307726A CN 113046852 B CN113046852 B CN 113046852B
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
- D01D5/30—Conjugate filaments; Spinnerette packs therefor
- D01D5/34—Core-skin structure; Spinnerette packs therefor
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- 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
- D01D5/0038—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion the fibre formed by solvent evaporation, i.e. dry electro-spinning
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
- D01D5/0069—Electro-spinning characterised by the electro-spinning apparatus characterised by the spinning section, e.g. capillary tube, protrusion or pin
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/24—Formation of filaments, threads, or the like with a hollow structure; Spinnerette packs therefor
Abstract
The invention discloses a device and a method for preparing a core-shell hollow structure. All parts can be disassembled, and the cleaning is convenient. The heat of the molten external liquid enables the solvent of the polymer internal liquid to be volatilized rapidly, the particles of the polymer internal liquid move to the molten external liquid and are adsorbed, the concentration and the viscosity of the polymer internal liquid are increased, and the polymer internal liquid and the molten external liquid start to jet together under the traction of the molten external liquid; the polymer particles are adsorbed on the inner layer of the molten material to form a particle film, so that the dissipation of gas is hindered, and uniform and continuous hollow nanofibers or hollow nanoparticles are formed. Solves the problems of high cost, difficult process control, complex preparation process and the like of the traditional preparation method. Especially, the melted external liquid is used to quickly volatilize the solvent of the polymer internal liquid, the process is simple, and the prepared hollow fiber or particle has good performance.
Description
Technical Field
The invention relates to the technical field of preparation of hollow nano structures and coaxial electrostatic jet, and relates to a method and a device for preparing a core-shell hollow structure.
Background
The core-shell structure can be used to combine different materials in a network communication system with novel characteristics and functions; the core material may be used to meet mechanical, chemical or electrical requirements, while the shell layer may be used to provide thermal stability, chemical resistance or surface functionality. The core-shell structure is beneficial to tissue engineering, biosensor technology, drug delivery, electronic equipment, optical equipment, catalysis and other applications; compared with the conventional nanofiber, on the premise of keeping the mechanical property, heat conduction and electric conduction and other properties of the hollow porous nanofiber, the hollow porous nanofiber has the advantages of lighter weight, larger specific surface area and better adsorption property, and has wide application prospects in the fields of biological materials and energy storage.
At present, a great number of researchers are conducting research on the aspect, and the specific surface area of the spinning fiber or the nano particle can be effectively improved by introducing a microporous hollow structure on the spinning fiber or the nano particle. The current effective methods for preparing hollow fibers comprise self-assembly, template methods, electrostatic spinning technologies and the like; the template method is an effective method for preparing the hollow microtube, but the obtained material is limited by the shape and structure of the template; hollow nanotubes with the size from nanometer to micrometer are prepared by using a self-assembly technology, the appearance is usually determined by two synergistic organizations of inorganic matters and organic matters, the length of the obtained nanotubes is usually in a micrometer or submicron range, and the formation of a hollow tubular structure is often accidentally uncontrollable; the electrostatic spinning technology can continuously produce hollow nano fibers with excellent performance, and has outstanding advantages compared with other methods, the introduction technology of the microporous structure of the electrostatic spinning fibers comprises the steps of doping a certain proportion of sacrificial materials during the preparation of electrostatic spinning solution, removing the sacrificial materials through post-treatment means such as solvent, thermal decomposition or photodegradation after the composite fibers are obtained through electrostatic spinning, and finally obtaining the porous nano fibers, but the process is complicated and is difficult to control; therefore, the method is improved on the basis of electrostatic spinning, realizes one-step preparation of the hollow fiber, shortens the preparation process and improves the efficiency.
Disclosure of Invention
In order to solve the problems, the invention discloses a method for preparing a hollow structure and a coaxial device. The invention adds the melted external liquid on the basis of coaxial electrostatic spinning to assist the volatilization of the high molecular internal liquid solvent, in the process of forming fibers or particles, the high molecular internal liquid solvent gradually volatilizes and the high molecular particles are converged on the outer wall of the melt to form a particle film, the particle film prevents the dissipation of gas to a certain extent, and the gas is converged in the fibers or the particles to form a hollow core-shell structure. Meanwhile, the method is simple to operate, has low requirements on equipment, and reduces the cost for preparing the core-shell hollow structure.
The invention also aims to provide a device for coaxially and electrostatically spinning the molten external liquid and the high polymer internal liquid, which can ensure that the high polymer internal liquid solvent flowing through the internal liquid channel cannot volatilize due to the heat of the molten external liquid before flowing out of a nozzle, can ensure that the molten external liquid keeps enough fluidity in the external liquid channel, can coaxially flow with the high polymer internal liquid and form a stable composite Taylor cone, is drawn and stretched by a high-voltage electric field, and is solidified and deposited on a collecting plate by coaxial jet flow along with the volatilization of the high polymer internal liquid solvent and the cooling and solidification of the molten external liquid, so as to obtain the core-shell hollow fibers or particles with better performance.
In order to achieve the purpose, the invention adopts the following technical scheme:
a coaxial nozzle for preparing a core-shell hollow structure comprises an inner nozzle, an outer nozzle, an inner liquid pipe, an outer liquid pipe, a heating rod, a heat conducting cylinder, a heat insulating cylinder, a coaxial fixing block and the like;
interior nozzle and interior liquid pipe pass through threaded connection and constitute interior liquid passageway, and the interior liquid pipe other end and liquid pipe connection, interior liquid outside of tubes cover has a heat-insulating section of thick bamboo to guarantee that the polymer liquid solvent can not volatilize in advance, liquid pipe intercommunication has the peristaltic pump, and the peristaltic pump intercommunication has the liquid storage pot, contains the polymer liquid in the liquid storage pot.
The outer liquid pipe and the heat insulation cylinder form an outer liquid channel, the outer nozzle is in threaded connection with the outer liquid pipe, the outer liquid pipe is axially provided with a threaded hole to be connected with a stainless steel hose, the stainless steel hose is communicated with a molten outer liquid storage cylinder, and the liquid storage cylinder needs to be placed on a heating seat to keep the fluidity of the molten outer liquid.
In a further improvement, the inner nozzle and the outer nozzle and the inner liquid pipe and the outer liquid pipe can be detached for cleaning, and the extension length of the nozzles can be adjusted through threads.
In a further improvement, the liquid storage cylinder is filled with the fused external liquid, and the piston moves in the liquid storage cylinder under the action of external force to extrude the fused external liquid to the external liquid channel.
In addition, four liquid passing ports are required to be formed in the circumferential direction of the coaxial fixing block for keeping the coaxiality of the outer nozzle and the inner nozzle, and the four liquid passing ports are uniformly distributed on the coaxial fixing block, so that the molten outer liquid can flow out uniformly.
In a further improvement, the inner nozzle is made of a heat insulating material, such as ceramic, glass and the like, so as to prevent heat from being transferred to the inner liquid to cause the inner nozzle to be blocked.
In a further improvement, three heating holes are formed in the circumferential direction of the heat conduction cylinder for placing heating rods, a hose channel and a convex groove are arranged in the axial direction, and the convex groove is convenient for positioning the opening of the hose channel and the opening of the outer liquid pipe.
A method and a process for preparing a core-shell hollow structure by volatilizing a molten external liquid auxiliary solvent comprise the following steps:
firstly, assembling a coaxial nozzle, wherein a coaxial fixed block is in transition fit with the nozzle, an outer nozzle is connected with the anode of a high-voltage electrostatic generator through an anode lead, and a collecting plate is connected with the cathode of the high-voltage electrostatic generator through a grounding lead;
and step two, placing the macromolecule internal liquid in a liquid storage tank, wherein the liquid storage tank is connected to a peristaltic pump through a liquid conduit, and the other end of the peristaltic pump is connected with an internal liquid pipe. Putting the molten external liquid material into a liquid storage cylinder, opening a heating seat switch to heat, starting heating by a heating rod, and connecting the liquid storage cylinder with an external liquid pipe through a stainless steel hose;
step three, starting a peristaltic pump to drive the polymer inner liquid, extruding the molten outer liquid by a piston in a liquid storage cylinder under the action of external force, and starting power supply by a high-voltage electrostatic generator;
regulating voltage parameters, piston extrusion speed, flow of a peristaltic pump and distance of a collecting plate to enable the molten external liquid and the polymer internal liquid to form a composite Taylor cone at a nozzle;
step five, starting jet flow by a composite Taylor cone formed by the molten external liquid under the action of a high-voltage electric field, volatilizing a high-molecular internal liquid solvent close to the molten external liquid in the composite Taylor cone, increasing the concentration of a high-molecular solution close to the molten external liquid, and moving and adsorbing high-molecular particles to the molten external liquid; the concentration of the polymer inner liquid close to the molten outer liquid is increased, the viscosity is increased, and the molten outer liquid pulls the polymer inner liquid to jet together;
step six, when the viscosity of the molten external liquid and the polymer internal liquid is large, the electric field force and the traction force are not enough to break the molten external liquid and the polymer internal liquid; in the process of jet flow, the composite Taylor cone is continuously stretched and thinned, the polymer inner liquid solvent is further volatilized, polymer particles are further adsorbed on the surface of the molten outer liquid to form a particle film, the particle film can keep a fiber structure and prevent gas from escaping out of the fiber, the gas release rate is greater than the gas escape rate on the surface of the fiber, at the moment, the polymer particles move towards the molten outer liquid, the gas moves towards the center of the fiber and is gathered, and hollow fibers are obtained on the collecting plate.
Optionally, when the viscosity of the molten outer liquid and the viscosity of the polymer inner liquid are not high enough, the electric field force is greater than the viscous force of the molten outer liquid, the molten outer liquid is broken to form particles, the traction force of the molten outer liquid to the polymer inner liquid in the jet flow process is greater than the viscous force of the molten outer liquid, the polymer inner liquid is broken and is wrapped by the molten outer liquid, the volatilization of the solvent of the polymer inner liquid enables the polymer particles to move and adsorb to the molten outer liquid, a particle film is formed to prevent gas from escaping out of the particle surface, and the hollow particles with the core-shell structure can be obtained on the collecting plate along with the cooling and solidification of the molten outer liquid and the volatilization and solidification of the solvent of the polymer inner liquid.
Drawings
FIG. 1 is a schematic view of the construction of the coaxial device of the present invention;
FIG. 2 is a schematic structural view of a heat-conducting cartridge according to the present invention;
FIG. 3 is a schematic structural view of a coaxial fixing block according to the present invention;
FIG. 4 is a schematic diagram of the formation of the core-shell hollow fiber of the present invention;
FIG. 5 is a cross-sectional view of a core-shell hollow fiber according to the present invention;
FIG. 6 is a schematic diagram of the formation of the core-shell hollow particles of the present invention;
FIG. 7 is a cross-sectional view of a core-shell hollow particle of the present invention;
in the figure, 1 a liquid storage tank, 2 high polymer inner liquid, 3 a heat conducting cylinder, 4 a heating rod, 5 an outer liquid pipe, 6 a heat insulating cylinder, 7 an inner liquid pipe, 8 a coaxial fixing block, 9 an outer nozzle, 10 an inner nozzle, 11 a collecting plate, 12 a grounding lead, 13 a high-voltage electrostatic generator, 14 a positive lead, 15 a stainless steel hose, 16 a heating seat, 17 a molten outer liquid, 18 a liquid storage cylinder, 19 a piston, 20 a liquid guide pipe, 21 a peristaltic pump, 22 hollow fibers and 23 hollow particles
201 high molecular solvent bubble, 202 high molecular particle
301 convex groove, 302 heating hole, 303 hose channel
801 internal nozzle fixing hole, 802 liquid passing port
2201 fiber composite Taylor cone, 2202 fiber particle film, 2203 fiber outer wall and 2204 fiber air hole
2301 granule composite Taylor cone, 2302 granule particle film, 2303 granule outer wall, 2304 granule air hole
Detailed Description
The following describes embodiments of the present invention in detail, which are implemented on the premise of the technical solution of the present invention, and detailed embodiments and specific operation procedures are provided, but the scope of the present invention is not limited to the following embodiments.
Example 1
The invention discloses a coaxial device for preparing a core-shell hollow structure by volatilizing a molten external liquid auxiliary solvent, which mainly comprises a heat conduction cylinder 3, a heating rod 4, an external liquid pipe 5, a heat insulation cylinder 6, an internal liquid pipe 7, a coaxial fixed block 8, an external nozzle 9, an internal nozzle 10 and the like as shown in figure 1.
The inner liquid channel is formed by connecting an inner nozzle 10 and an inner liquid pipe 7, a heat insulation cylinder 6 is sleeved outside the inner liquid pipe 7, and the heat insulation cylinder 6 ensures that the solvent cannot volatilize before the macromolecule inner liquid 2 contacts the fused outer liquid 17; the upper end of the inner liquid pipe 7 is connected with a peristaltic pump 21 through a liquid conduit 20; the outer liquid channel is formed by a heat insulation cylinder 6 and an outer liquid pipe 5, the lower end of the outer liquid pipe 5 is fixedly connected with an outer nozzle 9, and the upper end of the outer liquid pipe 5 is tightly connected with an inner liquid pipe 7;
the inner nozzle 10 passes through an inner nozzle fixing hole 801 on the coaxial fixing block 8 to keep high coaxiality with the outer nozzle 9, four liquid passing holes 802 are uniformly distributed on the circumference of the coaxial fixing block 8 to ensure that the molten outer liquid 17 uniformly flows out of the outer nozzle 9, and sealing rings are arranged at each joint to prevent leakage of the high-molecular inner liquid 2 and the molten outer liquid 17;
the outer liquid pipe 5 is provided with a threaded hole connected with a stainless steel hose 15, the stainless steel hose 15 is communicated with a fused outer liquid storage cylinder 18, the fused outer liquid 17 is placed in the liquid storage cylinder 18, the liquid storage cylinder 18 is placed on a heating seat 16, the fused outer liquid 17 is heated and melted by the heating seat 16, a piston 19 moves in the liquid storage cylinder 18 under the driving of external force to extrude the fused outer liquid 17 into an outer liquid channel, the heat conducting cylinder 3 transmits the heat of the heating rod 4 to the outer liquid pipe 5 to keep the flowability of the fused outer liquid 17, and the peristaltic pump 21 pumps the macromolecule inner liquid 2 into the inner liquid pipe 7.
Example 2
The embodiment is a step and a forming process for preparing a core-shell hollow structure:
assembling all parts together, transitionally matching a coaxial fixing block 8 with an inner nozzle 10 and an outer nozzle 9, connecting the outer nozzle 9 with a high-voltage electrostatic generator 13 through a positive lead 14, and connecting a collecting plate 11 with the high-voltage electrostatic generator 13 through a grounding lead 12;
and step two, placing the polymer particle solution 2 in a liquid storage tank 1, wherein the liquid storage tank 1 is connected to a peristaltic pump 21 through a liquid conduit 20, and the other end of the peristaltic pump 21 is connected with an inner liquid pipe 7. Putting the melted external liquid material 17 into a liquid storage cylinder 18 to start heating and melting, preheating the heating rod 4, and connecting the liquid storage cylinder 18 with an external liquid pipe 5 through a stainless steel hose 15;
step three, starting the peristaltic pump 21 to drive the polymer inner liquid 2, extruding the molten outer liquid 17 by the piston 19 in the liquid storage cylinder 18 under the action of external force, and starting power supply by the high-voltage electrostatic generator 13;
regulating voltage parameters of the high-voltage electrostatic generator 13, the extrusion rate of the piston 19, the flow of the peristaltic pump 21 and the distance of the collecting plate 11 to enable the molten external liquid 17 and the polymer internal liquid 2 to form a composite Taylor cone at a nozzle;
step five, starting jet flow on the outer layer of the composite Taylor cone formed by the molten external liquid 17 under the action of a high-voltage electric field, volatilizing the high-molecular internal liquid solvent close to the molten external liquid 2 in the composite Taylor cone to form high-molecular solvent bubbles 201, increasing the concentration of the high-molecular particle solution 2 close to the molten external liquid 17, and enabling the high-molecular particles 202 to move towards the molten external liquid 17 and be adsorbed; the concentration of the polymer inner liquid close to the molten outer liquid is increased, the viscosity is increased, and the molten outer liquid 18 pulls the polymer inner liquid 2 to jet together;
step six, when the viscosity of the molten external liquid 18 and the polymer internal liquid 2 is higher, the electric field force and the traction force are not enough to break the molten external liquid 18 and the polymer internal liquid 2; in the process of jet flow, the composite taylor cone 2201 is continuously stretched and thinned, the polymer internal liquid solvent is further volatilized, the polymer particles 202 are further adsorbed on the surface of the molten external liquid to form a particle film 2202, the particle film 2202 can maintain the fiber structure and prevent gas from escaping out of the fiber, the gas release rate is higher than the gas escape rate from the surface of the fiber, at the moment, the polymer particles 202 move towards the molten external liquid, the gas moves towards the center of the fiber and is gathered to form the fiber air holes 2204, and then the hollow fiber 22 can be obtained on the collecting plate.
Optionally, when the viscous force of the molten external liquid 18 and the polymer internal liquid 2 is not large enough, the pulling force of the molten external liquid 18 on the polymer internal liquid 2 is greater than the viscous force of the molten external liquid in the jet process, the polymer internal liquid 2 is pulled off and wrapped by the molten external liquid 18, the electric field force is greater than the viscous force of the molten external liquid 18, the molten external liquid 18 is pulled off to form particles, the solvent of the polymer internal liquid 2 is further volatilized to enable the polymer particles 202 to move towards the molten external liquid 18 for adsorption, a particle film 2302 is formed to prevent gas from escaping out of the particle surface, and the hollow particles 23 with the core-shell structure can be obtained on the collecting plate along with the cooling and solidification of the molten external liquid 17 and the volatilization and solidification of the solvent of the polymer internal liquid 2.
The above examples are set forth to illustrate the present invention more clearly and should not be construed as limiting the scope of the invention, which is defined in the appended claims to which all modifications of equivalent forms to the present invention that would occur to one skilled in the art after having read the present invention are deemed to fall within the scope of the invention.
Claims (8)
1. A coaxial device for preparing a core-shell hollow structure is characterized by comprising a heating rod, a heat conducting cylinder, a heat insulating cylinder, an inner liquid pipe, an outer liquid pipe, an inner nozzle, an outer nozzle and a coaxial fixing block;
the inner nozzle and the inner liquid pipe are connected to form an inner liquid channel, and a heat insulation cylinder is sleeved outside the inner liquid pipe; the heat insulation cylinder and the outer liquid pipe form an outer liquid channel, the outer liquid pipe is connected with the outer nozzle, and a threaded hole is formed in the axial direction of the outer liquid pipe and fixedly connected with a stainless steel hose; the outer liquid pipe is sleeved with a heat conducting cylinder, and a heating rod is placed in the heat conducting cylinder; a coaxial fixed block is adopted between the inner nozzle and the outer nozzle to keep high coaxiality, four liquid passing ports are required to be formed in the circumferential direction of the coaxial fixed block, and the four liquid passing ports are uniformly distributed on the coaxial fixed block;
2. the coaxial device for preparing the core-shell hollow structure according to claim 1, wherein the inner and outer nozzles and the inner and outer liquid pipes are tightly connected through threads, so that the device is convenient to disassemble and clean, and the extension length of the nozzles can be adjusted.
3. The coaxial device for preparing the core-shell hollow structure as claimed in claim 1, wherein the inner nozzle is made of heat-insulating glass or heat-insulating ceramic to prevent the nozzle from being blocked due to the volatilization of the solvent caused by the heat transferred to the polymer inner liquid.
4. The coaxial device for preparing the core-shell hollow structure according to claim 1, wherein the heat conducting cylinder has three heating holes for placing heating rods in the circumferential direction, and has a hose passage and a convex groove in the axial direction, and the convex groove is used for positioning the screw thread openings on the hose passage and the outer liquid pipe.
5. A method for preparing a core-shell hollow structure by volatilizing a molten external liquid auxiliary solvent is characterized by comprising the following steps:
firstly, assembling a coaxial nozzle, wherein a coaxial fixed block is in transition fit with the nozzle, an outer nozzle is connected with the anode of a high-voltage electrostatic generator through an anode lead, and a collecting plate is connected with the cathode of the high-voltage electrostatic generator through a grounding lead;
secondly, placing the macromolecule internal liquid in a liquid storage tank, wherein the liquid storage tank is connected to a peristaltic pump through a liquid conduit, and the other end of the peristaltic pump is connected with an internal liquid pipe; putting the molten external liquid into a liquid storage cylinder, opening a heating seat switch to heat, starting heating by a heating rod, and connecting the liquid storage cylinder with an external liquid pipe through a stainless steel hose;
step three, starting a peristaltic pump to drive the polymer inner liquid, extruding the molten outer liquid by a piston in a liquid storage cylinder under the action of external force, and starting power supply by a high-voltage electrostatic generator;
regulating voltage parameters of the high-voltage electrostatic generator, the piston extrusion speed, the flow of the peristaltic pump and the distance of the collecting plate to enable the molten external liquid and the polymer internal liquid to form a composite Taylor cone at the nozzle;
step five, starting jet flow by a composite Taylor cone formed by the molten external liquid under the action of a high-voltage electric field, volatilizing a high-molecular internal liquid solvent close to the molten external liquid in the composite Taylor cone, increasing the concentration of a high-molecular solution close to the molten external liquid, and moving and adsorbing high-molecular particles to the molten external liquid; the concentration of the polymer inner liquid close to the molten outer liquid is increased, the viscosity is increased, and the molten outer liquid pulls the polymer inner liquid to jet together;
step six, when the viscosity of the molten external liquid and the polymer internal liquid is large, the electric field force and the traction force are not enough to break the molten external liquid and the polymer internal liquid; in the process of jet flow, the composite Taylor cone is continuously stretched and thinned, the solvent of the polymer inner liquid is further volatilized, the polymer particles are further adsorbed on the surface of the molten outer liquid to form a particle film, the particle film can keep a fiber structure and prevent gas from escaping out of the fiber, the gas release rate is greater than the gas escape rate from the surface of the fiber, at the moment, the polymer particles move towards the molten outer liquid, the gas moves towards the center of the fiber and is gathered, and the hollow fiber with the core-shell structure is obtained on a collecting plate;
when the viscous force of the outer molten liquid and the inner polymer liquid is not large enough, the electric field force is larger than the viscous force of the outer molten liquid, the outer molten liquid is pulled off to form particles, the traction force of the outer molten liquid to the inner polymer liquid in the jet flow process is larger than the viscous force of the inner polymer liquid, the inner polymer liquid is pulled off and is wrapped by the outer molten liquid, the volatilization of the solvent of the inner polymer liquid enables the polymer particles to move and adsorb to the outer molten liquid, a particle film is formed to prevent gas from escaping out of the surface of the particles, and the hollow particles with the core-shell structure can be obtained on the collecting plate along with the cooling and solidification of the outer molten liquid and the volatilization and solidification of the solvent of the inner polymer liquid.
6. The method for preparing the core-shell hollow structure according to claim 5, wherein the molten external liquid is a high molecular polymer comprising polyformaldehyde, polylactic acid and polycaprolactone, the melting temperature is 50-300 ℃, and the conductivity is poor in the molten state, so that the inner nozzle and the high molecular internal liquid are uncharged; the boiling point of the polymer internal liquid solvent is lower than the temperature of the molten material, and the polymer internal liquid solvent has higher solubility on polymer particles.
7. The method for preparing a core-shell hollow structure according to claim 5, wherein the voltage of the positive electrode of the external nozzle is adjusted within a range of 0-10 kV, the distance between receiving plates is 0-50 mm, the extrusion rate of the molten external liquid is 0-60 ml/h, the flow rate of the polymer internal liquid is 0-50 ml/h, and the extrusion rate of the molten external liquid is greater than the flow rate of the polymer internal liquid, so that the internal liquid particles are completely wrapped by the molten external liquid.
8. The method for preparing the core-shell hollow structure according to claim 5, wherein the final product is different when the viscosity of the molten external liquid is different from that of the polymer internal liquid; when the viscosity of the molten external liquid and the polymer internal liquid is greater than the electric field force and the traction force, the core-shell hollow fibers can be obtained on the collecting plate, and when the viscosity of the molten external liquid and the polymer internal liquid is less than the electric field force and the traction force, the core-shell hollow particles can be obtained on the collecting plate.
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| KR100549140B1 (en) * | 2002-03-26 | 2006-02-03 | 이 아이 듀폰 디 네모아 앤드 캄파니 | A electro-blown spinning process of preparing for the nanofiber web |
| ES2326455B2 (en) * | 2007-11-27 | 2010-02-26 | Universidad De Sevilla | PROCEDURE FOR THE MANUFACTURING IN AMBIENT TEMPERATURE OF MICRO AND NANOFIBERS OF LIGNINA AND OTHER RESINOSUS COMPOUNDS. |
| US8518320B2 (en) * | 2009-05-21 | 2013-08-27 | University Of Cincinnati | Methods for electrospinning hydrophobic coaxial fibers into superhydrophobic and oleophobic coaxial fiber mats |
| KR101060224B1 (en) * | 2009-06-12 | 2011-08-29 | 주식회사 아모그린텍 | Spray nozzle for electrospinning and electrospinning apparatus using the same |
| CN201924106U (en) * | 2010-11-22 | 2011-08-10 | 北京化工大学 | Device adopting electrostatic spinning for continuous preparation of non-woven fabric products |
| CN203728972U (en) * | 2014-02-19 | 2014-07-23 | 厦门大学 | Fused core-casing micro-nanofiber preparation device |
| CN105926055B (en) * | 2016-06-23 | 2018-06-15 | 浙江大学 | The electrospinning process of regulation and control micro/nano-fibre configuration of surface in situ |
| JP6982698B2 (en) * | 2017-12-12 | 2021-12-17 | パク， ジョン−スＰＡＲＫ， Ｊｏｎｇ−Ｓｕ | Double nozzle for coaxial control |
| CN109023561B (en) * | 2018-10-26 | 2023-08-15 | 青岛科技大学 | Electrostatic spinning device for preparing core-shell structure fibers in batches |
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